JPH09328521A - L-ascorbate-modified polyvinyl alcohol and production thereof - Google Patents
L-ascorbate-modified polyvinyl alcohol and production thereofInfo
- Publication number
- JPH09328521A JPH09328521A JP16863996A JP16863996A JPH09328521A JP H09328521 A JPH09328521 A JP H09328521A JP 16863996 A JP16863996 A JP 16863996A JP 16863996 A JP16863996 A JP 16863996A JP H09328521 A JPH09328521 A JP H09328521A
- Authority
- JP
- Japan
- Prior art keywords
- ascorbic acid
- polyvinyl alcohol
- formula
- acid
- modified polyvinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸素還元性高分子
として有用なＬ−アスコルビン酸変性ポリビニルアルコ
ール及びその製造方法に関する。TECHNICAL FIELD The present invention relates to L-ascorbic acid-modified polyvinyl alcohol useful as an oxygen-reducing polymer and a method for producing the same.
【０００２】[0002]
【従来の技術】従来よりＬ−アスコルビン酸は、酸素を
還元するその性質を利用して、酸化防止剤の主成分とし
て、あるいは脱酸素材料の主成分として使用されてい
る。2. Description of the Related Art Conventionally, L-ascorbic acid has been used as a main component of an antioxidant or a main component of a deoxidizing material by utilizing its property of reducing oxygen.
【０００３】ところで、Ｌ−アスコルビン酸は、非常に
高い水溶性を有し、しかも酸化に対する安定性が著しく
低いために取扱性が劣るという問題があった。By the way, L-ascorbic acid has a problem that it is inferior in handleability due to its extremely high water solubility and its extremely low stability against oxidation.
【０００４】このため、Ｌ−アスコルビン酸をエチレン
−酢酸ビニル共重合体（ＥＶＡ）に練り込んだ酸素吸収
性ポリマー材料を脱酸素材料として使用することが試み
られたが、酸素吸収能の点で十分でなく、また、Ｌ−ア
スコルビン酸が高分子鎖に結合していないので耐水性や
耐溶媒性が不十分という問題があった。また、練り込み
時の加熱によりＬ−アスコルビン酸が分解することが懸
念される。Therefore, it has been attempted to use an oxygen-absorbing polymer material obtained by kneading L-ascorbic acid in an ethylene-vinyl acetate copolymer (EVA) as a deoxidizing material, but in view of oxygen-absorbing ability. There was a problem that water resistance and solvent resistance were insufficient because L-ascorbic acid was not bonded to the polymer chain. Further, there is a concern that L-ascorbic acid may be decomposed by heating during kneading.
【０００５】そこで、Ｌ−アスコルビン酸の耐水性や酸
化安定性を改善する目的で、高分子鎖にＬ−アスコルビ
ン酸セグメントを導入することが試みられている。この
ようなＬ−アスコルビン酸セグメントが導入された酸素
還元性高分子を製造するために必要なモノマーとして
は、Ｌ−アスコルビン酸の６位の水酸基に重合性の官能
基が導入されたＬ−アスコルビン酸メタクリル酸エステ
ルモノマーを挙げることができ、これらは（ａ）メタク
リル酸エノールエステルとＬ−アスコルビン酸とをリパ
ーゼの存在下で反応させる方法、（ｂ）メタクリル酸ク
ロライドとＬ−アスコルビン酸とを塩基性化合物の存在
下で反応させる方法、（ｃ）メタクリル酸無水物とＬ−
アスコルビン酸とを塩基性縮合剤の存在下で反応させる
方法により製造することが提案されている（特開平５−
３３１１５７号公報）。Therefore, for the purpose of improving the water resistance and oxidative stability of L-ascorbic acid, it has been attempted to introduce an L-ascorbic acid segment into the polymer chain. As a monomer necessary for producing such an oxygen-reducing polymer having an L-ascorbic acid segment introduced therein, L-ascorbic acid having a polymerizable functional group introduced at the 6-position hydroxyl group of L-ascorbic acid is used. Examples thereof include acid methacrylic acid ester monomers, which are (a) a method of reacting methacrylic acid enol ester and L-ascorbic acid in the presence of lipase, and (b) a methacrylic acid chloride and L-ascorbic acid as a base. Of reacting in the presence of an organic compound, (c) methacrylic anhydride and L-
It has been proposed to produce it by a method of reacting with ascorbic acid in the presence of a basic condensing agent (Japanese Patent Laid-Open No. HEI 5-
331157).
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上述の
方法（ａ）の場合、酵素反応を利用しているために大量
生産が困難であり、方法（ｂ）の場合、原料として使用
する酸クロライドの皮膚や粘膜に対する刺激性が高く、
しかも加水分解しやすく取扱性が低く、また、方法
（ｃ）の場合、反応系内の酸素の影響のために高い再現
性でＬ−アスコルビン酸メタクリル酸エステルモノマー
を製造することが困難である。そのために、従来より、
簡便な手法により、高分子鎖にＬ−アスコルビン酸で変
性した構造を導入することが求められていた。However, in the case of the above-mentioned method (a), it is difficult to mass-produce it because the enzyme reaction is used, and in the case of the method (b), the acid chloride used as a raw material is Highly irritating to skin and mucous membranes,
Moreover, it is easily hydrolyzed and has a low handleability, and in the case of the method (c), it is difficult to produce the L-ascorbic acid methacrylic acid ester monomer with high reproducibility due to the influence of oxygen in the reaction system. Therefore, from the past,
It has been required to introduce a structure modified with L-ascorbic acid into a polymer chain by a simple method.
【０００７】本発明は、以上の従来技術の問題を解決し
ようとするものであり、酵素や酸クロライドを利用する
ことなく、簡便な手法により主鎖にＬ−アスコルビン酸
ユニットが導入された高分子を提供できるようにするこ
とを目的とする。The present invention is intended to solve the above problems of the prior art, and is a polymer in which an L-ascorbic acid unit is introduced into the main chain by a simple method without using an enzyme or an acid chloride. The purpose is to be able to provide.
【０００８】[0008]
【課題を解決するための手段】上述の目的は、以下の本
発明により解決される。The above-mentioned object can be solved by the present invention described below.
【０００９】即ち、本発明は、式（１）又は式（２）That is, according to the present invention, the formula (1) or the formula (2) is used.
【００１０】[0010]
【化４】 で表される構造部分を有するＬ−アスコルビン酸変性ポ
リビニルアルコール（以下、式（１）又は（２）のＬ−
アスコルビン酸変性ポリビニルアルコールと略記す
る。）を提供する。Embedded image L-ascorbic acid-modified polyvinyl alcohol having a structural portion represented by (hereinafter, L-of formula (1) or (2)
Abbreviated as ascorbic acid-modified polyvinyl alcohol. )I will provide a.
【００１１】また、本発明は、酸化クロム−ピリジン錯
体からなる酸化剤又はクロロクロム酸ピリジニウムと酢
酸ナトリウムとの混合酸化剤でＬ−アスコルビン酸の６
位の水酸基を酸化してアルデヒド基に変換し、得られた
アルデヒド化合物でポリビニルアルコールをアセタール
化することを特徴とする式（１）のＬ−アスコルビン酸
変性ポリビニルアルコールの製造方法を提供する。Further, the present invention is an oxidant consisting of a chromium oxide-pyridine complex or a mixed oxidant of pyridinium chlorochromate and sodium acetate, which is used as a oxidant of L-ascorbic acid.
A method for producing an L-ascorbic acid-modified polyvinyl alcohol of the formula (1), characterized in that a hydroxyl group at a position is oxidized to be converted into an aldehyde group, and the obtained aldehyde compound acetalizes polyvinyl alcohol.
【００１２】また、本発明は、濃硫酸中に（メタ）アク
リル酸を溶解させ、その溶液にＬ−アスコルビン酸を添
加することによりＬ−アスコルビン酸の６位の水酸基を
（メタ）アクリル酸でエステル化し、得られたエステル
化合物とポリビニルアルコールとを硝酸セリウムアンモ
ニウムの存在下で重合させることを特徴とする式（２）
のＬ−アスコルビン酸変性ポリビニルアルコールの製造
方法を提供する。Further, in the present invention, (meth) acrylic acid is dissolved in concentrated sulfuric acid, and L-ascorbic acid is added to the solution to convert the 6-position hydroxyl group of L-ascorbic acid into (meth) acrylic acid. Formula (2) characterized by esterifying and polymerizing the obtained ester compound and polyvinyl alcohol in the presence of cerium ammonium nitrate.
The present invention provides a method for producing L-ascorbic acid-modified polyvinyl alcohol.
【００１３】更に、本発明は、上述のＬ−アスコルビン
酸変性ポリビニルアルコールを含有する脱酸素材料を提
供する。The present invention further provides a deoxidizing material containing the above-mentioned L-ascorbic acid-modified polyvinyl alcohol.
【００１４】[0014]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
【００１５】本発明の式（１）又は（２）のＬ−アスコ
ルビン酸変性ポリビニルアルコールは、その水酸基にＬ
−アスコルビン酸残基が導入されている。しかも、酸素
の還元に大きく寄与すると考えられているＬ−アスコル
ビン酸残基の２位と３位との水酸基はそのまま保持され
ている。従って、このＬ−アスコルビン酸変性ポリビニ
ルアルコールは酸素還元性高分子となる。The L-ascorbic acid-modified polyvinyl alcohol of the formula (1) or (2) of the present invention has L at its hydroxyl group.
-Ascorbic acid residues have been introduced. In addition, the hydroxyl groups at the 2nd and 3rd positions of the L-ascorbic acid residue, which are considered to largely contribute to the reduction of oxygen, are retained as they are. Therefore, this L-ascorbic acid-modified polyvinyl alcohol becomes an oxygen-reducing polymer.
【００１６】本発明の式（１）のＬ−アスコルビン酸変
性ポリビニルアルコールは、次のように製造することが
できる。The L-ascorbic acid-modified polyvinyl alcohol of the formula (1) of the present invention can be produced as follows.
【００１７】ピリジン０．１〜０．５モルを含むジクロ
ロメタン１００〜２５０ｍｌ／ＤＭＳＯ１００〜２５０
ｍｌに無水クロム酸０．０５〜０．２５モルを加えて、
窒素雰囲気下で室温で０．５〜２時間撹拌後、反応系を
０℃に冷却し、Ｌ−アスコルビン酸０．０１モルのＤＭ
ＳＯ溶液２０〜１００ｍｌを滴下する。ここで、酸化ク
ロム−ピリジン錯体に代えて、クロロクロム酸ピリジニ
ウムと酢酸ナトリウムとの混合酸化剤（モル比１：１〜
１：２（重量比））を使用してもよい。100 to 250 ml of dichloromethane containing 0.1 to 0.5 mol of pyridine / 100 to 250 of DMSO
Add 0.05-0.25 mol of chromic anhydride to ml,
After stirring at room temperature for 0.5 to 2 hours under a nitrogen atmosphere, the reaction system was cooled to 0 ° C. and 0.01 mol of L-ascorbic acid in DM was added.
20-100 ml of SO solution is added dropwise. Here, instead of the chromium oxide-pyridine complex, a mixed oxidant of pyridinium chlorochromate and sodium acetate (molar ratio 1: 1 to 1
1: 2 (weight ratio)) may be used.
【００１８】滴下終了後５〜３０℃で反応液を２〜６時
間撹拌して反応させる。After completion of the dropping, the reaction solution is stirred at 5 to 30 ° C. for 2 to 6 hours for reaction.
【００１９】反応終了後、沈殿物を濾別し、濾液を４０
℃以下の温度で減圧濃縮し、濃縮物を再度、メタノール
などの低級アルコール等に溶解させ、不溶解物を取り除
いた。得られた溶液を、大量のエーテル中に注ぎ入れ
る。After the reaction was completed, the precipitate was filtered off and the filtrate was washed with 40
The mixture was concentrated under reduced pressure at a temperature of not higher than 0 ° C., the concentrate was again dissolved in a lower alcohol such as methanol, etc., and the insoluble matter was removed. The solution obtained is poured into a large amount of ether.
【００２０】生じた沈殿物を減圧下で乾燥することによ
り、Ｌ−アスコルビン酸の６位の水酸基が酸化された式
（３）By drying the resulting precipitate under reduced pressure, the hydroxyl group at the 6-position of L-ascorbic acid is oxidized by the formula (3).
【００２１】[0021]
【化５】 のアルデヒド化合物が得られる。Embedded image The aldehyde compound of
【００２２】次に、このアルデヒド化合物０．０１モル
に対して、触媒量の酸（例えば、濃硫酸）の存在下で６
０〜７０℃に加温したポリビニルアルコール３．０〜２
６．０ｇと水５０〜５００ｍｌと低級アルコール２５〜
２５０ｍｌとの混合物を添加してアセタール化反応を行
う。反応終了後、反応液を大量のアセトンなどの溶媒に
注ぎ入れ、得られた沈殿物をアセトンで十分に洗浄した
後に乾燥することにより式（１）のＬ−アスコルビン酸
変性ポリビニルアルコールが得られる。Next, with respect to 0.01 mol of this aldehyde compound, 6 times in the presence of a catalytic amount of an acid (for example, concentrated sulfuric acid).
Polyvinyl alcohol heated to 0 to 70 ° C 3.0 to 2
6.0 g, water 50-500 ml, and lower alcohol 25-
The acetalization reaction is carried out by adding a mixture with 250 ml. After completion of the reaction, the reaction solution is poured into a large amount of a solvent such as acetone, and the obtained precipitate is thoroughly washed with acetone and then dried to obtain the L-ascorbic acid-modified polyvinyl alcohol of the formula (1).
【００２３】また、本発明の式（２）のＬ−アスコルビ
ン酸変性ポリビニルアルコールは次にように製造するこ
とができる。The L-ascorbic acid-modified polyvinyl alcohol of the formula (2) of the present invention can be manufactured as follows.
【００２４】まず、濃硫酸１４０ｍｌ中に（メタ）アク
リル酸０．０１〜０．１モルを、５〜３０℃で０．５〜
２時間撹拌しながら溶解させる。First, 0.01 to 0.1 mol of (meth) acrylic acid is added to 140 ml of concentrated sulfuric acid at 0.5 to 30 ° C.
Dissolve with stirring for 2 hours.
【００２５】次に、この溶液に、Ｌ−アスコルビン酸
０．０１〜０．１モルを少量づつもしくは数回に分けて
添加し、添加後に５〜３０℃の温度で６〜２４時間反応
させる。Next, 0.01 to 0.1 mol of L-ascorbic acid is added to this solution little by little or in several portions, and after the addition, the reaction is carried out at a temperature of 5 to 30 ° C. for 6 to 24 hours.
【００２６】反応終了後、反応液を氷中に徐々に注ぎ入
れ、生じた油状物をエーテル等で抽出し、抽出液を飽和
食塩水５００〜１０００ｇで洗浄した後に乾燥硫酸ナト
リウムなどで乾燥する。After completion of the reaction, the reaction solution is gradually poured into ice, the resulting oily substance is extracted with ether, etc., and the extract is washed with 500 to 1000 g of saturated saline and then dried with dry sodium sulfate or the like.
【００２７】硫酸ナトリウムを除去し、得られたエーテ
ル層を常法により濃縮することにより、Ｌ−アスコルビ
ン酸の６位の水酸基が（メタ）アクリル酸でエステル化
した式（４）のＬ−アスコルビン酸（メタ）アクリル酸
エステルの粗生成物が得られる。By removing sodium sulfate and concentrating the obtained ether layer by a conventional method, the hydroxyl group at the 6-position of L-ascorbic acid was esterified with (meth) acrylic acid to obtain L-ascorbin of the formula (4). A crude product of acid (meth) acrylic acid ester is obtained.
【００２８】[0028]
【化６】 この粗生成物の精製は、例えば、シリカゲルなどを担体
とするカラムクロマトグラフィー技術を利用することに
より行うことができる。この場合、Ｌ−アスコルビン酸
誘導体の重合を防止するために、カラムに冷却装置を取
り付けることが好ましい。[Chemical 6] The crude product can be purified by using, for example, a column chromatography technique using silica gel as a carrier. In this case, a cooling device is preferably attached to the column in order to prevent polymerization of the L-ascorbic acid derivative.
【００２９】次に、得られたＬ−アスコルビン酸（メ
タ）アクリル酸エステル０．０１モルに対して、ポリビ
ニルアルコール０．５〜２．５ｇと水５０〜２５０ｍｌ
とを添加し、溶解させ、その溶液に窒素雰囲気下で硝酸
セリウムアンモニウム硝酸水溶液（０．１モル／ｌ）
２．５〜２０モルをゆっくりと添加し、５〜３０℃の温
度で２〜６時間重合させる。Next, with respect to 0.01 mol of the L-ascorbic acid (meth) acrylic acid ester obtained, 0.5 to 2.5 g of polyvinyl alcohol and 50 to 250 ml of water are used.
And were added and dissolved, and the solution was added to a cerium ammonium nitrate nitric acid aqueous solution (0.1 mol / l) under a nitrogen atmosphere.
2.5 to 20 mol is slowly added, and polymerization is carried out at a temperature of 5 to 30 ° C. for 2 to 6 hours.
【００３０】反応終了後、反応液を大量のアセトンに添
加し、得られた沈殿物を濾過し、洗浄し、乾燥すること
により式（２）のＬ−アスコルビン酸変性ポリビニルア
ルコールが得られる。After completion of the reaction, the reaction solution is added to a large amount of acetone, and the obtained precipitate is filtered, washed and dried to obtain the L-ascorbic acid-modified polyvinyl alcohol of the formula (2).
【００３１】本発明のＬ−アスコルビン酸変性ポリビニ
ルアルコールは、その良好な酸素還元能（酸素吸収能）
を利用して脱酸素材料の酸素吸収成分として好ましく使
用することができる。この脱酸素材料を構成する他の成
分としては、特に制限はなく、酸素吸収成分として本発
明の酸素還元性高分子を使用する以外は、従来の脱酸素
材料の配合組成に準じて構成することができる。The L-ascorbic acid-modified polyvinyl alcohol of the present invention has a good oxygen reducing ability (oxygen absorbing ability).
And can be preferably used as an oxygen absorbing component of a deoxidizing material. There are no particular restrictions on the other components that make up the deoxidizing material, and the deoxidizing material should be constructed according to the conventional composition of the deoxidizing material except that the oxygen-reducing polymer of the present invention is used as the oxygen absorbing component. You can
【００３２】[0032]
【実施例】以下、本発明を実施例により具体的に説明す
る。The present invention will be described below in more detail with reference to examples.
【００３３】実施例１ フラスコ（２００ｍｌ）に、ピリジン４．０ｇを含むジ
クロロメタン／ＤＭＳＯ溶液（５０ｍｌ／５０ｍｌ）を
入れ、無水クロム酸２．５ｇを少しずつ加えた。窒素雰
囲気下で室温で１時間撹拌後、反応系を０℃に冷却し、
Ｌ−アスコルビン酸０．４４ｇを含むＤＭＳＯ溶液１０
ｍｌを滴下する。滴下終了後、室温で反応液を４時間撹
拌して反応させた。Example 1 A flask (200 ml) was charged with a dichloromethane / DMSO solution (50 ml / 50 ml) containing 4.0 g of pyridine, and 2.5 g of chromic anhydride was added little by little. After stirring for 1 hour at room temperature under a nitrogen atmosphere, the reaction system was cooled to 0 ° C,
DMSO solution 10 containing 0.44 g of L-ascorbic acid
Add ml dropwise. After completion of the dropping, the reaction solution was stirred at room temperature for 4 hours for reaction.
【００３４】反応終了後、沈殿物を濾別し、濾液を４０
℃以下の温度で減圧濃縮し、濃縮物を再度、メタノール
に溶解させ、不溶解物を取り除き、得られた溶液を、大
量のエーテル中に注ぎ入れ、生じた沈殿物を減圧下で乾
燥することにより、Ｌ−アスコルビン酸の６位の水酸基
が酸化された式（３）のアルデヒド化合物を収率３５％
で得た。After the reaction was completed, the precipitate was filtered off and the filtrate was washed with 40
Concentrate under reduced pressure at a temperature of ℃ or less, dissolve the concentrate again in methanol, remove insoluble matter, pour the obtained solution into a large amount of ether, and dry the resulting precipitate under reduced pressure. The yield of the aldehyde compound of formula (3) in which the 6-position hydroxyl group of L-ascorbic acid was oxidized was 35%.
Got with.
【００３５】次に、このアルデヒド化合物３．５ｇを、
触媒量の酸（例えば濃硫酸）の存在下で６０〜７０℃に
加温したポリビニルアルコール（重合度１７００、ケン
化度９８．５モル％）６．５ｇと水１５０ｍｌとメタノ
ール５０ｍｌとの混合物に添加してアセタール化反応を
行った。Next, 3.5 g of this aldehyde compound was added to
A mixture of 6.5 g of polyvinyl alcohol (polymerization degree 1700, saponification degree 98.5 mol%), 150 ml of water, and 50 ml of methanol heated to 60 to 70 ° C. in the presence of a catalytic amount of acid (for example, concentrated sulfuric acid) was added. An acetalization reaction was carried out by adding.
【００３６】なお、添加終了後に熱水（７０℃）５ｍｌ
と触媒量の濃硫酸とを更に添加し、室温で２時間撹拌し
た。After the completion of the addition, 5 ml of hot water (70 ° C.)
And a catalytic amount of concentrated sulfuric acid were further added, and the mixture was stirred at room temperature for 2 hours.
【００３７】反応終了後、反応液を大量のアセトンに注
ぎ入れ、得られた沈殿物をアセトンで十分に洗浄した後
に乾燥することにより式（１）のＬ−アスコルビン酸変
性ポリビニルアルコールを反応率６５％で得た。After completion of the reaction, the reaction solution was poured into a large amount of acetone, and the obtained precipitate was thoroughly washed with acetone and then dried to give a reaction rate of the L-ascorbic acid-modified polyvinyl alcohol of the formula (1) of 65. Earned in%.
【００３８】実施例２ 酸化クロム−ピリジン錯体に代えて、クロロクロム酸ピ
リジニウムと酢酸ナトリウムとの混合酸化剤（１：１
（モル比））６．６ｇを使用する以外は、実施例１と同
様の操作により式（１）のＬ−アスコルビン酸変性ポリ
ビニルアルコールを反応率５０％で得た。Example 2 Instead of the chromium oxide-pyridine complex, a mixed oxidant of pyridinium chlorochromate and sodium acetate (1: 1
(Molar ratio)) L-ascorbic acid-modified polyvinyl alcohol of the formula (1) was obtained with a reaction rate of 50% by the same operation as in Example 1 except that 6.6 g was used.
【００３９】実施例３ フラスコ（２００ｍｌ）に、濃硫酸を１４０ｍｌ投入
し、そこへアクリル酸２．９ｇをゆっくりと添加し、室
温で撹拌して溶解させた。１時間撹拌した後に、この溶
液に、５分毎にＬ−アスコルビン酸１．４ｇを５回添加
した。添加後、室温で２４時間反応させ、終了後反応液
を氷中に注ぎ入れた。Example 3 140 ml of concentrated sulfuric acid was put into a flask (200 ml), 2.9 g of acrylic acid was slowly added thereto, and the mixture was stirred at room temperature to dissolve it. After stirring for 1 hour, 1.4 g of L-ascorbic acid was added 5 times to this solution every 5 minutes. After the addition, the reaction was carried out at room temperature for 24 hours, and after the completion, the reaction solution was poured into ice.
【００４０】この水溶液を３回エーテルで抽出し、その
エーテル液を飽和食塩水で洗浄した後、硫酸ナトリウム
で乾燥した。The aqueous solution was extracted three times with ether, the ether solution was washed with saturated saline and then dried over sodium sulfate.
【００４１】エーテル溶液から硫酸ナトリウムを除去し
た後、エーテル液を減圧濃縮し、得られた濃縮液を、１
０℃以下でシリカゲルクロマトグラフィ処理して精製す
ることによりＬ−アスコルビン酸アクリル酸エステルを
約１５％の収率で得た。After removing sodium sulfate from the ether solution, the ether solution was concentrated under reduced pressure, and the obtained concentrate was
Purification by silica gel chromatography at 0 ° C. or lower gave L-ascorbic acid acrylate in a yield of about 15%.
【００４２】次に、Ｌ−アスコルビン酸アクリル酸エス
テル４．６ｇと、ポリビニルアルコール（重合度１７０
０、ケン化度９８．５モル％）２．０ｇとを水１００ｍ
ｌに溶解させ、窒素雰囲気下で、その溶液に硝酸セリウ
ムアンモニウム硝酸水溶液（０．１モル／ｌ）５ｍｌを
ゆっくりと添加し、室温で３時間重合させた。Next, 4.6 g of L-ascorbic acid acrylic acid ester and polyvinyl alcohol (polymerization degree 170
0, saponification degree 98.5 mol%) 2.0 g and water 100 m
5 ml of cerium ammonium nitrate nitric acid aqueous solution (0.1 mol / l) was slowly added to the solution under a nitrogen atmosphere, and polymerization was carried out at room temperature for 3 hours.
【００４３】反応終了後、反応液を大量のアセトンに添
加し、得られた沈殿物を濾過し、洗浄し、乾燥すること
により式（２）のＬ−アスコルビン酸変性ポリビニルア
ルコールを重合率７５％で得た。After the completion of the reaction, the reaction solution was added to a large amount of acetone, and the obtained precipitate was filtered, washed and dried to give the L-ascorbic acid-modified polyvinyl alcohol of the formula (2) with a polymerization rate of 75%. Got with.
【００４４】実施例４ 実施例１で得られた式（１）のＬ−アスコルビン酸変性
ポリビニルアルコール１ｇをフィルム状に成形すること
により脱酸素材料を作製し、それを多孔質フィルム袋
（旭化成（株）製）に入れ、更にそれを酸素バリヤー材
料としてアルミニウムを使用した５００ｍｌの容器中
に、２ｍｌの水と２００ｍｌの空気と共に密封し、密封
時（０日）、１日後、３日後及び７日後の密封容器中の
酸素濃度（％）を測定した。その結果（サンプル数ｎ＝
３の平均）を表１に示す。Example 4 A deoxidizing material was prepared by molding 1 g of L-ascorbic acid-modified polyvinyl alcohol of the formula (1) obtained in Example 1 into a film, which was then formed into a porous film bag (Asahi Kasei Co., Ltd.) and further sealed it in a 500 ml container using aluminum as an oxygen barrier material together with 2 ml of water and 200 ml of air, and at the time of sealing (0 days), 1 day, 3 days and 7 days later. The oxygen concentration (%) in the sealed container was measured. As a result (number of samples n =
The average of 3) is shown in Table 1.
【００４５】実施例５ 実施例３で得られた式（２）のＬ−アスコルビン酸変性
ポリビニルアルコール１ｇをフィルム状に成形すること
により脱酸素材料を作製し、それを多孔質フィルム袋
（旭化成（株）製）に入れ、更にそれを酸素バリヤー材
料としてアルミニウムを使用した５００ｍｌの容器中
に、２ｍｌの水と２００ｍｌの空気と共に密封し、密封
時（０日）、１日後、３日後及び７日後の密封容器中の
酸素濃度（％）を測定した。その結果（サンプル数ｎ＝
３の平均）を表１に示す。Example 5 1 g of L-ascorbic acid-modified polyvinyl alcohol of the formula (2) obtained in Example 3 was molded into a film to prepare a deoxidizing material, which was then formed into a porous film bag (Asahi Kasei Co., Ltd.) and further sealed it in a 500 ml container using aluminum as an oxygen barrier material together with 2 ml of water and 200 ml of air, and at the time of sealing (0 days), 1 day, 3 days and 7 days later. The oxygen concentration (%) in the sealed container was measured. As a result (number of samples n =
The average of 3) is shown in Table 1.
【００４６】比較例１ 式（１）のＬ−アスコルビン酸変性ポリビニルアルコー
ルに代えてＬ−アスコルビン酸０．１モルをＥＶＡ１
７．６ｇに練り込みシート状に成形したもの１ｇを使用
する以外は実施例４と同様に脱酸素材料を作製し、密封
容器に密封し、その中の酸素濃度を測定した。その結果
（サンプル数ｎ＝３の平均）を表１に示す。Comparative Example 1 0.1 mol of L-ascorbic acid was replaced with EVA1 in place of the L-ascorbic acid-modified polyvinyl alcohol of the formula (1).
A deoxidizing material was prepared in the same manner as in Example 4 except that 1 g of kneaded into 7.6 g and molded into a sheet was used, and the deoxidized material was sealed in a sealed container and the oxygen concentration therein was measured. The results (average of sample number n = 3) are shown in Table 1.
【００４７】[0047]
【表１】 密封容器中の酸素濃度（％） ０日 １日後 ３日後 ７日後 実施例４ 20.9 9.26 5.38 4.22 (式(1)のL-アスコルヒ゛ン酸変性ホ゜リヒ゛ニルアルコール) 実施例５ 20.9 5.15 3.12 2.65 (式(2)のL-アスコルヒ゛ン酸変性ホ゜リヒ゛ニルアルコール) 比較例１ 20.9 13.61 10.59 8.31 (L-アスコルヒ゛ン酸+EVA) [Table 1] Oxygen concentration in sealed container (%) 0 day 1 day 3 days 7 days Example 4 20.9 9.26 5.38 4.22 (Formula (1) L-ascorbic acid-modified polyvinyl alcohol) Example 5 20.9 5.15 3.12 2.65 (Formula (2) L-ascorbic acid-modified poly (vinyl alcohol)) Comparative Example 1 20.9 13.61 10.59 8.31 (L -ascorbic acid + EVA)
【００４８】表１から、実施例４及び５の脱酸素材料は
比較例１の脱酸素材料に比べ、酸素吸収能が優れている
ことがわかる。From Table 1, it can be seen that the deoxidizing materials of Examples 4 and 5 are superior to the deoxidizing materials of Comparative Example 1 in oxygen absorbing ability.
【００４９】[0049]
【発明の効果】本発明によれば、酵素や酸クロライドを
利用することなく、簡便な手法により主鎖にＬ−アスコ
ルビン酸残基が導入された高分子を提供できる。また、
得られる高分子は、良好な酸素還元性を有するので、こ
の酸素還元性高分子を使用することにより、良好な脱酸
素能を有する脱酸素材料が得られる。Industrial Applicability According to the present invention, a polymer having an L-ascorbic acid residue introduced into its main chain can be provided by a simple method without using an enzyme or an acid chloride. Also,
Since the obtained polymer has a good oxygen reducing property, by using this oxygen reducing polymer, a deoxidizing material having a good deoxidizing ability can be obtained.
Claims (4)
リビニルアルコール。1. A formula (1) or a formula (2): An L-ascorbic acid-modified polyvinyl alcohol having a structural portion represented by:
剤又はクロロクロム酸ピリジニウムと酢酸ナトリウムと
の混合酸化剤でＬ−アスコルビン酸の６位の水酸基を酸
化してアルデヒド基に変換し、得られたアルデヒド化合
物でポリビニルアルコールをアセタール化することを特
徴とする式（１） 【化２】 で表される構造部分を有するＬ−アスコルビン酸変性ポ
リビニルアルコールの製造方法。2. A compound obtained by oxidizing the 6-position hydroxyl group of L-ascorbic acid with an oxidizing agent comprising a chromium oxide-pyridine complex or a mixed oxidizing agent of pyridinium chlorochromate and sodium acetate to convert it into an aldehyde group. Formula (1) characterized in that polyvinyl alcohol is acetalized with an aldehyde compound. A method for producing an L-ascorbic acid-modified polyvinyl alcohol having a structural portion represented by:
せ、その溶液にＬ−アスコルビン酸を添加することによ
りＬ−アスコルビン酸の６位の水酸基を（メタ）アクリ
ル酸でエステル化し、得られたエステル化合物とポリビ
ニルアルコールとを硝酸セリウムアンモニウムの存在下
で重合させることを特徴とする式（２） 【化３】 で表される構造部分を有するＬ−アスコルビン酸変性ポ
リビニルアルコールの製造方法。3. A (meth) acrylic acid is dissolved in concentrated sulfuric acid, and L-ascorbic acid is added to the solution to esterify the hydroxyl group at the 6-position of L-ascorbic acid with (meth) acrylic acid. Formula (2) wherein the ester compound thus obtained and polyvinyl alcohol are polymerized in the presence of cerium ammonium nitrate. A method for producing an L-ascorbic acid-modified polyvinyl alcohol having a structural portion represented by:
ポリビニルアルコールを含有する脱酸素材料。4. A deoxidizing material containing the L-ascorbic acid-modified polyvinyl alcohol according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16863996A JPH09328521A (en) | 1996-06-07 | 1996-06-07 | L-ascorbate-modified polyvinyl alcohol and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16863996A JPH09328521A (en) | 1996-06-07 | 1996-06-07 | L-ascorbate-modified polyvinyl alcohol and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09328521A true JPH09328521A (en) | 1997-12-22 |
Family
ID=15871775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16863996A Pending JPH09328521A (en) | 1996-06-07 | 1996-06-07 | L-ascorbate-modified polyvinyl alcohol and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09328521A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000072959A1 (en) * | 1999-05-26 | 2000-12-07 | Eli Lilly And Company | Resins with immobilized ascorbic acid |
| WO2005070974A2 (en) * | 2004-01-21 | 2005-08-04 | University Of Massachusetts Lowell | Post-coupling synthetic approach for polymeric antioxidants |
| US7923587B2 (en) | 2004-07-23 | 2011-04-12 | Polnox Corporation | Anti-oxidant macromonomers and polymers and methods of making and using the same |
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-
1996
- 1996-06-07 JP JP16863996A patent/JPH09328521A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000072959A1 (en) * | 1999-05-26 | 2000-12-07 | Eli Lilly And Company | Resins with immobilized ascorbic acid |
| WO2005070974A2 (en) * | 2004-01-21 | 2005-08-04 | University Of Massachusetts Lowell | Post-coupling synthetic approach for polymeric antioxidants |
| WO2005070974A3 (en) * | 2004-01-21 | 2006-10-19 | Univ Massachusetts Lowell | Post-coupling synthetic approach for polymeric antioxidants |
| US7323511B2 (en) * | 2004-01-21 | 2008-01-29 | University Of Massachusetts Lowell | Post-coupling synthetic approach for polymeric antioxidants |
| US7923587B2 (en) | 2004-07-23 | 2011-04-12 | Polnox Corporation | Anti-oxidant macromonomers and polymers and methods of making and using the same |
| US8691933B2 (en) | 2004-12-03 | 2014-04-08 | Polnox Corporation | Stabilized polyolefin compositions |
| US8846847B2 (en) | 2004-12-03 | 2014-09-30 | Polnox Corporation | Macromolecular antioxidants based on sterically hindered phenols and phosphites |
| US9388120B2 (en) | 2005-02-22 | 2016-07-12 | Polnox Corporation | Nitrogen and hindered phenol containing dual functional macromolecular antioxidants: synthesis, performances and applications |
| US9523060B2 (en) | 2005-12-02 | 2016-12-20 | Polnox Corporation | Lubricant oil compositions |
| US8927472B2 (en) | 2005-12-02 | 2015-01-06 | Polnox Corporation | Lubricant oil compositions |
| US9193675B2 (en) | 2006-07-06 | 2015-11-24 | Polnox Corporation | Macromolecular antioxidants comprising differing antioxidant moieties: structures, methods of making and using the same |
| US9950990B2 (en) | 2006-07-06 | 2018-04-24 | Polnox Corporation | Macromolecular antioxidants comprising differing antioxidant moieties: structures, methods of making and using the same |
| US10294423B2 (en) | 2013-11-22 | 2019-05-21 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
| US10683455B2 (en) | 2013-11-22 | 2020-06-16 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
| US11060027B2 (en) | 2013-11-22 | 2021-07-13 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
| US11578285B2 (en) | 2017-03-01 | 2023-02-14 | Polnox Corporation | Macromolecular corrosion (McIn) inhibitors: structures, methods of making and using the same |
| WO2021049472A1 (en) * | 2019-09-10 | 2021-03-18 | 学校法人 関西大学 | Compound, resin, composition, resist film, pattern forming method, underlayer film, and optical article |
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