JP2547216B2 - Separation agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a separating agent using an optically active polyamide which is a very useful polymer as a functional material.

[Conventional technology]

There have been many reports on optically active polyamides, but there are very few synthetic examples of highly functional polymers that take advantage of the asymmetry.

[Means for solving problems]

As a result of earnest research on polyamides having optical activity, the present inventors have found that 1,2-diamine such as optically active 2,2′-diamino-1,1′-dinaphthyl or 1,2-diaminocyclohexane.
The inventors have found that an optically active polyamide can be easily produced from diaminocycloalkane and dicarboxylic acid and have excellent asymmetric discrimination ability, and have completed the present invention. Further, they have found that an optically active polyamide can be easily produced from an optically active 1,2-cyclohexanedicarboxylic acid and a diamine.

That is, the present invention provides the following general formulas (I), (II) and (II
The present invention relates to a separating agent using the optically active polyamide shown in any one of I).

[Wherein, m is a number of 1 to 4, X is an alkylene group having 1 to 10 carbon atoms, an aromatic residue, an alicyclic residue or a bond,
Y represents an alkylene group having 2 to 12 carbon atoms, an aromatic residue or an alicyclic residue, and n represents a degree of polymerization in the range of 2 to 1000. ] The optically active 1,2-diaminocycloalkane in the present invention has the formula And m is 1 to 4, but (+) or (−)-trans-1,2-diaminocyclohexane where m = 4 is preferable.

Further, the optically active dicarboxylic acid has the formula And m is 1 to 4, and trans-1,2-cyclohexanedicarboxylic acid in which m = 4 is preferable.

As the optically active 2,2'-diamino-1,1'-dinaphthyl, the d-form is preferable, but either the d-form or the 1-form may be used.

Examples of the dicarboxylic acid constituting X include oxalic acid, HOOC (CH
₂₎ l _'COOH (l: adipic acid represented by 1 to 10), alkylene dicarboxylic acids such as dodecanedioic acid, aromatic carboxylic acids, for example telephoto or isophthalic acid, alicyclic carboxylic acids,
For example, cyclohexanedicarboxylic acid can be used.

Further, as the diamine constituting Y, NH ₂ (CH ₂ )
_There are alkylenediamines represented by _{1 ′} NH ₂ (1 ′ = 2 to 12), such as hexamethylenediamine.

There are also aromatic diamines such as phenylenediamine and fatty acid diamines such as cyclohexanediamine. At least one of diamine and dicarboxylic acid is an optically active substance.

The polyamide of the present invention can be easily obtained from the above diamine and dicarboxylic acid dihalide, preferably dicarboxylic acid dichloride, by a conventional method. That is, using an aromatic solvent, ether, dimethylacetamide, dimethylformamide, dimethylsulfoxide, etc. as a solvent, the reaction is carried out at −20 to 100 ° C. in the presence of an alkali.After the reaction, the reaction solvent is poured into water or methanol to collect the precipitate. ,
It may be washed with water, methanol, etc. and dried.

In order to use the optically active polyamide of the present invention as a separating agent for the purpose of separating a compound or its optical isomer, it is common to use a chromatography method such as gas chromatography, liquid chromatography or thin layer chromatography. However, other membrane separation can also be performed.

In order to apply the optically active polyamide of the present invention to a liquid chromatography method as a separating agent, a method of packing it in a column as a powder is generally used, and as a method thereof, it is preferable to grind or bead-like particles. Is more preferably porous. Furthermore, the pressure resistance of the separating agent is improved,
It is preferable to support the optically active polyamide on a carrier in order to prevent swelling and shrinkage due to solvent substitution and to improve the theoretical plate number.

When used as a powder, the particle size and carrier size vary depending on the size of the column used, but
m to 1 mm, preferably 1 to 30 μm. The carrier is preferably porous and has an average pore size of 10Å
˜100 μm, preferably 50 Å to 5000 Å.
The amount of the optically active polyamide supported on the carrier is 1 to 100% by weight, preferably 5 to 50% by weight, based on the carrier.

The method of supporting the optically active polyamide on a carrier may be a chemical method or a physical method. As a physical method,
A method in which the optically active polyamide is dissolved in a soluble solvent and well mixed with a carrier, and the solvent is distilled off by an air stream under reduced pressure or heating, or the optically active polyamide is dissolved in a soluble solvent and well mixed with the carrier. Then, there is also a method of dispersing the soluble solvent by dispersing it in a solvent insoluble in the optically active polyamide. The separating ability of the separating agent thus obtained can be improved by performing appropriate treatments such as heating, addition of a solvent, and washing.

The carrier to be used may be a porous organic carrier or a porous inorganic carrier, preferably a porous inorganic carrier. Suitable examples of the porous organic carrier include polymeric substances such as polystyrene, polyacrylamide and polyacrylate. Suitable as the porous inorganic carrier are silica, alumina, magnesia, glass, kaolin, titanium oxide, silicate and the like, and these surfaces have good affinity with the optically active polyamide or the carrier itself. You may use what was processed in order to modify the characteristic of the surface. Examples of the surface treatment method include silanization treatment with an organic silane compound and plasma polymerization.

The developing solvent for liquid chromatography or thin layer chromatography is not particularly limited, except for those which dissolve or react with the optically active polyamide. When the optically active polyamide is bound to a carrier by a chemical method or is insolubilized by crosslinking, there is no particular limitation except that it reacts with this.

On the other hand, when performing thin layer chromatography, 0.1
A layer having a thickness of 0.1 mm to 100 mm consisting of the separating agent composed of particles of about μm to 0.1 mm and a small amount of a binder, if necessary, may be formed on the support plate.

When performing membrane separation, it is used as a hollow fiber or a film.

〔The invention's effect〕

The separating agent using the optically active polyamide of the present invention is a substance that is extremely useful as a functional material, is particularly useful for separating various compounds, and particularly is a separation of optical isomers that have been difficult to separate in the past, that is, optical resolution. It is useful as a filler for use.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

The definitions of terms used in the examples are as follows.

Example 1 (1) Synthesis of poly ((±) -trans-1,2-cyclohexaneterephthaloylamide) (A) 50 ml of dimethylacetamide (DMA, simple distillation followed by drying with molecular sieves) under nitrogen, triethylamine (single) 2.79 ml (0.02 mol) of distilled water and dried with KOH) and 2.5 g of anhydrous lithium chloride were added to the reaction vessel and stirred until the lithium chloride was dissolved. Furthermore, (±) -transformer-1,2-
Diaminocyclohexane (57.4-58.2 ℃, 17.0mmHg) 1.2
0 ml (0.01 mol) was added, and the mixture was water-cooled to 0 ° C. While stirring under water cooling, 2.03 g (0.01 mol) of terephthalic acid dichloride (purified by heating with thionyl chloride before reaction) was added to the reaction system little by little over about 10 minutes. Approximately 5 minutes after the start of addition, the reaction system began to become cloudy and the viscosity increased. After continuing cooling and stirring for 1 hour, pour into 500 ml of water (ion-exchanged water),
The precipitate was collected by centrifugation, washed with water and methanol,
After drying under reduced pressure with an aspirator in a desiccator, 45 ℃
After drying under reduced pressure and constant temperature for 4 hours, 2.04 g (83.6%) of white powder was obtained.

(2) Synthesis of poly ((-)-trans-1,2-cyclohexaneterephthaloylamide) (B) Similar to the synthesis of (A), 40 ml of DNA, triethylamine
2.23 ml (0.016 mol), anhydrous lithium chloride 2.00 g,
(−)-Trans-1,2-diaminocyclohexane (▲
0.914 g (0.008 mol) of [α] ²⁰ _D ▼ = −33.4 / C = 2, H ₂ O was mixed and cooled to 0 ° C. While stirring with ice cooling, 1.62 g (0.008 mol) of terephthalic acid dichloride was added at once and reacted for 1 hour, and then added to 400 ml of water. The precipitate was collected by centrifugation, washed with water and methanol, dried by an aspirator in a desiccator, and dried under reduced pressure at 50 ° C. for 2 hours to obtain 1.75 g (89.7%) of white powder.

 The analysis results of the polymers (A) and (B) are shown.

(I) IR spectrum The IR spectra of the synthesized polymers (A) and (B) are shown in FIG.

The IR spectra of (A) and (B) are almost the same, and NH stretching (3230 cm ^-1 ) and CO stretching (1630c
Absorption of m ^-1 ) and NH bending angle (1540 cm ^-1 ) is observed.

(Ii) Molecular Weight Intrinsic Viscosity; 0.12 dl / g Measuring Method; Measured by Ubbelohde viscometer at 30 ° C. using dichloroacetic acid as a solvent (iii) Elemental analysis The elemental analysis values of (B) are shown below.

The numbers in parentheses are The calculated value for the structure of is almost in agreement with the analytical value.

(Iv) Solubility of Polymers (A) and (B) showed similar solubilities, and did not dissolve in an amide solvent, which is usually a good solvent for polyamide, such as dimethyl sulfoxide.

Dissolution: Hexafluoroisopropanol (HFIP), HFIP
/ Chloroform (1: 9), phenol, dichloroacetic acid, trifluoroacetic acid Swelling: dimethylformamide, formic acid, chloroform (v) Optical rotation of optically active polymer (B) (B) Measurement results of optical rotation are shown.

(B): C = 1.00 g / dl, d = 0.5 dm, T = 25 ° C. solvent; dichloroacetic acid [α] ₅₈₉ = −211.0 [α] ₄₃₅ = −540.4 [α] ₅₇₇ = −223.6 [α] ₃₆₅ = -1151.4 [α] ₅₄₆ = -262.6 [M] ₅₈₉ = -515.5 (vi) ¹ H NMR (B) was dissolved in CF ₃ CO ₂ H, and ¹ H NMR was measured. 2.7PP
A peak due to a phenylene group at M, a peak due to a methine group at 4.2 PPM, and a peak due to a methylene group near 1.4 to 2.2 PPM were observed.

(Vii) Optical resolution a) Optical resolution column (B) 7.00 g was dissolved in 10 ml of hexafluoroisopropanol / chloroform (1: 1) and treated with 3-aminopropyltriethoxysilane-treated silica gel (Si-1000,1).
0 μm, RA-198-1) 2.80 g was loaded in 3 times to make a packing material, which was packed in a 25 cm × 0.46 (id) cm column by a slurry method to obtain an optical resolution column.

b) Table 1 shows the results of the optical division according to (B). Hexane-2-propanol (90/10) as eluent
(A) and hexane-2-propanol-chloroform (85/5/10) (b) were used. Addition of chloroform to the eluent has had considerable influence on the division ability, the 2, 6 (a), the 2, 3, 5, 6 have given good division result (b). Further, the compounds 3 and 6 having a carbonyl group, which were not eluted in (a), are eluted in (b) and are both separated. The chromatogram of 3 is characteristic, and the peak width of the (+) form is 13 minutes and that of the (-) form is
At 55 minutes, the peak of (-) form becomes four times as large. This is (+)
This is probably because there is a large difference in the interaction between the body and the (−) body polymer.

As the tendency of resolution in (b), compounds having a tertiary amino group such as 1 , 9 and the like, compounds having a carbonyl group such as 3 , 4 , 6 , 9 and hydroxyl groups such as 2 , 5 , 6 , 8 etc. It gives relatively good splitting results for the compounds it has.

Example 2 (1) Preparation of terephthalic acid dichloride (C) On the day before use, commercially available terephthalic acid dichloride was heated and stirred with thionyl chloride in dry hexane under a nitrogen atmosphere, and terephthalic acid dichloride was removed through a glass filter under a nitrogen atmosphere. It was recovered, washed with dry hexane, and dried under reduced pressure in a desiccator.

(2) Synthesis of d-2,2'-diamino-1,1'-dinaphthyl (D) dl-2,2'-diamino-1,1 obtained by reaction of 2-naphthol with hydrazine monohydrate The'-dinaphthyl was optically resolved in chlorobenzene-ethanol with D-camphorsulfonic acid to give d-2,2'-diamino-1,1'-dinaphthyl.

(3) Synthesis of poly (2,2'-binaphthylene terephthalamide) (E) Distilled water 39.6 ml, chloroform (single-distilled, alcohol removed with Moleschler sieves) 15.8 ml, sodium carbonate 0.560 g (5.28mmol), (D) 0.750g (2.640mmo
l) was added to the reaction vessel and vigorously stirred, and 0.535 g of (C) (2.6
4 mmol) dispersed in 15.8 ml chloroform for about 5
It was added dropwise over a period of minutes. After 15 minutes, 7.9 ml of petroleum ether was added and stirring was continued for about 150 minutes thereafter. The reaction solution was concentrated by evaporation, 100 ml of distilled water was added, and the resulting precipitate was collected with a glass filter, washed with water, methanol and acetone, and dried under reduced pressure with a desiccator.

Yield: 0.745 g Yield: 62.6% The analysis result of the above polymer (E) is shown.

The above-mentioned polymer is considered to have the following structural formula based on the analysis results described below.

(I) IR spectrum The IR spectrum of (E) is shown in FIG.

That is, absorption based on NHCO is observed at 1660 cm ^-1 .

(Ii) Molecular weight The molecular weight was determined by GPC measurement. Showa Denko S on the column
Hodex 80M, tetrahydrofuran was used as a mobile phase, a standard calibration curve was prepared from a polystyrene standard sample, and the molecular weight was determined.

n = 2,653 w / n = 1.63 ▲ ▼ = 5.88 (iii) Optical rotation C = 1.00 g / dl, l = 0.5 dm, T = 25 ° C. Solvent: Tetrahydrofuran [α] ₅₈₉ = −4.79 [α] ₅₇₇ = −7.39 [Α] ₅₄₆ = −16.57 [α] ₄₃₅ = −174.11 [α] ₃₆₅ = −86.06 These optical rotations have the opposite signs to the optical rotations of the optically active monomer (D) in the organic solvent.

(Iv) Optical resolution Preparation of optical resolution column 2.60 g of polymer (E) dissolved in 8 ml of tethydrofuran and surface-treated silica gel (MY-5,3-aminopropyltriethoxysilane treatment, 1000Å to 3 μm) Was loaded into the column three times and packed into the column by the slurry method to obtain a column for optical resolution.

Eluent: Hexane-2-propanol (90/10) Column: 25 cm × 0.46 (id) cm Flow rate: 0.5 ml / min, temperature: 25 ° C Eluent: hexane-2-propanol (90/1)
In addition to 0), we tried to resolve using hexane-2-propanol-chloroform (90/7/3), etc., but for many racemates, the peak was somewhat sharper than that of hexane-2-propanol. However, none of them greatly improved the dividing ability. Regarding the Trager base, α = 1.06 in hexane-2-propanol (90/10), but the peak became broader in the hexane-2-propanol-chloroform system, and α = 1 and resolution was observed. lost.

Example 3 (1) Synthesis of poly ((±) -trans-1,2-cyclohexaneadipoylamide) (F) Dry N, N-dimethylacetamide (DMA) under a nitrogen stream.
50 ml, lithium chloride 2.50 g, simple distilled triethylamine
2.79 ml (20.0 mmol), (±) -trans-1,2-diaminocyclohexane (57.4-58.2 ° C / 7 mmHg) 1.20 ml (10.0
mmol) was added to the reaction vessel and ice-cooled. Adipoyl chloride (68-69 ℃ / 1mmHg) while stirring under ice cooling under a nitrogen stream
1.45 ml (10.0 mmol) was added dropwise over 5 minutes. After the start of dropping
In about 5 minutes, the reaction system began to become cloudy and the viscosity increased.

One hour after the dropping was completed, the reaction solution was poured into 500 ml of water to form a white precipitate. The precipitate was collected by centrifugation, washed with water and methanol in this order, and dried under reduced pressure and constant temperature at 50 ° C. for 5 hours. 1.52 g (67.9%) of white powder was obtained.

(2) Synthesis of poly ((+)-trans-1,2-cyclohexaneadipoylamide) (G) Under a nitrogen stream, 30 ml of dry DNA, 1.32 g of lithium chloride, 1.46 ml (10.5 mmol) of single-distilled triethylamine, ( -)-Trans-1,2-diaminocyclohexane (73-74 ℃ / 16mm
Hg), ▲ [α] ²⁰ _D ▼ ＝ −36.1 °, C = 2.0, H ₂ O) 0.600g
(5.25 mmol) was added, and the mixture was stirred and ice-cooled. 0.763 ml (5.25 mmol) of adipoyl chloride was added dropwise over 5 minutes while stirring and cooling with ice. About 3 minutes after the start of dropping, the reaction system began to become cloudy and the viscosity increased.

One hour after the dropping was completed, the reaction solution was poured into 400 ml of water to form a white precipitate. The precipitate was recovered by centrifugation, washed with water and methanol in this order, and dried under reduced pressure and constant temperature at 50 ° C. for 5 hours. 0.756 g (64.1%) of white powder was obtained.

 The analysis results of the polymers (F) and (G) are shown.

(I) IR spectrum The IR spectrum of the synthesized polymer (G) is shown in FIG.

The IR spectra of (F) and (G) are almost equal, 3270 cm
^-1, 1630 cm ^-1, absorption by amide bond 1540 cm ^-1 is observed.

(Ii) Elemental analysis (Iii) Solubility (F) and (G) showed the same solubility in the solvents shown below.

Dissolution; hexafluoroisopropanol, phenol,
Dichloroacetic acid Swelling; Dimethyl sulfoxide, DNA insoluble; Chloroform, tetrahydrofuran, 1,4-dioxane (iv) Specific optical rotation of optically active polymer (G) C = 1.00 g / dl, d = 0.5 dm, T = 25 ° C. solvent; Dichloroacetic acid [α] ₅₈₉ = + 73.6 ° [α] ₅₇₇ = + 76.5 ° [α] ₅₄₆ = + 88.5 ° [α] ₄₃₅ = + 158.8 ° [α] ₃₆₅ = + 266.6 ° (v) Intrinsic viscosity Using dichloroacetic acid as a solvent, the intrinsic viscosity of (G) was determined by an Ubbelohde viscometer at 30 ° C.

[Η] = 0.10 dl / g (vi) ¹ H NMR of (G) ¹ H NMR (60 ° C. in CF ₃ COOD) shows that 3.84 PPM is a methine proton of a cyclohexyl ring and 2.42 PPM is a methylene adjacent to a carbonyl group. Absorption by the protons of the groups and the protons of the remaining methylene groups was observed around 1 to 2.2 PPM, and the peak area ratio was approximately 2: 4: 12, which is the expected value.

(Vii) Optical resolution (a) Preparation of column for optical resolution (G) 0.650 g was dissolved in hexafluoroisopropanol-chloroform (1: 1) 8 ml and treated with 3-aminopropyltriethoxysilane-treated silica gel (particle size 10 μm, Pore size
1000 Å) 2.60 g was loaded in two batches. The prepared packing material was packed in a 25 cm × 0.46 (id) cm column by a slurry method to obtain an optical resolution column.

(B) Resolution results Table 3 shows the results of optical resolution by the column prepared in (a).
Shown in

Example 4 (1) Poly ((+)-1,4-phenylene-trans-
Synthesis of 1,2-cyclohexanediamide) (H) Under nitrogen, 25 ml of N, N-dimethylacetamide (DMA)
Lithium chloride 1.25g, simple distilled triethylamine 1.41m
l (10.0 mmol) and 0.541 g (5.00 mmol) of p-phenylenediamine obtained by recrystallization from ethyl acetate were added and dissolved with stirring. (−)-Trans-1,2-dicarboxylic acid dichloride (▲ [α] ²⁵ _D ▼ ＝ -17.6 ° (CC
l ₄₎₎ was added dropwise 1.05g of (5.00 mmol) in 5 minutes. About 1 minute after the start of dropping, the reaction system became cloudy and the viscosity increased.

Two hours after the dropping was completed, the reaction solution was poured into 250 ml of water to form a white precipitate, and the precipitate was collected by centrifugation.
It was washed with water and methanol in this order. After drying in a desiccator, it was dried under reduced pressure at 50 ° C for 4 hours to give 1.18 g (69.7%) of a brown solid.
%) Was obtained.

(2) Poly ((+)-1,4-butane-trans-1,2-
Synthesis of cyclohexanediamide) (K) Under nitrogen, dry DMA 27.5 ml, simple distilled triethylamine 15.
3 ml (11.0 mmol), 1,4-diaminobutane (49.3-50.0 ° C)
0.485 ° C. (5.5 mmol) was added to the reaction vessel, and (−)-trans-1,2-dicarboxylic acid dichloride (▲ [α] ²⁵ _D ▼ = 17.6 ° (CCl ₄ )) was added while stirring with ice cooling. 1.15g
(5.50 mmol) was added dropwise over 5 minutes. Immediately after the start of dropping, the reaction system became cloudy and the viscosity increased.

Two hours after the dropping was completed, the reaction solution was poured into 300 ml of water to form a white precipitate, and the precipitate was collected by centrifugation.
It was washed with water and methanol in this order. After drying under reduced pressure and constant temperature for 4 hours at 50 ° C., 0.858 g (69.8%) of a brown solid was obtained.

 The analysis results of the polymers (H) and (K) are shown.

(I) IR spectra The IR spectra of (H) and (K) are shown in FIGS. 4 and 5, respectively.
Shown in the figure.

3280cm ^-1 in the IR spectrum of (H), 1660cm ^-1, 1550cm
^-1 , and the IR spectrum of (K) is 3300 cm ^-1 , 1640 cm ^-1 , 15,
Absorption by amide bond is observed at 50 cm ⁻¹ .

(Ii) Elemental analysis The elemental analysis values of (H) and (K) are shown below.

(Iii) Solubility The solubility of (H) and (K) in each solvent is summarized below.

(H) solvent; dichloroacetic acid swelling; trifluoroethanol, hexafluoroisopropanol, dimethylsulfoxide insoluble; tetrahydrofuran, chloroform (K) solvent; dichloroacetic acid, hexafluoroisopropanol swelling; trifluoroethanol insoluble; tetrahydrofuran (iv) specific optical rotation ( (In dichloroacetic acid) (H) (K) ▲ [α] ²⁵ ₅₈₉ ▼ = + 238.9 ° ▲ [α] ²⁵ ₅₈₉ ▼ = + 6
8.5 ° ▲ [α] ²⁵ ₄₃₅ ▼ = +60 7.7 ° ▲ [α] ²⁵ ₄₃₅ ▼ = +14
5.5 ° (v) Intrinsic Viscosity The intrinsic viscosities of (H) and (K) were determined with an Ubbelohde viscometer.

(H)… [η] = 0.16dl / g (30 ° C., Cl ₂ CHCO ₂ H) (K)… [η] = 0.15dl / g (30 ° C., Cl ₂ CHCO ₂ H) (vi) ¹ H NMR Spectra (in CF ₃ COOD, 60 ° C) (H) spectrum shows absorption by phenylene proton at 7.42PPM, methine proton at 2.98PPM, and methylene proton near 1.2-2.8PPM. Calculate the peak area ratio of methylene group and methine group 2.
It became 67 (theoretical value 2.50).

In the spectrum of (K), the absorption of the methylene group adjacent to the amino group at 3.37 PPM, the methine proton at 2.76 PPM, and the remaining methylene protons at around 0.8 to 2.4 PPM are observed. Almost agrees with the theoretical value of 4: 2: 12.

(Vii) Optical resolution (a) Preparation of column for optical resolution (a-1) Dissolve 0.675 g of (H) in 10 ml of dichloroacetic acid,
It was loaded on 2.70 g of 3-aminopropyltriethoxysilane-treated silica gel (particle size 10 μm, pore size 1000 Å) in three times.

(A-2) (K) 0.675 g was dissolved in hexafluoroisopropanol-chloroform (1: 1) 10 ml and treated with 3-aminopropyltriethoxysilane-treated silica gel (particle size).
10 μm, pore size 1000 Å) 2.70 g was loaded in two times.

The packing materials prepared as in (a-1) and (a-2) were packed in a column of 25 cm × 0.46 (id) cm for both (H) and (K) by a slurry method to obtain an optical resolution column.

(B) Resolution results The results of optical resolution by the column prepared in (a) are shown in Table 4 below.

[Brief description of drawings]

1 to 5 are diagrams showing IR spectra of the optically active polyamides of the present invention obtained in Examples.

Front Page Continuation (56) References US Patent 3418287 (US, A) US Patent 3432477 (US, A) J. Polym. Sci, Poly m. Chem. Ed. 23 [2] (1985) p. 575-579 J. Polym. Sci, Poly m. Chem. Ed. 22 [5] (1984) p. 1153-1177 Makromol. Chem. 116 (1968) p. 190-202

Claims (1)

(57) [Claims] 1. A separating agent using an optically active polyamide represented by any one of the following general formulas (I), (II) and (III). [Wherein, m is a number of 1 to 4, X is an alkylene group having 1 to 10 carbon atoms, an aromatic residue, an alicyclic residue or a bond,
Y represents an alkylene group having 2 to 12 carbon atoms, an aromatic residue or an alicyclic residue, and n represents a degree of polymerization in the range of 2 to 1000. ]