WO2017061435A1 - Method for functionalizing vinyl alcohol resin, and vinyl alcohol resin functionalizing agent - Google Patents
Method for functionalizing vinyl alcohol resin, and vinyl alcohol resin functionalizing agent Download PDFInfo
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- WO2017061435A1 WO2017061435A1 PCT/JP2016/079524 JP2016079524W WO2017061435A1 WO 2017061435 A1 WO2017061435 A1 WO 2017061435A1 JP 2016079524 W JP2016079524 W JP 2016079524W WO 2017061435 A1 WO2017061435 A1 WO 2017061435A1
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- benzoxabolol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
Definitions
- the present invention relates to a method for easily imparting functionality to a vinyl alcohol resin, which is usually difficult to impart functionality due to its high stability, and a substance used for this functionalization.
- This application claims priority based on Japanese Patent Application No. 2015-198316 filed in Japan on October 6, 2015, the contents of which are incorporated herein by reference.
- this application refers to the non-patent document “Yohei Kotushibashi and Mitshiro Hiro Ebara: Polymers 2006, 8 (2), 41, p1-11; doi: 10.3390 / polym8020041” and “SupplementaryMatter1”. (Incorporated herein by reference).
- ethylene-vinyl alcohol copolymer poly (ethylene-co-vinylcohol), such as EVAL (registered trademark) sold by Kuraray Co., Ltd., hereinafter abbreviated as EVOH
- EVAL registered trademark
- EVOH ethylene-vinyl alcohol copolymer
- EVOH is difficult to impart new functionality due to its high stability.
- a composite material can be formed by mixing a hydrophobic polymer with EVOH.
- a polymer mixed from a film, fiber, or the like formed using this composite material may leak out, which is a practical problem.
- Non-Patent Document 1 it is known that the benzoxabolol group has a stronger bond with diol than phenylboronic acid. Moreover, this inventor has announced that the gel with a sugar polymer is prepared using the benzoxabolol polymer which has this benzoxabolol group (nonpatent literature 2, 3).
- the object of the present invention is to solve the above-mentioned problems of the prior art and to provide a method for easily imparting various functions to EVOH and a substance used in the method.
- EVOH can change the ratio of its monomer, ethylene and vinyl alcohol, within a wide range, and in particular, the present invention can be applied even when ethylene is not included (that is, in the case of polyvinyl alcohol).
- the “vinyl alcohol resin” of the present invention is also used in the meaning of “ethylene-vinyl alcohol copolymer or polyvinyl alcohol”.
- a vinyl alcohol resin functionalizing method in which a benzoxabolol polymer containing a benzoxabolol structure and a vinyl alcohol resin are mixed and reversibly bonded.
- the desired functionality may be selected from the group consisting of temperature responsiveness, viscosity, electrospinning and dyeability.
- the desired functionality may be the functionality possessed by the benzoxabolol polymer.
- the benzoxabolol polymer may be a copolymer containing a monomer having a benzoxabolol structure and a monomer that gives the functionality.
- the benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
- a vinyl alcohol resin functionalizing agent comprising a benzoxabolol polymer containing a benzoxabolol structure is provided.
- the desired functionality may be selected from the group consisting of temperature responsiveness, viscosity, electrospinning and dyeability.
- the desired functionality may be the functionality possessed by the benzoxabolol polymer.
- the benzoxabolol polymer may be a copolymer containing a monomer having a benzoxabolol structure and a monomer that gives the functionality.
- the benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
- a benzoxabolol polymer containing a monomer-derived structure providing functionality and a benzoxabolol structure, and a vinyl alcohol resin having a diol structure, the benzoxabolol structure and the diol A mixed product of a benzoxabolol polymer and a vinyl alcohol resin, characterized by being reversibly bonded by bonding to the structure.
- the benzoxabolol polymer may be a copolymer of a monomer having the benzoxabolol structure and a monomer providing the functionality.
- the benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
- functionality can be imparted to EVOH by an extremely simple process of adding and mixing a functionalizing agent to ordinary EVOH.
- FIG. 4 A photograph showing the result of staining the accumulation shown in FIG. 4 (a) with methylene blue.
- Benzoxabolol represented by formula (2) that can be reversibly bound to benzoxazole (also called boroxole)
- a polymer having the following structure (hereinafter referred to as benzoxabolol polymer) was synthesized.
- the benzoxabolol polymer can be synthesized by radical polymerization that is commonly used for benzoxabolol monomers, and its structure and composition can be precisely controlled by using living radical polymerization. .
- a copolymer can be synthesized together with other monomers. Thereby, the molecular weight, molecular weight distribution, structure, etc. of the polymer can be controlled. Since various functionalities (for example, stimulus reactivity, biocompatibility, conductivity, fire resistance, etc.) can be imparted to the benzoxabolol polymer, no special functionality imparting treatment is applied to the EVOH side.
- the capacity of EVOH products can be improved.
- the present invention can be realized very simply by simply mixing a benzoxabolol polymer imparted with a desired functionality with EVOH in a solvent, so that it is very simple and low cost.
- a benzoxabolol polymer having a desired functionality a benzoxabolol polymer modified with a functional group as necessary to express the desired functionality, a monomer having a benzoxabolol structure and a desired
- Various embodiments such as copolymers with other monomers to provide the functionality of are possible.
- FIG. 1 shows an interaction between benzoxabolol itself and a diol, but this is an exemplary description, and the interaction is expressed by any compound having a benzoxabolol structure.
- Examples of such a compound having a benzoxabolol structure include, but are not limited to, a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton. It should be noted here that even if the polymer has high stereoregularity, if it has a benzoxabolol structure, the equilibrium reaction of the bond with the diol shown in FIG. 1 proceeds to some extent. Even if it becomes difficult, it will not change.
- FIG. 1 occurs by mixing the benzoxabolol polymer and EVOH, since both are simply mixed as processing, in the following, by mixing both, FIG. A product in which a reaction as shown in the figure has occurred may be referred to as a “mixed product”.
- EVOH and benzoxabolol polymer having temperature responsiveness and dyeability are combined to show that EVOH can have the functionality.
- temperature responsiveness even a polymer that easily dissolves at room temperature can be processed so that it can be adsorbed by the material.
- the viscosity generally increases. This viscosity is one of the functions.
- these mixed products having an appropriate viscosity can be electrospun to obtain mixed product fibers.
- the functionality that can be imparted to EVOH is not limited to temperature responsiveness, viscosity, dyeability, etc., and may be any functionality that can be imparted by the method described herein.
- EVAL manufactured by Kuraray Co., Ltd. (ethylene copolymerization ratio (molar ratio) 44%) was used as EVOH, but it is obvious that the generality is not lost.
- Example 1 ⁇ Benzoxaborol polymer with added functionality>
- EVOH is provided with functionality such as temperature responsiveness, gelation, and electrospinning properties
- the temperature responsiveness in this case is that the surface properties of a mixed product such as gel or fiber made of EVOH and benzoxabolol polymer can be controlled to be hydrophilic / hydrophobic depending on the temperature.
- 5-methacrylamido-1,2-benzoxaborole is a compound of 2- (2-methoxyethyl) ethyl methacrylate (MEO 2 MA) and oligo (ethyleneglycol) A temperature was selected to control the temperature responsiveness.
- the benzoxabolol polymer is based on these monomers, and can be obtained by copolymerization after further mixing with a monomer having the desired functionality. Since the copolymerization method itself used here is already known, a detailed description thereof will be omitted, but if necessary, refer to Non-Patent Documents 2 and 3 which are the articles of the present inventor.
- Units other than the benzoxabolol structure in the benzoxabolol polymer shown above have ethylene glycol type temperature responsiveness. Since the phase transition temperature of this polymer varies depending on the molecular weight and structure of these temperature-responsive units, an appropriate polymer can be obtained by appropriately selecting these monomers and copolymerizing them.
- FIG. 2 shows a photograph of a gel obtained by mixing EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO).
- EVOH and P MEO 2 MA-co-OEGMA-co-MAAmBO
- HFIP 1,1,1,3,3,3-3-
- Hexafluoropropanol was dissolved at room temperature.
- a three-dimensional cross-linked structure is constructed by the interaction between the two as shown in FIG. 1, it is possible to prepare a gel structure.
- the strength of the gel can be controlled by the polymer ratio to be mixed. Further, the viscosity in the sol state can be similarly controlled.
- the mixed product of EVOH and benzoxabolol polymer can be handled as either a sol or a gel depending on the concentration or mixing ratio in the solution, the molding process is easy. From a bulk state, a film-like thin film, a capsule, or a nanofiber can be formed and processed.
- Example 2 ⁇ Mixed product of EVOH and benzoxabolol polymer 2: nanofiber>
- FIG. 3 (B) shows an electrospinning solution in which EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA-co-MAAmBO) (concentration: 2.5 wt%) are mixed in HFIP. The SEM image of a result is shown. As can be seen from FIG.
- a nanofiber assembly can be obtained by electrospinning a mixed product 2 of EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO).
- the gaps between the fibers are relatively well aligned.
- the size of the gap can be controlled by adjusting the electrospinning conditions, the mixed product concentration, and the like.
- Example 3 ⁇ Mixed product of EVOH and benzoxabolol polymer 3: nanofiber>
- FIG. 3C shows an electrospinning solution in which EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA-co-MAAmBO) (concentration: 0.5 wt%) are mixed in HFIP. The SEM image of a result is shown.
- EVOH concentration: 3.5 wt%
- P MEO 2 MA-co-OEGMA-co-MAAmBO
- nanofibers are not formed despite the electrospinning of the mixed product 3 of EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO).
- 2 MA-co-OEGMA-co-MAAmBO is less than 0.5 wt% compared to 2.5 wt% in FIG. 3 (B) in Example 2, so that the viscosity of the mixed product 3 is as shown in FIG. This is because it is lower than in the case of B).
- FIG. 3A shows an SEM image as a result of electrospinning an HFIP solution containing EVOH (concentration: 3.5 wt%) alone.
- FIG. 3D shows EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA) (concentration: 2.5 wt%) (that is, a copolymer having no benzoxabolol structure).
- the SEM image of the result of electrospinning the solution which mixed) in HFIP is shown.
- FIG. 4 (a) An accumulation obtained by electrospinning a mixture product of EVOH and the benzoxabolol polymer was prepared as an object for a dyeing experiment. This accumulation is represented by the formula (6) methylene blue
- FIG. 4B A comparative assembly obtained by electrospinning the mixed product was prepared. Similarly to Example 4, the result of staining this aggregate with methylene blue represented by formula (6) is shown in FIG. 5 (b).
- the benzoxabolol polymer represented by the formula (5) in Example 4 is the formula (7) in Comparative Example 3. It can be seen that a structure derived from a relatively small monomer having a carboxyl group is added to the benzoxabolol polymer represented by As can be seen from FIG.
- the assembly made from the mixed product 4 of EVOH and a benzoxabolol polymer modified with a carboxyl group which is Example 4 of the present invention, is a benzoate not modified with a carboxyl group. It turns out that it is dye
- the reason why the accumulation produced by mixing EVOH and a benzoxabolol polymer modified with a carboxyl group in this way has higher dyeability is that it is ionized in the accumulation and exists in the form of -COO- This is because an electrostatic interaction occurs between the carboxyl group to be reacted and methylene blue which is a cationic dye.
- methylene blue was used as the dye, and the benzoxabolol polymer was modified with a carboxyl group.
- the present invention is not limited to this combination, and any functional group that ionizes negatively with any cationic dye. Improvement in dyeability can be achieved by combination with a benzoxabolol polymer modified with a group. On the contrary, the dyeability can be improved by a combination of any anionic dye and a benzoxabolol polymer modified with any functional group capable of positive ionization.
- EVOH uses existing materials that are easily available, and only by mixing a benzoxabolol polymer having a desired functionality with EVOH, the characteristics of EVOH can be obtained. Since the desired functionality can be imparted while maintaining it, the present invention is expected to be widely used for expanding the use of EVOH.
Abstract
Ethylene-vinyl alcohol copolymers (abbreviated to EVOHs) have high gas barrier properties and biocompatibility, but are difficult to be imparted with functionality because of their high stability. According to the present invention, by utilizing an interaction between benzoxaborole and a hydroxy group included in an EVOH as shown in the drawing, a benzoxaborole polymer having desired functionality and the EVOH are simply mixed and reversibly bound together, and, as a result, functionality can be easily imparted to the EVOH.
Description
本発明は安定性が高いために通常は機能性を付与することが困難なビニルアルコール樹脂に簡単に機能性を付与する方法並びにこの機能化のために使用する物質に関する。
本願は、２０１５年１０月６日に、日本に出願された特願２０１５－１９８３１６号に基づき優先権を主張し、その内容をここに援用する。また、本願は、非特許文献「Ｙｏｈｅｉ Ｋｏｔｓｕｃｈｉｂａｓｈｉ ａｎｄ Ｍｉｔｓｕｈｉｒｏ Ｅｂａｒａ： Ｐｏｌｙｍｅｒｓ ２０１６， ８（２）， ４１，ｐ１～１１；ｄｏｉ：１０．３３９０／ｐｏｌｙｍ８０２００４１」およびその「Ｓｕｐｐｌｅｍｅｎｔａｒｙ Ｍａｔｅｒｉａｌｓ Ｓ１～Ｓ３」の内容をここに援用する（ｉｎｃｏｒｐｏｒａｔｅｄ ｈｅｒｅｉｎ ｂｙ ｒｅｆｅｒｅｎｃｅ）。 The present invention relates to a method for easily imparting functionality to a vinyl alcohol resin, which is usually difficult to impart functionality due to its high stability, and a substance used for this functionalization.
This application claims priority based on Japanese Patent Application No. 2015-198316 filed in Japan on October 6, 2015, the contents of which are incorporated herein by reference. In addition, this application refers to the non-patent document “Yohei Kotushibashi and Mitshiro Hiro Ebara: Polymers 2006, 8 (2), 41, p1-11; doi: 10.3390 / polym8020041” and “SupplementaryMatter1”. (Incorporated herein by reference).
本願は、２０１５年１０月６日に、日本に出願された特願２０１５－１９８３１６号に基づき優先権を主張し、その内容をここに援用する。また、本願は、非特許文献「Ｙｏｈｅｉ Ｋｏｔｓｕｃｈｉｂａｓｈｉ ａｎｄ Ｍｉｔｓｕｈｉｒｏ Ｅｂａｒａ： Ｐｏｌｙｍｅｒｓ ２０１６， ８（２）， ４１，ｐ１～１１；ｄｏｉ：１０．３３９０／ｐｏｌｙｍ８０２００４１」およびその「Ｓｕｐｐｌｅｍｅｎｔａｒｙ Ｍａｔｅｒｉａｌｓ Ｓ１～Ｓ３」の内容をここに援用する（ｉｎｃｏｒｐｏｒａｔｅｄ ｈｅｒｅｉｎ ｂｙ ｒｅｆｅｒｅｎｃｅ）。 The present invention relates to a method for easily imparting functionality to a vinyl alcohol resin, which is usually difficult to impart functionality due to its high stability, and a substance used for this functionalization.
This application claims priority based on Japanese Patent Application No. 2015-198316 filed in Japan on October 6, 2015, the contents of which are incorporated herein by reference. In addition, this application refers to the non-patent document “Yohei Kotushibashi and Mitshiro Hiro Ebara: Polymers 2006, 8 (2), 41, p1-11; doi: 10.3390 / polym8020041” and “SupplementaryMatter1”. (Incorporated herein by reference).
エチレン－ビニルアルコール共重合体（ｐｏｌｙ（ｅｔｈｙｌｅｎｅ－ｃｏ－ｖｉｎｙｌａｌｃｏｈｏｌ）、例えば株式会社クラレから販売されているエバール（登録商標）等、以下、ＥＶＯＨと略称する）は高いガスバリア性を有する高分子であり、包装フィルムや燃料タンクに広く使用されている。ＥＶＯＨはまた高い生体適合性を示し、人工透析用の中空糸（ダイラタイザー）としても実用化されている。
An ethylene-vinyl alcohol copolymer (poly (ethylene-co-vinylcohol), such as EVAL (registered trademark) sold by Kuraray Co., Ltd., hereinafter abbreviated as EVOH) is a polymer having high gas barrier properties. Widely used in packaging films and fuel tanks. EVOH also exhibits high biocompatibility and has been put into practical use as a hollow fiber (dilator) for artificial dialysis.
しかしながら、ＥＶＯＨは、その高い安定性のために新たに機能性を付与することが困難である。機能性を付加するため、例えば、ＥＶＯＨのＯＨ基の酸化やＵＶ処理により、表面の性質を変化させることも可能であるが、この場合多くの作業工程を必要とし、また生成に時間を要するという問題もある。これに加えて、このような処理を行うことはＥＶＯＨ自体の構造を変化させることになるため、その特性への悪影響が懸念される。
他の方法として、ＥＶＯＨに疎水性のポリマーを混合することにより複合材料を形成することも可能である。しかし、条件によっては、この複合材料を用いて形成されたフィルムやファイバー等から混合したポリマーが漏れ出してしまうことがあり、実用上問題となる。
一方、フェニルボロン酸より、ベンゾオキサボロール基の方がジオールとの結合性が強いことが知られている（非特許文献１）。また、このベンゾオキサボロール基を有するベンゾオキサボロールポリマーを用いて糖ポリマーとのゲルを調製することは本願発明者が公表している（非特許文献２，３）。 However, EVOH is difficult to impart new functionality due to its high stability. In order to add functionality, it is possible to change the surface properties by, for example, oxidation of the OH group of EVOH or UV treatment. In this case, however, many work steps are required, and it takes time to produce. There is also a problem. In addition, since such a process changes the structure of the EVOH itself, there is a concern about adverse effects on its characteristics.
As another method, a composite material can be formed by mixing a hydrophobic polymer with EVOH. However, depending on conditions, a polymer mixed from a film, fiber, or the like formed using this composite material may leak out, which is a practical problem.
On the other hand, it is known that the benzoxabolol group has a stronger bond with diol than phenylboronic acid (Non-Patent Document 1). Moreover, this inventor has announced that the gel with a sugar polymer is prepared using the benzoxabolol polymer which has this benzoxabolol group (nonpatent literature 2, 3).
他の方法として、ＥＶＯＨに疎水性のポリマーを混合することにより複合材料を形成することも可能である。しかし、条件によっては、この複合材料を用いて形成されたフィルムやファイバー等から混合したポリマーが漏れ出してしまうことがあり、実用上問題となる。
一方、フェニルボロン酸より、ベンゾオキサボロール基の方がジオールとの結合性が強いことが知られている（非特許文献１）。また、このベンゾオキサボロール基を有するベンゾオキサボロールポリマーを用いて糖ポリマーとのゲルを調製することは本願発明者が公表している（非特許文献２，３）。 However, EVOH is difficult to impart new functionality due to its high stability. In order to add functionality, it is possible to change the surface properties by, for example, oxidation of the OH group of EVOH or UV treatment. In this case, however, many work steps are required, and it takes time to produce. There is also a problem. In addition, since such a process changes the structure of the EVOH itself, there is a concern about adverse effects on its characteristics.
As another method, a composite material can be formed by mixing a hydrophobic polymer with EVOH. However, depending on conditions, a polymer mixed from a film, fiber, or the like formed using this composite material may leak out, which is a practical problem.
On the other hand, it is known that the benzoxabolol group has a stronger bond with diol than phenylboronic acid (Non-Patent Document 1). Moreover, this inventor has announced that the gel with a sugar polymer is prepared using the benzoxabolol polymer which has this benzoxabolol group (
本発明は上述した従来技術の問題点を解消し、ＥＶＯＨに簡単に各種の機能性を付与するための方法及び当該方法に使用される物質を提供することをその課題とする。なお、ＥＶＯＨはそのモノマーであるエチレンとビニルアルコールとの比率を広い範囲で変化させることができ、特にエチレンを含まない場合（すなわちポリビニルアルコールの場合）でも本発明を適用できるため、本願ではＥＶＯＨをポリビニルアルコールまで含むポリマーの意味で使用する。また、本発明の「ビニルアルコール樹脂」も「エチレン－ビニルアルコール共重合体またはポリビニルアルコール」の意味で使用する。
The object of the present invention is to solve the above-mentioned problems of the prior art and to provide a method for easily imparting various functions to EVOH and a substance used in the method. EVOH can change the ratio of its monomer, ethylene and vinyl alcohol, within a wide range, and in particular, the present invention can be applied even when ethylene is not included (that is, in the case of polyvinyl alcohol). Used to mean a polymer containing up to polyvinyl alcohol. The “vinyl alcohol resin” of the present invention is also used in the meaning of “ethylene-vinyl alcohol copolymer or polyvinyl alcohol”.
本発明の一側面によれば、ベンゾオキサボロール構造を含むベンゾオキサボロールポリマーとビニルアルコール樹脂とを混合して両者を可逆的に結合する、ビニルアルコール樹脂機能化方法が与えられる。
ここで、前記所望の機能性は温度応答性、粘性、電界紡糸性及び染色性からなる群から選択されてよい。
また、前記所望の機能性は前記ベンゾオキサボロールポリマーが有する機能性であってよい。
また、前記ベンゾオキサボロールポリマーはベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとを含む共重合体であってよい。
また、前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーであってよい。
本発明の他の側面によれば、ベンゾオキサボロール構造を含むベンゾオキサボロールポリマーからなる、ビニルアルコール樹脂機能化剤が与えられる。
ここで、前記所望の機能性は温度応答性、粘性、電界紡糸性及び染色性からなる群から選択されてよい。
また、前記所望の機能性は前記ベンゾオキサボロールポリマーが有する機能性であってよい。
また、前記ベンゾオキサボロールポリマーはベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとを含む共重合体であってよい。
また、前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーであってよい。
本発明の別の側面によれば、機能性を与えるモノマー由来構造とベンゾオキサボロール構造とを含むベンゾオキサボロールポリマーと
ジオール構造を有するビニルアルコール樹脂と
を前記ベンゾオキサボロール構造と前記ジオール構造との結合によって
可逆的に結合してなることを特徴とする、ベンゾオキサボロールポリマーとビニルアルコール樹脂の混合生成物を与える。
前記ベンゾオキサボロールポリマーは前記ベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとの共重合体であってよい。
また、前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーであってよい。 According to one aspect of the present invention, there is provided a vinyl alcohol resin functionalizing method in which a benzoxabolol polymer containing a benzoxabolol structure and a vinyl alcohol resin are mixed and reversibly bonded.
Here, the desired functionality may be selected from the group consisting of temperature responsiveness, viscosity, electrospinning and dyeability.
The desired functionality may be the functionality possessed by the benzoxabolol polymer.
The benzoxabolol polymer may be a copolymer containing a monomer having a benzoxabolol structure and a monomer that gives the functionality.
The benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
According to another aspect of the present invention, a vinyl alcohol resin functionalizing agent comprising a benzoxabolol polymer containing a benzoxabolol structure is provided.
Here, the desired functionality may be selected from the group consisting of temperature responsiveness, viscosity, electrospinning and dyeability.
The desired functionality may be the functionality possessed by the benzoxabolol polymer.
The benzoxabolol polymer may be a copolymer containing a monomer having a benzoxabolol structure and a monomer that gives the functionality.
The benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
According to another aspect of the present invention, a benzoxabolol polymer containing a monomer-derived structure providing functionality and a benzoxabolol structure, and a vinyl alcohol resin having a diol structure, the benzoxabolol structure and the diol A mixed product of a benzoxabolol polymer and a vinyl alcohol resin, characterized by being reversibly bonded by bonding to the structure.
The benzoxabolol polymer may be a copolymer of a monomer having the benzoxabolol structure and a monomer providing the functionality.
The benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
ここで、前記所望の機能性は温度応答性、粘性、電界紡糸性及び染色性からなる群から選択されてよい。
また、前記所望の機能性は前記ベンゾオキサボロールポリマーが有する機能性であってよい。
また、前記ベンゾオキサボロールポリマーはベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとを含む共重合体であってよい。
また、前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーであってよい。
本発明の他の側面によれば、ベンゾオキサボロール構造を含むベンゾオキサボロールポリマーからなる、ビニルアルコール樹脂機能化剤が与えられる。
ここで、前記所望の機能性は温度応答性、粘性、電界紡糸性及び染色性からなる群から選択されてよい。
また、前記所望の機能性は前記ベンゾオキサボロールポリマーが有する機能性であってよい。
また、前記ベンゾオキサボロールポリマーはベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとを含む共重合体であってよい。
また、前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーであってよい。
本発明の別の側面によれば、機能性を与えるモノマー由来構造とベンゾオキサボロール構造とを含むベンゾオキサボロールポリマーと
ジオール構造を有するビニルアルコール樹脂と
を前記ベンゾオキサボロール構造と前記ジオール構造との結合によって
可逆的に結合してなることを特徴とする、ベンゾオキサボロールポリマーとビニルアルコール樹脂の混合生成物を与える。
前記ベンゾオキサボロールポリマーは前記ベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとの共重合体であってよい。
また、前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーであってよい。 According to one aspect of the present invention, there is provided a vinyl alcohol resin functionalizing method in which a benzoxabolol polymer containing a benzoxabolol structure and a vinyl alcohol resin are mixed and reversibly bonded.
Here, the desired functionality may be selected from the group consisting of temperature responsiveness, viscosity, electrospinning and dyeability.
The desired functionality may be the functionality possessed by the benzoxabolol polymer.
The benzoxabolol polymer may be a copolymer containing a monomer having a benzoxabolol structure and a monomer that gives the functionality.
The benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
According to another aspect of the present invention, a vinyl alcohol resin functionalizing agent comprising a benzoxabolol polymer containing a benzoxabolol structure is provided.
Here, the desired functionality may be selected from the group consisting of temperature responsiveness, viscosity, electrospinning and dyeability.
The desired functionality may be the functionality possessed by the benzoxabolol polymer.
The benzoxabolol polymer may be a copolymer containing a monomer having a benzoxabolol structure and a monomer that gives the functionality.
The benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
According to another aspect of the present invention, a benzoxabolol polymer containing a monomer-derived structure providing functionality and a benzoxabolol structure, and a vinyl alcohol resin having a diol structure, the benzoxabolol structure and the diol A mixed product of a benzoxabolol polymer and a vinyl alcohol resin, characterized by being reversibly bonded by bonding to the structure.
The benzoxabolol polymer may be a copolymer of a monomer having the benzoxabolol structure and a monomer providing the functionality.
The benzoxabolol polymer may be a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
本発明によれば、通常のＥＶＯＨに機能化剤を添加して混合するという極めて簡単な処理でＥＶＯＨに機能性を付与することができる。
According to the present invention, functionality can be imparted to EVOH by an extremely simple process of adding and mixing a functionalizing agent to ordinary EVOH.
上述の従来技術の問題点を解消するため、本発明の一態様において、式（１）で表すＥＶＯＨ
In order to solve the above-described problems of the prior art, in one embodiment of the present invention, EVOH represented by Formula (1)
と可逆的に結合できる式（２）で表すベンゾオキサボロール（ｂｅｎｚｏｘａｂｏｒｏｌｅ；ボロキソール（ｂｏｒｏｘｏｌｅ）とも呼ばれる）
Benzoxabolol represented by formula (2) that can be reversibly bound to benzoxazole (also called boroxole)
の構造を有するポリマー（以下、ベンゾオキサボロールポリマーと称する）を合成した。ベンゾオキサボロールポリマーはベンゾオキサボロールモノマーを一般に使用されているラジカル重合により合成することが可能であり、またリビングラジカル重合を使用することによって、その構造や組成を精密に制御することもできる。更に他のモノマーとともに共重合体を合成することもできる。これにより、ポリマーの分子量、分子量分布、構造等を制御することができる。各種の機能性（例えば刺激反応性、生体適合性、導電性、耐火性等）を当該ベンゾオキサボロールポリマーに付与することができるため、ＥＶＯＨ側には特段の機能性付与処理を施さなくても、ＥＶＯＨ製品の能力の向上が可能となる。また、本発明は、所望の機能性を付与したベンゾオキサボロールポリマーをＥＶＯＨと溶媒中で混合するだけで極めて簡単に実現できるので、非常に簡便かつ低コストである。なお、所望の機能性を有するベンゾオキサボロールポリマーとしては、所望の機能性を発現させるために必要に応じて官能基で修飾したベンゾオキサボロールポリマー、ベンゾオキサボロール構造を有するモノマーと所望の機能性を提供するための他のモノマーとの共重合体等の各種の態様が可能である。
A polymer having the following structure (hereinafter referred to as benzoxabolol polymer) was synthesized. The benzoxabolol polymer can be synthesized by radical polymerization that is commonly used for benzoxabolol monomers, and its structure and composition can be precisely controlled by using living radical polymerization. . Furthermore, a copolymer can be synthesized together with other monomers. Thereby, the molecular weight, molecular weight distribution, structure, etc. of the polymer can be controlled. Since various functionalities (for example, stimulus reactivity, biocompatibility, conductivity, fire resistance, etc.) can be imparted to the benzoxabolol polymer, no special functionality imparting treatment is applied to the EVOH side. However, the capacity of EVOH products can be improved. In addition, the present invention can be realized very simply by simply mixing a benzoxabolol polymer imparted with a desired functionality with EVOH in a solvent, so that it is very simple and low cost. In addition, as a benzoxabolol polymer having a desired functionality, a benzoxabolol polymer modified with a functional group as necessary to express the desired functionality, a monomer having a benzoxabolol structure and a desired Various embodiments such as copolymers with other monomers to provide the functionality of are possible.
ベンゾオキサボロールポリマーとＥＶＯＨとの可逆的な結合には、図１に示すような、ベンゾオキサボロール構造とＥＶＯＨが有する水酸基との相互作用を利用した。図１に示す可逆反応は、中性～アルカリ性では右側（ベンゾオキサボロール基とジオールとが結合する方向）へ、また酸性では左側（ベンゾオキサボロール基とジオールとが解離する方向）へ進む。なお、図１ではベンゾオキサボロールそれ自体とジオールとの相互作用が示されているがこれは例示的な記載であり、当該相互作用はベンゾオキサボロール構造を有する任意の化合物で発現する。このようなベンゾオキサボロール構造を有する化合物の例としては、これに限定するわけではないが、（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーがある。ここで注意すべき点として、たとえ立体規則性の高いポリマーであっても、ベンゾオキサボロールの構造を有していれば、図１に示したジオールとの結合の平衡反応は、ある程度進行しにくくなるとしても起こることに変わりはない。
For the reversible bond between the benzoxabolol polymer and EVOH, the interaction between the benzoxabolol structure and the hydroxyl group of EVOH as shown in FIG. 1 was used. The reversible reaction shown in FIG. 1 proceeds to the right (in the direction in which the benzoxabolol group and the diol are bonded) in neutral to alkaline, and to the left (in the direction in which the benzoxabolol group and diol are dissociated) in acidity. . Note that FIG. 1 shows an interaction between benzoxabolol itself and a diol, but this is an exemplary description, and the interaction is expressed by any compound having a benzoxabolol structure. Examples of such a compound having a benzoxabolol structure include, but are not limited to, a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton. It should be noted here that even if the polymer has high stereoregularity, if it has a benzoxabolol structure, the equilibrium reaction of the bond with the diol shown in FIG. 1 proceeds to some extent. Even if it becomes difficult, it will not change.
なお、ベンゾオキサボロールポリマーとＥＶＯＨとを混合することによって図１に示すような反応が起こるが、処理としては単に両者を混合するだけであるので、以下では両者を混合することによって図１に示すような反応が起こった状態の物を「混合生成物」と称することがある。
In addition, although the reaction as shown in FIG. 1 occurs by mixing the benzoxabolol polymer and EVOH, since both are simply mixed as processing, in the following, by mixing both, FIG. A product in which a reaction as shown in the figure has occurred may be referred to as a “mixed product”.
なお、ベンゾオキサボロール基とフェニルボロン酸とを比較すると、ベンゾオキサボロール基の方がジオールとの結合性が強いことが証明されている（非特許文献１）。従って、ベンゾオキサボロールポリマーを使用する場合、より効率的にゲル化等を引き起こすができる。
In addition, comparing the benzoxabolol group and phenylboronic acid, it has been proved that the benzoxabolol group has a stronger binding property to the diol (Non-patent Document 1). Therefore, when a benzoxabolol polymer is used, gelation or the like can be caused more efficiently.
以下の実施例ではＥＶＯＨと温度応答性や染色性を有するベンゾオキサボロールポリマーを結合させることにより、ＥＶＯＨに当該機能性を有するようにできることを示す。温度応答性を持たせることによって、室温中では容易に溶解してしまうポリマーであっても、材料により吸着できるような加工を行うことができる。また、ＥＶＯＨとベンゾオキサボロールポリマーとが図１に示すように結合すると、一般に粘性が大きくなる。この粘性も機能性の一つである。例えば、適切な粘性を有するこれらの混合生成物を電界紡糸することで、混合生成物のファイバーを得ることができる。もちろん、ＥＶＯＨに付与できる機能性は温度応答性、粘性、染色性等に限定されるものではなく、ここで説明される方法により付与可能な任意の機能性であって良い。
In the following examples, EVOH and benzoxabolol polymer having temperature responsiveness and dyeability are combined to show that EVOH can have the functionality. By giving temperature responsiveness, even a polymer that easily dissolves at room temperature can be processed so that it can be adsorbed by the material. In addition, when EVOH and a benzoxabolol polymer are bonded as shown in FIG. 1, the viscosity generally increases. This viscosity is one of the functions. For example, these mixed products having an appropriate viscosity can be electrospun to obtain mixed product fibers. Of course, the functionality that can be imparted to EVOH is not limited to temperature responsiveness, viscosity, dyeability, etc., and may be any functionality that can be imparted by the method described herein.
以下、実施例に基づいて本発明をさらに詳細に説明する。なお、以下ではＥＶＯＨとしてクラレ株式会社製のエバール（エチレン共重合比（モル比）４４％）を使用したが、もちろん一般性を失うものでないことは明らかである。
Hereinafter, the present invention will be described in more detail based on examples. In the following, EVAL manufactured by Kuraray Co., Ltd. (ethylene copolymerization ratio (molar ratio) 44%) was used as EVOH, but it is obvious that the generality is not lost.
［実施例１］
＜機能性を付与したベンゾオキサボロールポリマー＞
以下では、ＥＶＯＨに対して温度応答性、ゲル化、電界紡糸性等の機能性を持たせる例を示す。なお、この場合の温度応答性とは、ＥＶＯＨとベンゾオキサボロールポリマーから成るゲルやファイバーなどの混合生成物の表面性質を、温度により親水性／疎水性と制御することができることである。そのために使用することができるベンゾオキサボロールポリマーの例であるＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）の構造式を式（３）に示す。５－ｍｅｔｈａｃｒｙｌａｍｉｄｏ－１，２－ｂｅｎｚｏｘａｂｏｒｏｌｅ（ＭＡＡｍＢＯ）は、ベンゾオキサボロール構造の付与のため、２－（２－ｍｅｔｈｏｘｙｅｔｈｏｘｙ）ｅｔｈｙｌ ｍｅｔｈａｃｒｙｌａｔｅ（ＭＥＯ２ＭＡ）およびｏｌｉｇｏ（ｅｔｈｙｌｅｎｅ ｇｌｙｃｏｌ） ｍｅｔｈａｃｒｙｌａｔｅ（ＯＥＧＭＡ）は、温度応答性を示す温度を制御するために選択した。ベンゾオキサボロールポリマーは、これらのモノマーを基本とし、付与したい機能性を持つモノマーさらに混合後、共重合することで得られる。ここで使用される共重合法自体は既に知られている事項であるので具体的な説明は省略するが、必要に応じて本願発明者の論文である非特許文献２，３を参照されたい。 [Example 1]
<Benzoxaborol polymer with added functionality>
Hereinafter, examples in which EVOH is provided with functionality such as temperature responsiveness, gelation, and electrospinning properties will be described. The temperature responsiveness in this case is that the surface properties of a mixed product such as gel or fiber made of EVOH and benzoxabolol polymer can be controlled to be hydrophilic / hydrophobic depending on the temperature. The structural formula of P (MEO 2 MA-co-OEGMA-co-MAAmBO), which is an example of a benzoxabolol polymer that can be used for this purpose, is shown in Formula (3). 5-methacrylamido-1,2-benzoxaborole (MAAmBO) is a compound of 2- (2-methoxyethyl) ethyl methacrylate (MEO 2 MA) and oligo (ethyleneglycol) A temperature was selected to control the temperature responsiveness. The benzoxabolol polymer is based on these monomers, and can be obtained by copolymerization after further mixing with a monomer having the desired functionality. Since the copolymerization method itself used here is already known, a detailed description thereof will be omitted, but if necessary, refer to Non-Patent Documents 2 and 3 which are the articles of the present inventor.
＜機能性を付与したベンゾオキサボロールポリマー＞
以下では、ＥＶＯＨに対して温度応答性、ゲル化、電界紡糸性等の機能性を持たせる例を示す。なお、この場合の温度応答性とは、ＥＶＯＨとベンゾオキサボロールポリマーから成るゲルやファイバーなどの混合生成物の表面性質を、温度により親水性／疎水性と制御することができることである。そのために使用することができるベンゾオキサボロールポリマーの例であるＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）の構造式を式（３）に示す。５－ｍｅｔｈａｃｒｙｌａｍｉｄｏ－１，２－ｂｅｎｚｏｘａｂｏｒｏｌｅ（ＭＡＡｍＢＯ）は、ベンゾオキサボロール構造の付与のため、２－（２－ｍｅｔｈｏｘｙｅｔｈｏｘｙ）ｅｔｈｙｌ ｍｅｔｈａｃｒｙｌａｔｅ（ＭＥＯ２ＭＡ）およびｏｌｉｇｏ（ｅｔｈｙｌｅｎｅ ｇｌｙｃｏｌ） ｍｅｔｈａｃｒｙｌａｔｅ（ＯＥＧＭＡ）は、温度応答性を示す温度を制御するために選択した。ベンゾオキサボロールポリマーは、これらのモノマーを基本とし、付与したい機能性を持つモノマーさらに混合後、共重合することで得られる。ここで使用される共重合法自体は既に知られている事項であるので具体的な説明は省略するが、必要に応じて本願発明者の論文である非特許文献２，３を参照されたい。 [Example 1]
<Benzoxaborol polymer with added functionality>
Hereinafter, examples in which EVOH is provided with functionality such as temperature responsiveness, gelation, and electrospinning properties will be described. The temperature responsiveness in this case is that the surface properties of a mixed product such as gel or fiber made of EVOH and benzoxabolol polymer can be controlled to be hydrophilic / hydrophobic depending on the temperature. The structural formula of P (MEO 2 MA-co-OEGMA-co-MAAmBO), which is an example of a benzoxabolol polymer that can be used for this purpose, is shown in Formula (3). 5-methacrylamido-1,2-benzoxaborole (MAAmBO) is a compound of 2- (2-methoxyethyl) ethyl methacrylate (MEO 2 MA) and oligo (ethyleneglycol) A temperature was selected to control the temperature responsiveness. The benzoxabolol polymer is based on these monomers, and can be obtained by copolymerization after further mixing with a monomer having the desired functionality. Since the copolymerization method itself used here is already known, a detailed description thereof will be omitted, but if necessary, refer to
上に示したベンゾオキサボロールポリマー中のベンゾオキサボロール構造以外のユニットは、エチレングリコール型の温度応答性を有する。このポリマーの相転移温度はこれらの温度応答性を有するユニットの分子量や構造により変化するので、これらのモノマーを適宜選択して共重合させることにより適切なポリマーを得ることが可能である。
Units other than the benzoxabolol structure in the benzoxabolol polymer shown above have ethylene glycol type temperature responsiveness. Since the phase transition temperature of this polymer varies depending on the molecular weight and structure of these temperature-responsive units, an appropriate polymer can be obtained by appropriately selecting these monomers and copolymerizing them.
＜ＥＶＯＨとベンゾオキサボロールポリマーの混合生成物１：ゲル化＞
図２に、ＥＶＯＨとＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）とを混合して得られたゲルの写真を示す。ゲルの調製方法として、ＥＶＯＨおよびＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）を、それぞれ７０ｍｇ／ｍＬ、７０ｍｇ／ｍＬとなるようにＨＦＩＰ（１，１，１，３，３，３－ｈｅｘａｆｌｕｏｒｏｉｓｏｐｒｏｐａｎｏｌ）中に室温にて溶解させた。同体積の溶液を、室温にて混合することで、数分にてゲル状の混合生成物を得た。図１に示すような両者の相互作用により三次元的な架橋構造が構築されるため、ゲル構造を調製することが可能である。ゲルの強度は混合するポリマー比により制御することができる。また、ゾル状態における粘度についても同様に制御可能である。 <EVOH and benzoxabolol polymer mixed product 1: gelation>
FIG. 2 shows a photograph of a gel obtained by mixing EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO). As a gel preparation method, EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO) were mixed with HFIP (1,1,1,3,3,3-3-) so as to be 70 mg / mL and 70 mg / mL, respectively. Hexafluoropropanol) was dissolved at room temperature. By mixing the same volume of the solution at room temperature, a gel-like mixed product was obtained in a few minutes. Since a three-dimensional cross-linked structure is constructed by the interaction between the two as shown in FIG. 1, it is possible to prepare a gel structure. The strength of the gel can be controlled by the polymer ratio to be mixed. Further, the viscosity in the sol state can be similarly controlled.
図２に、ＥＶＯＨとＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）とを混合して得られたゲルの写真を示す。ゲルの調製方法として、ＥＶＯＨおよびＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）を、それぞれ７０ｍｇ／ｍＬ、７０ｍｇ／ｍＬとなるようにＨＦＩＰ（１，１，１，３，３，３－ｈｅｘａｆｌｕｏｒｏｉｓｏｐｒｏｐａｎｏｌ）中に室温にて溶解させた。同体積の溶液を、室温にて混合することで、数分にてゲル状の混合生成物を得た。図１に示すような両者の相互作用により三次元的な架橋構造が構築されるため、ゲル構造を調製することが可能である。ゲルの強度は混合するポリマー比により制御することができる。また、ゾル状態における粘度についても同様に制御可能である。 <EVOH and benzoxabolol polymer mixed product 1: gelation>
FIG. 2 shows a photograph of a gel obtained by mixing EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO). As a gel preparation method, EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO) were mixed with HFIP (1,1,1,3,3,3-3-) so as to be 70 mg / mL and 70 mg / mL, respectively. Hexafluoropropanol) was dissolved at room temperature. By mixing the same volume of the solution at room temperature, a gel-like mixed product was obtained in a few minutes. Since a three-dimensional cross-linked structure is constructed by the interaction between the two as shown in FIG. 1, it is possible to prepare a gel structure. The strength of the gel can be controlled by the polymer ratio to be mixed. Further, the viscosity in the sol state can be similarly controlled.
ＥＶＯＨとベンゾオキサボロールポリマーとの混合生成物は溶液中の濃度や混合比によりゾルとゲルの何れの状態としても取り扱えるため、その成形加工も容易である。バルク状態のものから、フィルム状薄膜、カプセル、またはナノファイバーにも形成加工することができる。
Since the mixed product of EVOH and benzoxabolol polymer can be handled as either a sol or a gel depending on the concentration or mixing ratio in the solution, the molding process is easy. From a bulk state, a film-like thin film, a capsule, or a nanofiber can be formed and processed.
［実施例２］
＜ＥＶＯＨとベンゾオキサボロールポリマーの混合生成物２：ナノファイバー＞
実施例１で得られた式（３）で表すベンゾオキサボロールポリマーＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）を用いた。図３（Ｂ）はＥＶＯＨ（濃度：３．５ｗｔ％）とＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）（濃度：２．５ｗｔ％）とをＨＦＩＰ中で混合した溶液を電界紡糸した結果のＳＥＭ像を示す。
図３（Ｂ）からわかるように、ＥＶＯＨとＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）との混合生成物２を電界紡糸することによってナノファイバーの集積体を得ることができる。この集積体では繊維間の隙間の大きさが比較的よくそろっている。なお、この隙間の大きさは、電界紡糸の条件や混合生成物濃度等を調節することによって制御可能である。 [Example 2]
<Mixed product of EVOH and benzoxabolol polymer 2: nanofiber>
The benzoxabolol polymer P (MEO 2 MA-co-OEGMA-co-MAAmBO) represented by the formula (3) obtained in Example 1 was used. FIG. 3 (B) shows an electrospinning solution in which EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA-co-MAAmBO) (concentration: 2.5 wt%) are mixed in HFIP. The SEM image of a result is shown.
As can be seen from FIG. 3B, a nanofiber assembly can be obtained by electrospinning amixed product 2 of EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO). In this aggregate, the gaps between the fibers are relatively well aligned. The size of the gap can be controlled by adjusting the electrospinning conditions, the mixed product concentration, and the like.
＜ＥＶＯＨとベンゾオキサボロールポリマーの混合生成物２：ナノファイバー＞
実施例１で得られた式（３）で表すベンゾオキサボロールポリマーＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）を用いた。図３（Ｂ）はＥＶＯＨ（濃度：３．５ｗｔ％）とＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）（濃度：２．５ｗｔ％）とをＨＦＩＰ中で混合した溶液を電界紡糸した結果のＳＥＭ像を示す。
図３（Ｂ）からわかるように、ＥＶＯＨとＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）との混合生成物２を電界紡糸することによってナノファイバーの集積体を得ることができる。この集積体では繊維間の隙間の大きさが比較的よくそろっている。なお、この隙間の大きさは、電界紡糸の条件や混合生成物濃度等を調節することによって制御可能である。 [Example 2]
<Mixed product of EVOH and benzoxabolol polymer 2: nanofiber>
The benzoxabolol polymer P (MEO 2 MA-co-OEGMA-co-MAAmBO) represented by the formula (3) obtained in Example 1 was used. FIG. 3 (B) shows an electrospinning solution in which EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA-co-MAAmBO) (concentration: 2.5 wt%) are mixed in HFIP. The SEM image of a result is shown.
As can be seen from FIG. 3B, a nanofiber assembly can be obtained by electrospinning a
［実施例３］
＜ＥＶＯＨとベンゾオキサボロールポリマーの混合生成物３：ナノファイバー＞
実施例１で得られた式（３）で表すベンゾオキサボロールポリマーＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）を用いた。図３（Ｃ）はＥＶＯＨ（濃度：３．５ｗｔ％）とＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）（濃度：０．５ｗｔ％）とをＨＦＩＰ中で混合した溶液を電界紡糸した結果のＳＥＭ像を示す。
図３（Ｃ）ではＥＶＯＨとＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）との混合生成物３を電界紡糸したにもかかわらずナノファイバーが形成されていないが、これはＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）の量が実施例２の図３（Ｂ）の２．５ｗｔ％に比べて０．５ｗｔ％と少ないために、混合生成物３の粘性が図３（Ｂ）の場合に比べて低下したためである。 [Example 3]
<Mixed product of EVOH and benzoxabolol polymer 3: nanofiber>
The benzoxabolol polymer P (MEO 2 MA-co-OEGMA-co-MAAmBO) represented by the formula (3) obtained in Example 1 was used. FIG. 3C shows an electrospinning solution in which EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA-co-MAAmBO) (concentration: 0.5 wt%) are mixed in HFIP. The SEM image of a result is shown.
In FIG. 3C, nanofibers are not formed despite the electrospinning of themixed product 3 of EVOH and P (MEO 2 MA-co-OEGMA-co-MAAmBO). 2 MA-co-OEGMA-co-MAAmBO) is less than 0.5 wt% compared to 2.5 wt% in FIG. 3 (B) in Example 2, so that the viscosity of the mixed product 3 is as shown in FIG. This is because it is lower than in the case of B).
＜ＥＶＯＨとベンゾオキサボロールポリマーの混合生成物３：ナノファイバー＞
実施例１で得られた式（３）で表すベンゾオキサボロールポリマーＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）を用いた。図３（Ｃ）はＥＶＯＨ（濃度：３．５ｗｔ％）とＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）（濃度：０．５ｗｔ％）とをＨＦＩＰ中で混合した溶液を電界紡糸した結果のＳＥＭ像を示す。
図３（Ｃ）ではＥＶＯＨとＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）との混合生成物３を電界紡糸したにもかかわらずナノファイバーが形成されていないが、これはＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ－ｃｏ－ＭＡＡｍＢＯ）の量が実施例２の図３（Ｂ）の２．５ｗｔ％に比べて０．５ｗｔ％と少ないために、混合生成物３の粘性が図３（Ｂ）の場合に比べて低下したためである。 [Example 3]
<Mixed product of EVOH and benzoxabolol polymer 3: nanofiber>
The benzoxabolol polymer P (MEO 2 MA-co-OEGMA-co-MAAmBO) represented by the formula (3) obtained in Example 1 was used. FIG. 3C shows an electrospinning solution in which EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA-co-MAAmBO) (concentration: 0.5 wt%) are mixed in HFIP. The SEM image of a result is shown.
In FIG. 3C, nanofibers are not formed despite the electrospinning of the
［比較例１］
＜ＥＶＯＨ単独のＨＦＩＰ溶液＞
図３（Ａ）はＥＶＯＨ（濃度：３．５ｗｔ％）単独のＨＦＩＰ溶液を電界紡糸した結果のＳＥＭ像を示す。
［比較例２］
＜ＥＶＯＨとベンゾオキサボロール構造を有しない共重合体の混合物＞
図３（Ｄ）には、ＥＶＯＨ（濃度：３．５ｗｔ％）とＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ）（濃度：２．５ｗｔ％）（すなわち、ベンゾオキサボロール構造を有しない共重合体）とをＨＦＩＰ中で混合した溶液を電界紡糸した結果のＳＥＭ像を示す。
実施例２と３の結果に対して、比較例１のＥＶＯＨ単独の場合（図３（Ａ））及び比較例２のＥＶＯＨと混合したポリマーがベンゾオキサボロール構造を含んでいない場合（図３（Ｄ））は、ＥＶＯＨの量は図３（Ｂ）の場合と同じく３．５ｗｔ％であったにもかかわらず、何れもナノファイバーが形成されなかった。これは、図１に示すような相互作用が起こっていないために粘度が低いままであったことによる。 [Comparative Example 1]
<HFIP single HFIP solution>
FIG. 3A shows an SEM image as a result of electrospinning an HFIP solution containing EVOH (concentration: 3.5 wt%) alone.
[Comparative Example 2]
<Mixture of EVOH and copolymer having no benzoxabolol structure>
FIG. 3D shows EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA) (concentration: 2.5 wt%) (that is, a copolymer having no benzoxabolol structure). The SEM image of the result of electrospinning the solution which mixed) in HFIP is shown.
In contrast to the results of Examples 2 and 3, when EVOH of Comparative Example 1 alone (FIG. 3A) and when the polymer mixed with EVOH of Comparative Example 2 does not contain a benzoxabolol structure (FIG. 3) In (D)), although the amount of EVOH was 3.5 wt% as in the case of FIG. 3B, no nanofiber was formed. This is because the viscosity remained low because no interaction as shown in FIG. 1 occurred.
＜ＥＶＯＨ単独のＨＦＩＰ溶液＞
図３（Ａ）はＥＶＯＨ（濃度：３．５ｗｔ％）単独のＨＦＩＰ溶液を電界紡糸した結果のＳＥＭ像を示す。
［比較例２］
＜ＥＶＯＨとベンゾオキサボロール構造を有しない共重合体の混合物＞
図３（Ｄ）には、ＥＶＯＨ（濃度：３．５ｗｔ％）とＰ（ＭＥＯ２ＭＡ－ｃｏ－ＯＥＧＭＡ）（濃度：２．５ｗｔ％）（すなわち、ベンゾオキサボロール構造を有しない共重合体）とをＨＦＩＰ中で混合した溶液を電界紡糸した結果のＳＥＭ像を示す。
実施例２と３の結果に対して、比較例１のＥＶＯＨ単独の場合（図３（Ａ））及び比較例２のＥＶＯＨと混合したポリマーがベンゾオキサボロール構造を含んでいない場合（図３（Ｄ））は、ＥＶＯＨの量は図３（Ｂ）の場合と同じく３．５ｗｔ％であったにもかかわらず、何れもナノファイバーが形成されなかった。これは、図１に示すような相互作用が起こっていないために粘度が低いままであったことによる。 [Comparative Example 1]
<HFIP single HFIP solution>
FIG. 3A shows an SEM image as a result of electrospinning an HFIP solution containing EVOH (concentration: 3.5 wt%) alone.
[Comparative Example 2]
<Mixture of EVOH and copolymer having no benzoxabolol structure>
FIG. 3D shows EVOH (concentration: 3.5 wt%) and P (MEO 2 MA-co-OEGMA) (concentration: 2.5 wt%) (that is, a copolymer having no benzoxabolol structure). The SEM image of the result of electrospinning the solution which mixed) in HFIP is shown.
In contrast to the results of Examples 2 and 3, when EVOH of Comparative Example 1 alone (FIG. 3A) and when the polymer mixed with EVOH of Comparative Example 2 does not contain a benzoxabolol structure (FIG. 3) In (D)), although the amount of EVOH was 3.5 wt% as in the case of FIG. 3B, no nanofiber was formed. This is because the viscosity remained low because no interaction as shown in FIG. 1 occurred.
［実施例４］
＜ＥＶＯＨとカルボキシル基を有するベンゾオキサボロールポリマーの混合生成物４：染色機能の付与＞
以下の式（４）で一般的に表現される構造を有する、骨格をカルボキシル基で修飾したベンゾオキサボロールポリマー [Example 4]
<Mixed product of EVOH and benzoxabolol polymer having carboxyl group 4: imparting dyeing function>
A benzoxabolol polymer having a structure generally expressed by the following formula (4) and having a skeleton modified with a carboxyl group
＜ＥＶＯＨとカルボキシル基を有するベンゾオキサボロールポリマーの混合生成物４：染色機能の付与＞
以下の式（４）で一般的に表現される構造を有する、骨格をカルボキシル基で修飾したベンゾオキサボロールポリマー [Example 4]
<Mixed product of EVOH and benzoxabolol polymer having carboxyl group 4: imparting dyeing function>
A benzoxabolol polymer having a structure generally expressed by the following formula (4) and having a skeleton modified with a carboxyl group
とＥＶＯＨとを混合することにより、カチオン性染料へのＥＶＯＨの染色性を向上させることができる。本実施例で使用したベンゾオキサボロールポリマーの具体的な構造は以下の式（５）通りである。
By mixing EVOH with EVOH, it is possible to improve the dyeability of EVOH on a cationic dye. The specific structure of the benzoxabolol polymer used in this example is as shown in the following formula (5).
ＥＶＯＨとこのベンゾオキサボロールポリマーとの混合生成物を電界紡糸して得られた集積物（図４（ａ））を染色実験の対象として準備した。
この集積物を式（６）で表すメチレンブルー An accumulation (FIG. 4 (a)) obtained by electrospinning a mixture product of EVOH and the benzoxabolol polymer was prepared as an object for a dyeing experiment.
This accumulation is represented by the formula (6) methylene blue
この集積物を式（６）で表すメチレンブルー An accumulation (FIG. 4 (a)) obtained by electrospinning a mixture product of EVOH and the benzoxabolol polymer was prepared as an object for a dyeing experiment.
This accumulation is represented by the formula (6) methylene blue
で染色した結果をそれぞれ図５（ａ）に示す。
［比較例３］
＜ＥＶＯＨとカルボキシル基を含まないベンゾオキサボロールポリマーの混合生成物＞
実施例４の式（５）で表すベンゾオキサボロールポリマーと比較して、カルボキシル基が修飾されていない点以外はほぼ同じ構造を有する式（７）で表すベンゾオキサボロールポリマー The results of staining with are shown in FIG.
[Comparative Example 3]
<Mixed product of EVOH and benzoxabolol polymer not containing carboxyl group>
Compared with the benzoxabolol polymer represented by formula (5) in Example 4, the benzoxabolol polymer represented by formula (7) having substantially the same structure except that the carboxyl group is not modified.
［比較例３］
＜ＥＶＯＨとカルボキシル基を含まないベンゾオキサボロールポリマーの混合生成物＞
実施例４の式（５）で表すベンゾオキサボロールポリマーと比較して、カルボキシル基が修飾されていない点以外はほぼ同じ構造を有する式（７）で表すベンゾオキサボロールポリマー The results of staining with are shown in FIG.
[Comparative Example 3]
<Mixed product of EVOH and benzoxabolol polymer not containing carboxyl group>
Compared with the benzoxabolol polymer represented by formula (5) in Example 4, the benzoxabolol polymer represented by formula (7) having substantially the same structure except that the carboxyl group is not modified.
との混合生成物を電界紡糸した比較対象集積物（図４（ｂ））を準備した。
実施例４と同様に、この集積物を式（６）で表すメチレンブルーで染色した結果をそれぞれ図５（ｂ）に示す。
なお、上記式（５）と（７）で表すこれら２種類のベンゾオキサボロールポリマーを比較すると、実施例４の式（５）で表すベンゾオキサボロールポリマーは比較例３の式（７）で表すベンゾオキサボロールポリマーに更にカルボキシル基を有する比較的小さなモノマー由来の構造を追加した構造になっていることがわかる。
図５からわかるように、本発明の実施例４である、ＥＶＯＨとカルボキシル基で修飾されたベンゾオキサボロールポリマーとの混合生成物４から作製された集積物はカルボキシル基で修飾されていないベンゾオキサボロールポリマーを使用した集積物に比べて強く染色されていることがわかる。なお、図５は白黒写真であるので、（ａ）側が（ｂ）側に比べて僅かに黒いように見えるだけであるが、実際には（ｂ）側が青色であるのに対して、（ａ）側は濃紺色に染色され、染色性の違いをはっきりと視認することができた。このようにＥＶＯＨとカルボキシル基で修飾されたベンゾオキサボロールポリマーとを混合して作成した集積物の方が高い染色性を有する理由は、集積物中で電離して－ＣＯＯ－の形態で存在するカルボキシル基とカチオン性の染料であるメチレンブルーとが静電相互作用を起こすためである。なお、本実施例では染料としてメチレンブルーを使用し、またベンゾオキサボロールポリマーをカルボキシル基で修飾したが、この組み合わせに限定されるものではなく、任意のカチオン性染料と負にイオン化する任意の官能基により修飾されたベンゾオキサボロールポリマーとの組み合わせにより染色性の向上を達成することができる。逆に、任意のアニオン性染料と正にイオン化する任意の官能基により修飾されたベンゾオキサボロールポリマーとの組み合わせででも染色性の向上が可能である。 A comparative assembly (FIG. 4B) obtained by electrospinning the mixed product was prepared.
Similarly to Example 4, the result of staining this aggregate with methylene blue represented by formula (6) is shown in FIG. 5 (b).
When these two types of benzoxabolol polymers represented by the above formulas (5) and (7) are compared, the benzoxabolol polymer represented by the formula (5) in Example 4 is the formula (7) in Comparative Example 3. It can be seen that a structure derived from a relatively small monomer having a carboxyl group is added to the benzoxabolol polymer represented by
As can be seen from FIG. 5, the assembly made from the mixed product 4 of EVOH and a benzoxabolol polymer modified with a carboxyl group, which is Example 4 of the present invention, is a benzoate not modified with a carboxyl group. It turns out that it is dye | staining strongly compared with the accumulation | aggregation which uses an oxabolol polymer. Since FIG. 5 is a black-and-white photograph, the (a) side only looks slightly black compared to the (b) side, but in fact the (b) side is blue, ) Side was dyed dark blue, and the difference in dyeability could be clearly recognized. The reason why the accumulation produced by mixing EVOH and a benzoxabolol polymer modified with a carboxyl group in this way has higher dyeability is that it is ionized in the accumulation and exists in the form of -COO- This is because an electrostatic interaction occurs between the carboxyl group to be reacted and methylene blue which is a cationic dye. In this example, methylene blue was used as the dye, and the benzoxabolol polymer was modified with a carboxyl group. However, the present invention is not limited to this combination, and any functional group that ionizes negatively with any cationic dye. Improvement in dyeability can be achieved by combination with a benzoxabolol polymer modified with a group. On the contrary, the dyeability can be improved by a combination of any anionic dye and a benzoxabolol polymer modified with any functional group capable of positive ionization.
実施例４と同様に、この集積物を式（６）で表すメチレンブルーで染色した結果をそれぞれ図５（ｂ）に示す。
なお、上記式（５）と（７）で表すこれら２種類のベンゾオキサボロールポリマーを比較すると、実施例４の式（５）で表すベンゾオキサボロールポリマーは比較例３の式（７）で表すベンゾオキサボロールポリマーに更にカルボキシル基を有する比較的小さなモノマー由来の構造を追加した構造になっていることがわかる。
図５からわかるように、本発明の実施例４である、ＥＶＯＨとカルボキシル基で修飾されたベンゾオキサボロールポリマーとの混合生成物４から作製された集積物はカルボキシル基で修飾されていないベンゾオキサボロールポリマーを使用した集積物に比べて強く染色されていることがわかる。なお、図５は白黒写真であるので、（ａ）側が（ｂ）側に比べて僅かに黒いように見えるだけであるが、実際には（ｂ）側が青色であるのに対して、（ａ）側は濃紺色に染色され、染色性の違いをはっきりと視認することができた。このようにＥＶＯＨとカルボキシル基で修飾されたベンゾオキサボロールポリマーとを混合して作成した集積物の方が高い染色性を有する理由は、集積物中で電離して－ＣＯＯ－の形態で存在するカルボキシル基とカチオン性の染料であるメチレンブルーとが静電相互作用を起こすためである。なお、本実施例では染料としてメチレンブルーを使用し、またベンゾオキサボロールポリマーをカルボキシル基で修飾したが、この組み合わせに限定されるものではなく、任意のカチオン性染料と負にイオン化する任意の官能基により修飾されたベンゾオキサボロールポリマーとの組み合わせにより染色性の向上を達成することができる。逆に、任意のアニオン性染料と正にイオン化する任意の官能基により修飾されたベンゾオキサボロールポリマーとの組み合わせででも染色性の向上が可能である。 A comparative assembly (FIG. 4B) obtained by electrospinning the mixed product was prepared.
Similarly to Example 4, the result of staining this aggregate with methylene blue represented by formula (6) is shown in FIG. 5 (b).
When these two types of benzoxabolol polymers represented by the above formulas (5) and (7) are compared, the benzoxabolol polymer represented by the formula (5) in Example 4 is the formula (7) in Comparative Example 3. It can be seen that a structure derived from a relatively small monomer having a carboxyl group is added to the benzoxabolol polymer represented by
As can be seen from FIG. 5, the assembly made from the mixed product 4 of EVOH and a benzoxabolol polymer modified with a carboxyl group, which is Example 4 of the present invention, is a benzoate not modified with a carboxyl group. It turns out that it is dye | staining strongly compared with the accumulation | aggregation which uses an oxabolol polymer. Since FIG. 5 is a black-and-white photograph, the (a) side only looks slightly black compared to the (b) side, but in fact the (b) side is blue, ) Side was dyed dark blue, and the difference in dyeability could be clearly recognized. The reason why the accumulation produced by mixing EVOH and a benzoxabolol polymer modified with a carboxyl group in this way has higher dyeability is that it is ionized in the accumulation and exists in the form of -COO- This is because an electrostatic interaction occurs between the carboxyl group to be reacted and methylene blue which is a cationic dye. In this example, methylene blue was used as the dye, and the benzoxabolol polymer was modified with a carboxyl group. However, the present invention is not limited to this combination, and any functional group that ionizes negatively with any cationic dye. Improvement in dyeability can be achieved by combination with a benzoxabolol polymer modified with a group. On the contrary, the dyeability can be improved by a combination of any anionic dye and a benzoxabolol polymer modified with any functional group capable of positive ionization.
以上詳細に説明したように、本発明においては、ＥＶＯＨは容易に入手可能な既存の材料を使用し、これに所望の機能性を有するベンゾオキサボロールポリマーを混合するだけで、ＥＶＯＨの特徴を維持したままで所望の機能性を持たせることができるので、本発明はＥＶＯＨの用途の拡大等に広く利用されることが期待される。
As described above in detail, in the present invention, EVOH uses existing materials that are easily available, and only by mixing a benzoxabolol polymer having a desired functionality with EVOH, the characteristics of EVOH can be obtained. Since the desired functionality can be imparted while maintaining it, the present invention is expected to be widely used for expanding the use of EVOH.
Claims (13)
- ベンゾオキサボロール構造を含むベンゾオキサボロールポリマーとビニルアルコール樹脂とを混合して両者を可逆的に結合することを特徴とする、ビニルアルコール樹脂機能化方法。 A method for functionalizing a vinyl alcohol resin, comprising mixing a benzoxabolol polymer containing a benzoxabolol structure and a vinyl alcohol resin and reversibly bonding them.
- 前記所望の機能性は温度応答性、粘性、電界紡糸性及び染色性からなる群から選択される、請求項１に記載のビニルアルコール樹脂機能化方法。 The vinyl alcohol resin functionalization method according to claim 1, wherein the desired functionality is selected from the group consisting of temperature responsiveness, viscosity, electrospinning property, and dyeability.
- 前記所望の機能性は前記ベンゾオキサボロールポリマーが有する機能性である、請求項１に記載のビニルアルコール樹脂機能化方法。 The vinyl alcohol resin functionalization method according to claim 1, wherein the desired functionality is a functionality of the benzoxabolol polymer.
- 前記ベンゾオキサボロールポリマーはベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとを含む共重合体である、請求項３に記載のビニルアルコール樹脂機能化方法。 4. The method for functionalizing a vinyl alcohol resin according to claim 3, wherein the benzoxabolol polymer is a copolymer containing a monomer having a benzoxabolol structure and a monomer imparting the functionality.
- 前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーである、請求項１に記載のビニルアルコール樹脂機能化方法。 The method for functionalizing a vinyl alcohol resin according to claim 1, wherein the benzoxabolol polymer is a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
- ベンゾオキサボロール誘導体を含むベンゾオキサボロールポリマーからなることを特徴とする、ビニルアルコール樹脂機能化剤。 A vinyl alcohol resin functionalizing agent comprising a benzoxabolol polymer containing a benzoxabolol derivative.
- 前記所望の機能性は温度応答性、粘性、電界紡糸性及び染色性からなる群から選択される、請求項６に記載のビニルアルコール樹脂機能化剤。 The vinyl alcohol resin functionalizing agent according to claim 6, wherein the desired functionality is selected from the group consisting of temperature responsiveness, viscosity, electrospinning property, and dyeability.
- 前記所望の機能性は前記ベンゾオキサボロールポリマーが有する機能性である、請求項６に記載のビニルアルコール樹脂機能化剤。 The vinyl alcohol resin functionalizing agent according to claim 6, wherein the desired functionality is a functionality of the benzoxabolol polymer.
- 前記ベンゾオキサボロールポリマーはベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとを含む共重合体である、請求項８に記載のビニルアルコール樹脂機能化剤。 The vinyl alcohol resin functionalizing agent according to claim 8, wherein the benzoxabolol polymer is a copolymer containing a monomer having a benzoxabolol structure and a monomer imparting the functionality.
- 前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーである、請求項６に記載のビニルアルコール樹脂機能化剤。 The vinyl alcohol resin functionalizing agent according to claim 6, wherein the benzoxabolol polymer is a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
- 機能性を与えるモノマー由来構造とベンゾオキサボロール構造とを含むベンゾオキサボロールポリマーと
ジオール構造を有するビニルアルコール樹脂と
を前記ベンゾオキサボロール構造と前記ジオール構造との結合によって
可逆的に結合してなることを特徴とする、ベンゾオキサボロールポリマーとビニルアルコール樹脂の混合生成物。 A benzoxabolol polymer containing a monomer-derived structure giving functionality and a benzoxabolol structure and a vinyl alcohol resin having a diol structure are reversibly bonded by the bond between the benzoxabolol structure and the diol structure. A mixed product of a benzoxabolol polymer and a vinyl alcohol resin. - 前記ベンゾオキサボロールポリマーは、前記ベンゾオキサボロール構造を有するモノマーと前記機能性を与えるモノマーとの共重合体である、請求項１１に記載の混合生成物。 The mixed product according to claim 11, wherein the benzoxabolol polymer is a copolymer of a monomer having the benzoxabolol structure and a monomer imparting the functionality.
- 前記ベンゾオキサボロールポリマーは（メタ）アクリルアミド型および（メタ）アクリレート型を基本骨格とするベンゾオキサボロールポリマーである、請求項１１に記載の混合生成物。 The mixed product according to claim 11, wherein the benzoxabolol polymer is a benzoxabolol polymer having a (meth) acrylamide type and a (meth) acrylate type as a basic skeleton.
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| WO2021055752A1 (en) * | 2019-09-20 | 2021-03-25 | Glyscend, Inc. | Benzoxaborole polymers and methods of use |
| US11484548B2 (en) | 2019-09-20 | 2022-11-01 | Glyscend, Inc. | Substituted phenyl boronic acid containing polymers and methods of use |
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| AKIHIKO KIKUCHI ET AL.: "Glucose-Sensing Electrode Coated with Polymer Complex Gel Containing Phenylboronic Acid", ANALYTICAL CHEMISTRY, vol. 68, no. 5, pages 823 - 828, XP000580391 * |
| YOHEI KOTSUCHIBASHI ET AL.: "Temperature, PH , and Glucose Responsive Gels via Simple Mixing of Boroxole- and Glyco-Based Polymers", ACS MACRO LETT., vol. 2, pages 260 - 264, XP055376139 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021055752A1 (en) * | 2019-09-20 | 2021-03-25 | Glyscend, Inc. | Benzoxaborole polymers and methods of use |
| US11484548B2 (en) | 2019-09-20 | 2022-11-01 | Glyscend, Inc. | Substituted phenyl boronic acid containing polymers and methods of use |
| US11491183B2 (en) | 2019-09-20 | 2022-11-08 | Glyscend, Inc. | Substituted phenyl boronic acid containing polymers and methods of use |
| US11491182B2 (en) | 2019-09-20 | 2022-11-08 | Glyscend, Inc. | Substituted phenyl boronic acid containing polymers and methods of use |
| US11576928B2 (en) | 2019-09-20 | 2023-02-14 | Glyscend, Inc. | Substituted phenyl boronic acid containing polymers and methods of use |
| EP4041740A4 (en) * | 2019-09-20 | 2023-10-25 | Glyscend, Inc. | Benzoxaborole polymers and methods of use |
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