DE1227431B - Cation exchanger - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Araneldag;
Display day:

BOIj

German KJ .: 12 g- 1/01

1227 431
N 24838 TV a / 12;
February 28, 1962
October 27, 1966

;, The present invention relates to the use of synthetic resins for Durfilifführung ypri kationenr as, stausiEhreaktiona, 'which have been produced in the sulfonation of kneaded copolymer and which have a high physical and mechanical strength and are free from internal stresses, cracks and other! Errors are,, grfirjiluogsr äß; are used for this purpose as cation exchanges, which are obtained by sulfonating a copolymerization of a main monomer, namely a pyjmonorneren containing an aromatic nucleus with _: a corrosion monomer and a possible addition of a secondary monomer and / or a solvent with the addition of acrylonitrile and / or Methacrylonitrile in a l ^ erjig ^ vqn. less than 20%> of the total weight of 4 monomers in the copolymer obtained was produced. ,.

,, In order to describe the invention in more detail, in the following, the physical and chemical properties of the to be used, novel, high molecular weight substances, djfts. Process for producing the same as well as the Jyiepfemale of the substances by reference examples be rubbed, whereupon the types of use are shown, which are based on the characteristics of the new, compounds are based. . :

The high molecular weight used according to the invention Compounds are cation exchange resins, the 4ureh sulfonation of a cross-linked MjschpoJjTOerisateS}. which by interpolymerization ejp.es vinyl monomers with an aromatic core with ^ Nitrile or / and eipem cross-linking monomers can be obtained. Copolymers, which contain kpin acrylonitrile and / or methacrylonitrile have no affinity whatsoever ziu sulfonating reagents and require rigorous Re ^ iktiptnsbedingungen and long times for proper .Reaktion the same, while a copolymer, like the resins used according to the invention, which are produced by copolymerization of a A good amount of one. Containing nitrile groups Monomers achieved sore, have a three-dimensional network structure, despite their insolubility and Non-shrinkability have a high affinity for polar reagents, these reagents allow easily penetrate into the same for the purpose of the reaction, and allow the reaction to be carried out in a short time under mild conditions, whereby the time required for production is significantly shortened and there are no cracks or cracks in the product iprie ^ e tensions remain.

Cation exchanger

Applicant:

Fa, S. ashichiro Nakanishi, Tokyo

Representative: 7 '

Dr. M. Eule, Dipl.'Chem. Dr, r <? R. nat W- J.; Bfrg and Dipl.-Ing. O.Stapf, patent attorneys; \. \
Munich 2, Hilblestr. 20 ^{Ί ·:;}

Named as inventor:

Hiroshi Kuyama,

Yoichi Utsunomiya, Tokyo ■ ■ ■ ■

Claimed priority:

Japan March 1, 1961 (7254)

Reactions with high molecular weight compounds, especially with cross-linked high molecular weight compounds, are carried out _: in contrast to the carrying out of chemical reactions with common molecules, very complicated factors play a role. Usually, the yield is low when such a high molecular compound is subjected to the same chemical reaction that can be carried out with low molecular compounds of the same series in a very high yield, and which high molecular compound requires, ever. according to the case, strict reaction conditions, often accompanied by side reactions. Such quervefbuiidene. Compounds are insoluble in solvents and do not melt when heated; they have no free movement of the molecules. Their ability to react depends entirely on the affinity between the reaction agents and the macromolecular compound. It is generally known that the high molecular weight compounds lack reactivity, especially when the reaction agent to be used is an inorganic, polar compound (e.g.

Sulfuric acid or nitric acid). The process for making ion exchange resins provides a

, - example of such a case; it requires the most complicated Operations or the use of tools, such as B. source agents, or it forces in addition, on some of the mechanical properties of the

609 708391

I 227 431

3 4

To waive the product. It is usually difficult- You will find that when "bridged."

rig, the chemical reaction of a basic substance, polystyrene, which contains no nitrile groups, with

such as B. a cross-linked high molecular weight concentrated sulfuric acid is to be sulfonated,

Basic connection of a certain size through - with interruption of the reaction after the initial

supply and thereby the original shape 5 borrowed sulfonating reaction and investigation

and mechanical strength of the connection after distribution of the sulfonic groups inside

The end of the reaction must be fully maintained because and on the surface of the pearls the groups

the chemical reaction evenly through the parts that are conspicuously located on the surface

total amount of the solid matter in question, are concentrated in their. If, on the other hand, something "bridged"

Both the surface and the interior are made of polystyrene containing nitrile groups on similar ones

must, so that there is no tension in the interior of the formation of sulfonic groups after the

gen lagging behind. Interruption of the original sulfonating

The chemical reaction begins, however, when the reaction is insoluble, so it will be found that

borrowed, fusible high molecular weight solids the reaction far more evenly than in the former case

with a three-dimensional network structure at certain 15 has been going on. Plus they keep going

Sections such as B. in the chemical reactions with other chemical reactions with such fundamental,

surfaces in contact with the substances. The high molecular weight basic substances produced resins

physical properties of a basic compound the physical and mechanical properties

before the reaction are clearly different from the previously known acrylonitrile-containing, fundamental

those after the reaction, due to the chemical 20 the copolymers.

Conversion of the substance, and this difference to the aromatic,

• causes strong tensions in the internal structure or unsaturated tensions that can be used as main monomers

the collapse of the event. These monomers' target include: styrene, vinyl alkylbenzenes, such as

The process is to remove such insoluble and insoluble z. B. vinyltoluin and vinylxylene, α- and / or / J-Al-

fusible, high molecular weight substances include kylstyrene, ß-methylstyrene, vinylnaphthalenes. Vinyl-

give high affinity to polar reagents alkylnaphthalenes, α- and / or / J-alkylvinylnaphtha-

and thereby the otherwise difficult to carry out, linear, analogous, the above connections

to facilitate chemical reaction of the same. corresponding anthracene and phenanthrene compounds

The previously generally used process for and their halogen- or alkoxy-substituted mono-production of cation exchange resins of suI- 30 mers.

Fonsäuretyp consisted in the fact that an insoluble, insoluble, high molecular weight basic compound, which can be melted to the suitable cross-linking agents, which include: divinylbenzene, divinylpyridine, divinyltoluins, by copolymers of an aromatic divinylnaphthalene, diallyl phthalate, ethylene glycol core-diacrylate-acrylate-acrylate-containing monomer , Divinylxylene, binding monomers was achieved, the Einwir- 35 Divinyläthylbenzol, Divinylsulfon, polyvinyl or kung of a sulfonating agent immediately after polyallyl ether of resorcinol, divinyl ketone, divinyl the copolymerization or after the sulfide, allyl acrylate, diallyl maleate, diiallyl fumarate following mixed polymerization Swelling in an allyl succinate, diallyl carbonate, diallyl malonate, diallyl solvent. Such oxalate, diallyl adipate, diallylsebacianate, divinyl seba basic compound lacks the affinity to sulfonate, diallyl tartrate, diallylsilicate, triallyl tricarballylate, the agents, it is initially triallylphosphate triallylphosphate under strict conditions . The like. sulfonated. The methylenediacrylamide, Ν, Ν'-methylenedimethacrylsulfonated parts form a compound such. B. amide, Ν, Ν'-ethylenediacrylamide, 1,2-di-a-methyF-high molecular benzenesulfonic acid, and acquire on methylensulfonamid) -ethylene, trivinylbenzene, Tridiese way the affinity to sulfonating agents. 45 vinyl naphthalene and polyvinyl anthracenes.
Then the reaction takes place through this layer to the particularly preferred polyvinylidine mono through in the direction of the interior. There are mers that are generally sulfonated as cross-linking agents in the course of the reaction and not known, include: polyvinylaromatic carbon sulfonated parts, and accordingly the hydrogens, such as. B. divinylbenzene, trivinylbenzene, degrees of swelling very different, which leads to the formation of 50 divinylnaphthalene, glycol dimethylacrylates, such as. B. cracks or, if this is not the case with the ethylene glycol dimethylaerylate and polyvinyl ether, leads to internal stresses, the closing polyhydric alcohols, such as. B. divinoxyethane lent to the collapse of the product in Ver and Trivinoxypropane. Sulfuric acid, fuming sulfuric acid, exchange resin will result as sulfonating agents during its repeated use as ionic acid. 55 Chlorosulfonic acid and sulfur trioxide preferred.

The interpolymerization of such a basic sub- The ratio of monovinyl monomers to the

punching with a small amount of acrylonitrile and / or polyvinylidine monomers can vary widely

Methacrylonitrile has unexpectedly great effects. ken and depends on the use for which

Even if the amount of nitrile or nitrile is only determined by the polymers.

0.5 to 1% of the weight of the total amount on 60 The ratio of acrylonitrile and / or meth-

Monomers is, the mixed polymer acrylonitrile behaves to the vinyl monomer, which for the

sat, compared to concentrated sulfuric acid, resin to be used for the purposes of the invention is

different from ordinary copolymers, which is different, can be made in accordance with the various

does not contain any nitriles as a result of interpolymerization, for the purpose of use it is chosen at will

and the reaction takes place at low temperature, 65 be. The preferred amount of acrylonitrile or /

takes place smoothly and in a short time. However, if the nitrile content and methacrylonitrile should be used for the present

is high, the copolymer develops heat, uses less than 20% of the total weight

absorbs concentrated sulfuric acid and swells. tes of the monomers. This is due to

that even a relatively small amount of acrylonitrile and / or methacrylonitrile are those described above Characteristics, and vice versa, if the amount is increased, so does the Ion exchange ability of the product. Those produced by various polymerization processes Copolymers have the chemical properties mentioned above, regardless of which Design form they exhibit.

The next for the invention resins to be used into consideration high molecular weight basic substances can be obtained by "^ mixing to a principal monomers from the above list with a cross-linking monomers, and acrylonitrile and / or methacrylonitrile in order ^ij! Preparation of a monomer mixture and if necessary the addition of a secondary monomers , a solvent not involved in the reaction, a plasticizer, etc. and, if necessary, by further adding a polymerization accelerator and subsequent polymerization of the mixture by any method of block, suspension, emulsion or solution polymerization the mixture can also be copolymerized by the "graft" polymerization process. Of course, the usual monomers do not necessarily have to be polymerized individually, but can be treated like any desired mixture of different monomers.

. The novel, strongly acidic sulphonic acid resins to be used according to the invention have a high Transparency and a beautiful appearance. They are used by one even for several thousand Cycles not destroyed and also not impaired by use in dry-wet cycles. Ion exchange resins made from conventional base materials that do not contain nitrile groups contain, on the other hand, are particularly susceptible to dry-wet cycles and tend to be strong Injuries. The resin to be used in the present invention is elastic and becomes even when used not destroyed under high pressure.

In addition, it is evident from infrared spectra that they are useful for the purpose described above copolymerized nitrile groups of acrylonitrile and / or methacrylonitrile by sulfonation in Amido acid and / or carboxylic acid groups are converted.

high pressure. It is usable in all fields so far that of ordinary cation exchange resins were taken, for example:

1. The resin takes basic substances out of the. liquid and vapor stage in the form of salts and elutes the salts after saturation by a regeneration process. Practically can this cycle of uptake, elution, regeneration and washing in water is endless be repeated.

2. In acidic or salt form, the resin takes metal ions and / or other inorganic and organic ones Cations from the liquid and vapor stage and elute and regenerate them. she includes softening, breaking down neutral salts and dealkalizing.

3. An "embedding" process is possible, which involves the simultaneous use of an anion exchange resin permitted in all ion exchange processes.

4. This high molecular weight compound can of course also be used like ordinary cation exchange resins can be used as an ion exchange membrane.

5. In the ion exchange process, this resin can be used for the separation process, by making use of selectivity in adsorption and elution.

6. There can be organic dyes and impurities that are present in the liquid stage are to retire.

7. It is insoluble and infusible and can be regenerated for reuse and requires no complicated isolation process such as B. Distillation. It is used either by passing the reagents out of the resin through a tube or by putting the resin in Introduces reaction system. It can be used as a strongly acidic catalyst after use by a simple process such as B. filtration, can be removed. this also applies when the resin is used as a hydrolyzing agent.

By each of the above modes of application, the great economic advantage of the invention is achieved

The present invention thus relates to the 50 compared to the replacement resins previously used

Use of such sulfonic acid type cation exchange resins as those shown above Have advantages.

These resins differ favorably from ordinary exchange resins in terms of ionic 55
interchangeability and are yours in terms of the
physical and mechanical properties
think. To be used according to the invention
Cation exchange resins are therefore most advantageous from the standpoint of the life of the resin, 60 total mixture 6 hours at 70 to 72 ° C, especially for use under harshly heated to form a spherical polymer conditions, and are not used by any of the conventional is washed with water, dried and loan exchanger with regard to the economic 6 hours at 12O ⁰ C heated (this yields the advantage achieved that lies in that the resin is a copolymer 1). It has a long service life in practically the same way if it is made from organic solvents as well as from mixed polymer 1 and styrene-divinylbenzene is produced without acrylonitrile in the gaseous stage because it is very resistant to dry-wet cycles (mixed polymer 2 ). Separately, 250 g of acrylic resistant. The resin is particularly useful among nitrile, 60 g of 53% divinylbenzene and 5 g of benzoyl

shown, which results from the features of the novel resin used according to the invention.

Note example 1

g of styrene, 33 g of acrylonitrile and 91.7 g of 53.6% strength divinylbenzene are intimately mixed. 4 g of benzoyl peroxide are dissolved in this mixture. A dispersant is added to 400 m ^{3 of} water and the above mixture is added with stirring and the

This means that 200 g of styrofoam, 7.2.4 g of acrylonitrile and 109.6 g of 6% moderate solution are mixed in to form an equal amount, from which dyrch, <tas. Diyinylbenzoi are intimately mixed and, "exactly the same procedure as with the copolymer j. Gin as given in Example 1, mixed polymer Mer. spherical copolymer 3-called Erzeug- 100 g of Mischpojynis prepared in the above manner is obtained. Now, the behavior DIE .5 merisates be init 580 g of _99? 14 ° / acetic & pivoting Felser three types copolymers opposite Sehwe- acid sulfonated at 80 ° C After one hour of reaction folic acid observed. If the three mentioned mixed polymers the ion exchange capacity of the mixed polyamine in 99% sulfuric acid for carpentry is 1.67 meq / ml, the mixed polymer is thrown at temperature, the mixed polymer remains - on the other hand only 0.5 meq / min. ■. .. polymer 2 (StyiolrDivinylberE.01) practically unchanged., ".., _ changes, while the mixed polymer 3 (acrylonitrile H ι η we ι sb e .. ie ρ 1 2;. Piyinylbenzpl) e.ine considerable amount abspr- acid 600 g styrene, 8.0 g of acrylonitrile and 102 g of 59 ⁰ / biert oiges and swells. That. Copolymer 1 (a cross-Diyinylbenzoi are intimately mixed and, just like connected 'polystyrene), which acrylonitrile in example '% specified, copolymerized. If it contains a polymeric state, the mixed polymer produced in this way is found to have no perspiration and is impregnated with sulfuric acid. 120 ° C 2.5 hours with 98.7 ° Mger sulfuric acid sul- "Of the three types known in the pbigen mixed, its ion exchange capacity increases, the mixed polymer 1 and 2 are 1.8 to 2.0 meq / ml. If what is produced in this way is sieved off according to grain size and the fractions of mixed polymer with ethylene dichloride or tetrachloro-30 to -40 measures for sulphonation are _{treated aside ao} ethane, if swelling is achieved. "■■ - ■ - ·· * drives, and then with 98.7% sulfuric acid under

1 «änifnnipmno K ^ i soo γ 'gradually increasing the temperature from 80 to

ι .. i? uitonierun | At ^ u ^ _{nQO Q} ^^ _{becomes) so} ^ _ηη - _e ^ similar Ipnen-

. With the use of sulfuric acid exchangeability can be achieved

pearls of the so-called ibgiden mixed polymer- 25 the exchangeability of the under the same condition

sulfonated at 80 ° C. The ion-exchangeable "gen> sulfated copolymers 2 according to the

The speed of the mixed polymer 1 reaches 0.9 to 1, Ö meqyiml in just one hint. * "". '

Hour 1.5 meq / mlj during that of the mixed polymer- "'' '■' '.' ■" - ■ "'■ -...- · /

sates. 2 does not reach 0 ^ 5meq / ml; in 2 hours be '■ Example l-.i.-.- :: ....: ■

carries the exchangeability deV Misehpplymerisa- 30 Eüi as indicated in reference example 2

tes 1 2.0 meq / ml. Sulfuric acid type catalyst exchange resin upd

""'"'"' 1 SnlfonieruniT at 100 ° Γ ^ ⁿ g ^e FÖbnlj.ches, by sulphonating a high mol-

. ,, »2. Sultpmerurig at WO C kularen, no acrylonitrile .du copolymeric state

Using a basic compound containing 99% sulfuric acid of the same cross-section

WfFdeja.die |? Eiden mentioned Iylischpplymerisate with 35 degree of connection as the above resin produced.

100 ° C "sulphonated V In one hour, the Aus Katione.naustauschharz reaches, both in the form of a Na-

exchangeability of the mixed polymer 1 1.8 ineq / ml, triuric salt, are sold under the same conditions'

during 4 the id.es mixed plymerisates 2 about 0.5 / meq / with infrared lamps at 75 to 80 ° C for 1.5 hours

ml reached. dried. Sodanni are both brewed in water

3. Sulphonation at 80 ° C with low -1 ° ^and again dried as above. These processes;

Untej. Verweridung of ^{99! L} / cent sulfuric täuschharzes destroyed while the resin after ^ h nd.elsübHcher quality are the two overall Hinweisbeispiel2 only 8.7% · loses ... "■ --nannten copolymers at 80 ° C sulfonated The 45 In order to emphasize this fact even more clearly - ion exchange capacity of the copolymer 1 len, caustic soda dissolved in hydrogenated methanol reaches 1.8 meq / ml in 3 hours, while this and the solution through a resin of the acidic type copolymer 2 practically is not sulfonated., after saturation with dilute hydrochloric acid re

4. -Beads of the -Mischpolymerisates 1, generated, 'washed with water, whereupon a further briefly at-low temperature ⁵ ° solution of caustic soda in hydrogenated methanol "

-.- '.: ■■ "" .. ■, the resin is passed, etc. Through the repetition

Most common ones are sulfonated of _{the o} bjg _{en cycle.}

The cation exchange resins produced from 'the copolymer 1 in ten to fifteen cycles' destroyed by the method described above at low, while according to the invention For a short time and depending on the case, the degree of destruction is between 5 and 5 8% sulphonated with low-concentration sulfuric acid moved,. '.

Pearls have a beautiful orange to light brown color · · 1 2 ■ '

Color and are practically free from cracks in the JS.e1sp.1ej. . -

whole bead. The ion exchange capacity per Vo- The cat-

The lumen unit is the same as that of ordinary manufactured ion exchange resin and has been used so far (this is 2 meq / ml) or higher. That from the sensitive, ordinary cation-exchangeable copolymer 1 produced cation exchangers used. Both are acid conditioned and hjaiz the sulphurous acid type has a high degree continuously subjected to 5000 cycles, each of which ': Cross connection "and a moisture content of cycle from the introduction of a caustic solution, about 40 ^ 0, that. by a hepatic grain procedure 65 washing with water, regeneration with hydrochloric acid. produced 'sulfuric acid resin with' such a high '' water washing and introducing a further degree of crosslinking had in most cases Ätznatrönlösüng existed. After 5000 zy jumps have elapsed inside the pearls. . "'" Klen are both examined microscopically, where'

the ordinary cation exchange resin causes considerable damage to the resin and great Pressure loss shows, while the resin to be used according to the invention has only limited damage to the Resin and has remarkably little pressure loss. The difference is particularly pronounced, when the rate of passage of the solution is high. Damaged resin goes out when washed out lost, and therefore the usual way of working makes a considerable addition to the Resin required. After 5000 cycles, the resin to be used according to the invention can be used in terms of of the degree of loss of ion exchange ability per volume compare well with ordinary resins.

When an ion exchange resin is used to treat fabrics such as B. city water is used, which Contains halogen, or in a process in which oxidizing substances occur, the loss forms ion exchange abilities due to oxidation pose a serious problem. in view of became the resin to be used in the present invention and a conventional replacement resin with each other compared. For this purpose, ordinary replacement resin and the resin after the note bed have been used 2 acid conditioned and for 6 months in 10 and 30 per cent solutions of hydrogen peroxide immersed, whereupon the ion exchange capacity per volume was determined. There was no difference between the two as the common exchange resin showed a 3 "Vo loss and that Resin according to reference example 2 also suffered a loss of the same percentage showed.

For the purpose of comparing the two resins in terms of deionizing and emollient Operations two resin columns with 5 cm internal diameter were made, one of which the In the form of an "embedding" mixed with another common exchange resin. To this Way, the two were at different stages of regeneration, such as. B. Adsorption and excretion processes, compared. The resin to be used in the present invention was as good as the ordinary one with regard to the ion exchange process in the initial stage, better than the latter in treatment with liquid at high speed and always performed better at continuous Works over a large number of cycles than traditional replacement resins. It made a smooth one Separation for regeneration if an "embedding" was used.

Example 3

A conventional ordinary replacement resin and one to be used in the present invention, according to Reference example 2 prepared cation exchange resin were used to test their effect on the Consider conversion of cane sugar to dextrose and levulose.

The above-mentioned two kinds of ion exchange resins were placed in an aqueous solution containing 20% cane sugar. While the solution was kept at 25 ^° C., the specific rotations were determined. There was no difference in the rate of reaction. However, when the cycle consisting of washing the resins with water after use and then immersing them in another 20% cane sugar solution was repeated, the ordinary replacement resin showed a higher degree of damage than the resin to be used in the present invention.

Claims (1)

Claim: The use of resins obtained by sulfonating one by interpolymerizing one Main monomers, namely a vinyl monomer containing an aromatic nucleus a crosslinking monomer and any addition of a secondary monomer, and / or a solvent with the addition of acrylonitrile and / or methacrylonitrile in one Amount of less than 20% of the total weight of the monomers obtained copolymer have been produced as a cation exchanger. 609 708/391 10.66 © Bundesdruckerei Berlin