DE831326C - Process for the production of linear polyamides with divalent sulfur in the chain - Google Patents

Description

Process for the production of linear polyamides with divalent Sulfur in the chain High molecular, linear polyamides with di- or polysulphide groups in the chain links are not yet described. This according to a known method produced by heat condensation of decamethylenediamine and dithio-diglycolic acid Polymer is a typical resin that softens below .4o °.

It has now been found that technically valuable, high-molecular, linear polymers are obtained if one has compounds which have two carbon atoms bonded to them Rhodan groups or a rhodan group and a thiosulfuric acid ester group and in the chain still contain amide and / or stilfon groups, in solution or dispersion with soluble sulfides or polysulfides. As the procedure preferably works under extremely mild conditions, so are not just starting materials can be used with the groupings customary in polyamide chemistry, but also many connections with groups that were previously less or not at all considered came because they cause disruptive side reactions in the heat condensation, z. B. cyclizations, Give cause.

In principle, any amide groups, so z. B. carboxamide, urea, urethane, sulfonamide or hydrazide groups, these last again in different bonds, ver be turned. Accordingly, come for that Methods of the invention include, for example, the following Amide compounds under consideration: Carhonic acid amides i. N - N'-Di- [@ -rhodativaleroyl] -hexametliyleti- diamine: NC S- (CH,) 4-C 0 -N H- (C 11,) s -NH-CO- (C1I2) 4-S CN, can be produced by converting hexamethylene diamine with d-chlorovaleroyl chloride and further con- densation with Kalitimrliodatiid in alcohol. 2. Sel> acinic acid-N -N'-di - [; - rhodatihexyl] amide: N CS- (CH,) s N H-CO- (CH2) s -C O- \ H- (C H.,) 6 -SCN, can be produced by heating sebacitic acid with z mol of chlorohexyl isocyanate and further condensation the dichloro compound finite alkali iodanide. 3. N-N'-Di [rhoclanacetyl] -pipei-azine: can be obtained from N # N'-di-cliloracetylpiperazine and Potassium rhodium. .I. N-N'-Di- [5-rliodanhexyl] -oxaniid: N CS- (CH2) s -NH-COCO - N H- (C H2) 6- SCN, obtainable by condensing oxalic acid diethyl ester with; -Chlorliexylamin and others Implementation with potassium rhodanide. Urethanes i. N - N'-Tetramethvlen @ bis-carbamidsätire- (S-rlio- danbutvlester: NC S- (CH,) 4-O-CO-NH - (CH,) 4-N H-CO-O- (C1-1,) 4-SON, adjustable by reacting tetramethylene isocyanate with 8-chlorobutyl alcohol and further con- condense the formed bis-urethane with alkali rhodanid. 2. N # N'-di- [Z-rhodanhexyl] -carliamic acid- tetranietethylene glycol ester: NC S- (C H. =) S N HC 0-0- (CH,) 4 -OC ON H- (C H. =) SS CN, can be produced by reacting 5-chlorohexyl isocyanate with tetramethylene glycol and condensate sizing the bis-urethane with potassium rhodanide in Alcohol. Ureas i. N - N'-di [5-rhodatiliexyl] urea NCS- (CH,) s -NH-CO -N H- (CH.) SS l 'N, can be prepared from N - N'-Di-S-chloro-xyllinea and Kalitinirhodanid. 2. c, i # (,) '- di- [5-rhodanhexyl] -liexamethylene-di- urea: SC N- (C H2) 6 -N HC 0-I-1 N- (C H2) 6 -N HC 0-N 11- (CH,) sS CN, obtainable by reacting Z-Chlorhexvl- isocvanate with Hexainetlivlen (Ilaniln and further con- densation with Alkalirliodanicl. 3. (,) - ( ,) '- Di - [; - rliodanbex _ \ -] @ -tetramethylene-1 »s- thiolar reagent N CS- (CH2) s N H-CS-NH- (CH2) 4 -NTH-CS-NH- (CH-) s-SCN, produced by reaction of tetramethylene clisenföl with -Rho <lanhexylamine. @. cu ro'-Di - [- rhodanhewl @ -N-llethvl-N -di- [;, - urei clopropyl] -atnin CS- (CH_) sN 1i- CO -NH- (CH,), C H3 i -N- (CH.,) 3-NH- ('O-NH - (CH,) s-SCN, produced by converting; -Chlorliexvl- isocyanate with N- \ fetliyl-N-lli- [y-aniitiopropyl] - amine and `Veiterkondensation with excess : \ lkalirliodaiiid in \ letliaiiol. 5. Quaternary anionic salt available from Reacting the compound 4 finitely Diinethvlsulfat. 6. cooi'-di- [5-rhodanhexyl] - @ 3-oxytrimethy @ endi- urea NCS- (CH2) 6- N H-CO-N H-CI.I. = - CI-1 OH -CH, -NH-CO-N H- (CII.,) S-SCN, produced by dissolving ß-Oxvtriinetliylen- diamine with @ -Chlorhexylisocyanat and boiling with potassium rhodanide in alcohol. 7. cu # (., 9'-Di- [5-rhodatiliexyl] -N-N'-di-carboxyl- methyl-NT - N'-dicarl) aminvlliexainetliylenediamine 2. N-h'-rliodanvaleroyl-b-aminobutylthiosulfuric acid sodium: NC S- (CH,) 4-CO-N H, - (CH2) 4 -S S O. Na, preparation analogously by reaction of b-amino- 1> Utyltliiosclisulfuric acid sodium with δ-rhodanvalerate acid chloride.

3. N -ethylcarbamic acid-b-rhodanebutylesterortliiosclisulfuric acid Sodium: N CS- (CH2) 4-OCO-NH-CH2 -C H2-S S 03 Na, produced by condensation of chloroformic acid diiodane butyl ester with ß-aminoethylthiosulfuric acid sodium.

Compounds in which the rhodan groups terminally to aliphatic radicals with at least two adjacent Cll. = groups are bound. In addition to amide and / or sulfone compounds of the type described Amide or sulfone compounds can also be used in the reactions in varying amounts be present with two thiosulfur acid ester groups, as well as simple, bifunctional ones Compounds with two rhodanic and / or thiosulfuric acid groups without @ 1mid- or sulfonic groups in the chain, e.g. B. i. Sodium hexamethylene-bis-thiosulfuric acid, 2. Sodium p-xvlvlen-bis-thiosulfuric acid. 3. hexamethylene dirhodanide, .1. tS-rhodanl) titvItliioscliwefelsaures Sodium (from α-8-chlorobromobutane and sodium nitrate in aqueous methanol .Io °).

All soluble sulfides and polysulfides are suitable for implementation with the dirhodane compounds, e.g. B. those of alkalis and alkaline earths, ammonia: and organic bases. The sultides can be applied in an approximately calculated amount (based on dirhodanide). In some cases it is better, with possibly considerable differences, e.g. B. those from 50 to 2000/0 to work. Excesses are better avoided if the rhodan groups adhere to a negatively charged carbon atom, e.g. B. Starting materials with the group> NC 0-CH, - SC N. In such cases, excesses cause yield losses due to hydrolytic cleavage. Compounds with the group 1-C H _, - CH, -SCN (where a strongly negative group, e.g. > CO, means) are sensitive to excesses of strongly alkaline sulfide compounds, at least in the warmth. Alan therefore works better under these circumstances with equivalent amounts and / or at lower temperature.

The unispositions are usually in the presence of organic solvents carried out, preferably such. that on the resulting polymers at least have a swelling or dissolving effect in the heat. Occasionally come z. B. into consideration alcohols such as ethatiol, ethanol, propanol, cyclohexanol, tetrahydrofurfural alcohol, Glykolniotio-tnethylädier, amides, like mono- and dimethylformamide, acetdimethylamide, a-pyrrolidone, N-methyl-a-pyrrolidone, dimethylcyanamide, sulfones, such as methylethyl sulfone, Tetr-amethylene sulfone, m-cresol and mixtures of solvents of this type.

The choice of solvents depends on the solvent and swelling properties of the final products to be addressed. Sometimes it is useful to the reaction mixture Add salting agents to facilitate the separation of the end products.

The reaction takes place very quickly even at ordinary temperature. However, especially when working in organic solutions, it is also advantageous to use work at a higher temperature, possibly even at temperatures above roo ° and under pressure in a stirred autoclave. One can use one of the reacting components (sulfide or dirhodanid) and gradually add the other. With the technical It is usually more advantageous to work with the reacting substances in the desired proportions to meet continuously, e.g. B. by having them together in an intensive mixer kept at reaction temperature or they on a rotating surface, e.g. B. in a centrifuge, mixes. For working dispersants, such as polyglycol derivatives, are advantageously used in dispersions high molecular weight alkyl compounds, e.g. B. the reaction products of excess Ethylene oxide with fatty acids, fatty alcohols, fatty amines, alkylphenols and salts of alkylnaphthalenesulfonic acids or paraffin sulfonic acids obtained by sulfonic chlorination high-boiling paraffin hydrocarbons and saponification of the chlorides. About education to prevent lumps in the case of low-melting substances, or to prevent the dispersing agent can easily be removed again in the form of soluble salts by adding acid slimy metal hydroxides, such as magnesium hydroxide, are added. To create products with the most uniform possible consistency is an intensive mechanical one Working through the reaction mass is advisable, especially when in high concentration is being worked on. In such cases it is advisable not to be content with ordinary ones Stirring devices, but used highly effective dispersing machines with strong Shear effect on the particles of the reaction product that are still in the state of swelling. Kneading pumps or screw pumps with z. B. two concurrent Screw spindles.

The polyamides or polysulfone compounds obtained are, insofar as they have a linear structure, depending on their bivalent sulfur content, based on the unit of the resulting chain links, more or less hard and tough to rubber-like elastic substances. Their physical behavior can be improved in a manner known per se in the case of thioplasts by adding or, if necessary, removing sulfur can be produced by reacting hexamethylene diamine-N-N'-di-acetic acid sodium with @ -Rho- daitliexylisocyanat at o °. Sulfonamides i. N - N'-Di - [# - r'hodanhexyl] -hexamethyletidisul- fonsäurediamid: NC S- (C H2) eN HS 0z (C H2) 6 -S 0.-N H- (CH,) BS CN, can be produced by condensing Fexaniethylen- disulfonic acid dichloride with s-chlorhexylamine and Further conversion with potassium iodide in alcohol. 2. Di- [3-rhodanltutvlsulfonvl] -liexametliylenedi- amine: NC S- (CHz) 4-S 0., - N 1-1- (C 1 - [_,) s -N HS O, - (CH,) 4-SCN, can be produced by condensing i-on d-chloro-butyl- sulfochloride with HexametliN'leii (liainln and others Cooking the reaction product in alcohol with Excess Kaliutnrliodaiii <l. 3. Disulfamide he formula: can be produced by reacting piperazine-N # N'- disulfochloride with @ -chlorhexylamine and condensate sation with potassium rhodanide in alcohol. Hydrazides i. Di- [s-rhoclancaproyl] hydrazine: NCS- (CH.). -CO-NH-NH-CO - (C H2) sS CN, can be produced by condensing @ -Chlor- caproic acid chloride with hydrazine according to Schotten - Baumann and further implementation with potassium rhodanide in aqueous alcohol. 2. Di- [o) -rhodanundecanoyl] hydrazine: NC S- (CH,) lo-CO-N HN H -CO- (CH,) io-S CN, can be produced by condensing vrBromun <le- cansättrechlorid with hydrazine and boiling with excess rhodanic potassium in alcohol. 3. Di- [co-rhodandecyl] hydrazodicarltonainide: NCS- (CH2) to -NH-CO-NH-NH -C O- N H- (CH,) to-S C - \ T, produced by converting (,) - Bromdecvl- isocyanate with hydrazine and heating with potassium rhodanide in methanol at 10 °. 4. Hydrazodicarboxylic acid di- [8-rliodatrltutyl] - ester: NC S- (CH2) 4-O-CO-NB-NH -C 0-O- (C H2) 4-SCN, produced by condensing chlorine iron acid-8-chlorobutyl ester with hydrazine and boiling with excess. Rhodanide in alcohol. Compounds with sulfonic groups t. Di - @ - rliodanhexyl sulfone: NC S- (CH 2) 6-SO2 - (C H2) sS CN, obtainable by condensation of # '- Chlorliexyl- alcohol with? \ sodium sulfide, acetylation of the Hydroxyl groups, oxidation with potassium permean ganat, boiling with 48% hydrogen bromide and reaction with potassium thodanide. , 2. Tetramethylene-1> is- (S-rlioclaiilltitylenstilfon: CS - (C H.,), 4- S O., - (C 1- S O., - (CH, 14-SCN, obtainable by condensing @crn () -OxvI) titvlmer- captan with Tetrainethy Lendichlorid Lind% \ - pus Implementation as under i. s s ulfon: 3 N NCS- (CHz) 4-CO- \ H- (CH, I, -SO, - (CH2), - NH-CO- (C 112) 4-SCN, can be produced -by condensation% -oii i3-j3'-I) iatnino- diätliylsulfon with b-Clilor @ -aleriatis'itireclilorid and Unisition with _ @ lkalirliodanid. Instead of the uniform inonotnolecular substances can also use linear-polymeric stilphons with rhodan end groups are used, e.g. 13th NC S- (C HI-) 6-1 S 0. = - (C 11-) c] 1 - S 0, - (C 11,) 6-S C N. Connections of this kind can be obtained by adding I'o15 # metlivletidilialogeni <le finit AIkali- sulfide in appropriate proportions sets, the terminally halogen-containing polythioethers with potassium permanganate in glacial acetic acid to form poly sul foils oxidized and finally the .I lodged against them Rhodan group exchanges. As a means of supply for the last reaction, especially the one cyclic mono-style foil, e.g. 13. Cyclotetra- methyletisulfone. Instead of or at the same time as the Dirhoda Niden can also be compounds with amide and bziv. or sulfonic groups @ -crivend be terminated. the in addition to a rhodan group, a thiosclive field acid ester group included. z. 13. Connections like i. ro- [S-rhodanhexyl] ioswiv- rock acid sodium: NCS- (CH,) s-NIi-CO-Nil - (CH,) cS S 03 Na. can be produced by reacting '-IZlioclaiiliexyl- isocyanate with; -aniinoliexvltllioscllwefelsatirein Na- trium at o °. Wish changed «- earth. The pure disulphide compounds show a particularly close resemblance to the lecatinized linear polyamides, that is, if they are sufficiently high, they can be oriented "Molecularly mechanically by stretching," Talzen or "Liehen. If they are converted and meltable, they can be melted from the melt into threads, bristles , Tapes or felts.: Some can also be processed from solutions, depending on their solubility, e.g. in dimethylformatnide, pyridine, ethylene chloride, onto moldings or coatings. between zoo and 200 °. Particularly high-temperature products are obtained by using I-1y drazidverlündungen as: \ starting material. Substances that become liquid higher than 1> ° i 17o 1> 1s 18o 'can no longer be processed from the melt in most fillings , but can also be shaped by compression, if appropriate in the presence of plasticizers such as phenols or amines lvstil-Fone, e.g. l3. 1'olytri- or -tetrastilfitle, are extremely thermo-plastic and can be processed using the usual methods for thermoplastics, e.g. I3. roll, press or spray.

Solubility, softness and elasticity can all play a role in linear condensation polyamides known way through mixed condensation, through the introduction of lateral substituents, z.13. Alkyl or alkoxy groups, or by chain-breaking links, such as ) N R groups, ether or thioether groups, erliölit. Substances with carboxyl and or or _ \ rtiinogrupl> eti can with a sufficient number of these groups in the molecule as such, or after salt formation with bases or acids in water or aqueous Solutions are resolved, resulting in special areas of application, e.g. 13. as protective colloids, Adhesives, finishing agents and dyeing additives. Polyamides with active Groups, such as hydroxyl or amino groups, formed by heat condensation according to the older -Processes are known to be very difficult to implement, have the advantage to be changed in various ways through post-treatment. For example They are cloned by the action of di- or polyalkylating or acidifying agents networked and made insoluble.

The polyamides according to the invention can be subjected to all known post-treatments for thioplasts, e.g. B. a heat treatment with sulfur and zinc oxide for the purpose of @ folekül enlargement, optionally in the presence of, here preferably acting as plasticizers vulcanization accelerators, such as', \, lercaptobenzothiazole, or ß-thionaphthol. Example i 20.56 g of N - N'-di- [Z-clilorliexyl] -tetramethylene glycol-liis-carliamic acid ester (0.05 mol) were added with t0.67 g (0.11 mol) of 1 # Zaliunirhodan, id in 6 Parts by volume of ethanol, based on rhodanide. cooked until the halogen is completely converted (70 hours). The clear solution sucked off by the salt was halogen-free. I / lo mol of a 20% aqueous solution of sodium disulfide (obtained by dissolving sulfur in sodium sulphide solution and heating at 85 ° for 4 hours) were added dropwise at 20 ° with stirring. The solution turned yellow and the almost colorless (very slightly yellowish) reaction product began to separate out immediately. After standing in the cold for 3 hours, the coarse precipitate was filtered off with suction and washed cold with water until an evaporation sample no longer left any residue. The polyamide melts at 10 to 116 ° to a colorless, viscous melt from which endless, easily stretchable and strong threads can be drawn. Yield about 85%.

The analysis indicates the presence of i: \ tom sulfur ie nitrogen atom. S found. i8, i6%, N found. ;, 91%, 18.430 / 0, 7.920 / 0. The Polvamid dissolves easily and colorlessly in cold in-cresol. It slowly dissolves in concentrated sulfuric acid with a strong yellow color and the development of S 02. Concentrated formic acid and acetic acid only dissolve when heated. In the cold, the polyamide separates out of these solutions. N-methyl-pyrrolidone and ethylene chlorohydrin behave in the same way. Double normal caustic soda at 80 ° apparently ineffective. Example 12 To a solution of 0.02 mol (6.85 g) of N # N'-di - [; - rhodanhexyl] urea (flakes of benzene, melting point 72 to 73 °) in 42 cc of ethanol is left at 25 to 27 ° 0.02 mol of sodium disulphide was added dropwise to two cc of water. The reaction product immediately precipitates as a fine, rapidly coarsening powder with complete discoloration. After standing in the refrigerator for 3 hours, it is filtered off and washed thoroughly with cold water until it is free of electrolytes. The polyamide dried at 50 ° melts between 113 and 114 °, yield 96% of theory. Conc. Sulfuric acid causes strong swelling without complete dissolution occurring even after prolonged standing. In m-cresol it dissolves easily even in the cold. The melt can be spun into endless threads that can be oriented by stretching. Example3 To a solution of 0.02 mol of N # W-di - [@ - rhodanhexyl] urea obtained by reacting N # N'-di [Z'-chlorhexyl) urea with potassium rhodanide in boiling ethanol, 0.022 mol Sodium tetrasulfide (produced by dissolving 3 g atoms of sulfur in a concentrated aqueous solution of crystalline sodium sulfide and heating in a boiling water bath for 4 hours) was added dropwise over the course of 12 minutes at 24 °. Initially, the dropwise solution was completely decolorized, and only at the end did the yellow coloration persist. The polyamide immediately precipitates out fine and can be filtered very easily after standing in the refrigerator for 5 hours. Practically quantitative yield. The light yellow polyamide melts at 97 to 100 °. Elastic threads can be drawn from the melt long after it has solidified.

If the polycondensation is carried out at 50 °, a more strongly colored polyamide is obtained in quantitative yield which also melts at 96 to 100 ° and which gives less strong threads. Example 4 0.04M01 sodium sulfide in 3.5 times normal aqueous solution is added dropwise at 25 ° to 30 ° to a solution of 0.02N-101 N # N'-di- [Z-rhodanhexyl] urea prepared as in Example 3. The reaction product separates out as a colorless, very fine, but nevertheless easily filterable precipitate. Yield 96% of theory. Melting point 118 to i21 °. The melt can be spun into threads that can only be oriented by stretching shortly after spinning. Example s To a solution of 0.1 mole of di - [@ - rhodanhexyl] sulfone in 4 times the amount of ethanol is added 20 ° with stirring o, 12 Alol potassium disulfide in con- centered alcoholic solution. The polysulfone Polydisulfide falls immediately as a fine, colorless powder the end. It melts at io5 ° and can be taken from the Melt to be spun into threads.

Claims (1)

PATENT CLAIMS: i. Method of making linear Polyamides with divalent sulfur in the Chain, characterized in that connection gen, the two bound to Kolilenstoftatome Rhodan groups or a rhodan group and a thiosulfuric acid ester group and in the Chain or aniide and / or sulfo groups contain finite soluble sulfides or poly- sulfides are implemented, preferably iii Presence of organic solvents. especially alcohols and ainides. 2. The method according to claim i, characterized in that indicates that the implementation at an early stage still free of amide and sulfone groups functional compounds with rhodan or or final thiosulfuric acid used will.