JPH0336843B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides, for example, artificial organs, their members,
N-glycoside/olefin compound copolymers having reducing sugar residues in side chains and not described in prior literature, which are useful for forming molded products such as other similar products;
The present invention relates to N-glycoside vinyl compounds which are useful as intermediates and which have not been described in the literature, and methods for producing them. More specifically, the present invention is based on the following formula (1)′, However, in the formula, R ₁ is

[Formula] -(CH ₂ -) _n [Here, m is an integer from 1 to 5] and

[Formula] [where n is an integer of 1 to 10] represents a group selected from the group consisting of _{a hydrogen atom and CH 3} ^; and X represents a reducing sugar residue. represents a group selected from the group consisting of a group consisting of a sulfuric acid ester residue thereof, and an alkali salt of the ester residue; and the following table (2)', However, in the formula, R ³ , R ⁴ and R ⁵ each represent a group selected from the group consisting of a hydrogen atom and CH ₃ , and R ⁶ is

[Formula] [Here, R ⁷ is a hydrogen atom, a C ₁ to C ₁₈ alkyl group, a C ₁ to _{C 5} hydroxyalkyl group, a cyclohexyl group, a C ₁ to _{C 5} aminoalkyl group, a di(C ₁ to _C2 alkyl) amino ( _C1 - _C5 alkyl) group, glycidyl group, tetrahydrofuran group, _benzyl group and -( _CH2CH2O- ) _y
A group selected from the group consisting of a CH ₂ CH ₂ OH group (y = an integer from 1 to 10);

[Formula] [Here, R ⁸ represents a hydrogen atom or a C ₁ to C ₄ alkyl group, and the two R ^8s may be the same or different]; -CN; -OH;

[Formula] [Here, R ⁹ represents a C ₁ to C ₃ alkyl group];

【formula】

【formula】

【formula】

[Formula] and

[Formula] [Here, R ¹⁰ represents a C ₁ to C ₅ alkyl group] A structural unit represented by: The present invention relates to a copolymer and a method for producing the copolymer. In (1)′ above, preferable R ¹ is

[Formula] or -(CH ₂ -), and preferable reducing sugar residues of X are xylose, ribose, glucose,
A reducing monosaccharide residue selected from the group consisting of galactose and mannose; selected from the group consisting of maltose, isomaltose, cellobiose, lactose, isomaltotriose, manninotriose, cellotriose, isomaltotetraose and cellotetrose. Residues of reducing oligosaccharides;
and a reducing polysaccharide residue selected from the group consisting of starch, cellulose, dextran, pullulan, curdlan, and partial hydrolysates thereof; and a reducing sugar residue selected from the group consisting of; Furthermore, the present invention provides the following formula (1) that can be used in the method for producing the above copolymer: However, in the formula, R ₁ is

[Formula] -(CH ₂ -) _n [where m is an integer from 1 to 5] and

[Formula] [where n is an integer of 1 ^to 10] represents a group selected from the group consisting of a hydrogen atom and CH ₃ ; and X represents a reducing sugar The present invention also relates to an N-glycoside vinyl compound represented by: a group selected from the group consisting of a residue, a sulfate ester residue thereof, and an alkali salt of the ester residue, and a method for producing the same. Preferred examples of reducing sugar residues for R ¹ and X in the above formula (1) are the same as those described for formula (1)'. Conventionally, a large number of polymer compounds in which a vinyl monomer is graft-copolymerized to a polysaccharide backbone polymer have already been disclosed. On the other hand, little has been disclosed about polymer compounds in which a vinyl monomer backbone polymer has a monosaccharide as a side chain. In particular, vinyl-based polymer compounds having oligosaccharides or polysaccharides in their side chains have rarely been disclosed so far because they can only be synthesized by more complicated methods. The present invention relates to a polymer compound that can be easily synthesized and has an olefinic backbone polymer with a monosaccharide, oligosaccharide, or polysaccharide as a side chain, which has not been described in any literature. The present inventors have conducted research on the development of N-glycoside/olefin compound copolymers. As a result, by reacting a reducing sugar with a vinyl monomer having an amino group, a macromer represented by the above formula (1) in which the anomeric carbon atom at the reducing end of the sugar and the nitrogen atom of the amino group are N-glycosidic bonded, which has not been described in any prior literature. discovered that it can be easily synthesized. Furthermore, by reacting the N-glycoside vinyl compound obtained in this manner with a polymerizable olefin compound in the presence or absence of a polymerization catalyst, the structural unit of formula (1)' can be obtained. formula
(2) It is possible to form an N-glycoside/olefin compound copolymer having a reducing sugar residue in the side chain, which has not been previously described in any literature, and the N-glycoside/olefin compound copolymer thus obtained has The olefin compound copolymer is a cast film-forming material, and the film has excellent anticoagulant properties and is suitable for forming molded products such as artificial organs, their parts, and other similar products. I learned that it is a substance that can be expected to have excellent usefulness. Therefore, an object of the present invention is to solve the problem of N
- To provide a glycoside-olefin compound copolymer and a method for producing the same. Another object of the present invention is to provide an N-glycoside vinyl compound useful as an intermediate for producing the above-mentioned copolymer, which has not been previously described in any literature, and a method for producing the same. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The following formula (1), which can be used as an intermediate for producing the N-glycoside/olefin compound copolymer, However, in the formula, R ¹ is

[Formula] -(CH ₂ -) _n [Here, m is an integer from 1 to 5] and

[Formula] [where n is an integer of 1 ^to 10] represents a group selected from the group consisting of a hydrogen atom and CH ₃ ; and X represents a reducing sugar Represents a group selected from the group consisting of a residue, a sulfate ester residue thereof, and an alkali salt of the ester residue; An N-glycoside vinyl compound represented by, for example, a reducing sugar and the following formula (3), However, in the formula, R ₁ is

[Formula] -(CH ₂ -) _n [Here, m is an integer from 1 to 5] and

[Formula] Represents a group selected from the group consisting of [where n is an integer of 1 to 10]; ^R2 represents a group selected from the group consisting of a hydrogen atom and _CH3 , an amino group represented by A vinyl compound having
It can be produced by reacting in a polar organic solvent or its water-containing solvent. Examples of the above polar organic solvents include methanol,
Examples include polar alcohol solvents such as ethanol, polar amide solvents such as dimethylformamide and formamide, dimethyl sulfoxide, and mixtures thereof, and further, water-containing solvents of these and water, for example, containing about 50 V/V% or less of water. Examples include these polar organic solvents. These solvents are preferably selected and used as appropriate depending on the types of reducing sugar and vinyl compound, the properties of the compound of formula (1) to be formed, and the like. Usually, a solvent is selected that dissolves the raw materials and products and is advantageous for purification. For example, when reacting oligosaccharides such as glucose and maltose with p-aminostyrene, methanol, ethanol, formamide, dimethylformamide, dimethylsulfoxide,
A mixture thereof or a solvent containing up to about 50 V/V% of water, preferably methanol or ethanol, particularly preferably about 3 V/V% to about 10 V/V
% water-containing methanol is preferably used. In addition, when reacting starch or dextran with p-aminostyrene, formamide, dimethylformamide, dimethyl sulfoxide, a mixture thereof, or a water-containing (approximately 50 V/V% or less) solvent, preferably water or formamide, is used in a solution of about 20% ~Approx. 50V/V
% of dimethylformamide is preferably used. The reaction is carried out, for example, by adding reducing sugar in a polar organic solvent or a water-containing solvent thereof such as those exemplified above at a rate of about 1 to about 50 g, more preferably about 5 g, per 100 ml of the solvent.
to about 20 grams per mole of reducing sugar, such as from about 1 to about
20 moles, more preferably from about 1 to about 10 moles of the formula
(3) This can be carried out by adding an amino group-containing vinyl compound and causing a reaction. The reaction temperature can be selected as appropriate, for example from about 0° to about
Examples include temperatures such as 100°C, more preferably about
Temperatures from 30° to approximately 70°C can be used. The reaction is preferably carried out under stirring conditions, and can be carried out, for example, for a reaction time of about 2 to about 5 hours. During the reaction, the reaction can be carried out in the presence of a catalyst, if desired, and is preferred. It is also possible and preferred to carry out the reaction in the presence of a polymerization inhibitor, if desired. Examples of such catalysts include sulfuric acid, ammonium sulfate, ammonium chloride, etc., and the amount used is about 5 to about 5% in the reaction system.
An example of the usage amount is 100 ppm. Further, as an example of the above-mentioned polymerization inhibitor, hydroquinone can be exemplified, and the amount used is about 100 to about 100% in the reaction system.
An example of a usage amount is 5000 ppm. The N-glycoside vinyl compound of formula (1) in which X is a reducing sugar residue, which can be formed as described above, can be separated and purified, for example, as described below. For example, when a relatively low boiling point solvent is used, the solvent is distilled off under reduced pressure, and a solvent that does not dissolve the reaction target of formula (1), such as ethyl ether,
It can be washed with a solvent such as acetone or a mixture thereof and dried under reduced pressure. Also, when a relatively high boiling point solvent such as dimethylformamide is used, a poor solvent such as ethyl alcohol, acetone, ethanol or a mixture thereof is preferably used, preferably about 3 to 10 parts of ethyl ether and acetone.
By adding a mixed solvent such as about 10 (V/V) in an amount of about 3 to about 10 times the reaction solvent (V/V), the reaction target product of the above formula (1) can be precipitated and separated. can. Furthermore, if necessary, dissolve the precipitate in dimethyl sulfoxide, add the same mixed solvent of ethyl ether and acetone, and reprecipitate the target product.
Further purification can be achieved by repeating this separation operation. Next, the compound of formula (1) can be separated and purified by washing with, for example, ether, acetone or ethanol and drying under reduced pressure. For example, the formula that can be obtained as above
In (1), the N-glycoside vinyl compound in which X is a reducing sugar residue is usually a white to pale yellow compound that is solid at room temperature.
^13C nuclear magnetic resonance spectrum of the compound (macromer) (solvent DMSO- _d6 ; concentration 16%;
(room temperature 25MHz) is shown in Figure 1 of the attached drawings. As shown in Figure 1, according to the ¹³ C nuclear magnetic resonance spectrum, the chemical shift value of the anomeric carbon atom participating in the N-glucoside bond of the macromer is shifted to the high magnetic field side compared to that of the free sugar. do. For example, the chemical shift value of the reducing end anomer carbon of styrylaminated maltose, which is an N-glucoside of maltose and p-aminostyrene, is about 85 ppm for the β type and about 82 ppm for the α type. On the other hand, the reducing end anomeric carbon of free maltose is approximately 97 ppm for the β form and 92 ppm for the α form. Also, N between dextran and p-aminostyrene
- Similar relationships apply to glucoside compounds. Furthermore, an infrared absorption spectrum diagram of the macromer shown in FIG. 1 above is shown in FIG. 2 of the accompanying drawings. As shown in FIG. 2, according to infrared absorption spectroscopy, the macromer exhibits a combination of absorption spectra of both the raw material reducing sugar and the amino group-containing vinyl monomer of formula (3), with new peaks particularly unacceptable. For example, the characteristic infrared absorption spectrum of styrylaminated maltose, which is a macromer composed of p-aminostyrene and maltose, is around 3400 cm ^-1 (O-H stretching vibration) and 1615 cm
These are peaks around ⁻¹ , around 1520 cm ⁻¹ (rose disubstituted benzene ring), and around 1030 cm ⁻¹ (C—O stretching vibration). Furthermore, by thin layer chromatography,
The macromer in which X in formula (1) is a reducing sugar residue can be confirmed. For example, 1-butanol-ethanol-
When developed with 0.1N acetic acid aqueous solution (1:1:2), p-aminostyrene-N-maltoside is
Rf = approximately 0.76, maltose has Rf = approximately 0.68,
In addition, the macromer consisting of p-aminostyrene and dextran with an average octamer has an Rf of about 0.76 and an average of 8
meric dextran has an Rf = approximately 0.58. In the formula (1) N-glycoside vinyl compound of the present invention,
The N-glycoside vinyl compound of formula (1) in which X is a sulfate ester residue of a reducing sugar residue or an alkali salt of the ester residue is an ester of the compound of formula (1) in which X is a reducing sugar residue as described above. It can be easily formed by a conventional salt-forming reaction. The above esterification is carried out using a solvent capable of reacting in a homogeneous system, such as formamide, dimethylformamide, or a mixture thereof.
In 100 ml, a macromer in which X is a reducing sugar residue in the above formula (1) is dissolved in an amount of, for example, about 1 g to about 30 g, more preferably about 3 g to about 10 g, for example,
About -5°C to about 20°C, more preferably about 0°C to about 10°C
This can be carried out by adding a sulfuric acid esterifying agent such as chlorosulfuric acid or sulfuric anhydride under relatively low temperature conditions such as ℃. At this time, it is preferable to add an amine compound, for example, a basic amine compound such as triethylamine, tributylamine or pyridine, to the reaction system as a neutralizing agent in order to prevent hydrolysis. Further, preferably, a complex of a sulfuric acid esterifying agent and an amine compound as exemplified above, such as a sulfuric anhydride-triethylamine complex, can be used as the esterifying agent. The amount of the esterifying agent to be used can be selected as appropriate; for example, if a sulfuric acid esterified macromer of formula (1) with a high degree of substitution is desired,
OH of the macromer in which X is a reducing sugar residue in formula (1)
For example, about 2 to about 6 moles of the sulfuric acid esterifying agent may be added per mole of the group. In this way, about 5~
Sulfuric acid esterification can be carried out by stirring for about 48 hours. Next, a poor solvent such as ethyl ether, acetone, or a mixed solvent thereof can be added to the reaction system in an amount 2 to 10 times (V/V) the amount of the reaction solvent to precipitate the sulfuric acid ester. If necessary, it can be further purified by re-dissolving and reprecipitating, then thoroughly washed with a solvent such as ethyl ether, acetone, or a mixed solvent thereof, and then pressure-sensitive drying for separation and purification. The sulfuric acid esterified macromer of formula (1) obtained as described above can be obtained in the form of an amine salt when the reaction is carried out in the presence of the basic amine compound. Just as the sodium salt can be obtained by dissolving it, it can also be obtained by simply converting it into a salt of another monovalent cation. In the above formula (1), the N-glycoside vinyl compound of formula (1), in which X is a sulfate ester residue of a reducing sugar residue or an alkali salt thereof, is usually a light yellow to yellowish brown compound that is solid at room temperature. In general, the degree of substitution of the sulfate ester per anhydrous monosaccharide unit is:
It is about 0.1 to about 2.5. As an example, an infrared absorption spectrum diagram of the sulfuric acid esterified macromer of Example 5 is shown in FIG. 8 of the accompanying drawings. According to the infrared absorption spectrum, the sulfate-esterified macromer exhibits the following characteristic spectrum.
For example, as shown in FIG. 8, equation (1)
In the spectrum shown by the macromer in which X is a reducing sugar residue (see Figure 7), the absorption spectrum around 3400 cm ^-1 based on the stretching vibration of the O-H group is reduced, and the stretching vibration of SO ₂ is newly observed. An absorption spectrum appears around 1250 cm ^-1 based on In addition, the sulfur content of the sulfuric acid esterified macromer varies depending on the type of counter ion of the sulfuric acid group, the type of vinyl compound (3) having an amino group forming the sulfuric acid esterified macromer, etc. Although it is difficult to quantify the S content, it is generally less than 20%, with approximately 2.5 sulfate groups per anhydrous monosaccharide unit.
It usually contains sulfur equivalent to less than The measurement of sulfur content is based on the Japanese Pharmacopoeia (No. 9).
(Revised), General Test Methods, Oxygen Flask Combustion Method. The N-glycoside/olefin compound copolymer having the structural unit represented by the formula (1)' and the structural unit represented by the formula (2)' of the present invention can be obtained, for example, as described above. . The following formula (1), However, in the formula, R ₁ is

[Formula] -(CH ₂ -) _n [Here, m is an integer from 1 to 5] and

[Formula] [where n is an integer of 1 ^to 10] represents a group selected from the group consisting of a hydrogen atom and CH ₃ ; and X represents a reducing sugar An N-glycoside vinyl compound represented by the following formula (2), which represents a group selected from a group consisting of a residue, a sulfuric ester residue thereof, and an alkali salt of the ester residue; However, in the formula, R ³ , R ⁴ and R ⁵ each represent a group selected from the group consisting of a hydrogen atom and CH ₃ , and R ⁶ is

[Formula] [Here, R ⁷ is a hydrogen atom, a C ₁ to C ₁₈ alkyl group, a C ₁ to _{C 5} hydroxyalkyl group, a cyclohexyl group, a C ₁ to _{C 5} aminoalkyl group, a di(C ₁ to _C2 alkyl) amino ( _C1 - _C5 alkyl) group, glycidyl group, tetrahydrofuran group, _benzyl group and -( _CH2CH2O- ) _y
A group selected from the group consisting of a CH ₂ CH ₂ OH group (y = a positive number from 1 to 10);

[Formula] [Here, R ⁸ represents a hydrogen atom or a C ₁ to C ₄ alkyl group, and the two R ^8s may be the same or different]; -CN; -OH;

[Formula] [Here, R ⁹ represents a C ₁ to C ₃ alkyl group];

【formula】

【formula】

【formula】

[Formula] and

[Formula] [Here, R ¹⁰ represents a C ₁ to C ₅ alkyl group] A polymerizable olefin compound represented by It can be formed by reacting in its absence. The reaction can be preferably carried out by copolymerizing the compound of formula (1) and the polymerizable olefin compound of formula (2) using a polar solvent in which the N-glycoside vinyl compound of formula (1) is soluble. The copolymerization can be carried out in any desired polymerization format, such as solution (or homogeneous) polymerization, suspension polymerization, or emulsion polymerization, and various combinations of these polymerization formats can also be employed. For example, a polar solvent in which the N-glycoside vinyl compound of formula (1) is soluble, such as dimethylformamide,
For example, about 1 to about 50 g of the compound of formula (1) is added to 100 ml of a solvent using formamide, dimethyl sulfoxide, water, or a mixed solvent of at least two of these.
More preferably, it is dissolved in an amount of about 5 to about 30 g,
Add a suitable polymerization initiator if desired, and
This can be carried out by adding a polymerizable olefin compound of formula (2). In this case, when the polymerization solvent is an organic solvent, it is preferable to use benzoyl peroxide, mazobisisobutyronitrile, ammonium persulfate, etc., preferably azobisisobutyronitrile, as a polymerization initiator, and the amount used is For example, about 0.005 mol/~0.5 mol/, based on the polymerization solvent.
More preferably about 0.01 mol/~0.05 mol/
An example of the usage amount is as follows. In addition, when water is used as the polymerization solvent, it is preferable to use ammonia persulfate, potassium persulfate, etc. as a polymerization initiator, and the amount used is, for example, about 0.001 mol/~0.5 mol per water. /, more preferably about 0.005
An example of the amount used is from mol/ to about 0.05 mol/. The compound of formula (1) and the polymerizable olefin compound of formula (2) can be used singly or in combination. The amount of the compound of formula (2) to be added can be appropriately selected, for example, depending on the chain length of the reducing sugar residue X in the compound of formula (1). To name a few examples, for example, equation (1)
In the case of maltose in which the middle and X moieties are disaccharides,
The formula (1) compound is added to about 100 moles of the formula (2) compound.
The proportion is preferably 400 mol or less, preferably about 3 mol to about 100 mol. For example, in the case of dextran in which the X moiety is an octasaccharide in the formula (1), the compound of the formula (2)
About 100 mol or less of the compound of formula (1) per 100 mol,
Preferably, the proportion is about 1 mol to about 10 mol. Further, at this time, when water is used as the polymerization solvent and a water-insoluble compound of formula (2) is used, it is preferable to add an emulsifier such as sodium dodecylbenzenesulfonate to the polymerization system in advance. The addition ratio can be selected as appropriate, for example, about 10W/W% or less, preferably about 10W/W% or less based on water.
An example of a usage amount is 1 W/W% to about 5 W/W%. The reaction is preferably carried out in the substantial absence of oxygen, for example, by degassing the polymerization system and/or purging with nitrogen to create a substantially oxygen-free atmosphere. The reaction can be carried out under stirred or static conditions at a temperature of, for example, about 20° to about 100°C, more preferably about 40° to about 70°C. The polymerization time may be, for example, about 10 minutes to about 5 hours. In carrying out this copolymerization reaction, a wide range of polymerization conditions can be selected depending on the purpose. For example, if a relatively hydrophilic copolymer with a relatively high intrinsic viscosity is desired, the formula ( 2) It is preferable to use acrylonitrile as the compound, and it is further preferable to use dimethyl sulfoxide, which has a small chain transfer constant, as the polymerization solvent. By carrying out the copolymerization under such preferable conditions, the copolymerized compound having an intrinsic viscosity [η] of 25° C. and DMSO of 2 or more can be obtained relatively easily. For example, when the intrinsic viscosity is relatively high and it is desired to impart hydrophobicity, a part of the acrylonitrile, for example, about 10 mol % to about 30 mol %, can be replaced with styrene as the compound of formula (2). preferable. Furthermore, for example, when it is desired to impart more hydrophobicity, it is preferable to use styrene as the compound of formula (2), and as the polymerization solvent, dimethylformamide or a mixture of dimethylformamide and dimethylsulfoxide (1:0.5 to 2W/ V) is preferably used. After carrying out the copolymerization reaction as described above, the polymerization product system is cooled with ice water, for example, and a poor solvent such as methanol, ethanol, or acetone is added at a concentration of about 2 to about 5 times the polymerization solvent (V/ V) amount can be added and the insoluble matter, which is a copolymer, can be separated and collected. If necessary, for example, redissolve or redisperse in dimethyl sulfoxide or dimethylformamide, then add methanol, ethanol or acetone in an amount of about 2 times to about 5 times (V/V) the amount of the solvent in which it was dissolved or dispersed, Purification can be achieved by repeating the operation of separating insoluble matter. Then, for example, insoluble matter can be washed with methanol or ethanol and dried under reduced pressure. For example, as described above, in the compound of formula (1),
The N-glycoside/olefin compound copolymer of the present invention which can be obtained from the compound of formula (1) and the compound of formula (2) in which is a reducing sugar residue is usually a white to yellow compound that is solid at room temperature. When copolymerized in an aqueous medium, it often exhibits a brown or brown color. As an example of the N-glycoside/olefin compound copolymer obtained as described above, an infrared absorption spectrum diagram of the N-glycoside/olefin compound copolymer obtained in Example 6 is shown in FIG. 10 of the attached drawings. Indicated. As shown in FIG. 10, the N-glycoside/olefin compound copolymer is a polymerizable olefin compound copolymerized with the absorption spectrum of the compound of formula (1) (X is a reducing sugar residue). Both absorption spectra of (2) are shown together. For example, a copolymer compound of styrylaminated maltose and acrylonitrile consisting of maltose and p-aminostyrene, which is a type of macromer of the formula (1), has a characteristic spectrum of styrylaminated maltose around 3400 cm ^-1 and 1030 cm ^-1 It also shows absorption near 2250 cm ^-1 (-C=N), which is the characteristic spectrum of acrylonitrile. Furthermore, for example, a copolymer compound of styrene and styrylaminated dextran, which is a type of macromer of formula (1), and p-aminostyrene, has a characteristic spectrum of styrylaminated dextran around 3400 cm ^-1 and 1030 cm -1. ^-1 area and around 1500 cm ^-1 which is the characteristic spectrum of styrene (

[Formula]) and around 700cm ^-1 (

It also shows the absorption of [Formula]). Furthermore, whether or not the copolymer is actually copolymerized can be determined by the solubility of the obtained copolymer. For example, a copolymer of styrylaminated dextran and acrylonitrile containing a large number of styrylaminated dextran moieties is soluble in water, whereas polyacrylonitrile is not soluble in water. Furthermore, for example, a copolymer of styrylaminated maltose and styrene containing a large number of styrylaminated maltose moieties dissolves in dimethyl sulfoxide, but polystyrene does not dissolve in this solvent. Furthermore, regarding the compound shown in Figure 10 above,
^{The 13} C nuclear magnetic resonance spectrum (solvent DMSO-d ₆ concentration 15%; room temperature 25 MHz) is shown in FIG. 9 of the attached drawings. As shown in FIG. 9, the compound of formula (1) (X
No signals attributed to the vinyl group of the reducing sugar residue) or the >C=C< group of the polymerizable olefin compound (2) are observed, but signals attributed to the methine carbon and methylene carbon are observed. On the other hand, the formula
The chemical shift values of carbon atoms other than vinyl groups in the macromer (1) and the compound of formula (2) do not change much even when they are copolymerized. Furthermore, the sugar content in the copolymer can vary widely depending on the polymerization conditions used, and is generally about 80% W/W or less. The method for quantifying sugar in this case was as follows. That is, 10 mg to 50 mg of the copolymer is dissolved or dispersed in about 10 ml of a 2N aqueous hydrochloric acid solution, kept at 95 to 100°C for about 5 hours with stirring, and if there is any insoluble material, the solution is adjusted to 50 ml, and if necessary, Dilute and use as a test solution for sugar determination. Then water 25
Mix 1 ml of the test solution with 5 ml of the coloring test solution, which is made by dissolving 200 mg of Antholone in a mixture of 1.5 ml and 75 ml of sulfuric acid, and heat in a 100°C water bath for 10 minutes to develop color. Separately, a standard test solution containing the same sugar as the sample and having a known concentration is similarly colored. The absorbance of these was measured at a wavelength of 620 nm, and Lambert-Baer (Lambert-Baer)
The sugar content in the copolymer compound is determined according to Beer's law. Above, in the compound of formula (1), the formula where X is a reducing sugar residue
The copolymerization mode and product of the compound (1) and the polymerizable olefin compound of formula (2) have been described above, and in the compound of formula (1), X is a sulfate ester residue of the reducing sugar or an alkali salt thereof. Formation of a copolymer of the compound of formula (1) and the compound of formula (2) can also be carried out in substantially the same manner as described above. For example, using a solvent in which the esterified or alkali salt macromer of formula (1) is soluble, such as dimethylsulfoxide, dimethylformamide, formamide, methanol, ethanol, water, and combinations thereof, preferably dimethylsulfoxide or dimethylformamide, solvent 100
ml of the esterified macromer of formula (1), preferably its N ⁺ H(C ₂ H ₅ ) ₃ salt, more preferably the esterified macromer of formula (1) having an average degree of ester substitution of about 1 or more per anhydrous monosaccharide unit. For example, about 50 g or less, more preferably about 5 g to about 30 g, is dissolved. Next, a polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, ammonium persulfate, potassium persulfate, etc. is added. In this case, when an organic solvent is used as the copolymerization medium, azobisisobutyronitrile is preferred, and the amount of the solvent is, for example, about 0.005 mol/~0.5 mol/more preferably about 0.01 mol/~0.05 mol/. When water is added and used as a copolymerization medium, ammonium persulfate or potassium persulfate is preferred, e.g.
0.5 mol/more preferably about 0.005 mol/~
Add about 0.005 mol/degree. Next, the polymerizable olefin compound of formula (2) can be added to carry out a reaction. At this time, the addition ratio of the formula (1) esterified macromer and the formula (2) compound can be selected widely depending on the purpose, but the range of addition ratio depends on the chain length of the sugar moiety of the formula (1) esterification macromer. It is best to change the selection as appropriate. For example, when the sugar moiety of the esterified macromer of formula (1) is maltose, the esterified macromer of formula (1) is, for example, about 200 mol or less per 100 moles of the total number of moles of the compound of formula (2), More preferably, it is used in a proportion of about 2 mol to about 50 mol. For example, when the sugar moiety of the esterified macromer of formula (1) is octamer dextran,
The esterified macromer is preferably used in a proportion of, for example, 50 mol or less, more preferably about 0.2 mol to about 10 mol, per 100 mol of the total number of moles of the compound of formula (2). Then, copolymerization can be carried out in the same substantially oxygen-free atmosphere as described above at a temperature of, for example, about 20°C to about 100°C, more preferably about 40°C to about 70°C. The polymerization time can be changed as appropriate depending on the conditions and purpose, and is generally about 30 minutes to about 7 minutes.
It's time. The polymerization system is then cooled and treated with a poor solvent such as ethyl ether, methanol, ethanol, or acetone, preferably ethyl ether or an ethyl ether-methanol mixture (4:
1 to 2) in about 3 to about 6 times the amount of the polymerization solvent (V/V)
The desired copolymer can be separated and collected as an insoluble matter. If necessary, the collected insoluble matter is redissolved or dispersed in, for example, dimethylformamide or dimethyl sulfoxide.
Purification can be achieved by repeating the same procedure of adding a poor solvent and re-precipitating the insoluble matter. Next, this insoluble material can be washed with an acetone-methanol mixture (1:1-2) and then dried under reduced pressure. For example, as described above, in the compound of formula (1),
The N-glycoside/olefin compound copolymer of the present invention, which can be obtained from the compound of formula (1) and the compound of formula (2) in which is a sulfuric ester residue of a reducing sugar or an alkali salt thereof, usually has a pale yellow to pale yellow color. It is a yellow compound that is solid at room temperature and may take on a brown to brown color when copolymerized in an aqueous medium. Example 9 is an example of the N-glycoside/olefin compound copolymer obtained as described above.
The infrared absorption spectrum of the N-glycoside/olefin compound copolymer obtained in is shown in Figure 11 of the attached drawings.
It was shown to. As shown in FIG. 11, the copolymer combines the characteristic absorption spectrum of the esterified macromer of formula (1) with the characteristic absorption spectrum of the copolymerized compound of formula (2). show. For example, the copolymerized compound of formula (1) esterified macromer, sulfate/triethylamine salt of styrylaminated dextran, and acrylonitrile has a characteristic spectrum of 1250 cm ^-1 of the sulfuric ester/triethylamine salt of styrylaminated dextran.
(SO ₂ ), an absorption peak near 1030 cm ^-1 (C-O), and an absorption peak near 2250 cm ^-1 (C≡N), which is a characteristic absorption spectrum of acrylonitrile, are shown together. Furthermore, whether or not the copolymer is actually copolymerized can be determined by the solubility of the obtained copolymer. For example, a copolymer of sulfuric acid ester/triethylamine salt of styryl aminated dextran and acrylonitrile with a small proportion of acrylonitrile is soluble in water, but polyacrylonitrile is not soluble in water. Furthermore, for example, the sulfate ester of styryl aminated dextran,
A copolymer of triethylamine salt and styrene with a small proportion of styrene dissolves in dimethyl sulfoxide, but polystyrene does not dissolve in dimethyl sulfoxide. From this, it is understood that they are not just a mixture but a copolymer. Furthermore, the sugar sulfate ester content in the copolymer is
It can be changed greatly depending on the polymerization conditions,
Generally, it is about 70 W/W% or less. In this case, the sugar sulfate ester was determined by converting the sugar content determined according to the sugar determination method described above. The N-glycoside/olefin compound copolymer of the present invention has film-forming properties, and can be molded from its solution into, for example, a film, a sheet, or any other form that can be molded by a drooling method. For example, an N-glycoside/olefin compound copolymer, preferably the sugar content of the copolymer is about
10 W/W% to about 70 W/W%, and the copolymer has an intrinsic viscosity [η] of 25°C DMSO of about 1 or more,
More preferably, the copolymer in which the sugar moiety in the formula (1) macromer forming the copolymer is 4 or more sugars is preferably about 20 g or less, more preferably about 2
g to about 10 g, e.g. dimethylformamide,
Dissolve in 100ml of dimethyl sulfoxide,
The solution is then cast onto a clean flat surface, for example a glass plate, dried under reduced pressure or normal pressure, for example with an infrared lamp, preferably below 50°C, and then the film is peeled off, for example by immersion in water, After further washing with water, this membrane can be immersed in methanol or ethanol and dried to form a membrane. The membrane thus obtained is usually pale yellow to yellowish brown and transparent, and the infrared absorption spectrum of this membrane shows the same pattern as that of the copolymer from which it is made. Furthermore, in the present invention, an N-glycoside/olefin compound copolymer in which X in formula (1)' is a sulfuric ester residue of a reducing sugar or an alkali salt thereof is also a film-forming substance, and Similarly, it can be drool molded. That is, the copolymerized polymer compound preferably has a content of sulfated esterified sugar of about 10 W/W% to about 50 W/W%, and has an intrinsic viscosity [η] of ²⁵ °C. _DMSO is about 0.5
The above copolymerized polymer compound, more preferably, the sugar moiety of the esterified macromer of formula (1) forming the copolymerized polymer compound is 4 or more sugars, and the degree of substitution of the sulfate ester group is per anhydrous monosaccharide unit. About 20 g or less, preferably about 2 g to about 10 g of one or more of the copolymerized polymer compounds, particularly preferably the triethylamine salt of the copolymerized polymer compound, are dissolved in 100 ml of dimethylformamide or dimethyl sulfoxide, and then placed on a clean flat surface, e.g. The solution is cast onto a glass plate and heated to preferably 50° C. or lower using, for example, an infrared lamp under reduced pressure or normal pressure. After drying, the membrane is peeled off by immersing it in water, and after further washing with water, the membrane is immersed in methanol or ethanol and dried. The film thus obtained is pale yellow to yellowish brown and transparent, and the infrared absorption spectrum of this film shows the same pattern as that of the copolymerized polymer compound that is the raw material. Further, a film obtained from an organic amine salt, such as a triethylamine salt, of the copolymerized polymer compound can be easily converted into a sodium salt by immersing it in an aqueous sodium carbonate solution, for example. The membrane thus obtained, particularly the membrane prepared from a copolymerized polymer compound having a sulfate ester group, has excellent anticoagulability. For example, the membrane prepared in Example 10 has m−1 compared to the solidification time of glass.
Blood coagulation time was 3.2 times longer, m-2 was 4.4 times longer, and m-3 was 6.0 times longer. The blood coagulation time was measured by the partial thromboplastin time method using rabbit plasma. That is, 50μ of rabbit plasma and platelin (General
Diagnostics, Division of Warner-Lambert) (manufactured by Warner-Lambert) was added dropwise and the two liquids were mixed by shaking gently. After 3 minutes, drop 50μ of 0.025MCaCl ₂ aqueous solution, shake gently, and start timing at the same time. The time when fibrin fibers are first observed is defined as the blood coagulation time. Hereinafter, several aspects of the present invention will be explained in more detail with reference to Examples. Example 1 3.6 g (20 mmol) of glucose, 80 mg of hydroquinone, 40 ml of ethanol containing V/V% water and p-aminostyrene are mixed and heated under reflux for about 4 hours while stirring. After cooling, it is filtered, concentrated under reduced pressure, and further dried. Next, the residue was stirred with 60 ml of ethyl ether-acetone (2:1 V/V) mixture for about 1 hour, filtered through a glass filter, and dried under reduced pressure after repeating the procedure four times. Yield 5.4g. Elemental analysis C H N Calculated value 59.77% 6.81% 4.98% Analytical value 59.60% 6.95% 4.88% ¹³ C-NMR spectrum: Shown in FIG. IR: Spectrum: Shown in Figure 2. Example 2 Hydrous maltose (C ₁₂ H ₂₂ O ₁₁・H ₂ O) 3.6 g (10
mmol), hydroquinone 180 mg, methanol 36
ml, 2MH ₂ SO ₄ 36μ and p-aminostyrene
2.4 g (20 mmol) are mixed and heated under reflux for about 2 hours while stirring. After cooling, if any insoluble matter is present, it is filtered, concentrated under reduced pressure, and further dried. The solid content was then stirred for about 1 hour in 60 ml of a 2:1 (V/V) mixture of ethyl ether and acetone, filtered through a glass filter, and dried under reduced pressure after repeating the procedure four times. yield
4.2g. Elemental analysis C H N Calculated value 54.17% 6.59% 3.16% Analytical value 54.23% 6.67% 3.11% ¹³ C-NMR spectrum: Shown in FIG. 3. IR: Spectrum: Shown in Figure 4. Example 3 4.54 g (7 mmol) of dextran with an average molecular weight of 64.9 and 60 mg of hydroquinone were dispersed in 30 ml of DMF, then 30 μ of 2MH ₂ SO ₄ and 3.36 g (28 mmol) of p-aminostyrene were added, and the mixture was stirred for 45 min.
Keep at ℃~50℃ for 3 hours. After cooling, add 160 ml of a 1:3 (V/V) mixture of ethanol and ethyl ether,
The precipitate is centrifuged. The precipitate obtained was dissolved in 15 ml of dimethyl sulfoxide and then dissolved in 160 ml of a 1:3 (V/V) mixture of ethanol-ethyl ether.
is added and the precipitate is centrifuged. The precipitate is a 1:3 (V/V) mixture of ethanol and ethyl ether.
Stir in 60 ml for about 30 minutes, filter and filter three times, then dry under reduced pressure. Yield: 5.2g. Elemental analysis N Calculated value 1.86% Analytical value 1.90% ¹³ C-NMR spectrum: Shown in Figure 5. IR: Spectrum: Shown in Figure 6. Example 4 4.1 g (3.2 mmol) of dextran with an average molecular weight of 1285 and 70 mg of hydroquinone were dissolved in a mixed solvent of 21 ml of dimethylformamide and 14 ml of water, and then
Add 70 µ of 2MH ₂ SO ₄ aqueous solution and 2.3 g (19.2 mmol) of p-aminostyrene and stir for 41~
Keep at 45℃ for 5 hours. After cooling, 170 ml of a 1:2 (V/V) mixture of methanol and ethyl ether was added, and the precipitate was centrifuged. Add 100 ml of :2 (V/V) mixture and centrifuge the precipitate. The obtained precipitate was stirred in an equal volume mixture of methanol and ethyl ether (60 ml) for about 30 minutes, filtered and separated three times, and then dried under reduced pressure. Yield: 4.4g. Elemental analysis N, 1.01% (calculated value), 0.93% (analytical value) IR spectrum: Shown in FIG. Example 5 10.9 g of anhydrous triethylamine sulfate complex was dissolved in a mixed solvent of 15 ml of dimethylformamide and 28 ml of formamide, and the mixture was kept at about 0°C with ice water to obtain the compound of formula (1) in the claims obtained in Example 4. Add 1.7g and stir at about 0°C for 24 hours. Then, 400 ml of an equal amount of acetone-ethyl ether mixture is added and the precipitate is separated. The precipitate is dimethylformamide 10
ml of acetone-ethyl ether 3:1
The operation of adding 100 ml of (V/V) mixed solvent and separating the precipitate was repeated three times. Next, this precipitate was stirred with 60 ml of ethyl ether for 1 hour, filtered and filtered three times, and then dried under reduced pressure. Yield: 4.4g.
S content, 11.7 W/W% (average degree of substitution per anhydrous monosaccharide unit, 1.86). IR: Spectrum: Shown in Figure 8. Example 6 A series of copolymerization experiments shown in Table 1 were conducted. That is, in a polymerization tube, a predetermined amount of the compound of formula (1) (abbreviated as SAM) synthesized in Example 2 and a predetermined amount of azobisisobutyronitrile corresponding to 0.5 mol% of the total monomer amount were added. of dimethyl sulfoxide (abbreviated as DMSO), then add a predetermined amount of acrylonitrile (abbreviated as AN), cooled to about -78°C, degassed several times, and melt-sealed. 60±
Polymerize at 0.5℃ for a specified time. After cooling in ice water, the package is opened, the polymerization system is diluted with dimethyl sulfoxide if necessary, methanol is added in an amount four times the amount of dimethyl sulfoxide, and the precipitate is separated. The obtained precipitate was redissolved in 5 to 15 ml of dimethyl sulfoxide, 0.05 to 0.1 ml of saturated saline was added, then 4 times the amount of methanol as dimethyl sulfoxide was added, and the precipitate was separated three times. Repeat several times. For this separation operation, filtration or centrifugation using a glass filter or the like is sufficient. Next, the precipitate was stirred in 60 ml of methanol, and the filtering operation was repeated three times, followed by drying under reduced pressure.

[Table] Here, the sugar content refers to the sugar content in the obtained copolymer. Moreover, [η] is the intrinsic viscosity number at 25°C in dimethyl sulfoxide. ¹³ C-NMR spectrum (solvent DMSO-D ₆ ; concentration 6%; room temperature; 25 MHz): Shown in FIG. IR spectrum: Shown in Figure 10. Example 7 A series of copolymerization experiments shown in Table 2 were conducted. That is, in a polymerization tube, a predetermined amount of the compound of formula (1) (abbreviated as SAD [4]) synthesized in Example 3 and azobisisobutyronitrile corresponding to 0.5 mol% of the total monomer amount were added. Weigh out and dissolve in a predetermined amount of dimethyl sulfoxide (abbreviated as DMSO).
Then a predetermined amount of acrylonitrile (abbreviated as AN)
is added, cooled to approximately -78°C, degassed several times, and melt-sealed. Polymerize at 60±0.5℃ for a specified time. After cooling in ice water, the package is opened, the polymerization system is diluted with dimethyl sulfoxide if necessary, methanol is added in an amount three times the amount of dimethyl sulfoxide, and the precipitate is separated. The obtained precipitate was dimethyl sulfoxide 5
Re-dissolve the precipitate in ~15 ml, add 0.05-0.1 ml of saturated saline, then add 3 times the amount of methanol as dimethyl sulfoxide, and repeat the operation 3 times to separate the precipitate.
Repeat several times. Next, the precipitate was stirred in 60 ml of methanol, filtered and filtered three times, and then dried under reduced pressure.

[Table] Here, the sugar content refers to the content of sugar in the obtained copolymer. [η] is the intrinsic viscosity number at 25°C in dimethyl sulfoxide. Example 8 A series of copolymerization experiments shown in Table 3 were conducted. That is, the claims synthesized in Example 4 in the polymerization tube
A predetermined amount of the compound of formula (1) (abbreviated as SAD [8]) and azobisisobutyronitrile corresponding to 0.5 mol% of the total monomer amount are weighed out, and a predetermined amount of dimethyl sulfoxide (abbreviated as DMSO) is weighed out. ) dissolves in
Then a predetermined amount of acrylonitrile (abbreviated as AN)
is added, cooled to approximately -78°C, degassed several times, and melt-sealed. Polymerize at 60±0.5℃ for a specified time. After cooling in ice water, open the package, dilute the polymerization system with dimethyl sulfoxide if necessary, add methanol in an amount 2.5 times the amount of dimethyl sulfoxide, and separate the precipitate. The obtained precipitate was redissolved in 5 to 15 ml of dimethyl sulfoxide, and 0.05 to 0.1 ml of saturated saline was added.
The operation of adding dimethyl sulfoxide, then adding methanol in an amount 2.5 times the amount of dimethyl sulfoxide, and separating the precipitate is repeated three times. Then, add 60ml of methanol to the precipitate.
After stirring in a vacuum chamber, the procedure of filtering and filtering was repeated three times, followed by drying under reduced pressure.

[Table] Here, the sugar content refers to the sugar content in the obtained copolymer. [η] is the intrinsic viscosity number at 25°C in dimethyl sulfoxide. Example 9 A series of copolymerization experiments shown in Table 4 were conducted. That is, the claims synthesized in Example 5 to the polymerization tube
Weigh out a predetermined amount of the compound of formula (2) (abbreviated as SAD-S) and azobisisobutyronitrile corresponding to 0.5 mol% of the total monomer amount, and add a predetermined amount of dimethyl sulfoxide (abbreviated as DMSO). dissolve in
Acrylonitrile (abbreviated as AN) and styrene (abbreviated as St) are then added, cooled to about -78°C, degassed several times, and melt-sealed. Polymerize at 60±0.5℃ for a specified time. After cooling in ice water, open the package, dilute the polymerization system with dimethyl sulfoxide if necessary, and then add an ether-methanol mixed solvent (4:1 V/V) in an amount five times that of dimethyl sulfoxide.
Separate the precipitate. Next, in the case of C-31, the precipitate was dissolved in a 2:1 (V/V) mixture of methanol and acetone.
Stir in 50 ml for 2 hours, filter out insoluble matter, repeat the process three times, and then dry under reduced pressure. Another lot was stirred in 50 ml of methanol for 2 hours, the insoluble matter was filtered out, and the procedure was repeated three times, followed by drying under reduced pressure.

[Table] Prevalence rate
IR spectrum (C-32): Shown in FIG. 〃 〃 (C-34): Shown in Figure 12. Example 10 Prepare the following DMSO solution. m-1: 0.33 g of C-32 copolymer of Example 9
Dissolve in 3.6ml of DMSO. m-2: 0.3 g of C-32 copolymer of Example 9 and
0.15 g of polyacrylonitrile having an intrinsic viscosity of 2.18 at 25° C. in DMSO is dissolved in 5.0 ml of DMSO. m-3: 0.45 g of C-33 copolymer of Example 9
Dissolve in 4.0ml of DMSO. 1.5 ml of each of these DMSO solutions is thinly cast onto a glass plate and irradiated with an infrared lamp at a temperature below 45°C. After completely drying, it is immersed in a 2.5% aqueous sodium carbonate solution for 15 minutes, then washed three times with water, further washed three times with methanol, and dried under reduced pressure. Obtain a transparent film approximately 10 cm in diameter. IR spectrum: Shown in FIG. 13.

[Brief explanation of the drawing]

In the accompanying drawings, Figure 1 shows the compound obtained in Example 1.
¹³ C-NMR spectrum, Figure 2 is its IR spectrum, and Figure 3 is ¹³ C-NMR spectrum of the compound obtained in Example 2.
-NMR spectrum diagram, Figure 4 is its IR spectrum diagram, Figure 5 is ^{the 13} C- of the compound obtained in Example 3.
NMR spectrum diagram, Figure 6 is the IR spectrum diagram, Figure 7 is the IR spectrum diagram of the compound obtained in Example 4, Figure 8 is the IR spectrum diagram of the compound obtained in Example 5, and Figure 9 is the IR spectrum diagram of the compound obtained in Example 5. of the compound obtained in Example 6.
¹³ C-NMR spectrum diagram, Figure 10 is its IR spectrum diagram, Figures 11 and 12 are Example 9.
IR spectrum diagram of the compound obtained in
The figure is an IR spectrum diagram of the compound obtained in Example 10.

Claims (1)

[Claims] 1 The following formula (1)' However, in the formula, R ₁ is [formula] - (CH ₂ -) _n [where m is an integer from 1 to 5] and [formula] [where n is an integer from 1 to 10]. ^R2 represents a group selected from the group consisting of a hydrogen atom and _CH3 ; and X represents a reducing sugar residue, its sulfate ester residue, and an alkali salt of the ester residue. The structural unit represented by represents a group selected from the group, and the following table (2)′ However, in the formula, R ³ , R ⁴ and R ⁵ each represent a group selected from the group consisting of a hydrogen atom and CH ₃ ; R ⁶ represents ^a group selected from the group consisting of a hydrogen atom and CH ₃ ; ₁₈ alkyl group, _C1 - _C5 hydroxyalkyl group, cyclohexyl group, C1 _{- C5 aminoalkyl group, di(C1-C2 alkyl )} amino( _C1 - _C5 alkyl) group, glycidyl group , tetrahydrofuran group, benzyl group and -(CH ₂ CH ₂ O-) _y
Indicates a group selected from the group consisting of CH ₂ CH ₂ O group (y = positive number from 1 to 10)],
[Formula] [Here, R ⁸ represents a hydrogen atom or a C ₁ to C ₄ alkyl group, and the two R ^8s may be the same or different], -CN, -OH,
[Formula] [Here, R ⁹ represents a C ₁ to C ₃ alkyl group],
[Formula] [Formula] [Formula] [Formula] and [Formula] [wherein R ¹⁰ represents a C ₁ to C ₅ alkyl group] A structural unit represented by , the sugar or sugar ester content is within the range of 10 to 87 w/w%, and the intrinsic viscosity at 25°C in dimethyl sulfoxide is 0.16 to 2.65.
A substantially linear N-glycoside/olefin compound copolymer having a reducing sugar residue in its side chain, which falls within the range of 2. The copolymer according to claim 1, wherein in the above (1)', R ¹ is [Formula] or -(CH ₂ -). 3 In the above formula (1)', the reducing sugar residue of X is a residue of a reducing monosaccharide selected from the group consisting of xylose, ribose, glucose, galactose, and mannose; Residues of reducing oligosaccharides selected from the group consisting of maltotriose, manninotriose, cellotriose, isomaltotetraose and cellotetrose; or from starch, cellulose, dextran, pullulan, curdlan and partial hydrolysates thereof The copolymer according to claim 1, which is a residue of a reducing polysaccharide selected from the group consisting of: 4 The following formula (1) However, in the formula, R ¹ is [formula] - (CH ₂ -) _n [where m is an integer from 1 to 5] and [formula] [where n is an integer from 1 to 10]. ^R2 represents a group selected from the group consisting of a hydrogen atom and _CH3 ; and X represents a reducing sugar residue, its sulfate ester residue, and an alkali salt of the ester residue. An N-glycoside vinyl compound represented by, which represents a group selected from the group, and the following formula (2) However, in the formula, R ³ , R ⁴ and R ⁵ each represent a group selected from the group consisting of a hydrogen atom and CH ₃ ; R ⁶ represents ^a group selected from the group consisting of a hydrogen atom and CH ₃ ; ₁₈ alkyl group, _C1 - _C5 hydroxyalkyl group, cyclohexyl group, C1 _{- C5 aminoalkyl group, di(C1-C2 alkyl )} amino( _C1 - _C5 alkyl) group, glycidyl group , tetrahydrofuran group, benzyl group and -(CH ₂ CH ₂ O-) _y
Indicates a group selected from the group consisting of CH ₂ CH ₂ OH group (y = integer from 1 to 10)],
[Formula] [Here, R ⁸ represents a hydrogen atom or a C ₁ to C ₄ alkyl group, and the two R ^8s may be the same or different], -CN, -OH,
[Formula] [Here, R ⁹ represents a C ₁ to C ₃ alkyl group],
[Formula] [Formula] [Formula] A polymerizable olefin represented by a group selected from the group consisting of [Formula] and [Formula] [where R ¹⁰ represents a C ₁ to C ₅ alkyl group] based compound and the N-
A method for producing an N-glycoside/olefin compound copolymer, which comprises reacting the glycoside vinyl compound at a ratio of 0.2 to 400 moles in the presence or absence of a polymerization initiator.