JPH11142388A - Method for analyzing terminal group of hydroxyl terminal group-containing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To quality, determine two or more hydroxyl terminals of different properties in polyether ester simultaneously and individually by changing the hydroxyl terminal of the hydroxyl terminal group-containing polymer to a derivative with the use of a compound of a specific formula and measuring the derivative. SOLUTION: A reagent of the formula wherein R1-R5 is a proton, an alkyl group, halogen is added to a polyether ester polymer dissolved in an organic solvent, and left standing at room temperatures, whereby a hydroxyl terminal is turned to a fluorine derivative. The changed polymer is reprecipitated with cyclohexane, dried in vacuum, dissolved in dichloroform and measured by<19> F-NMR after ethyl trifluoroacetate is added. In other words, each hydroxyl terminal in the polyether ester is qualified from a chemical shift based on a chemical shift of hexafluorobenzene. At the same time, each terminal is determined from peak area values thereof and a corresponding internal standard. Two or more hydroxyl terminals of different properties can be qualified, determined individually at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for analyzing the hydroxyl end of macromolecules containing hydroxyl end groups, especially polyetheresters. More particularly, the present invention is a hydroxyl-terminated group-containing polymer, especially present in the polyether esters of high molecular weight, two or more types of hydroxyl-terminated with different properties to fluorine derivatized, ¹⁹ F-N
Analytical methods for the qualification and quantification of each hydroxyl end simultaneously and by individual hydroxyl end by MR.

[0002]

2. Description of the Related Art Polyetheresters have the following general formula:
There are a hydroxyl terminal derived from a polyether represented by (3) and a hydroxyl terminal derived from a polyester represented by the following general formula (4). Although they have the same hydroxyl end, they behave differently in reactivity during polymerization.

Embedded image (Where X ¹ is a linear alkylene group having 2 to 18 carbon atoms,
An alicyclic alkylene group having 6 to 12 carbon atoms, at least one group selected from 4-oxyphenylene, 4-oxydiphenylene, oxy-1,4-phenylene-isopropylidene-1,4-phenylene, p and q are each an integer of 5 or more; m and n are integers of 2 to 8;
Or represents 1. )

Embedded image (Where R ₈ is an aromatic group having 6 to 12 carbon atoms, 2 carbon atoms)
Represents at least one group selected from a straight-chain alkylene group having from 22 to 22 and an alicyclic alkylene group having from 6 to 14 carbon atoms;
₉ represents at least one group selected from an aromatic group having 6 to 12 carbon atoms, a linear alkylene group having 2 to 22 carbon atoms, and an alicyclic alkylene group having 6 to 14 carbon atoms. )

That is, the hydroxyl terminal derived from the polyether represented by the general formula (3) is
Condensation with the hydroxyl terminal derived from the polyester as shown in (4). On the other hand, the hydroxyl terminal derived from the polyester represented by the general formula (4) is the same as the hydroxyl terminal derived from the polyether represented by the general formula (3),
Further, it also condenses with a hydroxyl terminal derived from a polyester as represented by the general formula (4). At the time of polymerization, if the proportion of the terminal represented by the general formula (3) increases, the degree of polymerization hardly increases. Therefore, in order to control the degree of polymerization, it is important to grasp the terminal abundance.

[0004] A common method that has been used to determine the hydroxyl end groups of a polyetherester is to titrate the carboxyl end of the polymer after treating the polyetherester with succinic anhydride and titrate the succinic anhydride. In this method, the difference from the carboxyl terminal of the polymer that has not been subjected to the acid treatment is determined as the amount of hydroxyl terminal groups. This method is complicated in operation, and even if the total hydroxyl terminal in the polymer can be measured, it is possible to measure the hydroxyl terminal derived from a polyether represented by the general formula (3) and the polyester represented by the general formula (4). It is not possible to distinguish and quantify the origin of the hydroxyl terminal.

In addition, ¹ H-NMR is used to directly determine the hydroxyl terminal derived from the polyether represented by the general formula (3) and the hydroxyl terminal derived from the polyester represented by the general formula (4) from the chemical shifts. However, it is difficult to measure a high molecular weight product because methylene in the main chain interferes. That is, in the conventional method for analyzing a hydroxyl terminal, it is possible to separately measure the hydroxyl terminal derived from a polyether represented by the general formula (3) and the hydroxyl terminal derived from a polyester represented by the general formula (4). It was not impossible or easy.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a method for producing a hydroxyl-terminated polymer, particularly a high-molecular-weight polyether ester, which comprises a hydroxyl group derived from a polyether represented by the following general formula (3): It is an object of the present invention to provide a method for distinguishing and measuring hydroxyl terminals derived from a polyester as represented by the formula (4).

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have reached the following important findings and completed the present invention. That is, a hydroxyl terminal group-containing polymer, in particular, a hydroxyl terminal group present in a polyetherester is reacted with a compound having fluorine to derivatize the hydroxyl terminal to a terminal group containing fluorine, and this is subjected to ¹⁹ F-NMR by ¹⁹ F-NMR. By measuring, from the chemical shift of NMR, the hydroxyl terminal derived from the polyether represented by the general formula (3) in the polyether ester and the hydroxyl terminal derived from the polyester represented by the general formula (4) are distinguished from each other. The present inventors have found a method for measuring, and have reached the present invention.

The present invention is as follows. The hydroxyl terminal of the polymer having a hydroxyl terminal group is derivatized using a compound represented by the following general formula (1), and ¹⁹ F-
An end group analysis method for a polymer containing a hydroxyl end group, wherein the end is measured by NMR is provided. Also,

Embedded image (Here, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a proton, an alkyl group, and a halogen.) A compound represented by the following general formula (2) and / or a compound represented by the following general formula (3)
The present invention provides an end group analysis method for a hydroxyl end group-containing polymer, wherein the hydroxyl end of the hydroxyl end group-containing polymer is derivatized with an acid anhydride of the above, and the end is measured by ¹⁹ F-NMR. Also,

Embedded image (Here, R ₆ and R ₇ represent a proton, an alkyl group, a halogenated alkyl group, and a halogen.)

A polymer having a structure having a hydroxyl end group-containing polymer represented by the following general formula (3):
It is also characterized in that it is a polyetherester containing a component having the structure represented by (4). Also,

Embedded image (Where X ¹ is a linear alkylene group having 2 to 18 carbon atoms,
An alicyclic alkylene group having 6 to 12 carbon atoms, at least one group selected from 4-oxyphenylene, 4-oxydiphenylene, oxy-1,4-phenylene-isopropylidene-1,4-phenylene, p and q are each an integer of 5 or more; m and n are integers of 2 to 8;
Or represents 1. )

Embedded image (Where R ₈ is an aromatic group having 6 to 12 carbon atoms, 2 carbon atoms)
Represents at least one group selected from a straight-chain alkylene group having from 22 to 22 and an alicyclic alkylene group having from 6 to 14 carbon atoms;
₉ represents at least one group selected from an aromatic group having 6 to 12 carbon atoms, a linear alkylene group having 2 to 22 carbon atoms, and an alicyclic alkylene group having 6 to 14 carbon atoms. )

Hereinafter, the present invention will be described in detail. [1] Regarding hydroxyl terminal group-containing polymer: The method for analyzing a hydroxyl terminal of the present invention can be applied to any hydroxyl terminal group-containing polymer, and in particular, polyetherester, particularly high molecular weight polyether Applicable to esters. That is, the component having the structure represented by the general formula (3) and the polyetherester having the structure represented by the general formula (4) are generally linear, alicyclic and aromatic. And polycondensation of at least one alkyl ester of dicarboxylic acid selected from the group consisting of a compound represented by the following general formula (5).

Embedded image (Where X ₁ is a linear alkylene group having 2 to 18 carbon atoms,
An alicyclic alkylene group having 6 to 12 carbon atoms, at least one group selected from 4-oxyphenylene, 4-oxydiphenylene, oxy-1,4-phenylene-isopropylidene-1,4-phenylene, and p and q is an integer of 5 or more, m and n are integers of 2 to 8, y is 0
Or represents 1. )

The compound represented by the general formula (5) includes, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, ethylene glycol / propylene glycol block copolymer and the like. In addition to polyoxyalkylene glycol, hydroquinone, 4,4'-dihydroxydiphenyl, 4,4'-
Dihydroxydiphenyl ether, bisphenol-A
And ethylene oxide adducts and propylene oxide adducts. These compounds may be used alone or in combination of two or more.

Examples of the dicarboxylic acid ester used for the polymerization of the polyether ester include aromatic dicarboxylic acids having 6 to 12 carbon atoms such as terephthalic acid, phthalic acid and isophthalic acid; and carbon atoms such as adipic acid, sebacic acid and malic acid. 2 to 22 linear dicarboxylic acids; cyclohexyl-
Examples thereof include methyl, ethyl, propyl, and butyl esters of an alicyclic dicarboxylic acid having 6 to 14 carbon atoms such as 1,4-dicarboxylic acid.

(II) Fluorine-derivatizing reagent: In the present invention, the reagent used for fluorine-derivatizing a hydroxyl terminal group-containing polymer, particularly a polyetherester, has the following general formula (1) and / or Or
Those having the structure of (2) are mentioned.

Embedded image (Here, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a proton, an alkyl group, and a halogen.)

Embedded image (Here, R ₆ and R ₇ represent a proton, an alkyl group, a halogenated alkyl group, and a halogen.)

More specifically, the compounds of the above general formula (1) include fluoroacetone, 1,1,1-trifluoroacetone, 3-bromo-1,1,1-trifluoroacetone and hexafluoroacetone. And the like. Compounds of the above general formula (2) include difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid,
Heptafluorobutyric acid, tridecafluoroheptanoic acid and the like and acid anhydrides thereof are mentioned, and hexafluoroacetone or trifluoroacetic anhydride is preferable.

(III) Reaction mechanism between the fluorine-derivatizing reagent and the polymer having a hydroxyl terminal group, particularly the hydroxyl-terminal in the polyetherester, etc .: In the case of the compound of the general formula (1), the terminal is a polymer terminal of a hemiacetal structure, and in the case of the compound of the general formula (2), the terminal is a polymer terminal of an ester structure (for example, FF
-L. Ho, Anal.Chem., 45, 603 (1973) and SLManatt, DDL
awson, JDIngham, NSRapp, JPHardy, Anal.Chem., 38,
1063 (1966). ).

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to examples, but these do not limit the scope of the present invention. < ¹⁹ F-NMR hydroxyl end group-containing polymer,
In particular, the method for measuring various hydroxyl end groups in polyetherester> In the present invention, the derivatization reaction of a hydroxyl end group-containing polymer, particularly a polyetherester with a fluorine derivatization reagent was specifically performed by dissolving in an organic solvent. The reaction is completed by adding a fluorine-derivatizing reagent directly or diluted with an organic solvent to the polyetherester polymer and leaving it at room temperature for several tens minutes. The derivatized polymer was reprecipitated using cyclohexane or the like, dried in vacuum, dissolved in deuterated chloroform, added with ethyl trifluoroacetate as an internal standard, and measured by ¹⁹ F-NMR (JEOL JNM -LA400).

Next, using hexafluorobenzene as the standard of chemical shift (0 ppm), qualitative analysis was carried out from the chemical shift of each hydroxyl terminal in the polyetherester after derivatization. In addition, the chemical shift of each hydroxyl terminal after derivatization was determined based on similar compounds. The quantification was determined from the peak area value of each terminal after derivatization and the peak area value of the internal standard. That is, when hexafluoroacetone is used as a derivatization reagent, terminal OH (mo
l) = Internal standard (mol) × (terminal NMR peak area / internal standard NMR peak area) ÷ 2. The analytical method of the present invention enables the qualitative and quantitative determination of two or more types of hydroxyl terminals having different properties present in hydroxyl terminal group-containing polymers, particularly polyetheresters.

[0018]

Example 1 The composition and ratio determined by ¹ H-NMR were as follows: 30% by weight of polyethylene terephthalate (PET) as a polyester component, 55% by weight of polyethylene glycol (PEG) as a polyether component, and polytetramethylene glycol (PTMG). 0.149 g of a 15% by weight polyetherester was dissolved in 3.04 g of chloroform. 1.50 g of a 5% hexafluoroacetone ethyl acetate solution was added, and the mixture was reacted with stirring for 30 minutes. Thereafter, cyclohexane was added for reprecipitation and purification, and the obtained polymer was dried at 50 ° C. for 8 hours. The polymer after drying was dissolved in a heavy chloroform solution containing 7.19 × 10 ⁻⁵ mol of ethyl trifluoroacetate (ETA) as an internal standard, and ¹⁹ F-NMR was measured.

After derivatization, the spectrum was observed at 83.6 ppm for the hydroxyl terminal of the PET component, 82.9 ppm for the hydroxyl terminal of the PEG component, and 83.8 ppm for the hydroxyl terminal of the PTMG component (hexafluorobenzene was added). 0 ppm). From these peak area values and the ETA area value of the internal standard, the number of mo
It was calculated that the hydroxyl terminal of the PET component was 0.48 × 10 ⁻⁶ mol / g, the hydroxyl terminal of the PEG component was 1.47 × 10 ⁻⁶ mol / g, and the hydroxyl terminal of the PTMG component was 0.22 × 10 ⁻⁶ mol / g.

[0020]

Example 2 A polyether ester whose composition and ratio determined by ¹ H-NMR were 30% by weight of polyethylene terephthalate (PET) as a polyester component and 70% by weight of polyethylene glycol (PEG) as a polyether component was used. ¹⁹ F-NMR was measured in the same manner as in Example 1. Each spectrum of the sample after derivatization was observed in the same manner as in Example 1, and then 1 g of the polymer was observed.
Per mole of each hydroxyl end per PET, the hydroxyl end of the PET component was 0.4
0 × 10 ⁻⁶ mol / g and the hydroxyl terminal of the PEG component were 1.72 × 10 ⁻⁶ mol / g.

[0021]

Example 3 The composition and ratio determined by ¹ H-NMR were as follows: 30% by weight of polyethylene terephthalate (PET) as a polyester component, 55% by weight of polyethylene glycol (PEG) as a polyether component, and polytetramethylene glycol (PTMG). 0.154 g of a 15% by weight polyetherester was placed in 1.49 g of chloroform containing 5.5% trifluoroacetic anhydride, and
The reaction was carried out with stirring for 0 minutes. Observing the spectrum of each sample after derivatization in the same manner as in Example 1, and then calculating how many moles of each hydroxyl terminal per g of polymer, the hydroxyl terminal of the PET component was 0.51 × 10 ^−6. mol / g, hydroxyl end of PEG component is 1.44 × 10 ⁻⁶ mol / g, PTM
The hydroxyl terminal of the G component is 0.20 × 10 ⁻⁶ mol /
g.

[0022]

Example 4 A polyether ester whose composition and ratio determined by ¹ H-NMR were 30% by weight of polyethylene terephthalate (PET) as a polyester component and 70% by weight of polyethylene glycol (PEG) as a polyether component was obtained. As in the case of No. 3, it was dissolved in chloroform containing 5.5% trifluoroacetic anhydride and reacted. The spectrum of each sample of the derivatized sample was observed in the same manner as in Example 1, and then the number of moles of each hydroxyl terminal per gram of the polymer was calculated. As a result, the hydroxyl terminal of the PET component was 0.37 × 10 ^−6.
mol / g, the hydroxyl end of the PEG component is 1.68.
× 10 ⁻⁶ mol / g.

[0023]

Reference Example The following is a reference example showing that the quantitative value of this analysis method is accurate and that this analysis method can be applied to a high molecular weight hydroxyl-end group-containing polymer, particularly a polyetherester polymer. Using a standard homopolymer of a known polyethylene glycol (polyethylene oxide) having a small molecular weight distribution (Mw / Mn ≦ 1.15) used for the GPC calibration curve, the same method as in Example 1 (however, (No purification). The polyethylene glycol (polyethylene oxide) used has a molecular weight of 126,000, 22.000 at both terminal hydroxyls and a molecular weight of 501,000, 300,000 and 1.5 million at one terminal hydroxyl.

The hydroxyl terminal of each polyethylene glycol (polyethylene oxide) was derivatized with hexafluoroacetone, and the measurement results of the hydroxyl terminal determined by ¹⁹ F-NMR were 126,000, 22.280,
1.5 million for 501,000, 300,000 and 1.5 million
5 × 10 ⁻⁴ mol / g, 8.82 × 10 ⁻⁵ mol / g,
1.97 × 10 ⁻⁵ mol / g, 3.37 × 10 ⁻⁵ mol
/ G, 6.75 × 10 ⁻⁵ mol / g, which is the value of the hydroxyl terminal obtained by calculation from the number average molecular weight.
61 × 10 ⁻⁴ mol / g, 8.77 × 10 ⁻⁵ mol / g
g, 2.01 × 10 ⁻⁵ mol / g, 3.33 × 10 ⁻⁵ m
ol / g and 6.67 × 10 ⁻⁵ mol / g, respectively. As shown above, when the analysis method for the hydroxyl terminal group-containing polymer, in particular, the hydroxyl terminal in the polyetherester polymer, is performed, the quantitative value is accurate and can be applied to the high molecular weight polyetherester polymer. Is clear.

[0025]

According to the method of the present invention, it is possible to simultaneously and simultaneously qualify and quantify individual hydroxyl terminals of two or more types of hydroxyl terminals having different properties in a hydroxyl terminal group-containing polymer, in particular, a polyether ester. . That is,
According to the method of the present invention, it is necessary to grasp the abundance of various hydroxyl terminals of a high-molecular-weight product according to the method of the present invention. Can be.

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[Procedure amendment]

[Submission date] January 9, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 3

[Correction method] Change

[Correction contents]

Embedded image (Where X ₁ is a linear alkylene group having 2 to 18 carbon atoms,
An alicyclic alkylene group having 6 to 12 carbon atoms, at least one group selected from 4-oxyphenylene, 4-oxydiphenylene, oxy-1,4-phenylene-isopropylidene-1,4-phenylene, p and q are each an integer of 5 or more; m and n are integers of 2 to 8;
Or represents 1. )

Embedded image (Where R ₈ is an aromatic group having 6 to 12 carbon atoms, 2 carbon atoms)
Represents at least one group selected from a straight-chain alkylene group having from 22 to 22 and an alicyclic alkylene group having from 6 to 14 carbon atoms;
₉ represents at least one group selected from an aromatic group having 6 to 12 carbon atoms, a linear alkylene group having 2 to 22 carbon atoms, and an alicyclic alkylene group having 6 to 14 carbon atoms. )

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction contents]

[0001]

The present invention relates to a novel method for analyzing the hydroxyl end of macromolecules containing hydroxyl end groups, especially polyetheresters. More particularly, the present invention is a hydroxyl-terminated group-containing polymer, in particular present in the polyether esters of high molecular weight, and fluorinated derivatives of two or more different hydroxyl-terminated natures, ¹⁹ F-
NMR to analyze each hydroxyl terminal simultaneously and qualitatively and quantitatively for each hydroxyl terminal
Concerning.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0002

[Correction method] Change

[Correction contents]

[0002]

2. Description of the Related Art Polyether esters have a hydroxyl terminal derived from a polyether represented by the following general formula (3) and a hydroxyl terminal derived from a polyester represented by the following general formula (4). Although they have the same hydroxyl end, they behave differently in reactivity during polymerization.

Embedded image (Where X ₁ is a linear alkylene group having 2 to 18 carbon atoms,
An alicyclic alkylene group having 6 to 12 carbon atoms, at least one group selected from 4-oxyphenylene, 4-oxydiphenylene, oxy-1,4-phenylene-isopropylidene-1,4-phenylene, p and q are each an integer of 5 or more; m and n are integers of 2 to 8;
Or represents 1. )

Embedded image (Where R ₈ is an aromatic group having 6 to 12 carbon atoms, 2 carbon atoms)
Represents at least one group selected from a straight-chain alkylene group having from 22 to 22 and an alicyclic alkylene group having from 6 to 14 carbon atoms;
₉ represents at least one group selected from an aromatic group having 6 to 12 carbon atoms, a linear alkylene group having 2 to 22 carbon atoms, and an alicyclic alkylene group having 6 to 14 carbon atoms. )

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

The polymer having a hydroxyl terminal group is also characterized in that it is a polyetherester containing a component having a structure represented by the following general formula (3) and a component having a structure represented by the following general formula (4). Having. Also,

Embedded image (Where X ₁ is a linear alkylene group having 2 to 18 carbon atoms,
An alicyclic alkylene group having 6 to 12 carbon atoms, at least one group selected from 4-oxyphenylene, 4-oxydiphenylene, oxy-1,4-phenylene-isopropylidene-1,4-phenylene, p and q are each an integer of 5 or more; m and n are integers of 2 to 8;
Or represents 1. )

Embedded image (Where R ₈ is an aromatic group having 6 to 12 carbon atoms, 2 carbon atoms)
Represents at least one group selected from a straight-chain alkylene group having from 22 to 22 and an alicyclic alkylene group having from 6 to 14 carbon atoms;
₉ represents at least one group selected from an aromatic group having 6 to 12 carbon atoms, a linear alkylene group having 2 to 22 carbon atoms, and an alicyclic alkylene group having 6 to 14 carbon atoms. )

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

The hydroxyl terminals of each polyethylene glycol (polyethylene oxide) were derivatized with hexafluoroacetone, and the measurement results of the hydroxyl terminals obtained from ¹⁹ F-NMR were 12,000 and 2.22.
1.55 × 10 ⁻⁴ mol / g and 8.82 × 10 ⁻⁵ m for 10,000, 500,000, 300,000 and 1.5 million, respectively
ol / g, 1.97 × 10 ⁻⁵ mol / g, 3.37 ×
10 ⁻⁶ mol / g and 6.75 × 10 ⁻⁷ mol / g, which are 1.61 × 10 ⁻⁴ mol / g and 8.77, which are the values of hydroxyl terminals calculated from the number average molecular weight.
× 10 ⁻⁵ mol / g, 2.01 × 10 ⁻⁵ mo1 /
g, 3.33 × 10 ⁻⁶ mol / g, 6.67 × 10
^-7 mol / g agreed well with each other. As shown above, when the analysis method for the hydroxyl terminal group-containing polymer, in particular, the hydroxyl terminal in the polyetherester polymer, is performed, the quantitative value is accurate and can be applied to the high molecular weight polyetherester polymer. Is clear.

Claims (3)

[Claims] 1. A method for derivatizing a hydroxyl terminal of a polymer having a hydroxyl terminal group by using a compound represented by the following general formula (1), and measuring the terminal by ¹⁹ F-NMR. Molecular end group analysis. Embedded image (Here, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a proton, an alkyl group, and a halogen.) 2. A compound and / or an acid anhydride with a derivative of the hydroxyl-terminated hydroxyl end group-containing polymer of the following general formula (2) of the following general formula (2), ¹⁹ F-NMR
A method for analyzing a terminal group of a polymer having a hydroxyl terminal group, wherein the terminal is measured by the following method. Embedded image (Here, R ₆ and R ₇ represent a proton, an alkyl group, a halogenated alkyl group, and a halogen.) 3. A polymer having a hydroxyl terminal group-containing polymer having a structure represented by the following general formula (3):
The method for analyzing a terminal group of a polymer having a hydroxyl terminal group according to claim 1 or 2, wherein the method is a polyether ester containing a component having a structure represented by the following formula: Embedded image (Where X ¹ is a linear alkylene group having 2 to 18 carbon atoms,
An alicyclic alkylene group having 6 to 12 carbon atoms, at least one group selected from 4-oxyphenylene, 4-oxydiphenylene, oxy-1,4-phenylene-isopropylidene-1,4-phenylene, p and q are each an integer of 5 or more; m and n are integers of 2 to 8;
Or represents 1. ) (Where R ₈ is an aromatic group having 6 to 12 carbon atoms, 2 carbon atoms)
Represents at least one group selected from a straight-chain alkylene group having from 22 to 22 and an alicyclic alkylene group having from 6 to 14 carbon atoms;
₉ represents at least one group selected from an aromatic group having 6 to 12 carbon atoms, a linear alkylene group having 2 to 22 carbon atoms, and an alicyclic alkylene group having 6 to 14 carbon atoms. )