DE1493047C - Inclusion resins and processes for their preparation - Google Patents

Description

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Take place: Once at least some of the hy- aldehyde groups are formed which take the place

hydroxyl groups of cyclodextrin with epichlorohydrin, the secondary hydroxyl groups of cyclodextrin

Dichlorohydrin, diepoxybutane, diepoxypropyl ether, occur. These products are sensitive to alkalis

Diepoxypropyläther of ethylene glycol or their constantly and are particularly suitable for separation

Mixtures of sulphites in an alkaline medium at 30 to -90 ° C 5. The oxidized resins can still

are crosslinked, treating 0.5 to 20 parts by weight with hydroxylamine; in this case

Epoxy compounds with one part by weight of cyclo are available as reaction products' oximes, which are opposite

dextrin converts. Metal ions have a remarkable affinity.

According to the second alternative, at least one of the structure of the oxidizing resins can be exemplified of the hydroxyl groups of cyclodextrin with 0.25 ίο also by reduction with sodium borohydride to 10 parts by weight of formaldehyde per part by weight or lithium aluminum hydride can be modified. Cyclodextrin cross-linked in the presence of an acid. Modify it wearily by, for example

The reaction with the epoxy compounds can be done again with a weak oxidizing agent,

are preferably carried out in a medium, 15 preferably oxidized with sodium chloride in order to

to obtain a solvent for at least one of the reactive carbonic acid derivatives, the stable salts

represents capable substances. Often used to form with heavy metal ions. These resins are suitable

you can use water as a solvent, but you can also use it as an exchange resin for the specified

other organic solution ions have the same success.

agents such as formaldehyde, dimethylformaldehyde and the inclusion resins according to the invention can

use similar connections. ^; can be used for various purposes. One can

At the beginning, the reaction is exothermic, for example by adding inclusion complexes of these

however, it may be advantageous, during the trans-formation process, to form compounds or specific mixtures,

setting to keep the temperature at 30 to 90 ⁰ C. contained in a mixture or in a solution

Generally the reaction time is about 25%, selective recovery. You can do that here

3 to 20 hours. The crosslinking agent against resin is simply in the form of a powder or in the form

Sensitive to oxygen, the conversion of grains into a solution that contains the desired sub-

preferably under an inert gas such as nitrogen or punch containing, enter, the mixture

Carbon dioxide through. so adjusted that one equilibrium conditions

For the reaction with formaldehyde in aqueous 30 is obtained. ' The ^: inclusion complex formed in the process can

Medium can be used for acidification z. B. hydrogen chloride filtered off or decanted. The enclosed

acid or sulfuric acid can be used. Further substance can then, for example by loading

In addition, the cyclodextrin can be treated with 5 to 40% at high temperature or by distillation,

Formaldehyde solution can be dissolved. Be released from the complex at this work,

wisely there is no need to use a solvent. 35 According to a further embodiment, the

The duration of the reaction, depending on the reaction-inclusion complexes, is also formed by

conditions generally between 5 and 30 hours to find a solution that contains the substance you are looking for.

the. ; ■ holds, through a column with a certain

The third alternative to making the 'inclusion. final resin conducts.

Resins according to the invention consists in that the inclusion resins can advantageously also

Cyclodextrin in a polymeric, water-insoluble sub- to concentrate and stabilize unstable ones

includes punch, the polymeric substance being a compound, for example of vitamins, flavors

Polyamide, polyvinyl acetate, epoxy resin, nitrocellulose, and volatile components of aromatic substances,

Acetyl cellulose, ethyl cellulose, polyacrylamide, poly- especially for food, can be used. A

methacrylamide, polyacrylate or polymethacrylate are other interesting areas of application for these

and where optionally the cyclodextrin is in the resin in the chromatography, namely for the

corresponding monomers or in a mono- Isolation of individual substances from mixtures. One meren mixture dispersed and then the monomer. such isolation can be carried out in a column

has been polymerized. The cyclodextrin will be at the -specific temperature-, pH- or

in this way has 50 solvent gradients uniformly in the polymeric matrix, the selection

distributed. -. the actual conditions of the "respectively

In particular, one can depend on the cyclodextrin in a turned reactant. With these

Solution of the polymeric substance in a solution reactions represent the inclusion resins described

agent, for example in acetone, ethyl acetate or a type of matrix that is able to produce certain

Butyl acetate, whereupon the solution can be used, depending on the form of the substances or mixtures

medium, for example by evaporation, removed. To hold back molecules.

This way you get a. Inclusion resin in the ·. .

solid state, which can be repeated in Example 1 before use

powder or dry. Of course, the 35 g of a mixture of cyclodextrin homologues depends

Selection of the. Solvents of the type of 60 (main component ^ -cyclodextrin) are with 15 ecm

turned away polymeric substance; continue to mix the water. Then, you give 37.5 ecm one

Solvent to be inert to your cyclodextrin. warm, 50 ° / ₀ sodium hydroxide solution to the

The. Inclusion resins according to the Erfincjung let mixture, whereby one thereby formed suspension

modify themselves in terms of their structure, which stirs !. 40 g of epichlorohydrin are also added

its reactivity changes without affecting its 65 and stirs the mixture until a

Sorption properties are influenced. Example permanent emulsion that forms at a temperature

they can be solidified by oxidation, for example at from 20 to 25 ° C. The mass will be 15 hours

Period data, can be modified. Maintained at this temperature by the oxidation, then they are heated

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5 hours to 50 ^° C. Then the mass is held. There are 30 micromoles of benzaldehyde on the resin

In the presence of acetone it is greatly crushed and absorbed with acetone, while 50 micromoles in solution

and washed with water until it reacts neutrally, whereupon remain.

the product is washed again with acetone and application example 5

dries under vacuum. A white, heavy 5 is obtained

Permanent powder capable of absorbing 1 to 3 times the Ig of the inclusion prepared according to Example 2 by weight in water. Resin is in 50 ecm of a potassium iodide solution, the ^. . Contains 800 micromoles of iodine. The mixture example L _is equilibrated within 20 hours

Keep 20 g of a mixture of cyclodextrin homologues io. 500 micromoles of iodine are absorbed in the resin,

(Main component / S-cyclodextrin) were thoroughly remain while 300 micromoles in the solution, with 5 g of an aqueous 40 ° / _o solution of formaldehyde

and 2 g of concentrated hydrochloric acid

mixes. The separation of o- and p-nitrophenol, which solidifies after a few hours, with the help of

Sfu- ^ISC io ^ ^ird ^ hours at a temperature of 15 of _an inclusion resin
Maintained at 20 to 25 C. Then it is heated for 3 hours

to 60 ° C., it is crushed thoroughly in the presence of 5 g of an inclusion water prepared according to Example 1 and dry it. resin are placed in a column with a height of

A white powder with a 20 cm water carrier is obtained: The column is at 50 ° C. with the aid

Absorption capacity of 0.5 to 1.5 g per gram of powder 20 of a phosphate buffer solution (pH value = 8) in the same

. brought in weight. Then you give 10 ecm of a solution,

Example i _the 0.05 percent by weight o-nitrophenol and the

1 g of a mixture of cyclodextrin homologues contains the same amount of p-nitrophenol, at the top of the

(Main ingredient / S-cyclodextrin) is carefully added to the column, whereupon the phosphate solution is heated to 50 ^° C

introduced with a 30 ° / ₀ solution of acetyl cellulose in 25th After adding 80 ecm of phosphate solution

Acetone mixed. The suspension is poured onto a glass; the o-nitrophenol fraction is found in 90 ecm eluate.

poured plate to evaporate the acetone. The column is then ^{heated to 8O 0} C, whereupon

The film obtained is then finely divided and added to the same eluent. The p-nitro

Vacuum dried. The product has a phenol fraction with 180 ml of eluate at the bottom of the

Negligible water absorbency, contains 30 columns each. ■
but 80 ⁰ / o of the original cyclodextrin in

active form. Application example 7

Application example 1 Separation of phenylalanine and tryptophan

. ,, _. . .., _{x 11x} _. ,. "With the help of an inclusion resin

1 g of the inclusion 35 prepared according to Example 1.

Resin is, in 50 ecm of water, the 80 micromoles of 8 g of an inclusion Congo red prepared according to Example 1 contains, registered. The mixture will be in a column with a height of resin Balanced for 20 hours. 30 cm entered. The column is with the help of

Analysis of the solution reveals that only 4 micromoles of water were equilibrated. 3 ecm one

Congo red will remain in the solution while 76 micro- 40 solution containing 0.05 percent by weight L-phenylalanine and

mol are absorbed on the resin. . contains the same amount of L-tryptophan, will be on

. j,. . , "Head of the column abandoned, whereupon the latter at Raum-

Application Example 2 is washed with water temperature. At the foot of the

1 g of the inclusion column prepared according to Example 1 are fractions of 5 ecm each.

Resin is in 50 ecm of water that will catch 140 micromoles 45. The pure L-phenylalanine is found in the

contains p-nitrophenol. The mixture of fractions 5 to 7, while the pure L-trypto-

phan is obtained in fractions 9 to 16 in the equilibrium for 20 hours with stirring,
held.

Analysis of the mixture shows that Application Example 8

92 micromoles of p-nitrophenol are absorbed on the resin, 50 oxidation of an inclusion resin
while 48 micromoles remain in the solution.

. j,. . . _ 7 g of an inclusion resin of the cyclodextrin type

Application example 3 Epichlorohydrin are added to a solution,

1 g of inclusion resin with a cyclodextrin structure containing 3 percent by weight sodium chloride and 100 ecm

prepared according to Example 1, contains 50 ecm 'of water containing 55% sodium periodate (0.4 molar). The reaction

which contains 140 micromoles of o-nitrophenol, entered. mixture is stored for 24 hours at 4 ° C in the dark

The mixture is kept the same with stirring for 20 hours.

weight held; after this time there are 50 micromoles. The dialdehyde derivative of the resin is formed

o-Nitrophenol absorbed on the resin, and washed 90 micromoles with ethylene glycol and then with water

remain in the solution. 60 freed from iodate. Eventually it gets with acetone

. ,,. . ,. ■ washed and dried under vacuum.

Use Example 4 1 g of the oxidized resin is in 100 ecm of a

Ig of an inclusion 0, lnormal bisulfite solution prepared according to Example 1 was entered. After one-

resin is added to 50 ecm of water, the position of equilibrium has the resin 5 milli-

Contains 80 micromoles of benzaldehyde. The mixture is 65 equivalents (i.e. greater than 50%) of what is present

sulfite is absorbed in equilibrium with stirring for 20 hours.

Claims (6)

1 2 have shaft, represent molecules in the form of cylindrical patent claims: threshing or spiral tubes and are, as a result of the cavity formed by them, able to 1. Inclusion resins, characterized by an inclusion effect on various organic ones distinguishes that they exert at least 5 or inorganic compounds through crosslinking. the at least some of its hydroxyl groups with inclusion complexes thus formed Epichlorohydrin, dichlorohydrin, diepoxybutane, di- two defined components, namely the absorbing epoxypropyl ether of ethylene glycol or form - the and the absorbed molecules. aldehyde insoluble in water or in a The forces that the absorbent molecules with polymeric, water-insoluble substance connected to the absorbed molecules, are van-der- contain closed cyclodextrin, the Waals forces, i.e. H. Forces of more physical polymeric substance a polyamide, polyvinyl acetate, as a chemical type. These complexes are relatively Epoxy resin, nitrocellulose, acetylcellulose, ethyl-moderately resistant, and the absorbed molecules that cellulose, polyacrylamide, polymethacrylamide, poly- generally have a low volatility, acrylate or polymethacrylate and the weight 15 are for example against enzymatic and oxidative relationship between the polymeric substance and its effects. The inclusion complexes the cyclodextrin is between 1: 1 and 100: 1. which consists of a carbohydrate as an absorbing molecule 2. Processes for the production of inclusion holdings, however, can only be used to a limited extent, in resins according to claim 1, characterized in particular because they are soluble in water, that at least part of the hydroxyl 20 As these complexes usually in an aqueous medium groups of cyclodextrin with epichlorohydrin, they are very difficult to make from Isolate dichlorohydrin, diepoxybutane, diepoxypropyl reaction medium. ether, diepoxypropyl ether of ethylene glycol It is known that certain carbohydrates and or their mixtures in an alkaline medium in the case of polyhydrates by crosslinking to make them insoluble in water 30 to 90 ⁰ C crosslinked, where 0.5 to 20 can be made. For example, dextrans parts by weight epoxy compound with a weight according to Patent No. 27,389 of the Office for partly converts cyclodextrin. Inventions and patents in East Berlin with epi- 3. Process for the production of inclusion chlorohydrin implemented, whereby the previously water resins according to claim 1, characterized in that soluble dextrans in water-insoluble, but with that. at least one part of the hydroxyl-water derivatives which are still highly swellable are converted groups of cyclodextrin with 0.25 to 10 Ge. Via corresponding cross-linking of cycle light parts Formaldehyde, nothing is known per part by weight of cyclo- dextrins. Even if you had dextrin, crosslinked in the presence of an acid. can assume that cyclodextrins by 4. Process for the production of inclusion wetting would be water-insoluble, so was not resin beforehand according to claim 1, characterized in that the containment capacity of the cyclodass you can still get cyclodextrin into a polymeric, water-dextrin even after crosslinking includes insoluble substance, which would remain polymeric. An alternative of the invention is based Substance a polyamide, polyvinyl acetate, epoxy- based on this knowledge. resin, nitrocellulose, acetyl cellulose, ethyl cellu- The invention relates to inclusion resins, loose, polyacrylamide, polymethacrylamide, poly- 40 which are characterized in that they are made of veracrylate or polymethacrylate and wherein at least part of its hydroxyl groups are crosslinked if necessary, the cyclodextrin in the corresponding epichlorohydrin, dichlorohydrin, diepoxybutane, the monomers or in a monomer diepoxypropyl ether of ethylene glycol or a mixture of molds dispersed and then the monomer aldehyde made water-insoluble or in a poly-polymerized has been. 45 mers, water-insoluble substance included 5. The method according to claim 4, characterized in that they contain cyclodextrin, the polymeric substance indicates that the cyclodextrin is in a polyamide, polyvinyl acetate, epoxy resin, nitro solution the polymeric substance in a solution cellulose, acetyl cellulose, ethyl cellulose, polyacrylic agent dispersed and the solvent removed. amide, polymethacrylamide, polyacrylate or poly- 6. The method of claim 4 and 5, characterized in 50 methacrylate and the weight ratio between characterized in that the solvent Ace- the polymeric substance and the cyclodextrin zwiton, Ethyl acetate or butyl acetate is used. see 1: 1 and 100: 1 lies. 7; Use of the inclusion resins according to The water-insoluble inclusion resins according to the saying 1 to separate ,. Isolation and / or invention both exert a containment effect Stabilizing chemical compounds. 55 organic as well as inorganic substances out. They are also characterized by their selective sorption effect and by the fact that the selective activity on the shape of the absorbed molecules and does not depend on their load or weight. By using the inclusion resins of the invention The term "inclusion resins" can be used to create a type of chromatography that includes synthetic resins or mixtures of synthetic materials, in which at least two structural isomers of resins are understood that are insoluble in water and can be separated from one another,
which have certain sorption properties. For the preparation of the inclusion resins according to the certain carbohydrates such as cyclodextrin 65 invention all cyclodextrin modifications can tend to form complexes which are capable of ver (alpha, beta and gamma form) and mixtures of these compounds with a low Include molecular weight cyclodextrins used as starting materials. The carbohydrates that these intrinsic can be produced in three different ways