BRPI0812148B1 - RUBBER NITRILE, PROCESS FOR THE MANUFACTURE OF RUBBER Nitrile FOR POLYMERIZATION, RUBBER Nitrile hydrogenated, USE OF RUBBER Nitrile, vulcanizable MIX, PROCESS FOR THE MANUFACTURE OF A MIXTURE vulcanizable, PROCESS FOR PARTS MANUFACTURING FRAMED THE BASIS OF A RUBBER NITRILE, AND ASK FRAMED - Google Patents

Description

(54) Title: NITRILE RUBBER, PROCESS FOR THE MANUFACTURE OF NITRILLIC RUBBERS BY POLYMERIZATION, HYDROGENATED NITRILLIC RUBBERS, USE OF NITRILLIC RUBBER, VULCANIZABLE MIXTURE, A PROCESSED MACHINING PROCESS NITRILE RUBBER, AND MOLDED PIECE (51) lnt.CI .: C08C 1/14; C08C 1/15; C08F 6/14; C08L 9/02 (30) Unionist Priority: 22/05/2007 DE 102007024011.4 (73) Holder (s): ARLANXEO DEUTSCHLAND GMBH (72) Inventor (s): WERNER OBRECHT (85) National Phase Start Date: 23 / 11/2009

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NITRILLIC RUBBER, PROCESS FOR THE MANUFACTURE OF NITRILLIC RUBBERS BY POLYMERIZATION, NITRILLIC RUBBERS, HYDROGENATED, USE OF NITRILLARY RUBBERS, VULCANIZABLE MIXTURE, PROCESS FOR THE MANUFACTURING OF A MACHINING MACHINERY MOLDED [001] The invention relates to a nitrile rubber, a process for its manufacture, vulcanizable mixtures based on this nitrile rubber, in addition to a process for the manufacture of vulcanized products from these mixtures, as well as the vulcanized products thus obtained.

[002] By nitrile rubbers, also known for short as NBR, is meant copolymers or terpolymers of at least one alpha nitrile, betainsaturated, at least one conjugated diene and, possibly, one or more additional copolymerizable monomers.

[003] Such nitrile rubbers and processes for the manufacture of such nitrile rubbers are known, for example, in W. Hofmann, Rubber Chem, Technol, 36 (1963) 1 and Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft, Weinheim, 1993, S. 255-261. In these publications, there is no indication as to whether it is possible or, possibly, how the vulcanization speed of such rubbers and their characteristics profile, in particular, the level of the modulus values are influenced.

[004] NBR is manufactured by emulsion polymerization, in which, first, an NBR latex is obtained. The solid NBR material is isolated from this latex by coagulation. For coagulation, salts and acids are used. About the coagulation of latex with metal salts it is known that they are

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2/52 noticeably greater electrolyte amounts of monovalent metal ions, for example in the form of sodium chloride, than of polyvalent metal ions, for example in the form of calcium chloride, magnesium chloride or aluminum sulphate (Kolloid-Z. 154, 154 (1957)). It is also known that the use of polyvalent metal ions leads to a greater or lesser incorporation of the emulsifier in the product (Houben-Weyl (1961), Methoden der Org. Chemie, Makromolekulare Stoffe 1, S. 484). According to Houben-Weyl (1961), Methoden der Org. Chemie, Makromolekulare Stoffe 1, page 479, not only must the electrolytes used be carefully washed, but the final product must also be free of catalysts and emulsifiers from the beginning. Only small residues of electrolytes result in cloudy and cloudy pressed and injected parts, deteriorating electrical characteristics and increasing the water absorption capacity of the final product (mentioned). In Houben-Weyl, there is no trace of how a latex must be restored to obtain nitrile rubbers with rapid vulcanization and which, after vulcanization, have a high level of modulus values.

[005] From DD 145 702 a process is known for the radical copolymerization of butadiene and acrylonitrile in emulsion, which is controlled by a special computer-controlled dosing program, suitable for monomers, such as tert-dodecyl-mercaptan , and in which the latex obtained by coagulation is restored, in an acid medium, to solid rubber. The main advantage of the process is the fact that resin and / or fatty acid soaps, used as emulsifiers,

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3/59 remain in the rubber due to the use of acids in coagulation, not being washed, therefore, as in other processes. Here, in addition to the advantage of good NBR characteristics, it is also claimed to improve the economics of the process and to avoid the effluent load by washed emulsifiers. For acrylonitrile butadiene copolymers obtained with 10-30% by weight of acrylonitrile, it is described that they stand out for their good elasticity characteristics and low temperatures, combined with an increased resistance to turgor and an advantageous processability. However, it is not possible to obtain from the teachings of this patent, measures by which it is possible to influence the vulcanization speed of nitrile rubber or the characteristics profile of the vulcanized NBR.

[006] DE JP 27902/73 (Appl. 69 32,322) it is known that, by using amines in the coagulation of latex with magnesium salts, for example by combining diethylenetriamine and magnesium chloride, the rate of pre-treatment is reduced and, thus, the resistance to pre-curing of nitrile rubbers can be improved. Further evidence is not available from this state of the art.

[007] From DE-OS 23 32 096 it is known that rubbers can be precipitated from their aqueous dispersions with the help of methylcellulose and an alkaline, alkaline earth, aluminum or zinc water-soluble salt. As the preferred water-soluble salt, sodium chloride is used. As an advantage of this process, it is described that a coagulate practically free of impurities is obtained, such as emulsifiers, catalyst residues and the like, since

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4/59 these impurities are removed in the separation of the coagulate, together with water and any remaining remnants, being washed thoroughly with additional water. No statements are made regarding the vulcanization behavior of rubbers manufactured in this way. In DE-OS 24 25 441, 0.10% by weight (relative to rubber) of water-soluble C2-C4 alkylcelluloses in combination with 0 are used as auxiliary means in the coagulation in rubber latex electrolyte, instead of methylcellulose. , 02 to 10% by weight (relative to rubber) of an alkaline, alkaline earth, aluminum or zinc water-soluble salt. Here too, sodium chloride is used as the preferred water-soluble salt. The coagulate is mechanically separated, eventually washed with water and the remaining water removed. Also here it is described that the impurities, as in DE-OS 23 32 096, are effectively removed in their entirety together with water when the coagulate is separated, and any remaining remains are washed thoroughly with additional water.

[008] DE-OS 27 51 786 shows that the precipitation and isolation of rubbers from their aqueous dispersions can be carried out with a small amount of (hydroxy) alkyl cellulose, when 0.02 to 0.25% are used in weight of a water-soluble calcium salt. It is described as an advantage that, through this process, an extremely pure coagulate is obtained, which is effectively free of impurities, such as emulsifiers, remains of catalysts and the like. These impurities are removed with water in the separation of the coagulate and any remaining lines can be washed with water. Additionally, it is described that the characteristics of the isolated rubbers are not influenced

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5/59 disadvantageously because the coagulation was carried out with a calcium salt. On the contrary, a rubber would be obtained in which the vulcanization characteristics are not compromised and which would be completely satisfactory. This is presented as surprising, since a compromise in the characteristics of the rubber would often be observed, when polymers are precipitated from dispersions with the help of polyvalent metal ions, such as calcium or aluminum ions. As evidence for the latter statement, Houben-Weyl (1961), Methoden der Org. Chemie, Makromolekulare Stoffe 1, pages 484/485 will be used. DE-OS 27 51 786 rubbers, on the contrary, did not show any delay or worsening, for example, in pre-curing and / or complete vulcanization.

[009] From none of the documents DE-OS 23 32 096, DE-OS 24 25 441 and DE-OS 27 51 786 it is possible to derive which measures should be taken to achieve a fast vulcanization and good vulcanized characteristics.

[0010] In the same way as in the patents described above, it is also the objective of DE-OS 30 43 688 to strongly reduce the amount of electrolyte necessary for the coagulation of latex. This is achieved through the teachings of DE-OS 30 43 688, using, for the coagulation of latex in electrolysis, in addition to the inorganic coagulator, auxiliary means such as materials of protein origin from plants or polysaccharides, as for example, starch and, possibly, polyamine compounds. As inorganic coagulators, preferably alkali metal or alkaline earth salts are described. Special additives reduce the amounts of salt

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6/59 required for quantitative latex coagulation. From DEOS 30 43 688 there is no indication of how to achieve rapid vulcanization through the manufacture and / or restoration of nitrile rubber.

[0011] In US-A-4,920,176 it is described, and supported by experimental data, that in the coagulation of a nitrile rubber latex with inorganic salts, such as sodium chloride or calcium chloride, high levels of nitrile rubber remain sodium, potassium and calcium and additionally emulsifiers. This is, however, undesirable, and in order to obtain nitrile rubber with the highest possible purity, nitrile rubber latex coagulation is used, according to the teachings of Na US-A-4,920,176, water-soluble cationic polymers instead of salts inorganic substances, such as epichlorohydrin and dimethylamine. These auxiliary means aim to achieve a significant reduction in the remaining amounts of salt in the product. The vulcanized products thus obtained, have a low turgor when stored in water, as well as a greater electrical resistance. In the report of this patent, the mentioned property improvements are simple and qualitatively related to the minimum levels of cations remaining in the product. An additional explanation of the observed phenomena is not given. US-A-4,920,17 also makes no statement as to whether it is possible or how it influences the vulcanization behavior and module level through the manufacture and restoration of nitrile rubber.

[0012] The purpose of EP-A-1 369 436 is to provide high purity nitrile rubbers. The

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7/59 residual levels of emulsifiers of these nitrile rubbers are, in particular, very low. Also, the determined levels of cations in the form of sodium, potassium, magnesium and calcium contents are very low. Nitrile rubbers are manufactured by carrying out emulsion polymerization in the presence of fatty acids and / or salts of resin acids as emulsifiers, after which the latex is coagulated with acids, possibly by adding precipitation agents. As acids, all mineral and organic acids can be used to adjust the desired pH values. As additional precipitating agents, for example, alkaline salts of inorganic acids are used. In addition, the resulting fatty and resin acids are washed with aqueous alkaline hydroxy solutions and the polymer subsequently subjected to a shear, until a residual humidity of less than or equal to 20% is established. EP-A-1 369 436 does not provide evidence for the manufacture of nitrile rubbers that exhibit rapid vulcanization and, after vulcanization, a high level of modulus.

[0013] EP-A-0 692 496, EP-A-0 779 301 and EP-A0 779 300 describe, respectively, nitrile rubbers based on unsaturated nitrile and a conjugated diene. Common to all nitrile rubbers is the fact that they have 10-60% by weight of unsaturated nitrile and a mooney viscosity in the range of 15-150, or according to EP-A-0 692 496, of 15-65 and all present, at least at least 0.03 mol of a C12-C16 alkylthiol group per 100 mol of monomer units, and that this alkylthio group comprises at least three tertiary carbon atoms and a sulfur atom, which is

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8/59 attached directly to at least one of the tertiary carbon atoms.

[0014] The manufacture of nitrile rubbers occurs respectively in the presence of a corresponding Ci2-Ci6-alkyl-thiol as a molecular weight regulator, which acts as a chain transfer agent and, thus, is embedded as a final group in the polymeric chain.

[0015] For nitrile rubbers according to EPA-0 779 300, it is described that they have a width ΔΑΝ ”(AN means acrylonitrile), of the composition distribution of unsaturated nitrile in the copolymer, in the range of 3 to 20. The process for its manufacturing differs from that of EP-A-0 692 496 in that only 30-80% by weight of the total monomeric amount is used at the beginning of the polymerization, and that the remaining monomer amount is added only from a polymerization rate of 20-70% by weight.

[0016] For nitrile rubbers according to EPA-0 779 301, it is described that they have 3-20% by weight of a fraction with low molecular weight with an average molecular weight M _n less than 35,000. The manufacturing process differs from that of EP-A-0 692 4 96 in that only 10-95% by weight of the alkyl thiol are mixed in the monomeric mixture before polymerization, and the remaining amount of the alkyl thiol is added only on reaching a polymerization rate of 20-70% by weight.

[0017] In relation to the coagulation of latex, is described in all the three patent deposits EP-A-0 692 496, EP- -A-0 779 301 and EP-A-0 779 300, which can to be

any coagulants are employed. As inorganic coagulants, calcium chloride and

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9/59 aluminum chloride. According to EP-A-0 779 301 and EP-A-0 779 300, there is a preferential modality of execution through a nitrile rubber that, substantially, is free of halogens and is obtained through the execution of the coagulation of the latex in the presence of a nonionic and superficially active auxiliary medium, and using halogen-free metal salts, such as aluminum sulfate, magnesium sulfate and sodium sulfate. Preferably, coagulation is indicated using aluminum sulfate or magnesium sulfate. The halogen-free nitrile rubber thus obtained, has a halogen content of a maximum of 3 ppm.

[0018] In comparative example 6 of EP-A-0 779 300 and in comparative example 7 of EP-A-0 779 301, the latex coagulation is performed with a mixture of NaCl and CaCÍ2, where CaCÍ2 is used in large quantities and the weight ratio between NaCl and CaCl2 is 1: 0.75. Regarding the pre-curing time and the tension with 100% stretch, no significant differences are found in comparison to the other examples listed in the respective tables 12 and 13.

[0019] For the manufacture of nitrile rubbers according to EP-A-0 692 496, EP-A-0 779 300 and EP-A-0 779 301, it is essential that, as molecular weight regulators, alkyl thiols in the form of compounds 2,2,4,6,6-pentamethyl-heptanethiol-4 and 2,2,4,6,6,8,8 heptamethyl-nonanethiol-4. For this, it is implicitly remembered that, in the use of the commonly known tert-dodecylmercaptan as a regulator, nitrile rubbers with worse properties are obtained.

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2,2,4,6.6-pentamethyl-heptanothioM fH, ÇH, CH, r ι

H.C-C-CH — p

-CH— C-CH,

CH,

CH,

2,2.4,6,6,8,8-heptamethyl-nonanethiol-4

ÇH, CH,

H, CCH.

SH

-CH — Ç-CH — j: -CH,

CH, CH, [0020] For nitrile rubbers manufactured in EP-A-0 692 496, EP-A-0 779 300 and EP-A-0 779 301, it is stated that they have an advantageous profile of characteristics, enabling a good processability of rubber mixtures and a low degree of mold contamination during processing. The vulcanized products obtained, supposedly have a good combination between resistance to low temperatures and oil and have good mechanical characteristics. Additionally, it is stated that, in the manufacture of nitrile rubbers by high polymerization rates, of more than 75%, preferably greater than 80%, high productivity can be achieved and that the speed of vulcanization in vulcanization with sulfur or peroxides is also high, especially in NBR types for injection processing. Additionally, it is shown that nitrile rubbers have a short pre-curing time and a high crosslink density. As proof for the rapid vulcanization of nitrile rubbers manufactured according to EP-A-0 692 496, EPA-0 779 300 and EP-A-0 779 301, the pre-curing time (the so-called scorch time (measured as T5 )), which, incidentally, merely represents a measure for the speed of pre-set. No statements are made about the speed of total vulcanization or how it might be influenced. The crosslink density is only described by indicating the maximum torque value (measured as Vmax)

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11/59 [0021] In practice, short pre-curing times are not desirable continuously, since the respective rubber mixtures, due to such a quick pre-curing, are not reliable to be processed. In particular in injection, a quick pre-cure is not enough. Decisive for economically viable processing is the establishment of short cycle times. For short cycle times, the difference between vulcanization speed and pre-cure speed is decisive. This is measured as t9o-uncle, where t90 is the time taken to complete 90% of the vulcanization and uncle is the time taken to complete 10% of the vulcanization. Through the regulators 2,2,4,6,6-pentamethyl-heptanethiol-4 and 2,2,4,6,6,8,8-heptamethyl-nonanethiol-4 used in EP-A-0 692 496, EP- A-0 779 300 and EP-A-0 779 301, however, the establishment of a fast vulcanization characteristic as well as that of a high module level is not necessarily possible.

[0022] EP-A-0 692 496 describes, among others, that, for the establishment of high vulcanization speeds, many methods have already been suggested, for example, the use of minimal amounts of emulsifiers and precipitation agents, so that only minimal amounts of emulsifiers and precipitation agents remain in the NBR. According to EP-A-0 692 496, however, these measures are not sufficient.

[0023] In summary, it should be noted that, despite the comprehensive literature, to date there are still no known measures by which it is possible to influence the total vulcanization speed and, especially, the difference between the vulcanization speed and the speed

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12/59 pre-cure (t9o-unio), without compromising other important characteristics of nitrile rubber, such as, in particular, the characteristics of vulcanized products.

[0024] That said, the task of the present invention was to make available a process, through which nitrile rubbers are obtained, which, following their processing, allow rapid pre-curing and vulcanization and, thus, leading to vulcanized products with good profile of characteristics.

[0025] It has been found that nitrile rubbers with excellent vulcanization speed are obtained, as well as exceptional vulcanized characteristics, when emulsion polymerization is performed by choosing special molecular weight regulators and, simultaneously, latex coagulation is performed in such a way that nitrile rubbers are characterized by a special cation content.

[0026] The object of the present invention is, therefore, a process for the manufacture of nitrile rubbers by emulsion polymerization of at least one alpha, beta-unsaturated nitrile, at least one conjugated diene and, possibly, one or more additional monomers copolymerisables, in which the latex initially resulting from polymerization, containing nitrile rubber, is subjected to coagulation and the coagulated nitrile rubber obtained in addition is washed, characterized in that (i) the emulsion polymerization is carried out in the presence of at least one alkyl- thiol, which has 12-16 carbon atoms and at least three tertiary atoms of

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13/59 carbon, where the sulfur is attached to one of these tertiary carbon atoms, and (ii) the latex, obtained in emulsion polymerization, adjusted to a pH value of at least 6, and then coagulated with the use of at least one salt of a monovalent metal, in which a maximum of 5% by weight of salts of a divalent metal may be present in the coagulation, relative to the total amount of all salts used in the coagulation, and (iii) be a temperature of at least 50 ° C is adjusted, both in the coagulation of the latex and in the additional washing.

present nitrile, from at least one invention [0027] object, additionally, a rubber alpha, beta unsaturated nitrile repeating units, at least one conjugated diene and, possibly, one or more additional copolymerizable monomers, and for possessing a characteristic ion index (IKZ), of the generic formula (I), in the range of 7 to 26 ppm x mol / g,

C (Cs characteristic number üe ion - 40 β / παϊ c ( ^Ma 7 e | K *) g / moí 30 g / mol where c (Ca ²⁺ ), c (Na ⁺ ) and c (K ⁺ ) indicate the concentration in ppm of calcium, sodium and potassium ions in nitrile rubber.

[0028] Nitrile rubbers with a characteristic ion index within the mentioned ranges lead to a high vulcanization speed, characterized by

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14/59 difference between the vulcanization time and the pre-cure time (t9o-unio), and the good vulcanization characteristics (in particular a high level of modulus values).

[0029] Similar nitrile rubbers are not known in the prior art.

[0030] In the examples of EP-A-1 369 436 the cation contents are given for the nitrile rubbers described. Based on these data, the characteristic ion numbers can be calculated. They are outside the values observed for nitrile rubbers according to the invention: In example 1 of EP-A-1 369 436, a characteristic ion number of -12.5 ppm x mol / g is shown in example 2, if a characteristic ion number of -7.9 ppm x mol / g. At the same time, EP-A-1 369 436 has no indication that the cation mix has an influence on the total vulcanization speed, let alone how the cation mix should be in order to obtain a nitrile rubber that has the desired high pre-curing and vulcanization speeds and, at the same time, a good profile of characteristics.

[0031] In the examples of US-A-4,920,176, the cation contents for nitrile rubbers are also indicated. Based on these data, the characteristic ion indices can, according to formula (I) above, be calculated. If NaCI, considered as state of the art by US-A4,920,176, is used for the coagulation of latex, then the characteristic ion indices are obtained, which are in the range of 26.5 to 44.2 ppm x mol / ge , thus, above the characteristic ion index of nitrile rubbers according to the invention. If agents are employed according to US-APetição 870180065835, of 07/30/2018, p. 20/74

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4,920,176, named according to the invention of polymeric precipitation agents, then characteristic ion indices will be obtained that are less than 3.8 ppm x mol / g, and thus, visibly below the characteristic ion indices of the nitrile rubbers of the present invention. With the use of MgSCU in the coagulation of latex, according to the teachings of US-A-4,920,176, characteristic ion indexes of 5.7 and 6.5 ppm x mol / g result, that is, these values are also visibly below characteristic ion indices according to the invention. With the use of calcium chloride as a precipitation agent, according to US-A-4,920,176, characteristic ion indices result from 63 to 135 ppm x mol / g, that is, well above the characteristic ion indices according to the invention.

[0032] In the examples EP-A-0 692 496, EP-A-0 779

300 and EP-A-0 779 301, are used for the coagulation of latex calcium chloride, aluminum sulfate and magnesium sulfate. With the use of sodium chloride, in comparative example 6 of EP-A-0 779 300 and comparative example 7 of EP-A-0 779 301, 0.75 parts in weight by part of sodium chloride are used weight of calcium chloride. As the content of calcium ions enters factor 3 in the characteristic ion index, it must be assumed for these tests that the resulting nitrile rubbers have very high characteristic ion indexes (see US-A-4,920,176). In addition, the patent documents do not provide any indication as to whether and how the mix of cations remaining in the nitrile rubber influences the vulcanization characteristic.

Determination of cation contents:

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16/59 [0033] For the determination of the cation contents for the determination of the characteristic number of IKZ ions, according to the present invention, the following method has been successful, which will be used: 0.5 g of nitrile rubbers are disintegrated by incineration dry at 550 ° C in a platinum crucible with subsequent dissolution of the ashes in hydrochloric acid. After the appropriate dilution of the disintegrated solution with deionized water, the metal contents are determined by means of ICP-OES (inductively coupled plasma-

optical emission spectometry), against a solution calibration adjust with acid matrix, in the following wavelengths: Calcium: 317.933 nm, Magnesium: 285.213 nm and Potassium: 766.491 nm, Sodium: 589.592 nm. [0034] According to the concentration of

elements in the disintegrated solution and sensitivity of the measuring device used, the concentrations of the test solutions are adjusted to the linear range of the calibration for the respective wavelengths used. (B. Welz Atomic Absorption Spectrometry, 2nd Ed., Verlag Chemie, Weinheim 1985).

[0035] In the characteristic ion index, according to formula (I), the metal contents are divided by the atomic weights of the respective metals. For this reason, the IKZ size is ppm x mol / g.

[0036] The characteristic ion index is preferably in the range of 8 to 26 ppm x mol / g and, especially preferred, in the range of 10 to 26 ppm x mol / g.

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Nitrile rubber:

[0037] Nitrile rubbers, according to the invention, have repeating units of at least one alpha, beta-unsaturated nitrile, at least one conjugated diene and, possibly, one or more additional copolymerizable monomers.

[0038] The conjugated diene can be of any nature. Preferably, conjugated dienes (C4-C6) are used. Especially preferred are 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene, 1,3-pentadiene or mixtures thereof. Especially preferred are 1,3butadiene and isoprene or mixtures thereof. Especially preferred is 1,3-butadiene.

[0039] As alpha, beta-unsaturated nitrile, any alpha, beta-unsaturated nitrile can be used, with preferential nitriles (C3-C5) - alpha, beta-unsaturated as acrylonitrile, methacrylonitrile, 1-chloro-acrylonitrile, ethacrylonitrile or mixtures of these . Especially preferred is acrylonitrile.

[0040] An especially preferred nitrile rubber is therefore a copolymer of acrylonitrile and 1,3-butadiene.

[0041] In addition to the conjugated diene of alpha nitrile, beta-unsaturated, one or more additional copolymerizable monomers can be used, for example, alpha, beta-unsaturated mono or dicarboxylic acids, their esters or amides. Such nitrile rubbers are also commonly referred to as carboxylated nitrile rubbers, or XNBR for short.

[0042] As alpha mono or dicarboxylic acids,

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18/59 beta-unsaturated can be used, for example, fumaric acid, maleic acid, acrylic acid, methacrylic acid, crotonic acid and itaconic acid. Preferred are maleinic acid, acrylic acid, methacrylic acid and itaconic acid.

[0043] As an ester of alpha carboxylic acids, beta-unsaturated are used, for example, alkyl ester, alkoxyalkyl ester, hydroxyalkyl ester or mixtures thereof.

[0044] Especially preferred alkyl esters of alpha, beta-unsaturated carboxylic acids are methyl (meta) acrylate, ethyl (meta) acrylate, propyl (meta) acrylate, n-butyl (meta) acrylate, hexyl (meta) acrylate, 2- ethylhexyl (meta) acrylate, octyl (meta) acrylate and lauryl (meta) acrylate. In particular, n-butylacrylate is used.

[0045] Especially preferred alkoxyalkyl esters of alpha, beta-unsaturated carboxylic acids are methoxyethyl (meta) acrylate, ethoxyethyl (meta) acrylate and methoxyethyl (meta) acrylate. In particular, methoxyethylacrylate is used.

[0046] Especially preferred hydroxyalkyl esters of alpha, beta-unsaturated carboxylic acids are hydroxyethyl (meta) acrylate, hydroxypropyl (meta) acrylate and hydroxybutyl (meta) acrylate.

[0047] As esters of alpha, beta-unsaturated carboxylic acids, additionally employed are polyethylene glycol (meta) acrylate, polypropylene glycol (meta) acrylate, glycidyl (meta) acrylate, epoxy (meta) acrylate and urethane (meta) acrylate.

[0048] Other possible monomers are vinyls

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19/59 aromatics such as styrene, alpha-methylstyrene and vinylpyridine.

[0049] The participation of conjugated dienes and alpha, beta-unsaturated nitriles in nitrile rubbers according to the invention can vary in wide ranges. The participation or the sum of the conjugated dienes is normally in the range of 20 to 95% by weight, preferably in the range of 40 to 90% by weight, especially preferred in the range of 60 to 85% by weight, relative to the total polymer. The participation or sum of alpha, beta-unsaturated nitriles is normally in the range of 5 to 80% by weight, preferably in the range of 10 to 60% by weight, especially preferable in the range of 15 to 40% by weight, relatively to the total polymer. The combined monomer holdings make up 100% by weight, respectively.

[0050] The additional monomers can be in amounts from 0 to 40% by weight, preferably from 0.1 to 40% by weight, especially preferably from 1 to 30% by weight, relative to the total polymer. In this case, corresponding holdings of the conjugated or dienes and / or of the alpha, beta-unsaturated nitriles are replaced by the holdings of these additional monomers, in which, in addition, the holdings of all monomers combined form, respectively, 100% in Weight.

[0051] When esters of methacrylic acid are used as additional monomers, this commonly occurs in quantities of 1 to 25% by weight.

[0052] When alpha, beta-unsaturated mono- or dicarboxylic acids are used as additional monomers, this commonly occurs in amounts less than 10% by weight.

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20/59 [0053] The nitrogen content of nitrile rubbers according to the invention is determined, according to DIN 53 62 4, by the Kjeldahl method. Based on the content of polar comonomers, nitrile rubbers are usually soluble in methyl ethyl ketone at 20 ° C, greater than or equal to 85% by weight.

[0054] Nitrile rubbers have mooney viscosities (ML (1 + 4 at 100 ° C)) from 10 to 150, preferably 20 to 100 mooney units. The mooney viscosity (ML (1 + 4 at 100 ° C)) is determined, according to DIN 53523/3 and ASTM D 1646 at 100 ° C, by means of a shear disc viscometer.

[0055] The vitrification temperatures of nitrile rubbers are in the range of -70 ° C to + 10 ° C, preferably in the range of -60 ° C to 0 ° C.

Preferred are nitrile rubbers according to the invention, which have repeating units of acrylonitrile, 1,3-butadiene and, possibly, one or more additional copolymerizable monomers. Equally preferred are nitrile rubbers that have repeating units of acrylonitrile, 1,3-butadiene and one or more alpha, beta-unsaturated mono- or dicarboxylic acids, their esters or amides and, in particular, alkyl repeating units of a alpha carboxylic acid, beta-unsaturated, especially preferred methyl (meta) acrylate, ethyl (meta) acrylate, propyl (meta) acrylate, n-butyl (meta) acrylate, tbutil (meta) acrylate, hexyl (meta) acrylate, 2ethylhexyl (meta ) acrylate, octyl (meta) acrylate or lauryl (meta) acrylate.

Process for the manufacture of rubbers

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21/59 nitriles:

[0057] The manufacture of nitrile rubbers occurs, according to the process according to the invention, by emulsion polymerization.

[0058] As emulsifiers salts of anionic emulsifiers or neutral emulsifiers can also be used. Anionic emulsifiers are preferably used.

[0059] As anionic emulsifiers, modified resin acids, obtained by dimerization, disproportionalization, hydrogenation or modification of mixtures of resin acids containing abietinic acid, neoabietinic acid, palustrinic acid, levopimaric acid, can be used. An especially preferred modified resinic acid is disproportionate resinic acid (Ullmann's Encyclopedia of Industrial Chemistry, 6. Edition, Volume 31, pages 345-355).

[0060] Fatty acids can also be used as anionic emulsifiers. These contain 6 to 22 carbon atoms per molecule. They can be completely saturated or also have one or more double bonds in the molecule. Examples of fatty acids are capric acid, lauric acid, myristinic acid, palmitic acid, stearic acid, oil acid, linolic acid, linolenic acid. Carboxylic acids are usually based on oils or fats from specific sources, such as castor oil, cottonseed oil, peanut oil, flaxseed oil, coconut oil, palm seed oil, olive oil, canola, soy oil, fish oil and beef tallow etc. (Ullmann's Encyclopedia of Industrial Chemistry, 6.

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22/59

Edition, Volume 31, pages 75-108). Preferred carboxylic acids are derived from coconut fatty acid and bovine tallow and are partially or fully hydrogenated.

[0061] Such carboxylic acids based on resinous acids or modified fatty acids are used as water-soluble salts of lithium, sodium, potassium and ammonia. Preferred are sodium and potassium salts.

[0062] Anionic emulsifiers are, in addition, sulfonates, sulfates and phosphates, which are linked to an organic residue. As organic remainder, aliphatic, aromatic, alkylated, condensed aromatic compounds are possible, as well as aromatic compounds with methylene bridges, in which aromatic compounds with methylene bridges and condensates can be additionally alkylated. The length of the alkyl chains is 6 to 25 carbon atoms. The length of the alkyl chains attached to the aromatic compounds is between 3 and 12 carbon atoms.

[0063] Sulphates, sulfonates and phosphates are used as salts of lithium, sodium, potassium and ammonia. Preferred are the sodium, potassium and ammonia salts.

[0064] Examples of such sulphates, sulphonates and phosphates are sodium lauryl sulphate, sodium alkyl sulphate, sodium alkylaryl sulphate, sodium salts of aryl sulphonates with methylene bridges, sodium salts of alkylated naphthalene sulphonates as well as the salts of naphthalene sulfonates with methylene bridges, which can also be oligomerized, where the degree of oligomerization is between 2 and 10. Normally alkylated naphthalene acids and sulfonated naphthalene acids with methylene bridges (and,

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23/59 possibly alkylated), are presented as mixtures of isomers, which may also have more than one sulfonic acid group (2 to 3 sulfonic acid groups) in the molecule. Especially preferred are sodium lauryl sulfate, mixtures of sodium alkyl sulfonates with 12 to 18 carbon atoms, sodium alkylaryl sulfonates, sodium diisobutylene naphthalene sulfonate, mixtures of polyphthalene sulfonates with methylene bridges as well as mixtures of aryl sulfonates with methylene bridges .

[0065] Neutral emulsifiers are derived from ethylene oxide addition products in compounds with

That of and the oxide of sufficiently acidic hydrogen. These include, for example, phenol, alkylated phenol and alkylated amines. The average degrees of polymerization of epoxides are between 2 and 20. Examples of neutral emulsifiers are ethoxylated nonylphenols with 8, 10 and 12 ethylene oxide units. Neutral emulsifiers are not normally used alone, but in combination with anionic emulsifiers.

Preferred are the sodium and potassium salts of disproportionalized abietinic acid and tallow acid, as well as mixtures thereof, sodium lauryl sulfate, sodium alkyl sulfonates, sodium alkyl benzol sulfonate, as well as alkylated naphthalene sulfonic acids and with methylene bridges.

[0067] Emulsifiers are used in an amount of 0.2 to 15 parts by weight, preferably from 0.5 to 12.5 parts by weight, especially preferred from 1.0 to 10 parts by weight, relative to 100 parts in weight of the monomeric mixture.

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24/59 [0068] Emulsion polymerization is performed using the aforementioned emulsifiers. If, after the end of the polymerization, there are latex deaths that, due to a certain instability, tend to premature autocoagulation, the aforementioned emulsifiers may also be used for the post-stabilization of the latex. This may be necessary, especially before the removal of unprocessed monomers by treatment with water vapor, as well as before storage of the latex.

[0069] For the regulation of the molecular weight of the resulting nitrile rubber, at least one alkyl thiol is used, containing 12-16 carbon atoms and at least three tertiary carbon atoms, in which sulfur is attached to one of these atoms of tertiary carbon. These mercaptanes can be used alone or in mixtures. Suitable compounds are, for example, hydrogen sulfate addition compounds in oligomerized propene, in particular tetramer propene, or in oligomerized isobutene, in particular trimeric isobutene, which in the literature are often called tertiary dodecyl mercaptan (t-DDM) .

[0070] Such alkyl thiols and mixtures of alkyl thiol isomers can be purchased or also manufactured using processes widely described in the literature (see, for example, JP 07-316126, JP 07-316127 and JP 07-316128, as well such as GB 823,823 and GB 823,824).

[0071] A preferred example for an alkylthiol that meets the above definition is 2,2,4,6,6,8,8 pentamethyl-heptanethiol-4.

[0072] Especially preferable is, in addition, a new mixture of C12 mercaptan containing

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25/59

2.2.4.6.6- pentamethyl-heptanethiol-4,

2.4.4.6.6- pentamethyl-heptanethiol-2,

2.3.4.6.6- pentamethyl-heptanethiol-2 and

2,3,4,6,6-pentamethyl-heptanethiol-3, which, together with a process for its manufacture, is described in an order filed on the same day by Lanxess Deutschland GmbH. Preferably, this new special mixture is obtained by transformation of hydrogen sulfate with triisobutene in a continuous process at temperatures from 0 ° C to -60 ° C, in which (a) the hydrogen sulfate is subjected to drying before transformation, (b) the employed triisobutene has a water content of a maximum of 70 ppm, (c) boron trifluoride is used as a catalyst in amounts of a maximum of 1.5% by weight with respect to the triisobutene used, (d) the transformation takes place in the absence of complexing compounds of the trifluoride boron and (e) subsequent to transformation, the reaction mixture is brought into contact with an aqueous alkaline solution and the catalyst is removed.

[0073] The molecular weight regulator is used in an amount of 0.05 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight, relative to 100 parts by weight of the monomeric mixture. The regulators can be used alone or also as mixtures of different regulators.

[0074] The dosage of the molecular weight regulator or mixtures of molecular weight regulators takes place or at the

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26/59 initiation of polymerization or also portioned during the course of polymerization, in which the addition of portioned form of all components or components isolated from the mixture of regulators, during polymerization, is preferable.

[0075] The molecular weight regulator is, due to its function, somewhat in the form of final groups in nitrile rubber, that is, nitrile rubber has, in a certain way, alkyl thiol end groups. In the event that the new mixture described above with C12 mercaptanas is used, it is therefore the respective final thiol groups in the mixture of regulators contained in thiols, that is, final groups 2,2,4,6,6-pentamethyl- heptanethiol-4 and / or

2,4,4,6,6-pentamethyl-heptanethiol-2 pentamethyl-heptanethiol-2 heptanethiol-3.

[0076] For the emulsion, 2,3,4,6,62,3,4,6,6-pentamethyl / or initiation of polymerization in typically polymerization initiators are employed and / or decompose into radicals. These include compounds that contain a -0-0- (peroxo compound) or a -N = N- (azo compound) unit.

[0077] The peroxo compounds include hydrogen peroxide, peroxodisulfates, peroxodiphosphates, hydroperoxides and peroxides with two organic residues. Appropriate salts of peroxo sulfuric diacid and peroxy phosphoric diacid are the sodium, potassium and ammonium salts. Suitable hydroperoxides are, for example, t-butylhydroperoxide, cumol hydroperoxide and pmethane hydroperoxide. Suitable peroxides, with two organic residues, are dibenzoyl-peroxide, 2,4-dichloro-benzoyl-peroxide, di-tPetition 870180065835, of 30 / 07/2018, p. 32/74

27/59 butyl-peroxide, dicumyl-peroxide, t-butyl-per-benzoate, t-butyl-per-acetate etc. Suitable azo compounds are azobisisobutyronitrile, azo-bis-valeronitrile and azo-bisciclohexanonitrile.

[0078] Hydrogen peroxide, hydroperoxides, peracids, peracid esters, peroxodisulfate and peroxodiphosphate are also used in combination with reducers. Suitable reducers are sulfenates, sulfinates, sulfoxylates, dithionite, sulfite, metabisulfite, disulfite, sugar, carbamide, thio carbamide, xanthogenates, thioxanthogenates, hydrazinium salts, amines and amine derivatives such as aniline, dimethylaniline, monoethanolaniline or diethanolamine. Activating systems, obtained by combining an oxidizing agent and a reducing agent, are called redox systems. In the use of redox systems, salts of transient metallic compounds such as iron, cobalt or nickel are often used in combination with appropriate complexing agents, such as sodium-ethylene-diametetracetate, sodium nitrile triacetate, as well as potassium diphosphate.

Preferred redox systems are, for example: 1) sodium peroxodisulfate in combination with triethanolamine, 2) ammonia peroxodiphosphate in combination with sodium metabisulfite (Na2S205), 3) pmethane / sodium formaldehyde sulfoxylate hydroperoxide in combination with Fe-11-sulfate (FeS04 * 7 H20), sodium-ethylene-diaminoacetate and trisodium phosphate; cumol hydroperoxide / sodium formaldehyde-sulfoxylate in combination with Fe-II-sulfate (FeS04 * 7 H20), sodium-ethylene-diamino-acetate and diphosphate

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28/59 tetrasodium.

[0080] The amount of oxidants is from 0.001 to 1 parts by weight, relative to 100 parts by weight of monomer. The molar amount of reducing agent is between 50% and 500%, relative to the molar amount of the oxidant employed.

[0081] The molar amount of complexing agent refers to the amount of transient metal used and is equimolar.

[0082] In order to carry out the polymerization, all components of the activator system, either alone, are added at the beginning of the polymerization or during the polymerization.

[0083] The portioned addition of all as well as isolated components of the activator system is preferred during polymerization. Through the sequential addition, you can control the reaction speed.

[0084] The polymerization time is in the range of 5 h to 15 h and depends, fundamentally, on the acrylonitrile content of the monomeric mixture and on the polymerization temperature.

[0085] The polymerization temperature is in the range of 0 to 30 ° C, preferably in the range of 5 to 25 ° C.

[0086] In reaching rates in the range of 50 to 90%, preferably in the range of 70 to 85%, polymerization is halted.

[0087] For that, a paralyzing agent is a reaction mixture. Suitable for this are, dimethyl-dithio-carbamate, sodium nitrite, hydroxylamine, as well as the derived salts added to, for example, hydrazine and of these, as

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29/59 hydrazinium sulfate and hydroxylammonium sulfate, diethyl hydroxylamine, diisopropylhydroxylamine, water-soluble salts such as hydroquinone, sodium dithionite, phenylalpha-naphthylamine and aromatic phenols such as tert-butylbenzocatechol or phenothiazine.

[0088] The amount of water used in emulsion polymerization is in the range of 100 to 900 parts by weight, preferably in the range of 120 to 500 parts by weight, especially preferred in the range of 150 to 400 parts by weight, relative to 100 parts by weight of the monomeric mixture.

[0089] For the reduction of viscosity during polymerization, for the adjustment of pH, as well as for the function of pH buffer, salts can be added to the aqueous phase in emulsion polymerization. Typical salts are monovalent metal salts in the form of sodium and potassium hydroxide, sodium sulfate, sodium carbonate, sodium hydrogen carbonate, sodium chloride and potassium chloride. Preferred are sodium and potassium hydroxide, sodium hydrogen carbonate and potassium chloride. The quantities of these electrolytes are in the range of 0 to 1 parts by weight, preferably 0 to 0.5 parts by weight, relative to

100 parts by weight of the monomeric mixture. [0090] THE polymerization can be performed discontinuous form or continuous in a cascade of reactors mixers.

[0091] In order to achieve a uniform polymerization process, only part of the activating system is used at the beginning of the polymerization, the rest being added during the polymerization. Normally starts Petition 870180065835, from 07/30/2018, p. 35/74

30/59 if polymerization with 10 to 80% by weight, preferably 30-50% by weight of the total amount of activator. Further dosing of components isolated from the activator system is also possible.

[0092] If the intention is to manufacture uniform products, acrylonitrile or butadiene are added later, when the composition is outside the azeotropic butadiene / acrylonitrile ratio. Preferably, a later dosage is made in NBR types with acrylonitrile contents of 10 to 34, as well as types with 40 to 50% by weight of acrylonitrile (W. Hofmann, Rubber Chem. Technol. 36 (1963) 1). The subsequent dosing takes place - as indicated, for example, in DD 154 702 - preferably controlled by a computer based on a computer program.

[0093] For the removal of unprocessed monomers, as well as surface components, the paralyzed latex is subjected to distillation with water vapor. For that, temperatures are preferably applied in the range of 70 ° C to 150 ° C, and at temperatures below 100 ° C, the pressure is reduced.

[0094] Before the removal of surface components, post-stabilization of the latex with emulsifiers may occur. For this, the emulsifiers mentioned above are appropriately used in amounts of 0.1 to 2.5% by weight, preferably 0.5 to 2.0% by weight, relative to 100 parts by weight of nitrile rubber.

Latex coagulation:

[0095] Before or during latex coagulation, antidegradants can be added to the latex. For this purpose, phenolic, amine and anti-degrading agents are

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31/59 other anti-degraders.

[0096] Suitable phenolic anti-degraders are alkylated phenols, styrenized phenols, sterically hindered phenols such as 2,6-di-tert-butyl-phenol, ditherc-butyl-p-kresol (BHT), 2,6-di-tert-butyl -4-ethylphenol, sterically hindered phenols containing ester groups, sterically hindered phenols containing thiol-ether, 2,2-methylenebis- (4-methyl- € -tert-butyl-phenol) (BHP), as well as thio-bisphenols sterically hindered.

[0097] If a rubber stain does not make a difference, amine antidegradants may also be used, for example, mixtures of di-aryl-p-phenyldiamine (DTPD), octylated diphenylamine (ODPA), phenyl-alpha-naphthylamine (PAN) , phenyl-beta-naphthylamine (PBN), preferably also those based on phenyldiamine. Examples of phenyldiamines are N-isopropyl-N'-phenyl-p-phenylenediamine, Nl, 3-dimethylbutylN'-phenyl-p-phenylenediamine (6PPD), Nl, 4-dimethylpentyleneN'- phenyl-p-phenylenediamine (7PPD), N , N'- bis- 1,4- (1,4dimethylpentylene) - p-phenylenediamine (77PD) etc.

[0098] Other anti-degraders include phosphites such as tris- (nonylphenyl) phosphite, polymerized 2,2,4-trimethyl1,2-dihydroquinoline (TMQ), 2mercaptobenzimidazole (MBI), methyl-2-mercaptobenzimidazole (MMBI), zinc-methyl- mercaptobenzimidazole (ZMMBI). Phosphites are generally used in combination with phenolic anti-degraders. TMQ, MBI and MMBI are mainly used for peroxidically vulcanized NBR types.

[0099] For coagulation, latex is used with a pH value of at least 6, preferably> 6.

Eventually, this pH value is adjusted by adding

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32/59 of a base, preferably of ammonia or sodium or potassium hydroxide.

[00100] For the coagulation of the latex at least one monovalent metal salt is used, preferably a sodium or potassium salt.

[00101] Suitable are, for example, halides of a monovalent metal such as sodium chloride and potassium chloride, nitrates of a monovalent metal like sodium nitrate and potassium nitrate or sulfates of a monovalent metal like sodium sulfate and potassium sulfate .

[00102] Preferably, the salt of a monovalent metal cation with a monovalent anion is used. Especially preferred is sodium chloride.

[00103] It is also possible to employ a mixture of two or more salts of a monovalent metal. Here it can be different salts of the same monovalent metal, as well as several salts of different monovalent metals.

[00104] In the coagulation of latex, a maximum of 5% by weight of salts of a bivalent metal can be present, relative to the total amount of all salts used for coagulation, preferably an amount of at most less than 5% by weight and, especially preferred, an amount of at most less than 3% by weight.

[00105] If only sodium chloride is used as the salt of a monovalent metal, then calcium chloride may be present in the process according to the invention in quantities of a maximum of 5% by weight, preferably in quantities of less than 5% in weight and, especially preferred, in amounts less than 3% by weight.

[00106] If used, next to chloride

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33/59 sodium, also potassium chloride for NBR coagulation, so the amount of potassium chloride will preferably be X% by weight, where the amount of X% by weight results in a difference between 40% in weight and the possibly present amount in% by weight of CaCl2.

[00107] The concentration of the saline solution is usually 3 to 30% by weight. For the manufacture of the saline solution, deionized water (in practice often also abbreviated as DW) or non-deionized water, which then contains Ca ions (in practice often abbreviated as BW) can be used. DW is usually made of BW and can be treated with ion exchangers or distillation. If deionized water is used for the manufacture of the saline solution, the use of water containing Ca for the subsequent washing of the coagulated nitrile rubber has proven to be effective. In coagulation, water containing Ca, BW is preferably used for the manufacture of saline solution.

[00108] The amount of the monovalent metal salt (s) required for the coagulation of latex is 1,200 parts by weight, preferably 5-150 parts by weight, especially preferred 10 - 100 parts by weight, relative to 100 parts by weight of nitrile rubber.

[00109] Latex coagulation can be achieved by adding saline to the latex or, alternatively, presenting the latex and adding the saline solution. Latex coagulation occurs either continuously or discontinuously. Preferred is continuous coagulation, carried out with the aid of nozzles.

[00110] Beside the salts described above,

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34/59 for coagulation can be used as electrolytes also precipitating agents. As precipitating agents, for example, water-soluble polymers can be considered. Water-soluble polymers are non-ionic, anionic or cationic.

[00111] Examples of nonionic polymeric precipitation agents are modified celluloses such as hydroxy-alkylcellulose or methylcellulose, as well as adducts of ethylene oxide propylene oxide adducts in compounds with acidic hydrogen. Examples of compounds with acidic hydrogen are: fatty acid, sugar such as sorbitol, mono or di fatty glycerides, phenol, alkylated phenols, (alkyl) phenol / formaldehyde condensates, etc. The products of addition of ethylene oxide and propylene oxide to these compounds can be constructed statistically or in block form. Of these products, those in which solubility decreases with increasing temperature are preferred. Characteristic turbidity temperatures are in the range 0 to 100 ° C, especially in the range 20 to 70 ° C.

[00112] Examples of anionic polymeric precipitation agents are the homo and copolymers of (meta) acrylic acid, anhydride maleic acid etc. Preferred is the sodium salt of polyacrylic acid.

[00113] Cationic polymeric precipitation agents are commonly based on polyamine, as well as on homo or copolymers of (meta) acrylamides. Preferred are poly (meta) acrylamide and polyamine, especially based on epichlorohydrin and dimethylamine.

[00114] The amounts of polymeric precipitating agents matter from 0.01 to 5 parts by weight,

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35/59 preferably 0.05 to 2.5 parts by weight, relative to 100 parts by weight of nitrile rubber.

[00115] It is also possible to use others to be reminded that it is a process according to precipitation agents,

But it should be possible, without problems, to execute the invention, with the desired success, in the absence of additional precipitating agents, and thus, in particular, in the absence of C1-C4 alkylcelluloses, hydroxy alkylcellulose, materials of protein origin from plants or polysaccharides , such as starch and, where appropriate, water-soluble polyamine compounds.

[00116] The latex used in coagulation has an appropriate concentration of solid matter in the range of 1% to 40%, preferably in the range of 5% to 35% and, especially preferred, in the range of 15 to 30% by weight.

[00117] Latex coagulation is performed at a temperature above 50 ° C, preferably at a temperature in the range of 50 to 100 ° C, especially preferable at a temperature in the range of 55 to 90 ° C, especially at a temperature in the range of 60 to 90 ° C. In the execution of the coagulation of the latex it is also possible to mix lates and the solution of at least one salt of a monovalent metal initially at a temperature <50 ° C, decisive is that, subsequently, the temperature of the latex / salt mixture is raised to a temperature above 50 ° C.

Washing of coagulated nitrile rubber:

[00118] After coagulation, nitrile rubber usually appears in the form of so-called particles. The washing of coagulated NBR is therefore also called particle washing. For washing these particles

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36/59 coagulated, it can be used either deionized water, DW, or non-deionized, BW. While in the coagulation of latex with at least one magnesium salt, there is no calcium salt present in the indicated quantitative range (up to 5% by weight of all salts used), it has been proven to be effective, using non-deionized water, and water containing calcium ions, in the washing of coagulated NBR.

[00119] The washing is carried out at a temperature above 50 ° C, preferably at a temperature in the range of 50 to 90 ° C and, especially preferably, at a temperature in the range of 55 to 90 ° C.

[0012 0] The amount of the washing water is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight and, especially preferred, 1 to 5 parts by weight, relative to 100 parts by weight of rubber nitrile.

[00121] Preferably, the rubber particles are subjected to a washing of several stages, in which the rubber particles are partially dehydrated between each of the washing stages. The remaining moisture of the particles between each washing step is in the range of 5 to 50% by weight, preferably in the range of 7 to 25% by weight. The number of washing steps is usually from 1 to 7, preferably from 1 to 3. Washing is carried out in a batch or continuous manner. Preferably, a continuous process of several stages is used, in which, for the economical use of water, a counter-current wash is used.

Water removal and drying:

[00122] After the washing is finished, there is typically a dehydration of the rubber particles

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37/59 nitrile. This normally occurs in two stages. In the first stage, the rubber particles are mechanically pre-dehydrated. In the second stage, the remaining water is evaporated. Both pre-dehydration and drying occur, preferably, continuously. For mechanical pre-dehydration, strainer threads are used, in which water is laterally pressed through strainer slits or threads, in which mechanical dehydration occurs against the product flow stream (Welding principle).

[00123] The establishment of the remaining cation contents in nitrile rubber can, additionally and when desired, be influenced by the degree of mechanical pre-dehydration. This is advantageous, especially when inefficient washing is used. Efficient washing already provides the appropriate cation content. The water contents after mechanical pre-dehydration are in the range of 5 to 25% by weight. For the establishment of the remaining mixes in the product, it was contacted as efficient, that the water contents after mechanical pre-dehydration have 5 to 15% by weight, especially 5 to 10% by weight.

[00124] THE drying of nitrile rubber pre- dehydrated occurs in a hair dryer fluidized bed or on a plate dryer. At temperatures on drying they are in 80 to

150 ° C. Preferred is drying with a temperature program, in which, near the end of the drying process, the temperature is reduced.

[00125] It was found that nitrile rubbers, according to the invention, which have the described special cation content, and thus the characteristic ion index in the range

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38/59 indicated, as well as having the special magnesium content, have the desired high vulcanization speed (difference between vulcanization time and pre-curing time) and the vulcanized products obtained have a very good modulus level.

[00126] The object of the invention is, therefore, also the use of nitrile rubbers according to the invention for the manufacture of vulcanizable mixtures, containing at least one nitrile rubber according to the invention, at least one crosslinker and, possibly, other additives.

[00127] The manufacture of these vulcanisable mixtures occurs by mixing at least one nitrile rubber according to the invention, at least one crosslinker and, possibly, other additives.

[00128] As crosslinkers, for example, peroxidic crosslinkers such as bis (2,4-dichloro-benzyl) peroxide, dibenzoyl-peroxide, bis (4-chloro-benzoyl) peroxide, l, l-bis- (t-butyl- peroxy) -3,3,5trimethyl-cyclohexane, tert-butyl perbenzoate, 2,2-bis (tbutylperoxy) butene, 4,4-di-tert-butyl-peroxynonylvalerate, dicumylperoxide, 2,5-dimethyl-2,5- di (t-butylperoxy) hexane, tert-butyl-cumylperoxide, 1,3-bis (t-butyl-peroxy isopropyl) -benzol, di-t-butylperoxide and 2,5-dimethyl-2,5di (t-butylperoxy) - hexine-3.

[00129] It may be advantageous, alongside these peroxidic crosslinkers, to use other additives, with the help of which the crosslinking efficiency can be increased: for this purpose, for example, trialyl-isocyanide, trialyl-cyanide, trimethylol-propanotri (meta ) acrylate, trialyl trimellitate, ethylene glycol Petition 870180065835, of 07/30/2018, p. 44/74

39/59 dimethacrylate, butanediol-dimethacrylate, trimethylpropanetrimethacrylate, zinc diacrylate, zinc dimethacrylate, 1,2-polybutadiene or N, N'-m-phenylene-di-maleinimide.

total dos or crosslinkers can in elementary form also soluble can (DTDM), be or be

2 [00130] The amount of crosslinkers is normally in the range of 1 to 20 phr, preferably in the range of 1.5 to 15 phr and, especially preferable, in the range of 2 to 10 phr, in relation to nitrile rubber.

[00131] As employees, sulfur, insoluble, or sulfur donors.

[00132] As sulfur donors considered dithiodimorpholine disulfide morpholinodithiobenzothiazole (MBSS), caprolactam bisulfide, dipentamethylene tiuram tetrasulfide (DPTT) and tetramethyl tiuram disulfide (TMTD).

[00133] Also in the manufacture, by sulfur vulcanization, of nitrile rubbers according to the invention, it is possible to use additional additives, with the help of which the crosslinking performance can be increased. Fundamentally, crosslinking can also occur only with sulfur or sulfur donors.

[00134] On the contrary, the crosslinking of nitrile rubbers according to the invention, can occur only in the presence of the additives mentioned above, that is, without the addition of elemental sulfur or sulfur donors.

[00135] As additives, with the help of which the crosslinking yield can be increased, for example, dithiocarbamates, thiomes, thiazoles, sulfenamides, xanthogenates, guani derivatives, caprolactam and derivatives of

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40/59 thiocarbamides.

[00136] As dithiocarbamates can be used, for example: ammonium-dimethyl-dithiocarbamate, sodium diethyl-dithiocarbamate (SDEC), sodium dibutyldithiocarbamate (SDBC), zinc-zinc-dimethyldithiocarbamate (ZDMC), z-diethyl-dithiocarbamate (zinc) ), zinc dibutyl dithiocarbamate (ZDBC), zinc ethylphenyl dithiocarbamate (ZEPC), zinc dibenzyldithiocarbamate (ZBEC), zinc pentamethyl dithiocarbamate dithiocarbamate, ditiocarbamate, ditiocarbamate, ditiocarbamate, ditiocarbamate, diti nickel and zinc diisononyldithiocarbamate.

[00137] As tiuramas can be used, for example: tetramethyl disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), dimethyl diphenylthiuram disulfide, tetrabenzylthiulfide, dipenta-methylthiuram disulfide and tetraethyl disulfide.

[00138] As thiazoles can be used, for example: 2-mercaptobenzothiazole (MBT), dibenzothiazil disulfide (MBTS), zinc mercaptobenzothiazole (ZMBT) and zinc 2-mercaptobenzothiazole.

[00139] As sulfenamide derivatives can be

employees, for example: N- cyclohexyl- 2- benzothiazole- sulfenamides (CBS), N- tert- butyl- 2- benzothiazil- sulfenamide (TBBS), N, N'- dicyclohexyl- 2- benzothiazil-

sulfenamide (DCBS), 2-morpholino-thiobenzothiazole (MBS), Noxy-diethylene-thiocarbamyl-N-tert-butyl-sulfenamide and Noxi- diethylene-thiocarbamyl- N-oxyethyl-sulfenamide.

[00140] As xanthogenates can be used, for example: sodium dibutylxanthogengenate, isopropyl-dibutylPetition 870180065835, of 07/30/2018, p. 46/74

41/59 zinc xanthogenate and zinc dibutyl-xanthogenate.

[00141] As guani derivatives can be used, for example: diphenylguanidine (DPG), di-otolylguanidine (DOTG) and o-tolibiguanide (OTBG).

[00142] As dithiophosphates can be used, for example: zinc dialkyl dithiophosphate (length of the chain of C2 to C16 alkyl residues), copper dialkyl dithiophosphate (length of the chain of C2 to C16 alkyl remains) and polysulfite of dithiophosphorus.

[00143] As caprolactam can be used, for example, dithio-bis-caprolactam.

[00144] As derivatives of thiocarbamides can be used, for example: N, N'-diphenyl thiourea (DPTU), diethyl thiourea (DETU) and ethylene thiourea (ETU).

Also suitable as additives are, for example: zinc diamino-isocyanate, hexamethylenetetramine, 1,3-bis (citraconimidomethyl) benzol, as well as cyclic disulfans.

[00146] Both the mentioned additives and the crosslinking agents can be used both alone and in mixtures. Preferably, the following substances are used for the crosslinking of nitrile rubbers: sulfur, 2-mercapto-benzothiazole, tetramethyltiuram disulfide, zinc dibenzyl-dithio carbamate, dipentamethylene-thyme tetrasulfide, zinc dialhyldithiophosphate, di-dihydrol-dihydrofiltylate; tellurium, dibuti! nickel dithiocarbamate, zinc dibutyl dithiocarbamate and dithio-bis-caprolactam.

[00147] The crosslinking agents and additives mentioned above, can, respectively, be

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42/59 employees in quantities of approx. 0.05 to 10 phr, preferably 0.1 to 8 phr, in particular 0.5 to 5 phr (separate dosage, relative to the active substance).

[00148] In the cross-linking of sulfur it may possibly be sensible to use, in addition to the cross-linking agents and additives mentioned above, other inorganic and organic substances, for example: zinc oxide, zinc carbonate, lead oxide, magnesium oxide, organic fatty acids saturated or unsaturated and their salts of zinc, polyalcohols, aminoalcohols, such as triethanolamine, as well as, for example, dibutylamine, dicyclohexylamine, cyclohexylethylamine and polyetheramine.

[00149] In addition, pre-cure retardants can also be used. These include cyclohexylthiophthalimide (CTP), N, N 'dinitrosopentamethylenetetramine (DNPT), Terephetalic acid (PTA) and diphenylnitrosamine. Preferred is cyclohexylthiophthalimide (CTP).

[00150] Along with the addition of the crosslinker (s), the nitrile rubber according to the invention can also be mixed with other usual rubber additives.

[00151] These include, for example, substances known to the long-standing specialist, such as fillers, filler material activators, antiozonants, antidegraders, antioxidants, processing aids, expanding oils, softeners, reinforcing materials and release agents.

[00152] As filler materials, for example, soot, barium sulfate, titanium oxide, zinc oxide, calcium oxide, calcium carbonate, magnesium oxide, aluminum oxide, iron oxide, can be used.

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43/59 aluminum hydroxide, magnesium hydroxide, aluminum silicate, fossil flour, talc, kaolin, bentonite, carbon nanotubes, teflon (preferably powder) or silicates.

[00153] As filler activators, organic silanes are intended, such as vinyltrimethyloxysilane, vinildimethoxymethylsilane, vinyltriethoxysilane, vinyltris (2-methoxy-ethoxy) silane, Nylcyclohexyl-3-aminopropyltrimethoxyethyl, methoxyethylethyl, trimethylmethoxy, methoxy , isooctyltimethoxysilane, isooctyltrietorxisilane, hexadecyltrimethoxysilane or (octadecyl) methyldimethoxysilane. Other filler activators, for example, represent borderline substances such as triethanolamine and ethylene glycols with molecular weights from 74 to 10,000 g / mol. The amount of filler activators is usually 0 to 10 phr, relative to 100 phr of nitrile rubber.

[00154] As antidegradants, those already described in this application regarding latex coagulation can be added to the vulcanizable mixtures. They are commonly employed and quantities of approx. 0 to 5 phr, preferably 0.5 to 3 phr, relative to 100 phr of nitrile rubber.

[00155] As release agents should be considered, for example: saturated and partially unsaturated fatty and oleic acids and their derivatives (fatty acid esters, fatty acid salts, fatty alcohols, fatty amides), which find application, preferably, as components in

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44/59 mixing, additionally products applicable to the surface of the mold, such as products based on low molecular weight silicone compounds, products based on fluoropolymers, as well as products based on phenolic resins.

[00156] Release agents are used as mixing components in quantities of approx. 0 to 10 phr, preferably 0.5 to 5 phr, relative to 100 phr of nitrile rubber.

[00157] Reinforcement with glass resistance (fibers) carriers, according to the teaching of US-A4,826,721 is possible, as well as reinforcement by corduroy, fabrics, aliphatic and aromatic polyamide fibers (Nylon®, Aramida® ), polyester and natural fiber products.

[00158] It is additionally the object of the invention, a process for the manufacture of molded parts based on at least one nitrile rubber according to the invention, which is characterized by being the vulcanizable mixture described above, vulcanized in a molding process, preferably with the application of an injection process.

[00159] The object of the invention is, therefore, also the special molded part, which can be obtained through the vulcanization process mentioned above.

[00160] By means of this process, a plurality of molded parts can be manufactured, such as a seal, a cover, a hose or a membrane, in particular a seal ring, a flat seal, an axle seal ring, a gasket, a sealing cap, a dust cover, a plug seal, a hose for thermal insulation (with or without

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45/59 addition of PVC), an oil cooler hose, an air suction hose, a power steering hose or a pump diaphragm.

[00161] Alternatively to the direct manufacture of molded parts based on nitrile rubber according to the invention, it is also possible to add to the manufacture of nitrile rubber according to the invention or (i) a metathesis reaction, or (ii) a reaction of metathesis and subsequent hydrogenation, or (iii) just hydrogenation. These metathesis and hydrogenation reactions are both known for a long time by the specialist and described in the literature.

[00162] Metathesis, for example, is known from WO-A-02/100941, as well as from WO-A-02/100905.

[00163] A hydrogenation can be performed using homogeneous or heterogeneous hydrogenation catalysts. It is also possible to perform the hydrogenation in situ, that is, in the same reaction vessel in which, eventually, the reduction of the metathesis also occurred, and without the need to isolate the reduced nitrile rubber. The hydrogenation catalyst is simply added to the reaction vessel.

[00164] The catalysts used are normally based on rhodium, ruthenium or titanium, and platinum, iridium, palladium, ruthenium, osmium, cobalt or copper can also be used or as a metal or also, preferably, in the form of metallic compounds (see for example US-A-3,700,637, DE-A25 39 132, EP-A-0 134 023, DE-OS-35 41 689, DE-OS-35 40 918, EP-A-0 298 386, DE-OS-35 29 252, DE-OS-34 33 392, US-A4,464,515 and US-A-4,503, 196).

[00165] Suitable catalysts and solvents

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46/59 for homogenous hydrogenation, are described below and also known from DE-A-25 39 132 and EP-A-0 471 250.

[00166] Selective hydrogenation can, for example, be achieved in the presence of a catalyst containing rhodium or ruthenium. Employable, for example, is a catalyst of the generic formula (RSnB) iMX _n where M is ruthenium or rhodium, R ¹ are the same or different and represent a C 1 -C alkyl group, a C 4 -C 8 cycloalkyl group, a C 6- C15 aryl or a C7-C15 aralkyl group. B is phosphorus, arsenic, sulfur or a sulfoxide group S = 0, X is hydrogen or an anion, preferably halogen and, especially preferred, chlorine or bromine, 1 is 2, 3 or 4, mn is 1, 2 or 3, preferably 1 or 3.

preferred are rhodium chloride (I), rhodium chloride (III) and is 2 or 3 and

Tris (triphenylphosphino) tris (triphenylphosphino) chloride catalysts have been replaced by tris (dimethylsulfoxide) - rhodium (I) tricyclohexylphosphine, as well as tetrakis (triphenylphosphine) -rhodium hybrid of the formula (C6H5) 3P of the corresponding 4RhH compounds which triphenylphosphine is wholly or partially by a catalyst can be used in small quantities. An appropriate amount is in the range of 0.01 - 1% by weight, preferably in the range of 0.03 0.5% by weight and, especially preferably, in the range of 0.1 0.3% by weight, relative to weight of the polymer.

[00167] It is usually sensible to use the catalyst in conjunction with a co-catalyst, which is a binder of the formula R ^ mB, where R ¹ , m and B have the

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4.Ί / 5 $ meanings mentioned earlier for the catalyst. Preferred is m equal to 3, B equal to phosphorus and the remains R ¹ can be the same or different. Preferably, they are co-catalysts with trialkyl, tricycloalkyl, triaryl, triaralkyl, diaryl-monoalkyl, diaryl-monocycloalkyl, dialkyl-monoaryl, dialkyl-monocycloalkyl, dicycloalkyl-monoaryl or remnants of dicycloalkyl-monoaryl.

[00168] Examples of co-catalysts are found, for example, in US-A-4,631,315. A preferred catalyst is triphenylphosphine. The catalyst is used in quantities in the range of 0.3 - 5% by weight, preferably in the range of 0.5 - 4% by weight, in relation to the weight of the nitrile rubber to be hydrogenated. In addition, the weight ratio between the rhodium-based catalyst and the cocatalyst is preferably in the range of 1: 3 to 1:55, especially preferable in the range of 1: 5 to 1:45. For 100 parts by weight of nitrile rubber. to be hydrogenated, suitably, 0.1 to 33 parts by weight of the co-catalyst are used, preferably 0.5 to 20 and, especially preferred, 1 to 5 parts by weight, especially more than 2, but less than 5 parts by weight of the co-catalyst, relative to 100 parts by weight of the nitrile rubber to be hydrogenated.

[00169] The practical execution of this hydrogenation has been known for a long time by the specialist through US-A6,683,136. It normally occurs when the nitrile rubber is subjected to hydrogenation to hydrogen, in a solvent such as toluol or monochlorobenzol, at a temperature in the range of 100 to 150 ° C and a pressure in the range of 50 to 150 bar, for 2 to 10 h.

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48/59 [00170] Hydrogenation means, in the concept of this invention, a transformation of the double bonds of the initial nitrile rubber by at least 50%, preferably 70-100%, especially preferably 80100%.

[00171] When using heterogeneous catalysts, these are usually delayed palladium-based catalysts, which, for example, have been delayed in charcoal, silicic acid, calcium carbonate or barium sulphate.

[00172] The nitrile rubbers obtained, possibly hydrogenated, after the metathesis and / or hydrogenation reaction of the nitrile rubbers according to the invention, can, analogously to the nitrile rubbers of the invention, be added to vulcanizable compositions and used for the manufacture of vulcanized products and molded parts based on such vulcanized materials. These possibly hydrogenated nitrile rubbers have a mooney viscosity (ML (l + 4 at 100 ° C)) from 1 to 50, preferably from 1 to 40 mooney units.

Examples:

General data:

J_Determination of the cation contents for the characteristic ion index [00173] To determine the cation contents, 0.5 g of the nitrile rubbers were disintegrated by dry incineration at 550 ° C in a platinum crucible with subsequent dissolution of the ash in acid hydrochloric. After the appropriate dilution of the disintegrated solution with deionized water, the metal contents are determined by means of ICP-OES (inductively coupled plasma-optical emission

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49/59 spectometry), in the following wavelengths

Calcium: 317.933 nm,

Magnesium: 285.213 nm and

Potassium: 766.491 nm,

Sodium: 589,592 nm.

against a calibration solution adjusts with acid matrix. According to the concentration of the elements in the disintegrated solution and the sensitivity of the measuring device used, the concentrations of the test solutions are adjusted to the linear range of the calibration for the respective wavelengths used. (B. Welz Atomic Absorption Spectrometry, 2nd Ed., Verlag Chemie, Weinheim 1985).

II Pre-cure behavior and vulcanization speed [00174] The pre-cure behavior (mooney schorch), is determined with the aid of a shear disc viscometer, according to DIN 53523 at 120 ° C. For the determination, a small rotor (S) is used. MS 5 (120 ° C) means the time, in min, in which the mooney value rises by 5 mooney units relative to the minimum value.

[00175] The vulcanization speed is determined according to DIN 53 529, Part 3, at 160 ° C, with the help of a rheometer from Monsanto (MDR 2000E), as a difference between t90 - uncle, where uncle and t90 are the vulcanization times, in which 10% and 90%, respectively, of the final vulcanization degree are reached.

[00176] The vulcanization behavior of the mixtures was determined on the rheometer at 160 ° C, according to DIN 53

529. In this way, the characteristic vulcanization times tio and t90 were determined.

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50/59

III Mechanical characteristics [00177] The mechanical characteristics of the rubbers (such as stress value in different stretches, resistance to rupture and rupture elongation) are determined in vulcanized products according to DIN 53 504.

A_Manufacture of NBR by emulsion polymerization [00178] Based on the recipes indicated in Table 1 below, an NBR latex was manufactured. All parts used are indicated in parts by weight with respect to 100 parts by weight of the monomer mixture. The polymerization took place at a temperature of 17 ° C, for a duration of 13.5 hours until reaching a polymerization rate of 80%.

Table 1:

Materials used Parts by weight Butadiene 73 Acrylonitrile 27 Quant. total water 174 + 16 + 30 Erkantol® BXG ¹ * 3.67 Baykanol® PQ ² * 1.10 K salt of coconut fatty acid 0.73 KOH 0.05 t-DDM ³ * 0.24 + 0.24 Potassium peroxodisulfate ⁴ * 0.39 + 0.19 ⁵ * Tris- (α-hydroxy-ethyl) amine 0.55 Nationite ⁶ * 1.19 Potassium hydroxide 1.28 Vulkanox® KB ⁷ * 1.25

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51/59 b sodium salt of a mixture of mono and disulfonated naphthalene sulphonic acids with isobutylene oligomeric substituents.

²⁾ Sodium salt of methyl-bisnaphthalene sulfonate (Baykanol® PQ, Lanxess Deutschland GmbH) ³⁾ t-DDM (tertiary dodecyl-mercaptan); mixture of C12 mercaptan from Lanxess Deutschland GmbH ⁴ ) Aldrich code: 21,622-4 ⁵ ) Aldrich code: T5, 830-0 ⁶ ) Aldrich code: 15, 795-3 h 2,6-di-tert-butyl-p- cresol from Lanxess

Deutschland GmbH [00179] The manufacture of NBR latex was discontinuous in a 2m3 autoclave with mixer. To start, 350 kg of the monomeric mixture and a water quantity of 770 kg were used. In 609 kg of this amount of water, the emulsifiers Erkantol® BXG (12.85 kg), Baykanol® PQ (3.85 kg) and the potassium salt of coconut fatty acid (2.56 kg) with 84 were presented to the autoclave. g of potassium hydroxide and washed with a stream of nitrogen. After the end of the nitrogen wash, destabilized monomers (255.5 kg of butadiene and 94.5 kg of acrylonitrile) and a partial quantity of the t-DDM regulator (0.84 kg) were added to the reactor. The residual amount of water (161 kg) was used to manufacture the aqueous solutions of tris- (a-hydroxyethyl) amine, potassium peroxodisulfate and sodium dithionite.

[00180] By adding aqueous solutions of 1,365 kg of potassium peroxodisulfate (corresponding to 0.39

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52/59 parts by weight according to Table 1) and 1.925 kg of tris- (ohydroxy-ethyl) amine (corresponding to 0.55 parts by weight according to Table 1), polymerization was started at 17 ° C and maintained at this temperature for throughout its duration. The course of polymerization was accompanied by gravimetric yield determination. To a polymerization yield of 15%, 0.84 kg of the t-DDM regulator were added (corresponding to 0.24 parts by weight according to Table

1) and 0.665 kg of potassium peroxodisulfate (corresponding to 0.19 parts by weight according to Table 1). When 75% yield was reached after 10.5 h, polymerization was stopped by adding 4.165 kg of sodium dithionite (1.19 parts by weight) and 4.48 kg of potassium hydroxide (1.28 parts by weight) ) dissolved in 105 kg of water (30 parts by weight). Unprocessed monomers and other surface components were eliminated by distillation with water vapor.

[00181] The characteristic data of the obtained latex are summarized in Table 2 below:

Latex Particle diameter (d ₅ o) [nm] 360 Solid matter content [% by weight] 18.9 PH 8.9 Acrylonitrile content [% by weight] 28.9

[00182] Before the NBR latex coagulation, 1.25 parts by weight of Vulkanox® KB, relative to 100 parts by weight of the monomeric mixture used in the polymerization (see table 1) were added to the latex. Vulkanox® KB was added to the latex as a 50% aqueous dispersion.

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53/59 [00183] The aqueous dispersion of Vulkanox® KB was manufactured with the aid of an Ultraturrax at 95 to 98 ° C, and was composed of:

360 g deionized water (DW water) g alkylphenol-polyglycol-ether (Emulsifier NP10 from Lanxess Deutschland GmbH)

400 g 2 _r 6-di-tert-butyl-p-cresol (Vulkanox® KB from Lanxess Deutschland GmbH)

B_Restoration of latex [00184] The concentration of the saline solution as well as the amounts of salts used for precipitation, were calculated respectively without crystalline water. The salts used for the coagulation of the latex, the concentration of the saline solutions, the amounts of salts used in relation to the nitrile rubber, the temperature of the latex in the saline addition, the temperature of the latex / saline mixture, the temperature in the washing as well as the duration of washing, are listed in the following tables.

[00185] In the examples according to the invention, the minimum amounts of sodium chloride necessary for quantitative latex coagulation were determined in pre-tests, so that, in these examples, the minimum amounts of salts necessary for coagulation were used. quantitative analysis of latex.

[00186] 25 kg of latex were restored to the solid matter. Latex coagulation occurred discontinuously in an open container of 100 I capacity, with the possibility of mixing. Here, the latex was presented to the coagulation vessel, and subsequently heated to the temperatures mentioned in tables 3 and 4, column 6, since

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54/59 that these were above 20 ° C, the aqueous saline solution added, subsequently and under the effect of the mixer, at this temperature and then heated the reaction mixture to the temperatures indicated in tables 3 and 4, column 7.

[00187] For washing the particles, the 100 1 coagulation vessel was equipped with an affluent and a drain. On the inside of the container, two rails were arranged in such a way that the drain can be blocked with a sieve (weft width of 2 mm) before the washing is carried out, so that the coagulated particles are not discarded during the washing. The washing was carried out with a continuous water flow of 200 l / h. For washing, both deionized water (DW) and normal tap water (BW) were used.

[00188] In a large part of the assays, the latex serum resulting from the coagulation of the latex was not removed from the coagulation vessel before the start of the wash, that is, the latex serum was removed by dilution wash. The conditions applied for washing the particles (type of water, washing temperature, washing time etc.) are listed in the following tables.

[00189] After the end of the wash, the rubber particles were removed with a sieve and pre-dehydrated with a Welding thread to a residual moisture of 5 to 15% by weight and dried in a batch in a vacuum drying cabinet at 70 ° C, up to a residual moisture of <1.5% by weight.

[00190] The conditions applied to the restoration of nitrile rubber latex are summarized in tables 3, 4 and 5.

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55/59 [00191] Table 5 summarizes the characteristic ion indices for the examples according to the invention, as well as the comparative examples.

Table 3: Examples 1-5, according to the invention [00192] NaCI solutions, according to the examples

1-4, used for the coagulation of latex, were made with deionized water (DW). In example 5, the NaCI solution made with water containing Ca (BW).

Ex. Latex PH Precipitation conditions Wash conditions Salt type Conc. saline solution [% by weight] Quant. of salt relative to NBR [% by weight] Tenp. latex in the addition of salt [° C] Tenp. particle dispersion after heating [° C] Type in Water T [° C] Time [H] ΐυ 8.9 NaCI 15 85 45 70 BW 60 0.5 2 ²⁾ 8.9 NaCI 18 63 70 70 BW 70 5.0 3 ³⁾ 9.7 NaCI 26 54.3 20 60 BW 60 8 4 8.9 NaCI 26 28 60 60 BW 60 5.0 5 ³ > 9.7 NaCI 26 54.3 20 60 BW 60 8

¹ ) In test 1, the rubber particles obtained from the coagulation of the latex were washed in one step, in which the particles, before washing, were isolated from the serum of the coagulated latex through a sieve and dehydrated by gravity. The wash time was 0.5 h.

² ) In test 2, the latex was added to the mixed NaCI solution and heated to 70 ° C.

3) The pH adjustment of the latex occurred with a 5% potassium hydroxide solution, before the latex coagulation.

Table 4: Comparative examples V6-V13, not according to the invention

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56/59 [00193] In comparative example 9, water containing Ca (BW) was used to manufacture the NaCI solution used in the coagulation of latex. In the other comparative examples presented in table 4, deionized water (DW) was used to manufacture the electrolyte solution used in the coagulation of the latex.

Ex. Latex PH Precipitation conditions Wash conditions Salt type Conc. saline solution [% by weight] Quant. of salt relative to NBR [% by weight] Tenp. latex in the addition of salt [° C] Tenp. particle dispersion after heating [° C] Type in Water T [° C] Time [H] V6 ¹ ' 9.5 NaCI 15 150 20 20 BW 20 8.0 V7 8.4 NaCI 15 150 20 20 BW 20 2.5 V8 8.4 NaCI 26 54 50 50 BW 40 5.0 V9 8.4 NaCI 26 54 50 50 BW 30 9.0 V10 8.4 CaCl ₂ 0.3 3 20 20 DW 20 3.8 Vile 8.4 CaCl ₂ 0.6 6 20 20 DW 20 3.8 VI2 8.4 CaCl ₂ 1.2 12 20 20 DW 20 3.5 V13 ² >) 5.8 CaCl ₂ 1.2 12 20 20 DW 20 3.4

D 0 adjustment pH occurred with a solution watery in KOH in ç □ ro f before latex coagulation 2) 0 adjustment pH occurred with a solution watery in HCI in □ ro f before latex coagulation [00194] A determination From indexes

ion characteristics provides the following values:

Table 5: characteristic ion index of nitrile rubbers from examples 1-5 and 6-13

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57/59

Ex. Type of salt Ion content IKZ Here [ppm] Mg [ppm] At [ppm] K [ppm] 1 NaCI 620 22 570 17 21.3 2 NaCI 565 21 575 17 16, 9 3 NaCI 450 16 201 8 24.8 4 NaCI 435 14 105 10 25.7 5 NaCI 325 19 110 12 19.3 V6 NaCI 540 25 95 10 36.1 V7 NaCI 960 34 625 27 44.1 V8 NaCI 570 18 230 14 32.4 V9 NaCI 590 22 223 11 34.3 V10 CaCl ₂ 1190 6 17 1 88.5 Vile CaCl ₂ 1290 3 12 1 96.2 V12 CaCl ₂ 1240 2 6 1 92.7 V13 CaCl ₂ 1235 2 8 1 92.3

[00195] For the determination of the characteristics of non-vulcanized rubber and vulcanized rubber mixtures, rubber mixtures based on nitrile rubbers were manufactured in an internal laboratory mixer of 1.5 1 capacity, in which each of the components of the mixture were mixed in the sequence indicated in table 6. The components of the mixtures are indicated in parts by weight relative to 100 parts by weight of nitrile rubber. The characteristics of the vulcanized ones based on the nitrile rubbers of the invention and the comparative examples, are summarized in table 7.

Table 6:

Mixture components Quant. in parts by weight NBR 100.0

Stearic acid

2.0

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Mixture components Quant. in parts by weight Zinc oxide 5.0 Soot N 330 40.0 Phenolic resin / formaldehyde (Palstikator® FH) 5.0 N-cyclohexyl-benzothiazilsufenamide (Vulkacit® CZ) 0.9 Sulfur 1.5

Table 7: Other characteristics of the NBRs in examples 1-5 and 6-13

Ex. Type of salt IKZ Vulcanization Vulcanization characteristics MS 5 (120 ° C) [min] uncle [s] t ₉ 0 [s] teo-io [s] 0300 [MPa] Orna »[MPâ] and _b [%] 1 NaCl 21.3 47 6.5 10.7 4.2 8.5 22.4 579 2 NaCl 16, 9 43 6.2 11.4 5.2 8.7 24.2 595 3 NaCl 24.8 44 7 12.5 5.5 8.9 21.6 545 4 NaCl 25.7 44 6.9 11.6 4.7 8.5 23.8 611 5 NaCl 26.0 45 6.7 11.7 5.0 9.3 22.2 535 6 NaCl 36.1 46 6.4 12.6 6.2 7.9 21.0 581 7 NaCl 44.1 45 6, 6 12.6 6.0 8.3 22.0 569 8 NaCl 32.4 43 6.8 13.8 7.0 O 00 22.1 595 9 NaCl 34.3 45 6, 6 14.1 7.5 7.9 23.7 598 10 CaCl ₂ 88.5 56 7.1 14.7 7.6 7.4 21.0 608 11 CaCl ₂ 96.2 59 8.2 16, 7 8.5 7.1 21.5 649 12 CaCl ₂ 92.7 56 8.0 18.2 10.2 7.1 21.6 648 13 CaCl ₂ 92.3 62 8.7 17.6 8.9 7.0 21.6 651

[00196] In table 7 it can be recognized that nitrile rubbers, with the characteristic ion indexes according to the invention, have a higher tio-thio vulcanization speed, as well as presenting higher stress values at

300%. Through this comparison, the advantages of rubbers

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59/59 nitriles manufactured according to the invention are recognizable.

clearly

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1/6

Claims (6)

1. NITRILE RUBBER, characterized by having repetition units of at least one alpha nitrile, betainsaturated, at least one conjugated diene and, eventually, one or more additional copolymerizable monomers, and by having a characteristic ion index (IKZ), of the formula generic (I), in the range of 7 to 26 ppm x mol / g, 3 c (Ca = (Na ⁺ ) _c pc) * Ui 23 g / oiot 3 «g / mol in that c (Ca ²⁺ ), c (Na ⁺ ) and c (K ⁺ ) indicate the concentration in ppm of the ions calcium, sodium and potassium in nitrile rubber. 2. RUBBER, from according to claim 1, characterized by a characteristic ion index in the range of 8 to 26 ppm x mol / g. 3. RUBBER, according to claim 1 or 2, characterized by containing repeat units of acrylonitrile, 1,3-butadiene and, eventually, one or more additional copolymerizable monomers. 4. RUBBER, according to claim 3, characterized by repeating units of one or more alpha, beta-unsaturated mono or dicarbonic acids, of their esters or amides, preferably repeat units of an alkyl ester of an alpha carbonic acid , beta-unsaturated, especially methyl (meta) acrylate, ethyl (meta) acrylate, propyl (meta) acrylate, n-butyl (meta) acrylate, t-butyl (meta) acrylate, hexyl (meta) acrylate, 2-ethyl hexyl (meta) acrylate, octyl (meta) acrylate or lauryl (meta) acrylate. Petition 870180065835, of 07/30/2018, p. 66/74 2/6 RUBBER, according to any one of claims 1 to 4, characterized in that it has a mooney viscosity (ML (1 + 4 at 100 ° C)) from 10 to 150 mooney units. RUBBER, according to any one of claims 1 to 5, characterized by a glazing temperature in the range of -70 ° C to + 10 ° C. 7. PROCESS FOR THE MANUFACTURE OF NITRILE RUBBER BY POLYMERIZATION, in emulsion of at least one alpha, beta-unsaturated nitrile, at least one conjugated diene and, possibly, one or more additional copolymerizable monomers, in which the latex, initially resulting of the polymerization, containing the nitrile rubber, is subjected to coagulation and the obtained coagulated nitrile rubber is additionally washed, characterized in that (i) the emulsion polymerization is carried out in the presence of at least one alkyl thiol, which has 12-16 carbon atoms and at least three tertiary carbon atoms, where the sulfur is attached to one of these tertiary carbon atoms, and (ii) the latex, obtained in emulsion polymerization, adjusted to a pH value of at least 6 , and then coagulated with the use of at least one salt of a monovalent metal, in which, in the coagulation, a maximum of 5% by weight of salts of a bivalent metal, relative to the total amount of all salts used in coagulation, and (iii) a temperature of at least 50 ° C is adjusted, both in the coagulation of the latex and in the additional washing. Petition 870180065835, of 07/30/2018, p. 67/74 3/6 PROCESS, according to claim 7, characterized in that the emulsion polymerization is carried out in a discontinuous or continuous way in a cascade of mixing reactors. PROCESS, according to claim 7 or 8, characterized in that one or more antidegraders are added to the latex contained in the nitrile rubber, before or during coagulation. PROCESS according to any one of claims 7 to 9, characterized in that at least one sodium and potassium salt is used for the coagulation of the latex. 11. A process according to any one of claims 7 to 10, characterized in that at least one halogen of a monovalent salt, at least one nitrate of a monovalent metal or at least one sulfate of a metal is used in the coagulation of the latex. monovalent. PROCESS according to any one of claims 7 to 9, characterized in that at least the salt of a monovalent metal cation and a monovalent anion are used for the coagulation of latex. 13. PROCESS according to any one of claims 7 to 12, characterized in that a mixture of two or more salts of a monovalent metal is used for the coagulation of the latex, and in that case, several salts are used of the same monovalent metal or also of several salts of different monovalent metals. 14. PROCESS according to any one of claims 7 to 13, characterized in that a quantity of salts of a divalent metal not exceeding 5% by weight relative to the latex is present in the latex coagulation. Petition 870180065835, of 07/30/2018, p. 68/74 4/6 total amount of all salts used in coagulation. 15. PROCESS, according to any one of claims 7 to 14, characterized in that potassium chloride is used in the coagulation of latex, together with the use of sodium chloride for the coagulation of nitrile rubber, and because it is the quantity potassium chloride of X% by weight, where the amount of X% by weight results from the difference between 40% by weight, less the amount of% by weight of calcium chloride, if present. 16. PROCESS according to any one of claims 7 to 15, characterized in that the amount of the salt, or salts, of the monovalent metal, used for the coagulation of the latex, is 1 - 200 parts by weight, relative to 100 parts in weight of nitrile rubber. 17. PROCESS, according to any one of claims 7 to 16, characterized by a latex, used in coagulation, which has a concentration of solid matter in the range of 1% to 40% by weight. 18. PROCESS according to any one of claims 7 to 17, characterized in that the latex coagulation is carried out at a temperature in the range of 50 to 100 ° C. 19. PROCESS according to any one of claims 7 to 18, characterized in that the latex and the solution of at least one salt of a monovalent metal are initially mixed at a temperature <50 ° C and, subsequently, the latex / salt mixture is heated to a temperature above 50 ° C. 20. PROCESS according to any one of claims 7 to 19, characterized in that deionized water is used for washing coagulated nitrile rubber Petition 870180065835, of 07/30/2018, p. 69/74 5/6 (DW) or non-deionized water (BW), preferably non-deionized water, provided that, in the coagulation of latex with at least one monovalent metal salt, no calcium salt is present in the possible quantitative range of up to 5% by weight of all salts used. 21. PROCESS according to any one of claims 7 to 20, characterized in that the washing of the coagulated nitrile rubber is carried out at a temperature in the range of 50 to 90 ° C. 22. PROCESS according to any one of claims 7 to 21, characterized in that the nitrile rubber obtained is additionally subjected to either (i) only a metathesis reaction, or (ii) a metathesis reaction and a subsequent one hydrogenation, or (iii) just a hydrogenation. 23. HYDROGENED NITRILLIC RUBBER, characterized by being obtained with the process as defined in claim 22. 24. USE OF NITRILE RUBBER, as defined in any one of claims 1 to 6, or 23, characterized by being for the manufacture of vulcanizable mixtures. 25. VULCANIZABLE MIXTURE, containing at least one nitrile rubber as defined in any one of claims 1 to 6, or 23, characterized in that it contains at least one crosslinker and, possibly, other additives. 26. PROCESS FOR MANUFACTURING A VULCANIZABLE MIXTURE, as defined in claim 25, characterized by mixing at least one nitrile rubber as defined in any one of claims 1 to 6, Petition 870180065835, of 07/30/2018, p. 70/74 6/6 or 23, at least one crosslinker and, possibly, other additives. 27. PROCESS FOR THE MANUFACTURE OF MOLDED PARTS BASED ON A NITRILE RUBBER, as defined in any one of claims 1 to 6, or 23, characterized in that the mixture is vulcanizable as defined in claim 25, vulcanized in a molding process. 28. MOLDED PIECE, characterized by being obtained with the process as defined in claim 27. 29. MOLDED PIECE according to claim 28, characterized in that it is a seal, a cover, a hose or a membrane, in particular a sealing ring, a flat seal, an axle seal ring, a gasket , a sealing cap, a dust cover, a plug seal, a hose for thermal insulation (with or without the addition of PVC), an oil cooler hose, an air suction hose, a steering hose hydraulics or a pump membrane. Petition 870180065835, of 07/30/2018, p. 71/74