DE2015206A1 - Process for the production of exchange resins - Google Patents

Description

VEB CHEMIEKOMBINAT BITTERFEiId Bitterfeld, August 22, 1969

4.04.20 / 1106

Inventor: Dr. Klaus Häupke * Hall

Dr. Rüdiger Hauptmann, Halle
Dr. Ekkehard llösel, Dessau
Kurt Stelzner, Wolfen

Process for the manufacture of exchange resins

The invention relates to a process for the production of Ausaueoherharzeη with improved properties.

The synthesis of exchange resins duroh introduction of ionic Groups In a suitable copolymer of bifunctional parts Monomers (mostly styrene or derivatives of the Acrylic acid} 'and polyfunctional monomers (mostly divinylbenzene) tstr known for a long time. The ones known so far Types of exchange resins Jedooh have the Naohtell that It was not possible to combine the following two groups of beneficial properties in them

1. High diffusion coefficient for a given ion or Molecule la resin and thus good thawing news, wide

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Transport and Rθakti onsäume in the Harzkorn and thus the possibility of also binding large ions and molecules to the resin, high degree of conversion in the polymer-analogous reactions and thus high exchange capacity, based on the dry weight of the resin

2 · High density of functional groups and thus high

Exchange capacity, based on the volume of the equilibrated ^ lenen resin, slight change in resin volume during transition from a loading or swelling state to the other and thus high osmotic resistance as well good utilization of the pilter volume, high resistance to chemical attacks on the resin framework due to high Networking needs.

The characteristics mentioned under 1 are characteristic for resins with low crosslinking density and include those mentioned under 2, those for resins with high crosslinking density 'present from »

The macroporous Ilarze represent a certain knee profile. They have been prepared by carrying out the polymerization in the presence of an inert substance which can be mixed with the monomers but which does not swell or swells only insignificantly in the polymer. If a sufficient amount of this is used Substance and a sufficient Vernetserkonxentratlon, to

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phase separation occurs in the course of the polymerization instead of and you get a contiguous po- Lymeraggregaten submicroscopic expansion of existing material, which is made up of a coherent system of permanent pores is streaked. So you can both with the polymer, as well as with the exchange resin produced therefrom in the swollen state by adsorption of inert gases on their Evidence of an extensive specific surface area at the dew point. The pores represent transport routes that are also used by I. larger ions and molecules can be passed quickly, while the actual resin substance is strongly cross-linked and is therefore osmotic and chemically resistant

However, this procedure has the disadvantage that although the small proportion of the ionogenic groups, which lies directly in the walls of the pores, is easily accessible, most of them are not at all within the very strongly networked compact areas of the matrix of the material to be adsorbed or can only be reached very slowly. For the same reasons, the conversion of the polymer to the tempering resin is made more difficult »so that one always obtains lower capacities than with comparable resins of normal structure * / - ■ '■"■■' - · '/ ■'. '· - - .- "." .-, ^; : - \; " . '■ · .. -

For these reasons, many manufacturers already use steel the less crosslinker or less inert IHlrsstöii than

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sur the formation of the really macroporous structure is necessary, and sloh be content with an incomplete one Phase separation, which leads to inhomogeneities, which can be demonstrated by the optical cloudiness of the polymer and the exchange resin, but which does not go as far as that an open and coherent pore system is formed that can be detected by adsorption of inert gases * As a result however, the more highly crosslinked types made with less inert auxiliary material still lack the advantageous properties mentioned under 1, and those with an insufficient crosslinker content, al er relatively much inert auxiliary material produced, have the types mentioned under 2 only in to a small extent or not at all

Another way to solve the problem was the use of adjuvants, which dissolve the monomers and swell the polymer. It is true that this results in resins with a good working speed and a sufficiently wide-meshed structure; Of the advantages mentioned under 2, the best that can be used is chemical resistance «

The purpose and object of the invention was therefore to determine production processes which lead to exchange resins which have the properties mentioned under 1 and 2 unite in oneself.

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Bs has now been found that you can exchange resins that Combine properties mentioned under 1 and 2 and those in the other usage properties previous resins are at least equivalent, if one monovinyl compounds with Polyvinylyerbindüngen in the presence of HiI firmly open ,, üie the monomers ren loose, the Polymerenraber neither solve nooii quieten Iftsseny iind of auxiliaries which dissolve the monomers, the poly "©" - ^

: - ■■ "■■"'' ^; ■ "■■■ - - ■ ■ ■■■: - ■ ■" /. '■' -ν: -. -. V-. ■ .->^;-; - - ■ i

not dissolve, but let it swell, for example in aqueous suspension polymerized and introduces exchange-active groups in a known manner.

All Monavinylvelbindungen are mainly styrene and Sty * - rolderlvate as well as / verylic acid and its derivatives are used.

As polyvinyl vdrbiiuiung mainly divinylbenzene in Embossing.

As HllfHötiiffe, don't let the polymers swell, can be wounded: all phut-flat hydrocarbons and alcohols; also suitable for nmnoho lastor beef.

illUeJHtoffo ,, dio <Uo allow polymers to swell are aroma - / «ii, a I ky orte Aroniiiton, HaJ ogenkohlonw / iPflorst.of fe and

'■■■■ _ ■' BAD ORIGINAL

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In this context, auxiliary substances which swell are understood to mean those whose interaction parameters for the polymer are below 1. In the case of non-swelling substances, this value is greater than 1. Swelling substances are more simply defined with which a polymer which is produced only from the bifunctional main monomer (i.e. without crosslinker) can form homogeneous mixtures with an auxiliary substance content of over 25 % such a polyether added only in amounts below 10%.

The following requirements are also to be met by these additives • Share in order to be able to use it in the ion exchange synthesis: You must not react to any component of the poly-ionization system. If they are polymerized in suspension, they may not pass into the aqueous phase to a noticeable extent. They have to be sufficiently volatile so that they can only be lost to an insignificant degree during the polymerization. They have to be taken by suitable measures before or during the work-up of the polymer to the ion exchanger can be separated.

Their practical application is designed as follows: The monoieer is satisfied, as styrene or a homologue dee-styrenes heaivhungeweis · a derivative of Atlylüüure as bifunctional11 η monomers and a poly

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. '■■ ■■' ■. '"' ^{: Ί} - ■ · ■ ':

functional crosslinking monomers such as Divlhyl-.

benzene, ethyl glycol acetylate, triaryloyl perhydrotrlazine or any other connection with two or more fail conjugated double bond part, an amount of 10 to 150% by weight (based on the weight of the monomers) a mixture of at least one swelling and at least one non-swelling auxiliary to The ratio between swelling and non-swelling auxiliaries can be any value between 2: 98 and 98: 2 Assume wt .-%. The whole system is subject to conditions under which the monomers polymerize, usually polymerizing in suspension.

The auxiliaries are removed from the polymer obtained by drying, extraction or distillation with steam. You can do without this operation if you in the following polymer-analogous implementation of the polymerisation | te ion exchange resins complies with conditions that lead to the removal of auxiliary substances from the resin. The polymer-analogous reactions can be carried out in the known manner. For example, a weakly acidic cation exchanger is obtained by saponification of a crosslinked polyacrylic acid ester, a weakly basic anion exchanger by alinolysis, a strongly acidic cation exchanger by sulfonation of a crosslinked polystyrene and

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by chloromethylation and amination of the same, different types of anion exchanges depending on the type of

v doten amine.

The structure type of the Austauscherbarzes can be, depending on the ratio between bifunktI ₁ (MIeIlen monomers polyfunktlonellen monomers, swelling! Vary adjuvants and non-swelling excipients as desired, so that gel-like hoao-

“Genetic resins or those of a heterogeneous structure that either only visually as opacity or additionally by gas idsorptlon is demonstrable, arise

The performance advantage of these resins at a given ratio between bifunctional and polyfunctional monomers is that

1. The accessibility for large ions, the diffusion rate in the resin and thus the operating speed as well as the degree of conversion in the polymer-analogous reactions and thus the exchange capacity are better than with resins that have been produced entirely without the addition of auxiliaries during the polymerization.

2. the osmotic, chemical and mechanical resistance and the change in volume during reloading or during Changes in the nature of the surrounding liquid are less common in the case of resins which polymerize has used swelling auxiliary materials for me.

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3. The diffusion speed and thus the working speed and the degree of conversion in polymer-analogous reactions and thus the capacity are higher than with resins which can only be produced with the addition of non-swelling auxiliaries during polymerization Has. ·.

Furthermore, one achieves according to the method according to the invention a more favorable combination between high crosslinking efficiency te and wide-meshed structure and thus a cheaper one Connection between the groups of Properties than any other known process. Finally, the advantage is that the width of the Traneport and reaction spaces in the Harz are very even 1st, so that no irreversible adsorption of large ions or molecules takes place.

The following examples illustrate the application dee Λ described demonstrate the process in the synthesis of various lonenaustau- • oher types ifobel but iürf lndung not limited to these examples 1st.

Example 1 ■

Production of a strongly acidic catalyst exchange A mixture of 96 g styrene, 40 g technical vinylbenzene (49 # 1 ”), 35 g olnea technical alph. • ohe old sledge limits 110 to 175 ° (;, 35 g lathe-

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Bensol and 1 g of benzoyl peroxide was suspended in a suspension of 2 g frieoh precipitated magnesium hydroxide in 500 ml water ι by heating at 80 ⁰ C for 2 hours sur polymerization gebraoht and then cured for 6 hours at 95 ⁰ C.

The suspension was then made acidic and the inert excipients were distilled off while steam was passed through. The polymer was then isolated and dried. Subsequently, it was poured over 1 1 96% Lger sulfuric acid and the temperature increased while stirring within 2 hours at 110 ⁰ C. After maintaining these conditions for 6 hours, the product was separated from the excess acid and treated with hot air for 8 hours. Then it was brewed in a concentrated saline solution, followed by washing with water.

In this way, 780 ml of a strongly acidic cation exchanger were obtained _t of the type shown in Table 1 under! had compiled properties.

For comparison, well-known exchange resins were used in the Same catfish examined · The corresponding values are also recorded in Table 1. It means:

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II a corresponding resin without any auxiliaries

III a corresponding resin without any auxiliaries with a the amount of Divlny! benzene reduced to half

IV using 70 g of the aliphatic mixture as single excipient

V instead of the aliphatic mixture 70 g of diethylbenzene as

only excipient

The table clearly shows that a substantial improvement in the properties was achieved by the process according to the invention.

Example 2 Production of a strongly basic anion exchanger

In the manner indicated in Example i, a mixture of 98 g of styrene, 3.5 g of technical grade divinylbenzene (49 %), 70 g of aliphatic mixture, 20 g of diethylbenzene and benzoyl peroxide was polymerized and the polymer was freed from the auxiliaries. The polymer obtained was stirred with 1 liter of mono- norlordimethyl ether and 45 g of FeCl ₃ (anhydrous) were slowly added. Then, the temperature at 56 ⁰ C was adjusted and stirred for 6 hours under reflux. Then the excess monochlorodimethyl ether was separated and the

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ChloromethylHerte polymer washed with acetone. Ansohließend stirred with 1.5 1 ca. 20% trimethylamine solution for 8 hours at 50 ⁰ C, separated from the solution and washed with water.

The anion exchanger obtained has the properties given in Table 2 under I.

As in Example 1 (Table 1), comparative values for other resins were also determined here. The Roman numerals mean:

II a corresponding resin without any auxiliary substance

III a corresponding resin without any auxiliary substance but with an amount of vinylbenzene reduced by half

IV made with 90 g Aliphatengemisoh as an adjuvant V made with 90 g of diethylbenzene as an excipient

The comparison of the values again proves the superiority of the method according to the invention.

Example 3

Production of a weakly acidic cation exchanger A mixture of 350 g of ethyl acrylate, 50 g of technical grade Dlvinyibenzol (49%), 50 g of a technical

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Aliphatengemisches with the boiling range 110-175 ⁰ C and 50 g of diethylbenzene was dissolved in 1200 ml of an electrolyte solution containing 10% sodium chloride and 1% freshly precipitated magnesium hydroxide containing suspended, at 65 ⁰ C under Vervendung of 1 g Azodiisobuttereäurenitril as initiator per! Polymerized and then cured ^{at 90 °} C. for 6 hours. The polymer obtained after suction filtration and washing was separated from the inert auxiliaries by steam distillation and then saponified in 1500 oil 30% sodium hydroxide solution for 16 hours. After the saponifying agent had been filtered off with suction, the resin was washed, treated with excess dilute hydrochloric acid and then washed neutral with distilled water.

Table 3 compares the properties of the weakly acidic cation exchanger according to the invention according to Example 3 (Column I) with a weakly acidic resin of the same crosslinking, in which the proportion of swelling auxiliary material is due to the loading | sohriebene Allphatengemisoh was replaced (column II), and a sohwaoh acidic cation exchange resin of the same crosslinking without the addition of auxiliary substances. (Column III).

Example 4

Production of a sohwaoh basic anion exchanger an oenisoh, consisting of 24Θ g styrene, 26 g divinylbenzene (52.3 % ± g), 150 g aliphatic mixture and 125 g toluene,

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is suspended together with 2.75 g of azodiisobutyronitrile in 1 liter of water * O ₉ % Mg (OH) ₂ (based on the aqueous phase) is used as the suspension stabilizer. While fled distributes the oil phase in the water, the temperature of the suspension is increased to 70 ⁰ C · β At this temperature, is polymerized hours. Thereafter, the polymer is excavated cured for 2 hours at 90 ⁰ C. After cooling, the stabilizer is filled with H ₀ SO. dissolved and the resin

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freed from the inert substances by means of steam. The dried and classified polymer is known in Way with ifonoohlordimethyläther and Friedel-Crafts catalysts chloromethylated and then with dimethylamine converted to a weakly basic anion exchanger.

The obtained sobwach basisone exchange resin had the . characteristic values given in table 4, column I. In the wide

For comparison, the other columns show the characteristic values of a resin (II) produced analogously but without the use of inert substances and a resin (II) with only 275 g of aliphatic mixture Resin produced as an inert substance (ill) indicated.

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Claims (4)

2016 206 - 15 - 4.04.20 / 1106 Claims Process for the production of exchange resins with improved properties through suspension polymerization of monovinyl compounds with polyvinyl compounds and introduction of active exchange groups, characterized in that the monomer mixture contains auxiliaries which dissolve the monomers but neither dissolve nor swell the polymers, and * Auxiliaries which dissolve the monomers but do not dissolve the polymers but allow them to swell are added 2. The method according to claim 1, characterized in that that organic compounds which are liquid at room temperature and which are self-contained are used as auxiliaries the chemical system of suspension polymerization behave inertly, which are not soluble in water | and which are not substantially volatile in the range of the polymerization ^{temperatures between 50 °} C. and 100 ^{° C.} 3. The method according to claim 1 or 2, characterized in that the auxiliaries after the polymerization Drying, extraction or steam distillation can be removed. T 0 9 8 1 1/2 U 2 8 - ie - 4.04.20 / 1106 Tabel Resin pattern I II III IY V Capacity for Na ⁺ in meq / g dry matter 5.20 3.80 4.94 4.23 5.05 Capacity for (C ₃ Hg) ₃ N ⁺ in meq / g dry matter 4.90 0.21 1.82 3.85 4.55 Water content of the centrifugally moist resin (Na ⁺ form) in % 51.0 35.5 48.2 58.3 60.1 Increase in water content after 48 hours of treatment with 3% H ₃ O ₂ solution at 60 ⁰ C in % absolute 1.2 2.0 18.3 2.5 5.8 Half-life of the H / Na exchange the grain fraction 0.5 - 0.75 mm in seconds 662 141 123 79 Volume increase when reloading from the Na ⁺ - to the H ⁺ -Porm in % 9 15 0 8; ' -17- 4.04.20 / 1106 Ta be lie H ar ζ mu a ter I II III IV V Capacity for Cl "ΐη meq / g dry matter 4.10 3.08 3.95 3.72 4.05 Capacity for naphthalenesulfonic acid in meq / g dry substance 3.80 0.08 1.13 3.18 3.65 Water content of the centrifugally moist resin (Cl "-Porm)".. - "■ ■ in% 53.6 46.5 59.3 62.1 58.0 Half-life of the 0H "7ci ~ - Exchanges of the grain fraction 0.50-0.75 mm in seconds 32 138 55 72 Percentage of uninjured balls before / after 50 times reloading OH ~ / Cl "" - Porm 99/95 90/45 72/27 99/90 98/90 Volume increase when reloading from the Cl "" to the OH "form in % 24 15 40 18 109811/2028 4.04.20 / 1106 Table 3 Resin pattern II III Capacity for Na ⁺ in ■ eq / g dry matter 11.02 10.12 11.0 Capacity for Na ⁺ in meq / ml resin 3.60 2.91 3.86 Water content of the sole derfeuehten Harz (Na ⁺ form) in% 54.3 65.0 50.1 Half-life of the H ⁺ / Na ⁺ exchange of the grain fraction 0.5-0.75 mm in minutes 11.4 12.4 10.5 Resin grain strength very good good moderate Rbg / H 109811/2028 4.04.20 / 1106 Table 4 Harz must he II III Capacity for Cl "in meq / g dry matter 4.1 3.95 4.05 Capacity for Cl in meq / ml of the Cl "" form 1.6 1.25 Water content of the centrifugally moist resin (Cl ~ form) in % 51.0 40.5 53.2 Usable capacity under practical conditions in eq / 1 of the OH ~ form 1 * 2 0.1 0.9 Half-life of OH "* / C1 ~ - Exchange of the grain fraction 0.50 - 0.75 mm in seconds 120 15 000 380 R b g / H PdG 010/69/3465 / 69-30- 10 9811/2028