JP2004203870A - Urea derivative, method for producing the same and polymer of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a urea type glycoside vinyl monomer which is a derivative of glucose or cellobiose originating from cellulose and is not described in a literature, capable of being utilized as an adhesive or oxygen gas barrier coating agent, etc., a method for producing the same and a polymer produced therefrom. <P>SOLUTION: This urea derivative is expressed by formula (I) (wherein, R is H or CH<SB>3</SB>; and G is H, glucose or cellobiose residue) and obtained by performing the reaction of 1-aminosaccharide with a (meth)acryloylethyl isocyanate. Further the polymer is obtained by polymerizing the compound in the presence of a polymerization initiator. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a urea derivative having a sugar chain not described in any literature, useful as an adhesive, an oxygen gas barrier coating agent, and the like, a production method thereof, and a polymer produced therefrom.

Adhesives are used in many disposable containers and packaging materials. It is known that various natural sugars (starch, dextrin, etc.) or derivatives of natural products such as carboxymethylcellulose, starch-derived amylose and milk-derived casein that are biodegradable and have adhesive properties can be used for adhesive applications. Used in such packaging applications. However, they have been replaced by synthetics mainly due to their performance.
Further, in the fields of foods, pharmaceuticals, electronic parts and the like whose contents are easily deteriorated or deteriorated, excellent gas barrier properties such as oxygen gas barrier properties are required. Saccharides such as starches are excellent in gas barrier properties due to their hydroxyl groups and high hydrogen-bonding ability, but their mechanical strength is poor and their hydrophilicity is high, so oxygen gas barrier properties are significantly impaired under high humidity conditions. It is.

  New ideas regarding environmental issues or nature conservation have been made and emphasized, and the market for products based on renewable natural resources is expanding and is also prominent in the packaging field. It is becoming increasingly important to apply polymers made from natural resources as raw materials for various products, and it is hoped that natural polysaccharides, their degradation products or their derivatives can be used as adhesives and coating agents. It is rare.

  Conventionally, many compounds that can produce a polymer having a reducing sugar in the side chain have been reported (for example, JP-A-3-236395, Makromol. Chem. 1987, Vol. 188, 1217, J. Carbohydr. Chem. 1989). In addition, as a compound having a reducing sugar in the side chain and having a urea bond, for example, Patent Document 1 discloses a urea bond in a silica gel matrix. Disclosed is a glass coating or laminated glass interlayer resin in which saccharides are dispersed.

Japanese Patent Laid-Open No. 2002-60253

  However, these functions and actions are not sufficient, and more excellent materials are demanded.

Cellulose produced by photosynthesis is the most produced organic polymer on the earth. However, since cellulose has strong intermolecular and intramolecular hydrogen bonds, it is a highly crystalline and rigid polymer, and its processability is poor. Most of it is decomposed by microorganisms and enzymes, and the parts used are The value is very large if it can be converted into a usable form in terms of processability and the like.
Therefore, the present invention relates to effective use of cellulose, urea-type glycoside vinyl monomers not described in the literature, which are derivatives derived from cellulose, such as glucose and cellobiose, useful as adhesives, oxygen gas barrier coating agents, or biocompatible materials. It is an object to provide a polymer.

  As a result of diligent research to solve such problems, the inventors of the present invention simply aminated the reducing hydroxyl group of glucose, which is a constituent unit of cellulose, and reacted with (meth) acryloyloxyethyl isocyanate to easily form a urea skeleton. The present inventors have found that a sugar chain can be introduced into the polymer, that a polymer can be obtained from the derivative, and that the polymer has excellent adhesion and oxygen gas barrier properties.

（式中、Ｒは水素原子又はメチル基を、Ｇは水素原子、グルコース残基又はセロビオース残基を表す。）で表されるウレア誘導体。 That is, the present invention
(1) Formula (I):

(Wherein R represents a hydrogen atom or a methyl group, and G represents a hydrogen atom, a glucose residue or a cellobiose residue).

（式中、Ｇは水素原子、グルコース残基又はセロビオース残基を表す。）で表される１−アミノ糖と（メタ）アクリロイルオキシエチルイソシアネートとを反応させることを特徴とする、式（Ｉ）： (2) Formula (II):

(Wherein G represents a hydrogen atom, a glucose residue or a cellobiose residue), a 1-amino sugar represented by (meth) acryloyloxyethyl isocyanate is reacted, :

（式中、Ｒは水素原子又はメチル基を、Ｇは水素原子、グルコース残基又はセロビオース残基を表す。）で表されるウレア誘導体の製造方法、

(Wherein R represents a hydrogen atom or a methyl group, G represents a hydrogen atom, a glucose residue or a cellobiose residue),

（式中、Ｒは水素原子又はメチル基を、Ｇは水素原子、グルコース残基又はセロビオース残基を、ｎは２以上の整数を表す。）で表されるポリマー、
（４）上記（３）記載の式（III）で表されるポリマーを含有した酸素ガスバリアコート剤、及び、
（５）上記（３）記載の式（III）で表されるポリマーを含有した接着剤、
を提供するものである。 (3) Formula (III):

(Wherein R represents a hydrogen atom or a methyl group, G represents a hydrogen atom, a glucose residue or a cellobiose residue, and n represents an integer of 2 or more),
(4) an oxygen gas barrier coating agent containing a polymer represented by formula (III) described in (3) above, and
(5) an adhesive containing a polymer represented by the formula (III) described in (3) above,
Is to provide.

  As described above, according to the present invention, a urea-type glycoside vinyl monomer not described in any literature, which is a derivative of cellulose derived from cellulose, cellobiose, and the like, a method for producing the same, and a polymer produced therefrom are used for effective use of cellulose. Provided. The range of applications of the polymer produced from the monomer of the present invention is wide, and in particular, it can be used as an adhesive, an oxygen gas barrier coating agent or the like.

  As the urea derivative represented by the above formula (I) of the present invention, specifically, N- (meth) acryloyloxyethyl-N ′-(1- [1-deoxy-4-O- (β- D-glucopyranosyl)])-urea, N- (meth) acryloyloxyethyl-N ′-(1- [1-deoxy-4-O- (β-D-glucopyranosyl) -β-D-glucopyranosyl])-urea N- (meth) acryloyloxyethyl-N ′-(1- [1-deoxy-4-O- (α-D-glucopyranosyl) -α-D-glucopyranosyl])-urea, N- (meth) acryloyloxy Ethyl-N ′-(1- [1-deoxy-4-O- (β-D-glucopyranosyl) -4-O- (β-D-glucopyranosyl) -β-D-glucopyranosyl])-urea.

These urea derivatives are produced by reacting a 1-amino sugar represented by the above formula (II) with 2- (meth) acryloyloxyethyl isocyanate.
The starting 1-amino sugar can be easily produced from the corresponding sugar by a known method (for example, J. Carbohydr. Chem. 1989, Vol. 597).

The reaction is carried out in the presence of a solvent.
As the solvent that can be used, any solvent that can dissolve 1-amino sugar and does not inhibit the reaction may be used, and examples thereof include water, alcohol, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, and the like. Water is preferred.
By adding a basic substance such as sodium hydroxide or potassium hydroxide to the solvent, reaction by-products can be reduced. The addition amount of the basic substance is preferably about 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol / L with respect to the solvent.
The reaction conditions vary depending on the solvent used, but when the solvent is water, the reaction is preferably performed at about 0 ° C. to room temperature, and the reaction is completed in about 1 to 2 hours.
After completion of the reaction, the target product is filtered off the precipitated crystals, the filtrate is lyophilized, or an organic solvent that does not dissolve the target product is added to the filtrate, and the resulting crude product is recrystallized or subjected to a column or the like. It can be easily isolated by purification.

The present invention provides a polymer represented by the above formula (III) obtained by polymerizing a urea derivative represented by the above formula (I).
Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like. Solution polymerization is preferable, and the solvent used is a polar solvent soluble in urea derivatives represented by the formula (I) Examples thereof include water, dimethylformamide, dimethyl sulfoxide and the like, and water is particularly preferable.
The reaction is carried out in the presence of a polymerization initiator. As the polymerization initiator to be used, those usually used can be used, for example, 2,2-azobisisobutyronitrile, azobisvaleronitrile, 2,2-azobis [2- (2-imidazolin-2-yl ) Propane] Aliphatic azo compounds such as dihydrochloride, organic peroxides such as benzoyl peroxide and lauroyl peroxide, and inorganic peroxides such as ammonium persulfate and potassium peroxide.
The polymerization is preferably carried out in the substantial absence of oxygen, and the reaction temperature is not particularly limited, but the lower the tendency, the higher the degree of polymerization. A reaction time of about 1 hour to 1 day is sufficient.
After completion of the reaction, the polymer is isolated as an insoluble material by adding a polymer-insoluble solvent to the reaction solution, or by purifying the reaction solution by dialysis and then freeze-drying.

  Since the polymer of the present invention has a reducing sugar residue in the side chain, it can be applied in a wide range of biocompatible materials such as artificial organ (artificial blood) coating materials, adhesives, oxygen gas barrier coating agents, etc. It is.

Hereinafter, the present invention will be described in detail with reference to examples.
Example 1
Cellobiosylamine [4-O- (β-D-glucopyranosyl) -β-D-glucopyranosylamine] 10 g (purity 81%, 23.73 mmol) was dissolved in 100 ml of 1 × 10 ⁻³ M potassium hydroxide aqueous solution. I let you. To the solution, 9.20 g (59.33 mmol) of 2-isocyanate ethyl methacrylate was added, and the mixture was vigorously stirred for 12 hours while being kept at 3 ° C.
After completion of the reaction, the precipitated solid was removed by filtration, and the filtrate was washed 4 times with 50 ml of diethyl ether. The aqueous phase was then lyophilized to give a white solid.
The obtained white solid was dissolved in a mixed solvent of 2 ml of water and 10 ml of methanol, and dropped into a mixed solvent of 80 ml of diethyl ether and 20 ml of acetone and cooled. The deposited precipitate was separated by decantation and dried under reduced pressure to give a urea derivative (formula (I), R = methyl group, G = glucose residue) [N-methacryloyloxyethyl-N ′-(1 -[1-deoxy-4-O- (β-D-glucopyranosyl) -β-D-glucopyranosyl])-urea] 8.78 g was obtained.
Elemental analysis (as _{C 19 H 32 N 2 O 13} )
Calculated value C: 45.96% H: 6.49% N: 5.64%
Measurement value C: 44.56% H: 6.56% N: 5.29%
The resulting The infrared absorption spectrum of the urea derivative was measured (Fig. 1), a peak derived from each other stretching vibration of N-H in the vicinity of 1590 cm ^-1 is derived from the amide bond C = O stretching vibration 1640 cm ^-1 A peak derived from the C═O stretching vibration of the ester was confirmed at 1740 cm ⁻¹ . The proton nuclear magnetic resonance spectrum was measured, and the obtained results are shown in FIG.

Example 2
2.4 g (5.85 mmol) of the urea derivative obtained in Example 1 was dissolved in 10 ml of degassed water, and N ₂ aeration was performed for 30 minutes under ice cooling. Next, 0.585 mmol of N, N, N, N-tetraethylethylenediamine and 0.585 mmol of ammonium persulfate as an initiator were added, and the mixture was reacted under an N ₂ atmosphere for 3 hours under ice cooling.
After completion of the reaction, the reaction solution is diluted twice, put into a cellulose tube having a molecular weight cut off of 3000, purified by dialysis for 3 days, freeze-dried, and represented by the formula (III) (R = methyl group). 1.2 g of polymer was obtained.
When the molecular weight of the obtained polymer was calculated by size exclusion chromatography analysis, the molecular weight was 3.3 × 10 ⁶ (degree of polymerization 6700) using pullulan as a standard substance.
The infrared absorption spectrum of the obtained polymer is shown in FIG. 3, and the proton nuclear magnetic resonance spectrum is shown in FIG.

Example 3
Glucose 5 g was added to a saturated aqueous solution of ammonium bicarbonate (water 25 ml, ammonium bicarbonate 8.77 g) and reacted at 37 ° C. for 24 hours to obtain 1-glucosylamine (acetone recrystallization).
4 g (10.68 mmol) of 1-glucosylamine thus obtained was dissolved in 50 ml of 1.0 × 10 ⁻³ M potassium hydroxide aqueous solution, and 4.14 g (26.64 mmol) of 2-isocyanatoethyl methacrylate was added. Stir at 1 ° C. for 12 hours.
After completion of the reaction, the precipitated solid was removed by filtration, the filtrate was washed with diethyl ether to remove unreacted 2-isocyanatoethyl methacrylate, and the aqueous phase was lyophilized to obtain a white solid.
The resulting white solid was purified with acetone to give a urea derivative (formula (I), R = methyl group, G = hydrogen atom) [N-methacryloyloxyethyl-N ′-(1- [1-deoxy- 4-O- (β-D-glucopyranosyl)])-urea] was obtained.
Melting point: 106.5-107.2 ° C
The infrared absorption spectrum of the obtained urea derivative is shown in FIG. 5, and the proton nuclear magnetic resonance spectrum is shown in FIG.

Example 4
0.763 g (1.61 mmol) of the urea derivative obtained in Example 3 was dissolved in 5 ml of degassed water, and N ₂ aeration was performed for 30 minutes under ice cooling. Next, 27.8 mg (0.161 mmol) of N, N, N, N-tetraethylethylenediamine and 3.66 mg (0.0161 mmol) of ammonium persulfate as an initiator were added, and the mixture was ice-cooled under N ₂ atmosphere for 3 hours. Reacted.
After completion of the reaction, 10 ml of water was added, put into a cellulose tube having a molecular weight cut off of 3000, purified by dialysis for 3 days, freeze-dried, and polymer represented by the formula (III) (R = methyl group, G = hydrogen). Atom).
The infrared absorption spectrum of the obtained polymer is shown in FIG. 7, and the proton nuclear magnetic resonance spectrum is shown in FIG.

Example 5
In Example 1, urea was used in the same manner as in Example 1 except that maltosylamine [4-O- (α-glucopyranosyl) -α-D-glucopyranosylamine] was used instead of cellobiosylamine. Derivative (formula (I), R = methyl group, G = glucose residue) [N-methacryloyloxyethyl-N ′-(1- [1-deoxy-4-O- (α-D-glucopyranosyl) -α] -D-glucopyranosyl])-urea].

Example 6
In Example 2, the same procedure as in Example 2 was carried out except that 2.4 g of the urea derivative obtained in Example 5 was used instead of the urea derivative obtained in Example 1, and the polymer (formula (III)) , R = methyl group, G = glucose residue).

Example 7
100 mg (purity 86%, 0.17 mmol) of cellotriosylamine was dissolved in 1 ml of 1.0 × 10 ⁻³ M potassium hydroxide aqueous solution, and 0.06 mg (0.43 mmol) of 2-isocyanatoethyl methacrylate was added. Stir at 1 ° C. for 12 hours.
After completion of the reaction, the precipitated solid was removed by filtration, and the filtrate was washed with diethyl ether to remove unreacted 2-isocyanatoethyl methacrylate, and then the aqueous phase was lyophilized to obtain a white solid.
The resulting white solid was purified with acetone to give a urea derivative (formula (I), R = methyl group, G = cellobiose residue) [N-methacryloyloxyethyl-N ′-(1- [1-deoxy]. -4-O- (β-D-glucopyranosyl) -4-O- (β-D-glucopyranosyl) -β-D-glucopyranosyl])-urea] was obtained.
The infrared absorption spectrum of the obtained urea derivative is shown in FIG. 9, and the proton nuclear magnetic resonance spectrum is shown in FIG.

Example 8
In Example 2, it replaced with the urea derivative obtained in Example 1, and carried out according to Example 2 except having used 20 mg of urea derivatives obtained in Example 7, and polymer (formula (III), R = methyl group, G = cellobiose residue).
The infrared absorption spectrum of the obtained polymer is shown in FIG. 11, and the proton nuclear magnetic resonance spectrum is shown in FIG.

Example 9 Evaluation Example of Adhesive A 5% aqueous solution of the polymer obtained in Example 2 was prepared, applied to sulfuric acid paper and bonded, and dried at 100 ° C. for 30 minutes.
When the bonded surface was peeled off by hand, it was strongly bonded to the extent that the paper layer peeled off.

Example 10 Evaluation Example of Oxygen Gas Permeability A 5% aqueous solution of the polymer obtained in Example 2 was prepared and applied to a corona-treated nylon film having a thickness of 15 μm (manufactured by Kojin Co., Ltd., Bonyl RX) after applying 1.2 μm. An amount was applied with a Mayer bar, and then dried at 100 ° C. for 2 minutes to obtain a polymer coating film.
The resulting film was measured for oxygen gas permeability with a gas permeability meter (OX-TRAN100, manufactured by Modern Control). For comparison, the oxygen gas permeability of the corona-treated nylon film used in this example was measured without coating the polymer.
The results are shown in Table 1.

Example 11 Oxygen Gas Permeability Evaluation Example A 5% aqueous solution of the polymer obtained in Examples 2, 4, 6 and 8 was prepared and applied to a PET film having a thickness of 12 μm with a coating amount of 1.2 μm after drying. And then dried at 100 ° C. for 2 minutes to obtain a polymer coating film.
The obtained film was measured for oxygen gas permeability in the same manner as in Example 10.
The results are shown in Table 2.

1 is an infrared absorption spectrum of a urea derivative obtained in Example 1. FIG. 2 is a diagram showing a proton nuclear magnetic resonance spectrum of a urea derivative obtained in Example 1. FIG. 6 is a graph showing an infrared absorption spectrum of the polymer obtained in Example 2. FIG. 3 is a diagram showing a proton nuclear magnetic resonance spectrum of the polymer obtained in Example 2. FIG. 4 is a graph showing an infrared absorption spectrum of a urea derivative obtained in Example 3. FIG. 4 is a diagram showing a proton nuclear magnetic resonance spectrum of a urea derivative obtained in Example 3. FIG. 6 is a graph showing an infrared absorption spectrum of the polymer obtained in Example 4. FIG. 6 is a diagram showing a proton nuclear magnetic resonance spectrum of the polymer obtained in Example 4. FIG. It is a figure which shows the infrared absorption spectrum of the polymer obtained in Example 7. 6 is a diagram showing a proton nuclear magnetic resonance spectrum of the polymer obtained in Example 7. FIG. It is a figure which shows the infrared absorption spectrum of the polymer obtained in Example 8. 6 is a diagram showing a proton nuclear magnetic resonance spectrum of the polymer obtained in Example 8. FIG.

Claims (5)

Formula (I):

(Wherein R represents a hydrogen atom or a methyl group, and G represents a hydrogen atom, a glucose residue or a cellobiose residue). Formula (II):

(Wherein G represents a hydrogen atom, a glucose residue or a cellobiose residue), a 1-amino sugar represented by (meth) acryloyloxyethyl isocyanate is reacted, :

(Wherein R represents a hydrogen atom or a methyl group, and G represents a hydrogen atom, a glucose residue or a cellobiose residue). Formula (III):

(Wherein, R represents a hydrogen atom or a methyl group, G represents a hydrogen atom, a glucose residue or a cellobiose residue, and n represents an integer of 2 or more). An oxygen gas barrier coating agent containing a polymer represented by the formula (III) according to claim 3. An adhesive containing a polymer represented by the formula (III) according to claim 3.

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