JPH0627128B2 - Optically active polymerization catalyst with axial chirality - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention uses an optically active polymerization catalyst comprising an asymmetric ligand having axial asymmetry as an optically active element and an anionic polymerization initiator, and the catalyst. And to obtain an optically active polymer by polymerizing a polymerizable monomer.

[Conventional technology and problems]

Conventionally, as a polymerization catalyst for obtaining an optically active polymer,
(-)-Sparteine-butyllithium complex and lithium- (R) -N- (1-phenylethyl) anilide are known. However, these catalysts have the following drawbacks.

That is, when the (-)-sparteine-butyllithium complex is used, a polymer having a high degree of polymerization and insoluble in an ordinary organic solvent is likely to be formed. In addition, lithium- (R) -N- (1
When using -phenylethyl) anilide, only polymers with low optical rotation are obtained.

As a means for improving this, Japanese Patent Laid-Open No. 58-154703
In the publication, the following formula (1) or (2) (However, * represents an asymmetric carbon atom, R ₄ and R ₇ are -OR ₁₀ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are alkyl groups having 1 to 10 carbon atoms;
X represents hydrogen, an alkyl group having 1 to 10 carbon atoms or halogen, and n ′ represents a number from 1 to 4), and an optically active polymerization catalyst comprising an anionic polymerization initiator. Is disclosed.

[Means for solving problems]

The present inventors have found a catalyst having an optically active element different from the above-mentioned asymmetric ligand and having extremely excellent performance in the course of exploratory research of an optically active polymerization catalyst, and arrived at the present invention. .

That is, the present invention is a general formula (A), (B) or (C) (In the formula, Ar and Ar ′ represent an aromatic hydrocarbon having 6 to 14 carbon atoms, and are, for example, a phenyl, naphthyl or anthryl group. Further, Ar and Ar ′ may be the same or different. On the other hand, R ₁ , R ₂ , and R ₃ are hydrogen atoms or 1 to 1 carbon atoms.
It is a hydrocarbon group having 20 linear or branched chains, and the structure may contain an aromatic hydrocarbon. Preferably, it is a —CH ₃ group or a C ₂ H ₅ group. further,
m, n and p represent the number of methylene chains, and m and p are 0 to 4, preferably 0 or 1. n represents 1 to 5,
It is preferably 2 or 3, and most preferably 2. The present invention relates to an optically active polymerization catalyst used for the polymerization reaction of triphenylmethyl methacrylate, which comprises an optically active ligand having axial chirality represented by the formula (4) and an anionic polymerization initiator.

The catalyst of the present invention has the potential of being useful as a catalyst for asymmetric ring-opening polymerization as well as asymmetric anionic polymerization. Furthermore, the optically active polymers obtained by using these as catalysts,
It has the ability to identify molecular asymmetry and is expected as a high-performance separating agent.

Examples of the ligand having axial asymmetry used in the present invention are as follows.

(1) Represented by general formula (A) (hereinafter abbreviated as A type) (2) Represented by general formula (B) (hereinafter abbreviated as B type) (3) Represented by general formula (C) (hereinafter abbreviated as C type) Among these asymmetric ligands, for example, optically active N- (2
-Dimethylaminoethyl) -4 ', 1 "-dimethyl-2,7
-Dihydro-3,4,5,6-dibenzazepine (B type)
Can be synthesized by the following method. That is, using brucine, after obtaining an optically active 6,6'-dimethyldiphenic acid, through methyl esterification, reduction, bromination,
2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl and treated with 2-dimethylaminoethylamine to give the optically active N- (2-dimethylaminoethyl) -4 ', 1 "- Dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine was synthesized.

The anionic polymerization initiator for constituting the optically active polymerization catalyst of the present invention is any one used as an anionic polymerization initiator, as long as it can form a complex with the asymmetric ligand. good. Specifically, an alkali metal as a counter ion, an alkaline earth metal, aluminum or a similar metal, and carbon, nitrogen, oxygen as an anion,
An anionic polymerization initiator composed of anion such as sulfur is used. Anionic polymerization initiators composed of carbon anions are preferable, and examples thereof include the following.

RMgX, R ₂ Mg, RCaX, Al (C ₂ H ₅ ) ₃ , LiR, LiAlH ₄ , NaR, KR (however,
R has 1 to 5 carbon atoms such as butyl, benzyl and phenyl groups
0, preferably 1-20 alkyl, aralkyl or aromatic groups, and X is halogen).

Further, an anion polymerization initiator obtained from a nitrogen anion, that is, a secondary amine is also preferably used. Examples of such an anionic polymerization initiator are as follows.

(However, R'and R "have 1 to 50 carbon atoms, preferably 1 to
20 alkyl groups, aralkyl groups or aromatic groups, and M is a counterion).

A preferred method for preparing the optically active polymerization catalyst of the present invention is the above general formula prepared by dehydration and drying with an anionic polymerization initiator.
(A), (B) or an asymmetric ligand represented by (C), in a solvent,
For example, it is a method of forming a complex by mixing in a hydrocarbon solvent. The amount of the asymmetric ligand used here is 0.2 to 2 and preferably 0.5 to 2 in a molar ratio with respect to the anionic polymerization initiator.
Is. In order to polymerize triphenylmethyl methacrylate using the catalyst for polymerization of the present invention, triphenylmethyl methacrylate may be polymerized as it is or in a solvent. However, the solvent used should not inhibit anionic polymerization.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to synthesis examples and examples, but the present invention is not limited thereto.

Synthesis Example 1 (Synthesis of 2-amino-m-toluic acid ( 2 )) 2-Nitro-m-toluic acid (120 g, 0.66 mol) and tin powder (220 g, 1.85 mol) in 0.5 ethanol suspension system were mixed with 9N. -HCl
1.2 was dropped. The reaction temperature is 50 to 60
The temperature was controlled so as to be ℃. After allowing to cool, concentrated aqueous ammonia was added to make the solution basic, and the precipitate was filtered off. After concentration of the mother liquor, acetic acid was added to adjust the pH to 5, and the precipitated crystals were filtered off. Crystallization was performed from ethanol to obtain colorless 2-amino-m-toluic acid ( 2 ) crystals (87 g, yield 87%).

mp171-173 ° C IR spectrum (KBr), 3500,3300, -2500,1670 cm ^-1 Synthesis example 2 (Synthesis of 2-iodo-m-toluic acid ( 3 )) 33% Dilute sulfuric acid 0.9 2-amino-m- Toluic acid ( 2 ) (75 g, 0.5 mol) was added, and the mixture was stirred at room temperature for 1 hour to give a sulfate. 45g of sodium nitrite (0.65
mol) aqueous solution was added so as not to exceed 10 ° C. to obtain a uniform aqueous diazonium salt solution. After decomposing excess nitrous acid with urea, a saturated aqueous solution of 420 g (2.5 mol) of potassium iodide and 3 g of guttaman copper were added all at once and left overnight. The precipitate was filtered off, dissolved in ethyl acetate and washed with aqueous sodium sulfite solution. After drying, the solvent was removed, and the residue was recrystallized from hydrous ethanol to give 2-iodo-m-toluic acid ( 3 ).
Got

Yield 106 g Yield 81% mp 144-146 ° C. Synthesis Example 3 (Synthesis of methyl 2-iodo-m-toluate ( 4 )) 2-Iodo-m-toluic acid ( 3 ) (129 g, 0.49 mol) was added to 600 ml of methanol. It was dissolved and absorbed hydrogen chloride. After completion of the initial exothermic reaction, hydrogen chloride was blown in at the reflux temperature for another hour. After removing the solvent under reduced pressure,
The residue was extracted with ether and washed with aqueous sodium hydrogen carbonate solution and saturated brine. The solvent was removed, and the residue was distilled under reduced pressure to obtain methyl 2-iodo-m-toluate ( 4 ).

Yield 128 g Yield 94% b, p 115 ° C / 0.05 mmHg IR spectrum (liquid film) 1730,1295,1145 cm ^-1 Synthesis Example 4 (dimethyl 6,6'-dimethyldiphenate ( 5 ))
Synthesis of Methyl 2-iodo-m-toluate ( 4 ) (209g, 0.76mol) and copper powder (104g) in N, N-dimethylformamide.
g, treated with iodine and hydrochloric acid in acetone) and heated under reflux for 6 hours with stirring.

After removing the copper powder by filtration, the product was extracted with benzene and washed with dilute hydrochloric acid. After removing the solvent, the residue was distilled under reduced pressure to obtain dimethyl 6,6'-dimethyldiphenate ( 5 ).

Yield 107 g Yield 95% bp 140 ° C / 0.04 mmHg IR spectrum (liquid film) 1735,1280,1150 cm ^-1 Synthesis example 5 (synthesis of 6,6'-dimethyldiphenic acid ( 6 )) 6,6'-dimethyldiph Dimethyl enoate ( 5 ) (37g, 0.12mo
l) was refluxed in 340 g of 16% aqueous sodium hydroxide for 5 hours. After allowing to cool, it was poured into dilute hydrochloric acid to obtain a white precipitate.
The precipitate was filtered off and recrystallized from acetonitrile to give 6,6 '
-Dimethyldiphenic acid ( 6 ) was obtained.

Yield 30 g Yield 95% mp 240-241 ° C. IR spectrum (KBr) 3300-2400,1700 cm ^-1 Synthesis example 6 (optically active dimethyl 6,6'-dimethyldiphenate (R)-( 5 ), (S)) -(Synthesis of ( 5 )) 72 g (0.18 mol) of brucine was suspended in 300 ml of hot acetone. To this, 47 g of 6,6'-dimethyldiphenic acid ( 6 )
A solution of (0.17 mol) in acetone (200 ml) was added all at once and allowed to cool. After standing overnight, the crystals were separated by filtration and recrystallized from a mixed solution of methanol and acetone to obtain an optically active brucine salt of (R) -6,6'-dimethyldiphenic acid {(R)-( 6 )}. . ;
▲ [α] ²⁵ _D ▼ + 38.1 ° (C1.0, methanol).

Next, the mother liquor was concentrated and recrystallized from a mixture of acetone and petroleum ether to obtain optically active (S) -6,6'-dimethyldiphenic acid {(S)
A brucine salt of-( 6 )} was obtained; ▲ [α] ²⁵ _D ▼ -39.3 ° (C1.0, methanol).

The respective salts were decomposed in a mixture of ethyl acetate-1N hydrochloric acid, and the organic layer was concentrated to give optically active 6,6′-dimethyldiphenic acid {(R)-( 6 ) and (S)-( 6 )}. Obtained. The re-crystallized product of these has a degree of optical rotation of (R)-( 6 ): ▲ [α] ²⁵ _D ▼ -21.
3 ° (C1.0, methanol), (S)-( 6 ): ▲ [α] ²⁵ _D
▼ + 22.1 ° (C1.0, methanol).

These optically active 6,6'-dimethyldiphenic acids were esterified with hydrogen chloride in methanol without isolation and distilled under reduced pressure to obtain optically active dimethyl 6,6'-dimethyldiphenate {(R )-( 5 ) and (S)-( 5 ). The following yields were calculated based on the used 6,6'-dimethyldiphenic acid ( 6 ).

(R)-( 5 ) Yield 21.7g Yield 42% ▲ [α] ²⁵ _D ▼ -56.4 ° (C2.0, benzene) (S)-( 5 ) Yield 21.7g Yield 42% ▲ [α] ²⁵ _D ▼ -55.6 ° (C2.0, benzene) Synthesis Example 7 (optically active 2,2'-bis (hydroxymethyl))
-6,6'-Dimethylbiphenyl (R)-( 7 ), (S)-( 7 )
Synthesis of lithium aluminum hydride (3.1 g, 82 mmol) was suspended in 50 ml of dry ether. A solution of 12.2 g (41 mmol) of dimethyl (S) -6,6'-dimethyldiphenate dimethyl {(S)-( 5 )} in dry ether (70 ml) was added dropwise thereto at a gentle reflux rate. Ethyl acetate, hydrous ether, and 2N hydrochloric acid were added to the reaction mixture in this order, and the organic layer was separated. After removing the solvent, the oil was recrystallized from benzene (S) -2,2'-
Bis (hydroxymethyl) -6,6'-dimethylbiphenyl {(S)-( 7 )} was obtained.

Also for (R) -2,2'-bis (hydroxymethyl) -6,6'-dimethylbiphenyl {(S)-( 7 )}, dimethyl (R) -6,6'-dimethyldiphenate {( R)-( 5 )} could be obtained in the same manner.

Yield 9.6g Yield 97% Melting point 120-122 ° C (S-form) Optical rotation (R)-( 7 ) ▲ [α] ²⁵ _D ▼ + 110.1 ° (C1.0, benzene) (S)-( 7 ) ▲ [α] ²⁵ _D ▼ -111.6 ° (C1.0, benzene) IR spectrum ^{(KBr), 3400~3000,1010cm -1 1 H} -NMR spectrum _{(in CDCl 3, δppm):} 1.86 (s, 6H, ArCH 3 ), 2.94 (s, 2H, -OH), 4.09 (d, J = 7.2Hz, 2H, 4.28 (d, J = 7.2Hz, 7.2-7.4 (m, 6H, ArH), Synthesis Example 8 (optically active 2,2'-bis (bromomethyl) -6,
Synthesis of 6'-dimethylbiphenyl (S)-( 8 ), (R)-( 8 )) 240 ml of benzene has (S) -2,2'-bis (hydroxymethyl)
-6,6'-Dimethylbiphenyl {(S)-( 7 )} 16g
(66 mmol) was dissolved. Add phosphorus tribromide to this solution under reflux.
A solution of 7 ml (81 mmol) of benzene (20 ml) was added dropwise. After heating under reflux for a further 1 hour, the reaction mixture was poured into water and the organic layer was separated. The organic layer was washed with an aqueous sodium hydrogen carbonate solution, dried and concentrated. Vacuum distillation of the residue
(S) -2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(S)-( 8 )} was obtained.

For (R) -2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(R)-( 8 )} also (R) -2,2'-bis (hydroxymethyl) -6, It could be similarly obtained from 6'-dimethylbiphenyl {(R)-( 7 )}.

Yield 23 g Yield 93% bp 160 ° C / 0.05 mmHg ¹ H-NMR spectrum (in CDCl ₃ , δppm) 1.99 (s, 6H, ArCH ₃ ), 4.15 (s, 4H, ArCH _2- ), 7.3 ~ 7.5 (m, 6H, A
rH) Optical rotation (R)-( 8 ) ▲ [α] ²⁵ _D ▼ + 51.8 ° (C0.75, benzene) (S)-( 8 ) ▲ [α] ²⁵ _D ▼ -55.1 ° (C0.33, Benzene) Synthesis Example 9 (optically active N-12-dimethylaminoethyl)
-4 ', 1 "-Dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine (R)-( 1 ), (S)-( 1 ) Synthesis) 250 ml anhydrous tetrahydrofuran under nitrogen atmosphere On (S) -2,
2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(S)-( 8 )} 10.3 g (28 mmol) and 2-dimethylaminoethylamine 9.2 ml (84 mmol) were dissolved with stirring, and then 25
Heated to reflux for hours. After removing the solvent, the diluted hydrochloric acid-soluble portion was separated from the residue. The aqueous solution was made basic with ammonia and the liberated oil was extracted with ether. The ether layer was dried and then concentrated, and the oil was distilled under reduced pressure to obtain (S) -N- (2-dimethylaminoethyl) -4 ', 1 "-dimethyl-2,7-dihydro-3,4,5, 6-Dibenzazepine {(S)-( 1 )} was obtained.

Similarly, from (R) -2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(R)-( 8 )} to (R) -N- (2-
Dimethylaminoethyl) -4 ', 1 "-dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine {(R)-( 1 )} was obtained.

Yield 7.4g Yield 90% bp 145 ° C / 0.04mmHg IR spectrum (liquid film) 2810,2770cm ^{-1 1} H-NMR spectrum (in CDCl ₃ , δppm) 2.19 (s, 6H, ArCH ₃ ), 2.27 (s, 6H , NCH ₃ ), 2.4 ~ 2.6 (m, 4H, -NC
H ₂ CH ₂ N-), 2.99 (d, J = 12Hz, Hz, 2H, 3.49 (d, J = 12Hz, Hz, 2H, 7.1 to 7.3 (m, 6H, ArH), ¹³ C { ¹ H} NMR spectrum (inCDCl ₃ , δppm): δ = 19.8 (q), 46.0 (q), 52.8 (t), 55.4 (t), 58.0 ( t), 126.5
(d), 127.1 (d), 129.4 (d), 134.4 (s), 135.6 (s), 138.3 (s) MS (20eV): m / e 294 (M ⁺ ) Elemental analysis C ₂₀ H ₂₆ N ₂ (294.4 ) Calculated value C; 81.56, H; 8.90, N; 9.51% Measured value C; 81.29, H; 8.92, N; 9.26% Optical rotation (R)-( 1 ) ▲ [α] ²⁵ _D ▼ + 24.2 ° (C1 .0, ethanol) (S)-( 1 ) ▲ [α] ²⁵ _D ▼ -24.5 ° (C1.0, ethanol) Synthesis Example 10 (optically active 2,2'-bis (azidomethyl)-
Synthesis of 6,6'-dimethylbiphenyl (S)-( 10 )) 2,2'-bis (bromomethyl) -6 obtained in Synthesis Example 8
6'-Dimethylbiphenyl {(S)-( 8 )} (5.3g, 14.4mm
ol) in 16 ml of benzene solution, 15 ml of 16% aqueous sodium azide solution containing 0.5 g of tetrabutylammonium bromide
And vigorously stirred at room temperature for 1 day. After separating the organic layer, the solvent was removed and the oil was distilled under reduced pressure to obtain (S) -2,2'-bis (azidomethyl) -6,6'-dimethylbiphenyl {(S)-( 10 ).
Got

Yield 4.0g Yield 94% bp 125 ° C / 0.03mmHg Optical rotation ▲ [α] ²⁵ _D ▼ + 38.1 ° (C0.43, P
hH) IR spectrum (liquid film) 2100cm ^{-1 1 H-NMR} spectrum _{(in CDCl 3, δppm) 1.93} (s, 6H, ArCH 3) 3.94 (s, 4H, ArCH 2 N 3), 7.33 (bs, 6H, ArH) Synthesis Example 11 (optically active 2,2'-bis (aminomethyl)-
Synthesis of 6,6'-dimethylbiphenyl (S)-( 9 )) (S) -2,2'-bis (azidomethyl) -6,6'-dimethylbiphenyl {(S)-( 10 )} ( 1.2 g, 4.3 mmol) in 90 ml ether at reflux temperature lithium aluminum hydride 0.4 g
(Reduced with 10.6 mmol. After adding a sodium potassium tartrate aqueous solution to the reaction mixture while cooling and stirring, the ether layer was separated. The solvent was removed and the residue was distilled under reduced pressure to obtain (S) -2,2 ′. -Bis (aminomethyl) -6,6'-dimethylbiphenyl {(S)-( 9 )} was obtained.

Yield 0.83g yield 81% bp160 ℃ / 0.04mmHg Optical rotation ▲ [α] _{^{25 D ▼ -19.7 ° (C1.0,}} PhH) IR spectrum (liquid film): 3375,1580cm _-1 ¹ H-NMR spectrum (InCDCl ₃ , δppm): δ = 1.40 (s, 4H, NH ₂ ), 1.90 (s, 6H, CH ₃ ), 3.40 (s, 4H, ArCH
₂ N), 7.2 to 7.3 (m, 6H, ArH) Synthesis Example 12 (Synthesis of optically active 2,2'-bis (dimethylaminomethyl) -6,6'-dimethylbiphenyl (S)-( 11 )) (S) -2,2'-Bis (aminomethyl) -6,6'-dimethylbiphenyl {(S)-( 9 )} 0.25 g (1 mmol) in a solution of 0.25 g (1 mmol) in anhydrous tetrahydrofuran was washed with mineral oil to remove hydrogen. Sodium chloride (7 mmol) and dimethylsulfate 0.6 ml (6 mmol) were added, and the mixture was heated under reflux for 1 hour. After cooling, methanol was added, and the product was extracted with ether. The residue after removing the solvent was preparative thin-layer chromatography (alumina, 30% benzene-
(S) -2,2'-bis (dimethylaminomethyl) -6,6'-dimethylbiphenyl {(S)-( 11 )} was separated with (acetone) and further distilled under reduced pressure for purification.

Yield 0.14g yield 45% bp130 ℃ / 0.05mmHg ▲ [α] ²⁵ _D ▼ -10.1 ° (C1.0, benzene) IR spectrum (liquid film): 2825,2760cm ^{-1 1} H-NMR spectrum (in CDCl ₃ , δppm): δ = 1.87 (s, 6
H, ArCH ₃ ), 2.08 (s, 12H, NCH ₃ ), 2.74,2.88,2.97,3.11 (ABq,
_{ArCH 2 N), 7.09~7.47 (m} , 6H, ArH) MS spectrum (20eV): m / e240 ( M +) Elemental analysis _{C 16 H 20 N 2 (240.3} ) calc C; 79.99, H; 8.39, N 11.65% Measured value C; 79.65, H; 8.78, N; 11.25% Synthesis example 13 (optically active N, N'-ethylenebis (4 ',
Synthesis of 1 "-Dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine (S)-( 12 )) (S) -2,2'-bis ( Bromomethyl) -6,6'-dimethylbiphenyl {(S)-
( 8 )} 5.5 g (15 mmol), ethylenediamine 0.5 g (8 mmo
l) and 15 g of triethylamine were dissolved. After refluxing for 65 hours, low-boiling substances were removed under reduced pressure, and water-soluble substances were removed. The residue was purified by alumina column chromatography. As a developing agent, ethyl acetate was added to benzene to make the polarity inclined (0-100%). Isolated (S) -N, N'-
Ethylene bis (4 ', 1 "-dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine {(S)-(12)} was further purified by recrystallization from an acetonebenzene mixture. , And the optically inactive 2,2'-bis (bromomethyl) -6,6'-dimethylbiphenyl {(±)-( 8 )} was used, the meso form and the racemic form (12) were 1.1: 1. It was obtained with the ratio of.

(S)-(12) Yield 2.7 g Yield 76% mp 158.5-160 ° C Optical rotation ▲ [α] ²⁵ _D ▼ -113.9 ° (C1.0, ethanol) ¹ H-NMR spectrum (in CDCl ₃ , δppm) ): Δ = 2.19 (s, 12
H, ArCHO), 2.43-2.82 (m, 4H, NCH ₂ CH ₂ N), 2.96,3.08,3.44
(Meso 3.47), 3.56 (meso 3.59) (ABq, 8H, ArCH ₂ ), 7.10-
7.34 (m, 12H, ArH), MS spectrum (20eV): m / e472 (M ⁺ ) Elemental analysis C ₃₄ H ₃₆ N ₂ (472.7) Calculated value C86.40H7.68N5.93% Measured value C86.48H7.72N5 .77% Example 1 (S) -N- (2-dimethylaminoethyl) -4 ',
1 "-dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine {(S)-( 1 )}-BuLi complex in toluene,
Triphenylmethyl methacrylate at -78 ° C (hereinafter,
Asymmetric polymerization of TrMA) was performed as follows.

TrMA (1 g, 3.0 mmol) was placed in the sealed tube, and degassing nitrogen substitution was repeated. To this, 18 ml of anhydrous toluene was added and dissolved, and then cooled to -78 ° C.

Then both before connexion (S) - (1) was prepared at room temperature by mixing equimolar BuLi anhydrous toluene solution of (S) - (1) of -BuLi complex 2 ml (0.15 mmol) solution of the monomer solution in toluene In addition to that, polymerization was started. Polymerization was stopped with a small amount of methanol, the polymer was precipitated in 200 ml of methanol, centrifuged, dried under reduced pressure and weighed. THF was added to the polymer and stirred for several hours to separate into a THF insoluble portion and a soluble portion. TH
After measuring the optical rotation, the F-soluble portion is dissolved in THF,
It was precipitated in 10 times its volume of benzene-hexane (1: 1). This was centrifuged and benzene-hexane (1:
1) Separated into an insoluble portion and a soluble portion, dried under reduced pressure, and measured the specific optical rotation (▲ [α] ²⁵ _D ▼) of each. The results are shown in Table-1
It was shown to.

The optical rotation was measured using Union PM101.

Example 2 In the same manner as in Example 1, (R) -N- (2-dimethylaminoethyl) -4 ', 1 "-dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine { After synthesizing a complex of (R)-( 1 )} and BuLi, TrMA was polymerized, and the results are shown in Table 1.

Example 3 A complex of lithium (±) -N- (1-phenylethyl) anilide obtained from n-BuLi and (±) -N- (1-phenylethyl) aniline and (R)-( 1 ) was formed. rear,
TrMA (1 g, 3.0 mmol) was polymerized in the same manner as in Example 1.
The results are shown in Table-1.

Example 4 TrMA (1 g, 3.0 mmol) was used as n-BuLi and an optically active ligand.
Polymerization was carried out in the same manner as in Example 1 using (S) -2,2'-bis (aminomethyl) -6,6'-dimethylbiphenyl {(S)-( 9 )}. The results are shown in Table-1.

Example 5 TrMA (1 g, 3.0 mmol) was added to n-BuLi and optically active (S) -N, N'-
Polymerization was carried out in the same manner as in Example 1 using ethylene bis (4 ', 1 "-dimethyl-2,7-dihydro-3,4,5,6-dibenzazepine {(S)-( 12 )}. The results are shown in Table-1.

Example 6 TrMA (1 g, 3.0 mmol) was added to n-BuLi as an asymmetric ligand (R)-
Polymerization was carried out by changing the equivalent relation of ( 9 ). Table of polymerization results
Shown in 2.

Example 7 TrMA (1 g, 3.0 mmol) was added to 1/2 equivalent of (R)-with respect to n-BuLi.
Polymerization was carried out in the same manner as in Example 1 using ( 1 ), and the polymerization time and the specific optical rotation (▲ [α] ²⁵ _D ▼) of the obtained polymer were examined. The results are shown in Table-3.

The molecular weight and the degree of polymerization were measured by GPC (calibration curve PST).

Claims (1)

[Claims] 1. A general formula (A), (B) or (C) (In the formula, Ar and Ar 'represent aromatic hydrocarbons having 6 to 14 carbon atoms, and Ar and Ar' may be the same or different. On the other hand, R ₁ , R ₂ and R ₃ are hydrogen atoms. Or carbon number 1
It is a hydrocarbon group having a straight chain or branched chain of up to 20 and may contain an aromatic hydrocarbon in its structure. Further, m, n, p indicates the number of methylene chains, and m, p is 0 to
4, n is 1-5. ) Consisting of an optically active ligand having axial asymmetry and an anionic polymerization initiator,
An optically active polymerization catalyst used in the polymerization reaction of triphenylmethyl methacrylate.