DE1570904A1 - Process for the production of redox resins based on 2-isopropenylanthraquinone - Google Patents

Description

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GÖTTINGEN

Fritz-Haber Institute ^: ■ - ■■ '■ "■ Berlln-Dahlem, 1570904 Faradayweg 4> 6

Q / Sh. September 15, 1964

Process for the consultation of redox resins on the basis of ' 2-propenylanthraohinone '

Anthraquinone based redox resins have already been manufactured. So is z. -B- * known that the polymerization of 2-vinyl anthraquinone leads to products which cause reversible redox properties. The polymeric products are hydrophobic and insoluble in the common organic solvents, the reduced form, on the other hand, dissolves in alkali. The sulfonation of the poly (C4-vinylanthraquinone) thus produced leads to the degradation of the polymer. The bulk copolymerization, e.g. B. with styrene, results - due to the limited solubility of 2-vinylanthraquinone in styrene ■ - only resins with a maximum capacity of • about 1 alq / g. The copolymerization of vinyl anthraquinones with divinylbenzene in bulk or in solution also only leads to non-uniform resins with a low redox capacity (about 1 mJLq / g), di · Copölymerlnation, even those with crosslinking, in the various solvents, such as. B. benzene, toluene and alcohols, leads with low yields mostly only to powdery polymers. This is due to the low solubility of the copolymers of yinyl anthraquinones in the solvents used.

let . ~ "vnicto . a Terffthren for the production of cross-linked B« 4oxharz * n on BmIs known from Tinylanthr & quinon, in which

1 5 7 OSJ Λ -δι- or 2-vinyl anthraquinone bsw. whose Subetitutionsprodukte 'ύ-samaen old styrene and / or its Subetitutioneprodokten or homologues in the presence of crosslinking di- or polyvinyl using dimethyl sulfoxide as a solvent between 100 and 200 ⁰ C is polymerized in closed vessels and introduced into the polymers, where appropriate, in a known manner ionenaustauechende groups will. The resulting products have a uniform structure and are mechanically stable.

A process has now been found for the production of crosslinked redox resins based on a polymerizable anthraquinone derivative, which is characterized in that 2-Ieopropenylanthraquinone-9-10 is used together with other monomeric vinyl compounds in the presence of crosslinking di- or polyvinylaromatics at temperatures between 60 and 200 ⁰ O free-radically polymerized and optionally introduces ion-exchanging or hydrophilic groups into the polymers in a known manner.

The 2-isopropenylanthraquinone used according to the invention, 10 is new and can be prepared according to its own older proposal, for example, that 2-isopropenylanthraquinone with a brominating agent in an inert organic Solvent heated, from 2- (OC-BromisoproprlJ-a ^ tiiraciiinoa-gt splitting off hydrogen bromide with a base and the crude product natoh usual procedures worked up.

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All further monovinyl compounds can be used according to the invention, for example Styrene, vinyl toluene and other ring-substituted ones Vinylbenzale »Gv-Methylstyrene-Styrene-Geinieche, Acrylic acid ,. Methacrylic acid or the esters of these acids and the like. As well as mixtures can be used.

Divinylbiphenyl, Diviny! Naphthalene, trivinylbenzene and others, especially divinylbenzene, are used. The polymerization can be thermal or by radical initiators. Free radical polymerization catalysts suitable for the process are z. B. Azobisisobutyronitrii, lauroyl peroxide and the like., In particular Benzoyl peroxide.

The polymerization can be carried out by all customary polymerization processes, i.e. in bulk, in solution, in emulsion and in Suspension can be carried out.

The bulk polymerization can 60 and 200 ⁰ C, at temperatures between et · », are preferably carried out from 80 to 110 ⁰ C. The process of the invention can be carried out with good success because the 2-isopropenylanthraquinone is readily soluble in the comonomers. So ζ is. B. the solubility in styrene at 1QO ⁰ U for 2-vinylanthraquinone about 100 mg / ccm and for 2-isopropeneqflanthraquinone about> 2 g / ccm.

When carrying out the polymerization in solution come as Solvent aromatic hydrocarbons, nitrobenzene, Chloroform, tetrahydrofuran, dioxane, chlorobenzene and the like., insbefeo & fttre but dirnethyl sulfoxide in question. The cheapest Tea making range for this embodiment is between

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60 and 200 ⁰ C, preferably about 80 to 110 ^G C.

Carrying out the polymerization in suspension supplied, in wäsBriger Suepeneion, temperatures twiechtn about 60 and 120 ⁰ C, preferably 70 to 100 ° C, advantageously eind. In this Aueführungeform dae Polymerieat can be obtained in Perlfom. The design is technically easy to implement and is therefore used with preference. In the case of 2-vinyl anthraquinone, it is not possible to carry out a per / polymerisation due to its extremely low solubility.

The Honomerengemiech can both in the Polymerieation in substance and an organic one in solution as well as in ferl polymerisation Solvents are added, which lusts the monomeric compounds, but neither dissolves nor swells the polymeric ones. Such solvents are e.g. B. aliphatic hydrocarbon, Alcohols, ethers, esters, nitroalkanes, etc.

They are used in amounts of about 20 to 40 percent by weight of the dimethyl sulfoxide. With this type of implementation of the process, macroporous resins with a so-called sponge structure are obtained. Also with the following chemical * This sponge structure is retained in conversions.

According to the invention, the 2-isopropenylanthraquinone can be used in amounts of up to about 50 mol percent of the total comonomers. The di- or polyvinyl compound serving as all crosslinking agents is advantageously used in amounts of 5 to 30 percent by weight, based on the total monomers. The polymers obtained are hydrophobic substances. For example, you can use Duroh Hydro. analysis of the ester groups contained in the monomer into hydrophilic poly-

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mers that are wettable by water and have limited swelling are converted. This conversion of the ^ polymers takes place in a known manner. ^:

It is also possible to incorporate hydrophilic or ion-exchanging groups into the polymers obtained according to the invention by known processes, e.g. B. to introduce sulfonic acid, carboxylic acid or phosphonic acid groups . The polymers produced by the present process have a uniform structure and are mechanically stable. For example, they can be used to produce hydrogen peroxide by oxidizing water with air.

Example 1

2.5 g Ieopropenylanthrachinon-9,10, 885 mg of styrene, 350 mg of di-TinylbenBol (about 55 weight percent Divinylbenaol, residual ithyletyrol) and 55 ng of benzoyl peroxide were placed in a GlaaÄapulle gefOlit and a water bath at ca "90 ⁰ C aufgeechmoleen. After the aeon sheet was born with liquid air, the ampoule was evacuated and flushed several times with nitrogen. Sue conclusion was evacuated again and the ampoule-abgeachmol The ötmisch 110 hours at 105 ⁰ C was about polymerized *

jpobj "Polyaieriflat for 15 hours with benzene, extracted and dried at 60 ⁰ C. Yield: 3.2 g

The coarse pieces were chopped up and lived to 0.2 to 0.5 am . This sieve fraction was in about 20 «1 of 1,2-dichloroethane;

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Pre-swollen with stirring for 2 hours and sulphurised with 7 ml of chlorosulphonic acid, which was diluted with 2 ml of dichloroethane, for 20 hours to room temperature with stirring. The product was filtered off with suction, washed with dichloroethane and poured into water. The adhering dichloroethane was removed at 30 ⁰ C by evacuation and then the Wassere by about two hours Brw & rms to about 60 C, the hydrolysis of the sulfochloride ended. The resin was washed neutral and the plaques 0.2 to 0.5 mm sieved out under water.

By washing with 2N HCl, water and In IaOH, the Hars was in the Ia-Porm convicted. The resin was reduced with 1.5 Jtigsriumdithionite solution in 1N IaOH, using the reducing agent It was changed daily until only small amounts of anthraquinone, recognizable by the red magnifying glass, were released.

The resin was then freed from excess reducing agent with 1N _{IaOH and the redox capacity was determined by oxidation with (IH.) Pe (SO.J 2} solution and determination of ^{the amount of Pe ++} formed. Redox capacity: 4.6 mlq / g

Example 2

2.5 g Ieopropenylanthraquinone-9.10, 1.53 g methacrylic acid, 525 Bf Divinylbenzene (55 percent by weight divinylbenzene, remainder ethylstyrene) and 60 mg bensoyl peroxide were by the method of

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5> hours with 'ethanol extracted then'

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2.5% ^ etopa ^ pei ^ antlira ^ iiioilL, 4.75 £ styrene, 1, Ό5- g beüsoli (55 ilewfchtsprozexit DiViüylbeii ^ oly Reeit Ätl ^ lstyröl) tmci ö, Off g Binzoylperoxyd trardeii in 50 "& i '- * Ae6 «r ' _f which contains 0.1 ^ iolyvinylailcbhol and 10 5t HaCl dissolved, takes 20 hours at TO-G ^; and then bead polymerisation for 24" hours fcei'-10 "O ^: QC. 6.8 g Pearl polymer obtained, which after ten hours of extraction with benzene gave a yield of 92%.

After removal of adhering benzene, 5.3 g of the bead polymerizate was obtained in 55%! Dichloroethane swollen and with 19.5 ml Chlorosulfonic acid, dissolved in about 6 ml of dichloroethane, 20 hours sulphurised at home temperature.

The resin was worked up according to the procedure of Example 1 and measured the Eedoikapacity. ^ ■

Hedox capacity: 1.8 aAq / g

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Claims (5)

-β- 1670904 claims 1. Process for the production of crosslinked redox resins
Basis of a polymerizable anthraquinone derivative, thereby
characterized in that 2-isopropenylanthraquinone-9 »10 together with other monomeric vinyl compounds in the presence of crosslinking di- or polyvinylaromatics at temperatures between 60 and 20O ⁰ C radically polymerized and optionally in
the polymers in a known manner ion exchangers · or
introduces hydrophilic groups. 2. The method according to claim 1, characterized in that the polymerization is carried out in bulk. 3. The method according to claim 1, characterized in that the polymerization is carried out in suspension. 4. The method according to claim 1, characterized in that the polymerization is carried out in solution. 5. The method according to claim 1, characterized in that the polymerization is carried out so that an organic solvent is added to the monomer mixture, which the monomers
Dissolves vinyl compounds, but has neither a dissolving nor a swelling effect on the polymers formed. Le A 9024 909885/1580