DE1570762A1 - Process for the preparation of monomeric and polymeric organic sulfur compounds of the aromatic series - Google Patents

Description

The invention relates to a new method for making clay monomeric and polymeric organic Sulfur compounds of the aroaatiaohen series, which more as two aromatic heatβ (kernels), the old "white eggs" ore Sulfur atoms are bound, contain a.B.

Ar-S _n -Ar-S _n -Ar Ar- (S _n -Ar) _x -S _n -Ar

Such compounds can be organic sulphides or sulphides or polysulphides ι in which all organic heete "AJf" are either equal or Tereehieden, be considered Molecular weight of the bonds can be more than 3,000,000

009812/1688

BATH ORIGINAL ''

be.

Dl · «· Connection«! are inventions through! AUi catalysts coaaen metals of groups Jb, XIa and b ₉ HIa and b ₉

of the periodic table
ITa and b _v Ta and b _t Tllfund xanthanldon into consideration, sB * Oa ₉ Au, In, H ₉ Oa, Sl ₉ Ge, Aa ₉ Sb ₉ Mo, Xn ₉ Ve ₉ Pd ₉ Ib ₉ etc. The catalysts used can be activated in a special manner described below - this is why the boaction takes place with the formation of metal chlorides is atataa naaeendi.

Biaher was as known, some DAFL> ehwofelTorblndungen tos type A * "8 _a" Ar as well as some Harsø unknown structure at is leakHoa τοη aromatlaonen Torbindungen with Sohwof eleonoohlorld under the catalytic action τοη lluainiuatrlohlorid, linkdiohlorid "some other Metallonloridoa or tob metal 0Aleriden ₉ < Some of the other metal areas are "" ioraised in old "" and _{9 are} formed; Dabol were dia Kengen the aagewon4eten catalysts in the Orensen τοη 1 to 10; iewientepiw4ent der OoeaBtaenge «'>'

Bs ψκΗ · now found that the organic Sohwof el-;

•, i ί

Torbindangoa goaäfl of the discovery in the present τοη aetalliaohon Katalyaatarin under formation tob Metaalohlorldon la "status ϊ · horgesteUt can be, whereby dlo orequipment

009812/1688

BATH ORIGINAL

i «

Amount of Imtalyeators less than 1 <Jew. ~ £ der amounts to.

The IrIlady creates a process in which ans sr Use of a very low “close to catalyst” int maximum yield of products is obtained. Known in the iegensat «su 4ea> e The journey is made in the case of the journey; sur manufacturing the specified products in particular tin Oversohufi used sulfur halides. *

Some of the products manufactured according to the invention can be isolated by means of selective extraction . ^r i-? s ^ ' Xxtraktionen % r £ © Igen u.! ..-%; f application Iner- :, ·. · - ·: where ilt dattujig des ang # w «& i ^; , t®s solution :. desired degree of unity of the PJOduct «depends

If you experience the lower leap temperature of the reaction of charges sdt Soinwefelohlorldec not at AO ■■ - -'0 ^J 0.-. **! ia: c It: duag the under * Temperaturgrense in dtn lersicsl. r «* is « tws 1O ⁰ O up & rta extended.

The response can be carried out in the absence or in the presence of a medium in the course of the event. The course of the B @ e £ tion is fdraugawelse regulated in such a way tHe eioh the Beaktion in Ernest Taknu * τοπ developed 20 on Hg to 1 atm ·.

009812/1588
BATH ORIGINAL

In the case of some products, the solvent system used forms an essential characteristic for the condensation of the products, since without “in suitable lueunga agent systems, no separation of τοη pure single products is achieved. Si ·· applies in particular to polymers in which dl · Indio ·· ^N n ^N bsw. ^N z ⁿ in the general formulas given above is greater than 3 eihd. In these embodiments of the process according to the invention, the liedereehlagasystem consists of chloroform, petroleum ether, benzine fractions, ethers of the general formula EOR ₁ , in which R and Rj can be identical or different alkyl groups with 2 to 10 carbon atoms, primary, secondary or tertiary Alcohols of the general formula B-OH ₉ in which R 1 to 16 carbon atoms and can consist of «ines alkyl, aryl or aralkyl or their hydrogenated forms, chlorinated hydrocarbons and heterocyclic aromatic compounds with or without M atoms in the molecule and fae «« r. The ratio of the one component can vary from O ₉ I to 98 + .

The catalysts are used alone or then activated in the manner specified below a quantity of metal has been weighed out a few times « Sweeping in a Johüttel apparatus with 30 - 600 vibrations. per minute, one after the other and separately with the following Activators geeohuttelti solutions of alkali uai Irdalkalihydrozyden (Consentrations from 0.1 to 18 Ji), LOeimfen τοη

• ·

' ^X 009812/1588

BATH ORIGINAL

Mono- and polycarboxylic acids (e.g. acetic acid, adipic acid, citric acid etc., in Eonsentrationen τοη 0.1 to 35 #) »esters τοη organic and inorganic acids (e.g. ethyl acetate, triethyl phosphate, trioresyl phosphate etc.)» aliphatic, aromatic and arallcyl alcohols, hydrogenated forms 'τοη aromatic and aralkyl alcohols, primary, secondary and tertiary alcohols, ethers (melting point below 100 ⁰ O and boiling point below 275 ⁰ C) and buffer solutions (pH 4.6-1.2). The Sohüttelzeit with the individual AktiTatoren is τοη Hinuten 1-40 and the temperature is in the range τοη 15 - 120 ⁰ C, preferably in the range between 25 ° and 30 ⁰ O.

Elemental sulfur is removed from the reaction products by washing with solutions τοη hydroxides of the alkali and alkaline earth metals, the concentrations being based on the viscosity of the products and in the range of tone 1 to 55 i> , or with solutions τοη alkali sulfides, the concentrations of which correspond to the viscosity between 1 and 66 #, at temperatures that allow the best cleaning and are usually in the range τοη 15 - 140 ° C

The polymers obtained naoh the process according to the invention can subsequently be given a higher average Molecular weight can be polymerized, either by distillation in vacuo, under normal conditions or at elevated Druok or by heating the substance alone or in any inert solvent to the required temperature.

009812/1588

The working methods described near the advisory The products obtained can, according to the invention, be inert Solvent by means of aluminum oxide, magnesium sulfate, sodium sulfate and magneaium perehlorate are cleaned. '"

Naoh the retracts, according to the invention they g ^ vwoiinenen Terblndungen or their compositions may comprise as Ytilkanisationsmittel, Yulkanisationsbesohleunlger, dyes and * überaugsmaterialien ί \ 1τ all kinds of materials, plastics, Iaolatoren, fuels for special Zweoke or fuel additives, lubricants for normal and high Sruokbolastungen, Weed killers, insect pests, fungicides,% »dentiside _t components clay, pharmaceutical products, surface-active substances etc. can be used.

The invention is exemplified below by way of clay explained further, however, it is not limited to these particular embodiments.

example 1

Polyantrylpolyulde of the general fo) ^; C ^ H ^ - (S _n -O ^ H ₈ J _x S _n -C ^ Hg are obtained in the ** manner below! *

90 parts of anthracene, dissolved in 100 parts of chloroform, are placed in a flask with a * meohanieohen Kührer, a thermometer, a condenser and elms * AbIaB tube provided for the withdrawal of hydrogen chloride. This solution will be 0.022 Tolle tin, which is standing in the gate '

009812/1588 '

let b there ear! planar type Torbereitet been that Reaktionemisohung beigefügtf we, d, stirring at 30 ⁰ O erwäret "Then 10 parts 3ohwefelmonoohlorid, gamlsoht ■ it 50 parts of chloroform, hours in the course Sound 2 added and daa stirring is more Continued for 4 hours · For the entire duration of the reaction, the hydrogen chloride formed in the reaction is removed from the reaction mixture. They mixture is then allowed to stand for 12 hours at a temperature of 30 ⁰ O and then under constant RlIhreu 33 feile Bohwefelnonochloriö "mixed with 100 parts of chloroform» · Pas added stirring is continued ble formation Ohlorwmseerstoff tone is terminated,

When the reaction has ended, an orange-colored powder remains, which reappears on the surface. This product is separated off by filtration and petroleum ether is gradually added to the remaining chloroform solution, so that the solubilized polyanthene / oil-polysulphide of a lighter and dark brown color is deposited The liquid remaining in the TakuuB is now evaporated, leaving a reddish, puiyerfumlges material suriiok.

None of the substances obtained contain free chlorine or alcohol, even in trace amounts. The sulfur content of the landings obtained is within the limits of τοη 21 and 35 *.

Sin ¥ Mererwttx »en the obtained compounds to a temperature τοη 90 ⁰ O or above leads to the formation of τοη

009812/1588

BAD ORIGINAt.

Compounds with a high degree of polymerization, the color of which is τοη The oohulfur content varies from light yellow to dark brown over 40 J *.

A total of 110 different ropes Poljantrylpolysulfide be won what at one Einsäte tob 90 parts Anthraoen and 72.5 parts Sohwefelmonoohlorld a yield sound 89 i "entsprioht.

Example 2

In the manner described in Example 1 Yorriohtung 92 parts of toluene in (put waiting τοη 0.036 parts of tin, which has been aktiTiert in the manner described above, contacted with 73 hone Sohwefelmonoohlorid sur reaction; the SohwefelmonoohIorid is sugefttgt slowly with stirring warmed to 5O ⁰ C Beaktionsmlsohung · the reaction eehreitet stepwise under .Entwicklung τοη hydrochloric Toran, wherein iie temperature to 90-100 ⁰ C rises to Yorriohtung is old connected a water jet pump, which is se-regulated during the reaction that the Takuum τοη an initial value τοη 600 ■■ Hg. to 300 mm. Haoh termination increases the exothermic reaction, the mixture is heated to su sehwaohem BflekflvJ, with no loss sugelaesen by evaporation wiri · Vaoh 10 hours the reaction was terminated%, the product we · old steam distilled and with a 12prosentigen latrii hydroxydluaung ( three times with 25 parts at oinor temperature tone 95 ⁰ C) and then with a 15prosenti gene sodium sulfide

009812/1588
BAD K ^

solution (washed three times with 25 parts at a temperature τοη 35 ⁰ C); after separation, extraction is first carried out with toluene, while the residue is dissolved in chloroform. The addition of ethanol, ligroin and water in a mixing ratio 1i2i1, based on the solution, leads to the production of plastics with 29.5 $> üohwefelgehalt from toluene ext zakt and 33.0 # Sohwefelgehalt from the Ohloroformextrakt. The yield, calculated on toluene, is 69 »3 #«

In order to obtain polymers having a molecular weight of 50 000. The polymers obtained from the chloroform solution is heated in a Silioonöl up to a temperature of 278 ⁰ C. The product is purified by dissolving it in O'ioroform and shaking it with a mixture of aluminum trioxide and magnesium sulfate (1: 2). Then -as is isolated in the manner described above. The Aui ute is 97 #. The polymer is obtained in the form of a white powder.

Example 3 In the device according to Example 1, 212 Yoliuwn-

parts of toluene in the presence of 0.06 parts of activated sr

with 80 parts of Sohwefelmonoohlorid sur reaction gebrao) f

the sulfur monohydrate is slowly mx · ie while stirring

heated to 60 ⁰ O Reaktionsmlsoiiung "ugegeben. H ± 9 rction

so it rides step by step with the development of Ohlorwas · stoff

ahead and the temperature rises "uf 85-90 ⁰ C · The To lohtung

009812 / 1S88
BATH ORIGINAL

is connected to a water jet pump, old this we * the vacuum in the course of the reaction clay 600-650 ml Hf Mi increased to 500 am Hg

After the end of the reaction, the reaction amieehung is warmed to the reflux, with no additional evaporation allowed. After 4 hours, the reaction has ended. The product is evaporated in a vacuum (20-30 ml Hf) and the residue is distilled with steam, with 12prosentiger sodium hydroxide solution (three times with 50 lines at a temperature of 25 ⁰ G) and with 15 per «entiger ifatrium sulfide solution (three times with 50 parts at one Temperature tone 25 ⁰ C) washed. After separation, the product is dissolved in chloroform. The solution is treated with sodium sulfate and the chloroform is then evaporated. Ba becomes a product with 32.0 ^ sulfur content in a yield of 57t? i · received.

The embodiments of the invention described above can be modified in various ways, for example with regard to the materials used, the proportions used, the temperatures, the processing and control methods, etc., without departing from the scope of the invention. >

009812/1588
BATH ORIGINAL

Claims (1)

Patent claims 1 · Process for the hera division of monomeric and polymeric organic sulfur compounds of the aromatic series, characterized in that aromatic organic compounds or their derivatives are entapreohenden in the presence of clay catalysts Bit ücl. ^ efeichloriden su organleohen sulfides, dieulfides or! Polysulfide voo ϊ-yp Ar-U _n -Ar-S _n -Ar and U ₁₁ -Ar) _x -U _{11 -Ar 1 which} contain more than "two identical or different aromatic nuclei bonded with Kwei or very sulfur atoms and have a molecular weight of up to 3,000,000 or more, converts" 2 «Method according to claim 1, thereby known without, that a sulfur monoxide is used as the sulfur chloride. 3. The method according to claim 1 or 2, characterized in that « that the catalysts used are metals from groups Zb, II * «ad b, IHa and b, IVa and b, Va and b, VIII and Lanthanides are used, which have optionally been activated by treatment with activators in such a way that the reaction occurs 009812/1588 BATH ORIGINAL under formation Ton Hetallohlorlden la "statue nasoendi" expires. 4. Procedure naoh one of the / nsprohe 1-3, thereby characterized in that the catalyst is in an amount of clay less than 1 oew .- #, based on the total amount, susetit. 5. The method Mach one of claims 1 -V, daduroh characterized that the sohwefelohloride Iji üeeretlme "applies · 6. The method naoh 'one of claims 1- 5 *, characterized characterized in that one is one from the heat ion product Polymers with a certain degree of purity through selective extraction separated with inert solvents. 7. The method naoh one of claims 1-6, characterized in that the reaction is carried out at a temperature tone 1O ⁰ C upwards. Θ. Method according to one of claims 1 - 7 # This is characterized by the fact that the reaction is absent or in the presence of a solvent. 9. Procedure according to one of the tests 1-8 » daduroh characterized that one can react by applying a vacuum in the range τοη 20 mm Hg to 1 atm. 10. The method naoh one of .Ansprüche 1-9, characterized in that pure products, la where "n" and ^H x "are greater than 3, by precipitation with a solvent system of chloroform, petroleum ether, gasoline fractions, Itheinder the general formula ROI ₁ , in which K and I _{1 are the} same 0 0981 2/1588
BAD ORJGINÄL or different · Alkyl radicals with 1-10 carbon atoms aein can, primary, secondary and tertiary alcohols of the general formula R-OH, in which R 1 - 16 carbon atoms have and from an alkyl, aryl or aralkylreat odor a hydrogenated form thereof, chlorinated hydrocarbons and heteroyl aromatic compounds with od ^ r without hydrogen atoms in the molecule and water, where the Ratio of components in the range from 0.1 to 90? » lies, wins. 11. Process according to one of the Anajj * "^; che 1 - iO _t characterized in that catalysts are used which have been activated by shaking in a uchüttalvorriohtung, preferably at 30-600 cycles per minute, a few times in succession and separately with activators . 12. The method according to any one of claims 1-11, characterized in that the catalysts used h shaking in an IS ohüttelvorrichtung over a period of time from 1-40 minutes at a temperature in the range of 15 - 120 ° 0, especially between 25 ° and 30 ° G, with the activators have been activated. 13 · method according to one of the claims 1 -12, characterized in that the catalysts used have been activated with the following activators: Solutions of alkali and alkaline earth metal hydroxides in a concentration of 0.1 to 18 ji, solutions of mono- and polycarboxylic acids, wi Acetic acid, adipic acid, citric acid, etc., in consoutrations 009812/1588
BATH ORIGINAL Ton Ot 1 to 35 '> 0, esters τοη organic and inorganic acids, such as ethyl acetate, triethylphoephat _t trioresylphosphmt etc., aliphatic, aromatic and aralky! Alcohols, hydrogenated forms τοη aromatic and aralkyl alcohols, primary, secondary and tertiary alcohols, ethers bit one Melting point below 100 ⁰ C and a boiling point below 275 ⁰ O and buffer solutions with a pH of 4.6-7.2. 14. The method according to claims 1-13 »characterized in that the reaction products by washing with solutions τοη alkali and alkaline earth metal hydroajrden with concentrations τοη 1 - 55 #, depending on the viscosity of the products, and solutions τοη alkali sulfides with concentrations τοη 1 - 60 #, depending on the viscosity of the products, at temperatures which enable the cleaning and are in particular in the range τοη 15-140 ⁰ C, τοη elementary sulfur is freed. 15. Procedure according to one of the approaches 1 - 14 » characterized in that the products obtained are extracted by picking them up in an inert solvent and shaking the solutions with a mixture τοη Aluniniuatrioayd, Magnesium sulfate, sodium sulfate and magnesium perchlorate τοη Freed impurities. 16t method according to one of claims 1 * 15, daduroh characterized that the polymers obtained by distillation in vacuo, under normal conditions or bsi erfeuhtea Druok or duroh heating alone animal in 009812/1588
BAD ORlQfNAL an inert solvent to the desired temperature subsequently adjusted to a predetermined average molecular weight polymerized. 009812/1588