SK285498B6 - Vulcanizing agent and process for production thereof - Google Patents

Abstract

It is described a vulcanizing agent for the sulfur vulcanization of rubber mixes, which is the result of the addition to polyreactions of sulfur in the presence of at least one unsaturated C12-C22 aliphatic carboxyl acid with 1 to 4 double bonds in a molecule and/or their esters with C1-C4-alkanoles or C3-C18-alkenoles, eventually mixtures of monoene to polyene and an auxiliary substance or substances, whereby the total content of sulfur in the agent is 75 to 96 % by weight and a process for production thereof.

Description

Technical field

The invention relates to a vulcanizing agent for the sulfur vulcanization of a rubber or rubber composition based on at least one unsaturated rubber or a mixture thereof with other hydrocarbon macromolecular substances, as well as a process for the production of this vulcanizing agent by a sulfur addition process up to polyreaction with technically readily available unsaturated to polyunsaturated organic compounds.

BACKGROUND OF THE INVENTION

Despite the obvious advantages of polymeric, ie insoluble sulfur (in carbon disulphide and thus also in rubbers), compared to cyclooctamous sulfur as a vulcanizing agent for the vulcanization of unsaturated rubbers or their combinations with saturated rubbers, respectively. vulcanization of the rubber mixture, in the case of the application of polymeric sulfur as a vulcanizing agent, the problem, inter alia, is more difficult to homogenize the rubber mixture, mainly due to its insolubility. But also the technical and thus economic demands of its production. The problem was solved by using copolymers of sulfur with linseed oil and dicyclopentadiene at 125-135 ° C for 4 to 5 hours [US 3,264,239 (1966)] as a vulcanizing agent, but the physico-mechanical properties of the vulcanizates lag behind compared to the vulcanizates with the blend and in addition, during the preparation of the rubber mixture and in particular during vulcanization, probably part of the escaping vapors of the cyclo-resp. dicyclopentadiene, by their unpleasant odor, greatly impair the working environment of vulcanizate production. Similar problems are also encountered when using copolymeric sulfur with a partially hydrogenated copolymer with an unsaturation of 0.5 to 1 mol. % C ₄ to C ₆ conjugated dienes and C ₃ to C ₅ α, β-unsaturated nitriles [EP 0112109 (1984), DE 4310588 (1993)]. The use of a catalytic amount of phosphorus sulfide, such as e.g. P4S3, in the copolymerization of sulfur with cyclopentadiene, dicyclopentadiene and other conjugated diene dimers, and neither amine additives [US 3523926 (1971); 4311826 (1982) and 4097474 (1978); Romanian Patent 92799; Ochotina NA et. al. : Kaučuk i rezina 1997, no. 3, p. 33-35]. Of interest are also copolymers of sulfur with olefinic hydrocarbons at 140-160 in an aqueous reaction medium, in the presence of a basic dispersant catalyst (US 4739036 (1988)), which however has to be removed from the product. Similarly, sulfur copolymers with higher alkenes (Colvin H .: Gummi Fasem Kunststoffe 1997, 627) are well miscible in a rubber blend, as are sulfur copolymers with styrene [Meximov TV et al .: Žur. Ex. Chim., 69, 1543 (1996); US 4902775 (1990)], as well as, in addition, higher unconjugated dienes (GB 1083528), but the desired phytical-mechanical parameters of the vulcanizates, especially strength, especially after aging, are not achieved with their use. Nor is it sufficient to disperse cyclooctamic sulfur in liquid poly (-cis-isoprene) rubber [US 4564670 (1986)] if copolymerization of the sulfur with poly (-cis-isoprene) is not ensured at a temperature above 100 ° C. Similarly, a vulcanizing agent based on sulfur and dithiocarboxylic acid or a salt thereof [EP 0432416 (1991)] is not yet sufficient to achieve the desired quality of the rubber composition and in particular the vulcanizate, the sulfur component must be a sulfur polymer.

Thus, the prior art advantages of the known sulfur vulcanizing agents take advantage of and eliminate the drawbacks of the vulcanizing agent as well as the process for its production according to the invention.

SUMMARY OF THE INVENTION

The present invention provides a vulcanizing agent for the sulfur vulcanization of a rubber or rubber composition based on at least one unsaturated rubber or a mixture thereof with other hydrocarbon macromolecular substances, such as saturated rubbers, comprising products of addition to sulfur polyreactions in the presence of at least one unsaturated aliphatic carboxylic acid up to 4 double bonds per molecule, having a carbon number of 12 to 22 and / or esters thereof having a carbon number of 1 to 4, and / or an alkenyl of 3 to 18, or mixtures thereof, with at least one monoene to polyene, % of the sulfur or sulfur with the excipient in the vulcanizing agent is 75 to 96 wt. %.

Thereafter, a process for producing a vulcanizing agent for sulfur vulcanization of a rubber or rubber composition based on at least one unsaturated rubber or a mixture with other hydrocarbon macromolecular substances, such as saturated rubber, is carried out in such a way that at a temperature of 120 to 250 ° C 75 to 96 wt.% In a reaction to polyreaction mixture with 25 to 4 wt. % with at least one aliphatic carboxylic acid having a carbon number of 12 to 22 and / or an ester thereof, alkyls having a carbon number of 1 to 4 and / or alkenyls having a carbon number of 3 to 18 with one to three double bonds, or a mixture thereof % with one monoene to polyene, wherein after addition of the excipient (s) in an amount of 0.05 to 1.2 wt. % in the reaction to polyreaction mixture, the reaction to polyreaction mixture is rapidly cooled to a temperature below 50 ° C by at least one operation selected from dosing to cold water, dosing to cold aqueous solution, spraying to cold water or cold aqueous solution, spraying to spraying to cooled walls below 20 ° C, by spraying up to spraying into the cooled off-gas stream to temperatures below 20 ° C, pouring onto a deep-cooled metal support or deep-cooled conveyor belt, and subsequently treated by drying or directly disintegrating, optionally oiling and shaping into a well-applicable form as a vulcanizing agent.

The advantage of the vulcanizing agent of the present invention is good dispersibility and thus incorporation into the rubber composition, the size of the macromolecules without the potential "blooming" of the rubber composition during prolonged storage, uniform throughout the vulcanizate and high physico-mechanical parameters of the vulcanizates.

Advantages of its production are raw material availability, reliable reproducibility raw material and technological, relatively low energy intensity and technical availability of equipment, flexibility and last but not least, possibility to produce vulcanizing agents not only in terms of different total sulfur content in them, but possibly also containing other important ingredients in them for rubber mixtures and vulcanizates. The vulcanizing agent according to the invention is particularly suitable for the sulfur vulcanization of a rubber or rubber mixture based on at least one unsaturated rubber, such as natural, synthetic polyisoprene, polybutadiene, butadiene / styrene, ABS, etc., optionally together with saturated rubber such as ethylene / propylene / propylene / propylene / propylene , polyisobutylene, EPDM and other technically and commercially available unsaturated as well as saturated rubbers, polyolefins and higher molecular synthetic and mineral oils. Thus, the curing agent is the product of addition to polyaddition of sulfur from rhombic to sulfur by polymers insoluble in CS ₂ (δ _μ ,

_E N, _E N), which is already previously formed not only polymeric but also a copolymer of sulfur may be further adducted and polyadenylation especially the unsaturated or saturated aliphatic caboxylic acid C ₁₂ to C _22, with regard to at least one unsaturated carboxylic acid containing from one to four double bonds such as lauroleic, myristoleic, palmitoleic, behenic, elaidic, oleic, gadolenic and erucic. Then, diene to tetraeinic carboxylic acids: linoleic, linolenic, oleosteic, parinic and arachidonic. The most suitable are, in particular, C ₁₆ to C ₂₂ monoenoic and triene fatty acids, obtained by hydrolysis of mainly vegetable oils or by saponification with alkali metal hydroxides and mineral acid (HCl, H ₂ SO ₄ and p.) Converted to a mixture of predominantly unsaturated monoene to tetraene fatty acids. acids. Particularly suitable is a process for the transesterification of rapeseed, sunflower or linseed oil with methanol under the catalytic action of alkali metal hydroxides or carbonates. Thus, from rapeseed oil, by transesterification with methanol, a mixture of methyl esters of mainly oleic acid, linoleic acid, linolenic acid, small amounts of erucic acid, behenic and gadolenic acid, as well as saturated carboxylic acids: palmitic and stearic, is obtained. However, their presence practically does not reduce the quality of unsaturated fatty acids. According to the present invention, in addition to a mixture of predominantly unsaturated fatty acids or esters derived from rapeseed, flax and sunflower oil, useful but technically economically less suitable mixtures of fatty acids or their esters of hemp, poppy, nut, olive and soybean oil, even also from animal oils, such as sardine, sperm, whale, but also goose, horse fat, pork ointment, and others containing monoenoic to polyene fatty acids in glycerides. The alkyl esters are technically the most easily obtainable by transesterification of saturated alcohols of C] to C _4, or esterification of alkanols. In the case of alkenyl esters with one to four double bonds per molecule, it is also possible to use pre-esterification such as allyl alcohol, linaloyl alcohol, linolenyl alcohol or the like, or direct esterification of acids with unsaturated alcohols.

Monoenes to polyenes whose sulfur copolymers may be a component of the vulcanizing agent of the present invention, in addition to hydrocarbon monomers such as styrene, α-methylstyrene, vinyltoluenes, α-methylstyrene dimers, cyclopentadiene dimers to oligomers, butomers, trimers to pentamers, and pentamers, dienes and alkenes of pyrolysis C _{5 -} fraction, liquid polybutadiene rubber, products of thermal fission to pyrolysis of rubbers and rubber.

Excipients having a content of 0.05 to 1.2 wt. stabilizers or anti-reversing agents applied to polymeric sulfur such as halogens (Cl ₂ , Br ₂ , I ₂ ) SOCl ₂ , SO ₂ Cl ₂ , AlCl ₃ , SiCl ₄ , PCl ₅ , alkyl bromide, allyl chloride, peroxyacids , adipic acid, palmitic acid, stearic acid and others as well as surfactant impurities. Binders, such as solid paraffins, C- ₃₀ alkenes, etc., may also be included in the excipients, allowing the vulcanizing agent to be applied in the molded form.

The process is carried out by reacting sulfur, in particular, with unsaturated carboxylic acids and / or esters thereof, optionally also with hydrocarbon monoenes to polyenes at a temperature of 120 to 250 ° C. At temperatures above 140 ° C, sulfur can also react with any saturated carboxylic acids present. The reaction time depends in particular on the reaction temperature of the addition to the polyreaction of sulfur as with unsaturated carboxylic acids, with one to four double bonds per molecule and / or their alkyl- to alkenyl esters or mixtures thereof with hydrocarbon polyenes. The elemental to cyclooctamer sulfur is heated to 120 DEG-280 DEG C. for the reaction, and it is suitable, directly to the Claus process for producing sulfur from the sulfane from dehydrosulfurization of petroleum fractions without precooling, to conduct the reaction to polyreaction with unsaturated fatty acids directly and / or their esters or mixtures with hydrocarbons of monoenes to polyenes.

Preferably, addition to polyreaction is stopped by sudden cooling to below 50 ° C, most preferably when it is blended into water or aqueous solution to 2 to 20 ° C. In case of flowering to chilled areas also to a temperature below 0 ° C.

The most suitable reactants with all forms of sulfur include the individual unsaturated acids, both oleic acid and mixtures obtained from vegetable oils, in particular from rapeseed and linseed oil.

In the case of alkyl esters of carboxylic acids, methyl esters to butyl esters are sufficient. In the case of alkenyl esters having one to three double bonds in alkenyls, it is desirable to prepare them by esterifying unsaturated monoeno to tetraenoic fatty acids, in particular C ₁₂ to C _22, with unsaturated alkanols such as allyl alcohol, crotyl alcohol, oil alcohol, linol alcohol, linoleyl alcohol the reaction of sulfur, even with double bonds of alkenyls, optionally remaining for incorporation also by vulcanization of the rubber mixture to vulcanizates.

Further data on the composition of the vulcanizing agent, the method for its production, as well as other advantages thereof, are evident from the examples, in which the effect of the vulcanizing agent on the vulcanization of rubber mixtures and the physico-mechanical parameters of the vulcanizates obtained are presented.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

To 100 g of molten sulfur from the Claus process for producing sulfur from sulphate by its partial oxidation to sulfur dioxide, with conjugated reduction to sulphide to molten sulfur, at a temperature of 220 ° C to 230 ° C, 20 g of rapeseed acid mixture oil, with acid number = = 191.3 mg KOH / g, saponification number = 204.0 mg KOH / g, ester number = 12.7 mg KOH / g, bromine number = = 66.4 g Br ₂ / 100g, and iodic acid 98.5 g / 10g, containing (by weight%): oleic acid = 20, linolenic acid = = 10, palmitic acid = 3.2, stearic acid = 1.2, eicosanoic acid = 2, erucic acid 1 1, the unsaponifiable fraction = 0.4 and the phospholipids 2.1. Maintain in a nitrogen atmosphere at 225 ± 5 ° C for 80 min, while at 70 min. 0.4 g of iodine is added, with stirring for 10 min, for 1 min. The reaction mixture is poured into a cooled aqueous solution of partially saponified polyvinyl acetate (saponification degree to polyvinyl alcohol 73 mol%) at a concentration of 0.1 wt. % at 0 to 5 ° C maintained by the addition of ice. After 3 h, a sample (Example 1) of the copolymer was ground to below 0.07 mm and used as a vulcanizing agent in rubber mixtures.

Example 2

By pre-esterification of linseed oil with methanol under the catalytic action of an aqueous potassium hydroxide solution at 65 ± 1 ° C, the crude reaction mixture, after neutralization with hydrochloric acid, separating the upper methyl ester layer from the lower-aqueous sodium glycerol phase is withdrawn from the methyl esters under reduced pressure. the remainder of the methanol. The obtained mixture of methyl esters of carboxylic acids (in wt.%): Palmitic = 5.2, oleic = 68.2, linoleic = 14.1, linolenic = 17.5, arachenic = 2.9 and behenic = 2.5. This 1: 1 mixture of methyl esters is mixed with the predominantly unsaturated rapeseed oil mixture specified in Example 1. The liquid sulfur resulting from the Claus process is also slowly cooled to 180 ± 1 to prepare three samples of copolymer sulfur. ° C and in an inert atmosphere, 180 g of sulfur is mixed with a mixture of 20 g of methyl esters and acids (Experiment 2), then 170 g of sulfur with 30 g (Experiment 3) and finally 190 g of sulfur with 10 g of methyl ester and unsaturated acids (Experiment 4). . After 3 hours of vigorous stirring, 0.2 wt. % of bromine and after 10 min. For example, all 3 samples are similar to Example 1.

Example 3

The procedure is analogous to Example 2 except that, except for the mixture of methyl esters and unsaturated carboxylic acids, 3 wt. % monomers to polyenes: unsaturated dimers of α-methylstyrene (experiment 4), propylene tetramer (experiment 5), butene trimmers (experiment 6), rubber pyrolysis products (experiment 7), distillation residue of pyrolysis C ₅ fraction - mixture of dimers and cooligomers cyclCable 1 lopentadiene, piperylene and isoaylenes (Experiment 8), liquid polybutadiene rubber with an average molecular weight of 1000 (Experiment 9).

Then, based on polybutadiene, natural and butadiene styrene SBR (50 + 30 + 20 dsk) in the 1st stage with stirring at 145 ± 2 ° C, a rubber blend was prepared by adding 3 parts of zinc oxide, 5 parts of aromatic oil, 60 parts of carbon black N330, 2 dsk stearin, 1.5 dsk antiozonant, PPD (N-isopropyl-N'-phenyl-p-phenylenediamine), 1.2 dsk TMQ antioxidant, 1.5 dsk adhesive resin, 2 dsk micro wax (a mixture of higher n-alkanes with isoalkanes) and 3 dsk of processing additive.

In the second stage, 0.8 dsc of the CBS vulcanization accelerator, 0.1 dsk of the vulcanization inhibitor Duslin G-80 (N-cyclohexylthiophthalimide) and Xg are added at 110 ° C with stirring on a two-roll calender (fraction 1: 1.4). , respectively. dsk of the sulfur vulcanization system. The vulcanization characteristics are determined at 150 ° C on a Monsanto MDR 2000E, at 150 ° C. The physical properties were determined in vulcanization mixtures after the time of vulcanization t ₉ o according to ISO standards. The vulcanizing agents are dosed into individual rubber mixtures after conversion to the active substance sulfur. The results obtained for the physico-mechanical parameters of the vulcanized rubber mixtures with the samples from the experiments for the preparation of the vulcanizing agents of Experiments 1 to 9 are given in Table 1.

Vlastnosťparameter Experiments reference 1 2 3 4 5 6 7 8 9 10 vulcanizing agent experiment / dsk Crystex OT33 / 2.5 1 / 1.88 2 / 1.88 3 / 1.97 4 / 1.77 5 / 1.92 6 / 1.92 7 / 1.92 8 / 1.92 9 / 1.92 10 / 2.26 mixture density [gem · ³ ] 1.12 1.12 1.12 1.12 1.12 1.12 1.12 1.12 1.12 1.20 1.21 safety at 120 ° C [min] 47.45 45,22 45,37 43.80 46,21 45,73 46.01 46,51 45.92 45.60 46.81 strength before aging [MPa] 16.85 16.75 16.95 17.04 17.15 17.45 17.73 17.15 17.21 18.02 16.90 strength after aging [MPa] 12.75 13.90 15,01 14,60 13.95 14.64 15.22 13.53 13.84 14.14 12.82 tensibility [%] 490 495 489 493 460 475 450 460 485 505 550 module 300% [MPa] 8.83 8.95 8.45 8.32 9.05 8.53 8.79 8.63 9.01 9.18 7.75

Example 4

The copolymers of sulfur are prepared by addition to polyreactions (sulfur homopolymerization, cyclooctaumic and polymeric sulfur copolymerization with 10 wt.% Unsaturated fatty acids, especially C ₁₆ to C ₂₂ ) of molten sulfur from Claus process or natural, at a temperature of 180 ± 2 ° C with rapeseed oil ( experiment 11) with acid number = 3.41 mg KOH / g, saponification number 189 mg KOH / g, iodine number = 115.60 g 1/100 g, glycerides of 56% oleic acid, 1.7% stearic acid, 4 6% palmitic acid, 20% linoleic acid, 10.5% linolenic acid, behenic acid, gadoleic acid, erucic acid together 2.5 wt. %.

Furthermore, with a mixture of fatty, mainly unsaturated (with one to four double bonds per molecule) acids in admixture with their esters (Experiment 12), with an acid number = 78.8 mg

KOH / g, saponification number = 181 mg KOH / g and bromine number = 42.14 g Br / 100 g, as well as a mixture of almost pure unsaturated rapeseed oil fatty acids (Experiment 13) with an acid number = 98.58 mg KOH / g , saponification number = = 204.0 mg KOH / g, ester number = 12.7 mg KOH / g, bromine number = 66.4 g Br / 100 g and iodine number = = 98.5 g 1/100 g, pure acid oleic acid (Experiment 14), rapeseed oil methyl esters (Experiment 15). Reactions to polyreactions of all 5 experiments are carried out under an inert atmosphere for 240 minutes. At 230 min. 0.2 wt.% is added to each polyreaction mixture. % iodine, and at 240 minutes, each reaction mixture was poured into a cold 1-4 ° C aqueous solution of partially saponified polyvinyl acetate for 30 s, and after drying, each sample was ground and used as a vulcanizing agent in the side rubber mixture. Under otherwise similar conditions, the polyreaction of sulfur was carried out with oleic acid at 125 ± 1 ° C for 5 h (Experiment 16).

Test mixtures are prepared by two-stage mixing according to STN 621425, wherein samples of the predominantly copolymer compounds are admixed with the first stage of preparation of the masterbatch, but with only two unsaturated rubbers and other components qualitatively similar to those of Example 4, since it is mainly a comparison of vulcanizing agents. The results of the effect on the vulcanization characteristics, chemical and physico-mechanical properties of the vulcanizates with samples of experiments 11 to 16 are shown in Table 2.

Table 2

These results indicate that, in particular, in terms of the vulcanizate strength before and after aging, the lowest values are obtained using a sulfur-copolymer of rapeseed oil (Experiment 11). In further experiments copolymerizing sulfur and rapeseed oil with 4, 7, 12 and 15 wt. % in the reaction mixture, the obtained copolymers of sulfur has even less favorable results than the vulcanizing agent, in particular on the physico-mechanical properties; both in comparison with the commercial polymer sulfur and in virtually all of the experiments presented in Tab. Second

component Experiments Reference sN-S 11 12 13 14 15 ** 16 1st degree rubber compound [g] 979 979 979 979 979 979 979 Sulfenax CBS / MG 4.13 4.13 4.13 4.13 4.13 4.13 4.13 Duslin G-80 [g] 0.59 0.59 0.59 0.59 0.59 0.59 0.59 Vulcanising agent [g] 16.31 14.14 14.13 14,29 14,29 14.13 14,29 Properties of vulcanizate Density [g.cm ' ^J ] 1,120 1,120 1,121 1,123 1,122 1,120 1,122 MOONEY Viscosity [ML] 45.80 44.40 45.00 47.50 47.40 45.60 46.10 Security MOONEY [min] 47.40 45.80 44.72 39.80 46.39 6.73 45.20 Cure Optimum, 150 ° C [min], + 2min. 21.0 21.5 19.5 20.0 19.0 19.0 20.1 Strength before aging, lop. [MPa] 17,150 14,477 15,000 17,080 17,965 17,310 17,100 Strength after aging, 100 ° C, 72h, lop. [MPa] 13,320 8,400 8,548 13,910 10,990 11,965 10,993 Ductility [%] 502 470 485 553 513 553 535 Module 300% [MPa] 8,833 8,457 8,690 8,370 9,215 8,770 8,870 Hardness [ShA] 57.13 57,76 58.70 60.00 57.30 58,43 56.9 Hardness after aging 100 ° C, 72h, [ShA] 63.88 64,12 65.57 68,00 63.60 65.77 64,89 Reflection elasticity [%] 54,27 54.47 54,00 54,00 57.47 57.93 54,22 Structural strength (20 ° C) [kNm ¹ ] 49,480 48,763 48,490 49,040 47,827 49,060 49,211 Structural strength (90 ° C) [kNm · ¹ ] 38.20 40.39 41.36 38.95 37.82 43.21 41.27

Sulfenax GBS / MG accelerator (N-cyclohexyl-2-benzothiazolesulfenamide),

Dulin G-80 - vulcanization inhibitor (N-cyclohexylthiophthalimide) and no stabilizer was used.

Also noteworthy (the 15-copolymer sulfur experiment with rapeseed oil methyl esters) is valuable that the omission of the stabilizer does not appear to be significantly negative. In experiment 14, where stearic acid is used as a stabilizer instead of iodine, no negative effect is observed. Even without the use of a stabilizer (Experiment 15), the quality of this vulcanizing agent does not decrease. This is also related to a sufficiently long polyreaction time at a relatively high temperature.

Example 5

Further preparation of the "copolymeric sulfur" is carried out in a similar manner as in Example 3, in particular with a mixture of acids and rapeseed oil esters of 90 wt. % of the total sulfur, with 3/4 of a mixture of organic rapeseed acid and 1/4 of methyl rapeseed oil esters used for the vulcanizing agent of Experiment 17. For the vulcanizing agent of Experiment 18, the equilibrium ratio, i.e.. j. 50: 50% mixture of organic acids with methyl esters and experiment 19 with 1/4 mixture of acids with 3/4 methyl esters of rapeseed oil mixture. The reagents of Experiments 17-19 are stabilized with 0.2 wt% iodine.

In experiment 20, in a vulcanizing agent containing 10 wt. % of the total sulfur formed with unsaturated rapeseed oil esters alone and without the use of a stabilizer. In Experiment 21, this is a vulcanizing agent with 85 wt. % of total sulfur prepared by reactions to polyreactions only with rapeseed oil methyl esters, stabilized with 1 wt. % stearic acid. The results are shown in Tab. 3. The reference experiment, ie using polymer sulfur (sulfur -N), is shown in Tab. Second

The apparent decrease in physico-mechanical properties is at least 85 wt.% At the total sulfur content of the vulcanizate. % (experiment 21).

Example 6

Rape oil allyl esters prepared by alkaline catalyzed rapeseed oil ester esterification are used to prepare the vulcanizing agent, similar to the flax oil methyl esters of Example 2. However, the vulcanizing agent obtained by its vulcanizing characteristics of the rubber mixture as well as the physical-mechanical parameters of vulcanizates only by 3 to 10% exceeds the parameters achieved with sulfur-based vulcanizing agents and rapeseed or linseed oil methyl esters in combination with saturated monoenes to polyenes (Example 3).

In the case of esterification of rapeseed oil with a mixture of unsaturated C ₁₆ to C ₂₂ alcohols obtained by selective hydrogenation on a modified ruthenium catalyst by hydrogenating a mixture of unsaturated fatty acids from rapeseed oil to unsaturated C ₁₆ to C ₂₂ alcohols, it is also used to prepare the vulcanizing agent. A suitable total sulfur content is in particular in the range of 88 to 95 wt. %, which is related to the size of the molecules and the presence of two to six double bonds in the ester molecule. Vulcanization characteristics and vulcanizates have approximately the same good properties as those achieved with a copolymer of the sulfur-based or a mixture of unsaturated fatty acid C _i2 to C 22, and the methyl and allyl esters. However, their further advantage is the lubricating effect of the rubber mixture.

Example 7

The reaction of the reaction to polyreakcií unsaturated fatty acids _{C] 2} to C ₂₂ with 1 to 4 double bonds. In the molecule and / or their alkyl esters to alkenyl esters or mixtures thereof with monoene to polyenes, after at least a substantial part of the polyreactions have taken place, most preferably after addition of a stabilizer known to stabilize the polymeric sulfur, it is rectified either in cold water (below 50 ° C) or in an aqueous surfactant solution. agents, such as polyvinyl alcohol, partially saponified polyvinyl acetate, gelatin, and the like polyakralamidu., dried and comminuted as domieľaním, and is connected, as solid paraffins, 1 - C ₃₀ alkenes, and the like. Spraying into cold air or inert gas at a temperature below 20 ^° C or spraying onto a cold pad or conveyor belt cooled in a freezing tunnel at a temperature below 20 ° C is suitable to facilitate a fine change. Similarly, the sprayed molten sulfur or vulcanizing agent formed is conveniently sprayed into cold water or cold aqueous solution (below 50 ° C, most preferably below 5 ° C) of the surfactant present in an amount of 0.01 to 0.5% by weight.

Table 3

Component [g] experiments 17 18 19 20 21 Rubber mixture of grade I [g] 979 979 979 979 979 Sulfenax CBS / MG 4.13 4.13 4.13 4.13 4.13 Glin G-80 0.59 0.59 0.59 0.59 0.59 Vulcanising agent [g] 14.13 14.13 14.13 14.13 14.13 Properties of vulcanizate Density [g.cm ’·’] 1,121 1,122 1,122 1,122 1,124 Mooney Viscosity [ML] 48.2 47.7 47.6 45.60 44.0 Mooney Security, 120 ° C [min] 43,35 39.67 39,55 47,25 44.52 Optimum vulcanization, 150 ° C, + 2min. 19.5 19.0 21.0 19.0 20.0 Strength before aging, lop. [MPa] 17.07 18,08 17.70 17.31 14.40 Ductility [%] 546 580 541 553 443 Module 300% [MPa] 8,52 8.47 9.18 8.77 9.20 Hardness [ShA] 60.0 60.0 60.0 58.4 61.2 Hardness after aging (100 ° C, 72h) 68.0 68.0 68.0 65.8 68.4 Reflection elasticity [%] 54.6 53.80 54,60 53,93 53,33 Structural strength (20 ° C) [kNm ^-1 ] 46,02 47.70 51.40 49,06 52.64 Structural strength (90 ° C) [kNm ^-1 ] 40,82 43.70 36.72 43.21 38.03

Industrial usability

The vulcanizing agent and the process for its preparation are useful in the chemical industry, in particular for the recovery of cheap sulfur, e.g. from the Claus process, from gases containing sulphane desulfurization of petroleum fractions, especially in rubber production, in the manufacture of tires, conveyor belts, etc., and it is furthermore particularly attractive to employ technically readily available mainly mixtures of C ₁₆ to C ₂₂ unsaturated carboxylic acids and unsaturated methyl esters acids from vegetable oils, in particular rapeseed oil.

Claims (11)

PATENT CLAIMS CLAIMS 1. A vulcanizing agent for the sulfur vulcanization of a rubber or rubber composition based on at least one unsaturated rubber or a mixture thereof with other hydrocarbon macromolecular substances, such as saturated rubbers, characterized in that it consists of addition products through polyreaction of sulfur in the presence of at least one unsaturated aliphatic aliphatic acid. having 1 to 4 double bonds per molecule, having a carbon number of 12 to 22 and / or esters thereof having a carbon number of 1 to 4 and / or an alkenyl of 3 to 18, or mixtures thereof, with at least one monoene to polyene, the sulfur or adjuvant content of the curing agent is 75 to 96 wt. %. Vulcanising agent according to claim 1, characterized in that the product of addition to polyreaction of sulfur is formed from elemental, cyclooctamic to polymeric sulfur with at least one unsaturated carboxylic acid having a carbon number of 8 to 22 and / or at least one ester thereof. Vulcanising agent according to claims 1 and 2, characterized in that the polyreaction product is at least one product selected from copolymeric sulfur with at least one unsaturated carboxylic acid having one to four double bonds per molecule and / or an ester thereof, or a mixture thereof with monoenes to polyenes. The vulcanizing agent according to claims 1 to 3, characterized in that the aliphatic unsaturated carboxylic acids are selected from monoenoic fatty acids such as lauroleic acid, myristoleic acid, palmitoleic acid, elaidic acid, oleic acid, gadoleic acid and erucic acid, such as as well as polyenic fatty acids: linoleic, linolenic, oleoleosteic, parinaric, arachidinic and their isomers. The vulcanizing agent according to claims 1 to 4, characterized in that the alkyl esters of unsaturated higher fatty acids are formed by esterification and / or transesterification with saturated alcohols selected from methanol, ethanol, propanol, isopropanol, butanol and isobutanol and alkenyl esters with unsaturated alkanols, selected from allyl alcohol, crotyl alcohol, oil alcohol, linolyl alcohol, linolyl alcohol and oleostearyl alcohol. The vulcanizing agent according to claims 1 to 5, characterized in that at least one monoene is selected from hydrocarbon monomers such as styrene, α-methylstyrene, vinyltoluenes, dimer to tetramer of propylene, dimers to tetramers of butenes and dimers of α-methylstyrene, dipentenes and polyenes such as dimers to oligomers of cyclopentadiene, piperylene, co-oligomers of dimers with alkenes of pyrolysis C ₅ -fraction, liquid polybutadiene rubber, rubber pyrolysis products and rubbers. The vulcanizing agent according to claims 1 to 6, characterized in that, in the case of a content of a mixture of sulfur with excipient (s), the content of the vulcanizing agent is 0.05 to 1.2% by weight. % and are selected from polymeric sulfur stabilizers and surfactants. 8. A process for the production of a vulcanizing agent for the sulfur vulcanization of a rubber or rubber composition based on at least one unsaturated rubber or a mixture with other hydrocarbon macromolecular substances, such as saturated rubber, characterized in that at temperatures of 120 to 250 [deg.] C. in an amount of 75 to 96 wt. % in a reaction to polymer action mixture with 25 to 4 wt. % with at least one unsaturated aliphatic carboxylic acid having a carbon number of 12 to 22 and one to four double bonds and / or an ester thereof, an alkyl having a carbon number of 1 to 4 and / or alkenyls having a carbon number of 3 to 18 with one to three % of double bonds, or a mixture thereof with at least one monoene to polyene, wherein after addition of the adjuvant or adjuvants in an amount of 0.05 to 1.2 wt. % in the reaction to polyreaction mixture, the reaction to polyreaction mixture is rapidly cooled to a temperature below 50 ° C by at least one operation selected from dosing to cold water, dosing to cold aqueous solution, spraying to cold water or cold aqueous solution, spraying to spraying to cooled walls below 20 ° C, by spraying up to spraying into the cooled off-gas stream to temperatures below 20 ° C, pouring onto a deep-cooled metal support or deep-cooled conveyor belt, and subsequently treated by drying or directly disintegrating, optionally oiling and shaping into a well-applicable form as a vulcanizing agent. The process for producing the vulcanizing agent according to claim 8, characterized in that at least one monoene to polyene fatty is fed to the molten sulfur at a temperature of 120 to 250 ° C or starting from Claus's sulfur production process before cooling, singly or in portions until continuously. the C ₁₂ to C ₂₀ acid and / or an ester thereof, or a mixture thereof with at least one monoene to polyene, wherein an adjuvant or excipients selected from antireversion agents are introduced into it and / or the flowing solution before the polyreaction melt is suddenly cooled; and / or known stabilizers of metastable polymeric sulfur and surfactants. The process for producing a vulcanizing agent according to claim 8 and 9, wherein the monoenoic to polyeneic fatty acid is selected from: lauroleic, myristoleic, palmitoleic, oleic, elaidic, gadolenic, gadoelaidic, erucic, linoleic, linolenic, paroostearic, eleostearic. arachidonic acid as well as their isomers and esters of at least one monoene to polyene fatty acid C ₁₀ to C ₂₂ are prepared by esterifying them with alkanols having a carbon number of 1 to 4 and / or unsaturated alkanols having a carbon number of 3 to 18 and one to three triple bonds and / or transesterification with said alcohols of liquid glycerides containing predominantly C ₁₂ to C ₂₂ unsaturated carboxylic acids with one to four double bonds per molecule. Process for the production of a vulcanizing agent according to claim 8 to 10, characterized in that at least one additionally at least one additionally to at least one sulfur-polyunsaturated fatty acid, homopolymerization and copolymerization of sulfur with monoenoic to polyenoic fatty acids and their esters with saturated to unsaturated alcohols is added to the reaction medium. monoene to polyene, selected from hydrocarbon monomers such as styrene, α-methylstyrene, α-methylstyrene dimers, propylene dimers to tetraers, butene dimers to trimers, vinyltoluenes, ethylene oligomers, dimers to oligomers: cyclopentadiene, pipigensene, piperoisene, C _{5 -} fractions, liquid polybutadiene rubber, rubber pyrolysis products and rubbers.