JP2018109177A - Cyclic polyether-ester composition and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclic compound capable of increasing strength while maintaining extensibility of a resin.SOLUTION: A cyclic polyether-ester compound (P) is a cyclic compound comprising as a constitutional unit at least one group selected from the group consisting of a divalent group represented by general formula (1) having a specific repeating unit, a divalent group represented by general formula (2) having a specific repeating unit, and a divalent group represented by general formula (3) having a specific repeating unit, where such constitutional units are connected cyclically and the total number of specific repeating units included in the cyclic compound is a specific value.SELECTED DRAWING: None

Description

  The present invention relates to a cyclic polyether ester composition, a resin composition containing the same, and a method for producing the cyclic polyether ester composition.

Resin crosslinked products such as urethane elastomers, polyurethane foams, and polyacrylates are used in various industrial applications such as sealing materials, sheets, and films. As a method of crosslinking a resin, a method of reacting various monomers and prepolymers with a crosslinking agent is generally known. However, when a conventional cross-linking agent is used, it is necessary to increase the number of cross-linking points in order to increase the resin strength, and the polymer network structure is more strongly fixed. It was.
As a previous study using a cyclic compound as a cross-linking material, a ring gel containing a rotaxane having a polymer penetrated by cyclodextrin has been reported. However, adjustment requires a plurality of reactions, and the ring size is limited (see, for example, Patent Document 2).

JP 2005-225957 A International Publication No. 01/083566

  An object of the present invention is to provide a cyclic polyether ester composition capable of improving strength while maintaining the extensibility of a resin.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention comprises at least one group selected from the group consisting of a group represented by general formula (1), a group represented by general formula (2), and a group represented by general formula (3). A cyclic polyether ester composition (Q) comprising a cyclic polyether ester compound (P) which is bonded as a unit and satisfies the relational expression (1).

[In the general formula (1), ^{R 1} is a divalent hydrocarbon group having 2 to 21 carbon atoms. The hydrogen atom of R ¹ may be substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group. X ¹ is a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group or a thiocarbonyl group. Y ¹ and Y ² each independently represent an oxygen atom, a sulfur atom, or a divalent group represented by the general formula (4). ; ^{A 1} is a divalent hydrocarbon group having 2 to 8 carbon atoms. The hydrogen atom of A ¹ may be substituted with a halogeno group. ; _{N 1} is an integer of 0 or more. In the cyclic polyether ester composition (Q), when a plurality of R ¹ , A ¹ , X ¹ , Y ¹ and Y ² , n ₁ are contained, they may be the same or different. However, when the compound (P) is composed only of the group represented by the general formula (1), the case where all X ¹ are carbonyl groups and all Y ¹ are oxygen atoms is excluded. ]

[In the general formula (2), ^{R 2} is a divalent hydrocarbon group having 2 to 21 carbon atoms. The hydrogen atom of R ² may be substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group. X ² is a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group, or a thiocarbonyl group. Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are each independently an oxygen atom, a sulfur atom or a divalent group represented by the general formula (4); A ² and A ³ are each independently , A divalent hydrocarbon group having 2 to 8 carbon atoms. The hydrogen atoms of A ² and A ³ may be substituted with a halogeno group. ; _{N 2} and _{n 3} are each independently an integer of 0 or more. In the cyclic polyether ester composition (Q), when a plurality of R ² , A ² and A ³ , X ² , Y ^{3 to} Y ⁶ , n ₂ and n ₃ are contained, they may be the same or different from each other; . ]

[In General Formula (3), R ³ is a divalent hydrocarbon group having 2 to 21 carbon atoms. The hydrogen atom of R ³ may be substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group. X ³ and X ⁴ are a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group or a thiocarbonyl group; Y ⁷ and Y ⁸ are each independently an oxygen atom, a sulfur atom, A divalent group represented by formula (4); A ⁴ is a divalent hydrocarbon group having 2 to 8 carbon atoms; The hydrogen atom of A ⁴ may be substituted with a halogeno group. Z is at least one group selected from the group consisting of a group represented by the general formula (1), a group represented by the general formula (2), and a group represented by the general formula (5). ; _{N 4} and m are each independently an integer of 0 or more. In the cyclic polyether ester composition (Q), when a plurality of R ³ , A ⁴ , X ³ and X ⁴ , Y ⁷ and Y ⁸ , Z and n ₄ are contained, they may be the same or different. ]

[In General Formula (4), R ⁴ is a monovalent hydrocarbon group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a halogeno group. ]

[In General Formula (5), Y ⁹ is an oxygen atom, a sulfur atom, or a divalent group represented by General Formula (4). A ⁵ is a divalent hydrocarbon group having 2 to 8 carbon atoms. Hydrogen atoms of A ⁵ are, may be substituted with halogeno group. n ₅ is an integer of 0 or more. ]
<Relational expression (1)>
30 <a + b + c + d ≦ 2000 Relational expression (1)
[In the relational formula (1), a is the average number of added moles of groups represented by (Y ¹ -A ¹ ) contained in the cyclic polyetherester compound (P); The average added mole number of all the groups represented by (Y ³ -A ² ) contained in the polyether ester compound (P) and all (A ³ -Y contained in the cyclic polyether ester compound (P). ⁶ ) is the average number of moles added of the group represented by c); c is the average number of moles added of all the groups represented by (Y ⁷ -A ⁴ ) contained in the cyclic polyetherester compound (P). Yes; d is the average number of moles added of all the groups represented by (Y ⁹ -A ⁵ ) contained in the cyclic polyether ester compound (P). ]

  The cyclic compound in the cyclic composition of the present invention is excellent as a crosslinking agent that improves strength while maintaining the elongation of the resin.

  The cyclic polyether ester composition (Q) of the present invention comprises a group represented by the general formula (1), a group represented by the general formula (2), and a group represented by the general formula (3). A cyclic polyether ester compound (P) satisfying the relational expression (1) is contained by binding at least one group selected from the group consisting of as structural units.

Formula (1), in the general formula (2) and the general formula ^(3), R 1, ^{R 2} and ^{R 3} is a divalent hydrocarbon group having 2 to 21 carbon atoms. The hydrogen atoms of R ¹ , R ² and R ³ may each independently be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group.

  Examples of the hydrocarbon group having 2 to 21 carbon atoms include an alkylene group having 2 to 21 carbon atoms, an alkenylene group having 2 to 21 carbon atoms, an arylene group having 6 to 21 carbon atoms, and an aralkylene group having 7 to 21 carbon atoms. It is done.

  Examples of the alkylene group having 2 to 21 carbon atoms include a linear alkylene group having 2 to 21 carbon atoms (ethylene group, trimethylene group, tetramethylene group, pentamethylene group, tetradecamethylene group and n-henicosanylene group), and 3 carbon atoms. To 21 branched alkylene groups (1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylpropylene group 1-hexylpropylene group and 1-octylethylene group) and a cycloalkylene group having 4 to 21 carbon atoms (cyclobutylene group, cyclopentylene group, 2-methylcyclopentylene group, cyclohexylene group, 1,3- Dimethylcyclohexylene group, cycloheptylene group, 1-ethylcyclopentylene group, cyclooctylene Group, cyclononylene group, cyclodecylene group, cycloundecylene group, cyclododecylene group, cyclotridecylene group, cyclotetradecylene group, cyclopentadecylene group, cyclohexadecylene group, cycloheptadecylene group, cyclooctadecylene group, Cyclononadecylene group, cycloeicosylene group, norbornylene group, dicyclopentylene group, isopropylidene dicyclohexylene group, and cyclohexanedimethylene group).

  Examples of the alkenylene group having 2 to 21 carbon atoms include straight chain alkenylene groups having 2 to 21 carbon atoms (such as ethenylene group, propenylene group and henicosenylene group) and branched alkenylene groups having 3 to 21 carbon atoms (1-ethylethenylene group, 1, 2-dimethylethenylene group, 1-butylethenylene group, 1-hexylethenylene group, 1-octylethenylene group, etc.).

  Examples of the arylene group having 6 to 21 carbon atoms include o-, p- or m-phenylene group, 2,4-naphthylene group, biphenylene group, terphenylene group, anthrylene group, phenanthrylene group, fluorenylene group, pyrenylene group and group. Is mentioned.

  Examples of the aralkylene group having 7 to 21 carbon atoms include phenylmethylene group, diphenylmethine group, 1-phenylethylene group, o-phenyleneethyl group and naphthylmethylene group.

  Examples of the group in which at least one hydrogen atom of these groups is substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group include 1-bromo-trimethylene group, 1-acetyl-trimethylene group, 1-methoxy-trimethylene group And 1-phenoxy-trimethylene group and the like.

Among these, R ¹ , R ² and R ³ are preferably a straight chain having 3 to 16 carbon atoms or a branched alkylene group having 3 to 16 carbon atoms, more preferably a trimethylene group, from the viewpoint of reaction efficiency. A butylene group, a tetradecamethylene group, a 1-hexylpropylene group, a 1-hexylbutylene group, a 1-undecylpropylene group and a 1-undecylbutylene group;

In general formula (1), general formula (2) and general formula (3), X ¹ , X ² , X ³ and X ⁴ are each independently a residue obtained by removing two hydroxyl groups from phosphonic acid, carbonyl A group, a sulfonyl group or a thiocarbonyl group. The residue obtained by removing two hydroxyl groups from phosphonic acid has a hydrogen atom or a monovalent hydrocarbon group on the phosphorus atom. Examples of the hydrocarbon group include a linear or branched chain hydrocarbon group, a monocyclic hydrocarbon group having no side chain or having a side chain, and a polycyclic hydrocarbon group having no side chain or having a side chain. Alternatively, a chain hydrocarbon group substituted with the above monocyclic hydrocarbon group can be used.

In General Formula (1), General Formula (2), and General Formula (3), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ^7, and Y ⁸ are each independently an oxygen atom. , A sulfur atom, and a divalent group represented by the general formula (4).

In General Formula (4), R ⁴ is a monovalent hydrocarbon group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a halogen atom.
Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include saturated hydrocarbon groups having 1 to 12 carbon atoms (methyl group, ethyl group, propyl group, butyl group, decyl, dodecyl group, etc.), monovalent alicyclic ring. Examples thereof include a saturated hydrocarbon group (cyclohexyl group), an araliphatic hydrocarbon group (such as benzyl group), and a monovalent aromatic hydrocarbon group (such as phenyl group).

In General Formula (1), General Formula (2), General Formula (3), and General Formula (5), A ¹ , A ² , A ³ , A ^4, and A ⁵ are each independently a hydrogen atom is a halogen atom. A divalent hydrocarbon group having 2 to 8 carbon atoms which may be substituted with atoms (such as fluorine, chlorine, bromine and iodine).

  Among the divalent hydrocarbon groups having 2 to 8 carbon atoms, in the production method of the cyclic polyetherester compound (P) described later, preferred from the viewpoint of facilitating the production thereof are phenylethylene group, carbon number 2 And more preferable are linear alkylene groups having 2 to 4 carbon atoms (ethylene group, propylene group, butylene group, etc.) and branched alkylene groups having 3 to 4 carbon atoms (methylethylene group, ethyl group). Ethylene group, methylpropylene group, 2-methylpropylene, etc.), particularly preferred are straight-chain alkylene groups having 2 to 4 carbon atoms and branched alkylene groups having 3 to 4 carbon atoms, and most preferred is ethylene. Groups and propylene groups.

  In the general formula (3), each Z is independently selected from the group consisting of a group represented by the general formula (1), a group represented by the general formula (2), and a group represented by the general formula (5). At least one group selected.

In the cyclic polyetherester compound (P) of the present invention, when the cyclic polyetherester compound (P) is composed only of the group represented by the general formula (1), all X ¹ are carbonyl groups, and , Except that Y ¹ is an oxygen atom. That is, when the cyclic polyether ester compound (P) is composed only of the group represented by the general formula (1), X ¹ is not a carbonyl group, and Y ¹ and Y ² are not oxygen atoms. .

In General Formula (1), General Formula (2), General Formula (3), and General Formula (5), n ₁ , n ₂ , n ₃ , n ₄ , n ₅ , and _m are each independently an integer of 0 or more. It is.
N ₁ , n ₂ , n ₃ , n ₄ and n ₅ satisfy the relational expression (1).
<Relational Expression (1)> 30 <a + b + c + d ≦ 2000 Relational Expression (1)

In the relational expression (1), a is the average number of moles added of all the groups represented by (Y ¹ -A ¹ ) contained in the cyclic polyetherester compound (P). When the cyclic polyetherester compound (P) has a divalent group represented by the general formula (3) as a structural unit and Z is a group represented by the general formula (1), N _{1 in} Z is also summed to obtain the value of a.
Further, b represents the average added mole number of all the groups represented by (Y ³ -A ² ) included in the cyclic polyether ester compound (P) and all the groups included in the cyclic polyether ester compound (P). it is a sum of the average addition mole number of the group represented by (a 3 ^{-Y 6).}
When the cyclic polyetherester compound (P) has a divalent group represented by the general formula (3) as a structural unit and Z is a group represented by the general formula (2), N ₂ and n ₃ in Z are also summed to obtain the value of b.
C is the average number of moles added of all the groups represented by (Y ⁷ -A ⁴ ) contained in the cyclic polyetherester compound (P). d is the average number of moles of groups represented by all (Y ⁹ -A ⁵ ) contained in the cyclic polyetherester compound (P).

In addition, the value of “a + b + c + d” of the cyclic polyether ester compound (P) can be obtained by calculating the average number of moles added per repeating unit of each cyclic compound and obtaining the average value for all the cyclic compounds. Specifically, it can be confirmed by the following method.
1. First, the number of repeating units and the number of added moles of the cyclic compound corresponding to each peak are specified by time-of-flight mass spectrometry (hereinafter referred to as MALDI-TOF MS) using a matrix-assisted laser desorption / ionization method described later.
Here, the i-th peak intensity in the MALDI-TOF MS spectrum is I _i , the number of repeating units of the peak is J _i , and the number of added moles is K _i . The average added mole number K _i (average) of alkylene oxide per repeating unit of the i-th peak at this time is represented by the relational expression (2).
<Relational expression (2)>
K _i (average) = L _i / J _i relational expression (2)
2. The average value is calculated based on the peak intensity for the all-cyclic polyether ester compound (P) in the MALDI-TOF MS spectrum.
The average value is expressed by the relational expression (3).
<Relational expression (3)>
a + b + c + d = [ΣK _i (average) × I _i ] / ΣI _i = [ΣL _i / J _i × I _i ] / ΣI _i relational expression (3)
In the present invention, the value of “a + b + c + d” is determined based on the MALDI-TOF MS spectrum unless otherwise specified.

The value of “a + b + c + d” can also be obtained by GPC analysis described later based on the relational expression (4).
<Relational expression (4)>
a + b + c + d = [number average molecular weight of cyclic polyether ester compound (measured by GPC)] / [number average molecular weight of cyclic compound for comparison of molecular weight (GPC)] × [value of “a + b + c + d” of cyclic compound for comparison] 4)

When “a + b + c + d” is 30 or less, the elongation of the resin composition (F) to which the cyclic polyetherester compound (P) is added is insufficient, and when “a + b + c + d” exceeds 2000, the resin composition to which the cyclic compound is added The physical properties (strength, etc.) of the material (F) are lowered.
Further, “a + b + c + d” is preferably 31 or more and 1500 or less, more preferably 50 or more and 500 or less, particularly from the viewpoint of achieving both the elongation and strength of the resin composition to which the cyclic polyetherester compound (P) is added. Preferably they are 50 or more and 200 or less.

The total number of groups represented by the general formula (1), the group represented by the general formula (2) and the group represented by the general formula (3) constituting one molecule of the cyclic polyetherester compound (P) is as follows: At least one or more.
In addition, about said total number, cyclic polyetherester compound (P) has group represented by General formula (3) as a structural unit, and m is not 0, ie, in General formula (3), When the group represented by the general formula (1) and / or the group represented by the general formula (2) is included, the number thereof is also calculated in total.

In general formula (1), general formula (2), general formula (3), general formula (4), and general formula (5), R ^{1 to} R ⁴ , A ^{1 to} A ⁵ , X ¹ to X ⁴ , Y ^{1 to} Y ⁹ , Z, n _{1 to} n ₅ and m may be the same or different from each other.

The composition of R ^{1 to} R ⁴ , A ^{1 to} A ⁵ , X ^{1 to} X ⁴ , Y ^{1 to} Y ⁹ and Z in the case where there are a plurality is Polym. Chem. , 2014, 5, 6905. The structure of the cyclic polyetherester compound (P) can be identified by measurement and analysis by time-of-flight mass spectrometry (also referred to as MALDI-TOF MS) using the matrix-assisted laser desorption / ionization method described in 1).

The cyclic polyether ester compound (P) of the present invention may be used alone or in combination of two or more.
As preferable examples of the cyclic polyetherester compound (P) of the present invention, specifically, in the general formula (1), Y ¹ and Y ² are oxygen atoms, and A ¹ is an ethylene group, a propylene group, or a chloropropylene. A cyclic compound in which R ¹ is a trimethylene group, a pentamethylene group, a tetradecamethylene group or a vinylene group, and X ¹ is a sulfonyl group, and both ends of a divalent group are bonded. .
In the general formula (2), Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are oxygen atoms, A ² and A ³ are a propylene group, an ethylene group, a chloropropylene group or a phenylethylene group, and R ² Is an ethylene group, a propylene group or a vinylene group, and a cyclic compound in which both ends of a divalent group in which X ² is a carbonyl group are bonded.
In the general formula (3), Y ⁷ and Y ⁸ are oxygen atoms, A ⁴ is a propylene group, ethylene group, chloropropylene group or phenylethylene group, and R ³ is an ethylene group, propylene group or vinylene group. in and, m is an integer of 0 or more, the cyclic compounds which X ³ and X ⁴ are bonded to both ends of the group is a carbonyl group.

The adjustment of the value of “a + b + c + d” of the cyclic polyether ester compound (P) is carried out by using the cyclic compound (B) and the cyclic compound (C) described later in detail in the production method of the cyclic polyether ester compound (P) described later. This can be done by adjusting the ratio.
Moreover, the value of m in General formula (3) uses the compound represented by the below-mentioned general formula (6) as a cyclic compound (B), and also uses the following general formula (B) as a cyclic compound (B). It can adjust by using together the compound represented by 7) and / or the compound represented by the following general formula (8).
Incidentally, values of and m ⁿ 1 ~n ⁵ cyclic polyether ester compound (P) is, Polym. Chem. , 2014, 5, 6905. And can be confirmed by MALDI-TOF MS described in 1.

The number average molecular weight (hereinafter abbreviated as Mn) of the cyclic polyetherester compound (P) contained in the crosslinking agent of the present invention can be adjusted according to the molecular weight of the polymer compound (E), etc. From the viewpoint of achieving both elongation and strength of the resin composition containing the polyetherester compound (P), it is preferably 1,400 to 180,000, more preferably 2,200 to 60,000, particularly preferably. 2,200-25,000.
The Mn of the cyclic polyether ester compound (P) can be adjusted to the above preferred range by adjusting the number of added moles of the alkylene compound.

Mn of the cyclic polyether ester compound (P) can be measured under the following conditions using gel permeation chromatography (hereinafter abbreviated as GPC).
・ Device: “TOSOH ECO HLC-8320 GPC” [manufactured by Tosoh Corporation]
-Column: “Guardcolumn Super AW-H” (1), “TSKgel SuperAW2500, TSKgel SuperAW3000, 1 TSKgel SuperAW4000 each connected” [all manufactured by Tosoh Corporation]
Sample solution: 0.125 wt% DMF (LiBr 0.01 mol / L) solution Solution injection amount: 20 μL
・ Flow rate: 0.6 mL / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene oxide

  The cyclic polyether ester compound (P) of the present invention can be produced by the production method of the present invention described in detail below.

  The manufacturing method of the cyclic polyether ester compound (P) of this invention consists of a compound represented by the compound represented by General formula (6), the compound represented by General formula (7), and General formula (8). At least one cyclic compound (B) selected from the group, a C2-C8 cyclic ether in which a hydrogen atom may be substituted with a halogen atom, and a carbon number in which a hydrogen atom may be substituted with a halogen atom A step of reacting 2 to 8 cyclic thioethers and at least one cyclic compound (C) selected from the group consisting of cyclic imines having 2 to 8 carbon atoms in which hydrogen atoms may be substituted with halogen atoms (hereinafter referred to as reaction) It is manufactured by a manufacturing method including a process).

[In the general formula (6), ^{R 5} is a divalent hydrocarbon group having 2 to 21 carbon atoms. In addition, the hydrogen atom of R ⁵ may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. Each of X ⁵ independently represents a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group, or a thiocarbonyl group. ; Y ¹⁰ each independently represent an oxygen atom, a divalent group represented by a sulfur atom, the general formula (4). ]

[In General formula (7), R < ⁶ > is a C2-C21 bivalent hydrocarbon group. Further, the hydrogen atom of R ⁶ may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. Each of X ⁶ is independently a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group, or a thiocarbonyl group. ; ^{Y 11} and ^{Y 12} each independently represent an oxygen atom, a divalent group represented by a sulfur atom, the general formula (4). ]

[In the general formula (8), ^{R 7} is a divalent hydrocarbon group having 2 to 21 carbon atoms. In addition, the hydrogen atom of R ⁷ may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. Each of X ⁷ and X ⁸ independently represents a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group, or a thiocarbonyl group. ; Y ¹³ each independently represent an oxygen atom, a divalent group represented by a sulfur atom, the general formula (4). ]

In the reaction step, the cyclic compound (B) is cyclic between the X group (X ⁵ , X ⁶ , X ⁷ and X ⁸ ) and the Y group (Y ¹⁰ , Y ¹¹ , Y ¹² and Y ¹³ ). Reaction (carbonyl group and oxygen) in which a group derived from the compound (C) (for example, an oxyalkylene group when a C2-C8 cyclic ether in which a hydrogen atom may be substituted with a halogen atom is used) is inserted In a reaction in which an oxyalkylene group is inserted between atoms, an alkoxylation reaction occurs).
For example, when γ-butyrolactone is used as the cyclic compound (B) and ethylene oxide is used as the cyclic compound (C), Y ¹ is an oxygen atom and A ¹ is an ethylene group in the general formula (1). Y ² is an oxygen atom, R ¹ is a trimethylene group, and X ¹ is a carbonyl group. A cyclic compound is formed by directly bonding both ends of a divalent group represented by the following chemical formula (9) To do.

In this reaction step, the produced cyclic polyether ester compound (P) undergoes a reaction that once cleaves the bond directly connecting the X group and the Y group on the ring, and further the bond directly connecting the X group and the Y group is cleaved. Reaction with the other cyclic compound (at least one cyclic compound selected from the group consisting of P, C and B), and the Y group of one cyclic compound and the X group of the other cyclic compound bind to each other A reaction also occurs.
For example, as described above, when γ-butyrolactone is used as the cyclic compound (B) and ethylene oxide is used as the cyclic compound (C), both ends of the divalent group represented by the following chemical formula (10) are directly bonded. A cyclic polyetherester compound (P) is formed.
Then, when two molecules of this cyclic polyetherester compound (P) undergo the above cleavage reaction and insertion addition reaction, a reaction in which a cyclic compound having two divalent groups in one molecule is formed, and this cyclic compound A reaction in which three molecules react to form a cyclic compound having three divalent groups in one molecule also occurs.

By using together the cyclic compound represented by General formula (6), the cyclic compound represented by General formula (7), and the cyclic compound represented by General formula (8), said cyclic compound (A) Through a ring-opening reaction and an insertion addition reaction, a divalent group represented by the general formula (1), a divalent group represented by the general formula (2), and a divalent group represented by the general formula (3) A cyclic polyether ester compound (P) having a group as a structural unit can be obtained.
Depending on the amount of the cyclic compound represented by the general formula (6), the cyclic compound represented by the general formula (7), and the cyclic compound represented by the general formula (8), the ring-opening may be performed from these cyclic compounds. A cyclic polyether ester compound (P) having 4 or more divalent groups generated by the reaction can be obtained.

  The cyclic polyether ester composition (Q) is a composition containing one or more cyclic polyether ester compounds (P) having different numbers of structural units and different molecular weights. The cyclic polyether ester compound (P) is at least one selected from the group consisting of a group represented by the general formula (1), a group represented by the general formula (2), and a group represented by the general formula (3). A seed group is bonded as a structural unit, and the relational expression (1) is satisfied.

  In addition to the cyclic polyetherester compound (P), the cyclic polyetherester composition (Q) includes a solvent, catalyst (D), cyclic compound (B), cyclic compound (C), and chain polymer described later. May be included.

Formula (6), in the general formula (7) and the general formula ^(8), R 5, ^{R 6} and ^{R 7} is represented by the general formula (1), formula (2) or (3) The same thing as R < ¹ >, R < ² > and R < ³ > illustrated by description of a compound is mentioned, A preferable thing is also the same.

In the general formula (6), the general formula (7), and the general formula (8), X ⁵ , X ⁶ , X ^7, and X ⁸ are the general formula (1), the general formula (2), or the general formula (3). The same thing as X < ¹ >, X < ² >, X < ³ > and X < ⁴ > illustrated by description of the compound represented is mentioned, A preferable thing is also the same.

Formula (6), in the general formula (7) and the general formula ^{(8), Y 10, Y} 11, Y 12 and ^{Y 13} have the general formula (1), the general formula (2) or general formula (3) The same thing as Y < ¹ >, Y < ² >, Y < ³ >, Y < ⁴ >, Y < ⁵ >, Y < ⁶ >, Y < ⁷ > and Y < ⁸ > illustrated by description of the compound represented is mentioned, A preferable thing is also the same.

  Specific examples of the compound represented by the general formula (6) include lactone, sultone, lactam, thiolactam, sultam and the like exemplified below.

Examples of the lactone represented by the general formula (6) include β-lactone (β-propiolactone, β-butyrolactone, etc.), γ-lactone (γ-butyrolactone, etc.), δ-lactone (δ-valerolactone, etc.), ε-lactone (such as ε-caprolactone), lactone having a long chain alkyl group (such as γ-enanthlactone, γ-undecanolactone, γ-dodecanolactone and δ-dodecanolactone), γ-crotonolactone, α- Methylene-γ-butyrolactone, γ-methylene-γ-butyrolactone, α-bromo-γ-butyrolactone, α-chloro-γ-butyrolactone, α-iodo-γ-butyrolactone, tetronic acid, macrocyclic lactone (15-pentadecano Lactone) and aromatic lactone (3,4-dihydrocoumarin).
Moreover, D, L, D / L-lactide, poly-epsilon caprolactone, etc. can be used suitably as a lactone containing two or more carbonyl structures instead of the lactone represented by the general formula (6).
From the viewpoint of reactivity, β-lactone (β-propiolactone, β-butyrolactone, etc.), γ-lactone (γ-butyrolactone, etc.), δ-lactone (δ-valerolactone, etc.), ε-lactone (ε-caprolactone, etc.) Etc.), tetronic acid, macrocyclic lactone (15-pentadecanolactone) and aromatic lactone (3,4-dihydrocoumarin), particularly preferably γ-lactone (such as γ-butyrolactone), δ-lactone ( δ-valerolactone etc.) and ε-lactone (ε-caprolactone etc.) are preferred.
These lactones may be used alone or in combination of two or more.

As the sultone represented by the general formula (6), 1,3-propane sultone, 1,4-butane sultone, 1,5-pentane sultone, 1,6-hexanes sultone, 1,7-heptane sultone, 1, 8-octane sultone, 1,9-nonane sultone, 1,10-decane sultone, 1,11-undecane sultone, 1,12-dodecane sultone, sultone having an alkyl group (such as 1-methyl-1,3-propane sultone), etc. Is mentioned.
From the viewpoint of reactivity, 1,3-propane sultone, 1,4-butane sultone, 1,5-pentane sultone, 1,6-hexane sultone, 1,7-heptane sultone, 1,8-octane sultone, 1, 9-nonane sultone, 1,10-decane sultone, 1,11-undecane sultone, 1,12-dodecane sultone, and particularly preferably 1,3-propane sultone, 1,4-butane sultone, 1,5-pentane sultone, 1,6-hexane sultone is preferred.

As the lactam represented by the general formula (6), β-lactam (β-propiolactam, β-butyrolactam etc.), γ-lactam (γ-butyrolactam etc.), δ-lactam (δ-valerolactam etc.), ε-lactam (ε-caprolactam, etc.), lactam having a long chain alkyl group (γ-enantolactam, γ-undecanolactam, γ-dodecalactam, δ-dodecanolactam, etc.), lactam having a substituent at the N-position (N-methyl-γ-butyrolactam, N-allyl-γ-butyrolactam, N-vinyl-γ-butyrolactam, N-propargyl-γ-butyrolactam, N-methyl-ε-caprolactam, N-allyl-ε-caprolactam, N -Vinyl-ε-caprolactam, N-propargyl-ε-caprolactam) γ-crotonolactam, α-methylene-γ-butyrolas Tam, γ-methylene-γ-butyrolactam, α-bromo-γ-butyrolactam, α-chloro-γ-butyrolactam, α-iodo-γ-butyrolactam, macrocyclic lactam (15-pentadecanolactam) and aromatic lactam ( 3,4-dihydroquinoline) and the like.
From the viewpoint of reactivity, β-lactam (β-propiolactam, β-butyrolactam, etc.), γ-lactam (γ-butyrolactam, etc.), δ-lactam (δ-valerolactam, etc.), ε-lactam (ε-caprolactam, etc.) Etc.), lactams having a long-chain alkyl group (γ-enantolactam, γ-undecanolactam, γ-dodecanolactam, δ-dodecanolactam, etc.), lactams having a substituent at the N-position (N-methyl-γ- Butyrolactam, N-allyl-γ-butyrolactam, N-vinyl-γ-butyrolactam, N-propargyl-γ-butyrolactam, N-methyl-ε-caprolactam, N-allyl-ε-caprolactam, N-vinyl-ε-caprolactam, N-propargyl-ε-caprolactam), γ-crotonolactam, α-methylene-γ-butyrolactam, γ-methylene γ- butyrolactam is preferable. In addition, from the viewpoint of reducing by-products, a lactam having a substituent at the N position (N-methyl-γ-butyrolactam, N-allyl-γ-butyrolactam, N-vinyl-γ-butyrolactam, N-propargyl-γ-butyrolactam, N -Methyl-ε-caprolactam, N-allyl-ε-caprolactam, N-vinyl-ε-caprolactam, N-propargyl-ε-caprolactam) and γ-crotonolactam are preferred.

  Examples of the thiolactam represented by the general formula (6) include γ-butyrothiolactam, N-methyl-γ-butyrothiolactam (1-methylpyrrolidine-2-thione), ε-caprothiolactam and N- And methyl-ε-caprothiolactam. From the viewpoint of suppressing by-products, N-methyl-γ-butyrothiolactam (1-methylpyrrolidine-2-thione) and N-methyl-ε-caprothiolactam are preferable.

  Examples of the sultam represented by the general formula (6) include 1,3-propane sultam, N-methyl-1,3-propane sultam, 1,4-butane sultam, N-methyl-1,4-butane sultam and the like. Can be mentioned. From the viewpoint of reactivity, 1,3-propane sultam and N-methyl-1,3-propane sultam are preferable.

  Specific examples of the compound represented by the general formula (7) include 1,3,2-dioxathiolane 2,2-dioxide, 1,3,2-phosphorane 2-oxide, imidazolidinone, 1, Examples include 2,5-thiadiazoline 1,1-dioxide, carbonate, trithiocarbonate, and the like.

  Preferred examples of the 1,3,2-dioxathiolane 2,2-dioxide represented by the general formula (7) include 1,3,2-dioxathiolane 2,2-dioxide.

  Preferred examples of the phosphorane 2-oxide represented by the general formula (7) include 1,3,2-dioxaphosphorane 2-oxide and 4,4,5,5-tetramethyl-1,3,2 -Dioxaphospholane 2-oxide etc. are mentioned.

  Preferable examples of the imidazolidinone represented by the general formula (7) include 2-imidazolidinone and 1,3-dimethyl 2-imidazolidinone.

  Preferred examples of the 1,2,5-thiadiazoline 1,1-dioxide represented by the general formula (7) include 1,2,5-thiadiazoline 1,1-dioxide and N, N-dibenzyl-1,2 , 5-thiadiazoline 1,1-dioxide and the like.

  Preferable examples of the carbonate represented by the general formula (7) include ethylene carbonate, propylene carbonate, and 1,3-dioxane-2-one.

  Preferable examples of the trithiocarbonate represented by the general formula (7) include ethylene trithiocarbonate.

  Specific examples of the compound represented by the general formula (8) include acid anhydrides and cyclic imides.

  As acetic anhydride represented by the general formula (8), succinic anhydride, 3,3-diethyl succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, glutaric anhydride, Examples include 3,5-dimethylglutaric anhydride, 3,3-tetramethyleneglutaric anhydride, and 3-oxabicyclo [3,1,1] heptane-2,4-dinone.

  Examples of the cyclic imide represented by the general formula (8) include succinimide, N-methyl succinimide, 3,3-diethyl succinimide, N-methyl-3,3-diethyl succinimide, maleic imide, N-methylmaleic acid imide, phthalic acid imide, N-methylphthalic acid imide, trimellitic acid imide, N-methyltrimellitic acid imide, glutaric acid imide, N-methylglutaric acid imide, 3,5-dimethylglutaric acid imide, N-methyl-3,5-dimethylglutarimide, 3,3-tetramethyleneglutarimide, N-methyl-3,3-tetramethyleneglutarimide, 3-azabicyclo [3,1,1] heptane-2 , 4-dinone and N-methyl 3-azabicyclo [3,1,1] heptane-2,4-dinone.

From the viewpoint of reactivity, succinimide, N-methyl succinimide, 3,3-diethyl succinimide, maleic imide, N-methyl maleic imide, phthalic imide, and N-methyl phthalic imide are preferable.
From the viewpoint of reducing by-products, N-methyl succinimide, N-methyl-3,3-diethyl succinimide, N-methyl maleic imide, N-methyl phthalic imide, N-methyl trimellitic imide, N -Methylglutarimide, 3, N-methyl-3,5-dimethylglutarimide, N-methyl-3,3-tetramethyleneglutarimide, 3-azabicyclo [3,1,1] heptane-2,4 -Dinone and N-methyl 3-azabicyclo [3,1,1] heptane-2,4-dinone are preferred.

  Of the cyclic compounds (C) represented by the general formulas (6), (7), and (8), the general formulas (6) and (7) are preferable, and more preferably, from the viewpoint of reducing by-products. Is the general formula (6).

  A cyclic compound (B) may be used individually by 1 type, or may use 2 or more types together.

The cyclic compound (B) can be obtained by producing it by the following intramolecular condensation reaction or the like in addition to purchasing it as a reagent.
For example, the compound represented by the general formula (6) is a monovalent group in which a group represented by X ⁵ and a hydroxyl group are bonded to one end of a group represented by R ⁵ (for example, X ⁵ is a carbonyl group). In this case, a monovalent group in which a group represented by Y ¹⁰ and a hydrogen atom are bonded to the opposite end of the group represented by R ⁵ (for example, Y ¹⁰ group is an oxygen atom). In this case, a compound in which a hydroxyl group is bonded is used, a monovalent group in which a group represented by X ⁵ and a hydroxyl group are bonded, and a monovalent group in which a group represented by Y ¹⁰ and a hydrogen atom are bonded. It can be obtained by intramolecular condensation of the group.
As a method for synthesizing a lactone or the like by intramolecular dehydration, heat dehydration by a known method, J. Org. S. Nimitz, R.A. H. Wallenberg, Tetrahedron Lett. Known synthesis methods such as the method described in 1978, 19, 3523 and a method using an enzyme such as lipase can be used.

A monovalent group in which the group represented by X ⁵ and a hydroxyl group are bonded to one end of the group represented by “R ⁵ (for example, a carboxy group when X ⁵ is a carbonyl group) is bonded to one end of the group represented by R ⁵ , A compound in which a monovalent group in which a group represented by Y ¹⁰ and a hydrogen atom are bonded to a terminal opposite to the group represented by ⁵ (for example, a hydroxyl group in the case where the Y ¹⁰ group is an oxygen atom) is bonded As preferable examples of "", monohydroxymonocarboxylic acid having 4 to 22 carbon atoms and the like can be mentioned.
As monohydroxymonocarboxylic acid having 4 to 22 carbon atoms, linear hydroxycarboxylic acid having 4 to 22 carbon atoms (3-hydroxypropanoic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 15 -Hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid and 4-hydroxy-2-butenoic acid) and branched hydroxycarboxylic acids having 3 to 22 carbon atoms (3-hydroxybutanoic acid, 5-hydroxytridecanoic acid, 2-methylene- 4-hydroxybutyric acid, 4-phenyl-4-hydroxybutyric acid, 2,2-dimethyl-4-hydroxybutyric acid, 4-hexyl-4-hydroxybutyric acid, 4-hydroxy-2-methyl-2-butenoic acid, etc.) Can be mentioned.

Of the hydrogen atoms bonded to carbon atoms of the monohydroxymonocarboxylic acid having 4 to 22 carbon atoms, a hydroxycarboxylic acid in which at least one hydrogen atom is substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group is a molecule. A lactone having an internally dehydrated structure can also be used.
Among the monohydroxy monocarboxylic acids having 4 to 22 carbon atoms, examples of the hydroxy carboxylic acid in which at least one hydrogen atom bonded to the carbon atom is substituted with a halogeno group include 2-bromo-4-hydroxybutyric acid. Examples of the hydroxycarboxylic acid substituted with an acetyl group include 2-acetyl-4-hydroxybutanoic acid, and the hydroxycarboxylic acid substituted with an alkoxy group includes 2-methoxy-4-hydroxybutyric acid. Examples of the hydroxycarboxylic acid substituted with a phenoxy group include 2-phenyl-4-hydroxybutyric acid.

Examples of the cyclic ether having 2 to 8 carbon atoms include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, 1, Examples include 2-dichlorooxetane 1,2-pentylene oxide, 1,2-hexylene oxide, tetrahydrofuran, styrene oxide, cyclohexene oxide, epichlorohydrin, and epibromohydrin.
Among these, from the viewpoint of reactivity, ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, and 1,2-hexylene oxide are preferable, and ethylene oxide is more preferable. 1,2-propylene oxide, 1,2-butylene oxide, tetrahydrofuran and epichlorohydrin, particularly preferably ethylene oxide, 1,2-propylene oxide and epichlorohydrin.
A C2-C8 cyclic ether may be used individually by 1 type, or may use 2 or more types together.

Examples of the cyclic thioether having 2 to 8 carbon atoms include ethylene sulfide, propylene sulfide, 1,2-butylene sulfide, 2,3-butylene sulfide, 1,2-pentene sulfide, cyclohexan sulfide, styrene sulfide, epichlorothiosulfide, epi Examples thereof include bromothiosulfide and perchloropropylene sulfide.
Among these, from the viewpoint of reactivity, ethylene sulfide, propylene sulfide, epichlorothiosulfide, epibromothiosulfide and perchloropropylene sulfide are preferable, and ethylene sulfide, epichlorothiosulfide, epibromothiosulfide and perfluoroethylene sulfide are more preferable. Chloropropylene sulfide, particularly preferably ethylene sulfide and perchloropropylene sulfide.
A C2-C8 cyclic thioether may be used individually by 1 type, or may use 2 or more types together.

Examples of the cyclic imine having 2 to 8 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,2-penteneimine, cyclohexeneimine, styreneimine, epichloroimine, and epibromoimine Is mentioned.
Of these, ethyleneimine, epichloroimine and epibromoimine are preferred from the viewpoint of reactivity.
A C2-C8 cyclic imine may be used individually by 1 type, or may use 2 or more types together.

Of cyclic ethers, cyclic thioethers, and cyclic imines, from the viewpoint of reactivity, cyclic ethers and cyclic thioethers are preferable, and cyclic ethers are more preferable.

When two or more cyclic compounds (C) are used in combination, a divalent group represented by A (A ¹ , A ² , A ³ , A ⁴ and A ⁵ ) of the obtained cyclic polyether ester compound (P) Have different types of A corresponding to the type of cyclic compound (C) used.

This reaction step is preferably performed in the presence of a catalyst.
Catalysts used in the reaction process include metal halides (boron, tin, nickel, zinc, aluminum, etc.), inorganic acids (sulfuric acid, phosphoric acid, etc.), and alkali metals (lithium, sodium, potassium, cesium, etc.) hydroxylated. , Amine compounds (such as diethylamine and triethylamine), phosphazenes, double metal cyanide complex catalysts (two types of metals such as zinc hexacyanocobaltate described in JP-A-2005-53952 and JP-A-2006-6203) In the molecule), oxide composites described in JP-A No. 2000-354863, composite oxide of aluminum and magnesium (D1), layered double hydroxide, fired product thereof, and the like Can be used.

The layered double hydroxide used in the production method of the present invention is water of a divalent metal (magnesium, iron, zinc, calcium, nickel, cobalt, copper, etc.) and a trivalent metal (aluminum, iron, manganese, etc.). It means an inorganic layered compound in which a laminated structure is formed by combining with an oxide, and the general formula is [M ²⁺ _1-h M ³⁺ _h (OH) ₂ ] [(W ⁱ⁻ ) _{h / i} · jH ₂ O [Wherein M ²⁺ is a divalent metal, M ³⁺ is a trivalent metal, ^{Wi −} is an i-valent anion (HCO ₃ ⁻ , CO ₃ ²⁻ , PO ₄ ³⁻ , SO ₄ ²⁻ , Cl ⁻ , NO ₂ ^— and NO ₃ ^— etc.), h, i and j are each an independent positive number. ], And includes hydrotalcite, moscoleite, manacite, stichtite, pyroaulite, tacobite, eardrite, meixenelite, and the like. These layered double hydroxides are known as clay minerals, and may be contained in naturally occurring minerals or may be obtained by synthesis.

A catalyst may be used individually by 1 type, or may use 2 or more types together.
Among these, from the viewpoint of reaction efficiency, a fired product of a composite oxide (D1) of aluminum (hereinafter referred to as Al) and magnesium (hereinafter referred to as Mg) and a hydrotal having Al and Mg are preferable. It is a fired product of the site (D2).

The composite oxide (D1) used in the present invention is not particularly limited as long as it is an oxide having Al and Mg. Preferred composite oxides include compounds represented by the following composition formula (11) or (12) Is mentioned.
<Composition Formula 11>
[AMgO / Al ₂ O ₃ / bH ₂ O]
<Composition formula 12>
[Mg _s Al _t O _u ]

In the composition formula (11), a and b are each an independent positive number.
In the composition formula (12), s, t, and u are each an independent positive number.
From the viewpoint of reactivity, s / t is preferably 0.1 or more and less than 0.9. Examples of the composite oxide (D1) include 2.5MgO · Al ₂ O ₃ · bH ₂ O and Mg _0.7 Al _0.3 O _1.15. And KYOWARD 2000 [manufactured by Kyowa Chemical Industry Co., Ltd.].

Examples of the hydrotalcite (D2) used in the present invention include compounds represented by the following composition formula (13).
<Composition formula (13)>
[Mg _1-c Al _c (OH) ₂ ] ^{c +} [CO _{3c / 2} · dH ₂ O] ^c-

  In the composition formula (13), c is a number that satisfies 0 <c ≦ 0.33, and d is a number that satisfies 0 <d ≦ 1.0.

Examples of hydrotalcite (D2) include Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O and Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O. 500 [manufactured by Kyowa Chemical Industry Co., Ltd.] and Kyoward 1000 [manufactured by Kyowa Chemical Industry Co., Ltd.], etc. can be obtained from the market.

  As hydrotalcite (D2) used in the present invention, known minerals described in West German Patent Publication No. 1592126 and European Patent Publication No. 0207811 can also be used in addition to the above compounds.

(D1) and (D2) may be used individually by 1 type, respectively, or may use 2 or more types together.
Among these, composite oxide (D1) is preferable from the viewpoint of reactivity, and 2.5 MgO.Al ₂ O ₃ .nH ₂ O (n is a positive number) and Mg _0.7 Al ₀ are more preferable. _.3 O _1.15 .

The calcined product of the composite oxide (D1) of Al and Mg or the calcined product of the hydrotalcite (D2) having Al and Mg is the composite oxide (D1) or the hydrotalcite (D2) having Al and Mg. It can be obtained by a method of heat treatment under an air atmosphere, preferably under a nitrogen stream, preferably at 400 to 1500 ° C. (more preferably 600 to 1000 ° C.) for 1 to 48 hours.
The fired product of the composite oxide (D1) or the hydrotalcite (D2) containing Al and Mg is hereinafter referred to as a catalyst (D ′).

  In this reaction step, the content of the catalyst is not particularly limited, but from the viewpoint of reaction rate and filtration efficiency, 0.0001 to 60.0 weight with respect to the total weight of the cyclic compound (B) and the cyclic compound (C). % Is preferable, more preferably 0.0001 to 20% by weight, and still more preferably 0.01 to 20.0% by weight.

In this reaction step, a solvent may be added in addition to the cyclic compound (B), the cyclic compound (C) and the catalyst from the viewpoint of facilitating stirring.
Solvents include toluene, xylene, benzene, dimethyl sulfoxide, diglyme, triglyme, 1,4-dioxane, cyclohexane, hexane, diethyl ether, tetrahydrofuran, dimethylformamide, carbon tetrachloride, N-methylpyrrolidone, 1,2-dimethoxyethane. 1,2-dichloroethane, O-dichlorobenzene, chloroform and the like.
A solvent may be used individually by 1 type, or may use 2 or more types together.
Of these, toluene and xylene are preferred from the viewpoints of miscibility with the cyclic compound (B), the cyclic compound (C), and the like and ease of distillation.
The weight of the solvent used in this reaction step is preferably 0 to 90% by weight, more preferably 0, based on the total weight of the cyclic compound (B), the cyclic compound (C) and the catalyst from the viewpoint of reaction rate and the like. ~ 60% by weight.

In this reaction step, the temperature of the cyclic compound (B) and the cyclic compound (C) and, if necessary, the mixture of the catalyst and the solvent is preferably 90 to 250 ° C, more preferably 100 to 190 ° C. .
Further, the time for the above temperature is preferably 1 to 200 hours.

In this reaction step, the cyclic compound (B) and the cyclic compound (C) and, if necessary, a catalyst and a solvent are put into a reaction apparatus, and the inside of the system is replaced and sealed with an inert gas (nitrogen, argon, etc.). It can carry out by stirring and mixing under reaction temperature and reaction time.
As the reaction apparatus, a known reaction apparatus such as a mixing container (such as a flask with a stirrer and an autoclave) attached with a stirring apparatus and a heating apparatus can be used.

In the production method of the present invention, the product [that is, the mixture containing the cyclic polyetherester compound (P)] obtained by the above reaction step is further filtered (the method described in JP2011-213864 A). And a step of purification by a known method such as a gel permeation method and silica gel column chromatography (hereinafter abbreviated as a purification step) may be included.
Only the cyclic polyether ester compound (P) having a specific structure can be extracted by the above purification step.

  In addition to the cyclic polyether ester composition (Q) containing the cyclic polyether ester compound (P), the resin composition (F) of the present invention includes the solvent, a polymer compound (E), a catalyst (D) described later, And various resin additives and the like.

  Examples of resin additives include inorganic salts (such as calcium carbonate and barium sulfate), fillers such as inorganic fibers (such as glass fibers and carbon fibers), whiskers (such as potassium titanate whiskers); flame retardants [phosphate esters and Halogenated phosphoric acid esters (eg, chloroalkyl phosphates)]; metal chelating agents (heavy metal deactivators) [hydrazide and amides, etc.]; peroxide decomposing agents [phosphorus, sulfur]; Agent (hydrochloric acid scavenger) [metal soap (calcium-based, zinc-based)]; foam stabilizer [dimethylpolysiloxane-based foam stabilizer ("SH-200 oil" manufactured by Toray Dow Corning Silicone Co., Ltd.)] .

  Of the resin composition (F), the purity of the cyclic polyether ester composition (Q) (%) of the resin component not including the solvent, the polymer compound (E) and the catalyst (D) described later is In order to reduce the charging error of the resin (F) described later and maintain the resin strength, it is preferably 60% or more, more preferably 80% or more, and particularly preferably 95% or more.

  The resin composition (F) of the present invention has a structure in which the polymer component (E) that is the shaft component penetrates the ring component that is the cyclic polyetherester composition (Q). It is presumed that the strength is improved while keeping.

Examples of the polymer compound (E) contained in the resin composition (F) include polyurethane, polyester, poly (meth) acrylic acid, poly (meth) acrylic acid ester, poly (meth) acrylic acid amide, polysiloxane (polydimethyl). Siloxane etc.) and polyethers and polymers crosslinked with these are preferred,
Among these, polyurethane, polyether, poly (meth) acrylic acid ester, and poly (meth) acrylic acid amide are preferable from the viewpoint of compatibility with the cyclic polyether ester compound (P).
These polymers may be used alone or in combination of two or more.

Further, the polymer compound (E) may be a polymer into which a reactive functional group has been introduced. Examples of the reactive functional group to be introduced include an isocyanate group, an alkenyl group, an alkynyl group, a (meth) acrylate group, a hydroxyl group. , Carboxy group, ester group, aldehyde group, carbonyl group, halogeno group, sulfo group, phospho group, disulfide group, triazide group, cyano group, imine substituent, amidine group, oxime group, silyl group, siloxy group, amino group Thio group, hydroxyl group and maleimide group. Examples of the polymer compound (E) into which these reactive functional groups are introduced include terminal amine-modified polyethylene glycol, terminal thiol-modified polyethylene glycol, terminal maleimide-modified polyethylene glycol, and the like. It is available from NOF Corporation as a registered trademark of the company.
Polyurethane has an isocyanate group, a carboxy group, and a hydroxyl group at the end of the main chain. Polyester has a carboxy group, a hydroxyl group, and the like at the end of the main chain. Polyether has an end of the main chain. It has a hydroxyl group.

Although there is no restriction | limiting in particular in the number average molecular weight of a high molecular compound (E), From viewpoints, such as easiness of synthesis | combination, it is preferable that it is 1000-100,000.
The number average molecular weight of the polymer compound (E) can be measured under the following conditions using the following GPC.
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel”
Super H2000, TSKgel SuperH3000, and TSKgel SuperH4000 connected to each one "[all manufactured by Tosoh Corporation]
・ Sample solution: 0.25 wt% tetrahydrofuran solution ・ Solution injection amount: 10 μL
・ Flow rate: 0.6 mL / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene glycol

  The polymer compound (E) can be produced by a known polymerization method. In the case of polyurethane, polycondensation reaction between polyisocyanate and polyol; in the case of polyester, polycondensation reaction between polycarboxylic acid and polyol; in the case of polypolyacrylic acid, radical polymerization reaction of acrylic acid and / or acrylate ester In the case of polysiloxane, hydrolysis polycondensation reaction of alkoxysilane; in the case of polyether, a known method such as an alkylene oxide addition reaction to a compound having an active hydrogen group (alcohol, carboxylic acid, amine, etc.) is used. Can be manufactured.

In addition, from the viewpoint of stably maintaining the composite structure of the cyclic polyether ester composition (Q) and the polymer compound (E), a crosslinking agent (G) is used in combination during the production, and the crosslinking agent (G) It is desirable to crosslink the polymer compounds (E) having a reactive functional group.
The cross-linking agent (G) is not particularly limited as long as it is a compound having a reactive substituent having two or more functions, and examples thereof include glycerin, polyisocyanate compounds, and diacrylate compounds.

  On the other hand, when the crosslinking agent (G) is not used, the polymer compound (E) has a functional group and / or a bond that can form a pseudo-crosslink (hydrogen bond, ionic bond, intermolecular force, etc.). It is preferable to use the polymer compound (E).

  From the viewpoint of facilitating the formation of a composite structure of the above cyclic polyether ester composition (Q) and the polymer compound (E), the synthesis of the polymer compound (E) is performed as described later. It is preferable to carry out in the presence of the composition (Q).

  The resin composition (F) of the present invention may contain a solvent in addition to the cyclic polyether ester composition (Q) and the high molecular weight compound (B). In the case of using a solvent, it is preferable to appropriately select a solvent having high solubility for the cyclic polyetherester composition (Q). Preferred solvents include toluene, xylene, benzene, dimethyl sulfoxide, diglyme, triglyme, 1,4-dioxane, cyclohexane, hexane, diethyl ether, tetrahydrofuran, dimethylformamide, water, carbon tetrachloride, N-methylpyrrolidone, 1,2- Examples include dimethoxyethane, 1,2-dichloroethane, and chloroform.

When a solvent is not used, it is desirable that the compatibility between the cyclic polyetherester composition (Q) and the polymer compound (E) or various monomers constituting the polymer compound (E) is high.
For example, when the cyclic polyether ester compound (P) has a polyoxypropylene chain, it is preferable to use a polymer compound (polypropylene oxide or the like) having a polyoxypropylene chain as the polymer compound (E). When the cyclic polyetherester compound (P) has a polyoxyethylene chain, it is preferable to use a polymer compound (polyethylene glycol or the like) having a polyoxyethylene chain as the polymer compound (E).

  The resin composition (F) of the present invention may contain silica gel, lignin, cellulose nanofibers, and modified products thereof.

The resin composition (F) of the present invention has a structure in which the ring component in the cyclic polyetherester composition (Q) is penetrated by the polymer compound (E) as the shaft component. This can be confirmed by measuring diffraction and NMR spectra and observing with an atomic force microscope.
In the measurement of powder X-ray diffraction, a comparison is made with a diffraction peak shown by a known rotaxane, so that the presence or absence of rotaxane formation, that is, a polymer in which the ring component of the cyclic polyetherester compound (P) is the axial component Whether or not the compound (E) has penetrated can be confirmed, and the number of cyclic polyether ester compounds (P) penetrating to one molecule of the polymer compound (E) can be calculated from the NMR spectrum. .

  The resin composition (F) of the present invention preferably forms a composite structure by allowing one or more molecules of the polymer compound (E) to penetrate through the ring component in the cyclic polyether ester composition (Q). As described in the description of the cyclic polyetherester compound (P) constituting the cyclic polyetherester composition (Q), this composite structure is such that “a + b + c + d” satisfies 30 <a + b + c + d ≦ 2000, and is adjusted to a more preferable range. By doing so, it becomes easy to form.

  The weight ratio of the cyclic polyetherester composition (Q) and the polymer compound (E) contained in the resin composition (F) is the weight of the cyclic polyetherester composition (Q) with respect to the weight of the polymer compound (E). A ratio of 0.001 to 50% by weight is preferable, and a ratio of 0.01 to 10% by weight is more preferable.

The resin composition (F) of the present invention comprises a method of mixing a cyclic polyether ester composition (Q), a polymer compound (E) and other additives (solvents, etc.) if necessary, and a cyclic polyether ester composition The polymer compound (E) in the presence of (Q) can be produced by the method of polymerizing by the above method.
Among the production methods of the polymer compound (E), polycondensation of polyisocyanate and polyether polyol from the viewpoint of suppressing deterioration of the cyclic polyether ester composition (Q) during the reaction and maintaining the physical properties of the resin. Reaction (hereinafter referred to as urethanization reaction) and radical polymerization reaction (hereinafter referred to as radical polymerization) of a monomer having an unsaturated double bond (vinyl group, (meth) acryl group) are preferred.

As the polyisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate and the like and their modified products can be used.
Examples of the aliphatic diisocyanate include dodecamethylene diisocyanate, alicyclic polyisocyanate having 11 to 17 carbon atoms [dicyclohexylmethane diisocyanate, 2,2′-dicyclohexylpropane diisocyanate, and the like].

  As aromatic polyisocyanate, C6-C16 aromatic diisocyanate, C6-C20 aromatic triisocyanate, and crude products of these isocyanates (excluding carbon in the NCO group; the following isocyanates are also the same), etc. Is mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, 4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), and the like.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate, Α, Α, Α ′, Α′-tetramethylxylylene diisocyanate, and the like.

Specific examples of the modified polyisocyanate include diisocyanate-modified products such as isocyanurate-modified and burette-modified lysine diisocyanate, isocyanurate-modified and burette-modified nonamethylene diisocyanate, and isocyanurate of decamethylene diisocyanate. Modified products and burette modified products, isocyanurate modified products and burette modified products of dodecamethylene diisocyanate), isocyanurate modified products and burette modified products of isophorone diisocyanate, and isocyanurate modified products and burette modified products of dicyclohexylmethane diisocyanate. Etc.
Examples of other modified diisocyanates include urethane-modified MDI and carbodiimide-modified MDI.
Of these, aromatic polyisocyanates are preferable from the viewpoint of reactivity, and 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI) are particularly preferable. Crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI).

  Examples of polyether polyols include dihydric alcohols (ethylene glycol, propylene glycol, 1,4-butanediol, etc., 1,6-hexanediol, etc.), trihydric alcohols (glycerin, trimethylolpropane, etc.), and tetrahydric alcohols. (Pentaerythritol, methyl glucoside, etc.), pentavalent alcohol (2, 2, 6, 6, -tetrakis (hydroxymethyl) cyclohexanol, etc.), hexavalent alcohol (sorbitol, etc.), and octavalent alcohol (sucrose, etc.) And adducts of alkylene oxides of various alcohols.

Examples of the alkylene oxide constituting the polyether polyol include ethylene oxide, propylene oxide, 1,2-, 1,4- or 2,3-butylene oxide, styrene oxide, epichlorohydrin, and combinations of two or more thereof. Can be mentioned. In the case of combined use, the addition format may be either block or random.
Among these, from the viewpoint of compatibility with the cyclic compound, preferred are ethylene oxide, propylene oxide, and 1,4-butylene oxide, and particularly preferred is propylene oxide.

Examples of (meth) acrylic monomers [other than urethane (meth) acrylate described later] that can be used in the resin composition of the present invention include the following.
(1) Monofunctional monomer (meth) acrylic acid, (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, 2,3-dimethylhexyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) Acrylate, isostearyl (meth) acrylate, icosyl (meth) acrylate, n-docosyl (meth) acrylate, n-tetracosyl (meth) acrylate, n-hexaicosyl (meth) acrylate, n-octaicosyl (meth) Acrylate, n-triacontyl (meth) acrylate, n-dotriacontyl (meth) acrylate, n-tetratriacontyl (meth) acrylate, n-hexatriacontyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n- Butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate 4-bromobutyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxy (Meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) ) Acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2, 4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyl Roxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, Polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (Meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate , Oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified pheno Ru (meth) acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate and EO-modified-2-ethylhexyl (meth) acrylate, 2- (2-vinyloxyethoxy) Examples include ethyl (meth) acrylate, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, acrylamide, and acryloylmorpholine.

Among these (meth) acrylates and acrylamides, those having an acrylate and acrylamide structure from the viewpoint of reactivity and having 2 to 12 carbon atoms are preferable from the viewpoint of compatibility with the cyclic compound.
Specific examples of preferable monofunctional monomers include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 4-n-butylcyclohexyl acrylate, 2-ethylhexyl diglycol acrylate, and 2-chloroethyl acrylate. , Butoxymethyl acrylate, methoxypropylene monoacrylate, alkoxymethyl acrylate, alkoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, hydroxyalkyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxy Propyl acrylate, methoxytriethylene glycol acrylic Over DOO, N, N- dimethylacrylamide, N- isopropylacrylamide, diacetone acrylamide, acrylamide, and acryloyl morpholine.

(2) Polyfunctional monomer Ethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) ) Acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, sorbitol tri (meth) acrylate, pentaerythritol C2-C4 Alkylene oxide 1-30 mol adduct tri (meth) acrylate, ethoxylated glycerine tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, propionate dipentaerythritol tetra (meth) acrylate, pentaerythritol C2-C4 alkylene oxide 1-30 mol tetra (meth) acrylate Sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Ruby Tall hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  Among these polyfunctional monomers, from the viewpoint of reactivity and compatibility with cyclic compounds, ethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, polytetramethylene glycol diacrylate, trimethylolpropane triacrylate An alkylene oxide-modified triacrylate of acrylate, trimethylolethane triacrylate, or trimethylolpropane is preferred.

The urethane (meth) acrylate that can be used in the present invention can be synthesized by the following method.
Urethane (meth) acrylate can be obtained by reacting the above-mentioned polyisocyanate with the above-mentioned polyol and further reacting a (meth) acrylic acid derivative having a hydroxyl group with a known reaction.
It does not specifically limit as a (meth) acrylic acid derivative which has a hydroxyl group, For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl ( Of commercially available products such as (meth) acrylates and divalent alcohols such as (poly) ethylene glycol, (poly) propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol Mono (meth) acrylate, trimethylolethane, trimethylolpropane, mono (meth) acrylate or di (meth) acrylate of trivalent alcohol such as glycerin, epoxy (meth) acrylate such as bisphenol A modified epoxy (meth) acrylate, etc. But It is below.
Among these urethane (meth) acrylates, from the viewpoints of reactivity and compatibility with the cyclic polyether ester compound (P), urethane acrylate in which 2-hydroxyethyl acrylate and a polyol are bonded with polyisocyanate is preferable.

  As specific examples of preferred urethane (meth) acrylates, ethylene glycol diurethane acrylate, polypropylene glycol diurethane acrylate, polyethylene glycol diurethane acrylate, polytetramethylene glycol diurethane acrylate reacted with 2-hydroxyethyl acrylate , Trimethylolpropane triurethane acrylate, trimethylolethane triurethane acrylate, and trimethylolpropane alkylene oxide-modified triurethane acrylate.

  The cyclic polyether ester composition (Q) used for the production of the resin composition (F) of the present invention was obtained without a purification step in the production method of the cyclic polyether ester composition (Q) of the present invention. Even if the reaction product is used as it is, a cyclic polyetherester compound (P) having a specific structure obtained by carrying out a purification step and fractionating and purifying the reaction product may be used.

  As a method of mixing the cyclic polyether ester composition (Q) and the polymer compound (E), the cyclic polyether ester composition (Q) and the polymer compound (E) are stirred and mixed in a solvent-free or solvent. The temperature at the time of stirring and mixing is 0 to 250 ° C., preferably 10 to 200 ° C., and the mixing time is 1 second to 1 week, preferably 10 seconds to 3 days. The resin composition (F) in which the polymer compound (E) has penetrated the cyclic polyether ester compound (P) is a known solution such as reprecipitation, filtration, centrifugation, membrane separation and column chromatography after stirring and mixing. It can be isolated by separation methods.

A publicly known method can be used as a method of making the resin composition (F) polymerized by ultraviolet rays or heat. As a specific example, the cyclic polyether ester composition (Q), the polymer compound (E), and the radical initiator are mixed and then polymerized by ultraviolet rays or heat.
The weight percent before polymerization of the cyclic polyetherester composition (Q) is preferably 1 to 50%, more preferably 1 to 20%, and particularly preferably 5 to 10 from the viewpoint of achieving both strength and elongation of the resin. %. The weight percent of the initiator before polymerization is preferably from 0.01 to 20%, more preferably from 0.01 to 10%, particularly preferably from the viewpoint of improving the polymerization efficiency and suppressing deterioration in quality after polymerization. 0.01 to 5%.

The radical initiator that generates radicals by ultraviolet rays is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxy Benzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Pan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy- 2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl- 1- (4- (1-methylvinyl) phenyl) propanone) I can make it. One of these may be used alone, or two or more may be used in combination.
Among these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and 1,3,5-trimethylbenzoyldiphenylphosphine oxide are preferable from the viewpoint of preventing coloring of the cured product. is there.

Examples of radical initiators that generate radicals by heat include known azo initiators (azobisisobutyronitrile, azobisvaleronitrile, etc.), peroxide initiators (benzoyl peroxide, cumyl peroxide, lauryl peroxide). Oxides) and redox initiators (such as a mixture of benzoyl peroxide and tertiary amine). Furthermore, if necessary, a known chain transfer agent (such as an alkyl mercaptan having 2 to 20 carbon atoms) can also be used.
Among these, azobisisobutyronitrile and azobisvaleronitrile are preferable from the viewpoint of preventing coloring of the cured product.

If the polymerization is carried out by UV light, from the viewpoint of sufficiently proceed the polymerization, it is preferable to 50~1500mJ / cm ² exposure amount, more preferably 200~1500mJ / cm ^2, particularly preferably 500~1000mJ / cm ² . Although the ultraviolet irradiation time can be adjusted so as to be the above-mentioned exposure amount, it is preferably 1 minute to 30 minutes, more preferably 5 minutes to 30 from the viewpoint of suppressing deterioration of the resin composition due to a rapid heat change. Minutes, particularly preferably 10 to 30 minutes.

  When the polymerization is performed by heat, the temperature is preferably 50 to 150 ° C., more preferably 50 to 100 ° C., from the viewpoint of sufficiently proceeding the polymerization. The reaction time is preferably 1 minute to 10 hours, more preferably 30 minutes to 10 hours, and particularly preferably 30 minutes to 5 hours from the viewpoint of sufficiently allowing the polymerization to proceed and ensuring productivity.

  The resin composition (F) of the present invention is a resin excellent in the extensibility and strength of the resin, but since the following properties can also be expected, it can be used as a medical material such as a cell non-adhesive material.

In addition, the cross-linked product of the present invention (hereinafter referred to as gel) in which the polymer material (E) penetrates the cyclic polyether ester composition (Q) and is cross-linked with the cross-linking agent component (G) in the resin composition (F). ) Can disperse the force applied to the gel by stretching as the polymer slides, as in the case of conventional rotaxanes (such as the rotaxane described in WO 01/083566).
Therefore, like a conventional rotaxane, it can be added to a coating agent or the like and used as a self-repairing component.
Similarly to conventional rotaxanes, gels that have absorbed a solvent such as water can be used as functional materials for medical materials such as shock-absorbing materials and cell culture substrates.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In addition, the part in an Example shows a weight part.

<Production Example 1>
Kyoward 300 [chemical formula: 2.5 MgO.Al ₂ O ₃ .nH ₂ O (n is a positive number), manufactured by Kyowa Chemical Industry Co., Ltd.] is heated in an electric furnace at 900 ° C. for 24 hours in a nitrogen stream. And the catalyst used for Examples 1-20 was synthesize | combined by adjusting a baked product.

<Examples 1 to 20>
Steps 1 to 4 described in Table 1 were respectively performed to synthesize the intermediate of the cyclic compound of the present invention according to Examples 1 to 20, and the reaction mixture containing the intermediate was purified by the following method. A cyclic compound was obtained. It should be noted that the intermediates obtained in step 1 in the examples in which only the step 1 is the step according to each example in Table 1 and Table 2, and the intermediates obtained in the step 2 in the examples described up to the step 2 are used. In the examples described up to step 3, the intermediate obtained in step 3 is purified, and in the examples described up to step 4, the intermediate obtained in step 4 is purified by the following method. Such a cyclic compound of the present invention was obtained.
In steps 1 to 4 and the purification step, the following operations were performed.
(Step 1): Into a stainless steel autoclave equipped with a stirrer and a temperature adjusting function, the raw materials listed in Table 1 and the catalyst obtained in Production Example 1 were introduced in the number of parts described in Table 1, and reduced pressure (gauge pressure-0 0.1 MPa), and after carrying out nitrogen aeration for 1 hour, the temperature was raised to 150 ° C., and the alkylene oxides shown in Table 1 were injected over the reaction times shown in Table 1, followed by the time aging described in Table 1. As a result, intermediates (PP-_1) shown in Table 1 were obtained. In addition, the underscore (_) part in PP -_- 1 contains the same number as the number of the example, and represents an intermediate obtained in the example. (The same applies hereinafter.)

(Step 2): The intermediate product obtained in Step 1 and the catalyst obtained in Production Example 1 were introduced into a stainless steel autoclave equipped with a stirrer and a temperature control function in the number of parts shown in Table 1, and reduced pressure (gauge pressure − 0.1 MPa), and after carrying out nitrogen aeration for 1 hour, the temperature was raised to 150 ° C., and the alkylene oxide shown in Table 1 was injected over the reaction time shown in Table 1, and the time shown in Table 1 The intermediates (PP -_- 2) shown in Table 1 were obtained by aging.
In Step 2 of Example 3, the intermediate obtained in Step 1 and the catalyst obtained in Production Example 1 were introduced into the autoclave, and then 100 parts of xylene was added, followed by nitrogen aeration, temperature increase, and alkylene oxide. The reaction was aged.

(Step 3): The intermediate product obtained in Step 2 and the catalyst obtained in Production Example 1 were introduced into a stainless steel autoclave equipped with a stirrer and a temperature control function in the number of parts shown in Table 1, and reduced pressure (gauge pressure − 0.1 MPa), and after carrying out nitrogen aeration for 1 hour, the temperature was raised to 150 ° C., and the alkylene oxide shown in Table 1 was injected over the reaction time shown in Table 1, and the time shown in Table 1 The intermediates (PP -_- 3) shown in Table 1 were obtained by aging.

(Step 4): The intermediate product obtained in Step 3 and the catalyst obtained in Production Example 1 were introduced into a stainless steel autoclave equipped with a stirrer and a temperature control function in the number of parts shown in Table 1, and reduced pressure (gauge pressure − 0.1 MPa), and after carrying out nitrogen aeration for 1 hour, the temperature was raised to 150 ° C., and the alkylene oxide shown in Table 1 was injected over the reaction time shown in Table 1, and the time shown in Table 1 A product intermediate (PP -_- 4) described in Table 1 was obtained by aging.

(Purification process)
100 parts of toluene was added to 20 parts of each intermediate, and the temperature was adjusted to 50 ° C. and stirred uniformly. Then, 5 parts of Radiolite # 700 [manufactured by Showa Chemical Industry Co., Ltd.] as a filter aid and Kyward 600 [ Kyowa Chemical Industry Co., Ltd.] was filtered through a suction funnel in which 5 parts were packed in layers to separate the catalyst. Subsequently, xylene was distilled off under reduced pressure and concentrated. 20 parts of methanol is added to the concentrate and stirred, and 100 parts of water is added for reprecipitation, the precipitate is separated by decantation, and the precipitate is further dried under reduced pressure, whereby cyclic compounds (P-1) to ( P-13) and (P-15) to (P-20) were obtained (referred to as purification step 1). In Example 14, after the xylene was distilled off under reduced pressure and concentrated in the above method, 100 parts of methanol and 100 parts of xylene were added to the concentrate and stirred, and after the methanol layer was extracted, the methanol was distilled off under reduced pressure and concentrated. Thus, a cyclic compound (P-14) was obtained (referred to as purification step 2).

  About the cyclic compounds (P-1) to (P-20) obtained by purifying the produced intermediate, MALDI-TOF MS [MALDI mass spectrometer AXIMA-Performance, analysis by Shimadzu Corporation, and GPC measurement as necessary As a result, it was confirmed that the cyclic compounds obtained in each Example were as follows.

When the MALDI-TOF MS analysis was performed about the cyclic compound (P-1) obtained in Example 1, the cyclic compound (P-1) is a compound represented by the chemical formula (11) (the average value of a + b + c + d is 31). Met.
In chemical formula (11), n is an integer, k is an integer of 1 to 3, and A is a methylethylene group.

  When the MALDI-TOF MS analysis was performed on the cyclic compound (P-2) obtained in Example 2, the cyclic compound (P-2) was a mixture of compounds represented by the chemical formula (11) (a + b + c + d value was 100). )Met. In chemical formula (11), n is an integer, k is an integer of 1 to 3, and A represents a methylethylene group.

  When the MALDI-TOF MS analysis was performed about the cyclic compound (P-3) obtained in Example 3, the cyclic compound (P-3) is a compound represented by Chemical formula (11), and analysis by GPC measurement was performed. As a result, it was confirmed that the number average molecular weight was 11,6000 and the value of a + b + c + d was 2000. The cyclic compound (P-2) described in Example 2 was used as a cyclic compound for molecular weight comparison.

  When the cyclic compound (P-4) obtained in Example 4 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-4) was a compound represented by the chemical formula (12) (the value of a + b + c + d was 100). there were. In the chemical formula (12), n is each independently an integer, k is an integer of 1 to 3, and A represents a methylethylene group.

  When the cyclic compound (P-5) obtained in Example 5 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-5) was a compound represented by the chemical formula (13) (the value of a + b + c + d was 100). there were. In chemical formula (13), n is an integer, k is an integer of 1 to 3, and A represents a methylethylene group.

  When the MALDI-TOF MS analysis was performed on the cyclic compound (P-6) obtained in Example 6, the cyclic compound (P-6) was 100) in the compound a + b + c + d represented by the chemical formula (14). It was. In chemical formula (14), n is an integer independently, k is an integer of 1-3, and A represents a methylethylene group.

  When the cyclic compound (P-7) obtained in Example 7 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-7) was a compound represented by the chemical formula (15) (the value of a + b + c + d was 100). there were. In chemical formula (15), n is an integer, k is an integer of 1 to 3, and A represents a methylethylene group.

  When the cyclic compound (P-8) obtained in Example 8 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-8) was a compound represented by the chemical formula (16) (the value of a + b + c + d was 100). there were. In chemical formula (16), n is an integer, k is an integer of 1 to 3, and A represents a methylethylene group.

  When the cyclic compound (P-9) obtained in Example 9 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-9) was a compound represented by the chemical formula (17) (the value of a + b + c + d was 100). there were. In chemical formula (17), n is an integer independently, k is an integer of 1-3, and A represents a methylethylene group.

  When the cyclic compound (P-10) obtained in Example 10 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-10) was a compound represented by the chemical formula (18) (the value of a + b + c + d was 100). there were. In chemical formula (18), n is an integer, k is an integer of 1 to 3, and A represents a methylethylene group.

  When the cyclic compound (P-11) obtained in Example 11 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-11) was a compound represented by the chemical formula (19) (the value of a + b + c + d was 100). there were. In the chemical formula (19), n is each independently an integer, k is an integer of 1 to 3, and A represents a methylethylene group.

  When the MALDI-TOF MS analysis was performed about the cyclic compound (P-12) obtained in Example 12, the cyclic compound (P-12) is a compound (a + b + c + d value is 100) represented by Chemical Formula (20). there were. In chemical formula (20), n is an integer independently, k is an integer of 1-3, and A represents a methylethylene group.

  When the cyclic compound (P-13) obtained in Example 13 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-13) was a compound represented by the chemical formula (21) (the value of a + b + c + d was 100). there were. In the chemical formula (21), n is each independently an integer, k is an integer of 1 to 3, and A represents a methylethylene group.

  When the cyclic compound (P-14) obtained in Example 14 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-14) was a compound represented by the chemical formula (11) (the value of a + b + c + d was 100). there were. In chemical formula (11), n is an integer, k is an integer of 1 to 3, and A represents an ethylene group.

  When the cyclic compound (P-15) obtained in Example 15 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-15) was a compound represented by the chemical formula (11) (the value of a + b + c + d was 100). there were. In chemical formula (11), n is an integer, k is an integer of 1 to 3, and A represents an ethylethylene group.

  When the cyclic compound (P-16) obtained in Example 16 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-16) was a compound represented by the chemical formula (11) (the value of a + b + c + d was 100). there were. In chemical formula (11), n is an integer, k is an integer of 1 to 3, and A represents a butylene group.

  When the cyclic compound (P-17) obtained in Example 17 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-17) was a compound represented by the chemical formula (11) (the value of a + b + c + d was 100). there were. In chemical formula (11), n is an integer, k is an integer of 1 to 3, and A represents a (chloromethyl) ethylene group.

  When the cyclic compound (P-18) obtained in Example 18 was subjected to MALDI-TOF MS analysis, the cyclic compound (P-18) was a compound represented by the chemical formula (11) (the value of a + b + c + d was 100). there were. In chemical formula (11), n is an integer, k is an integer of 1 to 3, and A represents a phenylethylene group.

  When the MALDI-TOF MS analysis was conducted about the cyclic compound (P-19) obtained in Example 19, the cyclic compound (P-19) was a compound represented by the chemical formula (22) (the value of a + b + c + d was 100). there were. In the chemical formula (22), n is an integer, k1 + k2 is an integer of 1 to 3, and A represents a methylethylene group.

  When the MALDI-TOF MS analysis was conducted about the cyclic compound (P-20) obtained in Example 20, the cyclic compound (P-20) was a compound represented by the chemical formula (11) (the value of a + b + c + d was 100). there were. In chemical formula (11), n is an integer, k is an integer of 1 to 4, and A represents a methylethylene group.

<Comparative Example 1>
An ethylene oxide (6 mol) adduct of 15-pentadecanolactone, which is a comparative cyclic compound (HP-1), was synthesized according to the method of Example 1 of JP-A-2006-175898.

  Using the cyclic compounds (P-1) to (P-20) obtained in Examples 1 to 20 and the comparative cyclic compound (HP-1), the resin composition (F) and the comparative compound were compared in the following manner. A resin composition (F ′) was produced, and the breaking strength and breaking elongation were measured.

<Examples 21 to 40: Production of urethane resin composition (F1)>
Sannix GH-3000NS [Trifunctional Polypropylene Polyol (Hydroxyl Value: 56), Sanyo Chemical Industries, Ltd.] in the number of parts shown in Table 3 and Coronate T-80 (Tosoh Corporation) and 100 under nitrogen atmosphere The reaction was conducted at 0 ° C. to prepare the main agent.
Subsequently, each cyclic polyetherester compound (P) was dissolved in Sannics GH-3000NS at 80 ° C. in the number of parts described in Table 3 to prepare a curing agent.
Add the total amount of the prepared curing agent to the total amount of the prepared main agent at 100 ° C., stir uniformly, then pour into a mold and cure at 80 ° C. for 10 hours to cure urethane elastomer (E-1) and cyclic polyether ester Resin compositions (F1-1) to (F1-20) containing the compound (P) were obtained.

<Comparative Example 2: Production of Comparative Resin Composition (F1 ′)>
The same operation was performed except that the cyclic compound (P-1) was changed to the comparative cyclic compound (HP-1) in Example 20, and a comparative resin composition containing a urethane elastomer (E-1) ( F′-2) was obtained.

<Comparative Example 3: Production of resin composition for comparison (F1'-2)>
The same operation was performed except that the cyclic compound (P-1) was not added in Example 20, and a comparative resin composition (F1′-2) containing a urethane elastomer (E-1) was obtained.

Resin compositions (F1-1) to (F1-20) obtained in Examples 21 to 40 and comparative resin compositions (F1′-1) to (F1′-2) obtained in Comparative Examples 1 and 2 Is used to prepare a measurement sample for a tensile test by the method described in JIS-K7311, a tensile test is performed by an autograph “AGS-IS” manufactured by Shimadzu, and tensile strength and elongation are measured. And elongation at break.
Table 4 shows the measurement results. The measurement was performed at a pulling speed of 10 cm / min, a humidity of 50%, and a temperature of 25 ° C.

Resin compositions (F-1) to (F-20) containing the cyclic polyether ester compound (P) obtained in Examples 1 to 20 are comparative cyclic compounds (HP-1) with a small number of added moles. The breaking strength was improved as compared with the resin composition (F′-1) containing No. 1 and the comparative resin composition (F′-2) not containing the cyclic polyetherester compound (P).
This is probably because the polyurethane (E-1) penetrates the cyclic polyether ester compound (P) to form a composite structure.

<Examples 41 to 42, Comparative Examples 4 to 7: Production of acrylic resin composition (F2) and comparative resin composition (F2 ′)>
A radical curable resin composition was blended as shown in Table 5.
As the acrylic monomer, funcryl FA-THFA [manufactured by Hitachi Chemical Co., Ltd.] and NK ester A-PTMG-65 [manufactured by Shin-Nakamura Chemical Co., Ltd.] were used. As the radical initiator, Irga 184 [trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.], 2,2′-azobis (2,4-dimethylvaleronitrile) [manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as ADVN] is used. It was.

A silicon spacer mold having a thickness of 500 μm was prepared on a glass plate, and after pouring the compound, it was sandwiched between glass plates and cured in the next step.
Resin compositions (F2-1, F2′-1, F2′-2) according to Example 41 and Comparative Examples 4 to 5 which are irradiated with 1000 mJ / cm ² of light from an ultrahigh pressure mercury lamp for 10 minutes to perform UV curing. Got.
Resin compositions according to Example 42 and Comparative Examples 6-7 (F2-2, F2′-3, F2′-4) which were heated for 5 hours in a circulating drier controlled at 70 ° C. and thermally cured. Got.

  Resin compositions (F2-1) to (F2-2) obtained in Examples 41 to 42 and comparative resin compositions (F2′-1) to (F2′-4) obtained in Comparative Examples 4 to 7 Was peeled off from the mold and glass plate, and was punched into No. 3 dumbbell mold. A tensile test was conducted with Shimadzu autograph “AGS-IS” to measure the tensile strength and elongation. It was. Table 6 shows the measurement results. The measurement was performed at a pulling speed of 10 cm / min, a humidity of 50%, and a temperature of 25 ° C.

The ultraviolet curable resin composition (F2-1) containing the cyclic compound (P-2) obtained in Example 2 is a resin composition containing a comparative cyclic compound (HP-1) having a small number of added moles ( The breaking strength was improved as compared with a comparative resin composition (F2′-2) that does not contain F2′-1) and the cyclic polyether ester compound (P).
On the other hand, the thermosetting resin composition (F2-2) containing the cyclic compound (P-2) obtained in Example 2 is a resin composition containing a comparative cyclic compound (HP-1) with a small number of added moles. Compared with the comparative resin composition (F2′-4) which does not contain the product (F2′-3) and the cyclic polyether ester compound (P), the breaking strength is improved. ) Penetrates the cyclic polyether ester compound (P) to form a composite structure.

  The cyclic compound of the present invention is a crosslinkable molecule such as urethane elastomer, hard coat, film, urethane foam, paint, rubber, medical material, electronic material, lubricating oil additive, antistatic agent, vibration damping material, self-healing material, It is useful as a functional material used in other industries.

Claims (5)

Binding at least one group selected from the group consisting of a group represented by the general formula (1), a group represented by the general formula (2) and a group represented by the general formula (3) as a structural unit; A cyclic polyether ester composition (Q) comprising a cyclic polyether ester compound (P) satisfying the relational expression (1).


[In the general formula (1), ^{R 1} is a divalent hydrocarbon group having 2 to 21 carbon atoms. The hydrogen atom of R ¹ may be substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group. X ¹ is a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group or a thiocarbonyl group. Y ¹ and Y ² each independently represent an oxygen atom, a sulfur atom, or a divalent group represented by the general formula (4). ; ^{A 1} is a divalent hydrocarbon group having 2 to 8 carbon atoms. The hydrogen atom of A ¹ may be substituted with a halogeno group. ; _{N 1} is an integer of 0 or more. In the cyclic polyether ester composition (Q), when a plurality of R ¹ , A ¹ , X ¹ , Y ¹ and Y ² , n ₁ are contained, they may be the same or different. However, when the compound (P) is composed only of the group represented by the general formula (1), the case where all X ¹ are carbonyl groups and all Y ¹ are oxygen atoms is excluded. ]

[In the general formula (2), ^{R 2} is a divalent hydrocarbon group having 2 to 21 carbon atoms. The hydrogen atom of R ² may be substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group. X ² is a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group, or a thiocarbonyl group. Y ³ , Y ⁴ , Y ⁵ and Y ⁶ are each independently an oxygen atom, a sulfur atom or a divalent group represented by the general formula (4); A ² and A ³ are each independently , A divalent hydrocarbon group having 2 to 8 carbon atoms. The hydrogen atoms of A ² and A ³ may be substituted with a halogeno group. ; _{N 2} and _{n 3} are each independently an integer of 0 or more. In the cyclic polyether ester composition (Q), when a plurality of R ² , A ² and A ³ , X ² , Y ^{3 to} Y ⁶ , n ₂ and n ₃ are contained, they may be the same or different from each other; . ]

[In General Formula (3), R ³ is a divalent hydrocarbon group having 2 to 21 carbon atoms. The hydrogen atom of R ³ may be substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group. X ³ and X ⁴ are a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group or a thiocarbonyl group; Y ⁷ and Y ⁸ are each independently an oxygen atom, a sulfur atom, A divalent group represented by formula (4); A ⁴ is a divalent hydrocarbon group having 2 to 8 carbon atoms; The hydrogen atom of A ⁴ may be substituted with a halogeno group. Z is at least one group selected from the group consisting of a group represented by the general formula (1), a group represented by the general formula (2), and a group represented by the general formula (5). ; _{N 4} and m are each independently an integer of 0 or more. In the cyclic polyether ester composition (Q), when a plurality of R ³ , A ⁴ , X ³ and X ⁴ , Y ⁷ and Y ⁸ , Z and n ₄ are contained, they may be the same or different. ]


[In General Formula (4), R ⁴ is a monovalent hydrocarbon group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a halogeno group. ]


[In General Formula (5), Y ⁹ is an oxygen atom, a sulfur atom, or a divalent group represented by General Formula (4). A ⁵ is a divalent hydrocarbon group having 2 to 8 carbon atoms. Hydrogen atoms of A ⁵ are, may be substituted with halogeno group. n ₅ is an integer of 0 or more. ]
<Relational expression (1)>
30 <a + b + c + d ≦ 2000 Relational expression (1)
[In the relational formula (1), a is the average number of added moles of groups represented by (Y ¹ -A ¹ ) contained in the cyclic polyetherester compound (P); The average added mole number of all the groups represented by (Y ³ -A ² ) contained in the polyether ester compound (P) and all (A ³ -Y contained in the cyclic polyether ester compound (P). ⁶ ) is the average number of moles added of the group represented by c); c is the average number of moles added of all the groups represented by (Y ⁷ -A ⁴ ) contained in the cyclic polyetherester compound (P). Yes; d is the average number of moles added of all the groups represented by (Y ⁹ -A ⁵ ) contained in the cyclic polyether ester compound (P). ] In General Formula (1), General Formula (2), and General Formula (3), R ¹ , R ^2, and R ³ are each independently a linear alkylene group having 3 to 16 carbon atoms or a branch having 3 to 16 carbon atoms. An alkylene group, and A ¹ , A ² , A ³ , A ⁴ and A ⁵ are each independently a phenylethylene group, a linear alkylene group having 2 to 4 carbon atoms, or a branched alkylene group having 3 to 4 carbon atoms. The cyclic polyether ester composition according to claim 1. At least one selected from the group consisting of the cyclic compound (R) represented by the general formula (6), the compound (S) represented by the general formula (7), and the compound (T) represented by the general formula (8). Two kinds of cyclic compounds (B), a cyclic ether having 2 to 8 carbon atoms in which a hydrogen atom may be substituted with a halogeno group, and a cyclic thioether having 2 to 8 carbon atoms in which a hydrogen atom may be substituted with a halogeno group And a step of reacting at least one cyclic compound (C) selected from the group consisting of cyclic imines having 2 to 8 carbon atoms in which a hydrogen atom may be substituted with a halogeno group. A method for producing a cyclic polyether ester composition.

[In the general formula (6), ^{R 5} is a divalent hydrocarbon group having 2 to 21 carbon atoms. In addition, the hydrogen atom of R ⁵ may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. Each of X ⁵ independently represents a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group, or a thiocarbonyl group. ; Y ¹⁰ each independently represent an oxygen atom, a divalent group represented by a sulfur atom, the general formula (4). ]

[In General formula (7), R < ⁶ > is a C2-C21 bivalent hydrocarbon group. Further, the hydrogen atom of R ⁶ may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. Each of X ⁶ is independently a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group, or a thiocarbonyl group. ; ^{Y 11} and ^{Y 12} each independently represent an oxygen atom, a divalent group represented by a sulfur atom, the general formula (4). ]

[In the general formula (8), ^{R 7} is a divalent hydrocarbon group having 2 to 21 carbon atoms. In addition, the hydrogen atom of R ⁷ may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. Each of X ⁷ and X ⁸ independently represents a residue obtained by removing two hydroxyl groups from phosphonic acid, a carbonyl group, a sulfonyl group, or a thiocarbonyl group. ; Y ¹³ each independently represent an oxygen atom, a divalent group represented by a sulfur atom, the general formula (4). ] In the step of reacting the cyclic compound (B) and the cyclic compound (C), the fired product of the composite oxide (D1) of aluminum and magnesium and / or the hydrotalcite (D2) containing aluminum and magnesium The method for producing a cyclic polyetherester composition according to claim 3, which is a step performed in the presence of a fired product. A resin composition (F) comprising the cyclic polyether ester composition according to claim 1 or 2 and a polymer compound (E).