JPH05310625A - Separation method for polyglycerin composition - Google Patents
Separation method for polyglycerin compositionInfo
- Publication number
- JPH05310625A JPH05310625A JP4110246A JP11024692A JPH05310625A JP H05310625 A JPH05310625 A JP H05310625A JP 4110246 A JP4110246 A JP 4110246A JP 11024692 A JP11024692 A JP 11024692A JP H05310625 A JPH05310625 A JP H05310625A
- Authority
- JP
- Japan
- Prior art keywords
- polyglycerin
- polyglycerin composition
- molecular weight
- composition
- exchange resin
- 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.)
- Granted
Links
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリグリセリン組成物の
分離方法に関する。詳しくは、分子量分布の広いポリグ
リセリン組成物を原料として、特定のイオン交換樹脂を
用いたクロマト分離を行うことにより、所望の分子量分
布を有するポリグリセリン組成物を得る方法に関する。FIELD OF THE INVENTION The present invention relates to a method for separating a polyglycerin composition. Specifically, the present invention relates to a method for obtaining a polyglycerin composition having a desired molecular weight distribution by performing a chromatographic separation using a specific ion exchange resin using a polyglycerin composition having a wide molecular weight distribution as a raw material.
【０００２】[0002]
【従来の技術】ポリグリセリン組成物はグリセリンが種
々の重合度で重合した多価アルコール化合物で、古くか
ら保湿剤、増粘剤、可塑剤として用いられている。ま
た、ポリグリセリン組成物と脂肪酸とのエステル化合物
は食品用、化粧品用等の乳化剤として用いられている。2. Description of the Related Art Polyglycerin compositions are polyhydric alcohol compounds in which glycerin is polymerized at various degrees of polymerization, and have been used as moisturizers, thickeners and plasticizers for a long time. In addition, ester compounds of polyglycerin composition and fatty acids are used as emulsifiers for foods, cosmetics and the like.
【０００３】ポリグリセリン組成物を脂肪酸でエステル
化して乳化剤を製造する場合、親水性部分に当たるポリ
グリセリン組成物の重合度や組成によって、親水基と疎
水基（脂肪酸等）のバランス（ＨＬＢ）が異なってくる
ため、乳化剤としての機能は大きく影響を受ける。従っ
て、ポリグリセリン組成物の重合度や組成を変化させる
ことにより、様々な特徴ある機能を持った乳化剤を製造
することが可能である。ところが、乳化剤原料としての
ポリグリセリン組成物は、通常、グリセリンをアルカリ
触媒下で高温にて重合させる方法により製造されたもの
が用いられるが、この方法で製造したポリグリセリン組
成物は、重合度が１から１０以上の成分を含み、かつ、
どの成分も主成分たりえない広い分子量分布を持った組
成物となるため、特徴のある組成を有するポリグリセリ
ン組成物を乳化剤原料として用いるのは困難である。更
に、本方法でポリグリセリン組成物の製造を行った場
合、副生物として、安全性の点で不明な点の多い環状の
構造を持つ成分が生成するのを防ぐことができない。When an emulsifier is produced by esterifying a polyglycerin composition with a fatty acid, the balance (HLB) between the hydrophilic group and the hydrophobic group (fatty acid, etc.) varies depending on the degree of polymerization and the composition of the polyglycerin composition corresponding to the hydrophilic portion. Therefore, the function as an emulsifier is greatly affected. Therefore, it is possible to produce emulsifiers having various characteristic functions by changing the degree of polymerization or the composition of the polyglycerin composition. However, the polyglycerin composition as the emulsifier raw material is usually used those produced by a method of polymerizing glycerin at high temperature under an alkali catalyst, but the polyglycerin composition produced by this method has a degree of polymerization of Contains 1 to 10 or more components, and
It is difficult to use a polyglycerin composition having a characteristic composition as an emulsifier raw material because the composition has a wide molecular weight distribution in which none of the components is the main component. Furthermore, when the polyglycerin composition is produced by this method, it is not possible to prevent the production of a by-product having a cyclic structure, which has many unclear points in terms of safety.
【０００４】従って、何らかの方法で所望の分子量分布
を有するポリグリセリン組成物を得る方法が必要であ
る。例えば、特開平２−１７２９３８号公報には、反応
条件を特定してグリセリンを重合し、分子量の狭いポリ
グリセリン組成物を製造する方法が提案されている。し
かしながら、反応条件の変更のみでは、各々の用途に応
じた所望の分子量分布を有するポリグリセリン組成物を
得るためには限界がある。Therefore, there is a need for a method of obtaining a polyglycerin composition having a desired molecular weight distribution by some method. For example, Japanese Patent Application Laid-Open No. 2-172938 proposes a method of producing a polyglycerin composition having a narrow molecular weight by polymerizing glycerin by specifying reaction conditions. However, there is a limit in obtaining a polyglycerin composition having a desired molecular weight distribution according to each application, only by changing the reaction conditions.
【０００５】また、同公報には、グリセリンを重合後、
反応物をイオン交換樹脂にて脱塩後、乾燥して得られた
ポリグリセリン組成物の分子量分布を高速ゲルろ過クロ
マトグラフィーを用いて分析している。このゲルろ過ク
ロマトグラフィーを利用すれば所望の分子量分布を有す
るポリグリセリン組成物を分離することが可能と考えら
れる。しかしながら、ゲルろ過クロマトグラフィーでは
各成分の分離がなお充分ではない。また、該ゲルろ過グ
ラフィー用の充てん剤は一般に機械的強度が充分でな
く、工業用として長期間使用する場合には適用でない。Further, in the publication, after polymerizing glycerin,
The molecular weight distribution of the polyglycerin composition obtained by desalting the reaction product with an ion exchange resin and then drying it is analyzed by high performance gel filtration chromatography. It is considered possible to separate a polyglycerin composition having a desired molecular weight distribution by using this gel filtration chromatography. However, the separation of each component is still insufficient by gel filtration chromatography. Further, the filler for gel filtration chromatography generally has insufficient mechanical strength and is not applicable when it is used for a long time for industrial use.
【０００６】更に、ポリグリセリン組成物の製造法とし
て、グリセリンを重合させる方法の他に、グリセリンに
エピクロルヒドリンを付加重合させた後にアルカリで処
理する方法、グリセリンにグリシドールを付加重合させ
る方法等がある。しかしながら、エピクロルヒドリンや
グリシドールを用いる反応では、不快臭の発生を伴った
り、安全性に疑いのあるエポキシ骨格が微量ながら残存
する等の問題があり、食品、化粧品、医薬品等の用途に
は不適当である。Further, as a method for producing a polyglycerin composition, in addition to a method of polymerizing glycerin, there is a method of addition-polymerizing epichlorohydrin to glycerin and then treating with an alkali, a method of addition-polymerizing glycidol to glycerin, and the like. However, in the reaction using epichlorohydrin or glycidol, there are problems such as generation of an unpleasant odor, and a small amount of epoxy skeleton whose safety is suspected remains, and it is unsuitable for use in foods, cosmetics, pharmaceuticals, etc. is there.
【０００７】[0007]
【発明が解決しようとする課題】本発明の課題は、上記
の問題点に鑑み、簡便に所望の分子量分布を有するポリ
グリセリン組成物を得る方法を提供することにある。In view of the above problems, an object of the present invention is to provide a method for easily obtaining a polyglycerin composition having a desired molecular weight distribution.
【０００８】[0008]
【課題を解決するための手段】本発明者等は上記の課題
につき鋭意検討を行った結果、特定のイオン交換樹脂を
用いたクロマト分離の方法により該課題が達成できるこ
とを見い出し、本発明に到達した。すなわち、本発明
は、架橋度５〜８％のポリスチレン骨格を有するゲル型
の強酸性陽イオン交換樹脂を用いてクロマト分離するこ
とを特徴とするポリグリセリン組成物の分離方法に存す
る。Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the problems can be achieved by a method of chromatographic separation using a specific ion-exchange resin, and arrived at the present invention. did. That is, the present invention resides in a method for separating a polyglycerin composition, which comprises performing chromatographic separation using a gel-type strongly acidic cation exchange resin having a polystyrene skeleton with a degree of crosslinking of 5 to 8%.
【０００９】以下、本発明を詳細に説明する。本発明の
クロマト分離の対象となる原料としてのポリグリセリン
組成物は、前述のようにグリセリンを重合して得たもの
である。その分子量分布については特に限定されるもの
ではないが、本発明のクロマト分離においては重合度が
２〜８の成分間の分離が特に優れているので、重合度が
２〜８の成分を組成物全成分中において通常３０％以
上、好ましくは４０％以上含むものがよい。The present invention will be described in detail below. The polyglycerin composition as a raw material to be subjected to chromatographic separation of the present invention is obtained by polymerizing glycerin as described above. The molecular weight distribution is not particularly limited, but in the chromatographic separation of the present invention, the separation between components having a degree of polymerization of 2 to 8 is particularly excellent. The content of all components is usually 30% or more, preferably 40% or more.
【００１０】次に、本発明に用いるイオン交換樹脂は、
架橋度５〜８％のポリスチレン骨格を有するゲル型の強
酸性陽イオン交換樹脂である。該イオン交換樹脂は、モ
ノマー主成分としてスチレンを用い、架橋モノマーとし
て通常ジビニルベンゼン、場合によっては４−ビニルフ
ェニルメタン等を用いて共重合することにより得られた
三次元網目構造（ゲル型）の粒状の樹脂である。そし
て、該樹脂母体に、強酸性陽イオン交換基として、スル
ホン酸基を交換容量で、通常０．５〜３．０ｍｅｑ／m
l、好ましくは１．０〜２．０ｍｅｑ／mlを有するもの
である。イオン交換基に対する対イオンとしては、水素
イオン、ナトリウムイオンが一般的であるが、その他の
金属イオンとしてカリウム、リチウム等のアルカリ金属
のイオン、カルシウム、マグネシウム等のアルカリ土類
金属のイオン、銀等の遷移金属イオンも使用することが
できる。対イオンは複数種同時に使用することも可能で
あるが、クロマト再現性の立場から、通常、対イオンは
一種類に変換し、平衡後使用する。Next, the ion exchange resin used in the present invention is
It is a gel-type strongly acidic cation exchange resin having a polystyrene skeleton with a crosslinking degree of 5 to 8%. The ion exchange resin has a three-dimensional network structure (gel type) obtained by copolymerizing styrene as a main monomer component, usually divinylbenzene as a crosslinking monomer, and 4-vinylphenylmethane in some cases. It is a granular resin. Then, as a strongly acidic cation exchange group, a sulfonic acid group having an exchange capacity of usually 0.5 to 3.0 meq / m is added to the resin matrix.
1, preferably 1.0 to 2.0 meq / ml. As the counter ion for the ion exchange group, hydrogen ion and sodium ion are generally used, but as other metal ions, ions of alkali metals such as potassium and lithium, ions of alkaline earth metals such as calcium and magnesium, silver and the like. The transition metal ions of can also be used. It is possible to use a plurality of counter ions at the same time, but from the standpoint of chromatographic reproducibility, the counter ion is usually converted to one kind and used after equilibration.
【００１１】また、本発明では、イオン交換樹脂の全仕
込モノマー重量に対する架橋モノマー重量の割合として
定義される架橋度が５〜８％であることが必須要件であ
る。該架橋度の範囲では、原料のポリグリセリン組成物
中の分離が良好であり、特に重合度２〜８の各成分の分
離が良好である。架橋度５％未満では、ポリグリセリン
組成物中の各々の成分ピークが幅広くなる傾向が強まり
分離が不良となる。一方、架橋度が８％を越える場合
は、重合度が通常５以上の高分子量成分の溶出が早ま
り、該成分の分離が不良となるので好ましくない。In the present invention, it is essential that the degree of crosslinking, defined as the ratio of the weight of the crosslinking monomer to the total weight of the charged monomers of the ion exchange resin, is 5 to 8%. Within the range of the degree of crosslinking, the separation in the polyglycerin composition as the raw material is good, and particularly the separation of each component having a polymerization degree of 2 to 8 is good. If the degree of cross-linking is less than 5%, the peak of each component in the polyglycerin composition tends to be broadened, resulting in poor separation. On the other hand, if the degree of cross-linking exceeds 8%, high molecular weight components having a degree of polymerization of usually 5 or more will elute quickly and the separation of the components will be unfavorable.
【００１２】樹脂の粒径としては、通常２〜２０００μ
ｍと広範囲に渡るものがあるが、一般的には粒径を一定
の範囲にそろえたものを使用する。また、同一の樹脂を
用いた場合、粒径の細かいものを用いた方が分離が改善
できることは、当業者の常識であるが、いわゆる高速液
体クロマトグラフィーの領域に含まれる樹脂の平均粒径
が２〜３０μｍ程度の樹脂は経済的な理由により、通常
分析用もしくは実験室レベルでの分取目的に用いられ、
工業的には、平均粒径として通常５０〜５００μｍの樹
脂が使用されることが多い。The particle size of the resin is usually 2 to 2000 μm.
Although there is a wide range of particle diameters such as m, particles having a uniform particle size are generally used. Further, when the same resin is used, it is a common knowledge of those skilled in the art that using a finer particle size can improve the separation, but the average particle size of the resin contained in the area of so-called high performance liquid chromatography is A resin of about 2 to 30 μm is usually used for analysis or for preparative separation at a laboratory level for economical reasons.
Industrially, a resin having an average particle diameter of usually 50 to 500 μm is often used.
【００１３】以上のイオン交換樹脂をカラムに充填し、
該カラムに原料ポリグリセリン組成物を添加した後溶離
液を用いて溶出すると、重合度の高い成分（分子量の大
きな成分）から重合度の低い成分、グリセリン、続いて
重合度２〜４の環状ポリグリセリンの順に溶出されるの
で、各成分を分離することが可能である。溶離液として
は、イオン交換水、通常０．００１〜２％のリン酸、酢
酸等の酸水溶液、通常ｐＨ＝２〜５リン酸ナトリウム緩
衝液、硫酸ナトリウム、塩化ナトリウム等の塩水溶液等
から、イオン交換樹脂の対イオンの種類に対応させて種
々のものを使用することが可能である。また、対イオン
と溶離液の組み合わせによっては、ポリグリセリン組成
物中の特定成分間の分離能をより改善することが可能で
ある。The above-mentioned ion exchange resin is packed in a column,
When the raw material polyglycerin composition was added to the column and then eluted with an eluent, the component having a high degree of polymerization (a component having a large molecular weight) to the component having a low degree of polymerization, glycerin, and then the cyclic polyamine having a degree of polymerization of 2 to 4 Since the components are eluted in the order of glycerin, each component can be separated. As the eluent, ion-exchanged water, usually 0.001 to 2% phosphoric acid, an aqueous acid solution such as acetic acid, usually pH = 2 to 5 sodium phosphate buffer, sodium sulfate, salt aqueous solution such as sodium chloride, Various types can be used depending on the type of counterion of the ion exchange resin. Further, depending on the combination of the counter ion and the eluent, it is possible to further improve the separation ability between the specific components in the polyglycerin composition.
【００１４】なお、本発明のクロマト分離のメカニズム
の詳細は不明であるが、イオン交換樹脂の網目構造に基
づく分子排除作用と、イオン交換基、溶離液およびポリ
グリセリン組成物間のイオン的相互作用が複合されるこ
とにより、ポリグリセリン組成物各成分の分離向上に寄
与しているものと考えられる。原料のポリグリセリン組
成物に対するクロマト分離に必要なイオン交換樹脂の量
は特に限定はないが、通常５倍重量以上、好ましくは１
０倍量以上である。クロマト分離の方法は通常の方法と
何ら変わりはなく、分離されたものを実際に得る方法と
しては、カラムから溶出されてくる液を分取する方法
や、カラム途中から目的の成分を抜き出す方法等があ
る。また、分取物を再度クロマト分離してもよいし、リ
サイクルクロマトにより更に分離能を高めることも可能
である。Although the details of the chromatographic separation mechanism of the present invention are unknown, the molecular exclusion action based on the network structure of the ion exchange resin and the ionic interaction between the ion exchange group, the eluent and the polyglycerin composition. It is considered that the combination of these contributes to the improvement of the separation of each component of the polyglycerin composition. The amount of ion-exchange resin required for chromatographic separation with respect to the raw material polyglycerin composition is not particularly limited, but is usually 5 times by weight or more, preferably 1
The amount is 0 times or more. The method of chromatographic separation is no different from the usual method, and the method of actually obtaining the separated product is, for example, a method of collecting the liquid eluted from the column or a method of extracting the target component from the middle of the column. There is. Further, the separated product may be chromatographed again, or the resolving chromatograph may be used to further enhance the separation ability.
【００１５】[0015]
【実施例】以下、実施例を挙げて説明するが、本発明は
これらに限定されるものではない。 実施例１ 架橋度６％、ナトリウム型のポリスチレン−ジビニルベ
ンゼンゲルを母体とする強酸性カチオン交換樹脂（平均
粒径１０μｍ、交換容量１．６ｍｅｑ／ml）を充填剤と
した高速液体クロマトグラフィー用カラムＭＣＩ ＧＥ
Ｌ ＣＫ０６Ｓ（商品名、三菱化成（株）製、カラムサ
イズ８×３００mm）に８％塩酸を通液して交換基の対イ
オンをナトリウムイオンから水素イオンに変換した後、
０．１％リン酸を溶離液として、原料ポリグリセリン組
成物としてヘキサグリセリン＃５００（阪本薬品工業
（株）製）を分析装置：島津システムＬＣ−６Ａ、カラ
ム温度：６０℃、溶離液の流速：０．４ml／分、検出
器：日立示差屈折計Ｌ−３３００、サンプルの注入量：
２０μｌ、サンプル濃度：１重量％の条件で分離を行っ
た。得られたクロマトグラムを図１に示したが、重合度
２〜８までのポリグリセリン、グリセリンおよび環状ポ
リグリセリンの各成分間の分離は大変良好であった。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 A column for high performance liquid chromatography using a strongly acidic cation exchange resin (average particle size 10 μm, exchange capacity 1.6 meq / ml) having a degree of crosslinking of 6% and a sodium-type polystyrene-divinylbenzene gel as a matrix, as a packing material. MCI GE
After 8% hydrochloric acid was passed through L CK06S (trade name, manufactured by Mitsubishi Kasei Co., Ltd., column size 8 × 300 mm) to convert the counter ion of the exchange group from sodium ion to hydrogen ion,
Hexaglycerin # 500 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) as a raw material polyglycerin composition using 0.1% phosphoric acid as an eluent analyzer: Shimadzu System LC-6A, column temperature: 60 ° C., eluent flow rate : 0.4 ml / min, detector: Hitachi differential refractometer L-3300, injection amount of sample:
Separation was performed under the conditions of 20 μl and sample concentration: 1% by weight. The obtained chromatogram is shown in FIG. 1, and the separation between the components of polyglycerin, glycerin and cyclic polyglycerin having a degree of polymerization of 2 to 8 was very good.
【００１６】実施例２ 原料ポリグリセリン組成物としてデカグリセリン＃７５
０（阪本薬品工業（株）製）を用いた以外は実施例１と
同様の条件で分離を行ったときのクロマトグラムを図２
に示す。実施例１と同様に分離は良好であった。Example 2 Decaglycerin # 75 as a raw material polyglycerin composition
0 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) is used, and a chromatogram obtained when the separation is performed under the same conditions as in Example 1 is shown in FIG.
Shown in. The separation was good as in Example 1.
【００１７】実施例３、４ 架橋度８％、水素型のポリスチレン−ジビニルベンゼン
ゲルを母体とする強酸性カチオン交換樹脂（平均粒径１
０μｍ、交換容量１．６ｍｅｑ／ml）を充填剤とした高
速液体クロマトグラフィー用カラムＭＣＩ ＧＥＬ Ｃ
Ｋ０８ＥＨ（商品名、三菱化成（株）製、カラムサイズ
８×３００mm）を用い、０．１％リン酸を溶離液とし
て、実施例１と同様の条件で、ヘキサグリセリン＃５０
０およびデカグリセリン＃７５０（阪本薬品工業（株）
製）の分離を行った。得られたクロマトグラムを図３お
よび図４に示したが、重合度２〜５までのポリグリセリ
ン、グリセリンおよび環状ポリグリセリンの各成分間の
分離は大変良好であった。Examples 3 and 4 Strongly acidic cation exchange resin (average particle size: 1) having a crosslinking degree of 8% and hydrogen type polystyrene-divinylbenzene gel as a matrix.
High performance liquid chromatography column MCI GEL C with 0 μm and exchange capacity of 1.6 meq / ml as a packing material
Hexaglycerin # 50 was prepared under the same conditions as in Example 1 using K08EH (trade name, manufactured by Mitsubishi Kasei Co., Ltd., column size 8 × 300 mm) with 0.1% phosphoric acid as an eluent.
0 and decaglycerin # 750 (Sakamoto Yakuhin Kogyo Co., Ltd.)
Manufactured). The obtained chromatograms are shown in FIGS. 3 and 4, and the separation between the components of polyglycerin, glycerin and cyclic polyglycerin having a degree of polymerization of 2 to 5 was very good.
【００１８】比較例１、２ 架橋度４％、ナトリウム型のポリスチレン−ジビニルベ
ンゼンゲルを母体とする強酸性カチオン交換樹脂（平均
粒径１０μｍ、交換容量１．６ｍｅｑ／ml）を充填剤と
した高速液体クロマトグラフィー用カラムＭＣＩ ＧＥ
Ｌ ＣＫ０４Ｓ（商品名、三菱化成（株）製、カラムサ
イズ１０×２００mm）に８％塩酸を通液して交換基の対
イオンを水素イオンにした後、０．１％リン酸を溶離液
として、実施例１と同様の条件で、ヘキサグリセリン＃
５００およびデカグリセリン＃７５０（阪本薬品工業
（株）製）の分離を行った。得られたクロマトグラムを
図５および図６に示したが、全体にピークが幅広く良好
な分離結果が得られなかった。なお、比較例１、２のカ
ラムサイズは、実施例１〜４のものと異なるが、充填剤
量はほぼ等量であり、両者のクロマトグラムの比較上特
に問題となる差異ではない。Comparative Examples 1 and 2 High speed using a strong acidic cation exchange resin (average particle size 10 μm, exchange capacity 1.6 meq / ml) having a cross-linking degree of 4% and sodium-type polystyrene-divinylbenzene gel as a matrix. Liquid chromatography column MCI GE
8% hydrochloric acid was passed through LCK04S (trade name, manufactured by Mitsubishi Kasei Co., Ltd., column size 10 × 200 mm) to make the counter ion of the exchange group a hydrogen ion, and then 0.1% phosphoric acid was used as an eluent. Hexaglycerin # under the same conditions as in Example 1.
500 and decaglycerin # 750 (produced by Sakamoto Yakuhin Kogyo Co., Ltd.) were separated. The obtained chromatograms are shown in FIG. 5 and FIG. 6, but the peaks were broad and good separation results could not be obtained. The column sizes of Comparative Examples 1 and 2 are different from those of Examples 1 to 4, but the amounts of the fillers are almost the same, which is not a problematic difference when comparing the chromatograms of the two.
【００１９】上記の実施例１〜４および比較例１、２の
高速液体クロマトグラフィーの分析結果を参考として、
実施例１〜４で用いたイオン交換樹脂と主に平均粒径の
みが異なる工業分取用グレードのイオン交換樹脂を用い
て以下の実施例５〜７のクロマト分離を行った。With reference to the analysis results of the high performance liquid chromatography of Examples 1 to 4 and Comparative Examples 1 and 2 above,
Chromatographic separations of the following Examples 5 to 7 were performed using the ion exchange resins of the industrial preparative grades which differ from the ion exchange resins used in Examples 1 to 4 mainly in the average particle size.
【００２０】実施例５ 架橋度６％、ナトリウム型のイオン交換樹脂ダイヤイオ
ンＵＢＫ−５３０（商品名、三菱化成（株）製、平均粒
径２３０μｍ〜２４０μｍ、交換容量１．６ｍｅｑ／m
l）をガラス製のカラム（カラムサイズ１８×６００m
m）に１３０ml充填し、脱塩水で平衡化した後、デカグ
リセリン＃７５０（阪本薬品工業（株））６．８ｇを脱
塩水に溶解して１３mlにしてカラム上端に添加し、脱塩
水で１時間当り６５mlの流速で溶出を行なった。溶出開
始直後から、カラム終端より流出した最初の脱塩水４５
mlは廃棄し、その後、流出する液を４５ml採取して画分
１とし、続いて流出した４５mlを採取して画分２とし
た。分離前および分離後の各画分の分析は、実施例１の
方法に従い、高速液体クロマトグラフィーを用いて行っ
た。分離前の原料、画分１および２の組成を表−１に示
す。Example 5 Sodium type ion exchange resin Diaion UBK-530 (trade name, manufactured by Mitsubishi Kasei Co., Ltd., average particle diameter 230 μm to 240 μm, exchange capacity 1.6 meq / m)
l) is a glass column (column size 18 x 600 m)
m) in an amount of 130 ml and equilibrated with demineralized water, and then 6.8 g of decaglycerin # 750 (Sakamoto Yakuhin Kogyo Co., Ltd.) was dissolved in demineralized water to 13 ml and added to the top of the column. Elution was performed at a flow rate of 65 ml per hour. Immediately after the start of elution, the first demineralized water 45 flowing out from the end of the column
ml was discarded, and then 45 ml of the effluent was collected as fraction 1, and then 45 ml of the effluent was collected as fraction 2. The analysis of each fraction before and after separation was performed by high performance liquid chromatography according to the method of Example 1. The compositions of the raw materials and fractions 1 and 2 before separation are shown in Table-1.
【００２１】実施例６ 実施例５と同様の条件で、最初の４５mlを廃棄した後、
流出する液を３０mlずつ３画分採取してそれぞれ画分
１、画分２、および画分３とした。画分１、２および３
の組成を表−２に示す。Example 6 Under the same conditions as in Example 5, after discarding the first 45 ml,
The effluent was collected into 3 fractions of 30 ml, which were designated as fraction 1, fraction 2 and fraction 3, respectively. Fractions 1, 2 and 3
The composition of is shown in Table-2.
【００２２】実施例７ 架橋度６％、ナトリウム型のイオン交換樹脂ダイヤイオ
ンＵＢＫ−５３０（商品名、三菱化成（株）製、平均粒
径２３０μｍ〜２４０μｍ、交換容量１．６ｍｅｑ／m
l）をガラス製のカラム（カラムサイズ１８×６００m
m）に１３０ml充填し、２６０mlの８％塩酸を流して対
イオンをＨ+ に置換した後、脱塩水でカラムをカラムの
終端から流出する液が中性（ｐＨ７．０）になるまで充
分に洗浄し、０．１％リン酸で平衡化した。さらに、デ
カグリセリン＃７５０（阪本薬品工業（株））７．４ｇ
を脱塩水に溶解して１３mlにしてカラムの上端に添加
し、０．１％リン酸で１時間当り６５mlの流速で溶出
し、実施例５と同様にして４５mlずつ２つの画分（画分
１および２）を得た。画分１、２の組成を表−３に示
す。Example 7 Sodium ion exchange resin Diaion UBK-530 (trade name, manufactured by Mitsubishi Kasei Co., Ltd., average particle diameter 230 μm to 240 μm, exchange capacity 1.6 meq / m)
l) is a glass column (column size 18 x 600 m)
m) was filled with 130 ml, 260 ml of 8% hydrochloric acid was flowed to replace the counter ion with H + , and the column was washed with demineralized water until the liquid flowing out from the end of the column became neutral (pH 7.0). Washed and equilibrated with 0.1% phosphoric acid. In addition, 7.4 g of decaglycerin # 750 (Sakamoto Yakuhin Kogyo Co., Ltd.)
Was dissolved in demineralized water to make 13 ml and added to the upper end of the column and eluted with 0.1% phosphoric acid at a flow rate of 65 ml per hour. 1 and 2) were obtained. The compositions of Fractions 1 and 2 are shown in Table-3.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【表３】 [Table 3]
【００２６】[0026]
【発明の効果】本発明により、所望の組成を有するポリ
グリセリン組成物、例えば、環状成分を含まないもの、
重合度２〜７の成分に富んだもの等を製造することがで
きる。また、本発明により、ポリグリセリン組成物から
多様な親水性部分の組成を持つ乳化剤を製造することが
容易になる。According to the present invention, a polyglycerin composition having a desired composition, for example, one containing no cyclic component,
It is possible to produce those rich in components having a degree of polymerization of 2 to 7. The present invention also facilitates the production of emulsifiers having various hydrophilic moiety compositions from the polyglycerin composition.
【図１】実施例１のクロマトグラムを示す。1 shows a chromatogram of Example 1. FIG.
【図２】実施例２のクロマトグラムを示す。FIG. 2 shows a chromatogram of Example 2.
【図３】実施例３のクロマトグラムを示す。FIG. 3 shows a chromatogram of Example 3.
【図４】実施例４のクロマトグラムを示す。FIG. 4 shows a chromatogram of Example 4.
【図５】比較例１のクロマトグラムを示す。FIG. 5 shows a chromatogram of Comparative Example 1.
【図６】比較例２のクロマトグラムを示す。FIG. 6 shows a chromatogram of Comparative Example 2.
【符号の説明】 各ピーク上の数字は該当ピークの重合度を表わす。[Explanation of Symbols] The number on each peak represents the degree of polymerization of the corresponding peak.
Claims (1)
するゲル型の強酸性陽イオン交換樹脂を用いてクロマト
分離することを特徴とするポリグリセリン組成物の分離
方法。1. A method for separating a polyglycerin composition, which comprises performing chromatographic separation using a gel-type strongly acidic cation exchange resin having a polystyrene skeleton with a degree of crosslinking of 5 to 8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11024692A JP3166289B2 (en) | 1992-04-28 | 1992-04-28 | Method for separating polyglycerin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11024692A JP3166289B2 (en) | 1992-04-28 | 1992-04-28 | Method for separating polyglycerin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05310625A true JPH05310625A (en) | 1993-11-22 |
| JP3166289B2 JP3166289B2 (en) | 2001-05-14 |
Family
ID=14530822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11024692A Expired - Fee Related JP3166289B2 (en) | 1992-04-28 | 1992-04-28 | Method for separating polyglycerin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3166289B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005126A (en) * | 1997-08-08 | 1999-12-21 | Mitsubishiki Chemical Corporation | Solubilizing agent and hydrosol composition obtained by using the same |
| WO2004098544A1 (en) * | 2003-05-09 | 2004-11-18 | The Nisshin Oillio Group, Ltd. | Selfemulsifying oily liquid cosmetic |
| WO2005051334A1 (en) * | 2003-11-28 | 2005-06-09 | The Nisshin Oillio Group, Ltd. | Oil-in-water-type emulsified cosmetic preparation and process for producing the same |
| JP2007091823A (en) * | 2005-09-27 | 2007-04-12 | Mitsubishi Chemicals Corp | Method for purifying polyglycerol, purified polyglycerol obtained by the method, and manufacturing method of fatty acid polyglyceride using the purified polyglycerol |
| JP2009073763A (en) * | 2007-09-20 | 2009-04-09 | Tsukishima Kankyo Engineering Ltd | Method and apparatus for separating polyglycerol and polyglycerol |
| JP2011241229A (en) * | 2011-08-23 | 2011-12-01 | Mitsubishi Chemicals Corp | Method for production of polyglycerol fatty acid ester |
| JP2013519634A (en) * | 2010-02-12 | 2013-05-30 | エヴォニク ゴールドシュミット ゲーエムベーハー | Cosmetic composition containing polyglycerol partial ester |
| JP2013519633A (en) * | 2010-02-12 | 2013-05-30 | エヴォニク ゴールドシュミット ゲーエムベーハー | Cosmetic composition containing polyglycerol partial ester |
| WO2013172165A1 (en) * | 2012-05-18 | 2013-11-21 | 花王株式会社 | Method for producing refined glycerin alkyl ether |
| JP2015136641A (en) * | 2014-01-21 | 2015-07-30 | 太平洋セメント株式会社 | Method and apparatus for treating phosphoric acid waste liquid |
-
1992
- 1992-04-28 JP JP11024692A patent/JP3166289B2/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005126A (en) * | 1997-08-08 | 1999-12-21 | Mitsubishiki Chemical Corporation | Solubilizing agent and hydrosol composition obtained by using the same |
| US7687066B2 (en) | 2003-05-09 | 2010-03-30 | The Nisshin Oillio Group, Ltd. | Self emulsifying oily liquid cosmetic |
| WO2004098544A1 (en) * | 2003-05-09 | 2004-11-18 | The Nisshin Oillio Group, Ltd. | Selfemulsifying oily liquid cosmetic |
| WO2005051334A1 (en) * | 2003-11-28 | 2005-06-09 | The Nisshin Oillio Group, Ltd. | Oil-in-water-type emulsified cosmetic preparation and process for producing the same |
| US8501823B2 (en) | 2003-11-28 | 2013-08-06 | The Nisshin Oillio Group, Ltd. | Oil-in-water emulsion cosmetic composition and method for producing the same |
| JP2007091823A (en) * | 2005-09-27 | 2007-04-12 | Mitsubishi Chemicals Corp | Method for purifying polyglycerol, purified polyglycerol obtained by the method, and manufacturing method of fatty acid polyglyceride using the purified polyglycerol |
| JP2009073763A (en) * | 2007-09-20 | 2009-04-09 | Tsukishima Kankyo Engineering Ltd | Method and apparatus for separating polyglycerol and polyglycerol |
| JP2013519634A (en) * | 2010-02-12 | 2013-05-30 | エヴォニク ゴールドシュミット ゲーエムベーハー | Cosmetic composition containing polyglycerol partial ester |
| JP2013519633A (en) * | 2010-02-12 | 2013-05-30 | エヴォニク ゴールドシュミット ゲーエムベーハー | Cosmetic composition containing polyglycerol partial ester |
| JP2011241229A (en) * | 2011-08-23 | 2011-12-01 | Mitsubishi Chemicals Corp | Method for production of polyglycerol fatty acid ester |
| WO2013172165A1 (en) * | 2012-05-18 | 2013-11-21 | 花王株式会社 | Method for producing refined glycerin alkyl ether |
| JP2013256492A (en) * | 2012-05-18 | 2013-12-26 | Kao Corp | Manufacturing method for purified glycerine alkyl ether |
| US9371260B2 (en) | 2012-05-18 | 2016-06-21 | Kao Corporation | Method for producing refined glycerin alkyl ether |
| JP2015136641A (en) * | 2014-01-21 | 2015-07-30 | 太平洋セメント株式会社 | Method and apparatus for treating phosphoric acid waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3166289B2 (en) | 2001-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Barron et al. | Effect of functional group structure on the selectivity of low-capacity anion exchangers for monovalent anions | |
| CN105777896B (en) | A kind of purification process at antibody acidity peak | |
| JPH05310625A (en) | Separation method for polyglycerin composition | |
| Liao et al. | High performance displacement chromatography of proteins: separation of β-lactoglobulins A and B | |
| US4351909A (en) | High performance ion-exchange composition | |
| US20200264144A1 (en) | Ion exchange chromatography column, method, and system thereof | |
| Buytenhuys | Ion chromatography of inorganic and organic ionic species using refractive index detection | |
| Boschetti et al. | Preparative high-performance liquid chromatographic separation of proteins with HyperD ion-exchange supports | |
| Partridge et al. | Displacement chromatography on synthetic ion-exchange resins. 5. Separation of the basic amino-acids | |
| US5560827A (en) | Exclusion chromatographic separation of ionic from nonionic solutes | |
| KR20150050386A (en) | Method for separating antibody isoform by using cation exchange chromatography | |
| CN102659859B (en) | Application of monodispersed polymethacrylate ion exchange chromatography medium in column chromatography purification of fondaparinux sodium | |
| EP3762121A1 (en) | Composite material for bioseparations | |
| Adlof et al. | Partial argentation resin chromatography (PARC): III. the effects of sodium ion incorporation and solvent on the separation of mixtures of fatty acids, of fatty esters, and of triglycerides | |
| US9297050B1 (en) | Removing impurities from sugar solutions | |
| EP0104911A2 (en) | Column packing material and production thereof | |
| CA1321583C (en) | Production process of high-purity lactulose syrup | |
| Nakajima et al. | Ion chromatography on poly (crown ether)-modified silica possessing high affinity for sodium | |
| Ando et al. | High-performance liquid chromatography of underivatized gangliosides | |
| US5431822A (en) | Process for the chromatographic separation of a mixture of polyglycerols | |
| Josić et al. | High-performance concanavalin A affinity chromatography of liver and hepatoma membrane proteins | |
| EP1064312B1 (en) | Quaternary ammonium polymer, its preparation, its use for separating biomolecules | |
| JP6613334B2 (en) | Removal of impurities from sugar solutions | |
| Dufka et al. | “Synachrom”, a macroporous copolymer, as a sorption material for gas chromatography | |
| De Borba et al. | Determination of inorganic anions in environmental waters using a hydroxide-selective column |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090309 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090309 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100309 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |