JPH01284335A - Method and beads for separating and concentrating tocopherols - Google Patents

Abstract

PURPOSE:To separate and concentrate high purity tocopherols with high work efficiency in a high yield by passing the deodorized distillate of fats and oils through a column for liq. chromatography packed with beads made of a polyvinyl compd.-based porous polymer and having a certain particle size or above and a certain water content or above in the form of gel. CONSTITUTION:Porous polymer beads having >=10mum particle size and, >=30% water content in the form of gel are produced with methacrylic acid, sodium p-styrenesulfonate, polyvinyl alcohol, ethylene glycol dimethacrylate, glycidyl methacrylate, epichlorohydrin, 2,2-azobis-(2,4-dimethylvaleronitrile) and formic acid. A column is packed with the beads and the deodorized distillate of soybean oil, etc., is poured into the column. Methanol as a developing medium is then passed through the column to separate and collect tocopherols by liq. chromatography. The resulting high purity tocopherols are used as vitamin E, an antioxidant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application If) The present invention relates to beads used in separating and condensing tocopherols and a separation and concentration method.

(Prior art) α, β, γ and δ-tocopherols, etc. (hereinafter referred to as tocopherols) It is contained in the deodorizing distillate that is produced as a by-product in the process of deodorizing oil, etc.
In addition to tocopherols, hydrocarbons, sterins, glycerides, free fatty acids, etc. coexist in this deodorized distillate, so it is difficult to use it directly in medicines as vitamin E or in foods as an antioxidant. .

Conventionally, tocopherols/L/s in the deodorized distillate have been treated with MM.
Methods such as molecular distillation and ion-exchange resin treatment have been used to concentrate nitrogen, but with molecular distillation, it is difficult to perform separate operations, and it is extremely difficult to obtain a concentrate with a certain concentration in a good yield. Furthermore, in the ion-exchange resin treatment method, the resin specifically adsorbs tocopherols, so advanced techniques are required for preparative separation, and the resin must be regenerated, resulting in problems with solvent [housing]. It has the disadvantage that it requires complicated steps such as removal of the bathing agent.

(Problems to be solved by @Mei) An object of the present invention is to provide beads for separation and concentration that are suitable for separating and stacking tocopherols.

The object of the present invention is to provide a fractional concentration method for obtaining tocopherols from a deodorized distillate by liquid chromatography using the beads with good workability, high purity, and high yield. I'm in the middle of the day.

(Means for Solving the Problems) Beads for concentrating tocopherols that can achieve the above-mentioned object of the present invention are made of a porous polymer containing a polyvinyl compound as a main component, and the particle size of the aggregate is io, a or more and a gel moisture content of 30% or more.The four-ring method for tocopherols is performed after injecting the deodorized distillate into a column for liquid chromatography filled with the beads. This can be advantageously carried out by passing a developing solvent through, fractionating and collecting the target tocopherols.

The present invention will be described in detail below. The beads of the present invention are made of a porous 11 polymer having a polyvinyl compound of 60 i and a fit% or more, preferably 30% or more by weight, and the particle size of the composite is 10μ or more. , preferably 20 to 150μ,
and the gel moisture content of the beads is 30% or more, preferably 50%.
% or more.

Here, the polyvinyl compounds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetofethylene glycol diacrylate, and tetofethylene glycol diacrylate. Methacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylol (Methane acrylic acid polyol esters; vinyl methacrylate) such as methane tetophacrylate, tetramethylol methane tetoph methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, glycerin diacrylate, glycerin dimethacrylate, glycerin triacrylate, and glycerin trimethacrylate. , allyl methacrylate (methane acrylic vinyl ester);
diallyl maleate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl oxalate, diallyl diamide, diallyl sebacate, diallyl tartrate, diallylamine, triallylamine, triallyl phosphate, triallyl tricarballylate, Aconitic acid triallyl, citric acid triallyl, realyl cyanurate,
Polyallyl compound M such as triaryl isocyanurate
Examples include aromatic polyvinyl compounds such as divinylbenzene and trivinylbenzene.

In addition, other monomers that can be coelectrified with the above-mentioned monomers which are the main components may be used in combination as appropriate. Examples of such other monomers include ethyl acrylate, ethyl acrylate, and ethyl acrylate. , acrylic esters such as polyoxyalkylene acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, polyoxyalkylene methacrylate, and glycidyl esters of monovinyl carboxylic acid having 3 to 12 carbon atoms and carbon Examples include glycidyl ethers of monovinyl alcohol having numbers 8 to 12.

The above monomers are produced in an aqueous system using a known oil-soluble radical polymerization initiator in the presence of a diluent, which is an organic solvent that has excellent compatibility with the monomers but is not compatible with water. Well-known methods such as suspension polymerization can be carried out, for example, as disclosed in JP-A-59-28104 and JP-A-60-165647.
By employing the method described in the publication, beads made of porous polymer can be produced.

Next, we will discuss the concentration method using liquid chromatography. For the liquid chromatography according to the present invention, a known high-speed or industrial liquid chromatography column can be used, and the column is filled with the beads of the present invention,
After injecting the deodorized distillate, the target tocopherols can be easily obtained by the usual operation of passing a developing solvent and separating the eluted fraction of the tocopherols.

Here, the developing solvents include lower alkyl ketones such as acetone and methyl ethyl ketone; lower alkanols M such as methanol, ethanol, n-propanol, and 2-propanol; n-pentane, n-hexane, n-hebutane, Chain or cyclic saturated hydrocarbons having a prime number of 5 to 8, such as n-octane, isooctane, and cyclohexane. Lower alkyl ethers such as isopropyl ether and ethyl ether/I/, acetonitrile v, etc. ~ You may use seeds or a mixture of two or more maples. Among them, methanol and acetonitrile are preferred from the viewpoint of separation and concentration performance, industrial aspects, and the like.

(Effect of the invention) A method for separating and concentrating tocopherols from a deodorized distillate by liquid chromatography using a column packed with beads made of a porous polymer containing the polyvinyl compound of the present invention as a main component. , target tocopherol-/L/
Since pA can be efficiently fractionated and collected with high purity and high yield, and the beads used in the present invention can be easily produced industrially, it is possible to separate high-quality tocopherols/L/s at low cost. This is a noteworthy effect of the present invention.

(Examples) The present invention will be described in more detail by way of Examples below, but the scope of the present invention is not limited in any way by these descriptions. In the examples, parts and percentages are expressed on a weight basis unless otherwise noted. The gel moisture content is determined by centrifugal effect 2 of polymer particles sufficiently equilibrated with deionized water.
After removing water adhering to the particle surface by centrifuging at 000G, the weight (Wl) was measured, and then the polymer particles were dried and the dry weight (W2) was measured, and the following formula Calculated by.

Example 1゜Methacrylic acid/p-styrene sulfone moromi soda 70/
20 parts of water-soluble polymer of No. 30 and 2 parts of polyvinyl alcohol
1 part was dissolved in 656 parts of water, and the solution was charged into a 1-unit tank equipped with a stirrer.

2.2 to a mixture of 120 parts of epichlorohydrin as an agent.
-Azobis-(22 parts of 2,4-dimethylvaleronitrile was dissolved and charged into a polymerization tank, and polymerized at 60c for 8 hours.

Next, 5 parts of formic acid was added to the polymerization solution and subjected to AI heat treatment for 90 CXa hours to produce a porous bead-like polymer having a gel moisture content of 92%. Beads with a particle size of 30 μm were obtained.

The beads have an inner diameter of 151111. Packed into two columns with a length of l 000wn and connected in series, deodorized distillate of soybean oil containing 60% tocopherols was mixed with 2% methanol.
After injecting 2 gg/ml as a solution into the column, methanol was passed as a developing solvent at a flow rate of 8%-y110#/%, and fractionation was carried out as shown in the chromatogram of FIG.

As a result, the target α, β, r and di-tocopherols were collected with a purity of 95.2% and a yield of 90.5%.

Example 2゜Example 1. The beads obtained in the inner m16ax, length 2000
A silk column was packed, and a raw material containing 50% tocopherol acetate obtained by acetating the deodorized distillate of soybean oil was made into a 10% bath solution with methanol and 10 g/injected into the column. The flow velocity is 3.0 m//'! The mixture was passed through a chromatogram and fractionated as shown in the chromatogram in FIG.

As a result, the target tocopherol acetate was obtained with a purity of 96%.
%, with a yield of 92%.

[Brief explanation of the drawing]

FIG. 1 is a chromatogram obtained in Example 1, and FIG. 2 is a chromatogram obtained in Example 2. 7.10 Polish! (Phrase I) July 29, 1988

Claims (1)

[Claims] 1. Beads for separating and concentrating tocopherols, which are made of a porous polymer containing a polyvinyl compound as a main component, the particle size of the polymer is 10 μ or more, and the gel moisture content is 30% or more. . 2. When separating and concentrating tocopherols from a deodorizing distillate by-produced in the deodorizing process of fats and oils or a mixture obtained by subjecting the deodorizing distillate to an esterification reaction, the deodorizing distillate is placed in a column packed with beads according to claim 1. A method for separating and concentrating tocopherols, which comprises injecting an extract, passing a developing solvent through it, and fractionating and collecting a target tocopherol field by liquid chromatography.