DE2164810A1 - Process for inhibiting the premature vulcanization of rubber stocks - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENTANWÄLTE Z I OH Q IU

8 MUNICH 8O, MAUERKIRCHERSTR. 45

Dr. Barg Dipl.-Ing. Stopf, 8 Munich 80, Mauerkircherstroße 45

Your reference Your letter Our reference · Date

Attorney file 21 986

Monsanto Company
ot. Louis, Missouri / USA

"Process for inhibiting the premature vulcanization of rubber deposits"

.This invention relates to an improved method for Manufacture of vulcanized rubber, as well as rubber compounds made using the improved process can be obtained. The invention also relates to improved accelerator-inhibitor combinations for rubber, as well as compounds that act as inhibitors of the

48 70 43 <98 70 43) 48 33 10 (96 33 10) telegram! BERGSTAPFPATENT Munich TELEX 05 24 560 BERG d Bank t Bayariicha Verainibank Mönchen 453 100 Poiticheck: Manchen 653 43

_ ₂ _ 216481Q

early vulcanization are suitable for rubber, and in particular a process to avoid the premature vulcanization of Kuutschukansatz, as well as rubber approaches, obtained using this method.

In the manufacture of vulcanized rubber products becomes raw rubber with various other ingredients such as fillers, accelerators and anti-degradation agents combined to change and improve the processing of the rubber and the properties of the End product- to improve. The raw rubber is left go through various stages of the system before it is ready for the final stage of vulcanization. In general the rubber is mixed with carbon black and other ingredients besides the vulcanizing agent and accelerator. Then the vulcanization and acceleration funds added to this batch in a Banbury mixer or grinder. "Scorching", namely premature vulcanization, can occur at this stage of processing, during storage prior to vulcanization and occur during actual vulcanization. After the vulcanizing and accelerating agents are added, the mixture of raw rubber is ready for calendering or extrusion and vulcanization. If - during storage of the raw mixture or during processing before vulcanization -

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Premature vulcanization occurs, the processing operations cannot be carried out because of the pre-vulcanized Rubber is rough and lumpy and therefore worthless. Premature vulcanization is a major problem the rubber industry and must be avoided, uro ^ u allow the rubber mixture to be preformed and shaped before it cures or vulcanizes will.

Through the development of flame soot with a high p ^ value (furnace blacks (F.B.)), which lack the inherent inhibitory effect of acidic carbon blacks and which have Uses of certain phenylenediamine antidegradants that promote premature vulcanization are increasing stricter requirements are placed on the hardening system. The premature vulcanization has hitherto been partly due to accelerators with a retarding effect, in which the thiazole sulfenamides are a typical example, either alone or in combination with retarders and accelerators controlled. An accelerator selected for this procedural security may involve the use of a secondary Make accelerator necessary to achieve satisfactory curing properties. It was made by Tomlin (U.S. Patent 2,590,737) indicated that certain Sulfonamides are powerful vulcanization activators when used as secondary accelerators, though they have little accelerating effect when used alone

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Use. Such "retarders" include N-nitrosodiphenylamine, salicylic acid and a terpene resin acid mixture. See also Rubber World, "Compounding Ingredients for Rubber", 91-94- (3rd Ed., 1961). Acids' are generally ineffective or have an adverse effect as retarders with thiazole sulfenamide accelerators on the vulcanization process. Nitrosoamine retarders have only a limited ability to work thiazole sulfenamides derived from primary amines.

9k A class of sulfonamides has now been found that inhibit premature vulcanization. They are characterized by the presence of an organic thio substituent on the sulfonamide nitrogen. The characteristic nucleus is -SN-SOo-, although there may be more than one such nucleus. The term "sulfonamide" is used here in a mandatory manner and includes sulfonediamides or sulfamides, in which case the free valence on the -SOp group is linked to another nitrogen which may also contain a thio substituent. The ability to inhibit precure appears to be a common property of organic thio-substituted sulfonamides. Examples of monomeric thiosulfonamides which are suitable for inhibiting prevulcanization correspond to the following general formula

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where η = 1, 2 or 3 j η'- = 1 or η '= 1, 2, 3 or 4 and η = 1, the radicals R and R "are organic radicals and R' is hydrogen or an organic radical, wherein the organic radicals represented by R, R ¹ and R "are preferably hydrocarbons Mt 1 to 12 carbon atoms.

When n '= 1, R "is univalent and the links are Derivatives of monomercaptans. R "is then an aryl, alkyl, alicyclic radical or radicals, rings fused to aryl and alicyclic radicals or any combination the same, for example, alkaryl, aralkyl, alkylalicyclic rings or fused bicyclic rings belong, which have an aromatic ring condensed with a non-aromatic ring, such as tetrahydronaphthyl and indanyl. For the sake of simplicity, aryl is used in the usual general sense, including: is to be understood as any monovalent organic radical whose free valence is to an aromatic carbocyclic Core belongs and to which alkaryl, bicyclic radicals, which contain an aromatic ring, the valence to the ring belongs, and residues belong to that in the carbocyclic nucleus are substituted by alkoxy, chlorine, bromine, fluorine or iodine groups, but preferably not more than 12 carbon atoms and contain no more than one electronegative substituent tone. For example, the aryl radical Phenyl, iiaphthyl or xenyl, preferably unsubstituted,

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excluding lower alkyl. Alkyl is a monovalent aliphatic hydrocarbon radical of the series To understand C Hp ^, where η = 1 to 20, preferably 1 to 12, with the radical being primary, secondary or tertiary, the chain or chains beginning with the primary secondary or tertiary carbon atom are connected, straight or branched. Cycloalkyl includes cyclic ones aliphatic radicals, preferably with 5 to 12 carbon atoms in the carbocyclic ring to be understood, wherein the ring, except for lower alkyl, is unsubstituted. Under aralkyl is to be understood as meaning aryl-substituted alkyl. Lower alkyl radicals with 1 to 5 carbon atoms substituted by phenyl the preferred aralkyl substituents are.

Explanatory examples for R "now follow when n ¹ = 1, provided that the formula R ^ bO ₂ N (R ¹ ) -SRJ! 7 _n is: phenyl, o-, m- or p-tolyl, o -, m- or p-iithylphenyl, o-, m- or p-isopropylphenyl, p-tert-butylphenyl, o-, m- or p-chlorophenyl, o-, m- or p-3romphenyl, o-, m- or p-fluorophenyl, 2.5-dichlorophenyl, 2.4.5-trichlorophenyl, 2.4.6-trichlorophenyl, 2.5-dimethylphenyl, o-, m- or p-methoxyphenyl, pentachlorophenyl, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl , sec-butyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, tetradecyl, benzyl, decahydronaphthyl, cyclohexyl, cyclopentyl, cyclooctyl, oyclododecyl, 4-methylcyclohexyl, 5-indanyl, 2-

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_ 7 _.
Mesityl, xenyl and when R is lower alkyl, nitrophenyl.

When η = 1, E is of course monovalent and is independently selected from the same group of monovalent radicals as R ". Regardless of the value of η and n · R ^{1 is} hydrogen or is independently selected from the same group of monovalent organic radicals Radicals such as R "are selected or completed a thiobis sulfonamide, in which two sulfonamides are linked by nitrogen to form a divalent radical. Such thiobis sulfonamides, the starting materials of which are diamines, are a valuable class of compounds, examples of which compounds can be shown that R · «-AN-SO ₉ -R" ¹¹ and by the complete set

JJlIl

/ RSO ₂ NAN-SO ₂ R ""] _n , R ", V S- R ·" /

Formula of a typical subgroup of these diamines when η = 1, namely

S- R ¹

where A is an alkylene, arylene or cycloalkylene radical, preferably with "!" to 12 carbon atoms, such as, for example divalent radicals resulting from the removal of two hydrogen atoms from methane, propane, cyclohexane, isopropane, Butane, isobutane, pentane, hexane, heptane, octane, benzene, toluene, diphenyl or any methyl of p-xylene (phenylenedimethylene), which is regarded here as alkylene, where in the formulas R · "hydrogen,

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R "or R ¹¹ S, where R" is the same monovalent radical as above, R "" is a monovalent radical R "and the meaning of R" outside the brackets depends on ^{the value of n 1.} For example, when n ¹ = 2, R "is selected from the same group as A, and when n ¹ = 3 or 4, R" is trivalent or tetravalent, as explained below.

Sulphondiamides or sulphamides, which are characterized by having two nitrogen atoms linked to the same -ÖOp- group, are a valuable class of compounds, as a typical example being compounds which, when η = 1, by the general lormel ^ -N-UQpN (R ¹ ) sV, R "are shown

can, wherein R ^{1 has} the same meaning as above, but is preferably hydrogen or independently from the same group of monovalent radicals as R "is selected and R has the general formula R -N-

K " ¹

where R ^{v is} hydrogen or has the same meaning as the monovalent radical R "and R" ^{1 is} in turn hydrogen, R "or R ¹¹ S-, where u» is the same monovalent radical as above. The meaning of R "outside the brackets again depends on the fourth of n ¹ , where R" is monovalent if n ¹ = 1, is selected from the same group as A if n ¹ = 2, or three- and ■. - 9-

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are tetravalent organic radicals when n ¹ = 3 or 4-is.

! »! Sulphonamides, in which two sulphonamide nuclei are linked by -o0 ₂ ~ groups to form a divalent radical, can be used in a similar manner. Disulfonamides, in which n ¹ = 1, can be given by the following general formula

in which R is divalent and is selected from the same group as A, preferably hydrocarbon having 1 to 12 carbon atoms. R "is, as previously defined, a monovalent organic reads and R 'has the same meaning as before, however, is preferably hydrogen or becomes independent selected from the same group as R ".

Disulfon & raide, in which two dulfonamide nuclei are linked by a divalent sulfur atom to form a divalent radical R "(in which n ¹ = 2), are valuable precure inhibitors which are represented by the following general formula

-ü-J

where R "is an organic divalent Remainder isb and from the same group as A aus- ^ ■ ev / ahlb becomes and. preferably hydrocarbon with 1 to 12 Kotil-onsboffabomen isb, R a monovalent, organic

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SAD ORIGINAL

- ίο -

Remainder with the same meaning as before, if it is monovalent, and R * have the same meaning as before, but is preferably hydrogen or is independently selected from the same group as R.

When η = 3 and n ¹ = 1, the prevulcanization inhibitors have the general formula

N (R ¹ ) -SR ^ ₃ ,

wherein R is trivalent, for example phenenyl, R ^{1 has} the same meaning as above, but is preferably hydrogen or is independently selected from the same group of monovalent radicals as R "and R" is a monovalent radical as defined above.

The compounds corresponding to the preceding formulas are prepared by condensing an N-halosulfonamide with mono- or dimercaptans or converting the mercaptan to an oelfenyl halide and the halide with; a sulfonamide, ^v which has a reactive hydrogen on the nitrogen, condensed. If a dimercaptan is reacted with a sulphonamide that contains more than one reactive sulphonamide nucleus, polymers are formed which are also suitable as inhibitors of pre-vulcanization. If both radicals R and R "of the general formula of the monomers are converted into divalent radicals, one obtains poly-

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mere] forms of thiosulfonamides. For example arise from monomers of diamines of the general formula previously described below

-S-N - A-N - R '"λ R"

OO-qI *. hjxss ^ j.

where R is hydrogen, polymers when the hydrogen is displaced by reaction with a mercaptan with more than one mercaptan radical, in which case R "is more than monovalent. R" ¹ can be R ¹¹ B-, where R "is monovalent and R" outside the brackets can be divalent, which occurs when a hydrogen is replaced by reaction with a monomercaptan and the hydrogen of the second nitrogen is replaced by reaction with a di-, tri- or tetramercaptan. If, however, both R ″ and R ¹¹ S- are divalent or higher within the brackets and R ″ outside the brackets, polymers are obtained which can expediently be represented by the following, recurring unit

A-N-SA '- S -7.

where χ is an integer greater than 1 but probably 'less than 20 and the radicals R and R "" have the same meaning as the monovalent R ", A has the same meaning as above and A ^{1 is} independent of the same group as A is selected. Another typical

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cal polymer contains the recurring unit

/ ^ N - SO ₂ - R - SO ₂ - N - SA ¹ - S ^ _x , R ¹ R ¹

wherein χ is an integer greater than 1, probably less than 20, R has ^{the same meaning as above when it is divalent, and A 'and R 1 have} the same meanings as above. The polymers differ from the monomeric form of the disulfonamides described above, where two sulfonamide nuclei have P —S0 ₂ groups according to the following formula

R "-SN-S0 _o -R-S0 _o -N-SR ^u

% C- C- i

R * R ¹

are connected, vdftdsm'i the monovalent radicals R "become divalent and A ¹ the repeating unit

-SN-SO ₀ R-SO ₀ NSA ¹ --i c- ci

R ¹ R ¹
will.

The sulfamide polymers can by the following general formula

R ^V R ^V

I I

Cm .Λ.

are represented, wherein x, R ^v and A have the same meaning as before.

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-Ip-

Polymers can also be produced by the reaction of tri-

and tetranjercaptans and sulfonamides, which are more than one have reactive site are 'formed'. Me the production of such polymers and the production of monomers in which n 'is 3 or 4 are tri- and tetramercaptans necessary. These are available and are useful in making embodiments of the invention suitable pentaerylthritol tetra ^ mercaptopropionate,

₄ , Pentaerylthritol tetraCthioglycolat), ■, Triraethyloläthantri (3-mercaptopropionat),

_{5 , trimethylol ethane trithioglycolate} , and trimethylol propane trithioglycolate, 52225. Similarly, dimercaptans that are suitable for reaction with sulfonamides to form embodiments of the invention include esters of mercaptocarboxylic acids such as glycol dimercaptoacetate, C ₂ H ₄ (OOGCH ₂ SH) ₂ , glycol dimercaptopropionate, and other compounds of the formula Wiedrigalkyleribis / Ö0C (CH ₂ ) _n " _:: 7, where n" is 1 or 2.

The preferred inhibitors are those wherein R "is cyclohexyl or phenyl and various cycloalkylthiosulfonamides are used chosen to illustrate this phase of the invention. It should be noted that the corresponding phenyl compounds are similarly effective and that if one replaces cyclohexyl or phenyl by other radicals designated here as being typical of R ", one

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Compounds with valuable inhibiting properties which are not necessarily equivalent, however. There now follow for the explanation inhibitors, di @ the

• * '■

general formula R-SO ₂ N-SR "correspond (n and n ¹ = 1), in which R ^{1 is} hydrogen or one of the monovalent organic radicals mentioned above, to which R" belongs: N ~ (Gyclohexylthio) -benzenesulfonanilide, N- (Cyclohexylthio) -o-, p- or m-Tolylsulfonanilid or mixtures thereof,

^ N- (Oyclopentylthio) -benzenesulfonanilide, N- (Cyclooctyl- W

thio) -benzenesulfonanilide, N- (cyclododecylthio) -benzenesulfonanilide, N-Cyclohexylthio-N-cyclohexylbenzenesulfonamide, N-Cyclohexylthio-N-cyclohexyl-o-, p- or m-tolylsulfonamide or mixtures thereof, N-Cyclohexylthio-N-methylbenzenesulfonamide, N-Gyclohexylthio-N-methyl-o-, p- or m-tolylsulfonamide or mixtures thereof, N- (Oyclohexylthio) -benzenesulfonamide, N- (Oyclohexylthio) -methanesulfonanilid, N- (Oyclohexylthio) -ethanesulfonanilide, N- (Cyclohexylthio) -butanesulfonanilide, N- (Cyclohexylthio) -

^m N-butylbenzenesulphonamide, N-cyclohexylthio-N-butyl-pchlorobenzenesulphonamide, N-cyclohexylthio-N-isopropylbenzenesulphonamide, N-cyclohexylthio-N-2 · 5-dichlorophenyl-2 · 5-dichlorobenzenesulphonamide, N-cyclohexylthio .5-trichlorobenzenesulfonamide, N-cyclohexylthio-Np-chlorophenyl-2.4 »6-trichlorobenzenesulfonamide, N-cyclohexylthio-N-2. 4.6-trichlorophenyl-2.4.5-trichlorobenzenesulfonamide, N-cyclohexylthio-N-ethylbenzenesulfonamide,

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N-Cyclohexylthio-N-ethyl-p-ctilobenzenesulphonamide, N-Gy clohexylthio-N-sec.butylbenzenesulphonamide, N-Cyclohexylthio-N-isopropyl-p-toluenesulphonamide, N-Oyclohexylthio-N-butyl-sulfonyl-toluene N-butyl-o-toluenesulfonamide, N-cyclohexylthio-N-ethyl-o-isopropylbenzenesulfonamide, N- (Cyolohexylthio) -butansulfonamid, N- (cyclohexylthio) -octansulfonamid _f N- (cyclohexylthio) -. decahydrornaphthylensulfonamid, N- (Cyolohexylthio) -n-methyldodecanesulfonamid., N-Gyolohexyltb-io-N-benzyl - ^ - raethyloyclohexanesulfonamid ..

Examples of sulfonediamide inhibitors of the general
Formula R ^v -N-S0 _o N-SR "are N- (cyclohexylthio) -NN ^l -dicyclo- R" · - R ¹

hexylsulf - ^. amide, N- (Gycloh.exylthio) -sulfanilide, N- (Cycloliexylthio ) -sulfamide, N.N · - (Dicyclohexylthio) -N.N'-dimethylsulfamide.

Examples in which η = 2 are N- (Gyclohexyltb.io) - ^/ l-.4 ^I -biphenyldisulfonamide, N.N'-CDicyclohexylthio) - ^ -. ^ ¹ ^! -
phenyldisulfonamid, N-C-cyclohexylthio) ^. 5-benzenedisulfonamid, NN ^l - (dicyclohexylthio) -1.3-benzenedisulfonamid,
and where η = 3, N- (cyclohexylthio) -1.3.5-benzenetri-sulfonamide.

Inhibitors of the formula RSO ₀ N-AN-SO ₀ R ", those of diamines

originate are, for example, N- (Cyclohexylthio) -N.Ni-

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athylenbisraethansulfonaraid, N, N'-Dicyclohexylthio-N, N'-äthylenbismethansulfonamid, N-cyclohexylthio-NN ^f -äthylenbisbenzolsulfonamid, N, N'-Dicyclohexylthio-NN · -äthylenbisbenzolsulfonamid, N, N'-Dicyclohexylthio ^NN-1 -p-phenylenbismethansulfonamid ,

R ¹
Inhibitors of the formula (RSQpN-S) pR "ι derived from dimerοaptans are, for example, 1,2-bis (N-thiomethanesulfonumide) -ethane, 1,2-bis (N-thiobenzenesulfonamide) -ethane, 1,2-bis (N-thiotoluenesulfonamide) -ethane , 1.2-bis (N-methyl-N-thiomethanesulphonamide) -ethane, 1.2-bis (N-methyl-N-thiotoluenesulphonamide) -ethane, 1.6-bis (N-methyl-N-thiomethanesulphonamide) -hexane, 1. ^ - bisCN-methyl-N-thiomethanesulfonamide) -butane.

Rubber compositions having delayed action accelerators can be used in the process of this invention will. Cheaper, however, the premature vulcanization can use stronger introductory accelerators as well can be used with an excellent degree of improvement. The improved vulcanization process of this Invention can advantageously be used for processing batches containing furnace blacks, as well as for formulations containing other types of carbon black and fillers such as those used in the compounding of rubber The invention is equally applicable to

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Gumr- * lugs.

The invention is useful with rubber compounds, the sulfur vulcanizing agents, organic accelerators for vulcanization, and anti-degradation agents, none of which is the inhibitor used. Under Sulfur vulcanizing agents for purposes of this invention are elemental sulfur or a sulfur-containing one To understand vulcanizing agents, for example amine disulfide or polymeric polysulfide. Furthermore, the Invention applicable with vulcanization accelerators of various types. For example, rubber mixtures with the content of an aromatic thiazole accelerator, the N-cyclohexyl ^ -benzothiazolesulfenamide, 2-mercaptobenzothiazole, 2.2'-dithiobisbenzothiazole, N-tert-butyl-2-benzothiazolesulfenamide, 2-Benzothiazolyl diethyldithiocarbamate and 2-morpholinothio) benzothiazole is used will. Amine salts of mercaptobenzothiazole accelerators, for example the t-butylamine salt of mercaptobenzothiazole, Similar salts of morpholine and 2,6-dimethylmorpholine can be used in the invention. Thiazole accelerators other than aromatic can also be used. Approaches that accelerate such as Tetramethylthiuramdisulfid, Tetramebhylühiurammonosulfid, Aldehyde amine condensation products, thiocarbarnylsulfenamides, thioureas, metal dithiocarbamates, Alkyldithiocarbamates, hexamethylenetetramine,

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Containing xanthates and guanidine derivatives are significantly improved when using the method according to the invention. Examples of thiocarbamylsulfenamide accelerators are shown in U.S. Patent Nos. 2,381,392, 2,388,236, 2,424,927 and British Patent 880,912. The invention is applicable. In approaches that contain mixtures of accelerators and in approaches that Contain amine degradation agents. Rubber equipment, the anti-degradation agents, for example N-1,3-dimethylbutyl-N-phenylp-phenylenediamine, N.N'-bis (1,4-dimethylpentyl) -p-phenylenediamine and other phenylenediamines, ketones, ethers and hydroxy degraders, and mixtures thereof, become essential improved when using the method according to the invention. Mixtures of anti-degradation agents, for example a mixture of N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine and N.N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, provide a significantly improved end product when used with the inhibitors of this invention.

The inhibitors of the invention can be found in natural and synthetic rubbers and their mixtures are used. On synthetic rubbers that are affected by the Processes of this invention that can be improved include cis-4-polybutadiene, butyl rubber, ethylene propyl ether polymers, Polymers of 1,3-butadiene, for example 1,3-butadiene itself and isoprene, copolymers of 1,3-butadiene with other monomers, for example

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Styrene, acrylonitrile, isobutylene and methyl methacrylate. The invention also relates to diene rubbers and the terms rubber and diene rubber are for purposes this invention synonymous.

The compounds are preferably prepared by condensing the corresponding sulfenyl halide with a sulfonamide which contains reactive hydrogen on the amide nitrogen in the presence of a hydrogen halide acceptor. The general reaction, if one uses a sulf en yl chi or id and a sulfonamide, where n ¹ = 1, proceeds as follows:

R ¹ 'R ¹ -

I I

-g7 + nClSR "- ^

^ "~ LX

^ 7

Lx

Using "R-SO ₂ N (H) AN (H) SG ₂ R 'or R ¹¹¹¹ as starting materials, one or both of the nitrogen atoms is easily substituted with -SR" groups depending on the molecular ratio of ClSR ". Two Molecular proportions of ClSR "per mole of sulfamide lead to a substitution on both nitrogen atoms. Any hydrogen chloride acceptor can be used, for example tertiary material acceptors, for example tertiary amines and alkali metal hydroxides. The reaction can conveniently be effected in organic solvents, for example benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetrachloride or hexane. An aqueous phase

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Dilute alkali metal hydroxide may be present, being ale a suitable source of the hydrogen halide acceptor is used. The reactions are usually slightly exothermic and take place quickly at ordinary temperatures after mixing the reactants The reactions are ordinary substantially terminated after gradually adding a solution of sulfenyl halide to a solution of sulfonamide.

The preparation of the new compounds is illustrated in detail by the following typical examples.

example 1

A glass- or glass-lined reaction vessel is used with 23.3 g (0.1 mol) of benzenesulfonanilide, 11 g of triethylamine and charged 200 ml of benzene. Cyclohexylsulfenyl chloride is then added gradually at room temperature zu, which was prepared from 11.6 g of cyclohexyl mercaptan in hexane by adding chlorine. After completion the addition and brief stirring, the reaction mixture is poured into water, twice with 2 # sodium hydroxide solution, then extracted twice with water. The benzene layer is dried over sodium sulfate and the benzene removed by evaporation. The oily residue is mixed with a small amount of hexane to initiate crystallization treated and recrystallized the solid product from hexane.

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sated. This gives N- (cyclohexylthio) -benzolsulfonanilid as a cream colored solid, melting point 57 to 60 ⁰ G.

Used 24.7 S-W, instead of Benzylbenzolsulfonamid Benzolsulfonanilid, we obtain N-cyclohexylthio-N-benzylbenzolsulfonamid as a brown solid, melting point 46 to 48 ⁰ G.

Example 2

A glass- or glass-lined reaction vessel is used with 10.9 g (0.1 mol) of N-methyl methanesulfonamide, 11 g of tri-ethylamine and charged 100 ml of benzene. A benzene solution of 0.1 mol of p-nitrobenzenesulfenyl chloride is then gradually added to, this being prepared by adding 8 g of chlorine to 30.5 S of p-nitrophenyl disulfide in benzene was. 'During the dropwise addition of p-nitrophenylsulfenyl chloride a slightly exothermic reaction takes place. Finish the addition and continue for a short time of stirring, the reaction mixture is filtered to remove the TriäthylarainhydrοChlorids, with dilute Washed sodium hydroxide, dried and the benzene removed by evaporation to give N-p -nitrophenylthio-ii-methylmethanesulfonamide as a cream-colored solid, melting point 112 to 114 g. Another I-ienge is made from the triethylamine hydrochloride as the remainder Dissolve the salt in water.

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^BATH

If 17.1 g (0.1 mol) of p-toluenesulfonamide are used instead of N-methylmethanesulfonamide in the previous process, N-p-nitrophenylthio-p-toluenesulfonamide is thus obtained as a cream-colored solid, melting point 102 to 105 ° C.

Using 0.1 mole of benzenesulfenyl chloride instead of p-nitrobenzenesulfenyl chloride in the previous example, this gives N-phenylthio-N-methyl-methanesulfonamide. The benzene is removed from the filtered reaction mixture by evaporation, leaving a dark brown Liquid remains, which is extracted with cold hexane, dissolved in benzene and extracted three times with 100 ml of cold water will. The benzene layer is dried, treated with charcoal, filtered and the benzene by evaporation removed, giving the product previously described as a yellow oil. The analysis using KMR confirms his identity.

Using 0.1 mol. Cyclohexansulfenylchlorid instead of p-nitrobenzenesulfenyl chloride in the preceding method, we obtain N-cyclohexylthio-N-iuethylmethansulfonamid, melting point 30 to 32 ⁰ G. The filtered reaction mixture is washed three times with 100 ml portions of water in place of washing with extracted from dilute sodium hydroxide. After removal of the benzene, an oily residue is obtained which gradually crystallizes after treatment with cold hexane. The crystalline mass will be fine

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rinsed with cold hexane, which indicated the 'in advance Product is obtained as a pale yellow solid. The analysis by means of KMR confirms his identity.

Example 3 '

4-6 g (0.2 mol) of benzenesulfonanilide are added to a suitable reaction vessel. dissolved in a mixture of 100 ml of benzene, 10Q ml of water and 8 g of sodium hydroxide. A solution in benzene of 0.2 mol of benzenesulfenyl chloride, prepared from 22 g of thiophenol and 16 g of chlorine in benzene, is added dropwise to the solution produced in this way. When the addition is complete, stirring is continued for a short time. The water layer is then removed and the benzene layer extracted with 100 ml of 4 # sodium hydroxide and twice with 100 ml of water. The benzene is removed over sodium sulfate dried and purified by distillation to give N- (phenylthio) -benzolsulfonanilid the residue obtained, melting point 80 to 8J ⁰ O. After recrystallization from methyl alcohol to obtain a white solid, mp 86 ⁰ O.

Example 4

A suitable reaction vessel is filled with 17 »1 g (0.1 mol) N-methylbenzenesulfonamide, 4 g (0.1 mol) sodium hydroxide, 100 ml of water and 50 ml of benzene are charged to make a solution of N-methylbenzenesulfonamide. To this manufactured Solution are slowly 0.1 mol of cyclohexylsulfenyl

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chloride in 100 ml of benzene was added. After the addition and reaction are complete, the product is isolated by extracting the reaction mixture with water, drying it over sodium sulfate and evaporating the benzene. This gives N-cyclohexylthio-N-methyl-benzenesulfonamide as a crystalline solid, melting point 59 to 61 ⁰ O.

If 0.1 mole of p-toluenesulfonamide is used instead of N-methylbenzenesulfonamide in the foregoing process, N-cyclohexylthio-p-toluenesulfonamide is obtained as crystalline solid, melting point 95 »5 to 97 ° G.

Example 5

A glass or glass-lined reaction vessel is dissolved with 18.5 g (0.1 mol) of N-methyl-p-toluenesulfonamide charged in 100 ml of dichloromethane and 11 g of triethylamine. 0.1 is then gradually added at room temperature Moles of benzenesulfenyl chloride. After the addition is complete, the reaction mixture is washed with 100 ml of 2 # sodium hydroxide, then extracted with water. Without further purification, the product has a melting point of 69 to 71 ° 0. and the Analysis by KMR confirms that it is the desired N- (phenylthio) -N-methyl-p-toluenesulfonamide is.

Example 6

In a suitable reaction vessel, 6.5 g (0.0 ^ 5 moles) of N, N'-Diphenylsulfondiamid (0 H _r NH) pö0 _2, 6 g of triethylamine

-25-- 209830/0983

and introduced 100 ml of benzene. To this end, 0.075 mol of cyclohexylsulfenyl chloride is gradually added. When the addition is complete, the reaction mixture is filtered, the benzene is removed by distillation and the mince stand is treated with hexane, giving a dark solid which is recrystallized from methanol. The product is NN ^1-diphenyl-i \ f.N'-dicyclohexylthiosulfondiamid, a white solid, melting point 105 to 107 ⁰ C. Analysis by KHR confirmed its identity.

Replace N.N'-Diphenylsulfondiamid by an identical one molar length of N.W'-Ethylenebisbenzenesulfonamide, so obtained one N.N'-dicyclohexylthio-W.N'-athylenebisbenzenesulfonamide.

If cyclohexylsulfenyl chloride is replaced by an equal molecular amount of 1,2-ethanedisulfenyl chloride, a pre-vulcanization inhibitor is obtained in the form of a polymer which has the recurring unit -ü - Ii - o0 ₂ - N - SC ₂ H ₄ -

having.

Example 7

jj # in Gluij- or Glus-clad reaction vessel r; j ± t ^ 6 £ (0.2 Hol) U-Hobhyl-p-toiuolsulfonamid, 150 ml Benzene and 2 ^ g Triüühylatuin charged, then give all-

-26-

209830/0983 bathroom original

sec-butylsulfenyl chloride is gradually added at room temperature, this being prepared by "adding 7.5% chlorine to 17.8 g (0.2 mol) of sec-butyl disulphide in 100 ml of benzene. When the addition is complete, the product is isolated by adding to the benzene with two 100 ml portions of 2 $ dger sodium hydroxide solution, then extracted two water washes. the benzene is dried over sodium sulfate and removed by evaporation. the oily residue is washed several times with tk cold hexane and an amount of unreacted N-methyl-pr -toluenesulfonamide is removed from the cold hexane wash liquor by carefully precipitating a hexane solution of the residue. After cooling, H-sec Products' is confirmed by means of KMR analysis.

Example 8

A glass- or glass-lined reaction vessel is used with 37 g (0.2 mole) of N-methyl-p-toluenesulfonaiaid, 24.5 g Golliden and 350 ml of dimethylformamide charged. One gives then gradually at room temperature essentially 0.1 molecular fraction · 1.2-Athandisulfenylchlorid au, which by Addition of 14 g of chlorine to 9.4 g of 1,2-ethanedithiol in benzene was produced. After the addition has ended, the cooling is continued for a few minutes, the reaction mixture filtered and the solvent from the i'iltrat through

-Z7- 209830/0983

Distillation removed. The remaining product is Λ .2-bis- (i> ii-ethyl-N-thio-p-toluenesulfonamide) -ethane, a solid which has a melting point of 1.2 to 174 ⁰ O after recrystallization from hexane. The analysis by means of KMR confirms its identity.

Example 9

A glass- or glass-lined reaction vessel is used with 43.6 g (0.4 mol) of N-methyltethanesulfonamide, 44 g of triethylamine and charged 300 ml of benzene. You then give all gradually 0.1 mole of a benzene solution of bulfenyl chloride to, this being prepared by adding chlorine to pentaerythritol tetra (thioglycolate). Triethylarainhydro chloride is removed from the reaction mixture and the desired product of the! formula

I \ stl

is from the reaction mixture, as described in Example 2, isolated.

The following examples illustrate the invention in more detail and the best method to carry it out, without that they are intended to limit the scope of the invention. With all tested and described rubber approaches, which serve to illustrate the invention, the "Mooney scorch" times were determined using a Mooney plastometer certainly. The time in minutes (tr) that is required

-28- 209830/0983

is that the Mooney reading increases five points above the minimum viscosity is recorded. Longer times indicate the effectiveness of the inhibitor. Longer times in the Mooney scorch test are desirable because they indicate greater procedural security. The curing properties are determined by means of the "Monsanto Oscillating Disk Rheometer", described by Decker, Wise and Guerry in Rubber World, 1962, page 68. In ™ the Eheometer data, R _{me is} "the maximum rotation

III ujt.

moment in rheometer units, % £ the time in minutes to rise two rheometer units above the minimum reading and t _go -t _{2 is} the time difference required to obtain a torque of. $ 90 of max and get tp.

Table I illustrates the results using N- (cyclohexylthio) -benzenesulfonanilide and N- (phenylthio) -fc N-methyl-p-toluenesulfonamide as inhibitors for premature Vulcanization in -approaches of natural rubber, which is a p-phenylenediamine antioxidant and Antiozonant and sulfenamide accelerator with delayed Contains effect. From the results in Table I it can be seen that the inhibitors explained here in the presence of the accelerator and the antioxidant as premature vulcanization inhibitors are fully effective.

209830/0983

Table I.

A. Weight .Parts D. 5 100 B. C. 100 2 Smoked natural
Rubber heads 45 100 100. 45 Flame black (ISAl ¹ ) 3 45 45 3 zinc oxide 2 3 3 2 Stearic acid 5 2 2 Hydrocarbon plasticizers 2 5 5 sulfur 2 2

14-1.3-dimethylbutyl-N'-phenylp-phenylenediamine

N-tert-butyl-2-benzothiazole sulfenamide

IN-Cyclohexylthiobenzenesulfonanilide

α-phenylthio-itf-methyl-ptoluenesulfonamide

Mooney Scorch at 121 ⁰ O

Kheometer at 144 ⁰ C

^t 9O " ^t 2

0.5 0.5 0.5 0.5

0.2 0.4

Max

0.4

27.7 38.8 46.4 47.1

7.6 9.6 11.5 10.8

12.6 12.4 12.6 12.0

64 66 66 69

Results are comparable to those in the table with; Inhibitors of this invention other than those exemplified here listed, obtained, whereby the usefulness of üöx · inhibitors is shown, experiments with regard to the concentration show that the inhibitors in rubber

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209830 / 09S3

BATH

in concentrations of 0.05 to 5 * 0 parts by weight per 100 wt. Parts of rubber, preferably in the range from 0.1 to 3 »0 parts by weight per 100 parts by weight of rubber can be used»

To the improvement obtained over a control batch, which has the composition of batch A, through Incorporation of $ 0.4 precure inhibitor the percentage of the increase in the scorch delay is calculated using the Mooney scorch time of the approach, containing the prevulcanization inhibitor, divided by the Mooney scorch time of the control batch multiplied and subtracted 100. These increases (summarized in Table II) show the percentage the improvement in the scorch delay compared to the control mixture, which contains no inhibitor.

Table II

»% Increase in scorch delay;

N-phenylthio-N-methyl-p-toluenesulfonamide 69

N-cyclohexylthio-p-toluenesulfonamide 75

N-Cyclohexylthio-h-methylbenzenesulfonamide 57

N-cyclohexylthio-iJ-benzylbenzenesulfonamide 40

M- (Phenylthio) -benzenesulfonanilide H4-

li (cyclohexylthio) benzenesulfonanilide 67

N-p-ifitrophenylthio-N-methylmethanesulfonaniide 28

iJ-p-Nitrophenylthio-p ~ toluenesulfonaraid $

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209830/0983

Table II (continued)

. % Increase in

Scoroh delay;

N-phenylthio-N-methyl methanesulfonamide N-cyclohexylthio-N-methylmethanesulfonamide ' N.N · -Diphenyl-ϊΤ.Ν'-dicyclohexylthiosulfondiamide N-sec-butylthio-N-methyl-p-toluenesulfonaramid

The adverse effect of the strongly electronegative nitro substituent can be found in the preceding figures.

Table III illustrates the premature vulcanization inhibitor properties for a styrene-butadiene rubber formulation. The basic preparation is made up of the following ingredients.

Parts by weight

Oil-extended styrene-butadiene rubber with a 37 »5 # highly aromatic content Oil 137 »5

"Intermediate super abrasion furnace

Black "65

Zinc oxide 3

Stearic acid 1

Hydrocarbon vigor 1.5

ii-tert-. Butyl-2-benzothiazole sulfene arid 1.0

H-1.3-diraethylbutyl-N'-phenyl-p-phenylenediamine 2.0

Sulfur 2.0

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209830/0983

0.4 parts by weight of a pre-vulcanization inhibitor are added to the basic preparation was added and the Mooney scorch time was determined at 135 ° C.

Table III

None - (control)

N-Cyclohexylthio-p-toluenesulfonamide

N-cyclohexylthio-N-methylbenzenesulfonamide N-Cyclohexylthio-N-benzylbenzenesulfonamide

N-phenylthiobenzenesulfonanilide N-Cyclohexylthiobenzenesulfonanilide

N-p-nitrophenylthio-N-methyl methanesulfonamide

Mooney Scorch at 135 0 (tr) minutes i_

20.1 23.6 24.6 22.1 22.1 '27.7 22.7

The invention includes all deviations and changes from the examples, which are for the purpose of illustration only were given, insofar as the deviations make use of the general inventive concept.

-Patent claims-

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209830/0983

Claims (1)

- 33 claims: {A method for inhibiting the premature vulcanization of a vulcanizable diene rubber containing a sulfur vulcanizing agent, characterized in that a sufficient amount of a material is introduced to inhibit the premature vulcanization (a) Monomer (s) of the formula where η = 1, 2 or 3 and n ¹ = 1, 2, 3 or 4, η and n 'are at the same time not greater than 1 and - when n ¹ = 1, R "is monovalent and · aryl, where aryl is phenyl, naphthyl or xenyl, substituted aryl, where the substituents are lower alkyl, halogen, lower alkoxy, combinations thereof or with the proviso that when η = 1 and R is a lower alkyl hydrocarbon, nitro sin <H, aryl hydrocarbons with 1 to 20 carbon atoms, phenyl-substituted lower alkyl hydrocarbons, unsubstituted mono- and bio-cycloalkyl with 5 to 12 ring members, lower alkyl-substituted mono- and bicycloalkyl with 5 to 12 ring members and fused phenyl rings / or is a non-aromatic hydrocarbon ring, - when n ¹ = 2, R "contains 1 to 12 carbon atoms -34- 209830/0983 and a divalent radical, namely alkylene, arylene, cycloalkylene and lower alkylene = / OC (CH ₂ ) _nll 7 ₂ ^isi M where η " - 1 or 2, - when n ¹ = 5, R "is lower-G / CH ₂ 00G (CH ₂ -) _{nU _7:,} wherein n '= 1 or 2; - when n '= 4-, R "is C / CH ₂ 00C (CH ₂ -) _nII _7 ₄ , in which n" = 1 or 2, - R 'independently has the same meaning as monovalent R' *, is hydrogen and / or -ANSO ₀ R ¹¹ ", in which ßn R ^"u are the same as monovalent R", A is the same meaning as divalent R "has, R ¹¹¹ is hydrogen, the same meaning as monovalent R" is or R "S, wherein R" has the meaning of monovalent R " Has, - R is an organic radical of valence η, where - when η = 1, R is independently the same meaning as monovalent R "and / or R ^v -rl-," wherein R ^{v is} hydrogen R "' is or has the same meaning as monovalent R "and R" ^{1 has} the same meaning as above, - when η = 2, R has the same meaning as divalent R "has, - when η = 3, R is phenenyl, (b) Polymer (s) with the repeating unit N - A - N - SA ¹ - ö - I I -55- 209830/0983 wherein "R and R" "have the same meaning as monovalent R "have the same meaning as above, and A 'is independently selected from the same group as A will, (c) Polymer (s) with the repeating units -N - SO ₀ R-SO ₀ -NOA ¹ -S R ¹ R ¹ wherein R ¹ and A ^{1 have} the same meaning as above and R has the same meaning as above when it is divalent, and (d) Polymer (s) with the repeating units R ^V R ^V wherein R ^v and A have the same meaning as above. 2. The method according to claim 1 characterized in that the rubber contains an organic Vulkanisationsbeschleunigungsmittel and is used as _o vulcanizing agent is elemental sulfur. 3. The method according to claim 2, characterized in that that an inhibitor is a mono- H
mer of the formula R-SO ₀ N-SR ¹¹ , where R and R "monovalent carbon • -36- 209830/0983 Hydrogen are and elemental sulfur is used as a vulcanizing agent. 4. The method according to claim 2, characterized that the inhibitor is a monomer of the formula R-OO ₂ N-SR ", in which R, R ¹ and R" are monovalent hydrocarbons, and elemental sulfur is used as the vulcanizing agent. 5. The method according to claim 2, characterized in that the inhibitor is a monomer of the formula R ^v -N-S0 _o N-SR ^M used, where R "means R ¹ " R ¹ is monovalent R ", R and R 'are hydrogen or are selected from the same group as monovalent R" and R " ^{1 is} hydrogen, monovalent R" or R ¹¹ S-, where R "is monovalent R" . 6. The method according to claim 2, characterized that the inhibitor is a monomer of the formula R-SO ₀ N AN-SO ₀ R "" is used, where R and R "" SR "R" ¹ ' have the meaning of monovalent R ", R" ^{1 is} hydrogen, monovalent R "or R ¹¹ S-, wherein R" has the meaning of monovalent R ". 7. The method according to claim 2 since g β - -37-209830 / 0983 J216481O AA AA t ~ * W -U Vf AA AA X- * W · \ A> ^ AW lit ^ A AA I ^ .JU. ttj -ki.A AJk »A · Jw * <A. W VVJ- V ^ JJ2 A AV- / UV of the formula MR-SO ₂ N (R ¹ ) -SJ ₂ R "is used, where R is the indicates that the inhibitor is a monomer Has the meaning of monovalent R ", R ^{1 is} hydrogen or has the meaning of monovalent R" and R "is divalent with the meaning of divalent R". 8. The method according to claim 2, characterized in that the inhibitor is a polymer with the recurring unit R ^v R ^V used. 9. Vulcanizable diene rubber preparation with improved Resistance to pre-vulcanization, characterized in that the vulcanizable Diene rubber, a sulfur vulcanization agent, an organic vulcanization accelerator and contains a material in an amount effective to inhibit prevulcanization, viz (a) Monomeree) of the formula where η = 1, 2 or 3 and n ¹ = 1, 2, 3 or 4, η and n ^{1 are} at the same time not greater than 1 and - when η '= 1, R "is monovalent, namely aryl, in which -38- 209830/0983 Aryl is phenyl, naphthyl or xenyl, substituted aryl, where the substituents are lower alkyl, halogen, lower alkoxy, Korabinations of the same or with the proviso that if η = 1 and R is a lower alkyl carbon dioxide, tfitro sand ,, alkyl hydrocarbon. with 1 to 20 carbon atoms, Phenyl-substituted lower alkyl hydrocarbon, unsubst it ensiles mono- and bicycloalkyl with 5 to 12 ring members, lower alkyl substituted mono- and isicycloalkyl with 5 to 12 ring members and fused bicyclic rings of phenyl and / or a non-aromatic Is a hydrocarbon ring, - when n ¹ · = 2, R "contains 1 to 12 carbon atoms and a divalent radical, namely alkylene, arylene, cycloalkylene and lower alkylene = ^ ÖbO (CH ₂ ) _ne 7 ₂ , in which η" = 1 or 2 , - if n ¹ = 3, R "Ni ^ g _n5 , where3? in n" = - 1 or 2, - when n '= 4, R "is G / GH ₂ 00C (CH2-) _n " _7 ₄ , where n "= ™ 1 or 2 ,. - R ¹ independently has the same meaning as monovalent R " is hydrogen and / or -ANSO ₀ R ¹¹¹¹ , wherein ι <- E "' R ^{"1 has} the same meaning as monovalent R" has a "has, S" has the same meaning as divalent R ¹ is hydrogen, the same meaning as monovalent R "is or R ¹¹ is S, wherein R" is monovalent R "has, 209830/0983 - R is an organic radical of valence ii, where - when η = 1, R independently has the same meaning v. ^: ie monovalent R "and / or R ^v -N-, wherein R ^{v is} hydrogen Match meanings like monovalent R "has and R" 'die has the same meaning as before, - if η = 2, R has the same meaning as divalent R ", - when η = 3, R is phenenyl, (b) polymer (s) with dev ^ repeating unit -NAN-SA ¹ -S-SO ₂ R wherein R and R ^H "have the same meaning as monovalent R", A has the same meaning as above and A ^{1 is} independently selected from the same group as A, (c) Polymerisatee) with the repeating units N - S
R ¹ wherein R ¹ and A ^{1 have} the same meaning as above and R has the same meaning as above when it is divalent, and (d) Polymer (s) with the repeating units R ^V R ^V 209830/0983 -40- wherein R, ^Y and A have the same meaning as above. 10. Preparation according to claim 9, characterized in that the accelerating agent a thiazole accelerator, arylguanidine accelerator, Thiuram sulfide accelerator, dithiocarbamate accelerator or a mixture thereof. 11. Preparation according to claim 10, characterized in that the accelerating agent is a benzothiazole sulfenamide accelerator. 12. Preparation according to claim 11, characterized in that the inhibitor has the formula is wherein R tolyl, phenyl, or lower alkyl and R ¹ m is water material or from the same group as R "is selected and R" are monovalent hydrocarbon. . 1'Y. Preparation according to claim 12, characterized that R "is cyclohexyl. 14-, material characterized by the content of 209830/0983 (a) Monomer (s) of the formula where η = 1, 2 or 5 and η ¹ - 1, 2, 3 or 4, η and n ^{1 are} at the same time not greater than 1 and - when n ¹ = 1, R "is monovalent and" is aryl, where aryl is phenyl, naphthyl or xenyl, substituted aryl, where the substituents are lower alkyl, ilalog, nie'drigalkoxy, combinations thereof or with the proviso that when η = 1 and R is a Niederre galkylkohlenv.'ass only off, nitro, aryl hydrocarbons with 1 to 20 carbon atoms, phenyl-substituted lower alkyl hydrocarbons, unsubstituted mono- and bicycloalkyl with 5 to 1.2 ring members, lower alkyl-substituted mono- and bicycloalkyl with 5 to 12 Ring members and fused bicyclic rings of phenyl and / or a non-aromatic hydrocarbon ring, - when n ¹ '= 2, R "contains 1 to 12 carbon atoms and a divalent radical, namely alkylene, arylene, cycloalkyl on and Niodrigalkylen = / Ö0C (0H ₂ ) _nIi 7p, where η" = 1 or 2 is , - if n ^f = 2, E "l \ ^{T is} lower alkyl-C / ÖH ₂ 00C (CII ₂ -) _nIl _7 ^, where n" = 1 or 2, - if η '- 4 eats, R "is C / ÖH _P OOC (CI1 _P -V _n J ^ ₁ , where n" = 1 or 2 , - K ¹ independently has the same meaning as monovalent R " has, Wanaorütoff and / or -AN3O _? R ^U "is where -42- 209830/0983 bad om _G , _NAL R "" has the same meaning as monovalent R ", A has the same meaning as divalent R", R " ^{1 is} hydrogen, has the same meaning as monovalent R", or R ^{11 is} S, where R "is monovalent R " Has, - R is an organic residue with the valence of η, whereby, - when η = 1, R is independently the same group as monovalent R "is taken and / or R is -N-, wherein R " ¹ R ^{v is} hydrogen or has the same meaning as monovalent R "and R"'has the same meaning as above, - when η * ± 2, R has the same meaning as divalent R "has, - when η = 3, R is phenenyl, (b) Polymer (s) with the repeating units NAN- SA ¹ · -S- I 'I wherein R and R "" have the same meaning as monovalent R ", A has the same meaning as above and A ¹ independently has the same meaning as in group A, (c) Polymer (s) with the repeating units N - SO ₀ R-SO ₀ -NS-A'-S R ¹ R ¹ wherein R 'and A ^{1 have} the same meaning as above -43- 209830/0983 have and E has the same meaning as before if it is divalent, and (d) Polymer (s) with the repeating units R ^V R ^V wherein R ^v and A have the same meaning as above. 15 · Material according to claim 14, characterized in that that it is a monomer of the formula R-SOp-W-SE "is where H and E" are monovalent hydrocarbons are. 16. Material according to claim 14, characterized that it is a monomer of the formula R ' R-SO ₂ -N-SR "is where R, E ¹ and R" are monovalent hydrocarbons. 17o material according to claim 14, characterized in that it is a monomer of the formula R-SO ₀ -WAN-OO ₀ -R ¹ " ¹ , where R and R" ^{1 have} the meaning C., _t C. SR "·
R " of monovalent R ", R" ^{1 is} hydrogen, monovalent R "and / or R ¹¹ S-, wherein R" has the same meaning as monovalent R ". 209830/0983 18. Material according to claim 14, characterized that it is a monomer of the formula (r - SO ₂ N (R ¹ ) -SJ 2 ^RU i ¹³ * »where R has the same meaning as monovalent R ″, R ^{1 has} hydrogen or the meaning of monovalent R "and R" is divalent, where it is has the meaning of divalent R ". 19. Material according to claim 14, characterized in that it is a monomer of the formula • R ¹ N-UCgH .. is where R is an aryl hydrocarbon and R ^{1 is} hydrogen or a hydrocarbon selected from the same group as monovalent R ". 20. Material according to claim 14, characterized in that that it is a monomer of the formula R ¹ R-S0 ₂ ~ NS-phenyl, where R is an aryl hydrocarbon and R ^{1 is} hydrogen or a hydrocarbon from the group such as monovalent R ″. 21. Material according to claim 14, characterized that it is a monomer of the formula R-SO ₂ -N-SR "is where R is lower alkyl, R ^{1 is} hydrogen, phenyl, cyclohexyl or lower alkyl and R" is phenyl or cyclohexyl. 209830/0983 216481Q - 45 22. Material according to claim 14, characterized in that it is a polymer with the R "R ^v _i ι _ repeating unit / -N-SO ₂ -MSAO- / is. 209830/0983 ORIg / jval inspected