DD203555A1 - METHOD FOR THE SIMULTANEOUS RENEWABILITY AND HALOGENAL CYLATION OF STYRENE-DIVINYLBENZEN COPOLYMERISATES - Google Patents

Abstract

The invention relates to a process for the simultaneous postcrosslinking and halomethylation of slightly crosslinked styrene-divinylbenzene copolymers, optionally containing small amounts of further copolymerized monomers in the presence of Friedel-Crafts catalysts by means Dihalogenalkanen having a number of hydrocarbon atoms from 1 to about 18. The reaction in a suspending agent containing preferably aliphatic and / or aromatic nitro compounds such as nitromethane, nitropropane, nitrobenzene, with metal halides as Friedel-Crafts catalysts, preferably aluminum trichloride, at temperatures between about 15 degrees C and about 170 degrees C within about 10 minutes and about 18 Hours performed. The products obtained show a significantly lower swelling capacity than the starting materials. They are useful as intermediates for the synthesis of certain types of ion exchangers as well as non-soluble carriers for peptide syntheses, catalysis resins, polymer reagents and the like, especially for all applications where low and medium degrees of substitution are required. Furthermore, the products according to the invention are suitable for separation from the reaction mixture for continued haloalkylation according to previously known processes.

Description

237249 5 -ι-

VEB CHBMIEKOMBIUAT BITTEBi ¹ ELD Bitterfeld, 2. 2. 1982

2215

Process for simultaneous Bach crosslinking and haloalkylation of styrene-vinylbenzene copolymers

Field of application of the invention

The invention relates to a process for the simultaneous Hachvernetzung and haloalkylation of styrene-divinylbenzene copolymers with low content of divinylbenzene, wherein the products obtained can be used as intermediates for the synthesis of ion exchangers and insoluble supports for peptide syntheses, catalysis resins, polymer reagents and similar use the products according to the invention obtained are further processed by subsequent haloalkylation and .aminierung by known methods for high-capacity anion exchangers.

-aFE & I982 * 98-8888

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Characteristic of the known technical solutions

The starting materials for the synthesis of ion exchangers, polymeric carriers and the like must be insoluble, since only in combination with the insolubility and the resulting properties products with good performance parameters can be produced. In the art one reaches their insolubility by copolymerization of a monomer a crosslinker "In most cases, styrene is used as well as divinylbenzene as a crosslinker. The amount of incorporated divinylbenzene decisively determines the structure and the swellability of the copolymers and the derived products derived therefrom. The more crosslinker is used, the lower is the swelling capacity, usually expressed as degree of swelling, representing the amount of Grammenge a QuellmitteIs per gram of dry polymer · Depending on the application, the monomer to be copolymerized mixture of styrene and divinylbenzene, for example, 1 to 8 Gew Crosslinking agent (swelling in toluene about 3.0 to about 0.6 g / g) in the case of Ionenausausausehervorprodukten included. A decisive disadvantage of crosslinking by copolymerization with divinylbenzene is the high price of this monomer. Furthermore, styrene-divinylbenzene copolymers have structural inhomogeneities due to the different reactivities of the monomers and the conditions of preparation used, which may be disadvantageous for the secondary products produced by polymer analogous reactions.

These facts have led to numerous attempts to eliminate or mitigate said disadvantages. It is possible to recognize two working directions, wherein the one of uncrosslinked Po Iystyren emanates and the other as a starting material with very little divinylbenzene, about 0.1 to about 1.2 percent by _e -%, partially crosslinked styrene-divinylbenzene copolymers used.

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When networking uncrosslinked ,. soluble pearly polystyrene can be carried out two different variants. Once a pure networking is described and on the other a networking, with simultaneous introduction of certain funktioneHer groups. DD-PS 126 741 and 126 738 describes the crosslinking of foam polystyrenes with simultaneous sulfonation. Similar methods "describe the crosslinking of polystyrene with halogen-sulfur compounds or formaldehyde or formaldehyde-emitting substances with simultaneous sulfonation, z" B. in DE-A 1 079 326 and DE-AS 1 025 145. Sin further method describes a cross-linking with simultaneous chloromethylation and subsequent crosslinking by means of tempering (E. Hauptmann, Dissertation, Martin-Luther-University Halle, 1967) Other crosslinking processes with similar objectives are described in DE-AS 1 495 851, 1 495 792, 1 495 768 and in DD-PS 149,672 and DD-PS 149,673.

A Baehteil in all these processes using directly or intermediately formed Monochlordimethylether is to be seen in the dangerousness of this substance, which is also harmful, and when working with him as a result of the hydrogen chloride formed, the technical equipment by increased corrosion affected.

Also known is a process from DD-PS 150 218, which, starting from closely linked styrene-divinyl benzene copolymers, by reaction with monochlorodimethyl ether leads to products with relatively low degree of swelling, when high molar amounts of Monochlordimethylethers, based on the polymer , are used. Thus, for example, when using 50 Mo.sup.1.sup.-1 or 100.sup.mol./monochlorodimethyl ether, the degree of swelling in toluene is about 0.95 g / g or about 0.50 g / g minimum.

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Disadvantage of this method is the one hand, the relatively high cost of crosslinkers to achieve low swelling and on the other hand that the method is not suitable to produce extremely low swelling products "Another major drawback" was already mentioned and consists in the use of health and Equipment damaging substance monochlorodimethyl ether.

Object of the invention

The aim of the invention is to develop a process for the simultaneous Haehvernetzung and haloalkylation of sehwach cross-linked styrene-divinylbenzene copolymers, which may also contain small amounts of other monomers, which allows the production of polymers with targeted and, if desired, low degree of swelling, but at the same time the products contain haloalkyl groups which can be used for puncturization.

Another object of the invention is the development of a process for the production of products with the said properties using technologically easy to handle substances that should be less harmful to health.

Explanation of the essence of the invention:

It is therefore an object of the invention to produce crosslinked polymers having the desired and, if necessary, low degree of swelling, containing haloalkyl groups, using only a small amount of harmful and easily handled substances.

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The essence of the invention is that styrene-divinylbenzene copolymers, optionally containing minor amounts of other Honomerer, containing 0.1 to 1.2 percent by weight of divinylbenzene or with degrees of swelling of 10 to 2j5 s / s in a suitable suspending agent and in the presence of a Friedel-Crafts catalyst with dihaloalkanes or mixtures thereof at elevated temperatures.

As suspending agent, various substances, such as eg

( Dimethylformamide, triethylamine, Hitrobenzen, ffitromethane, Uitropropan, methyl ethyl ketone and others whose mixtures with each other, but also mixtures with other chemically inert substances such as, for example, aliphatic hydrocarbons and similar use find · As crosslinkers 7 / earth dihalogenated aliphatic used such B * methylene chloride, bromochloromethane, methyl methoxide, dibromomethane, dichloroethane, dibromoethane, dichloropropane, di-chloro-butane, dibromobutane, higher dihalo-aliphatics and mixtures thereof Thus, at the same time as a suspending agent · Such a procedure is in some cases due to the low prices of some dihaloalkanes,

* . such as dichloroethane, especially economical. In all these cases, other solvents or swelling agents need only be used in small amounts.

For carrying out the process according to the invention, Friedel-Crafts catalysts or mixtures thereof are used, examples being titanium tetrachloride, iron trichloride, aluminum chloride, tin tetrachloride. These catalysts are dissolved in a suitable solvent selected from the organic substances mentioned above and used for the extraction. Their molar amount may be about 1.5 J 1 to about 1:10, based on the polymer.

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The process is simple and the order of addition of the individual components is not critical to the success of the reaction. Thus it is possible, for example, first to dissolve the catalyst, then to add the crosslinker and then to introduce the polymer. However, it is also possible to mix the polymer, the crosslinker and the solvent, then add the catalyst and carry out the reaction takes place at temperatures between about 15 ⁰ C and about 170 ⁰ C, preferably between 60 and 115 ⁰ G, in a period of 10 minutes to about 18 hours · In almost all cases, however, the reaction is essentially after a half to etv / a completed after 6 hours.

The products obtained have significantly lower degrees of swelling than the starting copolymers and degrees of substitution of haloalkyl groups up to about 50 %, which makes them suitable for a number of applications. Furthermore, they can additionally be halogenated by conventional methods if high-capacity ion exchangers are obtained should. It is not necessary to isolate the product from the reaction mixture, but the subsequent haloalkylation can be carried out using the catalyst already present ·

The process according to the invention is distinguished by a number of advantages over known processes. The use of dihaloalkanes for crosslinking said styrenic copolymers leads on the one hand to saving the expensive crosslinking agent divinylbenzene and eliminates on the other hand the disadvantages for the quality of the polymer compared with the different copolymerization behavior of the divinylbenzene Styren Adult · It is also possible to use as starting materials for the process copolymers of the styrene with divinylbenzene which contain small amounts of other monomers.

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Also compared to other (often) used crosslinkers such. B. xylylene dichloride or higher Halogenmethy! Aromatics, the Dihalogenalkane represent cheaper Eohstoffe, in particular, if you.leight, for example Dichlorethah as a crosslinking agent simultaneously lindin suspending agent sets · The advantages of the method over the linsatz the very health and apparate damaging substance monochlorodimethyl ether, if this substance is used as networking sagenz «

The possibility of using dihaloalkanes having different numbers of methylene groups in the molecule extends the scope of the process in terms of a modification of the structural properties of the end products.

The obtained halogen-containing crosslinked products can after punctionalization without additional prior haloalkylation for certain applications such. B, catalysis resins, peptide synthesis resins, where specifically low degrees of substitution are required, find application ·

Application example

Example 11:

In a flask, 0.01 mol of AlCl in 100 ml of lllitromethane are dissolved, 100 ml of dichloromethane and 10.4 g of styrene-divinylbenzene copolymer are added with a degree of swelling in toluene of 9.25 g / g. The mixture is allowed to stand over water 88 ⁰ O heated and then v / urther stirred for 5 hours · The ver crosslinked product is then filtered, washed with a mixture of equal parts by volume of acetone and 5 fSiger hydrochloric acid and then washed with pure acetone until free of chloride. The postcrosslinked copolymer! Sat is then dried and analyzed. It shows a degree of swelling in 2o luen of 5.00 g / g and a halogen substitution degree of 17

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Example 2:

In a flask, 0.05 mol of AlCl _{3 are dissolved} in 100 ml of uritromethane, 100 ml of dichloroethane and 10.4 g of styrene-divinylbenzene copolymer having a degree of swelling in toluene of 9.25 g / g was added. The mixture is allowed to stand over Facht, heated to 88 ⁰ C and then stirred for a further 5 hours. The product is worked up as described in Example 1. It shows a degree of swelling in toluene of 4.68 g / g and a halogen substitution degree of $ 26>.

Example 3:

In a flask, 0.02 mol of AlCl 2 dissolved in 100 ml of itrobenzene, 100 ml of chlorobromoethane and 10.4 g of a porous styrene-divinylbenzene copolymer having a degree of swelling in toluene of 2.32 g / g were added. The mixture is allowed to stand over Haeht at Bauiütemperatur, heated to 75 ⁰ C and then stirred for a further 10 hours. The product is worked up as described in Example 1. It shows a swelling degree in toluene of 1.50 g / g and a halogen substitution degree of 17 # ·

Example 4;

In a flask, 0.1 mol of AlCl. dissolved in 100 ml Nitro me than, 100 ml of dichloromethane and 10.4 g of styrene-divinylbenzene copolymer with a degree of swelling in toluene of 9.25 g / g was added. The mixture is allowed to stand laughed at tree temperature, heated to 88 ⁰ C and then stirred for 5 hours at this temperature. The product is worked up as described in Example 1. It shows a degree of swelling in toluene of 2.11 g / g and a halogen degree of substitution of 36%.

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Example 5:

In a flask, 0.1 mol of AlClO in 100 ml of IT nitrobenzene are dissolved, added 100 ml of chlorobromoethane and 10.4 g of styrene-divinylbenzene Coco polymer with a degree of swelling in toluene of 9.25 g / g. The mixture is stirred at room temperature for 15 minutes, heated to boiling temperature and then stirred for a further 6 hours. The product is worked up as described in Example 1. Is shows a degree of swelling in toluene of 3.0 g / g, a bromine substitution degree of only O fo and a chlorine substitution degree of 28 fo.

Example 6:

In a flask, 0.25 mol of AlCl 2 are dissolved in 500 ml of itrobenzene, 300 ml of dichlorobutane and 52.0 g of styrene-divinylbenzene copolymer are added with a degree of swelling in toluene of 8.14 g / g . The mixture is stirred for 15 minutes. Stirred room temperature, heated to 72 ⁰ C and then stirred for a further hour · The product is "worked up" as described in Example 1. It shows a degree of swelling in toluene of 5.20 g / g and a halogen degree of 30 ° h *

Example 7:

In a flask, 0.1 mol of AlClO in 100 ml of methylene chloride are dissolved, 100 ml of dibromoethane and 10.4 g of styrene-divinylbenzene copolymer are added at a degree of turbidity in toluene of 6.62 g / g . The mixture is stirred at room temperature for 15 minutes stirred, heated to 120 ⁰ C and then stirred for a further 2 hours · The product is worked up as described in Example 1 * Ss shows a degree of swelling in toluene of 1.76 g / g and a halogen degree of 18 %,

Example 8;

Experiment 7 \ is reacted 7obei held at 120 ⁰ C at only 60 ⁰ C is repeated. The product shows after workup,

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as described in Example 1, a degree of swelling in toluene of 4.24 g / g and a halogen substitution degree of 11 # "

Example 9:

In a flask, 1.0 l of AlCl 2 in 500 ml of ITitrobenzene and 500 ml of dibromomethane are dissolved and 10.4 g of a styrene-divinylbenzene copolymer having a degree of swelling in toluene of 7.80 g / g are added. The mixture \ vill 15 minutes at room temperature, stirred, heated to 95 ⁰ C and then stirred for an additional 1.5 hours · The product is prepared as described in Example 1, worked up · Ss shows a Quellungsgrad'in toluene of 1.51 g / g and a halogen substitution degree of 22 %,

Example 10;

Yersuch 9 is repeated, increasing the reaction time to 7.5 hours »The product shows a swelling degree in toluene of 1.46 g / g and a halogen substitution degree of $ 27.

Example 11: '

In a flask, 0.1 mol of A1C1 ~ dissolved in 100 ml of nitromethane, 100 ml of dichloroethane and 10.4 g of a styrene-divinylbenzene copolymer having a degree of swelling in toluene of 9.25 g / g was added. The mixture is stirred for 15 minutes at room temperature, heated to reflux and then stirred for 6 hours. The product is worked up as described in Example 1. It shows a swelling degree in toluene of 1.10 g / g and a halogen substitution degree of 40 %.

Example .12:

In a flask, 0.05 mol AlGI ^ dissolved in 100 ml Uitrobenzen and 100 ml of dichloroethane and treated with 10.4 g of a styrene-divinylbenzene ~ Co- polymerisate with a degree of swelling in toluene of 7.80 g / g. The product is stirred for 15 minutes at Räumteraperatur, heated to 95 ⁰ G and then more

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Stirred for 8 hours at die.ser temperature. The product is worked up as described in Example 1. It shows a swelling degree in toluene of 2.85 g / g and a halogen substitution degree of 44 % ·

Example 13:

In a flask 0 ^ 05 mol AlGl- dissolved in 30 ml Uitrobenzen, 10.4 S of a styrene-divinylbenzene copolymer with a degree of swelling in toluene of 7.80 g / g was added, mixed with 0.2 mol of dichloroethane. It is then added a mixture of aliphatic hydrocarbons having a boiling range of about 180 to 220 ⁰ C until Eührfähigkeit, heated to 90 ⁰ G and then stirred for a further 6 hours. The product is worked up as described in Example 1. Ss shows a swelling degree in toluene of 0.8 g / g and a halogen substitution degree of 27 % ·

Example 14:

In a flask, 0.1 mol of AlCl 2 dissolved in 100 ml of itrobenzene, 100 ml of dichloroethane and 10.4 g of a styrene-divinylbenzene copolymer having a degree of swelling in toluene of 7.80 g / g are added, with exclusion of moisture with occasional shaking let stand at hem temperature 8 weeks. The product is worked up as described in Example 1. It shows a degree of swelling in toluene of 3> 81 g / g and a degree of halogen substitution of 39 %.

Claims (8)

237249 5 - 12 - 2215 invention sanspruch 1, a process for simultaneous Hachvernetzung and halomethylation of styrene-divinylbenzene copolymers in the presence of Priede1-Crafts catalysts, characterized in that slightly crosslinked styrene-bivinylbenzene copolymers having a share of divinylbenzene between 0.1 and 1.2 percent by mass or with relatively high swelling levels, optionally containing small amounts of further copolymerized monomers, in the presence of Priedel graft s-catalysts or mixtures thereof by dihaloalkanes having a number of carbon atoms of 1 to 18 or mixtures thereof at temperatures between 15 and 170 ⁰ C, preferably between 60 and 115 ^° C., in a period of from 10 minutes to 18 hours in a suitable suspension medium. 2 «Method according to item 1, characterized by the use of a metal halide as Friedel-Crafts catalyst« 3. Process according to items 1 and 2, characterized by the use of, in particular, alraninium trichloride as a Friede1-Crafts catalyst » 237249 5 - 13 - 2215 4 «procedure after. Item 1, characterized by the use of suspending agents containing aliphatic and / or aromatic nitro compounds 5. Method according to points 1 and 4, characterized by the use of uritromethane and / or mercury salts in the suspending agent, 6 Process according to items 1, 4 and 5 characterized by the simultaneous use of the dihaloalkanes as the main constituent of the suspending agent 7 «Method according to items 1, 5 and 6, characterized by the use of a mixture of efitromethane and / or ITitrobenzene with dichloroethane as suspending agent without the addition of further dihaloalkanes» 8 * Process according to items 1 and 5, characterized by the use of a mixture of hitromethane and / or EFitrobenzen with aliphatic hydrocarbons as the suspension center 1 *