JPH0332576B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to rubber compositions that provide vulcanized products with improved physical properties. Methods of vulcanizing diene rubber by heating with sulfur and a vulcanization accelerator have been known for many years. Although this process results in vulcanized products having certain physical properties such as high levels of tensile strength, resilience and fatigue resistance, such vulcanized products have good aging properties. They tend not to have
Apart from the addition of antioxidants to retard oxidative thermal aging, other methods have been proposed to produce vulcanizates with improved aging properties compared to those used in conventional vulcanization. It consists of reducing the proportion of sulfur, increasing the proportion of promoter and partially or completely replacing the sulfur with other crosslinkers. Examples of such cross-linking agents are amine disulfides such as N,N-dithiodimorpholine, bis(sulfenamide) as described in GB 1409953 and US 3847880 and GB 1388279. Mention may be made of compounds consisting of two or more promoter groups linked through organic bridging groups as described in the specification. However, vulcanized rubbers made using such other systems tend to lack some of the advantages of sulfur-cured vulcanized rubbers. For example, lowering the sulfur/accelerator ratio or partially or completely replacing sulfur with amine disulfide results in vulcanizates with poorer dynamic properties.
The use of compounds containing bis(sulfenamide) and two or more promoter groups means that species with promoter action as well as species with cross-linking action are released into the vulcanization system. , thus the freedom for variations in formulation that is possible if the cross-linker and accelerator are added as separate entities is lost. According to the present invention, the inventor has found that by adding certain substances besides sulfur and vulcanization accelerators during the formulation of diene rubber, a vulcanized product with improved properties can be obtained. . These substances have the effect of stabilizing the properties of the vulcanized product when the temperature of the vulcanized product unavoidably remains high for a long period after curing and during the service life of the vulcanized product. , and is referred to herein as a stabilizer substance. The present invention includes a diene rubber, sulfur and a vulcanization accelerator, and further comprises a compound of the formula -S- _SO2R , where R is (a) a group OM, where M is a monovalent metal;
the equivalent of a polyvalent metal, the equivalent of a monovalent ion derived from the addition of a proton to a nitrogenous base, or the equivalent of a polyvalent ion derived from the addition of two or more protons to a nitrogenous base), or (b)
represents an organic group selected from an aliphatic group, a cycloaliphatic group, an aromatic group, a heterocyclic group, and a group that is a combination of two or more of such groups, A vulcanizable rubber composition characterized in that it contains a stabilizer substance having two or more groups, the groups being linked to each other by organic bridging groups or to an organic polymer chain. I will provide a. That is, these groups are the thiosulfate group -S- _SO2OM or the thiosulfonate group -S- _SO2R , where R is the above-mentioned organic group. A vulcanized product can also be obtained by heating the vulcanizable rubber composition of the invention at a vulcanization temperature. U.S. Pat. No. 3,535,249 discloses (a) at least one phenolic antioxidant, (b) at least one neutralizing agent that neutralizes the action of heavy metal ions, and
(c) Antioxidant compositions for polymers comprising at least one reducing agent are disclosed. In such compositions the reducing agent can be an organic or inorganic thiosulfate such as sodium benzylthiosulfate or sodium thiosulfate. According to U.S. Pat. No. 3,732,192, the formula R-
Thiosulfonates of S-SO ₂ R ¹ (wherein R and R ¹ are organic groups such as aryl, alkyl, cycloalkyl and substituted derivatives thereof) contain antiozonants and vulcanization accelerators. Useful for controlling premature vulcanization of vulcanizable diene rubbers. Compared to this prior art, the essential feature of the stabilizer substances used according to the invention is that they contain at least two thiosulfate or thiosulfonate groups. For example, stabilizer substances of the invention may be applied to vulcanized products and their two
Stabilization of the type such as reversion resistance due to functionality or polyfunctionality is not seen with prior art monothiosulfates and monothiosulfonates. Preferred stabilizer materials are those in which the thiosulfate or thiosulfonate group is the first of the bridging groups, respectively.
and polymers in which a thiosulfate or thiosulfonate group is attached to a primary carbon atom in a side chain that is attached to the polymeric backbone. That is, the thiosulfate or thiosulfonate group is usually -CH ₂
Exists in the form -S- _SO2R . The majority of the materials useful as vulcanizate stabilizers according to the invention are new and a further feature of the invention is that they contain two or more of the formula -S- _SO3M , where M is a monovalent equivalent weight of metal or polyvalent metal,
A substance containing a monovalent ion derived by adding a proton to a nitrogenous base or a multivalent ion derived by adding two or more protons to a nitrogenous base. and these substances are compounds in which these groups are bonded by organic bridging groups or polymers in which these groups are bonded to organic polymer chains, provided that the substances are A compound having the formula MO ₃ S-S-X'-S-SO ₃ M in which X' is a -(CH ₂ ) _x - group, where x is an integer with a value of 2 to 7, 10 or 12. ,
−CH ₂ −CH=CH−CH ₂ − group, −CH ₂ COCH ₂ −
group, -CH ₂ CH ₂ OCH ₂ CH ₂ - group, -
CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ − group, or − (CH ₂ )
When representing the n-group nC ₆ H ₄ (CH ₂ ), where n has a value of 1 to 3 and C ₆ H ₄ is p-phenylene, M is not sodium and X' is - When representing a (CH ₂ ) ₇ - group, M is not S-benzylisothiouronium. Stabilizers, which are compounds containing groups of the formula -S- _SO2R linked by organic bridging groups, usually contain two, three
or 4 -S- _SO2R groups. _Examples of _such compounds _include the formula or 4 and X represents the remainder of the bridging group). In compounds having two -S- _SO2R groups, the bridging group is divalent and such compounds can be represented by the formula _RO2S -S-X'-S- _SO2R . In the above formula, X' is, for example, a linear or branched alkylene or alkenylene group, preferably having from 2 to 5 to 40 carbon atoms, more preferably from 5 to 16 carbon atoms. It is possible to have the following. Examples of such groups include, for example, ethylene,
Pentamethylene, hexamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, 3-methyl-1,5-pentylene and 1,
6-hex-2-enylene is mentioned. In another embodiment, the divalent bridging group may be an alkylene or alkenylene group with one or more aryl (eg, phenyl) substituents. An example of such a group is 2-phenyl-1,4-butylene. In other cases, X' has a structure containing two or more alkylene units, in which pairs of such units are separated via an oxygen or sulfur atom or -
SO ₂ −, −NH−, −NH ⁺ ₂ −, −N (C _1-6 alkyl)
It is bonded via a - or -COO- group or via an arylene or cycloalkylene group. A representative example of such a structure is the following formula -CH ₂ )a-O-(CH ₂ )a- -(CH ₂ )a-O-CH ₂ -O-(CH ₂ )a- -(CH ₂ )b- Cyclohexylene -( _CH2 )b- -( _CH2 )c-COO-( _CH2 )a- -( _CH2 )c-COO-Y -OOC-( _CH2 )c-, [In the formula, each a and each c independently represents an integer of 2 to 20, each b independently represents an integer of 1 to 10, and Y is a -( _CH2 )c- group or -
(CH ₂ CH ₂ O) dCH ₂ CH ₂ - group (where d is 1 to 5
represents an integer of ). Preferred values for a are 3 to 8, preferred values for b are 1 to 4, and preferred values for c are 3 to 18, particularly preferably 3 to 12. Other examples of bridging groups X' include the formulas -( _CH2 ) _c - _SO2- (CH2)c--( _CH2 )c-NH-( _CH2 )c- and -( _CH2 )c- NH ⁺ ₂ −(CH ₂ )c− (wherein each c is independently 2 to 20, preferably 3
-18, more preferably 3-12). If the value of a, b or c exceeds 2, the polymethylene group can be linear or branched, but the terminal carbon atom to which the -SO ₂ OR group is attached is Preferably, it is a class carbon atom. Examples of stabilizer compounds having 3 or 4 thiosulfate or thiosulfonate groups include, for example, 3 or 4 -C _n H _2n -S-
The SO ₂ R group (where m typically has a value of 3 to 6) is present in an aromatic nucleus (which may further contain other substituents), such as a benzene nucleus or a naphthalene nucleus. or present as a substituent on one or more nuclei of di- or tri-nuclear aromatic compounds, such as biphenyl, diphenyl ether, diphenyl sulfone or benzophenone. Yet another example of a trivalent bridging group includes the formula ^-A1 - _OCH2CH ( ^OA1- ) _CH2OA1 ^- AC( ^AOOCA1- ) ₃ , where each ^A1 independently represents, for example, alkylene groups such as _C2-18 alkylene, preferably _C3-12 alkylene and A is _C1-6 alkyl), and also groups of the formula N[( _CH2 )-c] ₃ and H ⁺ N[(CH ₂ )-)] ₃ (wherein each c is independently 2 to 20, preferably 3
18, particularly preferably 3 to 12). Further examples of tetravalent bridging groups include formulas C(A ¹ )-) ₄ , Si(A ¹ )-) ₄ , and (A') ₃ Si-O-Si(A') ₃ (in the formula , A ¹ has the above definition) and a group having the formula C[CH ₂ OCO(CH ₂ ) c] ₄ where each c is independently 2-20, preferably 3
-18, more preferably 3-12). Examples of polymers include, for example, the formula The polymer represented by and the polymer chain are

【formula】

[expression] and

wherein R' represents a C _1-12 alkyl group and c has an integer value from 2 to 20, and at least 10% of the units in the polymer , preferably at least 20%, for example 25
Mention may be made of esterified or partially esterified polyvinyl alcohols containing ~75% -S- _SO2R groups. The thiosulfate or thiosulfonate group is attached to a bridging group of the aforementioned type in which two or more alkylene units are linked via atoms or groups, or the thiosulfate or thiosulfonate group is pendant from the polymeric chain. The optimal number of carbon atoms in the alkylene unit attached to the unit, the optimal number of m in the formula -C _n H _2n -S-SO ₂ R and the optimal number of carbon atoms in the group A ¹ are determined by Due to the remainder of the structure. For a compound to act as an effective stabilizer, it appears that the ability to adopt a certain molecular configuration, ie, some degree of flexibility (bendability), is required. A further requirement is that the relative positions of the thiosulfate or thiosulfonate groups should not be such that significant intramolecular cyclization can occur when the rubber composition containing the stabilizer material is heated. That's what it means. For example, compounds in which the bridging group is trimethylene or tetramethylene exhibit little stabilizer activity, which is thought to be due to the tendency of such compounds to cyclize. That is, varying degrees of stabilizer activity may be found among compounds having the above definition, but the method of evaluation described below is conventional and therefore it is important to note that a particular compound may be Determining whether a composition is usefully stabilized is a matter of simple and minimal experimentation for those skilled in the art. If M in the above formula of the stabilizer substance represents a monovalent metal, this can be, for example, an alkali metal such as sodium, lithium or potassium. Sodium is the more preferred alkali metal. Alternatively, M can represent an equivalent of a polyvalent metal such as magnesium, calcium, barium, zinc, nickel, cobalt or aluminum. When M represents a monovalent ion produced by adding a proton to a nitrogenous base, the nitrogenous base is ammonia or a simple primary, secondary or tertiary amine, i.e. R ² NH ₂ ,R ² R ³ NH or R ² R ³ R ⁴ N [In the formula, each of R ² , R ³ and R ⁴ independently represents an alkyl group (for example, a C _1-20 alkyl group), a C _5-9 cycloalkyl group (e.g. cyclohexyl group) or alkylcycloalkyl group (e.g. methylcyclohexyl group), benzyl group, phenyl group or substituted phenyl group (e.g. tolyl or chlorophenyl group), provided that one of R ² , R ³ and R ⁴ not more than one phenyl group or substituted phenyl group]. The amine is preferably relatively weakly basic.
Examples of these include weak bases such as tertiary alkyl groups, such as tertiary alkyl groups having 4 to 12 carbon atoms (e.g. tertiary butyl, tertiary alkyl groups, etc.).
Mention may be made of amines which are present as a result of steric hindrance around the nitrogen atom due to the presence of a tertiary amyl group or a 1,1,3,3-tetramethylbutyl group. Examples of such amines include secondary amines.
R ² R ³ NH (wherein one of R ² and R ³ is the third
and the other is a benzyl group, a cyclohexyl group, or an alkylcyclohexyl group). Or again,
Both R ² and R ³ can be tertiary alkyl groups. Yet another example is a tertiary amine in which R ² is a tertiary alkyl group and R ³ and R ⁴ are benzyl groups. Other suitable weakly basic amines are primary amines.
R ² NH ₂ (wherein R ² is a phenyl group or substituted phenyl group) and secondary amines R ² R ³ NH (wherein R ²
is a phenyl group or a substituted phenyl group, and
^R3 is a _C1-20 alkyl group, preferably a _C1-12 alkyl group). Examples of such amines include, for example, aniline, toluidines, N-methylaniline, N-butylaniline and N-isohexylaniline. A special class of such secondary amines are those in which R ² represents a secondary alkyl group, preferably a C _3-12 secondary alkyl group or a cyclohexyl group and R ³ represents a 4-phenylaminophenyl group. Consisting of Examples of these amines include, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-secondary butyl-N'-phenyl-p-phenylenediamine,
N-1,3-dimethylbutyl-N'-phenyl-
Mention may be made of p-phenylenediamine, N-1,4-dimethylpentyl-N'-phenyl-p-phenylenediamine and N-cyclohexyl-N'-phenyl-p-phenylenediamine. Such amines act as monoacid bases despite the presence of the second nitrogen atom in the 4-phenylaminophenyl group. This is because this second nitrogen atom actually has no basicity at all. Other examples of nitrogenous bases that form the thiosulfate salts of the present invention include, for example, [wherein each R ² is independently hydrogen, an alkyl group (e.g. a C _1-20 alkyl group), a C _5-9 cycloalkyl group or an alkylcycloalkyl group, a benzyl group, a phenyl group or a substituted phenyl group (e.g. tolyl group) and substituted guanidines of the formula (In the formula, R ⁵ represents a C _1-20 alkyl group, a C _5-9 cycloalkyl group, an alkylcycloalkyl group, or a benzyl group). Specific examples of substituted guanidines include diphenylguanidine and di-O-tolylguanidine, and specific examples of substituted isothioureas include S-ethylisothiourea and S-benzylisothiourea. Examples of bases from which such ions can be derived, where M represents the equivalent of a polyvalent cation produced by addition of two or more protons to nitrogen chlorine, include, for example, those of the formula R ² NH-A- ^NHR2 [wherein A is an alkylene group -( _CH2 )c-, where c has a value from 2 to 20, preferably from 2 to 12, and this group is linear or branched. ) or a phenylene group (e.g. m-phenylene group or p-phenylene group) and each R ² independently represents an alkyl group (e.g. a C _1-20 alkyl group), a C _5-9 cycloalkyl or alkyl group. a cycloalkyl group, benzyl group, phenyl group or substituted phenyl group, provided that when A is a phenylene group, R ² is neither a phenyl group nor a substituted phenyl group], an N,N'-disubstituted alkylene diamine; Mention may be made of alkylene diamines, phenylene diamines and N,N'-disubstituted phenylene diamines. In preferred amines where A represents an alkylene group, R ² is a tertiary alkyl group (e.g. tertiary
butyl group, tertiary amyl group or 1,1,3,
(3-tetramethylbutyl group) or phenyl group. Examples of such amines include N,
N'-diphenylethylenediamine, N,N'-ditert-butyl-1,4-tetramethylenediamine and N,N'-bis(1,1,3,3-tetramethylbutyl)-1,6- Examples include hexamethylene diamine. In preferred amines in which A represents a phenylene group, R ² represents a secondary alkyl group, preferably a C _3-12 secondary
alkyl group or cyclohexyl group. Examples of such amines include, for example, N,N'-di-sec-butyl-p-phenylenediamine, N,
N'-bis(1,3-dimethylbutyl)-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,
N'-bis(1-ethyl-3-methylpentyl)-
p-phenylenediamine, N,N'-bis(1-
Examples include methylheptyl)-4-phenylenediamine and N,N'-dicyclohexyl-p-phenylenediamine. Examples of possible bases also include the formula R ² NH-(A'-NH)n-A'NHR ² , where A' represents an alkylene group having 2 to 8 carbon atoms and n represents 1 to 8 carbon atoms. 5 and each R ² independently represents a C _1-20 alkyl group, a C _5-9 cycloalkyl or alkylcycloalkyl group, a benzyl group, a phenyl group or a substituted phenyl group) You can also give In other cases the nitrogen of the nitrogenous base is part of a heterocycle. The base can be a single ring, such as pyridine, or a compound in which a nitrogen-containing heterocycle is fused to another ring, such as quinoline. Furthermore, the heterocycle may be saturated, as in the case of morpholine or piperidine, or it may contain one or more double bonds, as in the case of pyrroline or 1,2-dihydroquinoline, for example. sell. Among the compounds where M represents such a base,
Preferred for use as vulcanizate stabilizers are compounds in which M represents a 1,2-dihydroquinolinium ion, optionally with ring substituents. Examples of such ions include 2,2,4-trimethyl-1,2-dihydroquinolinium, 2,2,4-trimethyl-6-(C _1-12
alkoxy)-1,2-dihydroquinolinium (e.g. 2,2,4-trimethyl-6-ethoxy-1,2-dihydroquinolinium), 2,2,
4-trimethyl-6-( _C1-18 alkyl)-1,2
-dihydroquinolinium (e.g. 2,2,4-
trimethyl-6-dodecyl-1,2-dihydroquinolinium) and 2,4-diethyl-2-methyl-1,2-dihydroquinolinium. Other types of bases that generate divalent cations by the addition of two protons have the general formula and [In the formula, A ² is -(CH ₂ )c- group (here, c is 2
~20, preferably from 3 to 12 and the group can be linear or branched),
or _C2-20 alkenylene or alkadienylene group (for example, but-2-enylene or octa-2,6-dienylene group). These bases are bis(isothiouronium) ion and bis(guanidinium) respectively
Generate ions. When R in the -S- _SO2R group of the stabilizer compound is an organic group, examples of aliphatic groups from which R may be selected include straight-chain and branched alkyl and alkenyl groups, more preferably having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, sec-butyl, tertiary-butyl, isoamyl, tertiary amyl, n-hexyl,
Mention may be made of hex-3-enyl, n-heptyl, n-octyl, 2-ethylhexyl and the decyl, dodecyl, pentadecyl and octadecyl groups. When R is cycloaliphatic it is usually a group having 5 to 8 ring carbon atoms which may be saturated or contain one or two olefinic bonds, such as a cyclopentyl, cyclohexyl or cyclohexenyl group. . Aromatic radicals R can be, for example, phenyl, naphthyl or biphenyl, and heterocyclic radicals can be, for example, pyridyl, imidazole-2
-yl group or thiazol-2-yl group. Examples of groups which are combinations of two or more of the above groups include, for example, alkylcycloalkyl groups (such as methylcyclohexyl), alkylaryl groups (such as tolyl, dimethylphenyl and ethylphenyl), arylalkyl groups (such as tolyl, dimethylphenyl and ethylphenyl), Examples include benzyl and phenethyl) and fused-ring aromatic-heterocyclic groups (such as quinolyl, benzimidazol-2-yl and benzothiazol-2-yl). Also included are groups having as substituents atoms or groups such as halogen (eg chlorine or bromine) or nitro, hydroxyl, carboxy, carbalkoxyl or alkylcarbonyl. Examples include chloroethyl, chlorotolyl, hydroxyphenyl, carboxypyridyl and nitrobenzothiazolyl. The stabilizer substances of the present invention, which are alkali metal salts, can be stabilized by reaction with an alkali metal thiosulfate.
They may be prepared by nucleophilic substitution of a halogen (usually chlorine or bromine) in a suitable starting material having 1 replaceable halogen atoms. Although sodium thiosulfate is preferred for economic reasons,
Other alkali metal thiosulfates such as lithium thiosulfate, potassium thiosulfate or rubidium thiosulfate may also be used. _{For stabilizer compounds with two thiosulfate} groups, the reaction is: can be shown. In prior art examples of processes of the type described above, the reaction is usually carried out in water or an aqueous alcoholic medium under reflux (for example "Rev. Pure
and Applied Chemistry” Volume 12, Page 72 (1962)
and “J.Chem.Soc.” 1965, p. 2901). The above reaction tends to be slow, especially when the halogen to be replaced is chlorine, and we have demonstrated that by carrying out the reaction in an autoclave, the reaction temperature is above the reflux temperature of the aqueous ethanol or methanol mixture at normal pressure. We have found it advantageous to use temperature. For example, this reaction
It may be carried out at a temperature of 100-150°C, more preferably 120-140°C. At these temperatures the reaction is usually substantially complete in a short time, e.g. 5-20 minutes, but
However, longer reaction times can be used if necessary. We add small amounts (typically 0.05 to 0.2 mole per mole of sodium thiosulfate) to the reaction mixture.
We have found it advantageous to add 50% of sodium sulfite. This has the effect of suppressing the formation of by-products. For solubility reasons, aqueous ethanol or aqueous methanol are generally more suitable reaction media than alcohol alone. Alkali metal thiosulfates, especially sodium thiosulfate, have sufficient solubility only in ethylene glycol and diethylene glycol, so that these glycols act as suitable reaction media. These glycols are therefore preferred reaction media when the halogen-containing starting materials contain hydrolyzable groups. When containing water of crystallization, e.g.
The water introduced with the thiosulfate reactant, which is Na ₂ S ₂ O ₃ 5H ₂ O, can be removed by distillation before adding the halide reactant. Furthermore, when using ethylene glycol or diethylene glycol, it is not necessarily necessary to operate under pressure in order to achieve reaction temperatures of 100° C. or higher. The amount of glycol used in the reaction medium should dissolve at least some of the alkali metal thiosulfate salt, but it is preferred to avoid more glycol than is necessary to bring it into solution. A glycol (or mixture of glycols) is essentially a single component of the reaction medium, although other miscible organic solvents need not be excluded if the glycol mixture is a major component of the reaction medium. preferable. The reaction time varies depending on the reaction temperature and the ease of substitution of the halogen atom. Typical reaction times for replacing chlorine at temperatures of 100-150°C are 60-15 minutes. The alkali metal halide as a by-product in the process of the present invention is insoluble in the reaction medium and precipitates as the reaction progresses. It can be removed by filtering the reaction mixture once the reaction is complete. The liquid is a solution of organic thiosulfate alkali metal salt. From this, the organic thiosulfate alkali metal salt can be precipitated by mixing with a solvent that is miscible with the glycol but is essentially a non-solvent for the alkali metal salt. An example of such a solvent is isopropanol. The alkali metal salts of organic thiosulfates thus produced and isolated may contain glycols relatively tightly bound in the crystals. As long as this thiosulfate is intended to be used as a rubber stabilizer, the presence of a small amount of glycol has no adverse effect;
If desired, the glycol can be removed by recrystallization from a non-glycolic solvent. The stabilizers of the present invention in which M represents potassium can be prepared by using potassium thiosulfate as the halogen substitution reaction component in the reaction described above. However, in the preparation of compounds with other M, it is often most convenient to prepare the sodium salt as an intermediate and then to replace the sodium with the other cation required. If the required product is water soluble such substitution may be carried out using a cation exchange resin carrying the other cations required. For example, when a solution of a sodium salt of organic thiosulfate is introduced into a column of a cation exchange resin whose exchangeable ion is nickel, a leachate (percolate) is produced.
as a solution of the nickel salt of the organic thiosulfate. By essentially the same method, magnesium, calcium, zinc, cobalt and guanidium salts of organic thiosulfates can be prepared using cation exchange resins that carry the required cations in the product. . Salts in solid form, often containing water of crystallization, are obtained by evaporation of the leachate. Barium salts of organic thiosulfates are less soluble in water than alkali metals and certain other metal salts, and the resulting solution can be crystallized by mixing hot concentrated solutions of barium chloride and sodium organic thiosulfate salts by cooling. let These barium salts are useful as intermediates in the production of other metal salts by metathesis. Addition of an aqueous solution of a sulfate of another metal to an aqueous solution of barium salt (which is obtained using a sufficient volume of water) results in the precipitation of barium sulfate. This is removed by filtration to give a liquid which is evaporated to give the desired metal salt of the organic thiosulfate. Ammonium salts and certain substituted ammonium salts may also be prepared by this operation. To prepare the stabilizer material of the invention, where M represents the equivalent of a monovalent ion produced by the addition of a proton to an organic nitrogen base or a multivalent ion produced by the addition of two or more protons,
Metathesis using alkali metal salts, especially sodium salts, and salts of nitrogenous bases with strong mineral acids, such as hydrochlorides, hydrobromides or sulfates, of organic thiosulfates as reaction components can be used. The by-product is an alkali metal salt of a strong mineral acid, such as sodium chloride or sodium sulfate, and its separation from the required product is usually directly dependent on their different solubility in the chosen solvent. It will be done. For example, sodium salts of organic thiosulfates are soluble in warm methanol to a limited extent, as are sulfates of certain amines, whereas sodium sulfate is essentially insoluble in methanol. Mixing a warm methanol solution of the sodium salt of the organic thiosulfate with a warm methanol solution of the amine sulfate precipitates sodium sulfate, which can be separated from the amine salt of the organic thiosulfate in solution by filtration. The amine salt itself is obtained by evaporating the solvent from the liquid. This method uses amine
Salts of R ² R ³ NH (wherein R ² represents a secondary alkyl group or a cyclohexyl group and R ³ represents a 4-phenylamino group) and 1,2-dihydroquinolites optionally substituted with cations. It can be used to make salts that are nium ions. In other cases, the amine salt of the organic thiosulfate is relatively insoluble in water or an aqueous alcohol solution and can be crystallized from a solution obtained by mixing an aqueous solution of the amine hydrochloride or an aqueous alcohol solution with an aqueous solution of the sodium salt of the organic thiosulfate. do. N-tertiary alkyl-N-benzylammonium salts, diphenylguanidinium salts and certain isothiouronium salts can be prepared by this method. The stabilizer compound in which R in the -S-SO ₂ R group represents an organic group is a nucleophilic compound of the halogen, usually chlorine or bromine, in a suitable starting material having at least two substitutable halogen atoms. (nucleofil) can be produced by substitution. This reaction occurs in compounds with two substitutable halogen atoms,
_{Formula 2RSO 2} ^{SM 2} ₊ ^_ represents an alkali metal ion and Hal represents a halogen).
This type of reaction is known for example in US Pat. No. 3,047,393.
BrX ¹ (where X ¹
is _{a C2-10 alkylene} group) to obtain a compound of the formula ^{R2SO2SX1SSO2R2 ,} where ^R2 is ^a p-tolyl group. . Alternatively, the general method 2 RSO ₂ Cl + HS-X-SH base --→ RSO ₂ -S-X-S-SO ₂ R (wherein R has the meaning as originally defined which also includes the presence of OM) can be used. Specific compounds or classes of compounds useful as vulcanizate stabilizers of the present invention include, for example, pentamethylene bisthiosulfate, hexamethylene bisthiosulfate, heptamethylene bisthiosulfate, octamethylene bisthiosulfate, sulfate, nonamethylene bisthiosulfate, decamethylene bisthiosulfate, dodecamethylene bisthiosulfate and hexadecamethylene bisthiosulfate and as cations sodium, magnesium, calcium, barium, zinc, Salts with cobalt and nickel, ammonium as cation, N (C _4-12 tertiary
alkyl)-N-benzylammonium, such as N-tert-butyl-N'-benzylammonium and N-(1,1,3,3-tetramethylbutyl)-N-benzylammonium, N-isopropyl-N-( 4-phenylaminophenyl) ammonium, N-(1,3-dimethylbutyl)-N
-(4-phenylaminophenyl)ammonium,
N-cyclohexyl-N-(4-phenylaminophenyl)ammonium, 2,2,4-trimethyl-1,2-dihydroquinolinium, 6-ethoxy-2,2,4-trimethyl-1,2- Dihydroquinolinium, salt with guanidium and benzylisothiouronium, with the formula R ² N ⁺ _H2 −A−N ⁺ _H2 R ² as a divalent cation, where A represents p-phenylene and R ²
is a C _3-12 secondary alkyl group, such as a 1,4-dimethylpentyl group) and the formula [(NH ₂ ) ₂ CS(CH ₂ ) cSC(NH ₂ ) ₂ ] ⁺⁺ [where c is 2 to 12 such that (CH ₂ )c represents, for example, tetramethylene, pentamethylene, hexamethylene, octamethylene or decamethylene.
Salts with ions having any of the integer values of . Other types of compounds useful as vulcanized rubber stabilizers in the present invention include the compounds O[( _CH2 ) _a'S2O3Na ] ₂ , where a' is a value of 3, ₄ , 5, and 6. ) and compounds Compound ・CH ₂ [O(CH ₂ )a′S ₂ O ₃ Na] ₂ (wherein a′ has any of the values of 3, 4, 5 and 6), Compound C ₆ H ₁₀ [( CH ₂ ) b′S ₂ O ₃ Na], where c′ has any of the values 1, 2, 3 or 4 and C ₆ H ₁₀ is cyclohexamethylene, the compound NaO ₃ S ₂ (CH ₂ )c′COO (CH ₂ )a′S ₂ O ₃ Na (where c′ is an integer value from 3 to 10 with any of the values 3, 4, 5, and 6 for a′ ), the compound NaO ₃ S ₂ (CH ₂ )c′COO(CH ₂ ) c″OOC(CH ₂ )c′S ₂ O ₃ Na (where each c′ is 2 for c″ having any integer value from 3 to ₁₀ with any _integer value from ~12), the _{compound NaO3S2} ( _CH2 )c'COO( _CH2CH2O )d' _CH2CH2OOC ( CH ₂ ) c′S ₂ O ₃ Na (wherein each c′ has any of the integer values from 3 to 10 with any of the values of 1, 2 and 3 for d′) and the corresponding potassium salt , magnesium salt, calcium salt, barium salt, zinc salt, nickel salt and cobalt salt, compound O(CH ₂ )a′S ₂ O ₃ M ₂ (where a′ is any of the values 3, 4, 5 and 6) ) and the compound MO ₃ S ₂ (CH ₂ )c′COO (CH ₂ )a′S ₂ O ₃ M [with any of the values 3, 4, 5 and 6 for a′ in the formula ' has any integer value from 3 to 10 and in each case M is the cation N( _C4-12 tertiary alkyl)-N-benzylammonium, such as N-tert-butyl-N'- Benzyl ammonium and N-[1,1,3,3-tetramethylbutyl)-N-benzylammonium, N-isopropyl-N-(4-phenylaminophenyl) ammonium, N-(1,3-dimethylbutyl) )-N
-(phenylaminophenyl)ammonium, N
-Cyclohexyl-N-(4-phenylaminophenyl)ammonium, 2,2,4-trimethyl-1,2-dihydroquinolinium, 6-ethoxy-2,2,4-trimethyl-1,2-dihydro Equivalents of quinolinium, guanidium and benzylisothiouronium and divalent cations R ² N ⁺ _H2 −A−N ⁺ _H2 R ² where A represents p-phenylene and
^R2 is a _C3-12 secondary alkyl group, e.g. 1,4-dimethylpentyl group) and a divalent cation [( _NH2 ) _2CS ( _CH2 )cSC( _NH2 ) ₂ ] ⁺⁺ (formula where c has any integer value from 2 to ₁₂ ], the compound _NaO3S2 -[( _CH2 ) _4O- ]m ( _{CH2 ) 4S2O3Na m} =1 −10 CH ₃ N [(CH ₂ ) ₃ S ₂ O ₃ Na] ₂ Pentamethylenebis(phenylthiolsulfonate), hexamethylenebis(phenylthiolsulfonate), octamethylenebis(O-tolylthiolsulfonate), decamethylenebis(p-tolylthiolsulfonate), decamethylenebis(methylthiolsulfonate) , decamethylene bis(p-chlorophenylthiol sulfonate ₎ , formula _MO3S2- ( _CH2 )c- _SO2- ( _CH2 ) _cS2O3M , _where M represents sodium or 2
M together represent zinc, nickel or cobalt and each c has an integer value from 3 to 12 ₎ and the formula _MO3S2- ( _CH2 )c-NH-( _CH2 )c-
_{S2O3M or} [ _MO3S2- ( _CH2 )c- _NH2- ( _CH2 ) _c-
S ₂ O ₃ M] ⁺ Hal ^- (wherein M represents sodium or two M together represent zinc, nickel or cobalt, each c has an integer value from 3 to 12 and Hal ^-
is a compound having a halide ion, such as a chloride ion or a bromide ion. The stabilizer materials are particularly effective in compositions where the rubber is cis-polyisoprene, either natural or synthetic, and in blends containing at least 25% by weight cis-polyisoprene with other rubbers. If it is a blend, the rubber is at least
Preferably it contains 40% by weight of cis-polyisoprene, more preferably at least 60% by weight. Examples of other rubbers that may be blended with cis-polyisoprene include, for example, poly-1,3-butadiene, copolymers of 1,3-butadiene and other monomers such as styrene, acrylonitrile, isobutylene and methyl methacrylate, and Examples include ethylene-propylene-diene terpolymers. The amount of stabilizer compound used in the compositions of the invention is usually 1 to 5 parts by weight, such as 1.5 to 5 parts by weight, preferably 2 to 4 parts by weight, per 100 parts by weight of rubber. In the compositions of the invention, the essential vulcanizing agent is sulfur, but other vulcanizing agents, such as amine disulfides, need not be excluded. The amount of sulfur in the composition is typically 2 to 3 parts by weight per 100 parts of rubber, but smaller or greater amounts may be used, such as 1 to 5 parts by weight on the same basis. A single accelerator or a mixture of accelerators may be used in the compositions of the invention. Examples of these include thiazole-based promoters such as 2-mercaptobenzothiazole, bis(2-benzothiazolyl) disulfide, benzothiazole-2-sulfenamides (e.g. N-isopropyl-
Benzothiazole-2-sulfenamide, N-
Tertiary butyl-benzothiazole-2-sulfenamide, N-cyclohexylbenzothiazole-2-sulfenamide, N,N-diisopropyl-benzothiazole-2-sulfenamide,
N,N-dicyclohexyl-benzothiazole-
2-sulfenamide) and 2(morpholinothio)benzothiazole, thiocarbamylsulfenamides (e.g. N,N-dimethyl-N',
N'-dicyclohexyl-thiocarbamylsulfenamide) and N(morpholinothiocarbonylthio)morpholine. Mixtures of thiazole-based promoters and diphenylguanidine may be used. Preferred accelerators are benzothiazole-2-sulfenamides. In the compositions of the invention these are usually 0.5 parts per 100 parts by weight of rubber.
Used in an amount of ~1.5 parts by weight. The vulcanized products used in the invention can be incorporated into the rubber in conventional mixing operations, for example by adding them into a Banbury mixer or adding them to the rubber on a mill. Usually, in the case of liquid or low-melting solid vulcanizate stabilizers no special precautions are required to obtain good dispersibility. However, when using higher melting point vulcanizate stabilizers it is recommended that they be ground to a fine powder, preferably to a particle size of 70 μm or less to ensure proper dispersibility. be done. Such powders may be treated to suppress dust, for example by the addition of oils, or they may be mixed with a binder, such as a polymer latex, and made into granules or pellets containing up to 5% by weight of binder. They can also be prepared as predispersions in certain rubbery polymers, such as EPDM or ethylene-vinyl acetate rubber, for example from 15 to 50% by weight.
may contain polymers of The rubber stock consists of reinforced carbon black, pigments such as titanium dioxide and silicon dioxide, metal oxide activators such as zinc oxide and magnesium oxide, stearic acid,
It may contain hydrocarbon softeners and extender oils, amine, ether and phenolic antioxidants, phenylene diamine anti-degradants and adhesives. The feedstock may also contain pre-vulcanization inhibitors, but their use is unnecessary in many feedstocks. In the following examples, the vulcanization properties are described in "Rubber World" by Decker Wise and Guerry et al. 1962.
The vulcanization temperature was measured using the Monsanto vibrating disc rheometer described in the December issue, page 68, at the vulcanization temperature shown in the table. Time required to reach maximum torque (maximum modulus) from rheometer data (tmax)
was recorded. The vulcanized products were prepared by press vulcanization at selected temperatures for the times indicated by the rheometer data to obtain maximum cure. Other vulcanization products were produced at the same temperature, but
However, it was held at this temperature for an extended period of time. Both types of vulcanized products were subjected to conventional physical testing procedures. Fatigue vs. failure measurements were carried out in Paper No. 21, DKG
Meeting, Wiesbaden' (19 May 1971) and resilience measurements were carried out in accordance with 'British Standard 903' Part A8 (1963). "Gutdrich Flexometer" data was obtained by the method of ASTM D623-78 Method A. The base temperature for heat build-up measurements was 50°C and the base temperature for blowout time measurements was 100°C. Various compounds useful as vulcanizate stabilizers were prepared as follows. Production method (i) Decamethylene bisthiosulfate disodium salt dihydrate Sodium thiosulfate pentahydrate (49.6 g, 0.2 mol) and 1,10-dibromodecane (30 g, 0.1
water (100ml) and ethanol (100ml)
The mixture was refluxed for 1.5 hours. The mixture was allowed to cool and the precipitate was filtered off. Drying in air (85°C) yielded decamethylene bisthiosulfate as a hydrated sodium salt with approximately 2 moles of water of hydration. The recrystallized sample gave the following elemental analysis values. Elemental analysis value (as C ₁₀ H ₂₄ Na ₂ O ₈ S ₄ ) C(%) H(%) S(%) Calculated value: 26.90 5.42 28.72 Actual value: 26.79 5.09 28.74 IR absorption (KBr wafer) 3500−3445cm ^{- 1} Crystal water 2920 2845cm ^-1 -CH ₂ - 1220 1050 1040 650cm ^-1 -S SO ₃ = Production method (ii) Hexamethylene bisthiosulfate disodium salt hydrate Reaction between sodium thiosulfate and 1,6-dichlorohexane The procedure was the same as in the above production method (i) except that the reflux time was extended to 6 hours. The reaction mixture was evaporated to dryness under vacuum and the residue was extracted with hot methanol. The sodium chloride was removed and the methanol solution was evaporated to yield the hydrated hexamethylene bisthiosulfate disodium salt. IR absorption 3555−3455cm ^-1 Crystal water 2920 2855 1465cm ^-1 −CH ₂ − 1220 1050 645cm ⁻¹ −S SO ₃ = Process (ii) (a), (b) and (c) Hexamethylene bis(thiosulfate) di Pentamethylene bis(thiosulfate) disodium salt hydrate, ethylene bis(thiosulfate) disodium salt hydrate and 1,4-dimethylenecyclohexyl bis(thiosulfate) in the same manner as described for sodium salt hydrate.
Disodium salt hydrate was produced. Production method (iii) Decamethylene bis(p-tolylthiol sulfonate) p-toluenesulfinate sodium salt (35.6
g, 0.2 mol) and sulfur (6.4 g, 0.2 gram atom) in ethanol (50 ml) containing 0.2 ml of tetrabutylammonium hydroxide (40% aqueous solution). After boiling for 15 minutes, the yellow suspension turned white. Then 1,10-dibromodecane (30g, 0.1
mol) was added and the mixture was refluxed for 3.5 hours. The mixture was then stirred rapidly for 1
of ice water gave a precipitate which was filtered, washed with water and dried under vacuum. Product (45g, 87.5
% yield) melted at 76-82°C. Elemental analysis value (as C ₂₄ H ₃₄ S ₄ O ₄ ) C (%) H (%) S (%) Calculated value: 56.00 6.66 24.91 Actual value: 55.87 6.75 25.06 Significant IR absorption 1330, 1140, 825, 660, 590, 520cm ^-
1 Preparation (iv) Decamethylene bis(methylthiol sulfonate) Decane-1,10- in CH ₂ Cl ₂ (250 ml)
Methylsulfonyl chloride (0.32 mol, 36.8 g) was added dropwise to a mixture of dithiol (0.16 mol, 33.1 g) and triethylamine (0.32 mol, 32.9 g). The temperature was maintained at -15°C during the addition. At the end of the addition, the temperature was allowed to rise to 25°C for 1 hour. 500ml of water was added and the organic phase was separated, dried over anhydrous sodium sulfate and evaporated under vacuum to give a white solid (mp 45-52°C). Yield was 25.0g (43%). Sulfur analysis: (as C ₁₂ H ₂₆ S ₄ O ₄ ) Calculated value: 35.37% Actual value: 34.90% The present invention will be explained below with reference to Examples. In all cases the polymethylene group (CH ₂ ) x (where x is 2
(which is an integer greater than or equal to) is linear. Reference example 1 This reference example is di-n-butyl ether-4,4'-
Bisthiosulfate sodium salt O
The method for producing [(CH ₂ ) ₄ S ₂ O ₃ Na] ₂ will be described. _Na2S2O3.5H2O ( _{1 mol} ) and 250 ml of _ethylene glycol were heated in a distillation apparatus equipped with a mechanical stirrer until the temperature reached 140-142<0>C. Approximately 45 ml of water was distilled at this stage. Then 4,4'-dichlorodibutyl ether (0.5 mol) was added and the mixture was stirred for 25 minutes at 125±3
Stir at ℃. After cooling to 80 °C, strain the mixture
Remove the NaCl and add 3.5 mL of the solution while stirring well.
of 2-propanol. The resulting slurry was cooled to -10°C and the white solid was collected by filtration and dried at room temperature in a vacuum oven until quantitative. The yield of crude product is the theoretical value.
It was 90%. This material was dissolved in 200 ml of hot methanol, filtered and the liquid was poured into a fresh 2-
Purified by pouring into propanol, cooling, filtering and drying. The product obtained had the following properties. Contains 92% of the title compound according to ^1HNMR ,
There are no significant organic or inorganic impurities other than 8% ethylene glycol (presumably present as a co-crystal molecule). ¹ HNMR: The chemical shifts (ppm) for dimethylsilylpropanesulfonic acid sodium salt as an integration standard in D ₂ O were:

[Table] IR spectrum in KBr is 1220cm ^-1 ,
Significant absorption of thiosulfate-S-ester was shown at 1030 cm ^-1 and 640 cm ^-1 . Reference Example 2 This reference example describes the preparation of cyclohexane-1,4-bismethylthiosulfate-S-ester disodium salt. Na ₂ S ₂ O ₃ .5H ₂ O (2 mol) and 400 ml of diethylene glycol were heated in a distillation apparatus with stirring until the temperature reached 132°C. 60ml of water was distilled. A condenser was then fitted for reflux and 1 mole of 1,4-bis(chloromethyl)cyclohexane was added at once. Reflux continued for 50 minutes. The hot mixture was then poured into 1 part methanol and the resulting suspension was filtered while still hot. The liquid was added to 2-propanol in step 4. Cool, filter, and dry as in Reference Example 1, then weigh 300g.
A white powder of (79% of theory) was obtained. The crude product could be crystallized from a methanol/2-propanol mixture. ¹ HNMR: The chemical shifts (ppm) from dimethylsilylpropanesulfonic acid sodium salt in D ₂ O were as follows. Mixture of cis and trans isomers (assignment not determined): 1:3.00, 3.10. IR showed absorptions at 12.20 cm ^-1 , 1035 cm ^-1 and 645 cm ^-1 characteristic of organic ester thiosulfate. Reference example 3 This reference example is NaO ₃ S ₂ (CH ₂ ) ₃ COO
The method for producing (CH ₂ ) ₄ S ₂ O ₃ Na is described. The above compound was prepared by the same procedure as described in Reference Example 1, except that Cl( _CH2 ) _3COO ( _CH2 ) _4Cl was used instead of 4,4'-dichlorodibutyl ether. The dichloro compound is 4- in the presence of zinc chloride.
It was produced by reacting chlorobutyryl chloride with tetrahydrofuran. The reaction time after addition of the dichloro compound to the thiosulfate solution at 125 °C is 0.5 h, and the yield is
The product was 80% crude (by ¹ H NMR), containing 83% disodium salt and 12% ethylene glycol. ¹ HNMR: The chemical shifts in ppm from dimethylsilylpropanesulfonic acid sodium salt in D ₂ O were as follows:

[Table] Reference example 4 This reference example is NaO ₃ S ₂ (CH ₂ ) ₅ COO
The method for producing (CH ₂ ) ₄ S ₂ O ₃ Na is described. The above compound was prepared by the same procedure as described in Reference Example 1, except that Cl( _CH2 ) _5COO ( _CH2 ) _4Cl was used instead of 4,4'-dichlorodibutyl ether. The dichloro compound was prepared by reacting thionyl chloride with ε-caprolactam in the presence of zinc chloride to obtain a reaction mixture containing 6-chlorohexanoyl chloride, to which tetrahydrofuran was then added. The final reaction mixture was washed with aqueous sodium carbonate solution and the required dichloro compound was isolated after drying by distilling the organic phase. The reaction of this dichloro compound with sodium thiosulfate gives a yield of 85% disodium salt and 15%
The product contained 75% of theoretical ethylene glycol.

[Table] Reference example 5 This reference example is NaO ₃ S ₂ (CH ₂ ) ₃ COO (CH ₂ ) ₆ OOC
The method for producing (CH ₂ ) ₃ S ₂ O ₃ Na is described. The above compound uses Cl( _CH2 ) _3COO ( _CH2 ) _6OOC instead of 4,4'-dichlorodibutyl ether.
It was produced in the same manner as in Reference Example 1 except for using (CH ₂ ) ₃ Cl. Dichloro compound is 1,6-
It was produced by the reaction of hexanediol and 4-chlorobutyryl chloride. The dichloro compound was reacted with sodium thiosulfate and the reaction mixture was treated by the procedure of Reference Example 1 to obtain a 30% yield of product containing 83% of the above identified sodium salt and 8% of ethylene glycol. Ta. ¹ HNMR: The chemical shifts in ppm from dimethylsilylpropanesulfonic acid sodium salt in D ₂ O were as follows:

[Table] Reference example 6 This reference example is NaO ₃ S ₂ (CH ₂ ) ₁₀ COO
_The method _for producing ( _CH2CH2O ) _3OC- ( _CH2 ) _10S2O3Na will _be described. This compound is Br( _CH2 ) _10COO
It was produced in the same manner as in Reference Example 2 except that (CH ₂ CH ₂ O) ₃ OC(CH ₂ ) ₁₀ Br was used instead of 1,4-bis(chloromethyl)cyclohexane.
Dibromo compound converts triethylene glycol into 11−
Produced by esterification with bromoundecanoic acid. Reaction of this dibromo compound with sodium thiosulfate gave a 60% yield of product containing 3.5% diethylene glycol. ¹ HNMR: The chemical shifts in ppm for dimethylsilylpropanesulfonic acid sodium salt in _D2O were:

[Table] Reference example 7 This reference example is NaO ₃ S ₂ (CH ₂ ) ₁₀ COO (CH ₂ CH ₂ O) ₂ OC
The method for producing (CH ₂ ) ₁₀ S ₂ O ₃ Na is described. This compound contains Br _{( CH2} ) _10COO (CH2CH2O) _2OC instead of 1,4- ₍ bis(chloromethyl)cyclohexane)
It was produced in the same manner as in Reference Example 2 except that (CH ₂ ) ₁₀ Br was used. The dibromo compound was prepared by esterifying diethylene glycol with 11-bromoundecanoic acid. Reaction of this dibromo compound with sodium thiosulfate gave an 80% yield of product containing 6.5% diethylene glycol. ¹ HNMR: Regarding dimethylsilylpropanesulfonic acid sodium salt in D ₂ O−CD ₃ OD
The chemical shifts expressed in ppm were as follows.

[Table] Reference example 8 This reference example is NaO ₃ S ₂ (CH ₂ ) ₄ OCH ₂ O
The method for producing (CH ₂ ) ₄ S ₂ O ₃ Na is described. This compound was produced in the same manner as in Reference Example 1 except that 4,4'-dichlorobutyl formal was used instead of 4,4'-dichlorodibutyl ether. 4,4'-dichlorobutyl formal was prepared from formaldehyde, HCl and tetrahydrofuran. Sodium thiosulfate and 4,
Reaction with 4'-dichlorobutyl formal gave an 80% yield of product containing 13% ethylene glycol. ¹ HNMR: The chemical shifts in ppm for dimethylsilylpropanesulfonic acid sodium salt in _D2O were:

Table Reference Example 9 This reference example describes a general method for the preparation of novel compounds of the invention which are nickel or cobalt salts. 200 g of commercial cation exchange resin in H ⁺ form was placed in a glass column and 60 g of NiSO ₄ 6H ₂ O or CoCl _{2.6H 2} O in 100 ml water.
Treat with a solution of The column is then washed with distilled water until the eluate is colorless and neutral. Then
A solution of 10 g of sodium bisthiosulfate salt in 100 ml of water is slowly passed through the column, followed by 100 ml of distilled water. The eluate is evaporated under vacuum to obtain quantitative yields of nickel or cobalt salts based on the sodium salt. This operation produces the following nickel salt and cobalt salt. O [(CH ₂ ) ₄ S ₂ O ₃ ] ₂ Ni, O [(CH ₂ ) ₄ S ₂ O ₃ ] ₂ CO,
CH ₂ [O(CH ₂ ) ₄ S ₂ O ₃ ] Ni, CH ₂ [O(CH ₂ ) ₄ S ₂ O ₃ ]
Co, C ₆ H ₁₀ (CH ₂ S ₂ O ₃ ) ₂ Ni, C ₆ H ₁₀
(CH ₂ S ₂ O ₃ ) ₂ Co, [O ₃ S ₂ (CH ₂ ) ₃ COO(CH ₂ ) ₄ S ₂ O ₃ ]
Ni, [O ₃ S ₂ (CH ₂ ) ₃ COO (CH ₂ ) ₄ S ₂ O ₃ ]Co, [O ₃ S ₂
(CH ₂ ) ₅ COO (CH ₂ ) ₄ S ₂ O ₃ ]Ni, [O ₃ S ₂
(CH ₂ ) ₅ COO (CH ₂ ) ₄ S ₂ O ₃ ]Co, [O ₃ S ₂
(CH ₂ ) ₃ COO (CH ₂ ) ₄ OOC (CH ₂ ) ₃ S ₂ O ₃ ]Ni,
[O ₃ S ₂ (CH ₂ ) ₃ COO (CH ₂ ) ₆ OOC (CH) ₃ S ₂ O ₃ ]Co,
[O ₃ S ₂ (CH ₂ ) ₁₀ COO (CH ₂ CH ₂ O) ₃ OC
(CH ₂ ) ₁₀ S ₂ O ₃ ]Ni, [O ₃ S ₂ (CH ₂ ) ₁₀ COO
(CH ₂ CH ₂ O) ₃ OC (CH ₂ ) ₁₀ S ₂ O ₃ ]Co, [O ₃ S ₂
(CH ₂ ) ₁₀ COO (CH ₂ CH ₂ O) ₂ OC (CH ₂ ) ₁₀ S ₂ O ₃ ]Ni,
[O ₃ S ₂ (CH ₂ ) ₁₀ COO (CH ₂ CH ₂ O) ₂ OC
(CH ₂ ) ₁₀ S ₂ O ₃ ]Co The following compound is also produced by the above operation. [O ₃ S ₂ (CH ₂ ) ₅ S ₂ O ₃ ]Ni, [O ₃ S ₂ (CH ₂ ) ₅ S ₂ O ₃ ]
Co, [O ₃ S ₂ (CH ₂ ) ₆ S ₂ O ₃ ]Ni, [O ₃ S ₂
(CH ₂ ) ₆ S ₆ O ₃ ]Co, [O ₃ S ₂ (CH ₂ ) ₈ S ₂ O ₃ ]Ni,
[C ₃ S ₂ (CH ₂ ) ₈ S ₂ O ₃ ]Co, [O ₃ S ₂ (CH ₂ ) ₁₀ S ₂ O ₃ ]
Ni, [O ₃ S ₂ (CH ₂ ) ₁₀ S ₂ O ₃ ]Co, [O ₃ S ₂
(CH ₂ ) ₁₂ S ₂ O ₃ ]Ni, [O ₃ S ₂ (CH ₂ ) ₁₂ S ₂ O ₃ ]Co Reference Example 10 This reference example describes the preparation of hexamethylene bis(thiosulfate) potassium salt. 1,6-dichlorohexane (54.6 g,
(0.35 mol) and K ₂ S ₂ O ₃ H ₂ O (163.4 g, 0.75 mol) was heated in an autoclave at 135° C. for 8 minutes. The resulting solution was filtered while still hot and the liquid was cooled to -10°C to obtain a solid which was collected by centrifugation. This solid was recrystallized from 250 ml of ethanol aqueous solution.
98g hexamethylene bis(thiosulfate)
Potassium salt was obtained. Reference Example 11 This reference example describes a method for producing hexamethylene bis(thiosulfate) barium salt. A hot solution of barium chloride (BaCl ₂ 2H ₂ O, 217 g) in water (450 ml) was prepared with stirring for 50 min. The hot solution was added slowly.
The solution was cooled to give a solid, which was collected by filtration and dried (308 g, 81.7% yield). The barium content (gravimetrically) corresponded to 97.5% of [(CH ₂ ) ₃ S ₂ O ₃ ] ₂ Ba.2H ₂ O and the sodium content was 2%, calculated as NaCl. Reference Example 12 This Reference Example describes the preparation of (A) hexamethylene bis(thiosulfate) cobalt salt and (B) decamethylene bis(thiosulfate) diammonium salt. (A) Hexamethylene bis(thiosulfate) barium salt (135 g, 0.276 mol) was dissolved in 1350 ml of water. Add the barium salt solution to the well-stirred barium salt solution.
CoSO ₄ 7H ₂ O (101 g _,
0.276 mol) was added over 35 minutes. The resulting slurry was shaken for 2 hours. This was filtered and the liquid was evaporated to give 131.2 g of a pink solid. Actual values of elemental analysis: C14.44%, H4.18%,
S25.60%, Co11.88%, Na1.97% This analytical value is calculated as hexamethylene bis(thiosulfate) cobalt salt hexahydrate (C ₆ H ₂₄ O ₁₂ S ₄ Co) contaminated with 5 wt% NaCl. corresponds well to the value. (B) Decamethylene bis(thiosulfate) diammonium salt (itself a reference Example 11
(produced from decamethylene bis(thiosulfate) disodium salt by a similar operation)
Manufactured from. Elemental analysis value: C (%) H (%) N (%) S (%) Calculated value: 29.98 7.14 6.99 32.01 Actual value: 29.81 7.15 6.84 31.83 Reference example 13 Hexamethylene bis(thiosulfate) nickel salt is CoSO ₄ 7H ₂ It was prepared from hexamethylene bis(thiosulfate) barium salt by essentially the same procedure as described in Reference Example 12, except that NiSO ₄ .6H ₂ O was used in place of O. Yield is 131.3
It was hot at g. Actual values of elemental analysis: C14.42%, H3.93%,
S25.32%, Ni11.90%, Na2.04% The above analysis values are for hexamethylene bis(thiosulfate) nickel salt hexahydrate (C ₆ H ₂₄ O ₁₂ S ₄ Ni) contaminated with 5.2 wt% NaCl. Corresponds well to calculated values. Reference Example 14 Various metal salts were prepared by passing an aqueous solution of hexamethylene bis(thiosulfate) sodium salt through a cation exchange resin column in the desired cation salt form and evaporating the permeate (percolate) to dryness. Under the conditions employed, the cation exchange was incomplete and a product was obtained with the following weight composition (HTSNa = hexamethylene bis(thiosulfate) sodium salt). (A) Hexamethylene bis(thiosulfate) zinc salt 97.5% HTSNa 2.5% (B) Hexamethylene bis(thiosulfate) magnesium salt 82.5%, HTSNa 17.5% (C) Hexamethylene bis(thiosulfate) calcium salt 91.9%, HTSNa 8.1% Hexamethylene bis(thiosulfate) lithium salt (D) was also prepared from the sodium salt by cation exchange. It was found that it is possible to purify the lithium salt by recrystallization from a mixed solvent with equal volumes of propanol/toluene in which HTSNa is insoluble. Reference Example 15 This reference example describes a method for producing a compound in which M in the general formula represents a substituted ammonium ion. (A) N-(1,1,3,3-tetramethylbutyl)benzylamine (8.8 g, 0.04 mol) in 200 ml of a water-methanol (1/1) mixture
was treated with HCl (to pH 4). To the resulting clear solution was added hexamethylene bis(thiosulfate) sodium salt dihydrate (7.8 g, 0.02 mol) in 100 ml of _H2O . The resulting slurry was cooled to 0°C and filtered. The product was washed with water and then dried. Yield of hexamethylene bis(thiosulfate) N-(1,1,3,3-tetramethylbutyl)-N-benzylammonium salt 13.6 g (87%), melting point 149-151°C. Elemental analysis value (as C ₃₆ H ₆₂ N ₂ O ₆ S ₄ ) C (%) H (%) N (%) S (%) Calculated value: 57.71 8.61 3.47 17.12 Actual value: 57.81 8.43 3.66 17.30 (B) N - tertiary butylbenzylamine (0.2 mol,
(32.6g) in 200ml water with dilute HCl (PH
5). Hexamethylene bis(thiosulfate) sodium salt dihydrate (0.1 mol, 39 g) in 400 ml of H ₂ O was added and the volume of the resulting solution was reduced to about 200 ml by evaporation. The precipitate formed was collected and dried under vacuum at room temperature. Hexamethylene bis(thiosulfate) N-tertiary butyl-N-
Yield of benzylammonium salt 60g (95%). (C) N-isopropyl-N'-phenyl-p-phenylenediamine (226 g, 1 mol) was dissolved in ethanol (500 ml) and the stirred amine solution was dissolved in 100 ml of ethanol.
H ₂ SO ₄ (96%, 51 g, 0.50 mol) was added dropwise.
The precipitated sulfate was collected by filtration, washed with ethanol and dried (258 g, yield 94
%). The above sulfate (27 g, 0.1 mol) was dissolved in methanol (300 ml) and hexamethylene bis(thiosulfate) sodium salt dihydrate (19.5 g, 0.15 mol) in 600 ml of warm methanol was dissolved in methanol (300 ml).
mol) was added. The precipitated Na ₂ SO ₄ was filtered off and the liquid was evaporated to dryness under vacuum. Yield of 34 g (92%) of hexamethylene bis(thiosulfate) N-isopropyl-N'-(p-phenylaminophenyl) ammonium salt. (D) Charge 1,4-bis(chloromethyl)cyclohexane (0.165 mol), sodium thiosulfate pentahydrate (0.369 mol), sodium sulfite (6.1 g), methanol (150 ml) and water (150 ml) into an autoclave. It was then heated at 135°C for 45 minutes. 1,4-dimethylcyclohexane-α,α
- The reaction mixture, a solution of sodium bis(thiosulfate) salt, was cooled and 400 ml of water was added to it. N-tert-butylbenzylamine (0.306 mol) in 150 ml methanol and 850 ml _H2O was adjusted to PH 4 with concentrated HCl and the resulting solution was added to the thiosulfate solution with stirring. The white precipitate was filtered off, washed with water and dried. 1,4-dimethylcyclohexane-α,α-bis(thiosulfate) N-tertiary
Yield of butyl, N-benzylammonium salt
92g (91%). Reference Example 16 This reference example describes the preparation of a compound in which M represents an ion derived from a cation-forming organic nitrogen base in addition to a simple amine. (A) Dibromohexane (24.3 g, 0.1 mol) and thiourea (15.2 g, 0.2 mol) were refluxed in 200 ml of ethanol for 2 hours. 200ml of water was added and the resulting solution was cooled to room temperature. 100ml
_{Hexamethylene} bis(thiosulfate) sodium salt dihydrate (39 g,
0.1 mol) was added dropwise with good stirring. The resulting slurry was cooled to 0°C and filtered. The filter cake was washed with ice water and dried to yield 50.1 g (92% yield) of hexamethylene bis(thiosulfate) 1,6-bis(isothiouronium) hexane salt. [(NH ₂ ) ₂ CS−(CH ₂ ) ₃ ] ₂ ⁺⁺ [O ₃ S ₂ −
(CH ₂ ) ₃ 〕 ₂ ^-- , mp.240℃. Elemental analysis value (as C ₁₄ H ₃₂ N ₄ O ₆ S ₆ ) C (%) H (%) N (%) S (%) Calculated value: 30.41 5.58 9.58 32.79 Actual value: 30.87 5.92 10.28 35.31 (B) 10.2 g (0.1 mol) of 96% H ₂ SO ₄ in 300 ml methanol of 2,2,4-trimethyl-
1,2-dihydroquinoline (34.6g, 0.2mol)
solution. To this solution was added hexamethylene bis(thiosulfate) sodium salt dihydrate (3.9 g, 0.1
mol) solution was added gradually. Filter the precipitated sodium sulfate and evaporate the liquid to dryness.
45 g of hexamethylene bis(thiosulfate) 2,2,4-trimethyl-1,2-dihydroquinolinium salt was obtained. (C) A glass column was packed with 300 g of strong acid ion exchange resin (1.8 me/ml) to which was added a solution of 30 g of guanidium hydrochloride in 150 ml of water. The column was washed with 300ml distilled water. A solution of 35 g of hexamethylene bis(thiosulfate) sodium salt in 400 ml of water was then passed through the column and the leachate was evaporated to dryness. The recovered solid [( _NH2 ) _2CNH2 ] ₂₊ ^[ _O3S2- ( _{CH2 ) 3 ] 2--57.5g} (79.2%) had a melting point ^of 172-175[deg.]C. Elemental analysis value (as C ₈ H ₂₄ N ₆ S ₄ O ₆ ) C (%) H (%) N (%) S (%) Calculated value: 22.43 5.61 19.83 29.91 Actual value: 22.24 5.33 19.80 27.56 (D) 70 A solution of hexamethylene bis(thiosulfate) sodium salt (100 g, 0.282 mol) in 500 ml of water at <0>C was slowly added to a stirred solution of 133 g (0.568 mol) of diphenylguanidine hydrochloride in 700 ml of water. The mixture was cooled and the solid that separated was collected. Recrystallization from a mixture of equal parts methanol/toluene gave 154 g (77.1%) of hexamethylene bis(thiosulfate) bis(diphenylguanidinium) salt, mp 151-153°C. Elemental analysis value (as C ₃₂ H ₃₆ N ₆ S ₄ O ₆ ) C (%) H (%) N (%) S (%) Calculated value: 50.85 5.65 11.86 18.08 Actual value: 52.25 5.54 11.39 17.38 (E) N ,N'-di(1,4-dimethylpentyl)-
p-phenylenediamine (3.04g, 0.01mol)
was dissolved in isopropyl alcohol (50ml) and treated with 1.02g of 96% H ₂ SO ₄ (0.01 mol). The formed precipitate was filtered and then washed with isopropyl alcohol, followed by methanol (50%
ml). The solution thus obtained was mixed with a methanolic solution of hexamethylene bisthiosulfate, sodium salt (4.1 g of 86% pure product, 0.01 mol). The precipitate that formed (Na ₂ SO ₄ ) was filtered and the resulting clear solution was evaporated to dryness. The residue was crystallized from absolute ethanol to give 2.1 g (34%) of N,N'-di(1,4) hexamethylene bisthiosulfate.
-dimethylpentyl)-p-phenylenediamine salt was obtained. IR spectrum: 3.450 cm ^-1 NH 1940 1590 1520 cm ^-1 1240 1170 1030 640 cm ^-1 S ₂ O ₃ ¹ HNMR confirmed a 1:1 ratio of amine moiety/hexamethylene bisthiosulfate moiety. (F) A solution of benzylisothiouronium chloride (40.5 g, _0.2 mol) in 100 ml water/ethanol (1/1) was dissolved in a solution of hexamethylene bisthiosulfate sodium salt (41 g, 86% purity, 0.1 mol) solution. The precipitate formed immediately at room temperature.
Stirred for 0.5 hour, then filtered and dried under vacuum to yield 57.3 g (89.1 g) of hexamethylene bisthiosulfate bisbenzylisothiouronium salt, mp 133-135°C. IR spectrum: 1215 1170 1025 645 cm ^-1 Thiosulfate 1670 720 700 cm ^-1 Benzylisothiouronium ¹ H NMR confirms a 1:2 ratio of hexamethylene bisthiosulfate to benzylisothiouronium. Reference example 17 This reference example is di-n-hexylsulfone-6,
6′-bis(thiosulfate) sodium salt
The method for producing NaO ₃ S ₂ −(CH ₂ ) ₆ SO ₂ (CH ₂ ) ₆ S ₂ O ₃ Na is described. The entire route was as follows. HO (CH ₂ ) ₆ OH + HCl → HO (CH ₂ ) ₆ Cl, H ₂ O () 2 () + Na ₂ S → HO (CH ₂ ) ₆ S (CH ₂ ) ₆ OH + 2NaCl () + 2SOCl ₂ → Cl (CH ₂ ) ₆ S (CH ₂ ) ₆ Cl+SO ₂ +2HCl () +2C ₆ H ₄ ClCOOOH→Cl (CH ₂ ) ₆ SO ₂ (CH ₂ ) ₆ Cl () +2Na ₂ S ₂ O ₃ → NaO ₃ S ₂ (CH ₂ ) ₆ SO ₂ (CH ₂ ) ₆ S ₂ O ₃ Na+2NaCl () The compound is from “Organic Syntheses” Volume 3
Produced by pp. 446-448. The compound is 60ml
(0.3 mol, 42 g) and Na ₂ S.9H ₂ O (0.15 mol, 36 g) dissolved in H ₂ O and 60 ml of EtOH.
Manufactured from. The mixture was refluxed with stirring for about 18 hours. The solution was evaporated under vacuum and the residue was dissolved in two portions at 130
Extract with ml ether. The extracts were combined, dried and evaporated. The residue was crystallized twice from petrol/toluene (1/2).
Yield 16.8g (48%), melting point 46-48°C. Repeated preparations gave a crude product (89%) (melting point 43-46°C), which was crystallized to give a yield of 71%. Melting point 50-51℃. Compound (135 g, 0.57 mol) and pyridine (5 mol) were added in a flask equipped with a reflux condenser.
ml), to which was added CHCl ₃ (1000 ml) and then SOCl ₂ (107 ml) was added dropwise over 50 minutes. The mixture was kept at 40°C for 5 hours. Water (200ml) was carefully added to the cooled mixture. The organic layer was worked up to obtain an oily liquid (175 g), which was
Distillation at 160°C/0.07mmHg yielded 81g (52.4%) of the compound. The compound was prepared in CH ₂ Cl ₂ (150 ml) by treatment (under reflux) with 85% m-chloroperbenzoic acid (37.5 g, 0.185 mol) in ether (150 ml) for 1.75 hours at 35°C. (20g, 0.074mol). The resulting mixture was washed with 2M NaOH (200ml) and the organic layer was evaporated under vacuum (crude yield 22.3g,
100%, mp 45-51°C) and the residue was crystallized from toluene/petrol (1/2). yield
18.6g (83%), melting point 50-52°C. Compound (15.4g, _0.05mol ), _{Na2S2O3 .}
5H ₂ O (25 g, 0.1 mol), water (50 ml) and methanol (25 ml) were charged into an autoclave and 20
Heated to 135°C for minutes. The mixture was filtered hot and the liquid was cooled to -30°C. The compound was crystallized from this solution and collected by centrifugation. Yield: 18.8g. Reference Example 18 This reference example describes the preparation of a compound in which two thiosulfate groups are linked by a nitrogen-containing bridging group. (a) Preparation of N ⁺ _H2 [(CH ₂ ) ₆ Cl] ₂ Cl ^- 6-bromohexanol (100 g, 0.553 mol)
and concentrated ammonia (390ml, 2.75mol) were heated to 100°C in an autoclave for 1 hour. Cool the mixture, evaporate it to dryness under vacuum and
220 ml of 2.5N NaOH (0.55 mol) was added. To this solution was added 6-bromohexanol (0.55 mol) and the mixture was boiled under reflux for 2 hours. Water was removed by evaporation and the residue was neutralized with NaOH (0.55 mol) as before. The organic phase consisting essentially of NH[(CH ₂ ) ₆ OH] ₂ was separated and collected. NH [(CH ₂ ) ₆ OH] ₂ (32.6 g, 0.15 mol)
Added to SOCl ₂ (42.8 g) in CHCl ₃ (30 ml) for 1.25 hours. The solution was kept overnight and then refluxed for 30 minutes. Evaporate CHCl ₃ to 32.9g (75.5%)
⁺ NH ₂ [(CH ₂ ) ₆ Cl] ₂ Cl ^- was obtained. (b) Preparation of bis(thiosulfate) ⁺ NH ₂ [(CH ₂ ) ₆ Cl] ₂ Cl ^- (25 g, 0.086 mol) and Na ₂ S ₂ O 3.5H ₂ in 80 ml of H ₂ O and 50 ml of methanol _. A mixture of O (42.6 g, 0.172 mol) was heated at 130° C. for 7 minutes in an autoclave.
The resulting solution was evaporated to dryness and the residue was extracted with hot methanol. Evaporated extract 35.6g
(88.6%) ⁺ NH ₂ [(CH ₂ ) ₆ S ₂ O ₃ Na]Cl ^- obtained as a white solid.The main IR absorptions are those of organic thiosulfate esters at 1200 cm ^-1 , 1025 cm ^-1 , and 640 cm ^-
It was ¹ . Elemental analysis value (as C ₁₂ H ₂₆ NS ₄ O ₆ Na ₂ Cl) C (%) H (%) N (%) S (%) Calculated value: 30.85 5.61 3.00 27.46 Actual value: 30.08 5.56 2.67 25.66 Reference example 19 This reference example describes the preparation of a compound containing three thiosulfate groups linked via a nitrogen-containing organic bridging group. NH produced as described in the above reference example
[(CH ₂ ) ₆ OH] ₂ (40 g) was reacted with 6-bromohexanol (18.2 g) by heating (105° C.) in 50 ml of butanol under reflux for 2 hours. The butanol was then evaporated under vacuum and the resulting oil was neutralized with NaOH and then distilled under vacuum. The main fraction distilling at about 190°C was found by NMR to be essentially pure tri(6-hydroxyhexyl)amine. N[(CH ₂ ) ₆ OH] ₃ (25 g, 0.055 mol) in CHCl ₃
(24 g, 0.2 mol) in SOCl ₂ (25 ml) for 1.25 hours. Keep this solution overnight and then
Refluxed for minutes. _CHCl3 was evaporated and the residue was used as such in the following step. 12 g of Na 2 S 2 O ₃ 5H 2 O in H ₂ O (40 ml) and methanol (20 ml) for 5 min _at 135° _C. in an autoclave _.
(20g). The solution was cooled, treated with charcoal, filtered and the liquid was evaporated. The residue was extracted with hot methanol and after filtration the extract was evaporated to give 14.6 g (71%) of an off-white solid. IR showed the disappearance of the CH ₂ Cl absorption band and the presence of an organic thiosulfate absorption band. N ⁺ _a
Analysis is consistent with the general structure ⁺ HN[(CH ₂ ) ₆ S ₂ O ₃ Na] ₃ Cl ^- . Reference Example 20 This reference example describes the preparation of a compound containing four thiosulfate groups. (a) 6-bromohexanoic acid (72.4g, 0.37mol)
and pentaerythritol (12.25g, 0.088
mol) in toluene in the presence of 6 ml H ₂ SO ₄ for 2 hours in a Dean-Stark apparatus. The black solid that separated was filtered and the solution was neutralized with aqueous caustic soda solution. The organic phase is separated, washed and evaporated to give the following IR absorption i.e. C=0 ester 1720 cm ^-1 CH ₂ Br 730
C ^[ _CH ^{2 OCO}
45 g of an oil containing (CH ₂ ) ₅ Br] ₄ as the main component was obtained. (b) The above tetrabromide (30 g, 0.035 mol) and Na ₂ S ₂ O ₃ .5H ₂ O (33.5 g, 0.135 mol) dissolved in 50 ml H 2 O/50 ml ethanol were heated to 135° C. for ₅ minutes in an autoclave. did. After cooling, the reaction was treated with activated charcoal, filtered and evaporated. The residue was dissolved in methanol (150
ml) and the solution was poured into 800 ml of isopropanol. The slurry was cooled to -10°C and filtered. The dried product, C[ _CH2OCO ( _CH2 ) _5S2O3Na ] _{4 , weighed} 27g (72.5%
yield). Reference Example 21 This reference example describes a method for producing polythiosulfate. A (a) 6-bromohexanoic acid (45 g, 0.23 mol) in 200 ml of CH ₂ Cl ₂ is treated with SOCl ₂ (35 g, 0.295 mol) in a flask equipped with a gas outlet through an efficient condenser. did. The reaction was kept overnight. The resulting solution was then added to a suspension of polyvinyl alcohol (38 g of 75% hydrolyzed PVA, ^MW 2000) in CH ₂ Cl ₂ (300 ml). The reaction was allowed to complete at room temperature for 2 days.
Evaporate the resulting solution to dryness and add 100 ml again.
All 6-bromohexanoic acid was removed by dissolving in CH ₂ Cl ₂ and then precipitating into 500 ml of diethyl ether. The so-called average formula of the polymer was approximately as follows. (b) 35 g of the above polymer was mixed with 40 g of Na ₂ S ₂ O ₃ .
It was added to a water-methanol (1/1) solution of 5H ₂ O. The mixture was refluxed (until homogeneous) for 1.5 hours. Evaporation to dryness followed by extraction with anhydrous methanol gave a solution which was left on a large plate to evaporate into a film. Yield 24 g of rubber-like translucent polymer. IR is the normal organic thiosulfate absorption band 1200 cm ^-1 , 1040
cm ^-1 , 640 cm ^-1 was shown. B (a) Preparation of poly(1-chloro-2,3-epoxypropane) AlCl ₃ in 10 ml of dry nitrobenzene
(0.023 mol, 3.1 g) and epichlorohydrin (0.2
mol, 18.5 g) was carefully added. Add 20 ml of water to the reaction mixture and decant the organic layer.
Dry over _CaSO4 . The solvent was removed and the brown liquid residue (13.9 g) was washed with petroleum ether to remove the last traces of nitrobenzene. (b) Preparation of polythiosulfate A mixture of sodium thiosulfate (0.15 mol, 37.8 g) and ethylene glycol (1.34 mol, 75 ml) was heated to 130°C to 140°C and the water was distilled off.
After cooling to 120°C, 13.9 g of polyepichlorohydrin from (a) were added over 5 minutes and the reaction mixture was stirred at 120-125°C for 15 minutes. The reaction mixture was then cooled and filtered to remove NaCl. The liquid was poured into 1 portion of well-stirred isopropanol and the solids precipitated. After this, methanol/isopropanol (500
ml/1000ml) from the mixture, and after drying, the structural unit 20.5 g of a polymer was obtained as a brown solid. Example 1 This example illustrates the use of a vulcanization stabilizer according to the invention in a natural rubber vulcanizate. The following composition: Parts by weight Natural rubber 100 Carbon black 50 Zinc oxide 5 Stearic acid 2 Process oil 3 N-Phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (anti-aging agent)
A masterbatch with 2 was prepared. Portions of the masterbatch were taken and mixed with 2.5 parts, 0.7 parts and 3.0 parts by weight of sulfur, 2-(morpholinothio)benzothiazole and a stabilizer compound, respectively, per 100 parts by weight of rubber. In practice, the stabilizer was introduced into the mixture as a suspension of finely divided solids in an equal weight of process oil. A further masterbatch portion with only sulfur and 2-(morpholinothio)benzothiazole was used as a control. The cure properties of the vulcanizable composition thus obtained and the physical properties of the vulcanized product were determined as described above. The results are shown below in Table 1, where A is decamethylene bis(thiosulfate) disodium salt hydrate and B is hexamethylene bis(thiosulfate).
Disodium salt hydrate, C is pentamethylene bis(thiosulfate)
D is ethylene bis(thiosulfate) disodium salt hydrate, and E is cyclohexylene-1,4-dimethylene bis(thiosulfate) disodium salt hydrate.

[Table] Lifespan reduction %
The beneficial effect of stabilizer compounds on the aging process, commonly referred to as "reversion," can be demonstrated by comparing the percentage retention of 300% modulus during overcure of samples containing stabilizer compounds with that of controls. This can be understood by The beneficial effect on flex life of the presence of stabilizer compounds is also evident. Example 2 This example illustrates the use of a vulcanization stabilizer according to the present invention in a blend of natural rubber and butadicane rubber. The following composition: Parts by weight Natural rubber 70 Butadiene rubber 30 Carbon black 50 Zinc oxide 5 Stearic acid 2 Process oil 6 N-Phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (anti-aging agent)
A masterbatch was prepared with 2. Take a part of the master bat and apply it to rubber 100
Controls were obtained by mixing 2.5 parts by weight and 0.7 parts by weight of sulfur and 2-(morpholinothio)benzothiazole, respectively. An additional portion of sulfur and 2-(morpholinothio)benzothiazole in equal amounts and 3.0 parts by weight of decamethylene bis(thiosulfate) disodium brine introduced as a dispersion of the finely divided solid in an equal weight of process oil. compound (A). The cure properties of the vulcanizable composition thus obtained and the physical properties of the vulcanized product were determined as described above. The results are as follows.

[Table] The advantageous effect on reversion can be seen by comparing the 300% modulus values. For the control, the modulus after 200 minutes of curing decreased to 88% of the maximum modulus, whereas the 300% modulus of the stabilizer compound-containing mixture cured for 200 minutes was slightly higher than the modulus after 60 minutes of curing (Rheo et al. maximum modulus versus time). Example 3 A control sample and a sample containing 3.0 parts by weight of stabilizer compound were prepared from a masterbatch as in Example 1. The test results are shown in Table 2, where F is decamethylene bis(methylthiol sulfonate)
and G is decamethylene bis(p-tolylthiol sulfonate).

[Table] Retention%
The beneficial effect of these stabilizers on the modulus is clear from the numerical values. The resilience values indicate that this property is less affected by overvulcanization in the presence of stabilizer than in the absence of it. Example 4 In the following example, a masterbatch having the same composition as Example 1 was used, except that it was made from a different lot of natural rubber. Collect a portion of the masterbatch and mix it into a rubber mixer.
Each 100 parts by weight was mixed with 2.5, 0.7 and 3.0 parts by weight of sulfur, 2(morpholinothio)benzothiazole and a stabilizer compound, respectively. Yet another portion of the masterbatch with only sulfur and 2(morpholinothio)benzothiazole added was used as a control. The cure properties of the vulcanizable composition thus obtained and the physical properties of the vulcanized product were determined as described above. The results set forth in Table 3 below demonstrate improved % modulus retention and % resilience retention upon overvulcanization.

[Table] ence retention%
Example 5 The following example used a masterbatch having the same composition as Example 22, except that it was made from a different lot of natural rubber. Take the masterbatch part and mix it with rubber 100% in a Banbury mixer.
parts by weight of sulfur and 2(morpholinothio)benzothiazole and the amounts shown in Table 4 below (rubber
(expressed in parts by weight per 100 parts by weight) of a stabilizer compound. Yet another portion of the masterbatch with only sulfur and 2(morpholinothio)benzothiazole added was used as a control. The cure properties of the vulcanizable composition thus obtained and the physical properties of the vulcanized product were determined as described above. The results listed in Table 4 below indicate that all compounds exhibited % modulus retention upon overvulcanization and that the compound of Reference Example 15A exhibited good activity in a relatively small amount (1.7 parts per 100 parts of rubber). It represents. The fatigue properties are particularly good for the compound of Reference Example 15C.

Table: Example 6 In the following example, a masterbatch having the same composition as Example 1 was used, except that it was made from a different lot of natural rubber. Take the masterbatch portion and mix it in a Banbury mixer to 2.5 parts by weight, 0.7 parts by weight and 3.0 parts by weight, respectively, per 100 parts by weight of rubber.
Mixed with parts by weight of sulfur, 2(morpholinothio)benzothiazole and a stabilizer compound. Yet another portion of the masterbatch with only sulfur and 2(morpholinothio)benzothiazole added was used as a control. The vulcanization properties of the vulcanizable composition thus obtained and the physical properties of the vulcanization product were determined as described above. The results are shown in Table 5 below. These results indicate that the presence of stabilizer compounds in overvulcanization
300% modulus has been shown to be well maintained or increased. Also, the % retention of resilience in overvulcanization is significantly greater than that of the control. The blowout time in the Gutsudritsu flexometer test increased during overvulcanization for all materials other than the control, and the increase was due to reference example 12,
13, 14A and 14B (cobalt salt, nickel salt,
This is particularly true for zinc and magnesium salts).

【table】

Table: Example 7 The following example used a masterbatch having the same composition as Example 1, except that it was made from a different lot of natural rubber. A portion of the masterbatch was taken and mixed in a Banbury mixer with 2.5, 0.7 and 3.0 parts by weight of sulfur, 2(morpholinothio)benzothiazole and a stabilizer compound per 100 parts by weight of rubber. Simply sulfur and 2
A further portion of the masterbatch containing only (morpholinothio)benzothiazole was used as a control. The cure properties of the vulcanizable composition thus obtained and the physical properties of the vulcanized product were determined as described above. All of the stabilizer compound containing feedstocks exhibited greater percent modulus retention than the control as shown by the entries in Table 6 below.

[Table] Lath retention%

Claims (1)

[Claims] 1 includes a diene rubber, sulfur and a vulcanization accelerator, and further has the formula -S-SO ₂ R [wherein R is (a) a group OM (where M is a monovalent metal,
the equivalent of a polyvalent metal, the monovalent ion derived by the addition of a proton to a nitrogenous base, or the equivalent of a polyvalent ion derived from the addition of two or more protons to a nitrogenous base), or (b)
represents an organic group selected from an aliphatic group, a cycloaliphatic group, an aromatic group, a heterocyclic group, and a group that is a combination of two or more of such groups, A vulcanizable rubber composition characterized in that it contains a stabilizer substance having two or more groups, the groups being linked to each other by organic bridging groups or to an organic polymer chain. . 2 In the compound stabilizer, each group -S-
SO ₂ R is attached to the primary carbon of the bridging group, or in polymeric stabilizer compounds each group -
A composition according to claim 1, wherein S- _SO2R is attached. 3. _{The stabilizer} substance has _the formula 4 and X represents the remainder of the crosslinking group. 4 The stabilizer substance has the formula RO ₂ S-S-X'-S-SO ₂ R [where X' represents an alkylene group or a group consisting of two or more alkylene units, in which case such Pairs of units can be formed through oxygen or sulfur atoms, -SO ₂ -, -NH-, -
NH ₂ ⁺ −, −N(C _1-6 alkyl)− or −COO−
or via an arylene or cycloalkylene group. 5 X' represents a C ₂ or C _5-16 alkylene group, or has the formula -(CH ₂ )a-O-(CH ₂ )a- -(CH ₂ )a-O-CH ₂ -O- (CH ₂ )a--( _CH2 )b-cyclohexylene-( _CH2 )b--( _CH2 )c-COO-( _CH2 )a--( _CH2 )c-COO-Y-OOC-(CH ₂ ) c- -( _CH2 )c- _SO2- ( _CH2 )c- or -( _CH2 )c- _NH2 ⁺ -( _CH2 )c- [wherein each a is independently 3 to b represents an integer of 1 to 4, c represents an integer of 3 to 12, Y represents a group -( _CH2 )c- or a group -
(CH ₂ CH ₂ O) dCH ₂ CH ₂ - (where d represents an integer from 1 to 5)] and R represents an OM group;
The composition described in Section. 5. A composition according to claim 4, wherein 6R represents a _C1-20 alkyl group or a phenyl group or a ( _C1-6 alkyl)-phenyl group. 7 M represents an alkali metal or one equivalent of magnesium, calcium, barium, zinc, cobalt or nickel and the stabilizer substance may further contain water of crystallization, R in the formula -S- _SO2R is OM Claims 1 to 4 represent
A composition according to claim 5 or a composition according to claim 5. 8. A composition according to claim 7, wherein 8M represents sodium. 9 M is an ammonium ion or an ion below R ² NH ₃ ⁺ , R ² R ³ NH ₂ ⁺ or R ² R ³ R ⁴ NH ⁺ (wherein each of R ² , R ³ and R ⁴ is independently
Represents a C _1-20 alkyl group, a C _5-9 cycloalkyl group or an alkylcycloalkyl group, a benzyl group, a phenyl group or a substituted phenyl group, but with the proviso that
in the formula ^-S - _SO2R , where not more than one of R2, ^R3 and ^R4 is a phenyl group or a substituted phenyl group, R is OM. A composition according to any one of claims 1 to 4 or a composition according to claim 5. 10 M is the ion R ² R ³ NH ₂ ⁺ (where R ² and R ³
one of which is a _C4-12 tertiary alkyl group,
the other is a benzyl group, or R ² and
The composition according to claim 9, wherein one of R ³ is a C _3-12 secondary alkyl group or a cyclohexyl group and the other is a 4-phenylaminophenyl group. . 11 M is the formula a guanidinium ion or a substituted guanidinium ion of; or a guanidinium ion of the formula _a substituted ^{isothiouronium} _ion of and R ⁵ is a C _1-20 alkyl group, a C _5-9 cycloalkyl or alkylcycloalkyl group, or a benzyl group), in which R in the formula -S-SO ₂ R is OM; Any one of claims 1 to 4
The composition according to claim 5 or the composition according to claim 5
The composition described in Section. Formula -S when 12 M represents an optionally ring-substituted 1,2-dihydroquinolinium ion
The composition according to any one of claims 1 to 4 or the composition according to claim 5, wherein R in _-SO2R is OM. 13 M has the formula R ² NH ₂ ⁺ -A-NH ₂ ⁺ R ² [wherein A is a group -(CH ₂ )c- (where c is 2 to
with a value of 20) or represents a phenylene group,
and each R ² independently represents a C _1-20 alkyl group, a C _5-9 cycloalkyl or alkylcycloalkyl group, a benzyl group, a phenyl group, or a substituted phenyl group, provided that when A represents a phenylene group, R ² is neither a phenyl group nor a substituted phenyl group], wherein R in the formula -S- _SO2R represents OM. or the composition according to claim 5. 14 A represents a p-phenylene group and each
14. A composition according to claim 13, wherein ^R2 represents a _C3-12 secondary alkyl group. 15 M is the formula or (wherein, c is an integer from 2 to 20), where R in the formula -S- _SO2R represents the equivalent weight of a divalent ion of OM
The composition according to any one of claims 1 to 4 or the composition according to claim 5, which represents: 16 The stabilizer substance has the formula MOO ₂ S-S-X'-S-SO ₂ OM, where X' represents a C _5-16 alkylene group and M represents sodium or magnesium, calcium, barium, zinc. , representing one equivalent of cobalt or nickel) and may also contain water of crystallization. 17 In the formula, X' represents a _C5-10 alkylene group and M represents sodium or one equivalent of zinc, cobalt or nickel, and the compound may further contain water of crystallization, Composition according to item 16. 18. The composition of claim 17, wherein the stabilizer substance is hexamethylene bis(thiosulfate) sodium salt or a hydrate thereof. 19 The stabilizer substance has the formula MOO ₂ S-S-X'-S-SO ₂ OM [where X' represents a C _5-16 alkylene group and M is N-tertiary (C _4-12 alkyl)]. -N-benzylammonium ion or N-(4-phenylaminophenyl)-N-(C _3-12 secondary alkyl)
2. The composition according to claim 2, which is a compound having a compound representing an ammonium ion. 20 The stabilizer substance has the formula MOO ₂ S-S-X'-S-SO ₂ OM [where X' is the group -(CH ₂ )c-COO(CH ₂ )a
-(Here, a represents an integer from 3 to 8, and c represents an integer from 3 to 8.
represents an integer of 12) and M represents sodium or magnesium, calcium,
1 equivalent of barium, zinc, cobalt or nickel] and may also contain water of crystallization. 21 Said patent in which the stabilizer substance is NaO ₃ S ₂ (CH ₂ ) ₃ COO (CH ₂ ) ₄ S ₂ O ₃ Na or NaO ₃ S ₂ (CH ₂ ) ₅ COO (CH ₂ ) ₄ S ₂ O ₃ Na A composition according to claim 20. 22. According to any one of the preceding claims, wherein the diene rubber is natural or synthetic cis-polyisoprene or a blend of rubbers containing at least 25% by weight cis-polyisoprene. Composition of. 23 The amount of stabilizer substance is 1 to 100 parts by weight of rubber.
23. A composition according to any one of claims 1 to 22, in an amount of 5 parts by weight. 24 Claims 1 to 2, wherein the vulcanization accelerator is benzothiazole-2-sulfenamide.
The composition according to any one of item 3.