JPH10218903A - Sugar chain polymer compound, its synthetic method and decomposition method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic method and a decomposition method of a sugar chain polymer composition which is recyclable and shows biodegradability. SOLUTION: This sugar chain polymer compound has at least two kinds of repetition units and at least one of them contains a sugar, and at least one of its decomposition products is a sugar, a polymer compound having the sugar as its main chain or at least one of the polymer compounds containing the sugar in its main chain, and it keeps a desirable structure at the end of its synthetic reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sugar chain polymer compound which can be used as various structural materials, molded articles, or electric or optical functional materials, and a method for synthesizing and decomposing the same. In particular, a method of synthesizing a sugar chain polymer compound having a desired shape at the time when the synthesis reaction is completed, and the same or different sugar chain polymer compound as before decomposition by re-polymerizing a decomposition product generated by decomposition. The present invention relates to a sugar chain polymer compound that can be used and a method for decomposing the same.

[0002]

2. Description of the Related Art The pollution of the global environment has become evident, and it has become necessary to consider not only industrial waste but also household waste as well as the environment. Various plastic resins, which are industrial materials, are no exception, and research and development of new materials that reduce the burden on the environment are required.

Conventionally, plastic resins have been reduced in environmental load mainly by thermal decomposition or chemical decomposition to reduce the molecular weight and reused again as a raw material for resin compositions. Landfill has been processed. As an example of reuse, for example, polystyrene is recovered as a styrene monomer or a dimer by catalytic cracking using a solid base catalyst, and supplied as a raw material for repolymerization. Polyethylene terephthalate is decomposed into dimethyl terephthalate, ethylene glycol, terephthalic acid, etc. by the methanolysis method using methanol, the glycolysis method using ethylene glycol, and the hydrolysis method using acids and bases. Used as a raw material and other chemicals. However, in order to extract a reusable component, the decomposition product needs to be separated and purified in many steps, and the cost is high. Further, polypropylene, polyethylene and the like are decomposed by catalytic cracking using a catalyst, and are also used as boiler fuel.

[0004] However, not only the above-mentioned resins but also general resin compositions are used in a wide range of areas, and they often contain various additives because of their various uses. Therefore, even if an attempt is made to collect the resin, it is impossible at present to collect all of the resin, resulting in a large cost.
In addition, the recovered resin often contains an additive and the like, so that it is often impossible to separate the resin for the process of reuse.

[0005] Further, incineration treatment involves the emission of carbon dioxide, which causes global warming and, if the resin contains halogen, sulfur or nitrogen elements, causes air pollution by harmful gases. Maybe. When landfilled, most resins currently in practical use remain in a long-term state. During this period, additives and the like flow out, which is one of the causes of soil contamination.

[0006] From the above, regarding the reuse of the recovered resin, the development of a resin composition that is more easily used has been awaited. In addition, development of a resin composition that does not adversely affect the global environment or the like when it is finally disposed of is also awaited. For this purpose, biodegradable resin compositions have been actively developed. Biodegradable resins are roughly classified into three types: microbial products, plant-derived natural products, and chemically synthesized products.

[0007] Examples of microbial products include Alicag
A copolymer of D-3-hydroxybutyrate and 3-hydroxyvalerate by enes Eutrophus is commercially available under the trade name Biopol. It is biodegraded by microorganisms. Natural products include collagen, gelatin, starch, cellulose, chitosan and the like. These are themselves biodegradable. Further, a mixture of starch and modified polyvinyl alcohol, a cellulose ester obtained by chemically modifying cellulose, a complex of cellulose and chitosan, and the like are also known. Among the chemically synthesized products, water-soluble polymers such as polyvinyl alcohol and polyethylene glycol, and aliphatic polyesters such as polyethylene adipate and polycaprolactone exhibit biodegradability. These biodegradable resin compositions are preferable materials compared to conventional non-biodegradable polyethylene, polypropylene, vinyl chloride resin, etc., at the time of landfill treatment, but have sufficient performance with respect to collecting and reusing the resin. Cannot be said to have.

[0008] Sugars include monosaccharides such as glucose, sucrose,
It is a well-known fact that oligosaccharides such as sugar beet honey and polysaccharides such as starch and cellulose exist widely in nature such as animals, plants and microorganisms, and are degraded by various enzymes. It is. But,
The use of a resin composition composed only of sugar is limited even from examples of cellulose and starch, and is not suitable as a general-purpose resin composition.

Further, in order to process a conventional resin composition into a desired shape, it is usually necessary to perform molding after synthesizing the resin composition. For example, in order to form a sheet, processing by a roll press or the like is necessary. Or,
It is also common practice to perform hot pressing in a mold having a desired shape. The biodegradable resin composition is used after being subjected to the same processing. Such post-synthesis processing also increases costs, and development of a synthesis method that does not require post-synthesis processing or that can reduce the number of processing steps is also awaited.

The biodegradable resin composition is usually landfilled, but few attempts have been made to actively reuse it before landfill disposal. In particular, a decomposition method for actively decomposing the resin and efficiently reusing the decomposition product is also important. As described above, in some resins, decomposed products are reused, but many decomposed products cannot be used, and the utilization rate of the decomposed products is small. For this reason, the development of a decomposition method that enables the decomposition products to be more effectively reused is also awaited.

[0011]

As described above, according to the present invention, a desired shape is obtained at the time when the synthesis reaction is completed, and when the sugar chain polymer compound is decomposed,
It is an object of the present invention to provide a sugar chain polymer compound which is capable of easily obtaining a polymerizable decomposition product and which is biodegradable even when it is buried, and a synthesis method and a decomposition method thereof.

[0012]

That is, a first invention of the present invention relates to a sugar chain polymer compound having at least two kinds of repeating units, wherein at least one of the repeating units contains a sugar, and At least one of the products is at least one of the saccharide, a high molecular compound having the saccharide as a main chain, or a high molecular compound having the saccharide in the main chain, and is desired when the synthesis reaction is completed. A sugar chain polymer compound having the following shape: It is preferable that at least one of the products generated by the decomposition reaction is a polymerizable substance.

The second invention of the present invention has at least two types of repeating units, and at least one of the repeating units
In a method for synthesizing a sugar chain polymer compound containing a sugar as a species, a reactant composed of a repeating unit or a constituent material thereof is prepared independently, and they are reacted with a catalyst having a desired shape to obtain a desired shape. A method for synthesizing a sugar chain polymer compound, characterized in that the sugar chain polymer compound is formed.

In the above method for synthesizing a sugar chain polymer compound, the catalyst is preferably an enzyme immobilized on the surface of a substrate having a desired shape. Further, in the method for synthesizing a sugar chain polymer compound, a catalyst is first supplied to a substrate surface having a desired shape, and then a reactant composed of a repeating unit or a constituent material thereof is supplied as a unit process. Preferably, it is repeated one or more times.

A third invention of the present invention has at least two types of repeating units, and at least one of the repeating units
In a method for decomposing a sugar chain polymer compound containing a sugar, the decomposition is performed using a catalyst in a solvent, and the decomposition is performed so that at least one of the decomposition products has a polymerizable functional group. This is a method for decomposing a characteristic sugar chain polymer compound.

In the method for decomposing a sugar chain polymer compound, at least one of repeating units or sugar units constituting the sugar chain polymer compound by cleaving a specific chemical bond in the sugar chain polymer compound by the catalyst. It is preferable to produce a product that can be a repeating unit of the chain polymer compound. Further, the catalyst is preferably an enzyme.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The sugar chain polymer compound of the present invention is a sugar chain polymer compound having at least two kinds of repeating units, wherein at least one of the repeating units contains a sugar, and At least one of the sugars being:
A sugar chain having at least one of a polymer compound having the sugar as a main chain or a polymer compound having the sugar in the main chain, and having a desired shape at the time when the synthesis reaction is completed. It is a polymer compound.

The sugar chain polymer compound of the present invention is, for example, a cellulose, oligosaccharide, or polysaccharide main chain, and an aliphatic polyester such as polyvinyl alcohol, polyethylene glycol, polyethylene adipate, or polycaprolactone in a side chain. Monomers, oligosaccharides, which have a sugar chain polymer compound and an oligosaccharide as one type of repeating unit, and the other repeating units are aliphatic compounds such as polyvinyl alcohol, polyethylene glycol, polyethylene adipate, and polycaprolactone. And copolymers of repeating units of an ester reaction product of a carboxylic acid, an aliphatic carboxylic acid, an unsaturated carboxylic acid and an aromatic carboxylic acid, and a copolymer of an oligosaccharide or polysaccharide with various amino acids.

The aliphatic carboxylic acids include butyric acid, valeric acid, caproic acid, lauric acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, cyclohexanehexacarboxylic acid, polymaleic acid, And polyacrylic acid.

As unsaturated carboxylic acids, acrylic acid,
Methacrylic acid, oleic acid, maleic acid, fumaric acid,
Aconitic acid and the like. Examples of the aromatic carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like. Monosaccharides include glucose, galactose,
Mannose, glucosamine and the like.

Oligosaccharides are usually those in which about 2 to 10 monosaccharides are bound, and if more than one monosaccharide is bound, they are classified as polysaccharides. Oligosaccharides are classified into homooligosaccharides composed of a single saccharide and heterooligosaccharides composed of two or more monosaccharides. Representative oligosaccharides include disaccharides such as maltose, cellobiose, lactose, isomaltose, sucrose, and chitobiose;
Examples of trisaccharides and tetrasaccharides such as cellotriose, maltotriose, and raffinose include stachyose, cellotetraose, cellopentaose, maltotetraose, and maltopentaose. As polysaccharides,
In addition to cellulose, starch, and glycogen, fructan, galactan, mannan, and porglucosamine are exemplified.

The repeating units may be directly bonded, or may be a cross-linking agent or various functional substances (for example, a compound having photochromic properties, a compound having photodecomposition properties, a compound having a non-linear optical effect, etc.). It goes without saying that they may be connected via a) or the like. Further, additives such as various pigments and plasticizers may be included. The sugar chain polymer compound of the present invention can be used as various structural materials, molded articles, or electric or optical functional materials.

The sugar chain polymer compound of the present invention preferably has a weight average molecular weight of 1,000 to 1,000,000.
The range is about 0. Next, a method for synthesizing the sugar chain polymer compound of the present invention will be described. The sugar chain polymer compound of the present invention is synthesized using a solid surface having a desired shape, and is obtained in the shape of the solid surface at the end of the synthesis.

The synthesis of a sugar chain polymer compound as described above is performed by
Synthesized by a chemical reaction using a catalyst. Any catalyst may be used as long as it is a polymerization catalyst for polymerizing the repeating unit constituting the sugar chain polymer compound. The catalyst is molded into a desired shape, processed, or fixed on a substrate of a desired shape by coating or bonding, and the catalyst is housed in a reaction vessel to cause a polymerization reaction on the catalyst surface. When the degree of polymerization increases, the reaction product precipitates as a solid on the catalyst surface.When the desired degree of polymerization is reached, the reaction product is taken out from the catalyst surface to capture the shape of the catalyst or the substrate on which the catalyst is fixed. A sugar chain polymer compound is obtained.

FIG. 1 is a principle diagram showing an example of a method for synthesizing a sugar chain polymer compound of the present invention. As an example of a method for synthesizing the sugar chain polymer compound of the present invention, for example, the principle of a synthesis method for synthesizing a sheet-shaped ester copolymer using oligosaccharides and aliphatic dicarboxylic acids as raw materials will be described with reference to FIG. explain. An organic solvent (for example, pyridine, dimethylformamide, tetrahydrofuran, etc.) is put in the container 1,
A substrate 3 having a hydrolytic enzyme (for example, lipase, prolease, protease, etc.) fixed on the surface thereof is fixed in a hollow manner by a support 5 as shown in FIG. In the organic solvent, the oligosaccharide and the aliphatic dicarboxylic acid are dissolved or dispersed in advance so as to obtain a desired resin composition to obtain a reaction solution 2.
Predetermined temperature (usually 30-60 ° C) depending on the enzyme used
And polymerize. The standard amount of the enzyme used is about 1 to 0.0001 parts by weight of the enzyme per 1 part by weight of the sugar chain polymer compound. During the reaction, the solution is stirred by the stirrer 4 so that the reaction proceeds uniformly. Since the reaction proceeds via the enzyme immobilized on the substrate 3, the sugar chain polymer compound precipitates on the substrate as the polymerization proceeds. When the desired degree of polymerization is reached, the substrate is taken out of the container and the sugar chain polymer compound is peeled off from the substrate to obtain a sheet-like sugar chain polymer compound having the same size as the area on which the enzyme is immobilized. The reaction time varies depending on the type of the reactant and the enzyme.
A polymer having a molecular weight of about 1,000 to 100,000 can be obtained in about 30 days to about 30 days.

The synthesis conditions may be set depending on the target sugar chain polymer compound, and the catalyst is not limited to the above-mentioned enzymes. For example, a catalyst that can be used in ordinary polymerization reactions such as a metal catalyst, a metal oxide catalyst, and a metal complex catalyst, as long as it can be molded into a desired shape, processed, or fixed to a substrate processed into a desired shape by coating or the like. No restrictions. The material for the substrate on which the catalyst is fixed is not limited as long as it does not hinder the polymerization reaction. The substrate may be constituted by the catalyst itself. There is no limitation on the shape of the catalyst, and the sugar chain polymer compound can be synthesized not only in the above-mentioned sheet shape but also in any shape such as unevenness, hollow, and spherical shape.

The stirring method and stirring speed may be selected in accordance with the solubility of the reactant in the solvent, the shape of the catalyst, and the like. It goes without saying that the reaction atmosphere may be stirred by rotating or vibrating the catalyst itself.

The polymerization reaction is not limited to the above-mentioned organic solution, but may be carried out on the surface of the catalyst in a gaseous state by evaporating the reactants under a reduced pressure atmosphere. In any case, the synthesis conditions may be selected depending on the target sugar chain polymer compound. For example, different reactions such as a gas phase reaction and a reaction in a solvent may be continuously or sequentially repeated. The catalyst is not limited to one type, and a plurality of catalysts may be used simultaneously or sequentially.

Next, a method for decomposing the sugar chain polymer compound of the present invention will be described. In the method for decomposing a sugar chain polymer compound of the present invention, the sugar chain polymer compound of the present invention is decomposed into a reusable state after being used for a predetermined application. For this reason, in the present invention, the activation energy of the decomposition reaction is reduced by using a catalyst, and the decomposition reaction proceeds under milder conditions, thereby suppressing the side reaction of the decomposition.

FIG. 2 is a conceptual diagram showing a method for decomposing a sugar chain polymer compound of the present invention. As an example of the method for decomposing a sugar chain polymer compound of the present invention, degradation of a sugar chain polymer compound synthesized from the above-described oligosaccharide and aliphatic dicarboxylic acid will be described. The basic concept of the decomposition is shown in FIG. In the figure, reference numeral 21 denotes a sugar chain polymer compound of the present invention synthesized using oligosaccharide 23 and aliphatic dicarboxylic acid 22 as synthesis raw materials. Here, the linear structure is shown, but the resin structure is not limited to this. In addition, disaccharide is shown as an oligosaccharide, but this is not limited to disaccharide. In the figure, part A is an ether bond between monosaccharides, and part B is an ester bond formed from a sugar and a carboxylic acid. That is, the sugar chain polymer compound 21 is constituted by repeating ether bonds and ester bonds.

According to the present invention, the ester bond or the ether bond is selectively decomposed to form an aliphatic dicarboxylic acid 22,
It is intended to obtain a decomposed product such as the oligosaccharide 23 or the sugar-containing compound 24. In the case of FIG. 2, the aliphatic dicarboxylic acid 22 and the oligosaccharide 23 of the decomposed product are the sugar chain polymer compound 2
Since it is one repeating unit, it can be used as it is as a polymerization raw material for the sugar chain polymer compound 21.

It is also possible to use the aliphatic dicarboxylic acid 22 or the oligosaccharide 23 of the decomposed product as a resin different from the sugar chain polymer compound 21 or as a raw material for synthesizing other chemical substances. Furthermore, the sugar-containing compound 24 of the decomposition product
Has an OH group derived from a sugar at the molecular terminal, and can be used again as a raw material for polymerization. By polymerizing the sugar-containing compounds 24 together, a sugar chain polymer compound 21 can be obtained.
By reacting 4 with aliphatic dicarboxylic acid 22,
A sugar chain polymer compound having a structure different from that of 21 may be used.

When esterase is used as a decomposition catalyst, the pH of the solution is adjusted to 7.5 to 9.0, and then a decomposing sugar chain polymer compound is added to adjust the temperature to 20 to 55 ° C. At this time, the standard ratio of the sugar chain polymer compound to the enzyme is about 0.001 to 1 part by weight of the enzyme per 1 part by weight of the sugar chain polymer compound. However, the amount of the enzyme used varies depending on the purity of the enzyme used and the origin of the enzyme. The ester bond of the sugar chain polymer compound 21 is selectively cleaved by the enzyme catalyst, and the resulting decomposed products are the oligosaccharide 23 and the aliphatic dicarboxylic acid 22. Enzymes, oligosaccharides and aliphatic dicarboxylic acids can be separated by means such as filtration and column chromatography.

The oligosaccharide and the aliphatic dicarboxylic acid, which are decomposed products, have their ester bonds cleaved, and
The H group and aliphatic carboxylic acid can be used again as a raw material for synthesis because the COOH group is the terminal. In the case of a decomposition product, particularly an oligosaccharide, the molecular weight distribution may be different from that of the initial synthesis raw material depending on the type and purity of the catalyst. Depending on the application, it can be used again as a raw material for synthesis as it is. It can be made the same as the initial component by supplementing the missing molecular weight component if necessary.

The decomposition catalyst is not limited to an enzyme catalyst. For example, when decomposing an esterified resin, a hydrolysis reaction using an acid or an alkali catalyst may be used.

When the decomposed product obtained by decomposition according to the present invention is reused, the handling method is not limited at all, and the handling method may be selected according to the purpose. It goes without saying that the decomposition according to the invention is not restricted to ester and ether bonds. The present invention selectively cuts a specific bond dispersed and present in a sugar chain polymer compound. The bond may be broken not only by an enzyme but also by photolysis using a photocatalyst or thermal decomposition using a solid catalyst.

[0037]

Hereinafter, the present invention will be described in more detail with reference to specific examples.

Example 1 A sugar chain polymer compound was synthesized by the synthesis method of the present invention shown in FIG. 1 is a container, 2 is a reaction solution in which a reactant is dissolved or dispersed, 4 is a stirrer, 5 is a substrate on which a catalyst is attached 3
It is a support base that supports. The legs of the support are provided with holes serving as passages for the reaction solution so that the reaction solution is uniformly stirred by the stirring.

In this embodiment, cellobiose and bis (2,
2,2-trifluoroethyl) adipate was added to a dimethylformamide solvent at a molar ratio of 2: 1 to prepare a reaction solution. The substrate 3 was provided with a sheet in which lipase was immobilized on porous polypropylene. Lipase having a purity of 30 to 80% is added in an amount of 0.1 to 500 per gram of porous polypropylene.
Fixed at a rate of mg. This polypropylene is 3cm
It is a sheet having a size of × 2 cm. After blowing nitrogen gas into the reaction solution and filling the space 6 above the reaction solution in the reaction vessel 1 with nitrogen gas, the reaction solution was kept at 45 ° C. by a heating device (not shown). The stirring speed is 250 rpm.
High performance liquid chromatography monitored the decrease in signal intensity of cellobiose or bis (2,2,2-trifluoroethyl) adipate. After the start of the reaction, 10
Film formation was observed on the catalyst of the substrate in 15 days, and thereafter, the reaction was stopped when the signal of the raw material (cellobiose or bis (2,2,2-trifluoroethyl) adipate) became about 1/7. . The reaction was stopped by removing the substrate 3 from the reaction solution and peeling off the film formed from the substrate.

The obtained sugar chain polymer compound was a sheet having the same size as the porous polypropylene on which the enzyme was immobilized. From the infrared and NMR spectra of this resin, it was confirmed that the obtained resin was an esterified polymer in which cellobiose and bis (2,2,2-trifluoroethyl) adipate were reacted by a transesterification reaction. The molecular weight was about 2000 to 5000 as measured by GPC using polystyrene standards. In the structure of the obtained resin, an ester bond was formed mainly at the OH group at the 6-position of the glucopyranose ring from the NMR spectrum. This is considered to indicate that the obtained sugar chain polymer compound has a substantially linear structure.

When the reaction was continued for about 10 days without stopping in 10 to 15 days, the appearance hardly changed, but the NMR spectrum showed that the esterification reaction was found to occur even at the 2- and 3-positions of the glucopyranose ring. Admitted. This is considered to indicate that the molecular structure of the sugar chain polymer compound produced by increasing the reaction time has changed from a linear structure to a partially branched structure. The molecular weight was about 3000 to 6000.

The porous polypropylene on which the enzyme is immobilized is
For example, when the sugar chain polymer compound was cut out into a U-shape and allowed to react, the resulting sugar chain polymer compound became a U-shape. Although a sugar chain polymer compound may be generated in places other than the polypropylene, the sugar chain polymer compound was easily separated by removing the substrate 3 from the reaction solution.

The sugar chain polymer compound synthesized in this manner can be decomposed by an esterase enzyme regardless of the molecular structure, and it is confirmed by liquid chromatography that cellobiose and adipic acid are contained in the decomposition product. Was confirmed. This indicates that the sugar chain polymer compound of the present invention is biodegradable.

Also, when cellobiose is cellotriose, cellotetraose or cellopenterose, a sugar chain polymer compound containing about 10 to 30 saccharides in the molecule can be obtained, which is also used as an enzyme. The same shape was obtained.

Example 2 Cellulose having a molecular weight of about 10,000 to 100,000 was reacted in the same manner as in Example 1. However, for the synthesis, a proleather enzyme immobilized on alumina was used. For the enzyme, a groove having a meandering structure was formed in a glass plate (Corning 7059), and alumina fixed with the enzyme was spread in the groove. The solvent is pyridine, and cellulose and bis (2,2,2-
Trichloroethyl) adipate in a weight ratio of 100: 4
And stirred. The reaction temperature is 45 ° C. Five days later, when the glass plate was taken out of the reaction solution, a sugar chain polymer compound having a meander structure was obtained. From the NMR spectrum, it was confirmed that in this sugar chain polymer compound, at least the 6-position OH group of the glucopyranose ring constituting cellulose was esterified. The molecular weight is 2
0000 to 300,000.

When this resin was treated with an esterase enzyme, cellulose and adipic acid were gradually produced. After separating the enzyme by filtration, the digestion solution was dried, and adipic acid and cellulose could be separated from the solid obtained by ethanol extraction. The molecular weight of the cellulose obtained was almost the same as before synthesis, which could be used again for the reaction with adipic acid, aconitic acid, polymaleic acid or their esters. Further, when the sugar chain polymer compound obtained by the synthesis method of the present invention was buried in soil,
In one year, it was disassembled until its original shape was lost.

Example 3 A reaction was carried out in the same manner as in Example 2 using chitin having a molecular weight of about 2,000 to 200,000. In the obtained sugar chain polymer compound, the OH group at the 6-position of N-acetyl-D-glucosamine is esterified, and the molecular weight is 4000 to 1
It was about 000000. The shape of the obtained resin was the same as the shape of the enzyme catalyst. This resin was also a biodegradable resin as in Example 2.

Example 4 FIG. 3 is a conceptual diagram showing another example of the method for synthesizing the sugar chain polymer compound of the present invention. A sugar chain polymer compound was synthesized by the synthesis method of the present invention shown in FIG. The inside of the vacuum chamber 14 is depressurized by a vacuum exhaust device (not shown). In this device, 2
The pressure was reduced to × 10 ⁻⁶ Torr. Glucose and bis (2,
2,2-trifluoroethyl) adipate and titanium tetraisopropoxide were placed in independent containers 7, 8,
9 and heated by a heating device 10 on the outer periphery of the container to evaporate. Note that containers other than glucose are liquid at room temperature, so that the containers 8 and 9 are provided outside the vacuum container 14 and the gas introduction pipe 11 is provided.
, Vaporized vapor was introduced into the vacuum vessel. Containers 7, 8, 9
May be arranged either outside or inside the vacuum container depending on the material used. Next, the shutters 12, 13
Allows the vapors from the containers 7, 8, 9 to be alternately
To be deposited.

In this embodiment, first, the shutter 13 for the substrate 3 is opened, and only the shutter of titanium tetraisopropoxide as a catalyst is opened to evaporate the catalyst. Then, the shutter for the catalyst is closed, and the shutters of glucose and bis (2,2,2-trifluoroethyl) adipate, which are the reactants, are opened. The time during which the shutter is open is approximately 0.0 l of catalyst based on the total amount of reactant evaporating.
It controls so that it may become wt%. The amount of the evaporated vapor can be easily measured by a film thickness meter using a quartz oscillator near the substrate and / or in the vicinity of the shutter 13, an absorption analysis using a laser beam, or the like.

The catalyst and the reactants are alternately vaporized repeatedly as many times as necessary. The substrate 3 is fixed to the substrate holder 15 using a glass plate (here, Corning 7059 glass is used). A heater is embedded in the substrate holder 15 so that the substrate can be heated while rotating. In this embodiment, the substrate is 100 to 150
C. and spun at 10-30 rpm. Container 7,
The heaters of the heating devices 10 of 8 and 9 were controlled to evaporate the catalyst and the reactant at 2 ° / sec and 4 ° / sec, respectively. The shutter was repeatedly opened and closed 30 times to form a sugar chain polymer compound on the substrate.

The obtained sugar chain polymer compound was obtained in the same shape as the glass plate of the substrate. If the glass plate was flat, a sheet-shaped sugar chain polymer compound was obtained. If the glass plate was spherical, a spherical sugar chain polymer compound was obtained. . When a mask having a desired pattern formed thereon was placed on a glass plate, the same pattern of the sugar chain polymer compound as the mask pattern was obtained.

From the infrared and NMR spectra of the sugar chain polymer compound peeled from the glass plate, the obtained resin was a substance in which the OH group of glucose was esterified, It was a substance reacting at the position. In addition, when the molecular weight was measured by GPC, it was a mixture in which at least two kinds of substances having about 800 and 1200 in terms of polyethylene glycol were present.

Examples 5 to 9 Cellobiose, cellotriose, cellotetraose, cellopentaose and cellohexaose, which are oligosaccharides from cellulose, were reacted with bis (2,2,2-trifluoroethyl) adipate to give sugars. It was a chain polymer compound. In the synthesis, a substrate in which an enzyme (pro-leather or the like) fixed to alumina is arranged in a plane on a glass plate (in this example, alumina having the enzyme fixed to an area of 2 cm × 2 cm and spread to a thickness of 1 mm) in a pyridine solution The oligosaccharide and bis (2,2,2-trifluoroethyl) adipate were reacted in a nitrogen atmosphere at a molar ratio of 2: 1.
A white film was deposited on the substrate, and the white film was removed from the substrate to obtain a sheet-like sugar chain polymer compound.

The sugar chain polymer compound is an esterified product of an oligosaccharide and bis (2,2,2-trifluoroethyl) adipate, and is characterized by a C ＝ O stretch derived from an ester bond in an infrared absorption spectrum. It was confirmed from the observation of the vibration. The molecular weight was determined by GPC measurement using polystyrene as a standard. In each case, about 10 to 30 sugars were contained in the molecule. From the NMR spectrum, it was confirmed that the esterification reaction mainly occurred at the OH group at the 6-position of the glucopyranose ring in each oligosaccharide.

When the sugar chain polymer compound thus obtained was decomposed with an esterase enzyme, oligosaccharide, adipic acid and adipic acid ester having a sugar at a terminal were confirmed in the decomposition solution. Confirmation of the decomposition product was performed by liquid chromatography. These degradation products could be used again for the synthesis of polyesters containing oligosaccharides.

Examples 10 to 14 In the same manner as in Example 5, an oligosaccharide from cellulose was transesterified with pimelic acid diester to synthesize a sugar chain polymer. In this case, lipase was used as the enzyme, and the enzyme used was immobilized on foamed polyethylene. The obtained sugar chain polymer compound could be obtained in the same sheet shape as the polyethylene on which the enzyme was immobilized. From the infrared and NMR spectra, it was confirmed that the obtained sugar chain polymer compound was an ester condensed compound of oligosaccharide and pimelic acid diester. These molecular weights are
Determined by 5000 to 10 in terms of polystyrene
It was about 000.

When the obtained sugar chain polymer compound was decomposed with an esterase enzyme, it was confirmed by GC-MS (gas chromatography) that oligosaccharides, pimelic acid and other low molecular weight substances were formed in the decomposition solution. Mass spectrometry). Many of the low molecular weight substances appear to be sugar pimelic esters containing sugar at the end. Among these decomposed products, at least the oligosaccharide could be used again as a raw material for resin synthesis. Also. Pimelic acid was also mixed with the oligosaccharide and melted to obtain a polyester resin. Further, pimelic acid is dimethyl esterified by, for example, an esterification reaction with methanol,
It could also be used as a raw material for synthesizing the sugar chain polymer compound of the present invention.

Examples 15 and 16 The sugar chain polymer compound of this example was synthesized from cellulose having a molecular weight of about 10,000 to 100,000, and chitin and bis (2,2,2-trifluoroethyl) adipate. Cellulose and chitin used were mechanically crushed in advance. As the catalyst, one obtained by fixing pro-leather to porous polyethylene was used. A glass plate on which the polyethylene was cut into a meander structure was placed in pyridine, and cellulose, chitin and bis (2,2,2-trifluoroethyl) adipate were added to the pyridine in a weight ratio of 100: 4: 110. 45 ° C
And stirred. Five days later, when the glass plate was taken out of the reaction solution, a sugar chain polymer compound was formed on the polyethylene on which the meander-structured enzyme was immobilized, and could be easily peeled off.

The NMR spectrum of this resin was measured. Cellulose was at the 6-position of glucose, and chitin was N-acetyl-
It was confirmed that the OH group at the 6-position of D-glucosamine was esterified. The molecular weight of the obtained sugar chain polymer compound was 20,000 to 300,000, and a sugar chain polymer compound having a molecular weight of 2 to 3 times that of the cellulose chain and chitin before the reaction was obtained.

When these sugar chain polymer compounds were treated with an esterase enzyme, cellulose or chitin and adipic acid were gradually produced as decomposition products. After the enzyme was separated by filtration, the digestion solution was dried, and riadipic acid was easily separated from the solid obtained by ethanol extraction. Cellulose and chitin produced by decomposition have almost the same molecular weight as before synthesis, and they are used again as raw materials for the reaction with bis (2,2,2-trifluoroethyl) adipate, aconitic acid, and polymaleic acid. We were able to. Further, when the sugar chain polymer compound of this example was buried in soil, it was decomposed in one year until the initial shape was lost. This indicates that the sugar chain polymer compound of the present invention has biodegradability.

Example 17 A method for decomposing the sugar chain polymer compound shown in Example 5 will be described.
It was shown in Example 5 that this resin had a structure in which cellobiose and adipic acid were ester-bonded. Then, this resin was decomposed by Meiselase (Meiji Seika). Decomposition conditions are 0.1 to 0.1 per gram of the sugar chain polymer compound.
The pH of the aqueous solution to which 0.05 g of the enzyme was added was adjusted to 4 to 5 with a citrate buffer solution, and the decomposition temperature was set to 40 to 45 ° C.
After 48 hours, the reaction solution obtained by filtering and separating the enzyme from the decomposition solution was analyzed by GC-MS.

From the reaction solution, glucose and adipic acid diester having glucose at both ends and other unidentified substances were detected. According to the NMR spectrum, the ester compound of adipic acid and glucose was mainly esterified with the OH group at the 6-position of glucose. This is considered to indicate that the decomposition of the present invention mainly occurs in part B of FIG.

The adipic acid diester was separated by liquid chromatography and reacted with bis (2,2,2-trichloroethyl) adipate. When the same enzyme catalyst as in Example 5 was used, a sugar chain polymer having a molecular weight of about 2,000 to 6,000 was obtained. When the NMR spectrum of the sugar chain polymer compound was measured, esterification occurred not only at the 6-position but also at the 2- and 3-positions of the glucopyranose ring, and as a result, it was confirmed that the adipic acid ester was polymerized. .

Example 18 Oligosaccharide containing saccharides from monosaccharide to tetrasaccharide (by liquid chromatography, monosaccharide: disaccharide: trisaccharide: tetrasaccharide = 1: 3.1: 1)
5.4: 2.8 (molar ratio) and bis (2,2,2)
2-Trichloroethyl) adipate was mixed so that the primary OH group of the oligosaccharide (for example, the OH group at the 6-position of glucose) and the ester group COO of the adipate were in a molar ratio of 1: 1. The sugar chain polymer compound synthesized by reacting in the same manner as in 5 to 9 was converted to esterase and β-
Degraded using glucosidase.

For the decomposition, first, esterase adjusted to pH 7.5 to 9 was added to 0.04 g of the sugar chain polymer compound.
01 to 0. Ig was added at a rate of 40 to 45 ° C. After 48 hours, the esterase enzyme was filtered and then β
-Glucosidase was added (pH was adjusted from 4.0 to 4.5) and the mixture was decomposed at 50 ° C for 48 hours. The amount of the enzyme added was 1 g of the sugar chain polymer compound before being decomposed by the esterase.
0.1 to 0.5 g. After 48 hours, the decomposition solution was set at 85 ° C. to inactivate the enzyme, and separated by filtration. Oligosaccharides and adipic acid were detected from the digested solution.

The composition of the oligosaccharide is monosaccharide: disaccharide: trisaccharide: 4
Sugar = 7.5: 2.6: 0.1: 0 (molar ratio).
It is considered that the decomposition in the present example is that the esterase firstly decomposes in part A of FIG. 2 and then the ether bond of the oligosaccharide is decomposed from the terminal. As a result, it is considered that the composition of the oligosaccharide was greatly changed, and that the monosaccharide became dominant after the decomposition. The obtained oligosaccharide and adipic acid were able to synthesize a sugar chain high molecular compound again not only by a synthesis method using an enzyme catalyst but also by, for example, a method of melting them.

[0067]

As described above, the sugar chain polymer compound of the present invention can be formed into a desired shape at the time when the synthesis reaction is completed, and the decomposition product can be reused during the decomposition treatment. Yes, biodegradable during landfill disposal. In other words, unlike conventional resins, recycling is also possible,
The present invention has made it possible to provide a sugar chain polymer compound that also exhibits biodegradability.

Further, according to the synthesis method of the present invention, since the sugar chain high molecular compound obtained at the end of the synthesis reaction has a desired shape, the molding process can be simplified as compared with the conventional resin. Became. Further, the decomposition method of the present invention makes it possible to use the decomposition product again as a raw material for a sugar chain polymer compound.

[Brief description of the drawings]

FIG. 1 is a principle diagram showing an example of a method for synthesizing a sugar chain polymer compound of the present invention.

FIG. 2 is a conceptual diagram showing a method for decomposing a sugar chain polymer compound of the present invention.

FIG. 3 is a conceptual diagram showing another example of the method for synthesizing a sugar chain polymer compound of the present invention.

[Explanation of symbols]

 Reference Signs List 1 container 2 reaction liquid 3 substrate 4 stirrer 5 support 6 space 7, 8, 9 container 10 heating device 11 gas introduction tube 12, 13 shutter 14 vacuum container 15 substrate holder 21 sugar chain polymer compound 23 oligosaccharide 22 aliphatic Dicarboxylic acid 24 sugar-containing compound

Continued on the front page (72) Inventor Toshihiko Takeda 3- 30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Toyoko Kobayashi 3- 30-2, Shimomaruko 3-chome, Ota-ku, Tokyo Canon Inc.

Claims (8)

[Claims] 1. A sugar chain polymer compound having at least two kinds of repeating units, wherein at least one kind of the repeating units contains a saccharide, and at least one kind of a product by a decomposition reaction contains the saccharide and the saccharide as a main chain. Or at least one of the high molecular compounds containing the sugar in the main chain, and having a desired shape at the time of completion of the synthesis reaction. Molecular compound. 2. The sugar chain polymer compound according to claim 1, wherein at least one of the products generated by the decomposition reaction is a polymerizable substance. 3. A method for synthesizing a sugar chain polymer compound having at least two types of repeating units, wherein at least one of the repeating units contains a sugar, wherein a reactant composed of the repeating unit or a constituent material thereof is used as a component. Prepared independently, react them with a catalyst of desired shape,
A method for synthesizing a sugar chain polymer compound, which comprises forming a sugar chain polymer compound having a desired shape. 4. The method for synthesizing a sugar chain polymer compound according to claim 3, wherein the catalyst is an enzyme immobilized on a substrate surface having a desired shape. 5. The method according to claim 1, wherein a catalyst is first supplied to the surface of the substrate having a desired shape, and then a reactant composed of a repeating unit or its constituent material is supplied as a unit step, and this step is repeated at least once. Claim 3
Or a method for synthesizing a sugar chain polymer compound according to item 4. 6. A method for decomposing a sugar chain polymer compound having at least two kinds of repeating units, wherein at least one of the repeating units contains a sugar, wherein the decomposition is carried out using a catalyst in a solvent, and A method for decomposing a sugar chain polymer compound, comprising decomposing at least one of the decomposition products so as to have a polymerizable functional group. 7. The method according to claim 7, wherein the chemical bond is broken by the catalyst to form at least one of the repeating units constituting the sugar chain polymer compound or the repeating unit of the sugar chain polymer compound. 7. The method for decomposing a sugar chain polymer compound according to claim 6, wherein a product is produced. 8. The method for decomposing a sugar chain polymer compound according to claim 6, wherein the catalyst is an enzyme.