JPH0649165A - Biodegradable, optically active polymer, intermediate prepolymer therefor, and production thereof - Google Patents

Abstract

PURPOSE:To obtain in an industrially advantageous manner a polymer which is an optically active, biodegradable and hydrolyzable functional material by addition-polymerizing a specified optically active oligomer with a specified compound. CONSTITUTION:An optically active prepolymer of formula I [wherein R<1> is 1-5 C alkyl; R<3> is 2-6C branched or linear alkylene, 4-6C linear alkenylene, linear alkynylene, 5-8C oxyalkylene or 1,4-phenylenedimethylene: R<4> is 1-10 C alkylene, (substituted) phenylene, (substituted) biphenylene or (substituted) methylenebiphenyl; Y<1> and Y<2> are each O or NH; m and should Wt be 0 at the same time and are each 0 or 1-20; and x is 0.5-2] is addition-polymerized with a compound of formula II (wherein R<5> is R<3>; Y<3> and Y<4> are each Y<1> or Y<2>) to produce an optically active polymer of formula III (wherein all of the signs are as defined above). According to this process, a functional polymer excellent in biodegradability and hydrolyzability can be produced in an industrially advantageous manner.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a biodegradable optically active polymer, a method for producing the same, a prepolymer which is an intermediate of the polymer, and a method for producing the prepolymer. More specifically, a prepolymer obtained by reacting an optically active oligomer having a (R) -3-hydroxyalkanoic acid ester (hereinafter abbreviated as (R) -3HA) unit with a diisocyanate ester and its production. The present invention relates to a method, a biodegradable optically active polymer obtained by addition-polymerizing the prepolymer and a monomer, and a method for producing the same.

The polyester-polyurethane and polyester-polyurethane-polyurea according to the present invention are thermoplastic resins having optical activity, biodegradability and hydrolyzability, and are decomposed by microorganisms existing in soil or water, thus polluting the environment. It is useful as a functional polymer that can be widely used as a clean plastic.

[0003]

2. Description of the Related Art In recent years, there are known microorganisms that accumulate a polymer of (R) -3-hydroxybutyric acid, which corresponds to a part of the optically active polymer of the present invention, in cells (PA Holmes, Phys. Technol., 1985 (16), p. 32), this polymer is attracting attention as a new type of functional material due to its biodegradable or enzymatically degradable, hydrolyzable and biocompatible properties ( Biodegradable polymer material, p. 19, Yoshiharu Dohi, Industrial Research Society, published 1990).

Further, an optically active polyester obtained by ring-opening polymerization of D-(+)-β-butyrolactone is a polymer letter.
s, 9 , 173 (1970). However, since the microbiological synthesis method utilizes a microorganism or an enzymatic reaction, it requires a complicated process such as separation of a polymer from bacterial cells,
Regarding the ring-opening polymerization method of D-(+)-β-butyrolactone, there is no method for simply synthesizing the optically active D-(+)-β-butyrolactone as a raw material, and all of them are industrially expensive. Has many problems.

Therefore, an object of the present invention is to provide a novel biodegradable optically active polymer having an (R) -3HA unit excellent in biodegradability and hydrolyzability, and an industrially advantageous production method thereof. Especially.

[0006]

As a result of intensive studies to solve the above problems, the present inventors have found that an optically active prepolymer (diisocyanate derivative) having a (R) -3HA unit is a monomer (diol). , Diamine or aminoalcohol) to easily obtain an optically active polymer corresponding to the present invention, thereby completing the present invention.

That is, the present invention includes 1) the general formula (IV)

[0008]

[Chemical 7]

(In the formula, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ³ and R ⁵ each independently have 2 to 6 carbon atoms.
A branched or straight chain alkylene group, a straight chain alkenylene group or a straight chain alkynylene group having 4 to 6 carbon atoms, and 5 to
8 represents an oxyalkylene group or a 1,4-phenylenedmethylene group, and R ⁴ represents an alkylene group having 1 to 10 carbon atoms, an optionally substituted phenylene group, an optionally substituted biphenylylene group or a substituted group. Optionally represent a methylenebiphenyl group, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent O or NH, m and n represent 0 or an integer of 1 to 20, and x represents 0.5 to 2 Represents the number of. However, m and n do not represent 0 at the same time. ) An optically active polymer represented by the formula: 2) General formula (I)

[0010]

[Chemical 8]

(Wherein R ¹ , R ³ , R ⁴ , Y ¹ , Y ² ,
m, n and x have the same meanings as described above. And optically active prepolymer represented by), the formula ^{(V) H-Y 3 -R} 5 -Y 4 -H (V) ( wherein, R ^5, Y ³ and Y ⁴ are as defined above.) Represented by the general formula (IV) characterized by addition-polymerizing at least one compound represented by

[0012]

[Chemical 9]

(Wherein all symbols have the same meanings as described above), 1) a method for producing an optically active polymer, 3) the general formula (I)

[0014]

[Chemical 10]

(Wherein R ¹ , R ³ , R ⁴ , Y ¹ , Y ² ,
m, n and x have the same meanings as described above. ), And 4) the general formula (II)

[0016]

[Chemical 11]

(Wherein R ¹ , R ³ , Y ¹ , Y ² , m and x have the same meanings as described above) and an optically active oligomer represented by the following general formula (III) OCN-R ⁴ -NCO (III) General formula (I), characterized in that at least one compound represented by the formula (wherein R ⁴ has the same meaning as described above) and 1.5 to 3 times the molar amount thereof are subjected to addition polymerization.

[0018]

[Chemical 12]

(Wherein all symbols have the same meanings as described above), the process for producing an optically active prepolymer according to item 3) is provided. Hereinafter, the present invention will be described in detail. In the present invention, the oligomer represented by the formula (II), which is one of the starting materials for the prepolymer (I), can be prepared by the method disclosed by the applicant in Japanese Patent Application No. 426262, that is, according to the following process formula It can be manufactured.

[0020]

[Chemical 13]

(In the formula, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ¹ , R ³ , Y ¹ , Y ² , m and n have the same meanings as described above.) In the above step, The optically active 3-hydroxyalkanoic acid alkyl ester represented by the formula (VI) as a starting material is prepared by the method disclosed by the applicant in JP-A-63-310847.
That is, the general formula

[0022]

[Chemical 14]

(Wherein R ¹ and R ² have the same meanings as described above), and the β-ketoesters can be easily obtained by asymmetric hydrogenation using a ruthenium-optically active phosphine complex as a catalyst. You can Further, the prepolymer of the present invention, which is a raw material of the polymer of the present invention, has the general formula (II)

[0024]

[Chemical 15]

An oligomer represented by the formula (wherein R ¹ , R ³ , Y ¹ , Y ² , m and n have the same meanings as described above) is placed in a reaction vessel in the presence of an inert gas such as nitrogen or argon. Charge, methylene chloride, dimethylformamide (D
MF) or the like at 45 to 50 ° C. to give the compound of the general formula (II
^{I) OCN-R 4 -NCO (} III) ( wherein, R ⁴ are as defined above.) At 20 to 50 ° C. was added a diisocyanate esters represented by 1-2
It can be obtained by reacting for a time.

In this reaction, the diisocyanic acid ester represented by the general formula (III) is mixed in an amount of 1.5 to 3 times, preferably 2 to 2. with respect to the oligomer represented by the general formula (II).
Using 5 times mole, x (average value) in the general formula (I) is
A prepolymer of 0.5-2 is obtained. When the diisocyanate ester is used in an amount of 2 times or more, that is, when x is 0.5 or more and less than 1, it means that the prepolymer represented by the general formula (I) contains unreacted diisocyanate ester. The prepolymer of the present invention also includes in its range a composition containing a part of unreacted diisocyanate esters. The excess diisocyanate ester becomes a constituent component (hard segment) of the polymer in the subsequent addition polymerization step. When the proportion of the diisocyanate ester is 3 times or more moles (that is, x is 0.5 or less), in the polymer of the present invention obtained in the subsequent addition polymerization step, the optically active oligomer moiety is reduced and biodegradability is lowered. On the other hand, the proportion of diisocyanate esters is 1.
If it is less than 5 mol (that is, x is 2 or more), the amount of the optically active oligomer component in the polymer increases, but the amount of the diol, diamine or aminoalcohol unit decreases, and the polymer strength becomes poor. Not preferable. The prepolymer thus obtained can be used in the subsequent addition polymerization step without isolation and purification.

The polymer of the present invention comprises the prepolymer obtained by the above method and the formula (V) H--Y ³ --R ⁵ --Y ⁴ --H (V) (wherein R ⁵ , Y ³ and Y ⁴ are The same meanings as described above) are reacted for 12 to 24 hours under atmospheric pressure at a temperature of 45 to 50 ° C. in the presence of an inert gas such as nitrogen or argon. Can be manufactured by.

Examples of the diisocyanate represented by the formula (III) include hexamethylene diisocyanate (HMDI), toluene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate,
Examples thereof include o-xylylene diisocyanate and m-xylylene diisocyanate.

The diols, diamines or amino alcohols represented by the above formulas (V) and (VII) include the following. Examples of the diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,
3-propanediol, cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, 2-
Butyne-1,4-diol, 1,6-hexanediol, 1,10-decanediol, xylylene glycol, diethylene glycol, triethylene glycol,
1,4-phenylenedimethanol, 2,2-bis (4 '
-Hydroxyphenyl) propane (bisphenol A)
Examples of diamines include p-phenylenediamine, ethylenediamine, and 4,4′-methylenebis (2-chloroaniline). Examples of amino alcohols include ethanolamine and propanolamine. Is mentioned. These are at least 1
Seeds can be used, and if necessary, several types can be used in combination.
The ratio of the prepolymer of formula (I) and the monomer of formula (V) to be subjected to addition polymerization varies depending on the physical properties of the target polymer (molecular weight, melting point, glass transition temperature, decomposition temperature, etc.), but The monomer of formula (V) is 0.5 to 2.0 moles relative to the prepolymer.

[0030]

INDUSTRIAL APPLICABILITY According to the present invention, an optically active prepolymer having a (R) -3HA unit (diisocyanate derivative) and a monomer (diol, diamine or aminoalcohol) are polymerized by addition polymerization. A novel polymer, which is a useful functional material having degradability and hydrolyzability, can be easily produced by an industrially advantageous method.

[0031]

The present invention will be described in more detail with reference to examples and test examples, but the present invention is not limited to these examples. The analytical instruments used in the examples and the instruments used in the biodegradability test are as follows.

Differential scanning calorimeter (DSC): DSC50
(Manufactured by Shimadzu Corporation); Thermogravimetric analyzer (TGA): TGA50 (manufactured by Shimadzu Corporation); Molecular weight: D-2520 GPC Integrator (manufactured by Hitachi, Ltd.); Biodegradability test: Takasago International Using activated sludge from a corporation, "About the test method for new chemical substances" (Environmental Protection No. 5, Yakuhin No. 615, 49 Units 392, 1974, 7
"Decomposition test by chemical substances by microorganisms, etc." and "Y.Doi, A. Segawa, and M. Kunioka,"
Int. J. Biol. Macromol., 1990, Vol.12.April, 106
It was performed in accordance with the contents described in "Page".

Example 1 : 12 in 1,4-butanediol
A double molar amount of methyl (R) -3-hydroxybutyrate (hereinafter,
Abbreviated as 3HB. Of a telechelic oligomer obtained by condensation of) and 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) to synthesize a prepolymer (Ia) 13.33 g of oligomer in a 100 ml reaction vessel ( (11.9 mmol) and purging with nitrogen, 20 ml of methylene chloride was added and dissolved, and 5.94 g (23.7 mmol) of MDI was added at 45 ° C. and reacted for 1 hour to obtain a prepolymer (Ia).

Example 2 Synthesis of Polyurethane-Polyester (IVa) by Addition Polymerization from Prepolymer (Ia) Obtained in Example 1 and p-Xylylene Glycol Prepolymer (Ia) Obtained in Example 1 P-xylylene glycol 1. in its 100 ml container without isolation.
64 g (11.9 mmol) was added and the mixture was stirred at 45 ° C. for 12 hours. Put 30 ml of methylene chloride in a reaction vessel and 500 m
lMethanol was added to cause precipitation, washed with 500 ml of ether, and 20.8 g of the title polymer (IVa) (yield 9
9.6%). Weight average molecular weight (Mw): 60000; Number average molecular weight (Mn): 32000; Glass transition temperature: 13 ° C; Melting point: 84 ° C; Decomposition temperature: 277 ° C.

Example 3 : 12 in 1,4-butanediol
A telechelic oligomer obtained by condensing a double molar amount of 3HB and 2,4-tolylene diisocyanate (hereinafter, referred to as T
Abbreviated as DI. ) Prepolymer by addition polymerization from
Synthesis of (Ib) 11.34 g (10.1 mmol) of oligomer was placed in a reaction vessel, 3.52 g (20.2 mmol) of TDI was added, and a prepolymer (Ib) was obtained by the same method as in Example 1.

Example 4 Synthesis of Polyurethane-Polyester (IVb) by Addition Polymerization from Prepolymer (Ib) Obtained in Example 3 and p-Xylylene Glycol Prepolymer (Ib) Obtained in Example 3 P-xylylene glycol 1. in its 100 ml container without isolation.
13.43 g (yield 82.6%) of the title polymer (IVb) was prepared in the same manner as in Example 2 except that 40 g (10.1 mmol) was used.
%) Was obtained. Weight average molecular weight (Mw): 66000; Number average molecular weight (Mn): 35000; Glass transition temperature: 28 ° C; Melting point: 130-144 ° C; Decomposition temperature: 276 ° C.

Example 5 : Synthesis of polyurethane-polyester (IVc) by addition polymerization from prepolymer (Ia) obtained in Example 1 and 1,4-butanediol Prepolymer (Ia obtained in Example 1 ) 15.26 g (9.4 mmol) were isolated by the same method as in Example 2 except that 0.85 g (9.4 mmol) of 1,4-butanediol was used in the 100 ml container without isolation.
15.37 g (yield 93.3%) of (IVc) was obtained. Weight average molecular weight (Mw): 60000; Number average molecular weight (Mn): 35000; Glass transition temperature: 23 ° C; Melting point: 126 ° C; Decomposition temperature: 279 ° C.

Example 6 : 12 in 1,4-butanediol
Prepolymer by addition polymerization from telechelic oligomer obtained by condensing double molar amount of 3HB (I
Synthesis of c) 16.13 g (14.36 mmol) of oligomer was placed in a reaction vessel, and 5.39 g (21.54 mmol) of MDI was added thereto to prepare Example 1.
A prepolymer (Ic) was obtained by the same method as described above.

Example 7 : Synthesis of polyurethane-polyester (IVd) by addition polymerization from prepolymer (Ic) obtained in Example 6 and 1,4-butanediol Prepolymer (Ic obtained in Example 6 ) Was isolated in its 100 ml container with 1,5-butanediol 0.65
20.61 g (yield 93.0 g) of the title polymer (IVd) was prepared in the same manner as in Example 2 except that g (7.18 mmol) was used.
%) Was obtained. Weight average molecular weight (Mw): 51000; Number average molecular weight (Mn): 26000; Glass transition temperature: 19 ° C; Decomposition temperature: 279 ° C.

Example 8 : Synthesis of polyurethane-polyester (IVe) by addition polymerization of prepolymer (Ib) obtained in Example 3 and ethylene glycol 14.45 g of prepolymer (Ib) obtained in Example 3 ( The title polymer (IVe) was prepared in the same manner as in Example 2 except that 0.61 g (9.82 mmol) of ethylene glycol was used in the 100 ml container without isolation.
10.74 g (yield 71.3%) was obtained. Weight average molecular weight (Mw): 33000; Number average molecular weight (Mn): 20000; Glass transition temperature: 28 ° C; Melting point: 127-141 ° C; Decomposition temperature: 280 ° C.

Example 9 : Synthesis of polyurethane-polyester (IVf) by prepolymer (Ib) obtained in Example 3 and 1,4-butanediol by addition polymerization Prepolymer (Ib obtained in Example 3 ) 14.88 g (10.1 mmol) were isolated but without isolation, 0.91 g (10.1 mmol) of 1,4-butanediol was used in the 100 ml container, but the procedure of Example 2 was repeated.
(IVf) 11.94 g (yield 83.8%) was obtained. Weight average molecular weight (Mw): 59000; Number average molecular weight (Mn): 34000; Glass transition temperature: 21 ° C; Melting point: 141 ° C; Decomposition temperature: 276 ° C.

Example 10 : 2,2-dimethyl-1,3-
Synthesis of prepolymer (Id) by addition polymerization of telechelic oligomer obtained by condensing 14-fold molar amount of 3HB with propanediol and 13.15 g (10.04 mmol) of oligomer in a reaction vessel and 5.56 g of MDI ( A prepolymer (Id) was obtained by the same method as in Example 1 except that 22.2 mmol was added.

Example 11 : Synthesis of polyurethane-polyester (IVg) by prepolymer (Id) obtained in Example 10 and 1,4-butanediol by addition polymerization Prepolymer (Id obtained in Example 10 ) Is not isolated, and 1,4-butanediol 1.
By the same method as in Example 2 except that 10 g (12.18 mmol) was used, 17.05 g of the title polymer (IVg) (yield 8
6.1%). Weight average molecular weight (Mw): 40,000; Number average molecular weight (Mn): 21000; Glass transition temperature: 32 ° C; Melting point: 78 ° C; Decomposition temperature: 290 ° C.

Example 12 : 2,2-dimethyl-1,3-
Synthesis of prepolymer (Ie) by addition polymerization of telechelic oligomer obtained by condensing 20 times molar amount of 3HB with propanediol and 18.26 g (10.0 mmol) of oligomer in a reaction vessel and 5.01 g of MDI ( 20.0 mmol) was added and the prepolymer (Ie) was obtained by the same method as in Example 1.

Example 13 : Synthesis of polyurethane-polyester (IVh) by addition polymerization from prepolymer (Ie) obtained in Example 12 and 1,4-butanediol Prepolymer (Ie obtained in Example 12 ) Was isolated in its 100 ml container without adding 1,4-butanediol.
21.21 g (yield 87.7) of the title polymer (IVh) was prepared in the same manner as in Example 2 except that 90 g (10.0 mmol) was used.
%) Was obtained. Weight average molecular weight (Mw): 24000; Number average molecular weight (Mn): 14000; Glass transition temperature: 23 ° C; Melting point: 126 ° C; Decomposition temperature: 279 ° C.

Example 14 : 2,2-dimethyl-1,3-
Synthesis of prepolymer (If) by addition polymerization of telechelic oligomer obtained by condensing 20 times molar amount of 3HB with propanediol and 17.2 g (9.45 mmol) of oligomer in a reaction vessel, and 3.29 g of TDI ( 18.9 mmol) was added and a prepolymer (If) was obtained by the same method as in Example 1.

Example 15 : Synthesis of polyurethane-polyester (IVi) by addition polymerization of prepolymer (If) obtained in Example 14 and p-xylylene glycol Prepolymer (If) obtained in Example 14 P-xylylene glycol in its 100 ml container without isolation.
By the same method as in Example 2 except that 1.31 g (9.45 mmol) was used, 17.99 g of the title polymer (IVi) (yield 8
2.3%) was obtained. Weight average molecular weight (Mw): 27000; Number average molecular weight (Mn): 17000; Glass transition temperature: 27 ° C; Melting point: 116-145 ° C; Decomposition temperature: 282 ° C.

Example 16 : 1 in 1,4-butanediol
A telechelic oligomer obtained by condensing 2 times the molar amount of 3HB and hexamethylene diisocyanate (hereinafter,
Abbreviated as HMDI. Synthesis of Prepolymer (Ig) by Addition Polymerization from 10.) 10.14 g (9.03 mmol) of oligomer was placed in a reaction vessel, and 3.04 g (18.1 mmol) of HMDI was added to Example 1.
A prepolymer (Ig) was obtained by the same method as described above.

Example 17 : Synthesis of polyurethane-polyester-polyurea (IVj) by addition polymerization from prepolymer (Ig) obtained in Example 16 and p-phenylenediamine. Prepolymer obtained in Example 16 (Ig ) Without isolation of p-phenylenediamine in its 100 ml container.
By the same method as in Example 2 except that 98 g (9.03 mmol) was used, 12.82 g (yield 90.6) of the title polymer (IVj) was obtained.
%) Was obtained. Weight average molecular weight (Mw): 23000; Number average molecular weight (Mn): 16000; Glass transition temperature: 0 ° C; Decomposition temperature: 267 ° C.

Example 18 : 1 in 1,4-butanediol
Synthesis of prepolymer (Ih) by addition polymerization of telechelic oligomer obtained by condensing 2 times molar amount of 3HB and HMDI 12.24 g (10.9 mmol) of oligomer was put in a reaction vessel and 2.75 g of HMDI (16.35 mmol) Was added to obtain a prepolymer (Ih) by the same method as in Example 1.

Example 19 : Synthesis of polyurethane-polyester-polyurea (IVk) by addition polymerization from prepolymer (Ih) obtained in Example 18 and ethylenediamine. Prepolymer (Ih) obtained in Example 18 0.33 g of ethylenediamine in the 100 ml container without separating
By the same method as in Example 2 except that (5.45 mmol) was used, 8.04 g (yield 52.5%) of the title polymer (IVk) was obtained. Weight average molecular weight (Mw): 25000; Number average molecular weight (Mn): 15000; Glass transition temperature: -3 ° C; Melting point: 80 ° C; Decomposition temperature: 262 ° C.

Example 20 : 2,2-dimethyl-1,3-
Synthesis of prepolymer (Ii) by addition polymerization of telechelic oligomer obtained by condensing 14-fold molar amount of 3HB to propanediol and 13.09 g (10.0 mmol) of oligomer in a reaction vessel, and 3.36 g of HMDI ( 20.0 mmol) was added and Example 1 was added.
A prepolymer (Ii) was obtained by the same method as described above.

Example 21 : Synthesis of polyurethane-polyester-polyurea (IVl) by addition polymerization from prepolymer (Ii) obtained in Example 20 and propanolamine. Prepolymer (Ii) obtained in Example 20 0.75 g of propanolamine in its 100 ml container without isolation
13.83 g (yield 80.2%) of the title polymer (IVl) was prepared in the same manner as in Example 2 except that (10.0 mmol) was used.
Got Weight average molecular weight (Mw): 22000; Number average molecular weight (Mn): 14000; Glass transition temperature: 1 ° C; Melting point: 75 to 103 ° C; Decomposition temperature: 263 ° C.

The structural formulas of the prepolymers and polymers according to the invention prepared in Examples 1 to 21 are summarized below.

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

Test Example 1 : Biodegradability test of polymer (IVe) of Example 8 The acclimatized species (aerobic sludge) of the returned sludge at Takasago International Corporation's Hiratsuka Plant was 500 ppm (600 ml), pH 6.0-.
Used under the conditions of 7.0 and 30 ° C., a thin film of the polymer obtained in Example 8 having a size of 1 cm × 2 cm and a thickness of 0.05 to 0.1 mm (the polymer is dissolved in methylene chloride or chloroform or hexafluoroisopropanol and poured into a petri dish, 20 to 30 mg (formed into a film by evaporating the solvent) was placed in a 50 ml flask, and the test was conducted using a shaking constant temperature water bath manufactured by Titec Co., Ltd. After 4 weeks, the weight of the polymer was measured to determine the residual weight ratio. The result is shown in FIG. From this result, the polymer film obtained in Example 8 was obtained after 4 weeks.
It was found to have decomposed 14.3%.

Test Example 2 : Biodegradability test of polymer (IVk) of Example 19 Test Example 1 was carried out on the polymer (IVk) obtained in Example 19.
A biodegradation test was conducted in the same manner as in. The result is as shown in FIG. 1, and it was found that the decomposition was 26.5% after 4 weeks.

Test Example 3 : Biodegradability test of polymer (IVl) of Example 21 Test Example 1 was carried out on the polymer (IVl) obtained in Example 21.
A biodegradation test was conducted in the same manner as in. The results are shown in Fig. 1, and it was found that the decomposition was 37.9% after 4 weeks.

[Brief description of drawings]

FIG. 1 is a graph showing a change with time in a residual weight ratio of a polymer in Test Examples 1 to 3.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Motoki Suzuki 3-19-22 Takanawa, Minato-ku, Tokyo Takasago International Corporation

Claims (4)

[Claims] 1. A compound represented by the general formula (IV): (In the formula, R ¹ represents an alkyl group having 1 to 5 carbon atoms, R ^1
3 and R ⁵ are each independently a branched or linear alkylene group having 2 to 6 carbon atoms, a linear alkenylene group or linear alkynylene group having 4 to 6 carbon atoms, an oxyalkylene group having 5 to 8 carbon atoms or 1 , 4-phenylenedimethylene group, R ⁴ is an alkylene group having 1 to 10 carbon atoms, an optionally substituted phenylene group, an optionally substituted biphenylylene group or an optionally substituted methylenebiphenyl group. Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent O or NH, m and n represent 0 or an integer of 1 to 20, and x represents a number of 0.5 to 2.
However, m and n do not represent 0 at the same time. ) An optically active polymer represented by. 2. The general formula (I): (Wherein R ¹ , R ³ , R ⁴ , Y ¹ , Y ² , m, n and x have the same meanings as described in claim 1), and an optically active prepolymer of the formula (V) (wherein, R ^5, Y ³ and Y ⁴ represent. the same meanings as described claim ^{1) H-Y 3 -R 5} -Y 4 -H (V) and at least one compound represented by General formula (IV) characterized by addition polymerization (Wherein all symbols have the same meanings as described above), The method for producing an optically active polymer according to claim 1. 3. The general formula (I): (In the formula, R ¹ , R ³ , R ⁴ , Y ¹ , Y ² , m, n and x have the same meanings as described in claim 1.). 4. A compound represented by the general formula (II): (In the formula, R ¹ , R ³ , Y ¹ , Y ² , m and n have the same meanings as described in claim 1.) and an optically active oligomer represented by the following general formula (III) OCN-R ⁴ — NCO (III) (In the formula, R ⁴ has the same meaning as described in claim 1.)
Wherein at least one kind of compound represented by (Wherein all symbols have the same meanings as described above), The method for producing an optically active prepolymer according to claim 3.