JPH0437842B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to an adsorbent for optical resolution comprising a novel graft polymer having polyamino acid residues grafted thereto, and a method for producing the same. Prior Art and its Problems Polymers having polyamino acid residues grafted thereto are very important polymers because they have uses such as adsorbents for optical ratios that separate racemic mixtures into optical antipodes. As a conventional method for producing this polymer, there is a method in which a polymer having an aminomethylated phenyl group is reacted with α-amino acid N-carboxy anhydride (hereinafter referred to as amino acid NCA) (Japanese Patent Publication No. 52-197).
9478). Although this method is a method for easily and efficiently obtaining a polymer compound obtained by graft polymerizing amino acids, it is difficult to synthesize the polymer having an aminomethylated phenyl group to be used by a simple method. . A conventional method for synthesizing a polymer having an aminomethylated phenyl group is to heat a polymer having a chloromethylated phenyl group with liquid ammonium in a pressurized container for a long time (96 hours and 144 hours) at a low temperature (5°C). (Journal of the American Chemical Society, Vol. 97, No.
1575 (1975), etc.), or a method of obtaining a polymer having aminomethylated phenyl groups by reacting a polymer having chloromethylated phenyl groups with potash phthalimide, first converting it into phthalimide, and then reacting with hydrazine (American method). Journal of the Japanese Society of Chemistry, Vol. 98, p. 7357 (1976), etc.)
Neither method is easy. In addition, when a polymer having an aminomethylated phenyl group is reacted with an amino acid NCA to graft-bond a polyamino acid residue, if the degree of crosslinking of the backbone polymer is high, the amino acid
The polymerization reaction of NCA is slow to proceed, making it extremely difficult to graft polyamino acid residues efficiently. In addition, when the polyamino acid graft polymer is used as an adsorbent for optical resolution, since there is no space between the polyamino acid residue in the graft portion and the backbone polymer, separation occurs due to steric hindrance of the backbone polymer. Contact between the target optical isomer and the polyamino acid residue is often prevented, resulting in inefficient separation. Based on the above findings, the present inventor came to the conclusion that it is necessary to introduce a spacer group between the polyamino acid residue of the graft portion and the polymer of the backbone. Concerning polymers graft-bonded with such a spacer group, there are no known ones. Means for Solving the Problems An object of the present invention is to provide an adsorbent made of a novel graft polymer that can solve the above-mentioned problems, and a method for producing the same. As a result of various studies on methods of introducing a spacer group having a primary amino group at the end into the side chain of a polymer, the present invention was developed by directly reacting an alkylene diamine or an arylene diamine with a polymer having a chloromethylated phenyl group. very easily,
The present invention was achieved by discovering that a spacer group having a primary amino group at the end can be introduced. That is, according to the method of the present invention, a chloromethyl group is converted to an N-(aminoalkyl)aminomethyl group or an N-(aminoaryl)aminomethyl group, and a secondary amino group, a spacer group, and a primary amino group are introduced. Ru. In general, secondary amino groups also have the ability to initiate polymerization of amino acid NCA, and in that case, a single polymer of polyamino acids that is not bonded to the amino group at the polymerization initiation point is produced as a by-product. As a result of various studies, it was surprisingly found that the secondary amino group bonded to the backbone polymer is an amino acid.
There was no ability to initiate NCA polymerization at all, and only graft polymerization by the terminal primary amino group bonded to the spacer group proceeded efficiently. Moreover, the graft polymerization proceeded extremely easily even when the degree of crosslinking of the backbone polymer was high due to the effect of the spacer group. Furthermore, when optical resolution was performed using an adsorbent made of a graft polymer having the above-mentioned spacer group, compared to one without a spacer group,
It showed superior separation properties. The present invention was made based on the above findings, and has the general formula (In the formula, n is an integer of 1 or more, A is the base polymer, R is an alkylene group including an arylene group, R' is an organic group, R'' is H or an alkyl group, R
The present invention relates to an adsorbent made of a graft polymer having a spacer group R grafted with a polyamino acid residue represented by (H or an organic group) and a method for producing the same. The polymer or copolymer having a chloromethylated phenyl group used as the base polymer in the present invention is, for example, polystyrene, a copolymer of styrene and another comonomer, or a copolymer of these with a crosslinking agent such as divinylbenzene. It is crosslinked.
The degree of crosslinking changes depending on the presence or absence of porosity, but the degree of crosslinking when not porous is 0.01 to 10%, preferably 1 to 8%, and the degree of crosslinking when porous is
It is 0.1-50%, preferably 2-30%. Spacer group R in the graft polymer of the present invention
Examples include alkylene groups or arylene groups having a chain length of 2 to 16 carbon atoms, which may contain a heteroatom such as oxygen or nitrogen in the chain, and may be substituted with various groups. You can leave it there. Examples of the substituent include halogen, nitro, and nitrile. Further, the spacer group does not necessarily have to be linear, and may contain a branch. Polyamino acid residue as a graft component of the graft polymer of the present invention

The organic group R′ in [Formula] may be any type of organic group, but examples include an alkyl group, an aromatic group such as a phenyl group, an aralkyl group, and a heterocycle-containing group containing nitrogen as a ring member. , or R' and N may be combined to form a ring. These may be substituted with various groups, examples of substituents include -
Examples include OH, -COOH, -SH, _-NH2 , _-SCH3 , and the like. When having the above substituent, the substituent can also be in the following form. That is, −OH,
-SH is an ether (e.g. methyl ether, benzyl ether), an acyl group attached, -
COOH is in an ester form, an amide form, _-NH2 is in a form with a carbobenzoxy group, etc. R'' is hydrogen or an alkyl group, and examples of the alkyl group include a methyl group and an ethyl group. Urethane-type protecting groups such as carbobenzoxy group, tert-butoxycarbonyl group, formyl group, acetyl group, benzoyl group, phthalyl group,
Examples include acyl-type protecting groups such as tosyl group, alkyl-type protecting groups such as trityl group, and the like. In this case, a protective group that is chemically stable and difficult to remove is preferable; for example, even if the same acyl type protective group is used, formyl group (HCO−)
An acetyl group (CH ₃ CO-) or a benzoyl group (C ₆ H ₅ CO-) is more preferable. The above polyamino acids

【formula】 is the constituent unit of

[Formula] Namely, specific examples of α-aminocarboxylic acids include amino acids constituting proteins, such as alanine, valine, leucine, phenylalanine, proline, etc.
and β-benzylaspartate, γ-methylglutamate, γ-benzylglutamate, ε-
L of derivatives of protein-constituting amino acids such as carbobenzoxylysine, δ-carbobenzoxyornithine, O-acetyltyrosine, O-benzylserine, etc.
In addition to α-aminocarboxylic acids other than protein-constituting amino acids (for example, sarcosine) and derivatives thereof, in addition to the amino acid, D-isomer, D-isomer, and DL-isomer, are used. In the above general formula, n (degree of polymerization of polyamino acid) is generally 1 or more and 100 or less, but 5 or more is particularly preferable because it provides selectivity as an adsorbent. Although the content of polyamino acid residues in the graft polymer of the present invention can be selected as appropriate, it is preferably 10 to 60% when used as an adsorbent. Furthermore, since the adsorption effect of an adsorbent is influenced by the functional groups, stericity, etc. of the substance to be adsorbed, the type of amino acid in the graft polymer of the present invention can be changed as appropriate depending on these factors. For example, the amino acid constituent units R', R'', and R may be varied in one molecule.
However, when used as an adsorbent for optical resolution, the polyamino acid in the polymer needs to be optically active. The graft polymer of the present invention can be produced by the following method. First, the general formula: (In the formula, R' is an organic group) The N-carboxy anhydride (amino acid NCA) of the amino acid or its side chain derivative is reacted with the corresponding amino acid or its side chain derivative by a known method, for example, with phosgene. Synthesize by Details of this method can be found, for example, in Murray Gutsman (M.
Goodman), Biopolymers,
15, p. 1869 (1976). Next, a polymer having chloromethylated phenyl groups is produced by a known method and reacted with alkylene diamine or arylene diamine to introduce a spacer group having a primary amino group at the end. The amino acid NCA is polymerized using the introduced primary amino group as an initiator to obtain a polymer graft-bonded with polyamino acid residues. The graft polymer of the present invention differs from solution polymerization of amino acid NCA using a low-molecular primary amine as an initiator;
The base polymer adsorbs the amino acid NCA and forms a state in which it is easy to react, accelerating the reaction rate and allowing grafting with a yield of 90% or more. In the grafting reaction, a single amino acid NCA
In addition to graft polymerization of a solution of NCA, a graft copolymer in which the polypeptide chain is a random copolymer can be obtained by reacting a solution containing two or more different amino acids NCA. Furthermore, by sequentially reacting solutions of two or more different amino acid NCAs, a graft copolymer in which the polypeptide chain is a block copolymer can be obtained. Graft-bonded polyamino acid residues whose side chains can be converted can be converted into polyamino acids having other chemical structures by chemical conversion, such as converting an ester group into an amide group. can. When converting an ester group to an amide group, in addition to the usual ammonolysis, after converting the ester to an active ester with an electron-withdrawing substituent such as cyanoethyl ester, chloroethyl ester, trichloroethyl ester, or trifluoroethyl ester, benzyl It can also be carried out by reacting with amines such as amine, cyclohexylamine, L-α-phenylethylamine, and L-α-amino-ε-caprolactam. This chemical conversion is one of the very important manufacturing steps in obtaining an adsorbent suitable for the separation target because it allows the introduction of functional groups that interact with each other such as hydrogen bond interactions. In this case, the terminal amino group of the polyamino acid is protected as necessary before or after this conversion reaction. The polymer having a chloromethylated phenyl group, which is the starting material for the graft polymer of the present invention, can be obtained by introducing a chloromethyl group into the base polymer having a phenyl group, such as the aforementioned polystyrene. Methods for introducing this include chloromethylating the phenyl group of the base polymer by reacting with chloromethyl methyl ether, etc., or using chloromethylstyrene as a comonomer when polymerizing the base polymer. There is. Further, the base polymer is produced by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like. The polymer having a chloromethylated phenyl group obtained by the above method can be reacted with an alkylene diamine or an arylene diamine to introduce a spacer group having a primary amine at the end by the following method. In the reaction, first, the polymer is swollen or dissolved in a solvent such as toluene, and then alkylene diamine or arylene diamine is added.
This can be done by heating to ℃ and reacting for 5 to 24 hours.
In this case, if the concentration of chloromethylated phenyl groups in the polymer is high, an alkaline aqueous solution may be present in order to remove hydrochloric acid generated in the reaction. The speed of the reaction is greatly influenced by the degree of crosslinking of the base polymer, the type of diamine used, the amount of aqueous alkaline solution added, and the like. As a general tendency, the higher the degree of crosslinking of the backbone polymer and the larger the molecular weight of the diamine, the longer it is necessary to carry out the reaction at a higher temperature. The resulting polymer into which a spacer group having a primary amino group has been introduced at the terminal is isolated and purified, then completely dehydrated by Soxhlet extraction or the like, and thoroughly dried under heating and reduced pressure. The graft polymerization reaction of the amino acid NCA with the primary amino group introduced into the backbone polymer is carried out by suspending the backbone polymer in a solution in which the amino acid NCA is dissolved, and stirring while introducing an inert gas at a temperature of 50°C or less. A period of 72 hours is advantageous. In this reaction, it is necessary to prevent moisture from entering the reaction system from outside in order to improve the yield. The solvent used in the graft polymerization reaction is amino acid
A substance that dissolves NCA well and is inert against NCA polymerization, such as dioxane, anisole, methylene chloride, dichloroethane, chloroform, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, etc. be. The concentration of primary amino groups introduced into the backbone polymer is
Preferably 3 μmol to 0.3 mmol per 1 g of base polymer
It is. At a primary amino group concentration within this range, the degree of polymerization of the grafted polyamino acid can be controlled by changing the ratio of the amino acid NCA to the primary amino group. After the graft polymerization reaction is completed, it is desirable to thoroughly wash with a polymerization solvent or a solvent that dissolves the polyamino acid in order to remove unreacted components. The graft polymer obtained by the present invention exhibits amide and amide absorptions, which are characteristic absorptions of polyamino acids, at around 1650 and 1540 cm ^-1 in its infrared absorption spectrum, confirming that the polyamino acid component is graft polymerized. be done. Separation methods using the adsorbent of the present invention generally include batch methods and column chromatography methods. When performing highly difficult separation such as separation of optically active substances, the base polymer having a chloromethylated phenyl group of the present invention is obtained in the form of beads by suspension polymerization, and then classified. It is preferable to perform a grafting reaction, etc. according to the method described above, and then perform separation by column chromatography using this as an adsorbent. Column chromatography is usually performed using the following steps. First, the adsorbent is suspended in the solvent used for elution, and the suspension is transferred to the column. The substance to be separated is dissolved in a small amount of solvent, this solution is transferred to the top of the column, and the column is treated with an eluent.
The eluate is collected into fractions in a conventional manner. The degree of resolution of the racemate can be determined by measuring the optical rotation of each fraction. The solvent used for elution here needs to be a solvent that has affinity with the base polymer, for example an organic solvent such as toluene or dioxane, as the main solvent. By doing this, the interaction between the separation target and the backbone polymer is suppressed, and the separation target effectively interacts only with the graft-bonded polyamino acid, resulting in excellent separation performance. That's what I do. Using the graft polymer adsorbent according to the invention, it is possible to resolve a large variety of racemic mixtures. For example, hydroxycarboxylic acids, amino acids and derivatives of these compounds, such as phenylalanine, valine, leucine, tryptophan, serine, methionine,
-carbobenzoxy derivatives, N-benzoyl derivatives, hydantoin derivatives, chlorthalidone,
It is very useful as an adsorbent for optical resolution of pantoyllactone, etc. EXAMPLES The present invention will be specifically explained in the following Examples, but the present invention is not limited to these Examples. Example 1 Chloromethyl group concentration 0.129m obtained by suspension polymerization
mol/g of 50% cross-linked divinylbenzene-styrene-chloromethylstyrene copolymer (pore volume 1.4
cc/g, specific surface area 300m ² /g) 5g of dioxane
The mixture was swollen to 20 ml, 20 ml of 30% NaOH aqueous solution and 5.92 g of hexamethylene diamine were added, and the mixture was stirred at 90°C for 10 hours. After the reaction, the obtained aminated polymer was taken, thoroughly washed with dioxane, water, and acetone in that order, and then completely dried. The nitrogen content in the polymer is
The amount of primary amino groups introduced was calculated from this value to be 0.071 mmol/g (reaction rate of chloromethyl groups 55%). 4.45 g of the aminated polymer having hexamethylene group as a spacer group obtained in the above reaction and β-
1.02 g of benzyl-L-aspartate NCA was stirred in 44.5 ml of dioxane at 35° C. under nitrogen for 72 hours to polymerize NCA. After the polymerization, the resulting graft polymer was taken, washed thoroughly with dioxane, N,N-dimethylformamide, and acetone in that order, and dried (yield: 5.25 g). Collect oral fluid during washing,
After concentration under reduced pressure, the mixture was poured into a large amount of methanol, and although it became slightly cloudy, nothing resembling a polyamino acid was observed. The nitrogen content of the obtained graft polymer was 1.17%. The content of poly(β-benzyl-L-aspartate) in the graft polymer calculated from this value was 15.8%, and the degree of polymerization (n) was 11.9. The reaction rate of graft polymerization was 98%. Figure 1 shows the infrared absorption spectrum of this material, around 1650 cm ^-1 and 1530 cm
The absorption around ⁻¹ is the characteristic absorption of amide and amide based on the graft-bonded polyamino acid, and the absorption around 1720 cm ⁻¹ is the absorption based on the benzyl ester of the polyamino acid. From the above results, we found that amino acids can be produced by introducing a spacer group with a primary amino group at the end.
It can be seen that the polymerization of NCA proceeds easily, no side reactions occur, and polyamino acids can be efficiently grafted. Comparative Example 1 The 50% cross-linked divinylbenzene-styrene-chloromethylstyrene copolymer used in Example 1 was prepared using the method described in the literature, that is, first, it was mixed with potassium phthalimide.
After reacting at 120℃ for 10 hours, phthalimidation was performed, and after isolation and purification, it was further reacted with hydrazine at 90℃.
The chloromethyl group was converted to an aminomethyl group by a method of reaction for 10 hours. The nitrogen content in the polymer was 0.13%, and the concentration of aminomethyl groups calculated from this value was 0.093 mmol/g. (72% reaction rate of chloromethyl group). The obtained polymer having an aminomethylated phenyl group was treated in exactly the same manner as in Example 1 to obtain β-benzyl-L-aspartate.
The graft polymerization reaction rate after 72 hours of reaction was 33%. Then further at 40℃
Polymerization was continued for 30 hours, but the reaction rate was 47%.
It was extremely difficult to proceed with the polymerization further.
After polymerization, when the graft polymer was sampled and the liquid was poured into methanol, a large amount of precipitate was formed, indicating that free polyamino acids not grafted were produced. Examples 2-5 Chloromethyl group concentration 0.160m obtained by suspension polymerization
mol/g of 30% cross-linked divinylbenzene-styrene-chloromethylstyrene copolymer (pore volume 1.5
cc/g, specific surface area 103m ² /g) 25g toluene 150
ml, and after adding 6.5 g of 30% NaOH aqueous solution,
It was reacted with 0.08 mol of various diamines at 95°C for 10 hours. Figure 2 shows the relationship between the amount of primary amino groups introduced into the polymer and the reaction time.According to the method of the present invention, by appropriately selecting the reaction time, the amount of primary amino groups introduced into the polymer can be easily reduced. It turns out that it is possible to control. Controlling the amount of primary amino groups introduced in this way is extremely important as it is related to the degree of polymerization of the polyamino acid to be grafted next, but this was difficult with the conventional method shown in Comparative Example 1. . Next, various aminated polymers after 10 hours reaction 15.9
g and 5.06 g of various amino acids NCA were dispersed in 127 ml of dichloroethane and stirred under nitrogen at 25 to 35°C for 48 to 72 hours to polymerize NCA. Table 1 summarizes the results. It can be seen that polyamino acids are efficiently grafted in all cases. In the infrared absorption spectra of the graft polymers, absorption based on the styrene skeleton of the backbone polymer and amide and amide absorption based on the grafted polyamino acid were observed in all cases.

【table】

[Table] Example 6 The polyamino acid side chain methyl ester of the graft polymer obtained in Example 4 was converted to benzylamide by the method shown below. First, poly(γ-methyl-L-glutamate)
240g of the polymer grafted with dichloroethane
Disperse 2200ml ethylene cyanohydrin 181.2
g and p-toluenesulfonic acid (1
After adding 66 g of hydrate), the mixture was stirred at 60°C for 3 hours, and then the reaction system was reduced in pressure, and the reaction system was further stirred for 6 hours while the methanol produced by the reaction was distilled off together with the solvent to carry out transesterification. After the reaction, the cyanoethyl esterified graft polymer is isolated,
After thorough washing, it was completely dried. In the infrared absorption spectrum of this product, a characteristic absorption of nitrile groups was observed at 2250 cm ^-1 . 225g of this cyanoethyl esterified graft polymer was
- Dispersed in 1800 ml of dimethylformamide, added 225 g of benzylamine, stirred at 55°C for 24 hours, and then isolated and purified. In the infrared absorption spectrum
The nitrile absorption at 2250 cm ^-1 disappeared, the ester absorption near 1740 cm ^-1 decreased, and the amide absorption near 1650 cm ^-1 increased, indicating that the cyanoethyl ester was converted to benzylamide.
The conversion rate estimated from the reduction in ester absorption is approximately 70
It was %. Elemental analysis values C: 83.37 (%) H: 7.77 N: 2.93 200 g of this benzylamide graft polymer was dispersed in a solution of 1200 ml of dioxane and 40 ml of acetic anhydride, stirred at 30°C for 24 hours, and then isolated and purified. .
When the acid adsorption capacity of the graft polymer after reaction was measured using an N/50-HCl dioxane solution, the adsorption capacity was approximately O meq/g, indicating that the terminal amino groups of the polyamino acid graft were completely protected by acetyl groups. I understand that. Incidentally, almost no changes were observed in the infrared absorption spectrum and elemental analysis values. In order to evaluate the end-protected benzyl amidated graft polymer thus obtained as an adsorbent for optical resolution, it was classified using 250 mesh and 400 mesh metal sieves, and those having a diameter of 37 to 63 μm were collected. This classified polymer was used as a packing material and packed into a stainless steel column under the following conditions. Shimadzu LC for liquid pump
-Using a 4A high performance liquid chromatography device,
A large police car made by Gascro Industries was used as the police car. The filling was carried out using a constant pressure method. Column: inner diameter 16.7 mm, length 500 mm Packing liquid: 4:1 toluene-dioxane mixture Pressure: 80 atm Temperature: room temperature Next, using this packed column, D and L-mandelic acids were analyzed using chromatography. The retention time of each was measured and the separation ability of the adsorbent was evaluated. A Shimadzu LC-4A high performance liquid chromatography system was used for liquid delivery and detection. The conditions for chromatography are as follows. Eluent: 4:1 toluene-dioxane mixture Flow rate: 2 ml/min Temperature: 10°C Detection: Differential refractometer Sample amount: 2 ml of 2% solution The results of measuring each retention time are shown. The separation coefficient α, which represents the optical resolution ability of the adsorbent, was calculated using the following formula. α=T _D −T _O /T _L −T _O T _D : Retention time of D-mandelic acid T _L : Retention time of L-mandelic acid T _O : Retention time of toluene When α=1, the separation coefficient is completely This indicates that there is no optical resolution, and the larger the difference from 1, the higher the optical resolution.

[Table] Comparative Example 2 The 30% crosslinked divinylbenzene-styrene-chloromethylstyrene copolymer used in Examples 2 to 5 was prepared in exactly the same manner as in Comparative Example 1, and the chloromethyl groups in the polymer were replaced with aminomethyl groups. Converted to . The concentration of aminomethyl groups in the polymer after conversion is 0.129m
It was mol/g. (Reaction rate of chloromethyl group 80
%). The obtained polymer having an aminomethylated phenyl group was reacted with γ-methyl-L-glutamate NCA in exactly the same manner as in Example 4 to polymerize NCA. The nitrogen content of the obtained graft polymer is
It was 2.21%. Poly(γ-methyl-L-glutamate) in the graft polymer calculated from this value
The content of is 20.1%, and its degree of polymerization (n) is 13.14
It was hot. Next, in exactly the same manner as in Example 6, the polyamino acid side chain methyl ester of the graft polymer was converted to benzylamide, and then the terminal amino group of the polyamino acid graft was protected with an acetyl group. Elemental analysis values C: 82.25 (%) H: 7.42 N: 2.99 The end-protected benzyl amidated graft polymer thus obtained was classified in exactly the same manner as in Example 6, and after filling a column, D and L-mandel The retention time of each acid was measured. The results are shown in Table 2. It can be seen that, compared to the adsorbent of Example 6 which has a spacer group, the adsorbent of this comparative example which does not have a spacer group has a separation coefficient (α) of 1.04, which indicates that only inefficient separation is performed. Example 7 Chloromethyl group concentration 0.101m obtained by suspension polymerization
250 g of 1.5% cross-linked divinylbenzene-styrene-chloromethylstyrene copolymer (mol/g) was swollen in 2500 ml of toluene, and 60% of ethylenediamine was added thereto.
g was added thereto and stirred at 90°C for 10 hours to convert the chloromethyl groups in the polymer to N-(aminoethyl)aminomethyl groups. The nitrogen content after isolation and purification is
The concentration of primary amino groups in the polymer calculated from this value was 0.086 mmol/g (reaction rate of chloromethyl groups: 85%). 220 g of the aminated polymer having an ethylene group as a spacer group obtained in the above reaction was dispersed in a solution of 33 g of γ-methyl-D-glutamate NCA and 2640 ml of 1,2-dichloroethane, and the mixture was heated at 25°C under nitrogen.
The mixture was stirred for 48 hours to graft-polymerize NCA. The nitrogen content after graft polymerization is 1.13%, and the content of poly(γ-methyl-D-glutamate) in the graft polymer calculated from this value is 11.0%, and its degree of polymerization (n) is 24.2. It was hot. Moreover, the reaction rate of graft polymerization was 95%. Infrared absorption spectrum: 1650cm ^-1 (amide) 1540cm ^-1 (amide) 1730cm ^-1 (ester) The obtained graft polymer was treated in exactly the same manner as in Example 6, and the polyamino acid side chain methyl ester was converted to benzylamide. Then, the terminal amino group of the polyamino acid was protected with an acetyl group. Elemental analysis values C: 85.50 (%) H: 7.48 N: 1.47 The end-protected benzyl amidated graft polymer thus obtained was classified in the same manner as in Example 6,
The column was packed. In this case, filling was carried out at 30 atmospheres to avoid compaction. When DL-isopropylhydantoin was resolved using this column under the following conditions, it was almost completely separated into D and L optical isomers, the respective retention times were 64.88 minutes and 70.47 minutes, and the separation factor was 1.25.
It was hot. Eluent: 3:1 toluene-dioxane mixture Flow rate: 2 ml/min Temperature: 10°C Detection: Differential refractometer Sample amount: 2 ml of 0.5% solution Effects of the invention The polyamino acid residues of the present invention were grafted together. Graft polymers having spacer groups are completely new, and adsorbents for optical resolution made from them are extremely useful. The method of the present invention, in which a polymer having a chloromethylated phenyl group is reacted with an arylene diamine or an alkylene diamine and then reacted with an amino acid NCA, yields a polymer grafted with a polyamino acid at a high reaction rate, and This is an industrially extremely advantageous method for producing adsorbents. The adsorbent for optical resolution made of the graft polymer of the present invention suppresses steric hindrance caused by the backbone polymer due to the effect of the spacer group, and as a result, exhibits excellent separation properties and is a highly practical adsorbent. .

[Brief explanation of drawings]

Figure 1 shows poly(β-benzyl-L-aspartate) added to an aminated polymer having a hexamethylene group as a spacer group obtained by reacting divinylbenzene-styrene-chloromethylstyrene copolymer with hexamethylene diamine. This is an infrared absorption spectrum of the grafted polymer. Figure 2 shows the relationship between the amount of primary amino groups introduced into the polymer and the reaction time when various diamines are reacted with a polymer having chloromethylated phenyl groups. This is what is shown.

Claims (1)

[Claims] 1. General formula (In the formula, n is an integer of 1 or more, A is the base polymer, R is an alkylene group including an arylene group, R' is an organic group, R'' is H or an alkyl group, R
An adsorbent made of a graft polymer having a spacer group R grafted with a polyamino acid residue represented by H or an organic group. 2. A general formula characterized by reacting a polymer having a chloromethylated phenyl group with an arylene diamine or an alkylene diamine, and then reacting with an α-amino acid N-carboxylic anhydride. (In the formula, n is an integer of 1 or more, A is the base polymer, R is an alkylene group including an arylene group, R' is an organic group, R'' is H or an alkyl group, R
A method for producing an adsorbent comprising a graft polymer having a spacer group R grafted with a polyamino acid residue represented by H or an organic group.