JP2000119360A - Optically active aromatic isocyanate polymer or copolymer, and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a polymer compound which can be expected as an optically functional material such as an optically active substance separating material. SOLUTION: An optically active aromatic isocyanate polymer or copolymer mainly composed of the structural unit (I) or the structural units (I) and (VI) and having a degree of polymerization of 5 or more, and a method for producing the same . Embedded image [In the formula, R ¹ represents an optically active ether group (II). Embedded image (R ² , R ³ and R ⁴ are respectively different groups and represent a monovalent aromatic group, an alkyl group having 1 to 14 carbon atoms or a hydrogen atom. N
Is an integer of 0 or more indicating the number of methylene groups.) (Wherein, R ⁵ has 1 to 1 carbon atoms which may contain elements other than carbon.
It is a 14 alkyl group or a monovalent aromatic group. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer or copolymer of an optically active aromatic isocyanate and a method for producing the same. This optically active aromatic isocyanate polymer or copolymer has a large optical rotation, and can be expected as an optically functional material such as an optically active substance separating material.

[0002]

2. Description of the Related Art Many polymer compounds used as functional materials such as an optical resolving agent, a liquid crystal material and a nonlinear optical material are known. For example, the optically active polymer of triphenylmethyl methacrylate disclosed in JP-A-56-106907 has a high optical rotation due to having a helical structure, and this compound itself is useful as an optical resolving agent. It is stated that there is. Japanese Patent Application Laid-Open No. 63-1446 discloses an optically active poly (meth) acrylamide compound. The asymmetric structure of the compound based on the optically active side chain makes it possible to form a racemic mixture into an optically active material. It describes that it is effective as an adsorbent for separating into palms. JP-A-1-79230 discloses a liquid crystal composition using an optically active polymer compound. Furthermore, the present inventors have found that a polymer or copolymer of an aromatic isocyanate having an optically active amide group or ester group has a stable helical structure even in a solution, and that excellent optical physical properties can be expected. Filed (Japanese Unexamined Patent Application Publication No. 10-12
No. 0751 and Japanese Patent Application No. 9-286819).

[0003] As described above, polymer compounds having various asymmetric structures exhibit various performances as unique optical functional materials, and have been applied to various uses. At present, research is ongoing to search for materials with even more unique performance and functions.

Accordingly, it is an object of the present invention to provide a polymer compound having unexpected and unique performance and function and a method for producing the same under such a background.

[0005]

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 obtained a novel optically active aromatic isocyanate having an optically active ether group introduced on the aromatic group. The present inventors have found a polymer or a copolymer, and have completed the present invention. That is, the present invention relates to a polymer of an optically active aromatic isocyanate having an optically active ether group in a side chain, having a structural unit represented by the following formula (I) as a main component and having a degree of polymerization of 5 or more, and It provides a manufacturing method.

[0006]

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[Wherein R ¹ is the formula (II)

[0008]

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(R ² , R ³ and R ⁴ are each a different group,
It represents a monovalent aromatic group, a linear or branched alkyl group having 1 to 14 carbon atoms or a hydrogen atom, and may contain an element other than carbon. R ² and R ³ may be combined to form a ring. n is an integer of 0 or more indicating the number of methylene groups). Further, the present invention mainly comprises a structural unit represented by the above formula (I) and a structural unit represented by the following formula (VI), and has a degree of polymerization of 5:
An object of the present invention is to provide a copolymer of an optically active aromatic isocyanate having an optically active ether group in a side chain and an achiral isocyanate, and a method for producing the same.

[0010]

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(In the formula, R ⁵ is an alkyl group having 1 to 14 carbon atoms or a monovalent aromatic group which may contain an element other than carbon.)

[0012]

Embodiments of the present invention will be described below in detail.

The aromatic isocyanate polymer of the present invention mainly comprises a structural unit represented by the formula (I) in which an optically active ether group represented by the formula (II) is introduced on an aromatic group. Things. Formula (I) representing an optically active ether group
In I), R ² , R ³ and R ⁴ are each a different group,
It represents a monovalent aromatic group, a linear or branched alkyl group having 1 to 14 carbon atoms or a hydrogen atom, and may contain an element other than carbon. R ² and R ³ may be combined to form a ring. The ring formed by R ² and R ³ together is preferably a menthyl group. n is an integer of 0 or more indicating the number of methylene groups, preferably 0 to 5.

Particularly preferred groups among the optically active ether groups represented by the formula (II) are groups represented by the following formulas (III) to (V).

[0015]

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The aromatic isocyanate copolymer of the present invention has a structure represented by the formula (I) in which an optically active ether group represented by the formula (II) is introduced on the above aromatic group. It is mainly composed of a unit and a structural unit represented by the above formula (VI). In the formula (VI), R ⁵ represents an alkyl group having 1 to 14 carbon atoms or a monovalent aromatic group which may contain an element other than carbon, but is substituted by a phenyl group or an alkoxy group having 1 to 6 carbon atoms. A phenyl group and an alkyl group having 1 to 6 carbon atoms are preferred, and a methoxyphenyl group is more preferred.

The aromatic isocyanate polymer mainly comprising the structural unit represented by the formula (I) of the present invention is represented by the following formula (VII):
Can be produced by anionic polymerization of an optically active aromatic isocyanate represented by the following formula in the presence of a polymerization initiator.

[0018]

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(Wherein, R ¹ has the above-mentioned meaning.)
The copolymer of the optically active aromatic isocyanate and the achiral isocyanate, which is mainly composed of the structural unit represented by the above formula (I) and the structural unit represented by the above formula (VI), of the present invention, An optically active aromatic isocyanate represented by the formula (VII) and an achiral isocyanate represented by the following formula (VIII) R ⁵ —NCO (VIII) (wherein R ⁵ has the above-mentioned meaning) And anionic polymerization in the presence of a polymerization initiator.

The aromatic isocyanate having an optically active ether group introduced on the aromatic represented by the formula (VII) can be produced by the following method. That is, the alkoxy aromatic carboxylic acid obtained by the reaction of the corresponding hydroxy aromatic ester and the tosylate ester derived from the corresponding optically active alcohol is converted into an acyl azide, and then synthesized by the Curtius rearrangement reaction.

The polymerization initiator used in the anionic polymerization of the present invention is represented by the formula (IX) R ⁶ M (IX) (wherein R ⁶ represents an organic group, and M is Li, Na, K, Mg, Ca) , S
Indicates an alkali metal or alkaline earth metal such as r. Alkali metal or alkaline earth metal compound represented by) [e.g., SrR ⁷ ₂ (R ⁷ is a monovalent organic group. Hereinafter the _{^{same), CaR 7 2, R 7}} K, R 7 Na, R 7 Li , R ⁷ ONa, R ⁷ OLi
Etc.], R ⁷ OH, pyridine, amines (e.g., NR ⁷ ₃ etc.) and the like, represented by the formula (X) R ⁶ Li (X) (wherein, R ⁶ have the same meanings as defined above.) Lithium compounds are preferred, and lithium amides of n-butyllithium and piperidine are particularly preferred.

The anionic polymerization in the present invention is carried out in a solvent. The solvent may be any solvent as long as it dissolves the monomer and the polymer at least between the low polymers. However, any solvent that prevents anionic polymerization and optically active polymerization cannot be used. Specific examples of the solvent used include benzene, toluene, dioxane, diethyl ether, a hexane-benzene mixture, a hexane-toluene mixture, and tetrahydrofuran (THF). The polymerization temperature in the present invention is from -150 ° C to 0 ° C, preferably from -120 ° C to -50 ° C.

The production of the optically active aromatic isocyanate polymer and the copolymer of the optically active aromatic isocyanate and the achiral isocyanate of the present invention is carried out by living polymerization. It is preferable to end-block with.

An optically active aromatic isocyanate polymer having an optically active ether group introduced on the aromatic according to the present invention;
And the degree of polymerization of a copolymer of an optically active aromatic isocyanate having an optically active ether group introduced on the aromatic and an achiral isocyanate is 5 or more, preferably 20 to
100,000. This polymer is characterized by having a 1-nylon rigid main chain consisting only of amide bonds and having a high optical rotation.

[0025]

EXAMPLES The present invention will be described below in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited to these Examples. In the following Synthesis Examples and Examples, the optical rotation was measured with a Jasco DIP-181 polarimeter.
The molecular weight of the polymer was measured by a light scattering method using Shodex KF-806L, Shodex GPC SYSTEM-21 equipped with a KF-803 GPC column, and DAWN DSP-F. ¹ H-NMR spectrum is Varian VXR-500 (500 MHz) or Varian Gemini-2000 (400
MHz) at 60 ° C.

Synthesis Example 1 Synthesis of 3-[(R) -sec-butoxy] phenyl isocyanate (XI)

[0027]

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1-1: Synthesis of ethyl 3-hydroxybenzoate Under nitrogen, 3-hydroxybenzoic acid (73.0) was placed in a three-necked flask.
7 g (529 mmol), 220 ml of absolute ethanol and concentrated sulfuric acid 2
9.41 g (291 mmol) were sequentially added, and the mixture was heated and refluxed at 100 ° C. for 4 hours. After about half of the solvent was distilled off, 600 ml of water was added to the reaction mixture, whereby a white precipitate was deposited. After adding diethyl ether to the extent that the precipitate was dissolved, the aqueous layer was neutralized with sodium carbonate. After extracting the reaction product using diethyl ether as an extraction solvent, the collected organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain ethyl 3-hydroxybenzoate (white solid, yield 76.90 g, yield). 8
7.5%).

1-2: Synthesis of (S) -sec-butyl-p-toluenesulfonate Under nitrogen, in a three-necked flask, 120 ml of anhydrous pyridine and 10.32 g of a commercially available product (S)-(+)-2-butanol ( 139 mmol), and cooled to 0 ° C., and p-toluenesulfonic acid chloride 5
2.85 g (277 mmol) was added, and the mixture was stirred at 0 ° C. for 4 hours. Thereafter, the reaction vessel was placed in a refrigerator (3 ° C.) and left for 24 hours. The reaction mixture was poured into about 600 g of ice water, and 100 ml each of diethyl ether was used as an extraction solvent.
The reaction product was extracted twice. The collected organic layer was washed with 2N hydrochloric acid (500 ml each) four times, and after confirming that it had become acidic, a saturated sodium hydrogen carbonate aqueous solution (50 ml each) was used.
Washing was performed three times, and after confirming that the solution became alkaline, washing was further performed three times with 50 ml of a saturated saline solution. After placing in an ice bath and drying over anhydrous magnesium sulfate while keeping the temperature from rising, the solvent was distilled off under reduced pressure to obtain (S) -sec-butyl-p-toluenesulfonate (light yellow transparent liquid, yield 29.21 g, yield 91.9%).

1-3: Synthesis of ethyl 3-[(R) -sec-butoxy] benzoate 21.34 g of ethyl 3-hydroxybenzoate was placed in a three-necked flask.
(128 mmol), (S) -sec-butyl-p-toluenesulfonate (29.21 g, 128 mmol) and ethanol (107 ml) were added to form a homogeneous solution.
l) was added, and the mixture was heated under reflux for 6 hours. After adding 230 ml of 5N hydrochloric acid to the reaction mixture, chloroform and 200 ml each were added.
Extraction was performed three times with chloroform.
After washing four times with l and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product (light yellow transparent liquid). This is treated with diethyl ether / hexane = 1/10
Was purified by column chromatography using a developing solution of the above to obtain ethyl 3-[(R) -sec-butoxy] benzoate (yield 15.09 g, 53.1%).

1-4: Synthesis of 3-[(R) -sec-butoxy] benzoic acid 3-[(R) -sec- synthesized in 1-3 in a three-necked flask.
Butoxy] ethyl benzoate (15.24 g, 68.57 mmol), 2N aqueous sodium hydroxide solution (80.5 ml) and ethanol (80.5 ml) were added, and the mixture was heated under reflux for 1 hour. After standing to cool, 2N hydrochloric acid aqueous solution
80 ml was added to make the reaction mixture acidic, and the reaction product was extracted using diethyl ether as an extraction solvent. The collected diethyl ether was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 3-[(R) -sec-butoxy] benzoic acid (light yellow transparent liquid, yield 12.81 g, yield 97.2%). ).

1-5: Synthesis of 3-[(R) -sec-butoxy] phenyl isocyanate (XI) 3-[(R) -sec- synthesized in 1-4 in a three-necked flask.
Butoxy) benzoic acid (12.40 g, 63.8 mmol)
Dissolved in 220 ml. This acetone solution was cooled to 0 ° C. in an ice-salt solution bath, and anhydrous triethylamine 8.10 g (80.1 mmol)
Was added. When ethyl chloroformate (8.72 g, 80.4 mmol) was slowly added dropwise so that the temperature of the reaction system did not exceed 5 ° C., a white precipitate was deposited. After stirring at 0 ° C. for 1.5 hours, water 30 containing 7.52 g (116 mmol) of sodium azide was added thereto.
Then, the mixture was stirred at 0 ° C. for 1.5 hours. The resulting reaction mixture was poured into about 300 ml of ice water, and the separated oil was extracted with 200 ml of toluene. The solvent was distilled off under reduced pressure until the amount of the collected toluene extract became 50 to 100 ml, and anhydrous magnesium sulfate was added in an ice bath and dried. The toluene solution from which anhydrous magnesium sulfate was removed by filtration was transferred to a three-necked flask under nitrogen, heated in an oil bath at 120 ° C. to 130 ° C. for 3 hours, allowed to cool, and then toluene was distilled off under reduced pressure to obtain an appropriate amount. Concentrated. This concentrated liquid was transferred to an eggplant flask under nitrogen, and washed with dry chloroform. The solvent was distilled off under reduced pressure to obtain a pale yellow transparent liquid. This was distilled under reduced pressure to obtain 3-[(R) -sec-butoxy] phenyl isocyanate (XI) (bp. 61-64 ° C).
/0.5mmHg, pale yellow transparent liquid, yield 7.19g, yield 58.9
%, [Α] ²⁵ ₃₆₅ = -95 °, [α] ²⁵ _D = -33 ° (c
1.0, THF).

Synthesis Example 2 Synthesis of 3-[(S) -2-methylbutoxy] phenyl isocyanate (XII)

[0034]

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2-1: Synthesis of ethyl 3-hydroxybenzoate Ethyl 3-hydroxybenzoate was obtained in the same manner as in the above 1-1.

2-2: Synthesis of (S) -2-methylbutyl-p-toluenesulfonate Commercially available product (S)-(-)-2-methyl-in place of (S)-(+)-2-butanol 13.50 g of 1-butanol (1
53 mmol), and in the same manner as in 1-2 above,
(S) -2-Methylbutyl-p-toluenesulfonate was obtained (light yellow transparent liquid, yield 33.39 g, yield 90.0%).

2-3: 3-[(S) -2-methylbutoxy]
Synthesis of ethyl benzoate 24.57 g (148 mmol) of ethyl 3-hydroxybenzoate and 2-2
Using 33.39 g (138 mmol) of (S) -2-methylbutyl-p-toluenesulfonate obtained in the above, ethyl 3-[(S) -2-methylbutoxy] benzoate was obtained in the same manner as in 1-3. A crude product was obtained. This was purified by column chromatography using a developing solution of diethyl ether / hexane = 1/10 and distillation under reduced pressure to obtain ethyl 3-[(S) -2-methylbutoxy] benzoate (yield 22.21 g, yield 22.21 g).
68.2%).

2-4: 3-[(S) -2-methylbutoxy]
Synthesis of benzoic acid Using 22.21 g (94.0 mmol) of ethyl 3-[(S) -2-methylbutoxy] benzoate obtained in 2-3, the final purification was carried out in the same manner as in 1-4. By performing recrystallization from hexane twice, 3-[(S) -2-methylbutoxy] benzoic acid was obtained (white solid, yield: 9.94 g, yield: 50.8%).

2-5: 3-[(S) -2-methylbutoxy]
Synthesis of Phenylisocyanate (XII) Using 9.8 g (47.3 mmol) of 3-[(S) -2-methylbutoxy] benzoic acid obtained in 2-4, 3-[(( S) -2-Methylbutoxy] phenyl isocyanate was obtained (bp. 78-82 ° C./0.13 mmHg, pale yellow transparent liquid, yield 5.59 g, yield 57.6%, [α] ²⁵ ₃₆₅ = + 37.
°, [α] ²⁵ _D = + 9.7 ° (c 1.0, THF).

Synthesis Example 3 Synthesis of 3-[(S) -3,7-dimethyloctyloxy] phenyl isocyanate (XIII)

[0041]

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3-1: Synthesis of ethyl 3-hydroxybenzoate Ethyl 3-hydroxybenzoate was obtained in the same manner as in the above 1-1.

3-2: Synthesis of (S) -3,7-dimethyloctanol Under nitrogen, a commercially available product (S)-(-)-citronellol (19.51 g, 125 mmol) was placed in a three-necked flask, and ethanol (200 ml) was added.
Was dissolved. 1.22 g of palladium on activated carbon was added, and the mixture was stirred for 6 hours under a hydrogen atmosphere. After the active carbon-supported palladium was removed by filtration, ethanol was distilled off under reduced pressure. The above operation was repeated three times until the disappearance of the raw material (δ 5.1 ppm (t, 1H) by ¹ H-NMR) was confirmed.
0 ml was added to the reaction mixture, the activated carbon palladium was completely removed by celite filtration, and THF was distilled off under reduced pressure to obtain (S) -3,7-dimethyloctanol (13.01 g, 65.8% yield). ).

3-3: (S) -3,7-dimethyloctyl-
Synthesis of p-toluenesulfonate (S) -3,7-dimethyloctanol obtained in 3-2
(S) -3,7-Dimethyloctyl-p-toluenesulfonate was obtained using 12.10 g (76.4 mmol) in the same manner as in 1-2 above (light yellow transparent liquid, yield: 20.04 g, yield). 83.9%).

3-4: Synthesis of ethyl 3-[(S) -3,7-dimethyloctyloxy] benzoate 10.88 g (65.5 mmol) of ethyl 3-hydroxybenzoate and 3-3
Using 20.04 g (64.1 mmol) of (S) -3,7-dimethyloctyl-p-toluenesulfonate obtained in the above, 3-[(S) -3,7-dimethyloctyl) was obtained in the same manner as in 1-3. [Roxy] ethyl benzoate as a crude product. This was purified by column chromatography using a developing solution of diethyl ether / hexane = 1/15 to give 3-[(S)-
Ethyl [3,7-dimethyloctyloxy] benzoate was obtained (18.62 g, 94.7% yield).

3-5: Synthesis of 3-[(S) -3,7-dimethyloctyloxy] benzoic acid 3-[(S) -3,7-dimethyloctyloxy] benzoic acid obtained in 3-4 Using 18.62 g (60.8 mmol) of ethyl, 1-4
3-[(S) -3,7-dimethyloctyloxy] benzoic acid was obtained in the same manner as described above (yield 9.61 g, yield 34.5).
%).

3-6: Synthesis of 3-[(S) -3,7-dimethyloctyloxy] phenyl isocyanate (XIII) 3-[(S) -3,7-dimethyloctyl obtained in 3-5 Roxy] benzoic acid (9.61 g, 34.5 mmol) was used to obtain 3-[(S) -3,7-dimethyloctyloxy] phenyl isocyanate in the same manner as in 1-5 (bp. 135-136).
° C / 0.4-0.5mmHg, colorless transparent liquid, yield 3.42g, yield 36.
0%, [α] ²⁵ ₃₆₅ = -8.4 °, [α] ²⁵ _D = -2.7 ° (c
1.3, THF).

Synthesis Example 4 Preparation of Polymerization Initiator a Under a nitrogen atmosphere, 0.62 ml of a tert-butyllithium / pentane solution (1.85N) in a mixed solution of 0.10 g (1.2 mmol) of piperidine and 6.0 ml of THF distilled under vacuum at room temperature. (1.2 mmol) was added to prepare lithium amide of piperidine.

Synthesis Example 5 Preparation of polymerization initiator b In a nitrogen atmosphere, 0.07 g (0.86 mmol) of piperidine was mixed with 2.0 ml of THF distilled under vacuum to prepare a mixed solution. From this mixed solution, 0.6 ml (0.25 mmol of piperidine) was placed in another ampoule (under nitrogen), and 10 ml of vacuum distilled THF was added thereto.
tert-butyllithium / pentane solution (1.85N) 0.12ml
(0.22 mmol) was added at room temperature to prepare lithium amide of piperidine.

Example 1 Polymerization of 3-[(S) -sec-butoxy] phenyl isocyanate (XI) (1) The polymerization reaction was carried out in a glass ampoule under a nitrogen atmosphere.
In a glass ampoule, 0.50 g (2.6 mmol) of 3-[(S) -sec-butoxy] phenyl isocyanate (XI) and 5.0 ml of THF.
And cooled to −98 ° C., followed by polymerization initiator a of Synthesis Example 4.
Was added with a 1/50 equivalent syringe of monomer (XI) to initiate a polymerization reaction. After 0.5 hour, the reaction was stopped with hydrochloric acid-methanol 10 times the amount of the polymerization initiator, and then poured into a large amount of methanol to precipitate, collected by centrifugation, and dried in vacuum at room temperature. Yield 70% (methanol insolubles), number average molecular weight (Mn) =
3.1 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.1, [α] ²⁵
₃₆₅ = -3103 ° (THF).

Example 2 Polymerization of 3-[(S) -sec-butoxy] phenyl isocyanate (XI) (2) Example 1 was repeated except that the polymerization time was changed from 0.5 hours to 4 hours.
A polymerization reaction was carried out in exactly the same manner as described above. Yield 68% (methanol insolubles), number average molecular weight (Mn) =
2.8 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.2, [α] ²⁵
₃₆₅ = -3129 ° (THF).

Example 3 Polymerization of 3-[(S) -2-methylbutoxy] phenyl isocyanate (XII) (1) 0.5 g of 3-[(S) -2-methylbutoxy] phenyl isocyanate (XII) ( Using 2.4 mmol), a polymerization reaction was carried out in the same manner as in Example 1. Yield 77% (methanol insolubles), number average molecular weight (Mn) =
3.0 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.1, [α] ²⁵
₃₆₅ = + 1341 ° (THF).

Example 4 Polymerization of 3-[(S) -2-methylbutoxy] phenyl isocyanate (XII) (2) Example 3 except that the polymerization time was changed from 0.5 hours to 4 hours.
A polymerization reaction was carried out in exactly the same manner as described above. Yield 70% (methanol insolubles), number average molecular weight (Mn) =
3.4 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.1, [α] ²⁵
₃₆₅ = + 1331 ° (THF).

Example 5 Polymerization of 3-[(S) -2-methylbutoxy] phenyl isocyanate (XII) (3) The polymerization reaction was carried out in a glass ampoule under a nitrogen atmosphere.
3-[(S) -2-methylbutoxy] in a glass ampoule
Phenylisocyanate (XII) 0.50g (2.4mmol) and THF
After adding 5.0 ml and cooling to -98 ° C, the polymerization initiator b of Synthesis Example 5 was added with a 1/500 equivalent syringe of the monomer (XII) to start the polymerization reaction. After 0.5 hour, 10
After terminating the reaction with twice the volume of hydrochloric acid-methanol, the mixture was poured into a large amount of methanol to precipitate, collected by centrifugation, and dried at room temperature in vacuo. Yield 31% (methanol insolubles), number average molecular weight (Mn) =
14 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.4, [α] ²⁵ ₃₆₅
= + 1998 ° (THF).

Example 6 Polymerization of 3-[(S) -2-methylbutoxy] phenyl isocyanate (XII) (4) Example 5 was repeated except that the polymerization time was changed from 0.5 hours to 4 hours.
A polymerization reaction was carried out in exactly the same manner as described above. Yield 68% (methanol insolubles), number average molecular weight (Mn) =
36 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.3, [α] ²⁵ ₃₆₅
= + 2140 ° (THF).

Example 7 Polymerization of 3-[(S) -3,7-dimethyloctyloxy] phenyl isocyanate (XIII) (1) 3-[(S) -3,7-dimethyloctyloxy] phenyl isocyanate Using 0.5 g (1.8 mmol) of (XIII), a polymerization reaction was carried out in the same manner as in Example 1. Yield 87% (methanol insolubles), number average molecular weight (Mn) =
3.3 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.4, [α] ²⁵
₃₆₅ = + 218 ° (THF).

Example 8 Polymerization of 3-[(S) -3,7-dimethyloctyloxy] phenyl isocyanate (XIII) (2) Example 7 except that the polymerization time was changed from 0.5 hours to 4 hours.
A polymerization reaction was carried out in exactly the same manner as described above. Yield 106% (methanol insolubles), number average molecular weight (Mn)
= 5.3 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 1.3, [α] ²⁵
₃₆₅ = + 260 ° (THF).

From the measurement results of the optical rotation of the polymers obtained in Examples 1 to 8 and the strong CD absorption observed in the amide region of the main chain of these polymers, these polymers are mainly composed of the main chain. It is expected to show a helical structure offset in one direction winding.

Table 1 shows the results obtained by measuring the specific rotation of the isocyanate polymers of Examples 2, 4 and 8 while changing the temperature.
And FIG. As is clear from Table 1 and FIG. 1, it was confirmed that the lower the temperature, the greater the absolute value of the polymers of Examples 2 and 8. This is presumably because in a low temperature state, a unidirectionally wound helical structure was formed due to the chirality of the side chain. In the isocyanate polymer of Example 4, a phenomenon in which the specific rotation sign was reversibly inverted depending on the measurement temperature was observed, which is considered to be caused by the reversible helix-helix rearrangement due to the temperature.

[0060]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a graph showing the results obtained by measuring the specific rotation of the isocyanate polymers of Examples 2, 4 and 8 while changing the temperature.

Claims (8)

[Claims] 1. An optically active aromatic isocyanate polymer having an optically active ether group in a side chain and mainly comprising a structural unit represented by the following formula (I) and having a degree of polymerization of 5 or more. Embedded image [Wherein R ¹ is a group represented by the formula (II): (R ² , R ³ and R ⁴ are different groups, each representing a monovalent aromatic group, a linear or branched alkyl group having 1 to 14 carbon atoms or a hydrogen atom, and containing an element other than carbon. R ² and R ³ may be combined to form a ring. N is an integer of 0 or more indicating the number of methylene groups.
Represents an optically active ether group represented by ] 2. An optically active ether group represented by the following formula (III):
The polymer according to claim 1, which is a group represented by (V). Embedded image 3. An optically active ether group having a degree of polymerization of 5 or more, mainly composed of the structural unit represented by the above formula (I) and the structural unit represented by the following formula (VI), Copolymer of an optically active aromatic isocyanate and an achiral isocyanate. Embedded image (Wherein, R ⁵ has 1 to 1 carbon atoms which may contain elements other than carbon.
It is a 14 alkyl group or a monovalent aromatic group. ) 4. An optically active ether group represented by the above formula (III)
The copolymer according to claim 3, which is a group represented by (V). 5. The process according to claim 1, wherein an optically active aromatic isocyanate represented by the following formula (VII) is anionically polymerized in the presence of a polymerization initiator. Embedded image (Wherein, R ¹ has the meaning described above.) 6. An anionic polymerization of an optically active aromatic isocyanate represented by the above formula (VII) and an achiral isocyanate represented by the following formula (VIII) in the presence of a polymerization initiator. 5. The method for producing a copolymer according to claim 3, wherein R ⁵ −NCO (VIII) 7. The method according to claim 5, wherein the polymerization initiator is an alkali metal or alkaline earth metal compound represented by the following formula (IX). R ⁶ M (IX) (wherein, R ⁶ represents an organic group, and M represents an alkali metal or an alkaline earth metal.) 8. The method according to claim 7, wherein the alkali metal or alkaline earth metal compound represented by the formula (IX) is lithium amide of n-butyllithium or piperidine.