JPH0213387A - Preparation of castor oil fatty acid esteride - Google Patents
Preparation of castor oil fatty acid esterideInfo
- Publication number
- JPH0213387A JPH0213387A JP16454988A JP16454988A JPH0213387A JP H0213387 A JPH0213387 A JP H0213387A JP 16454988 A JP16454988 A JP 16454988A JP 16454988 A JP16454988 A JP 16454988A JP H0213387 A JPH0213387 A JP H0213387A
- Authority
- JP
- Japan
- Prior art keywords
- castor oil
- lipase
- fatty acid
- estolide
- oil
- 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
- 239000004359 castor oil Substances 0.000 title claims abstract description 54
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 54
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 54
- 239000000194 fatty acid Substances 0.000 title claims abstract description 27
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 26
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 26
- 150000004665 fatty acids Chemical class 0.000 title description 10
- 239000004367 Lipase Substances 0.000 claims abstract description 42
- 102000004882 Lipase Human genes 0.000 claims abstract description 42
- 108090001060 Lipase Proteins 0.000 claims abstract description 42
- 235000019421 lipase Nutrition 0.000 claims abstract description 42
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003921 oil Substances 0.000 claims abstract description 24
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 235000011187 glycerol Nutrition 0.000 claims description 18
- -1 fatty acid estolide Chemical class 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 150000002148 esters Chemical class 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 241000222120 Candida <Saccharomycetales> Species 0.000 abstract 1
- 150000002149 estolides Chemical class 0.000 description 25
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000539 dimer Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、ひまし油から実質的にグリセリンを含まない
ひまし油脂肪酸エストリドを製造する方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing substantially glycerin-free castor oil fatty acid estolide from castor oil.
従来、リパーゼを用いてひまし油を加水分解反応し、グ
リセリンと脂肪酸を得る方法は知られている。また、こ
の場合に、ひまし油脂肪酸エストリドが副生ずることも
知られていたが、従来のリパーゼを用いる加水分解反応
においては、エストリドの副生を抑制するようにして、
そして加水分解反応率が約７０％を越えないようにして
反応を行うもので、積極的にひまし油（ｍ肪酸エストリ
ドを生成させることは行われていなかった。Conventionally, a method of hydrolyzing castor oil using lipase to obtain glycerin and fatty acids is known. Furthermore, in this case, it was known that castor oil fatty acid estolide is produced as a by-product, but in the conventional hydrolysis reaction using lipase, the by-production of estolide is suppressed.
The reaction was carried out so that the hydrolysis reaction rate did not exceed about 70%, and the production of castor oil (m-fatty acid estolide) was not actively carried out.
一方、前記加水分解反応で生成するひまし油脂肪酸エス
トリドは、リシノール酸の水酸基とカルボキシル基とが
反応した分子間又は分子内縮重合体であり、界面活性剤
や化学中間原料として有用な物質である。On the other hand, castor oil fatty acid estolide produced in the hydrolysis reaction is an intermolecular or intramolecular condensation polymer obtained by reacting the hydroxyl group and carboxyl group of ricinoleic acid, and is a useful substance as a surfactant or a chemical intermediate raw material.
ひまし油からエストリドを化学的に得ようとすると、ひ
まし油を高温でアルカリ又は酸により化学的に処理して
いったん遊離の脂肪酸（リシノール酸）とした後に、少
なくとも７０℃の加熱下で必要に応じて硫酸、リン酸等
を用いて脱水縮合することが一般的である。When trying to chemically obtain estolide from castor oil, castor oil is chemically treated with an alkali or acid at high temperature to form a free fatty acid (ricinoleic acid), and then sulfuric acid is added as necessary under heating at at least 70°C. It is common to carry out dehydration condensation using , phosphoric acid, etc.
しかし、この方法においては、水酸基の脱水による不飽
和結合の生成、炭化水素鎖の切断、アルデヒド等の生成
などの副反応が起り、得られるエストリドは着色等の問
題を生じて品質の悪いものであった。However, in this method, side reactions occur such as the formation of unsaturated bonds due to dehydration of hydroxyl groups, the cleavage of hydrocarbon chains, and the formation of aldehydes, etc., and the resulting estolide has problems such as coloring and is of poor quality. there were.
本発明者らは、前記のようにひまし油脂肪酸エストリド
は有用な物質であることに着目し、エステル化能の高い
リパーゼをひまし油に対し１％以上の割合で使用し、エ
ストリド生成率９０％以上のひまし油脂肪酸エストリド
を得ることを先に提案した（特願昭６２−１７１８１８
号）。The present inventors focused on the fact that castor oil fatty acid estolide is a useful substance as described above, and used a lipase with high esterification ability at a ratio of 1% or more to castor oil to achieve an estolide production rate of 90% or more. It was previously proposed to obtain castor oil fatty acid estolide (patent application 171818/1986).
issue).
リパーゼを用いて得られるひまし油脂肪酸エストリドは
、通常、２〜５重景体が混合した状態のエストリドと、
ひまし油脂肪酸とからなる。リパーゼによるエストリド
生成は、化学的処理に比べて、重縮合が均一となり、重
合度分布がシャープとなる利点もある。しかし、使用す
るリパーゼの加水分解能とエステル化能とにより、エス
トリド生成物中にひまし油（トリグリセリド）が部分的
に加水分解された部分グリセリドが残留したり、グリセ
リン含有分子が副生ずるおそれがあった。Castor oil fatty acid estolide obtained using lipase usually contains estolide in a state in which 2 to 5 complexes are mixed,
Consists of castor oil fatty acids. Estolide production using lipase has the advantage that polycondensation is uniform and the degree of polymerization distribution is sharp compared to chemical treatment. However, depending on the hydrolysis ability and esterification ability of the lipase used, there is a risk that partial glyceride, which is obtained by partially hydrolyzing castor oil (triglyceride), may remain in the estolide product, or that glycerin-containing molecules may be produced as by-products.
本発明者らが先に提案したひまし油に対してリパーゼを
濃度１％以上で用いる高濃度リパーゼ法では、エストリ
ド生成率を９０％以上にすることにより、グリセリド等
の混入を防止した。In the high-concentration lipase method previously proposed by the present inventors, in which lipase is used at a concentration of 1% or more for castor oil, the contamination of glycerides and the like is prevented by increasing the estolide production rate to 90% or more.
本発明者らは、さらにリパーゼによるひまし油処理を検
討し、エストリド生成には不適当と考えられていた低濃
度におけるひまし油の加水分解処理について研究すると
共に、リパーゼによるひまし油脂肪酸エストリドを製造
する場合の工業性について検討した。The present inventors further investigated the treatment of castor oil using lipase, researched the hydrolysis treatment of castor oil at low concentrations that were considered inappropriate for the production of estolide, and also investigated the industrial use of castor oil when producing fatty acid estolide using lipase. We considered gender.
その結果、ひまし油に対して１重量％より少ないリパー
ゼ濃度においても、工業的に有用なひまし油脂肪酸エス
トリドを効率よく製造できることを見出し、本発明を完
成するに至った。As a result, it was discovered that industrially useful castor oil fatty acid estolide can be efficiently produced even at a lipase concentration of less than 1% by weight based on castor oil, and the present invention was completed.
本発明は、グリセリドのエステル部位全てに対して加水
分解能を有し、かつ脂肪酸炭素鎖中に存在する水酸基に
対してエステル化能を有するリパーゼをひまし油に対し
１重量％未満の割合で存在させ、かつ水／油分重量比が
１７１０以上の条件下、ひまし油を５０℃以下で反応処
理することにより、実質的にグリセリン成分を含有しな
いひまし油脂肪酸エストリドを製造する方法である。In the present invention, a lipase having a hydrolyzing ability for all ester moieties of glyceride and an esterifying ability for hydroxyl groups present in a fatty acid carbon chain is present in a proportion of less than 1% by weight based on castor oil, This is a method for producing castor oil fatty acid estolide substantially free of glycerin components by subjecting castor oil to a reaction treatment at 50° C. or lower under conditions where the water/oil weight ratio is 1710 or higher.
本発明で用いるエステル部位全てに対して加水分解能を
有し、かつ脂肪酸炭素鎖中に存在する水酸基に対してエ
ステル化能を有するリパーゼとは、グリセリドの３個の
エステル結合のいずれにも加水分解性を示し、ひまし油
脂肪酸中の水酸基の位置でカルボキシル基とエステル反
応性を示すものである。このようなリパーゼとしては、
キャソディダ属を起源とするもので１例えば、名糖産業
社製「リパーゼＯＦＪ、同社製「リパーゼＭＹＪ又は大
野製薬製［リパーゼ濃度Ｊ等がある。A lipase that has the ability to hydrolyze all the ester moieties used in the present invention and has the ability to esterify the hydroxyl groups present in the fatty acid carbon chain is a lipase that can hydrolyze any of the three ester bonds of glyceride. It exhibits ester reactivity with carboxyl groups at the hydroxyl positions in castor oil fatty acids. As such lipase,
Originating from the genus Cassodida, examples include "Lipase OFJ" manufactured by Meito Sangyo Co., Ltd., "Lipase MYJ" manufactured by Meito Sangyo Co., Ltd., and "Lipase Density J manufactured by Ohno Pharmaceutical Co., Ltd.".
本発明は、ひまし油を原料としてリパーゼを溶解させた
水溶液にひまし油を分散させ、この反応混合物を撹拌し
てエマルジョン状態で反応させる一工程法により実施さ
れる。この場合、加水分解反応とエステル縮合反応とが
出来るだけ逐次的に進行するようにする。そのため、本
発明では、反応温度は、５０℃以下とし、好ましくは１
０〜４０℃で行う。この反応温度では生成物の着色も防
止される。The present invention is carried out by a one-step method in which castor oil is dispersed in an aqueous solution in which lipase is dissolved using castor oil as a raw material, and the reaction mixture is stirred to react in an emulsion state. In this case, the hydrolysis reaction and the ester condensation reaction are made to proceed as sequentially as possible. Therefore, in the present invention, the reaction temperature is 50°C or lower, preferably 1
It is carried out at 0-40°C. This reaction temperature also prevents coloration of the product.
また、本発明では５反応混合物中の水／油分重量比は、
１／１０以上とし、好ましくは１７５〜２とする。In addition, in the present invention, the water/oil weight ratio in the 5 reaction mixture is
It should be 1/10 or more, preferably 175-2.
この条件の採用により、ひまし油の加水分解におけるグ
リセリンの生成を容易にし、かつその生成グリセリンの
水相への溶解移行を円滑に行うことができる。その結果
、加水分解により得られるひまし油脂肪酸とその縮合生
成物のエストリドとからなる油相へのグリセリンの残存
が回避される。By adopting these conditions, it is possible to facilitate the production of glycerin in the hydrolysis of castor oil, and to smoothly dissolve and transfer the produced glycerin into the aqueous phase. As a result, glycerin is prevented from remaining in the oil phase consisting of castor oil fatty acid obtained by hydrolysis and its condensation product estolide.
水／油分比が１７１０より低くなると、反応混合物のエ
マルジョン状態が安定せず、反応が円滑に進行しない。If the water/oil ratio is lower than 1710, the emulsion state of the reaction mixture will not be stable and the reaction will not proceed smoothly.
本発明におけるリパーゼの使用斌は、ひまし油に対して
１重量％未満であって、好ましくは０．０１〜０．８重
斌％である。ひまし油に対し１重量％未満のリパーゼを
用いることにより、加水分解により副生ずる部分グリセ
リドの油分への残留と、その部分グリセリドとひまし油
脂肪酸との反応によるグリセリン含有分子の生成が抑制
され、ひまし油の３つのエステル全てを完全に加水分解
した後に、エステル縮合が生起するようになる。The amount of lipase used in the present invention is less than 1% by weight, preferably 0.01-0.8% by weight based on castor oil. By using less than 1% by weight of lipase with respect to castor oil, the residual of partial glycerides produced by hydrolysis in the oil and the formation of glycerin-containing molecules due to the reaction of the partial glycerides with castor oil fatty acids are suppressed, and the 3% of castor oil is suppressed. After complete hydrolysis of all three esters, ester condensation begins to occur.
本発明において、１重量％以上のリパーゼを使用した場
合には、エストリド生成率が９０％以下では生成エスト
リド油中に部分グリセリドや、グリセリン含有分子が混
入し、エストリドの使用上好ましくないものとなった。In the present invention, when 1% by weight or more of lipase is used, if the estolide production rate is less than 90%, partial glycerides and glycerin-containing molecules will be mixed into the estolide oil produced, making it undesirable for the use of estolide. Ta.
この理由は明らかでないが、リパーゼ濃度が濃い状態で
はひまし油の部分的加水分解状態で部分グリセリドの炭
素鎖中のＯＨ基にリパーゼが作用し、部分グリセリドと
ひまし油脂肪酸とがエステル縮合し、グリセリン含有分
子が副生されるものと考えられる。これに対し。The reason for this is not clear, but when the lipase concentration is high, lipase acts on the OH group in the carbon chain of partial glyceride in the partially hydrolyzed state of castor oil, and the partial glyceride and castor oil fatty acid undergo ester condensation, resulting in glycerin-containing molecules. is considered to be a by-product. Against this.
リパーゼ濃度がひまし油に対し１重量％未満であれば、
加水分解とエステル縮合が逐次的に進行し、その結果、
エストリド生成率を９０％以下で反応を終了させても、
部分グリセリドやグリセリン含有物の副生が回避される
ものと考えられる。If the lipase concentration is less than 1% by weight based on castor oil,
Hydrolysis and ester condensation proceed sequentially, resulting in
Even if the reaction is terminated at an estolide production rate of 90% or less,
It is thought that by-products of partial glycerides and glycerin-containing substances are avoided.
本発明における反応時間は、リパーゼ使用量との関係に
依存し、通常、リパーゼ使用量がひまし油に対し１重量
％未満ではその使用量が多い程反応時間は少なくてよい
。この場合、エストリド生成率は、５０％以上であれば
よい。ひまし油脂肪酸の油分への残存は、生成エストリ
ドの工業的使用上問題はない。The reaction time in the present invention depends on the relationship with the amount of lipase used. Generally, when the amount of lipase used is less than 1% by weight based on castor oil, the reaction time may be shorter as the amount used is larger. In this case, the estolide production rate may be 50% or more. The residual castor oil fatty acid in the oil does not pose a problem in the industrial use of the produced estolide.
本発明で得られるニス１−リドの平均縮合度は約１．５
〜３であり、縮合生成物中の２量体又は３量体の組成割
合が３０重ｆｔ％以上のものであればよい。The average degree of condensation of the varnish 1-lid obtained in the present invention is about 1.5.
-3, and the composition ratio of the dimer or trimer in the condensation product is 30% by weight or more.
本発明を実施する場合、エストリド生成率、エストリド
の平均縮合度及び縮合生成物の２量体等の割合は１反応
時間、リパーゼ使用量を使用目的に応じて選択して、所
望の値が得られるようにする。When carrying out the present invention, desired values can be obtained by selecting the estolide production rate, the average degree of condensation of estolide, and the proportion of dimers in the condensation product depending on the reaction time and the amount of lipase used depending on the purpose of use. be able to do so.
なお、本明細書でいうエストリド生成率は次の式で定義
されるものである。Note that the estolide production rate referred to in this specification is defined by the following formula.
Ｒ＝−Ｘ１００（％）
Ｒ：エストリド生成率
Ａ：遊離脂肪酸およびエストリドの脂肪酸基準のモル数
Ｂ：エストリドの脂肪酸基性のモル数
〔発明の効果〕
本発明の方法で得られるひまし油脂肪酸エストリドは、
実質的にグリセリン成分を含有せず、かつ着色等の問題
のない高品質のものである。R=-X100 (%) R: Estolide production rate A: Number of moles of free fatty acids and estolide based on fatty acid B: Number of moles of fatty acid base of estolide [Effects of the Invention] The castor oil fatty acid estolide obtained by the method of the present invention is ,
It is of high quality and does not contain substantially any glycerin component and has no problems such as coloring.
本発明で得られるひまし油脂肪酸エストリドは。The castor oil fatty acid estolide obtained in the present invention is.
界面活性剤や化学中間原料として有利に用いられる。It is advantageously used as a surfactant or chemical intermediate raw material.
次に本発明を実施例によりさらに詳細に説明する。尚、
ひまし油部分グリセリド及びグリセリン含有化合物は、
薄層クロマトグラフィーおよび液体クロマトグラフィー
により測定した。縮重合度は酸価の値および液体クロマ
トグラフィーで測定した。Next, the present invention will be explained in more detail with reference to Examples. still,
Castor oil partial glycerides and glycerin-containing compounds are
Measured by thin layer chromatography and liquid chromatography. The degree of condensation polymerization was determined by acid value and liquid chromatography.
実施例１
ひまし油５００ｇとリパーゼ（名糖産業製、リパーゼＯ
Ｆ） Ｉｇを水５００ｇに溶解した水溶液を混合振とう
させてエマルジョン化し、撹拌しながらエマルジョン状
態で室温で３００時間反応させた。生成物を遠心分離し
、油相と水相とに分け、油分４４０ｇを回収した。この
油分は着色はなく、そのエストリド生成率は８６．１％
で、平均縮合度は２．５であった。また油分中の２量体
は４０．２％、３量体は３１．２％、４量体は１０．４
％、５量体以上は４．３％であった。Example 1 500g of castor oil and lipase (Meito Sangyo Co., Ltd., Lipase O)
F) An aqueous solution of Ig dissolved in 500 g of water was mixed and shaken to form an emulsion, and the emulsion was reacted at room temperature for 300 hours with stirring. The product was centrifuged and separated into an oil phase and an aqueous phase, and 440 g of oil was recovered. This oil has no coloration and its estride production rate is 86.1%.
The average degree of condensation was 2.5. Also, the amount of dimers in the oil is 40.2%, the amount of trimers is 31.2%, and the amount of tetramers is 10.4%.
%, and the percentage of pentamers or more was 4.3%.
ひまし油部分グリセリド及びグリセリン含有化合物は、
油分中には実質的に検出されなかった。Castor oil partial glycerides and glycerin-containing compounds are
It was virtually not detected in the oil.
実施例２
リパーゼ（名糖産業製、リパーゼＭＹ）２．５ｇを用い
た以外は全て実施例１と同様にして反応を行った。Example 2 The reaction was carried out in the same manner as in Example 1, except that 2.5 g of lipase (Lipase MY, manufactured by Meito Sangyo) was used.
反応時間９６時間後、油分４３８ｇを得た。この油分の
エストリド生成率は約８１％で、油分の着色は見られな
かった。ひまし油部分グリセリド及びグリセリン含有化
合物は検出されなかった。又、油分中２量体４０．８％
、３量体２８．９％、４量体９．６％、５量体以」二２
．４％で、平均縮合度は２．４であった。After 96 hours of reaction time, 438 g of oil was obtained. The estolide production rate of this oil was about 81%, and no coloration of the oil was observed. Castor oil partial glycerides and glycerin-containing compounds were not detected. Also, dimer content in oil is 40.8%
, 28.9% trimer, 9.6% tetramer, more than 22
．． 4%, the average degree of condensation was 2.4.
実施例３
リパーゼ（大野製薬製、リパーゼＡＹ）０．５ｇを用い
、反応温度３５℃、反応時間３４０時間とした以外は実
施例１と同様に反応を行った。得られた油分は４３７ｇ
であり、エストリド生成率は約７３％で、同様に；ｎ色
は観察されなかった。又、ひまし油部分グリセリド及び
グリセリン含有化合物も検出されなかった。この油分は
、２量体５１．９％、３ｇ体２０．２％、４量体以上２
．４％を含み、平均縮合度は２．０であった。Example 3 A reaction was carried out in the same manner as in Example 1, except that 0.5 g of lipase (Lipase AY, manufactured by Ohno Pharmaceutical Co., Ltd.) was used, the reaction temperature was 35° C., and the reaction time was 340 hours. Obtained oil content is 437g
The estride production rate was approximately 73%; similarly, no color was observed. Also, castor oil partial glyceride and glycerin-containing compounds were not detected. The oil content is 51.9% dimer, 20.2% 3g, and 2 or more tetramer.
．． 4%, and the average degree of condensation was 2.0.
実施例４
リパーゼ（名糖産業製、リパーゼＯＦ） ４ｇを用い、
反応温度１０℃１反応時間１５０時間とした以外は実施
例１と同様に反応を行った。得られた油分は４４０乙で
、エストリド生成率約８８％であり、油分の着色はなか
った。ひまし油部分グリセリド及びグリセリン含有化合
物も検出されなかった。油分中、２量体３８．３％、３
址体３０．５％、４量体１４．９％、５量体以上４．６
％で、平均縮合度は２．６であった。Example 4 Using 4 g of lipase (manufactured by Meito Sangyo, Lipase OF),
The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 10° C. and the reaction time was 150 hours. The obtained oil content was 440 Otsu, the estolide production rate was about 88%, and there was no coloration of the oil content. Castor oil partial glycerides and glycerin-containing compounds were also not detected. In oil, dimer 38.3%, 3
30.5% as a body, 14.9% as a tetramer, 4.6 as a pentamer or more
%, and the average degree of condensation was 2.6.
比較例
リパーゼ（名糖産業製、リパーゼＯＦ） ５ｇ（ひまし
油に対し１重量対）とし、実施例Ｉと同様にして反応を
行い、反応時間６０時間でエストリド生成率８５％とし
た。ここで得られた油分は４４３ｇで、平均縮合度は２
．５であった。ひまし油部分グリセリドが約５ｇ、グリ
セリン含有化合物が約７ｇが含まれていた。Comparative Example Lipase (manufactured by Meito Sangyo, Lipase OF) was used at 5 g (1 weight to castor oil), and the reaction was carried out in the same manner as in Example I, resulting in an estolide production rate of 85% in a reaction time of 60 hours. The oil content obtained here was 443 g, and the average degree of condensation was 2.
．． It was 5. It contained about 5 g of castor oil partial glyceride and about 7 g of a glycerin-containing compound.
Claims (1)
能を有し、かつ脂肪酸炭素鎖中に存在する水酸基に対し
てエステル化能を有するリパーゼをひまし油に対し１重
量％未満の割合で存在させ、かつ水／油分重量比が１／
１０以上の条件下、ひまし油を５０℃以下で反応させる
ことを特徴とする実質的にグリセリン成分を含有しない
ひまし油脂肪酸エストリドの製造方法。(1) A lipase having the ability to hydrolyze all the ester moieties of glyceride and the ability to esterify the hydroxyl groups present in the fatty acid carbon chain is present in a proportion of less than 1% by weight based on castor oil, and Water/oil weight ratio is 1/
1. A method for producing castor oil fatty acid estolide substantially free of glycerin components, which comprises reacting castor oil at 50° C. or lower under conditions of 10 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16454988A JPH0213387A (en) | 1988-06-30 | 1988-06-30 | Preparation of castor oil fatty acid esteride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16454988A JPH0213387A (en) | 1988-06-30 | 1988-06-30 | Preparation of castor oil fatty acid esteride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0213387A true JPH0213387A (en) | 1990-01-17 |
Family
ID=15795271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16454988A Pending JPH0213387A (en) | 1988-06-30 | 1988-06-30 | Preparation of castor oil fatty acid esteride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0213387A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011520870A (en) * | 2008-05-14 | 2011-07-21 | カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ | Castor oil fatty acid-based estolides and their derivatives as effective lubricant base stocks |
-
1988
- 1988-06-30 JP JP16454988A patent/JPH0213387A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011520870A (en) * | 2008-05-14 | 2011-07-21 | カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ | Castor oil fatty acid-based estolides and their derivatives as effective lubricant base stocks |
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