Oligomer, method for producing oligomer, and method for producing polymer

Abstract

To provide a new oligomer, and a method for producing the oligomer, and a method for producing a polymer.SOLUTION: An oligomer according to the present disclosure is represented by formula (1). (In formula (1), R1, R2, R11, R12, R13, and R14 each independently represent a hydrogen atom or an aliphatic hydrocarbon group, and any two adjacent ones among these groups may be bonded to each other to form a cyclic structure. n represents an integer of 0 to 3. X and Y are different from each other and are functional groups containing at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Z represents an optional repeating unit. m represents 3 to 248.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to oligomers, methods for producing oligomers, and methods for producing polymers.

[0002] Polyolefin polymers such as polyethylene are polymers that have excellent weather resistance, chemical resistance, and mechanical properties, and many products containing polyolefin polymers are used in our daily lives. In particular, polyethylene polymers are used as packaging materials for food, electronic components, and various everyday items due to their stability and light weight, thereby enriching our daily lives.

[0003] However, due to its stability, polyethylene polymers are hardly decomposed even when physically reduced to the smallest possible size. Therefore, if polyethylene polymers are disposed of in landfills, they will remain in the ground semi-permanently. Furthermore, if polyethylene polymers are dumped, they may become marine litter and have a negative impact on marine life.

[0004] Therefore, in order to reuse polyolefin polymers such as polyethylene contained in waste materials, a chemical recycling method is used in which raw material monomers obtained by decomposing the polyolefin polymers are reused. However, due to the large molecular weight of many polyolefin polymers, a huge amount of energy is required to decompose them into the original raw material monomers. Therefore, among chemical recycling methods, thermal recycling is used, but this method inevitably generates carbon dioxide and has a large environmental impact, so it is not a preferable method from the viewpoint of global environmental conservation.

[0005] Therefore, polyolefin polymers that can be easily chemically recycled without placing a burden on the environment have been proposed. For example, Patent Documents 1 to 5 and Non-Patent Documents 1 and 2 disclose polyolefin polymers containing structural units derived from ketene acetal in the main chain. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 04-081450 [Patent Document 2] Japanese Patent Application Publication No. 58-015508 [Patent Document 3] Japanese Patent Application Publication No. 04-081450 [Patent Document 4] Special Publication No. 06-504086 [Patent Document 5] U.S. Patent No. 5,281,681 [Non-patent literature]

[0007] [Non-Patent Document 1] iScience.,Volume23,Issue3,27 / March / 2020,100904 [Non-patent document 2] J.Environ.Polym.Degrad.,Volume6,p23-29(1998) Summary of the Invention [Problem to be solved by the invention]

[0008] Here, oligomers having molecular weights smaller than those of the polyolefin polymers described in the above Patent Documents 1 to 5 and Non-Patent Documents 1 and 2 would be useful as various industrial materials. The present invention aims to solve the above problems and to provide a novel oligomer, a method for producing the oligomer, and a method for producing the polymer. [Means for solving the problem]

[0009] As a result of investigations conducted by the present inventors in light of the above problems, the above problems were solved by the following means. [1] An oligomer represented by formula (1). [ka] (In formula (1), R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 each independently represents a hydrogen atom or an aliphatic hydrocarbon group, and any two adjacent groups among these groups may be bonded to each other to form a cyclic structure. n represents an integer of 0 to 3. X and Y are different from each other and are functional groups containing at least one atom selected from the group consisting of oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. Z represents any repeating unit. m represents 3 to 248. [2] The oligomer according to [1], wherein Z comprises a structure represented by formula (2): [ka] (In formula (2), R 3 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 3 ~R 6 At least one of them is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.) [3] The oligomer according to [1] or [2], wherein X and Y each independently represent a combination of -OH and -COOR, a combination of -COOR and -NHR, or a combination of -SH and -COOR, and R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. [4] The oligomer according to any one of [1] to [3], wherein the oligomer represented by formula (1) includes an oligomer represented by formula (3). [ka] (In formula (3), n represents an integer of 1 to 3. mp represents an integer of 2 to 247. R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 1 and R2 may be bonded to each other to form a cyclic structure. Z includes a structure represented by formula (2). [ka] (In formula (2), R 3 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 3 ~R 6 At least one of them is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.) [5] The oligomer according to any one of [1] to [4], wherein Z is derived from a radical polymerizable monomer. [6] The oligomer according to [5], wherein the radical polymerizable monomer comprises at least one selected from the group consisting of ethylene and olefins having 3 to 12 carbon atoms. [7] The oligomer represented by formula (1) includes an oligomer represented by formula (4), The oligomer according to any one of [1] to [6]. [ka] (In formula (4), R 3 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 3 ~R 6 At least one of the groups is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and mp represents an integer of 2 to 247. [8] A method for producing an oligomer represented by formula (1), A method for producing an oligomer, comprising decomposing a polymer (1-1) containing a structural unit represented by formula (1-A) and a structural unit represented by formula (1-B) by cleaving the xy portion. [ka] (In formula (1), R 1 , R 2 , R11 , R 12 , R 13 , and ,R 14 each independently represents a hydrogen atom or an aliphatic hydrocarbon group, and any two adjacent groups among these groups may be bonded to each other to form a cyclic structure. n represents an integer of 0 to 3. X and Y are different from each other and are functional groups containing at least one atom selected from the group consisting of oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. Z represents any repeating unit. m represents 3 to 248. [ka] (In formula (1-A) and formula (1-B), l and m0 represent integers that satisfy the condition 0.01≦l / (l+m0)≦0.20, and n represents an integer of 1 to 3. Z represents any repeating unit. R 1 and R 2 each independently represents a hydrogen atom or an aliphatic hydrocarbon group. 1 and R 2 may be bonded to each other to form a cyclic structure. xy is a group formed by the covalent bond between X and Y in formula (1). [9] The method for producing an oligomer according to [8], wherein the polymer (1-1) includes a recycled product.

[10] The method for producing an oligomer according to [8] or [9], wherein the decomposition of the polymer (1-1) is carried out by hydrolysis.

[11] The method for producing an oligomer according to [8], wherein the oligomer is the oligomer according to any one of [1] to [7].

[12] A method for producing a polymer, comprising polycondensing the oligomer according to any one of [1] to [7]. [Effects of the Invention]

[0010] The present invention makes it possible to provide novel oligomers, methods for producing oligomers, and methods for producing polymers. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as upper and lower limits. "A to B" means that the range is A or more and B or less. In addition, any combination of the upper and lower limit values ​​of the numerical values ​​in this specification is an example of this embodiment.

[0012] In this specification, "mol %" indicates the content ratio of a specific component contained in a total amount of 100 mol %. Furthermore, "mol %" and "wt %" have the same meaning.

[0013] As used herein, "optional" or "optionally" means that the subsequently described circumstance may or may not occur, and thus the description includes both the occurrence and non-occurrence of the circumstance.

[0014] In this specification, the term "structural unit" refers to a unit derived from a raw material compound used in the production of a polymer, formed by polymerization of the raw material compound, and a partial structure sandwiched between any linking groups in the resulting polymer. It also includes a partial structure at the terminal portion of a polymer, one of which is a linking group and the other of which is a polymerization reactive group. The structural unit may be a unit formed directly by the polymerization reaction, or may be a unit in which a portion of the unit is converted into a different structure by treating the resulting polymer.

[0015] In the general formulas herein, C represents a carbon atom, H represents a hydrogen atom, and O represents an oxygen atom. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it includes both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "alkyl group" includes not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). In this specification, when a notation does not specify whether they are substituted or unsubstituted, it is preferable that they be unsubstituted. Examples of the substituent herein include, preferably, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group; more preferably, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, or an acyl group; even more preferably, an alkyl group, an aryl group, an aryloxy group, or an alkenyl group; and even more preferably, an alkyl group. The formula weight of these substituents is preferably 15 or more and preferably 200 or less. For example, the formula weight of a methyl group (-CH3) is 15. These substituents may further have a substituent, but it is preferable that they have no substituent.

[0016] As used herein, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, as long as the intended effect of the step is achieved. All steps described herein can be performed in any suitable order unless otherwise specified in the specification or clearly contradicted by the context. If the measurement methods, etc. described in the standards shown in this specification change from year to year, they will be based on the standards in effect as of January 1, 2024, unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification are abolished as of January 1, 2024, they will be based on the standards in effect at the time of abolition.

[0017] The oligomer of this embodiment is characterized by being represented by formula (1). [ka] (In formula (1), R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 each independently represents a hydrogen atom or an aliphatic hydrocarbon group, and any two adjacent groups among these groups may be bonded to each other to form a cyclic structure. n represents an integer of 0 to 3. X and Y are different from each other and are functional groups containing at least one atom selected from the group consisting of oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. Z represents any repeating unit. m represents 3 to 248. In this specification, the "oligomer represented by formula (1)" may be referred to as the "oligomer of the present embodiment."

[0018] By using such oligomers, it becomes possible to provide raw materials for new polymers and other industrial materials. In particular, by incorporating the oligomer into a polymer, the resulting polymer can be decomposed. Therefore, the oligomer can be preferably used for producing a recyclable polymer. Furthermore, as will be described later, the oligomer of this embodiment can also be obtained by hydrolysis of a polymer (e.g., polymer (1-1)), so that recycled polymers can also be effectively utilized. For example, the following compound is an example of an oligomer represented by formula (1). When such an oligomer is polycondensed, the terminal OH group reacts with the terminal carboxy group to form an ester bond, resulting in a polyester. [ka] [ka]

[0019] Furthermore, the polymer obtained by the polycondensation can be decomposed by hydrolysis under heating. In other words, by incorporating the oligomer of this embodiment into a polymer, the polymer can be recycled. Furthermore, since a hydrolyzate of a polymer can be used as the oligomer of this embodiment, a recycled product of a polymer (for example, polymer (1-1) described below) can also be used. The oligomer of this embodiment can also be used for various applications such as adhesives.

[0020] First, the details of equation (1) will be explained. In formula (1), R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 each independently represents a hydrogen atom or an aliphatic hydrocarbon group, and preferably a hydrogen atom. The aliphatic hydrocarbon group is more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. The aliphatic hydrocarbon group is preferably an alkyl group or a cycloalkyl group.

[0021] R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 When is an alkyl group, it is preferably an alkyl group having 1 to 10 carbon atoms which may be branched, and more preferably an alkyl group having 1 to 5 carbon atoms which may be branched. R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 When is a cycloalkyl group, it is preferably a cycloalkyl group having 3 to 5 carbon atoms which may have a substituent.

[0022] R 1 , R 2 , R 11, R 12 , R 13 , and ,R 14 Examples of the substituent that the cycloalkyl group may have include an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.

[0023] R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 Examples of the alkyl group having 1 to 10 carbon atoms, which may have a branch, include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-hexyl group, and a 2-ethylhexyl group.

[0024] R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 Examples of the cycloalkyl group having 3 to 10 carbon atoms (if the cycloalkyl group has a substituent, the number of carbon atoms of the substituent is not included in this number of carbon atoms) which may have a substituent include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0025] The above R other than hydrogen atom 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 As the alkyl group, a methyl group, a tert-butyl group, and a cyclohexyl group are preferred, and a methyl group is more preferred.

[0026] Also, R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 Any two adjacent ones of these may be bonded to each other to form a cyclic structure. Also, R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 At least one of R may contain at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms. 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 Preferably, does not contain heteroatoms. R 1 , R 2 , R 11 , R 12 , R 13 , and ,R 14 Two adjacent groups among R may be bonded to each other to form a ring structure. 1 and R 2 are bonded to each other to form a benzomethylene structure.

[0027] In formula (1), n ​​represents an integer of 0 to 3. When n is 2 or 3, a plurality of R 1 and R 2 may be the same or different. n is preferably 2.

[0028] In formula (1), X and Y are different from each other and are functional groups containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of the functional group include -OH, -COOH, -NH2, and -SH. In this embodiment, X and Y are preferably a combination of -OH and -COOR, a combination of -COOR and -NHR, or a combination of -SH and -COOR, where R is each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0029] In formula (1), Z represents any repeating unit. The type of repeating unit is not particularly limited, but an olefin unit is an example of the repeating unit.

[0030] The Z preferably contains a structure represented by formula (2). [ka] (In formula (2), R 3 ~R 6 R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 3 ~R 6 At least one of them is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.)

[0031] When Z contains a structure represented by formula (2), Z may have only the structure represented by formula (2), or may have other structures. Z is preferably a structure represented by formula (2), or a combination of a structure represented by formula (2) and a structure selected from the group consisting of -C(=O)-, -O-, a structural unit derived from a diene which may contain a heteroatom, and a structural unit derived from a compound having a vinyl bond. Z preferably has a repeating unit having at least one alkyl group having 2 to 20 carbon atoms, which may be branched, and at least one cycloalkyl group having 3 to 20 carbon atoms, which may be substituted, on the side chain, and more preferably has a repeating unit having at least one alkyl group having 2 to 20 carbon atoms, which may be branched, on the side chain. By having a repeating unit with such a branched structure, an oligomer having better transparency and strength tends to be obtained. Here, the side chain refers to, for example, a group bonded to a carbon atom in the main chain of a polymer formed from a carbon-carbon double bond possessed by a radical polymerizable monomer. When there are two or more polymer chains formed from a carbon-carbon double bond possessed by a radical polymerizable monomer, the longest chain is considered to be the main chain.

[0032] A preferred example of Z is one having a branched structure represented by structural formula (Y). [ka] (In structural formula (Y), C a , C b , C c represents the methylene carbon adjacent to the branch carbon, and C br represents the methine carbon at the base of the branched chain, and P 1 , P 2 , P 3 represents a polymer residue.

[0033] The proportion of the structure represented by formula (2) (preferably an ethylene unit) in Z is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, still more preferably 95 mol% or more, even more preferably 99 mol% or more, and may be 100 mol%, when the total amount of Z contained in the oligomer of this embodiment is 100 mol%.

[0034] In formula (2), R 3 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 3 ~R 6 At least one of Z is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. 3 ~R 6 Among the m Z's contained in the oligomer of this embodiment, R 3 ~R 6 The ratio of at least one of the hydrocarbon groups having 2 to 20 carbon atoms, which may have a substituent, to the number of carbon atoms in the main chain of 1,000 (R 3 ~R 6is bonded to), the number of carbon atoms is preferably 10 or more, more preferably 15 or more, and more preferably 20 or more, and is preferably 70 or less, more preferably 65 or less, even more preferably 60 or less, and may be 55 or less. These upper and lower limits can be arbitrarily combined, and are preferably 10 to 50, more preferably 15 to 45, and even more preferably 20 to 40. The number of carbon atoms in the 1,000 main chain is measured as described in the Examples below. In addition, the oligomer of this embodiment is such that R of Z 3 ~R 6 It is preferable that a structure in which the moiety corresponding to the following is a methyl group is not detected when measured by the method described in the Examples below.

[0035] Z in formula (1) is preferably derived from a radical polymerizable monomer. The radical polymerizable monomer is preferably a radical polymerizable monomer that does not have a carbon-carbon double bond or a reactive functional group in the side chain when copolymerized. In this embodiment, the radical polymerizable monomer is preferably an olefin, more preferably an α-olefin. In formula (1), when the total amount of structural units represented by Z contained in formula (1) is taken as 100 mol%, the proportion of structural units derived from a radically polymerizable monomer (preferably an olefin, more preferably an α-olefin) is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, even more preferably 99 mol% or more, and may be 100 mol%.

[0036] The radical polymerizable monomer is not particularly limited, and examples thereof include vinyl aromatic hydrocarbons such as styrene, α-methylstyrene, p-methylstyrene, and m-methylstyrene; vinyl alicyclic hydrocarbons such as vinylcyclohexane, vinylcyclopentane, vinylcyclohexene, vinylcycloheptane, vinylcycloheptane, and vinylnorbornane; ethylenically unsaturated carboxylic acids such as maleic anhydride, maleic acid, and itaconic acid; olefins having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene; conjugated dienes such as butadiene, isoprene, and myrcene; acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ketone, and vinyl chloride. vinylidene chloride, vinylidene fluoride; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, pentadecyl (meth)acrylate, and dodecyl (meth)acrylate; (meth)acrylic acid derivatives such as 2-hydroxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, and benzyl (meth)acrylate;2-vinylfuran, 2-isopropenylfuran, 2-vinylbenzofuran, 2-isopropenylbenzofuran, 2-vinyldibenzofuran, 2-vinylthiophene, 2-isopropenylthiophene, 2-vinyldibenzothiophene, 2-vinylpyrrole, N-vinylindole, N-vinylcarbazole, 2-vinyloxazole, 2-isopropenyloxazole, 2-vinylbenzoxazole, 3-vinylisoxazole, 3-isopropenylisoxazole, 2-vinylthiazole, 2-vinylimidazole, 4(5)-vinylimidazole, N-vinylimidazole, N-vinylimidazoline, 2-vinylbenzimidazole, 5(6)-vinylbenzimidazole, 5-isopropenylpyrazole, 2-isopropenyl 1, Ethylenically unsaturated heterocyclic compounds such as 3,4-oxadiazole, vinyltetrazole, 2-vinylpyridine, 4-vinylpyridine, 2-isopropenylpyridine, 3-vinylpyridine, 3-isopropenylpyridine, 2-vinylquinoline, 2-isopropenylquinoline, 4-vinylquinoline, 4-vinylpyrimidine, 2,4-dimethyl-6-vinyl-S-triazine, 3-methylidenedihydrofuran-2(3H)-one, 4-methyl-3-methylidenedihydrofuran-2(3H)-one, and 4-decyl-3-methylidenedihydrofuran-2(3H)-one; and phosphate esters having an ethylenically unsaturated group such as dimethyl methacryloyloxymethyl phosphate and 2-methacryloyloxy-1-methylethyl phosphate.

[0037] The radical polymerizable monomer is preferably at least one selected from the group consisting of ethylene, an olefin having 3 to 12 carbon atoms, a (meth)acrylic acid alkyl ester, vinyl norbornene, vinyl acetate, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride, more preferably at least one selected from the group consisting of ethylene and an olefin having 3 to 12 carbon atoms, even more preferably at least one selected from the group consisting of ethylene and an α-olefin having 3 to 6 carbon atoms, and still more preferably ethylene. These radical polymerizable monomers may be used alone or in combination of two or more.

[0038] Specific examples of formula (2) include repeating units having a branched structure in low-density polyethylene structures known as LDPE and linear low-density polyethylene structures known as LLDPE.

[0039] In formula (1), m represents 3 to 248. The m is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, and even more preferably 7 or more, and is preferably 220 or less, more preferably 200 or less, even more preferably 150 or less, and even more preferably 100 or less, and may be 80 or less, 70 or less, 60 or less, or 50 or less. By setting the m at or above the lower limit, the difference between hydrophilicity and lipophilicity within the molecule becomes clear, and compatibility and adhesiveness tend to be further improved. By setting the m at or below the upper limit, the hydrophilic moieties within the molecule are not buried in the lipophilic moieties, and compatibility and adhesiveness tend to be further improved. Furthermore, the m can be any combination of the above upper and lower limits, and is, for example, preferably 4 or more and 220 or less, more preferably 5 or more and 200 or less, even more preferably 6 or more and 150 or less, even more preferably 6 or more and 100 or less, and even more preferably 7 or more and 100 or less.

[0040] The oligomer of this embodiment is preferably an oligomer represented by formula (3), and more preferably an oligomer represented by formula (4). [ka] (In formula (3), n represents an integer of 1 to 3. mp represents an integer of 2 to 247. R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 1 and R 2 may be bonded to each other to form a cyclic structure. Z includes a structure represented by formula (2). [ka] (In formula (2), R 3 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 3 ~R 6 At least one of them is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.)

[0041] n in formula (3) has the same meaning as n in formula (1), and the preferred range is also the same. In formula (3), mp is preferably 2 to 247, preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and even more preferably 6 or more. It is also preferably 219 or less, more preferably 199 or less, even more preferably 149 or less, and even more preferably 99 or less, and may be 79 or less, 69 or less, 59 or less, or 49 or less. By setting it to the upper limit or more, the difference between hydrophilicity and lipophilicity within the molecule becomes clear, and compatibility and adhesiveness tend to be further improved. Furthermore, by setting it to the upper limit or less, the hydrophilic portion within the molecule is not buried in the lipophilic portion, and compatibility and adhesiveness tend to be further improved. Furthermore, the mp can be any combination of the above upper and lower limits, and is, for example, preferably 3 or more and 219 or less, more preferably 4 or more and 199 or less, even more preferably 4 or more and 149 or less, even more preferably 5 or more and 9 or less, and even more preferably 6 or more and 99 or less.

[0042] In equation (3), R 1 and R 2 is R in Equation (1). 1 and R 2 The same applies to the preferred range. Z in formula (3) includes the structure represented by formula (2), which is a preferred range of Z in (1) above, and the same applies to further preferred ranges. In the explanation of formula (2), "among m Zs contained in the oligomer" should be read as "among m Zs contained in the oligomer."

[0043] [ka] (In formula (4), R 3 ~R 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 3 ~R 6 At least one of the groups is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and mp represents an integer of 2 to 247.

[0044] In formula (4), mp has the same meaning as mp in formula (3), and the preferred range is also the same. In formula (4), R 3 ~R 6 is R in Equation (2) 3 ~R 6 In the explanation of formula (2), "among m Z's contained in the oligomer" should be read as "among m Z's contained in the oligomer".

[0045] Next, preferred ranges of the physical properties of the oligomer represented by formula (1) will be described. The number average molecular weight of the oligomer of this embodiment is preferably 200 or more, more preferably 250 or more, even more preferably 280 or more, and even more preferably 300 or more, and is preferably 6,200 or less, more preferably 5,700 or less, even more preferably 4,300 or less, even more preferably 2,900 or less, and may be 2,500 or less, 2,000 or less, 1,800 or less, or 1,500 or less. By setting the number average molecular weight at or above the lower limit, the difference between hydrophilicity and lipophilicity within the molecule becomes clear, and compatibility and adhesiveness tend to be further improved. On the other hand, by setting the number average molecular weight at or below the upper limit, the hydrophilic portion within the molecule is not buried in the lipophilic portion, and compatibility and adhesiveness tend to be further improved. The upper and lower limits of the number average molecular weight of the oligomer can be arbitrarily combined, and are preferably 200 to 6,200, more preferably 250 to 5,700, even more preferably 280 to 4,300, and even more preferably 300 to 2,900.

[0046] The oligomer of this embodiment preferably has a melting point (Tm) of 70°C or higher, more preferably 75°C or higher, even more preferably 80°C or higher, even more preferably 85°C or higher, and even more preferably 90°C or higher; and preferably 135°C or lower, more preferably 130°C or lower, even more preferably 125°C or lower, even more preferably 120°C or lower, and even more preferably 115°C or lower. By setting the melting point at or above the lower limit, the heat resistance of the oligomer tends to be further improved. Meanwhile, by setting the melting point at or below the upper limit, the decorating and processability of the oligomer tends to be further improved. The upper and lower limit values ​​of the melting point (Tm) of the oligomer can be arbitrarily combined, and are preferably 70° C. to 135° C., more preferably 75 to 130° C., even more preferably 80° C. to 125° C., even more preferably 85 to 120° C., and still more preferably 90 to 115° C. Another example of a combination of the upper and lower limit values ​​of the melting point (Tm) of the oligomer is 90 to 130° C. When the oligomer has two or more melting points (Tm), it is preferable that at least one of the melting points falls within the above range, and it is more preferable that all of the melting points fall within the above range.

[0047] The crystallization temperature (Tc) of the oligomer of this embodiment is preferably 60°C or higher, more preferably 65°C or higher, even more preferably 70°C or higher, even more preferably 75°C or higher, and even more preferably 80°C or higher, and is preferably 125°C or lower, more preferably 120°C or lower, even more preferably 115°C or lower, even more preferably 110°C or lower, and even more preferably 105°C or lower. By setting the crystallization temperature at or above the lower limit, the powder manipulability of the oligomer tends to be further improved. On the other hand, by setting the crystallization temperature at or below the upper limit, the decorating ability, polycondensation ability, and processability of the oligomer tend to be further improved. The upper and lower limits of the melting point crystallization temperature (Tc) of the oligomer can be arbitrarily combined, and are preferably 60 to 125°C, more preferably 65 to 120°C, even more preferably 70 to 115°C, still more preferably 80 to 115°C, and even more preferably 80 to 110°C, and may be 80 to 105°C. When the oligomer has two or more crystallization temperatures (Tc), it is preferable that at least one of the melting points falls within the above range, and it is more preferable that all of the melting points fall within the above range.

[0048] Next, a method for producing the oligomer represented by formula (1) of this embodiment will be described. The oligomer represented by formula (1) can be produced by known methods, but is preferably produced by decomposing the xy portion of polymer (1-1) containing a structural unit represented by formula (1-A) and a structural unit represented by formula (1-B) through cleavage. [ka] (In formula (1-A) and formula (1-B), l and m0 represent integers that satisfy the condition 0.01≦l / (l+m0)≦0.20, and n represents an integer of 1 to 3. Z represents any repeating unit. R 1 and R 2 each independently represents a hydrogen atom or an aliphatic hydrocarbon group. 1 and R 2 may be bonded to each other to form a cyclic structure. xy is a group formed by the covalent bond between X and Y in formula (1).

[0049] In formula (1-A) and formula (1-B), l and m0 represent integers that satisfy the condition 0.01≦l / (l+m0)≦0.20, where l and m0 are molar ratios. Furthermore, the lower limit of the l / (l+m0) is preferably 0.01 or more, more preferably 0.015 or more, and even more preferably 0.02 or more. On the other hand, the upper limit of l / (l+m0) is not particularly limited, and from the viewpoint of the mechanical strength and heat resistance of the obtained polymer (B), it is preferably 0.20 or less, more preferably 0.17 or less, more preferably 0.15 or less, and even more preferably 0.13 or less. The upper and lower limits can be combined in any manner. For example, the (l / (l+m)) is preferably 0.01 or more and 0.20 or less, more preferably 0.015 or more and 0.17 or less, even more preferably 0.015 or more and 0.15 or less, and still more preferably 0.02 or more and 0.13 or less.

[0050] In formula (1-B), l is preferably an integer of 1 to 15, and more preferably an integer of 1 to 10. In formula (1-A), m0 is preferably an integer of 85 to 99, and more preferably an integer of 90 to 99.

[0051] In formula (1-A) and formula (1-B), n, Z, R 1 and R 2 are n, Z, and R in formula (1). 1 and R 2 The same applies to the preferred range.

[0052] In formula (1-B), XY is a group formed by the covalent bond between X and Y in formula (1), and is preferably an ester group, an amide group, or a thioester group, more preferably an ester group.

[0053] The weight average molecular weight (Mw) of the polymer (1-1) is preferably 5,000 to 100,000. The lower limit of the weight average molecular weight (Mw) of the polymer (1-1) is preferably 8,000 or more, and more preferably 10,000 or more, while the upper limit of the weight average molecular weight (Mw) of the polymer (1-1) is preferably 80,000 or less, more preferably 60,000 or less, even more preferably 40,000 or less, still more preferably 30,000 or less, and still more preferably 20,000 or less. The above upper and lower limits can be combined in any combination. For example, the weight average molecular weight (Mw) of polymer (1-1) is preferably 5,000 or more and 80,000 or less, more preferably 5,000 or more and 60,000 or less, even more preferably 8,000 or more and 40,000 or less, still more preferably 10,000 or more and 30,000 or less, and even more preferably 10,000 or more and 20,000 or less.

[0054] The molecular weight distribution (weight average molecular weight / number average molecular weight: Mw / Mn) of the polymer (1-1) is preferably 1.7 to 20, more preferably 1.7 to 15, even more preferably 1.7 to 10, still more preferably 1.7 to 5, still more preferably 1.7 to 3, even more preferably 1.8 to 3, and particularly preferably 1.9 to 3.

[0055] The Mw and Mw / Mn of the polymer (1-1) are values ​​measured by gel permeation chromatography (GPC), and the measurement conditions are as described in the examples below.

[0056] The Mw and Mw / Mn of the polymer (1-1) can be controlled arbitrarily by appropriately optimizing known conditions such as the polymerization method and polymerization conditions for the polymer (1-1), the types and blending ratios of the raw materials for the polymer (1-1), and the type and amount of the polymerization catalyst.

[0057] The polymer (1-1) can be synthesized, for example, according to the methods described in the above Patent Documents 1 to 5 and Non-Patent Documents 1 and 2, and these methods are incorporated herein. Specifically, the polymer (1-1) is more preferably produced by radically polymerizing a radically polymerizable monomer and a cyclic ketene acetal, and even more preferably produced by radically polymerizing a radically polymerizable monomer and a cyclic ketene acetal in the presence of a radical polymerization initiator. The radical polymerizable monomer has the same meaning as the radical polymerizable monomer explained in the section on Z in the above formula (1), and the preferred range is also the same. In particular, polymer (1-1) having a branched structure can be obtained by carrying out polymerization by heating under a pressure of 1 MPa to 20 MPa during heating. The pressure during polymerization is preferably 18 MPa or less, more preferably 16 MPa or less, even more preferably 10 MPa or less, even more preferably 7 MPa or less, more preferably 2 MPa or more, and even more preferably 2.5 MPa or more. By setting the pressure at or below the upper limit, the effect of (reducing the reactor for polymer production and its maintenance costs) tends to be further improved. Meanwhile, by setting the pressure at or above the lower limit, the effect of (reducing the polymerization activity and the molecular weight of the polymer) tends to be further improved. Also, The pressure during the polymerization can be arbitrarily combined, and is preferably 2 to 18 MPa, more preferably 2 to 16 MPa, even more preferably 2 to 10 MPa, still more preferably 2 to 7 MPa, and even more preferably 2.5 to 7 MPa. The heating temperature during the polymerization is preferably 60 to 85°C.

[0058] The method for producing the oligomer represented by formula (1) of this embodiment includes decomposing the polymer (1-1) by cleaving the xy moiety. The method for cleaving the xy moiety can be appropriately determined depending on the type of the xy bond, but hydrolysis is preferred.

[0059] The hydrolysis step is preferably carried out in the presence of a basic catalyst in an alcoholic solvent at a temperature in the range of 130° C. to 200° C.

[0060] The temperature during hydrolysis is preferably 140°C or higher, more preferably 150°C or higher, and preferably 190°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower. By setting the temperature at or above the lower limit, hydrolysis reactivity tends to be further improved. On the other hand, by setting the temperature at or below the upper limit, the pressure increase due to heating of methanol can be reduced, and safety tends to be further improved. The temperature may vary during the hydrolysis, and in this case, it is preferable that the average temperature is within the above range.

[0061] Furthermore, since the hydrolysis step is carried out at high temperatures, it is preferable to carry out the step in an inert gas atmosphere such as nitrogen.

[0062] The basic catalyst is not particularly limited, and may be any known basic catalyst used in a typical hydrolysis reaction, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, etc. The basic catalyst may be used alone or in combination of two or more.

[0063] The alcohol solvent is not particularly limited, and may be a known alcohol such as methanol, ethanol, or isopropyl alcohol, particularly a lower alcohol having 1 to 3 carbon atoms. The alcohol solvent may be used alone or in combination of two or more.

[0064] The lower limit of the amount of the basic catalyst used in the hydrolysis step is not particularly limited, and is usually preferably 0.8 equivalents or more, more preferably 1.0 equivalents or more, relative to the polymer (1-1). On the other hand, the upper limit of the amount of the basic catalyst used is not particularly limited, and is usually preferably 20 equivalents or less, more preferably 10 equivalents or less. When the amount of the basic catalyst used is the above lower limit or more, hydrolysis can be carried out at a sufficient hydrolysis rate. When the amount of the basic catalyst used is the above upper limit or less, post-treatment is easy and economical. The lower limit of the amount of the alcohol solvent used in the hydrolysis step is not particularly limited, and is usually preferably 500 parts by mass or more, more preferably 600 parts by mass or more, per 100 parts by mass of the total mass of the polymer (1-1). On the other hand, the upper limit of the amount of the alcohol solvent used is not particularly limited, and is usually preferably 4000 parts by mass or less, more preferably 3000 parts by mass or less, per 100 parts by mass of the total mass of the polymer (1-1). If the amount of the alcohol solvent used is not less than the above lower limit, the hydrolysis will proceed sufficiently, and if it is not more than the above upper limit, the hydrolysis will be efficient.

[0065] The basic catalyst is usually used as an aqueous solution of about 1 to 6N. Therefore, water is present in the reaction system of the hydrolysis step together with the alcohol-based solvent. The upper limit of the amount of water present is not particularly limited, and is usually preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, per 100 parts by mass of the total mass of the polymer (1-1). On the other hand, the lower limit of the amount of water present is not particularly limited, and is usually preferably 100 parts by mass or more, more preferably 200 parts by mass or more, per 100 parts by mass of the total mass of the polymer (1-1). If the amount of water present is equal to or greater than the lower limit, hydrolysis proceeds sufficiently, and if it is equal to or less than the upper limit, hydrolysis can be carried out efficiently.

[0066] After the hydrolysis of the polymer (1-1), it is preferable to carry out purification such as filtration, if necessary.

[0067] The oligomer of this embodiment exhibits excellent coating properties, printability, antistatic properties, inorganic filler dispersibility, adhesion to other resins, and compatibilization with other resins. Utilizing these properties, the copolymer of the present invention can be used in a variety of applications. For example, it can be used as a film, a sheet, an adhesive resin, a binder, a compatibilizer, and the like. [Example]

[0068] The present invention will be explained in more detail below by way of experimental examples in place of working examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. The following examples are merely illustrative and are not intended to limit any of the embodiments described herein. The following examples do not limit the present invention in any way. The values ​​of various manufacturing conditions and evaluation results in the following experimental examples are meant as preferred upper or lower limit values ​​in the embodiments of the present invention, and a preferred range may be defined by a combination of the above-mentioned upper or lower limit value and the values ​​of the following examples or values ​​of the examples themselves.

[0069] [Raw Materials Used] The abbreviations for the raw materials used in the examples and comparative examples are as follows. AIBN: Azoisobutylnitrile (trade name: 2,2'-azobis(isobutyronitrile), manufactured by Tokyo Chemical Industry Co., Ltd.) tBuOH: tert-butanol (Nacalai Tesque, Inc.) 2-Methylene-1,3-dioxepane (synthesized based on U.S. Patent Application Publication No. 2013 / 344159, U.S. Patent No. 5,455,361, and Journal of Organic Chemistry 1999, 64, 8386-8395)

[0070] [Evaluation method] In the following experimental examples, various physical properties were measured by the following methods. <Melting point (Tm) and crystallization temperature (Tc)> The melting point (Tm) and crystallization temperature (Tc) of the polymers and hydrolysis products obtained in the experimental examples were measured using a differential scanning calorimeter (DSC) (manufactured by Hitachi High-Tech Science Corporation, model name: TA7000 DSC7020 AS-3D) according to the following procedure. Approximately 1 mg of the polymer was placed in a sample container and held at 30°C for 3 minutes under a nitrogen gas atmosphere. The sample was then heated from 30°C to 210°C at a heating rate of 10°C / min and held at 210°C for 5 minutes. The sample was then cooled from 210°C to -10°C at a cooling rate of 10°C / min and held at -10°C for 5 minutes. The sample was then heated from -10°C to 210°C at a heating rate of 10°C / min, and the melting point (Tm) and crystallization temperature (Tc) (unit: °C) were determined.

[0071] <Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer obtained in the experimental examples were determined by gel permeation chromatography (GPC measurement) according to the following procedure. A polymer sample (approximately 20 mg) was placed in a vial for a high-temperature GPC sample pretreatment device (manufactured by Polymer Laboratory, model PL-SP 260VS), and an o-dichlorobenzene solution containing BHT as a stabilizer (BHT concentration: 0.5 g / L) was added so that the polymer concentration became 0.1% by mass. Next, the vial containing the sample was placed in the high-temperature GPC sample pretreatment device and heated to 135°C to dissolve the polymer, followed by filtration using a glass filter to obtain a sample for GPC measurement. In either case, no polymer was observed trapped on the glass filter.

[0072] Next, using a high-temperature GPC apparatus equipped with an RI detector (Tosoh Corporation, model name: HLC-8321GPC / HT, column: Tosoh Corporation TSKgel GMH-HT (30 cm × 4 columns)), GPC measurement was performed under the following measurement conditions: sample injection volume approximately 300 μL, column temperature 135°C, o-dichlorobenzene as the measurement solvent (mobile phase), and flow rate 1.0 mL / min. The molecular weight of the polymer was calculated based on a calibration curve relating retention time to molecular weight, which was created from the viscosity equation for ethylene polymers using commercially available monodisperse polystyrene as a standard sample. The viscosity equation is [η] = K × M α For polystyrene, K=1.38E -4 , α=0.70, and for ethylene polymers, K=4.77E -4 , α = 0.70 was used.

[0073] <Polymer composition analysis> 13 The composition of the polymer obtained in the experimental example was analyzed using a C-NMR measurement device (manufactured by Bruker, model name: AVANCE500MHz) according to the following procedure. 30 mg of the polymer was dissolved in 0.6 mL of ODCB (orthodichlorobenzene)-d4, and this was used as an NMR measurement sample. 13 Using a C-NMR measurement device, the measurement temperature was 130°C, pp: zgig (inverse gate decoupling 13C), the number of accumulations was 3000, and D1 was 14.8 seconds. 13 C-NMR measurements were performed. Branching was identified with reference to Macromolecules 1984, 17, 1756-1761. The ethylene chain length was calculated from the ratio of the number of protons of the methylene derived from -CH2COOH or the methylene derived from -CH2OH to the number of protons of the main chain methylene.

[0074] [Experimental Example 1] (Synthesis of Polymer (A-1)) As the polymer (A-1), an ethylene / 2-methylene-1,3-dioxepane (CKA) copolymer was synthesized by the following procedure. A mixture of CKA (30 mL, 29.1 g, 0.25 mol) and tBuOH (400 mL) was added to a 2 L pressure reactor (AC), followed by the addition of a solution (20 mL) of AIBN (0.66 g, 4.0 mmol) dissolved in CKA. The air in the AC was replaced with nitrogen gas (pressure 0.5 MPa) three times, and then the air in the AC was replaced with ethylene gas (pressure 0.2 MPa) three times. The temperature inside the AC was increased, and while supplying ethylene gas, the pressure inside the AC was maintained at 4.0 MPa and the temperature at 75°C, followed by stirring for 3 hours. Thereafter, the temperature inside the AC was cooled to room temperature (25°C), and the atmosphere inside the AC was replaced with nitrogen. The atmosphere inside the AC was replaced with nitrogen, and the polymerization solution was filtered from the bottom of the AC, washed with acetone (100 mL), and dried to obtain a white powder (19.82 g) of ethylene / CKA copolymer, which was designated as polymer (A-1). The resulting polymer (A-1) had a CKA-derived structural unit content of 7.5 mol % and an ethylene-derived structural unit content of 92.5 mol %, with the total structural units being 100 mol %. The polymer had Mw = 12,700, Mn = 5,800, and Mw / Mn = 2.2. Two melting points (Tm) were observed: 89°C and 96°C. The crystallization temperatures (Tc) were 85°C and 51°C. The average carbon length (k) calculated from the CKA-derived structural unit content in the polymer was k = 30, and the average ethylene sequence length (m) was m = 12.3.

[0075] [Experimental Example 2] (Synthesis of Polymer (A-2)) As the polymer (A-2), an ethylene / 2-methylene-1,3-dioxepane (CKA) copolymer was synthesized by the following procedure. Polymerization was carried out in the same manner as above except that CKA (66 mL) and tBuOH (800 mL) were used, to obtain a copolymer (16.7 g), which was designated as polymer (A-2). The resulting polymer (A-2) had a CKA-derived structural unit content of 5.1 mol % and an ethylene-derived structural unit content of 94.9 mol %, with the total structural units being 100 mol %. Its Mw was 12,000, Mn was 6,700, and Mw / Mn was 1.8. Two melting points (Tm) were observed: 100°C and 104°C. The crystallization temperatures (Tc) were 91°C and 54°C. The average carbon length (k) calculated from the CKA-derived structural unit content in the polymer was k=43, and its average ethylene length (m) was m=18.6.

[0076] [Experimental Example 3] (Synthesis of Polymer (A-3)) As the polymer (A-3), an ethylene / 2-methylene-1,3-dioxepane (CKA) copolymer was synthesized by the following procedure. Polymerization was carried out in the same manner as above except that CKA (30 mL) and tBuOH (800 mL) were used and the polymerization time was changed to 6 hours, to obtain a copolymer (5.9 g), which was designated as polymer (A-3). The resulting polymer (A-3) had a CKA-derived structural unit content of 2.4 mol % and an ethylene-derived structural unit content of 97.6 mol %, with the total structural units being 100 mol %. Its Mw was 16,400, Mn was 8,800, and Mw / Mn was 1.9. Two melting points (Tm) were observed: 104°C and 108°C. The crystallization temperatures (Tc) were 95°C and 57°C. The average carbon length (k) calculated from the CKA-derived structural unit content in the polymer was k=82, and its average ethylene length (m) was m=38.2.

[0077] [Experimental Example 4] Polymerization was carried out in the same manner as in Experimental Example 1, except that CKA (149 mL) and tBuOH (800 mL) were used and the polymerization time was changed to 5 hours, to obtain a copolymer (36.5 g), which was designated as polymer (A-4). The resulting polymer (A-4) had a CKA-derived structural unit content of 10.6 mol % and an ethylene-derived structural unit content of 89.4 mol %, with the total structural units being 100 mol %. Its Mw was 12,100, Mn was 5,900, and Mw / Mn was 2.1. Two melting points (Tm) were observed: 81°C and 90°C. The crystallization temperatures (Tc) were 79°C and 46°C. The average carbon length (k) calculated from the CKA-derived structural unit content in the polymer was k=23, and its average ethylene length (m) was m=8.5.

[0078] [Experimental Example 5] (Synthesis of Polymer (A-5)) As the polymer (A-5), an ethylene / 2-methylene-1,3-dioxepane (CKA) copolymer was synthesized by the following procedure. CKA (10 mL), tBuOH (200 mL), ethylene (5.5 MPa), and AIBN (0.0660 g, 0.40 mmol) were polymerized at 75°C for 6 hours to obtain a copolymer (5.3 g), which was designated polymer (A-5). The resulting polymer (A-5) contained 2.0 mol% of CKA-derived structural units and 98 mol% of ethylene-derived structural units, with the total structural units being 100 mol%. Its Mw was 18,200, Mn was 9,300, and Mw / Mn was 2.0. Two melting points (Tm) were observed: 108°C and 111°C. The crystallization temperatures (Tc) were 99°C and 62°C. The average carbon length (k) calculated from the CKA-derived structural unit content in the polymer was k=105, and its average ethylene length (m) was m=49.3.

[0079] [Example 1] Hydrolysis of polymer (A-1) A 2-L pressure reactor (AC) was charged with polymer (A-1) (23.23 g) and MeOH / 1N KOH (350 mL / 70 mL), and the atmosphere was replaced with nitrogen. The mixture was stirred for 5 hours at 160°C, and then the temperature inside the AC was cooled to room temperature (25°C). The resulting suspension was adjusted to pH 1-2 (acidic) using 1N HCl, and the resulting suspension was filtered, and the filtrate was added to distilled water (400 mL). Next, the distilled water containing the filtrate was stirred and then filtered, and the resulting filtrate was poured into acetone (400 mL). Next, the acetone containing the filtrate was stirred and then filtered, and the resulting filtrate was air-dried to obtain a white powder (15.9 g, 67% recovery), which was designated as oligomer (O-1). The ethylene number (m) of the obtained oligomer (O-1) was m = 10.3. From this value, the calculated Mn of the oligomer was 404. Two melting points (Tm) were observed, 94°C and 107°C. The crystallization temperatures (Tc) were 87°C and 96°C. The branching structure is summarized in Table 1.

[0080] [Example 2] Hydrolysis of polymer (A-2) A 2 L pressure reactor (AC) was charged with polymer (A-2) (45.77 g) and MeOH / 1N KOH (350 mL / 70 mL), and the atmosphere was replaced with nitrogen. The mixture was stirred for 5 hours at 160°C, and then the temperature inside the AC was cooled to room temperature (25°C). The resulting suspension was adjusted to pH 1-2 (acidic) using 1N HCl, and the suspension was filtered, and the resulting filtrate was poured into distilled water (400 mL). Next, the distilled water containing the filtrate was stirred and then filtered, and the obtained filtrate was poured into acetone (400 mL). Next, the acetone containing the filtrate was stirred and then filtered, and the resulting filtrate was air-dried to obtain a white powder (36.7 g, 80% recovery), which was designated as oligomer (O-2). The ethylene number (m) of the obtained oligomer (O-2) was m = 27.7. From this value, the calculated Mn of the oligomer was 891. Two melting points (Tm) were observed, 98°C and 110°C. The crystallization temperatures (Tc) were 89°C and 99°C. The branching structure is summarized in Table 1.

[0081] [Example 3] Hydrolysis of polymer (A-3) A 2 L pressure reactor (AC) was charged with polymer (A-3) (10.25 g) and MeOH / 1N KOH (350 mL / 70 mL), and the atmosphere was replaced with nitrogen. The mixture was stirred for 5 hours at 160°C, and then the temperature inside the AC was cooled to room temperature (25°C). The resulting suspension was adjusted to pH 1-2 (acidic) using 1N HCl, and the suspension was filtered, and the resulting filtrate was poured into distilled water (150 mL). Next, the distilled water containing the filtrate was stirred and then filtered, and the obtained filtrate was poured into acetone (200 mL). Next, the acetone containing the filtrate was stirred and then filtered, and the resulting filtrate was air-dried to obtain a white powder (8.93 g, 87% recovery), which was designated as oligomer (O-3). The ethylene number (m) of the obtained oligomer (O-3) was m = 44.0. The Mn of the oligomer calculated from this value was 1,346. The melting point (Tm) was 110°C. The crystallization temperature (Tc) was 102°C. The branching structure is summarized in Table 1.

[0082] [Example 4] Hydrolysis of polymer (A-4) A 2 L pressure reactor (AC) was charged with polymer (A-4) (34.33 g) and MeOH / 1N KOH (350 mL / 70 mL), and the atmosphere was replaced with nitrogen. The mixture was stirred for 5 hours at 160°C, and then the temperature inside the AC was cooled to room temperature (25°C). The resulting suspension was adjusted to pH 1-2 (acidic) using 1N HCl, and the suspension was filtered, and the resulting filtrate was poured into distilled water (400 mL). Next, the distilled water containing the filtrate was stirred and then filtered, and the obtained filtrate was poured into acetone (500 mL). Next, the acetone containing the filtrate was stirred and then filtered, and the resulting filtrate was air-dried to obtain a white powder (23.08 g, 67% recovery), which was designated as oligomer (O-4). The ethylene number (m) of the obtained oligomer (O-4) was m = 8.7. From this value, the calculated Mn of the oligomer was 358. Two melting points (Tm) were observed, 89°C and 102°C. The crystallization temperatures (Tc) were 83°C and 89°C. The branching structure is summarized in Table 1.

[0083] [Example 5] Hydrolysis of polymer (A-5) A 2 L pressure reactor (AC) was charged with polymer (A-5) (5.02 g) and MeOH / 1N KOH (350 mL / 70 mL), and the atmosphere was replaced with nitrogen. The mixture was stirred at 160°C for 5 hours, and then the temperature inside the AC was cooled to room temperature (25°C). The resulting suspension was adjusted to pH 1-2 (acidic) using 1N HCl, and the suspension was filtered, and the resulting filtrate was poured into distilled water (150 mL). Next, the distilled water containing the filtrate was stirred and then filtered, and the obtained filtrate was poured into acetone (200 mL). Next, the acetone containing the filtrate was stirred and then filtered, and the resulting filtrate was air-dried to obtain a white powder (4.07 g, 81% recovery), which was designated as oligomer (O-5). The ethylene number (m) of the obtained oligomer (O-5) was m = 44.7. From this value, the calculated Mn of the oligomer was 1,365. Two melting points (Tm) were observed, 112°C and 129°C. The crystallization temperatures (Tc) were 104°C and 114°C. The branching structure is summarized in Table 1.

[0084] The number of branches of the oligomers obtained in each example is shown below.

[0085] [Table 1]

[0086] In Table 1 above, the number of branches indicates the number per 1,000 carbon atoms in the main chain. In Table 1 above, Me branch means a branched methyl group, Et branch means a branched ethyl group, and Bu branch means a branched butyl group. Long-chain branch means a branched group having 5 or more carbon atoms. Complex type means that the branched chains are complexed (they cannot be distinguished because peaks appear in the same region in NMR), and examples of such structures include the following: [ka] R is an alkyl group.

[0087] [Comparative Example 1] 16-hydroxyhexadecanoic acid The melting point (Tm) of 16-hydroxyhexadecanoic acid purchased from Tokyo Chemical Industry Co., Ltd. was 94° C. The crystallization temperature (Tc) was 79° C. The methylene chain length (n) was 15.

[0088] Comparative Example 2 32-Hydroxydotriacontanoic acid The compound was synthesized according to Org. Lett. 2015, 17, 5456-5459. The melting point (Tm) was 105°C. The crystallization temperature (Tc) was 99°C. The methylene length (n) was n = 31.

[0089] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.

Claims

1. An oligomer represented by formula (1): 【Chemistry 1】 (In formula (1), R １ , R ２ , R １１ , R １２ , R １３ , and R １４ each independently represents a hydrogen atom or an aliphatic hydrocarbon group, and any two adjacent groups among these groups may be bonded to each other to form a cyclic structure. n represents an integer of 0 to 3. X and Y are different from each other and are functional groups containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Z represents any repeating unit. m represents 3 to 248.

2. The oligomer according to claim 1 , wherein Z comprises a structure represented by formula (2): 【Chemistry 2】 (In formula (2), R ３ ~R ６ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ３ ~R ６ At least one of the groups is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.

3. The oligomer according to claim 1, wherein X and Y each independently represent a combination of —OH and —COOR, a combination of —COOR and —NHR, or a combination of —SH and —COOR, and each R independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

4. 2. The oligomer according to claim 1, wherein the oligomer represented by formula (1) comprises an oligomer represented by formula (3): 【Transformation 3】 (In formula (3), n represents an integer of 1 to 3. mp represents an integer of 2 to 247. R １ and R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. １ and R ２ may be bonded to each other to form a cyclic structure. Z includes a structure represented by formula (2). 【Chemistry 4】 (In formula (2), R ３ ~R ６ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ３ ~R ６ At least one of the groups is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.

5. 2. The oligomer of claim 1, wherein Z is derived from a radically polymerizable monomer.

6. 6. The oligomer according to claim 5, wherein the radical polymerizable monomer comprises at least one selected from the group consisting of ethylene and olefins having 3 to 12 carbon atoms.

7. The oligomer represented by formula (1) includes an oligomer represented by formula (4): The oligomer of claim 1. 【Transformation 5】 (In formula (4), R ３ ~R ６ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ３ ~R ６ At least one of the groups is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and mp represents an integer of 2 to 247.

8. A method for producing an oligomer represented by formula (1), comprising the steps of: A method for producing an oligomer, comprising decomposing a polymer (1-1) containing a structural unit represented by formula (1-A) and a structural unit represented by formula (1-B) by cleaving the xy portion. 【Transformation 6】 (In formula (1), R １ , R ２ , R １１ , R １２ , R １３ , and R １４ each independently represents a hydrogen atom or an aliphatic hydrocarbon group, and any two adjacent groups among these groups may be bonded to each other to form a cyclic structure. n represents an integer of 0 to 3. X and Y are different from each other and are functional groups containing at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Z represents any repeating unit. m represents 3 to 248. 【Transformation 7】 (In formula (1-A) and formula (1-B), l and m0 represent integers that satisfy the condition 0.01≦l / (l+m0)≦0.20, and n represents an integer of 1 to 3. Z represents any repeating unit. R １ and R ２ each independently represents a hydrogen atom or an aliphatic hydrocarbon group. １ and R ２ may be bonded to each other to form a cyclic structure; and xy is a group formed by the covalent bond between X and Y in formula (1).

9. The method for producing an oligomer according to claim 8, wherein the polymer (1-1) contains a recycled product.

10. The method for producing an oligomer according to claim 8, wherein the decomposition of the polymer (1-1) is carried out by hydrolysis.

11. The method for producing an oligomer according to claim 8, wherein the oligomer is the oligomer according to any one of claims 1 to 7.

12. A method for producing a polymer, comprising polycondensing the oligomer according to any one of claims 1 to 7.

Images