TW201343677A - Purification of optionally hydrogenated nitrile rubber - Google Patents

Abstract

The present invention provides a novel process for the purification of an optionally hydrogenated nitrile rubber comprising contacting said optionally hydrogenated nitrile rubber with at least one ionic liquid thereby removing a broad variety of impurities, including various catalysts and degradation products thereof, iron containing residues and degradation products thereof, as well as compounds used either in the emulsion polymerisation for preparing the nitrile rubber or the optional subsequent metathesis and/or optional hydrogenation reaction or any degradation products thereof.

Description

Purification of selectively hydrogenated nitrile rubber

The present invention provides a process for purifying such selectively hydrogenated nitrile rubber by contacting a selectively hydrogenated nitrile rubber with a specific solvent.

Elastomers are widely used in many rubber industry products such as rubber tubing, drive belts, seals, diaphragms, textile coverings, soles, profile sections, films, packaging materials, and many others. . For applications in the field of injection molded articles, applications involving contact with food, applications in the medical field, applications in the electronics industry and as a further reaction, such as hydrogenation in the presence of sensitive transition metal catalysts For the application of the starting product, the elastomers need to remove impurities in a complicated manner. Such impurities and undesired compounds may result from an elastomeric production process in which different additives and complex metal catalysts are used, i.e., the process of free radical polymerization in an aqueous emulsion. Such additives and catalysts are also subjected to undesired degradation reactions which further lead to unwanted by-products.

In the medical industry and in contact with food, the use of elastomers with excessive levels of impurities is often greatly limited for toxicological reasons, and the limits on the level of impurities depend both on the type of impurities and on their concentration. . However, an impurity level of less than 2 wt.% is often required. The use of elastomers with excessive levels of impurities in electronic applications is often only conditionally possible. This is especially true when the impurities are hydrated and/or ionic, as these can greatly affect the corrosion behavior and conductive behavior of the electronic product, and they cannot always be removed by the action of heat without leaving a residue. In addition, with a total of based on these impurities and elastomers An elastomer having an impurity level greater than about 4 wt.%, often cannot be used in subsequent reactions that must be operated in the presence of a sensitive transition metal catalyst, such as, for example, metathesis and/or hydrogenation, because such impurities The reaction control becomes more difficult, the reaction time is prolonged, and the efficiency of the transition metal catalyst is lowered. In the case of hydrogenation, these impurities can additionally significantly promote corrosion and thus promote wear of such systems required for hydrogenation. For many other applications, such as injection molded articles or extruded articles, the use of elastomers having an excessively high level of impurities (greater than about 3 wt.%), due to efflorenscence phenomena, as well as due to mold contamination, can lead to the surface of such articles. The quality is reduced.

For such applications as described above, the purification of impurities with respect to such elastomers is typically by expensive neutralization, coagulation, precipitation, and in a suitable organic material (such as alcohols, ketones, ethers, water, And the washing process in their mixture). In its alternative, the impurities are removed by contacting the reaction mixture with an ion exchange resin that treats functional groups capable of binding to such impurities. Nonetheless, in principle, complete purification cannot be guaranteed.

A particular problem relates to the separation of low molecular weight, sometimes high boiling (above 150 ° C), poorly water soluble and/or water insoluble impurities such as emulsifiers, fatty acids, fatty acid salts, And fatty acid esters, monomers and derivatives thereof, such as dimers, oligomers, or other undesirable reaction products of such monomers with other components of the reaction system, organic catalyst residues and The sites, which remain in the elastomer when the elastomer has been prepared by emulsion polymerization followed by conventional purification methods.

Using conventional processing and purification methods known in the art, such impurities are often not sufficiently separated and can even be used only with significant economical expense because they are encapsulated during the latex condensation process of the elastomer and thus It is less easy to carry out the washing process. It is known that the elastomers are subjected to fractional precipitation from solution followed by a drying step to separate low molecular weight impurities and/or impurities which can be dissolved in various organic solvents (precipitants) in which the polymer system Insoluble, for example in the case of nitrile rubber and polychloroprene rubber, methanol is used as A solvent for such impurities. Such impurities are, for example, emulsifiers, fatty acids, fatty acid esters, sodium, potassium or calcium salts of fatty acids, unreacted monomers, molecular weight regulators, catalyst group classification, and any reaction products thereof. . However, such fractionated precipitation inevitably causes high costs on an industrial scale and is ecologically disadvantageous due to the large amount of solvent required and the precipitant.

A wide variety of ionic liquids have been investigated for the removal of certain additives from different organic media. WO 2002/34863 A teaches a process for removing mercaptans from a hydrocarbon stream (for example crude oil and natural gas) by a) adding a mercaptan-containing hydrocarbon feed stream to one or more basic metal salts. An ionic liquid solution or dispersion to form a thiolate, and then the thiolate dissolved or dispersed in the ionic liquid is precipitated from the solution, and b) the resulting mercaptan is separated from the ionic liquid (de-marcaptanized) hydrocarbon feed stream. Hydrocarbon sulfur can either flow through/through the ionic liquid or contact in a stirred tank. These alkali salts can be almost any base capable of reacting with a thiol to form a thiolate.

US 2004/0133058 A discloses a process for separating narrow boiling or azeotropic mixtures by using ionic liquids as selective additives in rectification. This method allows separation of a liquid or condensable gas in a condensed state in which a carrier is used, which is an ionic liquid and which causes a different separation factor from the component to be separated to be different from one. The ionic liquid is present in a total concentration of from 5 mol% to 90 mol%. This method is said to be superior to conventional extractive distillation in terms of cost and energy. As azeotropic mixtures, for example as suitable for the following applications, mention: amine/water, THF/water, formic acid/water, alcohol/water, acetone/methanol, acetate/water, acrylate/water; Or narrow boiling mixtures such as acetic acid/water, C4 hydrocarbons, C4 hydrocarbons, and alkanes/olefins.

US 2005/0010076 A discloses a process for purifying a hydrocarbon or hydrocarbon mixture by removing polarizable impurities with an ionic liquid. Of particular importance is the removal of sulfur-containing impurities from diesel fuel or other gasoline fractions to levels below 50 ppm, which is said to be significantly better than that removed by hydrogenation. In addition, the process also allows for a dehalogenation which avoids the typical disadvantages of dehalogenation by hydrogenation (e.g., high pressure and high temperature, releasing corrosive HCl gas).

US 2003/0085156 A also discloses a method for removing an organic sulfur compound from a hydrocarbon material by contacting a hydrocarbon material (diesel fuel, gasoline, aviation kerosene, etc.) with an ionic liquid, thereby extracting the sulfur compound to In the ionic liquid. The process can be carried out either batchwise or continuously. It is described that a counterflow contactor can be used which allows the hydrocarbon material to flow into the bottom of the contactor and rise through the ionic liquid (which enters through its top and exits from the bottom) and exits by the top . In another embodiment, a method of regenerating an ionic liquid by removing an organic sulfur compound from the ionic liquid by vaporization or solvent extraction is described.

US 2005/0090704 A relates to a process for liquid-liquid extraction or liquid-gas extraction from a mixture of olefinic and aliphatic organic compounds, wherein the olefins are extracted by a phase comprising at least one ionic liquid. Wherein the extraction is carried out in countercurrent and the phase comprises the ionic liquid.

Regarding the molecular weight degradation of a polymer by a metathesis reaction, the metathesis itself is also a well-documented method. For example, various rhodium-containing catalysts are known to be particularly suitable for the selective metathesis of nitrile rubbers, which include the carbon-carbon double bond present in the nitrile rubber but not accompanied by the reduction of the carbon-nitrogen triple bond.

US 2003/0088035 A teaches the use of bis(tricyclohexylphosphine)benzylidene ruthenium dichloride in such metathesis reactions. First, the rubber is dissolved in a suitable solvent to provide a viscous rubber solution. The catalyst solvent is then dissolved in the rubber solution and a co-olefin can be added to such a solution. After the metathesis of the nitrile rubber, the rubber solution can be selectively hydrogenated. Similarly, US 2004/0132891 A teaches the use of 1,2-bis-(2,4,6-trimethylphenyl)-2-imidazolidinyl)(tricyclohexylphosphine) -indole (phenyl phenyl) Methyl) dichloride is used for the metathesis of nitrile rubber, however, there is no co-olefin. The disclosure of conventional techniques for the potential separation of the metathesis catalyst from the polymer is relatively limited. In addition, there is no concern at all about the disclosure or teaching of any undesired by-products or impurities.

US 6,376,690 B1 relates to the removal of metal complexes from a reaction mixture and teaches the use of a separation process in which a solution containing a solubility-enhancing compound is added to the original reaction mixture containing the metal complexes. The solution added therein is immiscible with the original reaction mixture. Depending on whether the reaction mixture has an aqueous or organic nature (preferably based on CH ₂ Cl ₂ ), the second solution is exactly opposite and enhances the metal catalyst in the second solution Choose the way of solubility. Such solubility enhancing compounds include, for example, phosphines, sulfonated phosphines, phosphites, phosphinates, phosphonites, anthraquinones, Classes, ethers, amines, guanamines, imines, guanidines, carboxyls, nitrosonides, pyridines, and thioethers. Once reacted with a solubility-enhancing compound, for example based on cadmium, chromium, cobalt, copper, gold, ruthenium, iron, magnesium, manganese, mercury, molybdenum, nickel, ruthenium, palladium, platinum, rhodium, iridium, ruthenium, silver, Metal catalysts of techneticum, tungsten, and zinc migrate from the reaction mixture into the second phase. This solution was then removed from the reaction solution. This process is said to be particularly easy to carry out the separation of the ruthenium and osmium metathesis catalysts from the desired products. Disadvantageously, however, such methods involve the addition of additives which, if not completely removed, will later interfere with the hydrogenation catalyst which is typically used in a subsequent step to hydrogenate the nitrile rubber. Second, the separation of the two immiscible solutions, while relatively simple on a small scale, is a fairly complex process on a large commercial scale.

The prior art further describes other completely different methods for removing catalyst or catalyst degradation products derived from metathesis reactions.

WO-A-2006/047105 discloses a process for separating a homogeneous metathesis catalyst and optionally one or more homogeneous metathesis degradation products from a metathesis reaction mixture, the metathesis reaction mixture comprising, in addition to the metathesis catalyst and The metathesis degradation product further comprises one or more olefin decomposition products, one or more unconverted reactant olefins, and optionally a solvent. The method comprises contacting the metathesis reaction mixture with a nanofiltration membrane, such as a polyimine, to recover a permeate and a retentate comprising a majority of the olefin reaction product, unconverted The reactants are olefins, and optionally solvents, and the retentate comprises a metathesis catalyst, and a selectively metathesis catalyst degradation product. The metathesis reaction mixture used can be obtained by homogeneous metathesis, cross metathesis, ring closure metathesis, or ring-opening metathesis polymerization.

In Tetrahedron Letters, 1999, Vol. 40, 4137-4140 , the product of a ring closure metathesis reaction using RuCl ₂ (=CHPh) (PCy ₃ ) as a catalyst (especially diethyl diallyl malonate) is disclosed. The product can be successfully purified by using a water-soluble coordination phosphine that is easily coordinated to the hydrazine, and the hydroxymethylphosphine (ie, P(CH ₂ OH) ₃ ) successfully purifies the undesired hydrazine, thereby producing A water soluble complex. In Organic Letters, 2001, Vol. 3, No. 9, 1411-1413 , the treatment of the crude reaction product with triphenylphosphine oxide or dimethyl hydrazine using Grubbs-I or Grubbs-II catalyst is described. The colored by-products produced in the olefin metathesis reaction are removed by filtration through a cerium oxide gel.

Polymer hydrogenation is a well-known operation, for example, disclosed in US-A-4,396,761, US-A-4,510,293, US-A-5,258,467, and US-A-4,595,749 . However, subsequent separation of the hydrogenation catalyst from the polymer or degradation of its product is not always described in detail or not described at all.

More specifically, certain rhodium-containing catalysts are known to be particularly suitable for the selective hydrogenation of nitrile rubbers (i.e., reduction of carbon-carbon double bonds present in nitrile rubbers without concomitant reduction of carbon-nitrogen triple bonds). This hydrogenated nitrile rubber is less sensitive to thermally induced degradation than unsaturated nitrile rubber.

For example, US-A-4,464,515 teaches the use of a ruthenium (triphenylphosphine) ruthenium hydride catalyst, HRh(PPh ₃ ) ₄ , in a process for the selective hydrogenation of unsaturated nitrile rubber. After this hydrogenation, no further disclosure regarding the removal of the hydrogenation catalyst.

GB-A-1,558,491 teaches the use of chlorinated ginseng (triphenylphosphine) ruthenium (RhCl(PPh ₃ ) ₃ ) as a catalyst in a similar process for hydrogenating unsaturated nitrile rubber. The hydrogenated product is separated from the reaction solution by treatment with steam or by pouring into methanol and then dried at elevated temperature and under reduced pressure. Again, no teachings are provided on how the hydrogenation catalyst should be removed.

It is also known that certain rhodium-containing catalysts are particularly suitable for the selective metathesis or hydrogenation of nitrile rubbers. Processes for the homogeneous hydrogenation of nitrile rubber using ruthenium containing catalysts are also well known. In US 5,075,388 , a hydrogenated nitrile rubber is disclosed in the presence of a compound containing NH ₂ (selected from ammonia and a C ₁ - ₂₀ primary amine). US-A-6,084,033 teaches the use of a rhodium-iridium bimetallic miscible catalyst for the hydrogenation of nitrile rubber. However, there is no teaching at all how to remove the corresponding catalyst residue from the hydrogenated nitrile rubber.

US-A-4,631,315 teaches the use of a ruthenium-based catalyst for the hydrogenation of nitrile rubber dissolved in a low molecular weight ketone solvent. After hydrogenation, the polymer is separated from the solution by conventional methods, for example by (vacuum) evaporation, by blowing water vapor or by adding a non-solvent. A drying treatment is then carried out to remove residual solvent or water.

In the above references, the unsaturated nitrile rubber is first dissolved in a suitable solvent to provide a viscous rubber solution. The catalyst is then dissolved in the rubber solution. These hydrogenation processes are said to be homogeneous since the matrix and catalyst are contained in the same phase. An advantage of the above homogeneous hydrogenation processes is that they require a minimum amount of catalyst to carry out the hydrogenation. However, a major disadvantage of such processes is that it is difficult to remove the catalyst from the reaction mixture once the reaction is complete. By contrast, in a non-homogeneous process, i.e., wherein the catalyst is not dissolved in the reaction medium, the catalyst can be easily removed by filtration or centrifugation.

In addition to the ruthenium and osmium residues, iron residues may also be present in the hydrogenated nitrile polymer. Iron-containing residues can occur due to minimal corrosion or degradation that may occur in any metal vessel or pipe, or alternatively, because iron-containing compounds may have been used as activators in the polymerization of the nitrile rubber. A fact. Iron, bismuth, and lanthanum are effective catalytic metals, and it is therefore desirable to remove them from the nitrile rubber along with the hydrogenated rubber in order to improve the overall quality of the product. In addition, high-priced cesium provides economic incentives for recycling.

A different method for recovering certain catalysts from the reaction mixture and in particular the selectively hydrogenated rubber comprises the use of ion exchange resins.

US-A-4,985,540 discloses a process for removing ruthenium containing catalyst residues from hydrogenated nitrile rubber by contacting a functionalized ion exchange resin with a hydrocarbon phase comprising hydrogenated nitriles Rubber, ruthenium containing catalyst residue and a hydrocarbon solvent. This method is said to remove strontium from a viscous solution containing less than 10 ppm hydrazine (weight/solution weight). The ion exchange resins used are characterized by a large network and are modified with functional groups selected from the group consisting of amines, thiols, carbodithioates, thioureas, and dithiocarbamic acides. Functional group of the ester.

In US-6,646,059 B2 , the removal of iron-containing and cerium- containing residues from a hydrogenated nitrile rubber solution by hydrogenating a nitrile rubber in the presence of a ruthenium-based catalyst is disclosed. And get. This method utilizes a special monodisperse, macroporous, crosslinked styrene-divinylbenzene copolymer resin having a thiourea functional group. The fact that the ion exchange resin is monodispersed is believed to be important for successful implementation of the process.

US-A-5,208,194 further teaches the use of sulfonic acid functionalized ion exchange resins for the recovery of Group VIII metal complexes from dilute organic solutions. US 2004/0026329 A teaches recovering such metals by incorporating the transition metal onto the functionalized polymer fibers. The polymeric fiber is suitably a polyolefin, fluorinated polyethylene, cellulose, or viscose fiber functionalized by radiation grafting of at least one monomer.

Despite the above methods of the prior art, the removal of catalyst residues from both the nitrile rubber and the hydrogenated nitrile rubber along with other undesirable by-products, in particular in view of the solutions containing the above polymers, has a substantial There is still room for additional problems with viscosity.

The present invention relates to a process for purifying a selectively hydrogenated nitrile rubber comprising contacting a selectively hydrogenated nitrile rubber with at least one ionic liquid.

A detailed description

For the purposes of the present patent application and the invention, all definitions of the radicals, parameters or explanations given above or below in the general sense or in the preferred ranges may be combined with each other in any manner, ie including such corresponding A combination of ranges and preferred ranges.

With respect to a metathesis catalyst or a salt of the formula (I), the term "substituted" as used in the context of the present patent application means a radical in each case indicated by a hydrogen atom at a specified group or atom. Substituted by one of the regiments, the premise does not exceed the valence of the indicated atom and this substitution produces a stable compound.

In order to successfully carry out the process according to the invention, it is necessary to bring the selectively hydrogenated nitrile rubber into contact with at least one ionic liquid.

The ionic liquid system to be used in the process of the invention is at a temperature ranging from -20 ° C to 300 ° C, preferably from 0 ° C to 150 ° C, and particularly preferably from 20 ° C to 100 ° C of liquid salt or Salt mixture.

Ionic liquid systems are typically defined by both their cations and their anionic portions.

For the purposes of the present invention, ionic liquids may represent, but are not limited to, based on quaternary ammonium cations, quaternary phosphonium cations, selectively substituted pyridinium cations, selectively substituted imidazolium cations, selectively substituted pyrazole cations, and selection A compound of a pyrimidine cation that is sexually substituted.

Preferably, the process according to the invention is carried out using at least one ionic liquid selected from the group consisting of ionic liquids having the general formulae (1) to (5): Wherein A ^n- should mean an anion selected from the group consisting of hexafluorophosphate (PF ₆ ^- ), nitrate (NO ₃ ^- ), halide (preferably fluoride, chlorine) a compound, a bromide, or an iodide), a sulfate, a sulfonate, an aluminate, a carboxylate, a phosphate, and a borate, wherein n is 1, 2, or 3, depending on the negative charge of the anion described above, and thus (1/n) represents 1 for an anion with a double negative charge, 1/2 for an anion with a double negative charge, and 1/3 for an anion with a triple negative charge, X-based nitrogen or phosphorus, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and represent hydrogen, halide, alkoxy, alkyl, substituted alkyl, aryl, preferably phenyl. a substituted aryl group, and Z ¹ , Z ² , Z ³ are the same or different and represent carbon (C) or nitrogen (N), the first condition of which is at least one of Z ¹ , Z ² and Z ³ The nitrogen is present and the second condition is that when any of Z ¹ , Z ² , and Z ³ is nitrogen, the attached group of R ¹ , R ² , or R ³ is null. Preferably, the method according to the present invention is carried out in the presence of at least one ionic liquid according to one of the above formulas (1) to (5) (wherein n is 1), and A ^- represents PF ₆ ^- , NO ₃ ^- , F ^- , Cl ^- , Br ^- , I ^- , R ⁷ SO ₃ ^- , R ⁷ OSO ₃ ^- , R ⁷ CO ₃ ^- , BF ₄ ^- , and B(R ⁷ ) ₄ ^- , wherein R ⁷ They are the same or different and represent an alkyl group, a substituted alkyl group, an aryl group, more preferably a phenyl group, a substituted aryl group, or an alkoxy group. In a more preferred embodiment, the process according to the invention is carried out in the presence of at least one ionic liquid having the general formula (1) wherein n is 1 and A ^- represents PF ₆ ^- , NO ₃ ^{- , F -, Cl -, Br} -, I -, R 7 SO 3 -, R 7 OSO 3 -, R 7 CO 3 -, BF 4 -, and B (R ⁷⁾ ₄ ^-, wherein R ⁷ lines the same Or different and represents an alkyl group, a substituted alkyl group, an aryl group, even more preferably a phenyl group, a substituted aryl group, or an alkoxy group, an X-form nitrogen or phosphorus, and R ¹ , R ² , R ³ , And R ⁴ are the same or different and should mean an alkoxy group, an alkyl group, or an aryl group each having 1 to 25 carbon atoms. In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one ionic liquid having the general formula (2) wherein n is 1 and A ^- represents PF ₆ ^- , NO ₃ ^- , F ^- , Cl ^- , Br ^- , I ^- , R ⁷ SO ₃ ^- , R ⁷ OSO ₃ ^- , R ⁷ CO ₃ ^- , BF ₄ ^- , and B(R ⁷ ) ₄ ^- , wherein R ⁷ is the same Or different and represents an alkyl group, a substituted alkyl group, an aryl group, even more preferably a phenyl group, a substituted aryl group, or an alkoxy group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is the same or different and should mean an alkoxy group, an alkyl group, or an aryl group each having 1 to 25 carbon atoms. In another more preferred embodiment, the process according to the invention is carried out in the presence of at least one ionic liquid having the general formula (3) wherein n is 1 and A ^- represents PF ₆ ^- , NO ₃ ^- , F ^- , Cl ^- , Br ^- , I ^- , R ⁷ SO ₃ ^- , R ⁷ OSO ₃ ^- , R ⁷ CO ₃ ^- , BF ₄ ^- , and B(R ⁷ ) ₄ ^- , wherein R ⁷ is the same Or different and represents an alkyl group, a substituted alkyl group, an aryl group, even more preferably a phenyl group, a substituted aryl group, or an alkoxy group, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ They are the same or different and should mean an alkoxy group, an alkyl group, or an aryl group each having 1 to 25 carbon atoms. More preferably, the method according to the invention at least one system having the general formula (4) in the presence (lines where n 1) of the ionic liquid, and A ^- represents _{^{PF 6 -, NO 3 -,}} F -, Cl ^- , Br ^- , I ^- , R ⁷ SO ₃ ^- , R ⁷ OSO ₃ ^- , R ⁷ CO ₃ ^- , BF ₄ ^- , and B(R ⁷ ) ₄ ^- , wherein R ⁷ are the same or different and And an alkyl group, a substituted alkyl group, or an aryl group, preferably a phenyl group, a substituted aryl group or an alkoxy group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different. And it should mean an alkoxy group, an alkyl group, or an aryl group each having 1 to 25 carbon atoms. More preferably, the process according to the invention is carried out in the presence of at least one ionic liquid having the general formula (5) (where n is 1), and A ^- represents PF ₆ ^- , NO ₃ ^- , F ^- , Cl ^- , Br ^- , I ^- , R ⁷ SO ₃ ^- , R ⁷ OSO ₃ ^- , R ⁷ CO ₃ ^- , BF ₄ ^- , and B(R ⁷ ) ₄ ^- , wherein R ⁷ are the same or different and Represents an alkyl group, a substituted alkyl group, an aryl group, more preferably a phenyl group, a substituted aryl group, or an alkoxy group, and Z ¹ , Z ² , Z ³ are the same or different and represent carbon (C) or nitrogen (N), a first system condition Z ^1, at least one nitrogen-based system and a second condition in Z ² and Z ³ when Z ^1, Z ^2, any one containing nitrogen in Z ^3, the The group of attached R ¹ , R ² , or R ³ is null, and R ¹ , R ² , R ³ , R 4 , R ⁵ , and R ⁶ are the same or different and refer to each An alkoxy, alkyl, or aryl group having 1 to 25 carbon atoms.

In a specific embodiment, the method of the present invention is carried out using at least one ionic liquid selected from the group consisting of 1-ethyl-3-methyl-pyridine cation ethyl sulphate Salt, 1-ethyl-3-methyl-imidazolium ionic ethyl sulfate, 1-methyl-3-butylimidazolium chloride, 1-methyl-3-ethylimidazolium chloride, N-butyl-pyridine cation chloride, tetrabutylphosphonium chloride, ammonium hexafluorophosphate, ammonium tetrafluoroborate, ammonium toluenesulfonate, ammonium hydrogen sulfate, pyridine cation hexafluorophosphate, 1-methyl- 3-butylimidazolium hexafluorophosphate, pyridine cation tetrafluoroborate, pyridine cation hydrogensulfate, n-butylpyridine cation hexafluorophosphate, and two or more of the above ionic liquids combination.

Nitrile rubber:

For the purposes of the present invention, a nitrile rubber (also referred to simply as "NBR") containing repeating units is at least one alpha, beta-saturated nitrile, at least one conjugated diene, and optionally one or more additional copolymerizable monomers. Copolymer or terpolymer rubber.

Such nitrile rubbers and methods for producing such nitrile rubbers are well known, see for example, W. Hofmann, Rubber Chem. Technol. 36 (1963) 1 and Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft, Weinheim, 1993, pp. .255-261.

The conjugated diene in the nitrile rubber may be of any kind. It is preferred to use a (C ₄ -C ₆ ) conjugated diene. Particularly preferred are 1,2-butadiene, 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, or mixtures thereof. More particularly preferred are 1,3-butadiene, and isoprene, or mixtures thereof. 1,3-butadiene is especially preferred.

As the α,β-unsaturated nitrile , it is possible to use any known α,β-unsaturated nitrile, preferably a (C ₃ -C ₅ )α,β-unsaturated nitrile such as acrylonitrile, Methacrylonitrile, ethacrylonitrile, or a mixture thereof. Acrylonitrile is particularly preferred.

A particularly preferred nitrile rubber is a copolymer of acrylonitrile and 1,3-butadiene.

As the other copolymerizable trimonomer, it is possible to use, for example, an aromatic vinyl monomer, preferably styrene, α-methylstyrene, and vinylpyridine, fluorine-containing vinyl monomers , Preferred are fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-fluoromethyl styrene, vinyl pentafluorobenzoate, difluoroethylene and tetrafluoroethylene, or an additional copolymerizable anti-aging single body type, preferred is N- (4- anilinophenyl) acrylamide, N- (4- anilino-yl) methyl acrylamide, N- (4- anilinophenyl) cinnamic Amides , N-(4-anilinophenyl) crotonamide, N-phenyl-4-(3-vinylbenzyloxy)aniline, and N-phenyl-4-(4-vinylbenzyloxy)aniline And non-conjugated dienes such as 4-cyanocyclohexene and 4-vinylcyclohexene, or acetylenes such as 1- or 2-butyne.

Alternatively, as an additional copolymerizable tri-monomer, it is possible to use a carboxyl group-containing copolymerizable trimonomer, examples being α,β-unsaturated monocarboxylic acids, their esters, their guanamines, Alpha, β-unsaturated dicarboxylic acids, their monoesters or diesters or their corresponding anhydrides or guanamines.

As the α,β-unsaturated monocarboxylic acid , it is possible to use acrylic acid and methacrylic acid preferably.

It is also possible to use esters of such α,β-unsaturated monocarboxylic acids , preferably their alkyl esters or alkoxyalkyl esters. Preferred are alkyl esters, especially C ₁ -C ₁₈ alkyl esters of α,β-unsaturated monocarboxylic acids. Particularly preferred are alkyl esters of acrylic acid or methacrylic acid, especially C ₁ -C ₁₈ alkyl esters, more particularly methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tertiary butyl acrylate Ester, 2-ethylhexyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate. Also preferred are alkoxyalkyl esters of α,β-unsaturated monocarboxylic acids, more preferably alkoxyalkyl esters of acrylic acid or methacrylic acid, more particularly C of acrylic acid or methacrylic acid. ₂ -C ₁₂ alkoxyalkyl esters, very preferred is methoxymethyl acrylate, (meth) acrylate, ethoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, Methoxymethyl ester. It is also possible to use mixtures of alkyl esters (such as those mentioned above) with alkoxyalkyl esters (for example in the form of those mentioned above). It is also possible to use cyanoalkyl acrylate and cyanoalkyl methacrylate wherein the number of C atoms in the cyanoalkyl group is 2-12, preferably α-cyanoethyl acrylate or β-cyanoethyl acrylate. Ester and cyanobutyl methacrylate. It is also possible to use a hydroxyalkyl acrylate and a hydroxyalkyl methacrylate wherein the hydroxyalkyl group has a C atom number of from 1 to 12, preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 3-Hydroxypropyl acrylate; acrylate or methacrylate of a fluorine-substituted benzyl group may also be used, preferably fluorobenzyl acrylate and fluorobenzyl methacrylate. Fluorinated alkyl acrylates and methacrylates may also be used, with trifluoroethyl acrylate and tetrafluoropropyl methacrylate being preferred. It is also possible to use an amine group-containing α,β-unsaturated carboxylic acid ester such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate.

As other copolymerizable monomers, in addition, it is also possible to use α,β-unsaturated dicarboxylic acids , preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.

Further, an α,β-unsaturated dicarboxylic acid anhydride can be used , and preferred are maleic anhydride, itaconic anhydride, citraconic anhydride, and mesaconic anhydride.

Further, it is possible to use monoesters or diesters of α,β-unsaturated dicarboxylic acids .

Such α, β- unsaturated dicarboxylic acid monoester or diester may be, for example, alkyl esters, preferred are C ₁ -C ₁₀ alkyl, more particularly ethyl, n-propyl, isopropyl , n-butyl, tert-butyl, n-pentyl or n-hexyl ester; alkoxyalkyl ester , preferably C ₂ -C ₁₂ alkoxyalkyl, more preferably C ₃ -C ₈ alkane Alkoxyalkyl; hydroxyalkyl group , preferably C ₁ -C ₁₂ hydroxyalkyl group, more preferably C ₂ -C ₈ hydroxyalkyl group; cycloalkyl ester , preferably C ₅ -C ₁₂ ring An alkyl group, more specifically a C ₆ -C ₁₂ cycloalkyl group; an alkylcycloalkyl ester , preferably a C ₆ -C ₁₂ alkylcycloalkyl group, more preferably a C ₇ -C ₁₀ alkyl ring Alkyl; aryl esters , preferably C ₆ -C ₁₄ aryl esters, such esters are monoesters or diesters, and it is also possible in the case of diesters to be esters of such esters.

Particularly preferred alkyl esters of α,β-unsaturated monocarboxylic acids are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate , (butyl) (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 2-propyl heptyl (meth) acrylate Ester and lauryl (meth)acrylate. More specifically, n-butyl acrylate is used.

Particularly preferred alkoxyalkyl esters of α,β-unsaturated monocarboxylic acids are methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and methoxy(meth)acrylate Methyl ester. More particularly, methoxyethyl acrylate is used.

Particularly preferred hydroxyalkyl esters of α,β-unsaturated monocarboxylic acids are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.

Further esters of the α,β-unsaturated monocarboxylic acid to be used are, for example, (meth)acrylic acid polyethylene glycol, (meth)acrylic acid polypropylene glycol, (meth)acrylic acid glycidyl ester, (meth)acrylic acid. Epoxy ester, N-(2-hydroxyethyl) acrylamide, N-(2-hydroxymethyl) acrylamide, and urethane (meth) acrylate.

Examples of the α,β-unsaturated dicarboxylic acid monoester include: ‧ maleic acid monoalkyl esters, preferably monomethyl maleate, monoethyl maleate, monopropyl maleate And mono-n-butyl maleate; ‧ maleate monocycloalkyl esters, preferably monocyclopentanyl maleate, monocyclohexyl maleate and monocycloheptyl maleate; Preferred are monoalkylcycloalkyl esters, preferably monomethylcyclopentyl maleate, and monoethylcyclohexyl maleate; ‧ maleic monoaryl esters, preferably Is monophenyl maleate; ‧ maleic acid monobenzyl ester, preferably maleic acid monobenzyl ester; ‧ fumaric acid monoalkyl ester, preferably fumaric acid monomethyl Ester, monoethyl fumarate, monopropyl fumarate and mono-n-butyl fumarate; ‧ monocyclic alkyl fumarate, preferably monocyclopentan fumarate, fumaric acid Monocyclohexyl ester and monocycloheptyl fumarate; ‧ monoalkylcycloalkyl fumarate, preferably monomethylcyclopentyl fumarate, and monoethylcyclohexyl fumarate Ester; ‧ fumaric acid monoaryl ester, preferably monophenyl fumarate; Monobenzyl fumarate, preferably monobenzyl fumarate; ‧ monoalkyl citrate, preferably monomethyl citrate, monoethyl citrate, lemon Monopropyl propyl citrate and mono-n-butyl citrate; ‧ cyclamic acid monocyclic alkyl esters, preferably citraconic acid monocyclopentyl ester, citraconic acid monocyclohexyl ester and citraconic acid monocyclic ring Heptyl ester; ‧ citraconic acid monoalkyl cycloalkyl ester, preferably citraconic acid monomethylcyclopentyl ester, and citraconic acid monoethylcyclohexyl ester; ‧ citraconic acid monoaryl ester Preferred are phenyl citrate monophenyl ester; ‧ citraconic acid monobenzyl ester, preferably citraconic acid monobenzyl ester; ‧ itaconic acid monoalkyl ester, preferably Itaconic acid monomethyl ester, itaconic acid monoethyl ester, itaconic acid monopropyl ester and itaconic acid mono-n-butyl ester; ‧ itaconic acid monocycloalkyl ester, preferably itaconic acid monocyclopentane Ester, itaconic acid monocyclohexyl ester and itaconic acid monocycloheptyl ester; ‧ itaconic acid monoalkyl cycloalkyl ester, preferably itaconic acid monomethylcyclopentyl ester, and itaconic acid Monoethylcyclohexyl ester; ‧ itaconic acid monoaryl ester, preferably itaconic acid Ester; ‧ per itaconic acid mono benzyl ester, preferred is itaconic acid mono benzyl ester; ‧ per mesaconic acid monoalkyl esters, preferred are mesaconic acid monoethyl ester.

As the α,β-unsaturated dicarboxylic acid diesters , it is possible to use similar diesters based on the above monoester groups, and the ester groups may also be chemically different groups.

As further copolymerizable monomers, it is additionally possible to use radically polymerisable compounds which comprise two or more olefinic double bonds per molecule. Examples of such di- or polyunsaturated compounds are di- or polyunsaturated acrylates, methacrylates, or itaconates of polyols, such as, for example, 1,6-hexanediol diacrylate (HDODA). 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethyl propylene Acid ester, triethylene glycol diacrylate, butane-1,4-diol diacrylate, propane-1,2-diol diacrylate, butane-1,3-diol dimethacrylate , neopentyl glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate , trimethylolpropane triacrylate, trimethylolpropane trimethacrylate (TMPTMA), glyceryl diacrylate and triacrylate, pentaerythritol di, tri and tetraacrylate or methacrylate , dipentaerythritol tetra, five and hexaacrylate or methacrylate or itaconate, sorbitol tetraacrylate, sorbitol hexamethacrylate, diacrylate or dimethacrylate or 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-bis(4-hydroxyphenyl)propane, polyethylene glycol or oligoester or oligomeric with terminal hydroxyl groups A di- or polyunsaturated acrylate, methacrylate or itaconate of a urethane. As the polyunsaturated monomer, it is possible to use acrylamide such as, for example, methylenebis acrylamide, hexamethylene-1,6-bispropene decylamine, di-ethyltriamine methacryl Indoleamine, bis(methacrylamidopropoxy)ethane or 2-propenylamine ethyl acrylate. Examples of polyunsaturated vinyl compounds and allyl compounds are divinylbenzene, ethylene glycol divinyl ether, diallyl phthalate, allyl methacrylate, and diallyl maleate. A base ester, triallyl isocyanurate or triallyl phosphate.

When using this type of tri-monomer, it may be advantageous to successfully achieve a high conversion of the polymerization reaction and at the same time to prepare a relatively high average molecular weight Mw (weight average) and / or Mn (number average) Nitrile rubber, and still no gel.

The ratio of conjugated diene to α,β-unsaturated nitrile in the NBR polymer can vary over a wide range. The proportion of the conjugated dienes or the total amount thereof is typically in the range of from 40% to 90% by weight, preferably from 50% to 85% by weight based on the total polymer. The proportion or sum of the α,β-unsaturated nitriles is typically from 10% to 60% by weight, based on the total polymer, preferably from 15% to 50% by weight. The proportion of these monomers in each case amounts to 100% by weight. The additional monomer, depending on the nature of the three monomers or the three monomers, is present in an amount from 0 to 40% by weight based on the total polymer. In this case, the corresponding proportions of the or the conjugated dienes and/or the or such α,β-unsaturated nitriles are Instead, the ratio of all monomers in each case amounts to 100% by weight.

If esters of (meth)acrylic acid are used as additional monomers, they are usually used in an amount of from 1% to 25% by weight.

If an α,β-unsaturated monocarboxylic acid or dicarboxylic acid is used as the additional monomer, they are usually used in an amount of less than 10% by weight.

The nitrogen content of the nitrile rubber of the present invention is determined by the Kjeldahl method in accordance with DIN 53 625. Due to the content of polar comonomers, the nitrile rubber is usually in methyl ethyl ketone at 20 ° C by weight. 85% soluble.

The nitrile rubbers have a Mooney viscosity (ML (1 + 4 @ 100 ° C)) of from 10 to 150, preferably from 20 to 100 Munier units. The Mooney viscosity (ML (1+4 @100 °C)) was determined at 100 ° C by a shear disc viscometer according to DIN 53523/3 or ASTM D 1646.

The glass transition temperature range of the selectively hydrogenated nitrile rubber of the present invention is in the range of from -70 ° C to +20 ° C, preferably in the range of from -60 ° C to 10 ° C.

Preferred are nitrile rubbers comprising acrylonitrile, 1,3-butadiene, and optionally a plurality of repeating units of one or more additional copolymerizable monomers in accordance with the present invention. Also preferred are the following nitrile rubbers having repeating units of acrylonitrile, 1,3-butadiene, and one or more α,β-unsaturated monocarboxylic or dicarboxylic acids, esters thereof. Or a guanamine, and in particular repeats the alkyl esters of the unitary α,β-unsaturated carboxylic acid, very particularly preferably methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) Propyl acrylate, n-butyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate Or lauryl (meth)acrylate.

The preparation of nitrile rubber by emulsion polymerization of the above monomers is well known to those skilled in the art and is fully described in the polymer literature. Nitrile rubber may be used for the purposes of the present invention are also commercially available, such as for example product from Lanxess Deutschland GmbH (Lanxess Deutschland GmbH) name Perbunan ^® and Krynac ^® product range of products.

Prior to undergoing the process of the present invention, the nitrile rubbers can also undergo a metathesis reaction to reduce their molecular weight, as is known in the art and in the scientific literature and patents (for example, US 2003/0088035 A and US 2004/0132891). It is explained in A ).

The nitrile rubber which has not undergone the metathesis reaction to be subjected to the method of the present invention has a Mooney viscosity (ML 1+4 at 100 ° C) generally in the range of from 30 to 70, preferably from 30 to 50. Inside. This corresponds to a weight average molecular weight Mw in the range of 200,000 to 500,000, preferably in the range of 200,000 to 400,000. The nitrile rubber used also has a polydispersity PDI = Mw / Mn in the range of 2.0 - 6.0 and preferably in the range of 2.0 - 4.0, wherein Mw is a weight average molecular weight and a Mn coefficient average molecular weight.

The nitrile rubber previously subjected to the metathesis reaction to be subjected to the method of the present invention has a Mooney viscosity (ML 1+4 at 100 ° C) generally in the range of from 1 to 50, preferably from 1 to 30. Inside. This corresponds to a weight average molecular weight Mw in the range of 25,000-250,000, preferably in the range of 50,000-150,000. The nitrile rubber typically has a polydispersity PDI = Mw / Mn in the range of 1.5 to 5.0, and preferably in the range of 1.5 to 3.5, wherein Mw is a weight average molecular weight and a Mn coefficient average molecular weight.

Hydrogenated nitrile rubber:

The term hydrogenated nitrile rubber or the abbreviation "HNBR" is intended to mean all of the above-mentioned nitrile rubbers which have been subjected to hydrogenation. "Hydrogenated" in the present invention is intended to characterize a nitrile rubber in which a C=C double bond is selectively partially or fully hydrogenated. Preferred hydrogenated nitrile rubbers are those based on a degree of hydrogenation of the C=C double bond derived from the conjugated diene of at least 75%, preferably at least 95%, more preferably at least 98%. The degree of hydrogenation can be determined by NMR and IR spectroscopy.

For hydrogenation, the nitrile rubber obtained from the emulsion polymerization is converted into a solid rubber. Conversion of the nitrile rubber latex to the solid rubber is carried out by methods known to those skilled in the art. Dissolving the nitrile rubber from which the impurities have been removed in an organic solvent, if impurities are removed therefrom by such purification methods known to those skilled in the art, such as precipitation or coagulation and subsequent washing; or by The retentate solution obtained by the process of the invention (the retentate solution comprising such dissolved and purified nitrile rubber) directly has a transition metal catalyst suitable for use in hydrogenation, and is then hydrogenated.

Hydrogenation of nitrile rubbers is well known to those skilled in the art from US-A-3,700,637, 4,464,515, and DE A3-046,008, DE A3-227,650 and DE A3-329,974.

NBR and HNBR are also collectively referred to as (H)NBR in this application unless otherwise indicated.

Method according to the invention:

The process of the invention allows for the simultaneous purification of nitrile rubber and hydrogenated nitrile rubber in different aspects. It is possible to remove the following types of components (1) to (3) at the same time:

(1) A ruthenium, osmium, and ruthenium catalyst for catalyzing a metathesis reaction and/or a hydrogenation reaction, and any degradation products.

(2) iron-containing residues and their degradation products, and

(3) a compound or any degradation product thereof used in the emulsion polymerization process of the nitrile rubber and the selective subsequent metathesis reaction and subsequent selective hydrogenation reaction, including but not limited to: fatty acid emulsifiers and salts thereof, Na, K, Mg, a salt complex of Fe, a residual nitrile rubber molecular weight modifier, residual acrylonitrile, an antifoaming agent, and an anti-foaming agent.

Such extensive purification has not been disclosed anywhere in the prior art and is unexpectedly within its scope, although for methods involving different general olefins, such as olefin hydrogenation ( Dyson et al., J. of Organometallic Chem) , 2005, 690, p. 3552 ), metathesis of low molecular weight compounds ( Tang et al., Tetrahedron Letters, 2006, 47, 2921 ), hydroformylation ( Esterhuysen et al., J. of the Chemical Society-Dalton Transactions, 2002 , 1132 ), carbonylation ( Kollar et al., Chem. Communications, 2000 , 1695 ), carboxylation ( Arai et al., Catalysis Communications, 2004, 5, 8 ) and as a new solution for transition metal catalysis ( Wasserscheid et al. The ionic liquid of Man, Angew. Chem. Int. Ed., 2000, 39, 3772 ) gives considerable academic attention.

Similarly, the use of ionic liquids has been used in both recorded and historical organic and inorganic reactions, such as Diels-Alder ( Oh et al., Tetrahedron Letters, 2003, 44, 6465 ), Fu. - Friedel-Crafts alkylation ( Garcia et al, Catalysis Letters, 2002, 78, 115 ), Mannich type reaction ( Loh et al, Tetrahedron Letters, 2003, 44, 2405 ), and Heck (Heck) arylation reaction ( Muzart et al, J. of Organometallic Chem., 2001, 634, 153 ).

Ionic liquids have also been used as purification reagents. Haag et al. ( Angew. Chem. Int. Ed., 2002, 41, 3964 ) have taught the benefits of liquid-liquid phase separation by ionic liquids, since ionic liquids are not easily miscible with most organic solvents. fact. This benefit allows the impurities found in the organic phase to be easily removed by interaction, washing and/or agitation with an ionic liquid.

However, even in view of the references of many of the prior art, it is difficult to foresee that the removal of such different impurities contained in the nitrile rubber or the hydrogenated nitrile rubber can be achieved by contacting the polymer with an ionic liquid. Successfully removed because the solution of nitrile rubber together with hydrogenated nitrile rubber is highly viscous due to the high molecular weight of the polymers, and therefore any type of mixing system is very difficult and challenging, not to mention the removal of such impurities .

The use of an ionic liquid in the present invention allows for the accelerated separation of the catalyst, catalyst degradation products, and major products after completion of the reaction and makes it possible to reuse the catalytic system.

The elastomers obtained by the method according to the invention are known for a number of advantages. They exhibit less mold contamination in injection molding applications, and such purified elastomers can be used in contact with food and in the medical field due to the low probability of contamination. These purified elastomers can be used for insulation in the electronics field because there is only a reduced amount of electrically conductive ionic impurities, and environmentally unfriendly materials are not left behind when burned. Due to these properties, these elastomers are suitable for use in the cosmetic and medical fields, food contact, and electronics, as well as in the rubber industry because of their low level of impurities. For example, by saving catalyst and reducing maintenance costs (due to low corrosion potential), subsequent refining processes The cost savings (e.g., hydrogenation and metathesis) create additional advantages. The method is furthermore straightforward and it can be carried out almost completely continuously on an industrial scale.

The component (1) which can be removed according to the present invention is represented by a ruthenium catalyst and a degradation product thereof, a ruthenium catalyst and a degradation product thereof, and a ruthenium catalyst and a degradation product thereof.

The above ruthenium, osmium, and iridium catalysts, along with their corresponding degradation products, are used in the emulsion polymerization, selective metathesis reaction, and/or selective subsequent hydrogenation of the nitrile rubber.

The preferred catalyst used in the hydrogenation of the nitrile rubber is a rhodium or ruthenium containing catalyst, even more preferably a catalyst of the formula (R ¹⁰ _m B) _l MX _n,

Wherein M is hydrazine or hydrazine, the groups R ¹⁰ are the same or different, and each is a C ₁ -C ₈ -alkyl group, a C ₄ -C ₈ -cycloalkyl group, C ₆ -C ₁₅ - An aryl group or a C ₇ -C ₁₅ -aralkyl group. B is phosphorus, arsenic, sulfur or an sulfonium group S=O, X is hydrogen or anion, preferably halogen and particularly preferably chlorine or bromine, 1 series 2, 3 or 4, m system 2 or 3 And n is 1, 2 or 3, preferably 1 or 3. Preferred catalysts are chlorinated ginseng (triphenylphosphine) ruthenium (I), chlorinated ginseng (triphenylphosphine) ruthenium (III), chlorinated ginseng (dimethyl fluorene) ruthenium (III), and also There are hydrazine (triphenylphosphine) ruthenium of the formula (C ₆ H ₅ ) ₃ P) ₄ RhH and the corresponding compounds in which the triphenylphosphine has been completely or partially substituted by tricyclohexylphosphine.

The additional catalyst covered by component (1) has the general formula (A) , Wherein M is hydrazine or hydrazine, and X ¹ and X ² are the same or different, and are two ligands, preferably an anionic ligand, and L is the same or a different ligand, preferably It is an uncharged electron donor. R are the same or different and are each hydrogen; alkyl, preferably C ₁ -C ₃₀ -alkyl; cycloalkyl, preferably C ₃ -C ₂₀ -cycloalkyl; alkenyl, Preferred is C ₂ -C ₂₀ -alkenyl; alkynyl, preferably C ₂ -C ₂₀ -alkynyl; aryl, preferably C ₆ -C ₂₄ -aryl; carboxylic acid ester, preferably Is a C ₁ -C ₂₀ -carboxylate; an alkoxy group, preferably a C ₁ -C ₂₀ -alkoxy group; an alkenyloxy group, preferably a C ₂ -C ₂₀ -alkenyloxy group; Alkynyloxy, preferably C ₂ -C ₂₀ -alkynyloxy; aryloxy, preferably C ₆ -C ₂₄ -aryloxy; alkoxycarbonyl, preferably C ₂ -C ₂₀ - Alkoxycarbonyl; alkylamino group, preferably C ₁ -C ₃₀ -alkylamino group; alkylthio group, preferably C ₁ -C ₃₀ -alkylthio; alkylthio group, preferably C ₆ -C ₂₄ -arylthio; alkylsulfonyl, preferably C ₁ -C ₂₀ -alkylsulfonyl; or alkylsulfinyl, preferably C ₁ -C ₂₀ - An alkylsulfinyl group, wherein the groups are each optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl moieties, or alternatively, the two Group R The carbon atom to which they are bonded together is bridged to form a cyclic structure, is an aliphatic or aromatic nature on the ring structure, which may be substituted, and may contain one or more hetero atoms.

Different representative examples of catalysts of formula (A) are known in principle from WO-A-96/04289 and WO-A-97/06185 , for example.

In a preferred catalyst of the formula (A), one group R is hydrogen and the other group R is C ₁ -C ₂₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₂ -C ₂₀ -alkenyl, C ₂ -C ₂₀ -alkynyl, C ₆ -C ₂₄ -aryl, C ₁ -C ₂₀ -carboxylate, C ₁ -C ₂₀ -alkoxy, C ₂ -C ₂₀ -ene Oxy, C ₂ -C ₂₀ -alkynyloxy, C ₆ -C ₂₄ -aryloxy, C ₂ -C ₂₀ -alkoxycarbonyl, C ₁ -C ₂₀ -alkylamino, C ₁ -C ₂₀ - An alkylthio group, a C ₆ -C ₂₄ -arylthio group, a C ₁ -C ₂₀ -alkylsulfonyl group or a C ₁ -C ₂₀ -alkylsulfinyl group, wherein in each case, such Portions may be substituted by one or more groups of alkyl, halogen, alkoxy, aryl or heteroaryl groups.

In the catalyst of the formula (A), X ¹ and X ² are the same or different and are two ligands, preferably an anionic ligand.

X ¹ and X ² may be, for example, hydrogen, halogen, pseudohalogen, linear or branched C ₁ -C ₃₀ -alkyl, C ₆ -C ₂₄ -aryl, C ₁ -C ₂₀ -alkoxy, C ₆ -C ₂₄ -aryloxy, C ₃ -C ₂₀ -alkyldiketonate, C ₆ -C ₂₄ -aryldiketonate, C ₁ -C ₂₀ -carboxylate, C ₁ -C ₂₀ -alkyl sulfonate, C ₆ -C ₂₄ -aryl sulfonate, C ₁ -C ₂₀ -alkyl thiol, C ₆ -C ₂₄ -aryl thiol, C ₁ -C ₂₀ -alkyl Sulfonyl or C ₁ -C ₂₀ -alkylsulfinylene.

X ¹ and X ² may also be substituted by one or more additional groups, for example by halogen (preferably fluorine), C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -alkoxy or C ₆ a -C ₂₄ -aryl substituent, wherein the groups may again be substituted with one or more substituents selected from the group consisting of halogen (preferably fluorine), C ₁ -C ₅ -alkane a group, a C ₁ -C ₅ -alkoxy group and a phenyl group.

In a preferred embodiment, X ¹ and X ² are the same or different and are each halogen, especially fluorine, chlorine, bromine or iodine, benzoate, C ₁ -C ₅ -carboxylate, C ₁ -C ₅ -alkyl, phenoxy, C ₁ -C ₅ -alkoxy, C ₁ -C ₅ -alkylthiol, C ₆ -C ₂₄ -arylthiol, C ₆ -C ₂₄ -Aryl or C ₁ -C ₅ -alkyl sulfonate.

In a particularly preferred embodiment, X ¹ and X ² are the same and each is halogen (particularly chlorine), CF ₃ COO, CH ₃ COO, CFH ₂ COO, (CH ₃ ) ₃ CO, (CF _{3 2} (CH ₃ )CO, (CF ₃ )(CH ₃ ) ₂ CO, PhO (phenoxy), MeO (methoxy), EtO (ethoxy), tosylate (p-CH ₃ - C ₆ H ₄ -SO ₃ ), mesylate (CH ₃ -SO ₃ ) or CF ₃ SO ₃ (triflate).

In the general formula (A), the symbols L represent the same or different ligands, and are preferably an uncharged electron-donating ligand.

For example, the two ligands L may independently of one another be a phosphine, a sulfonated phosphine, a phosphate, a phosphinate, a phosphonite, a hydrazine, (stibine), ether, amine, decylamine, sulfonate, hydrazine, carboxyl, nitrosonyl, pyridine, thioether, imidazoline or imidazolium (the latter two are also combined to form an "Im" ligand) ).

The term "phosphinic acid ester" includes, for example, phenyl diphenylphosphinate, cyclohexyl dicyclohexylphosphinate, isopropyl diisopropylphosphinate, and methyl diphenylphosphinate.

The term "phosphite" includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tributyl phosphite, triisopropyl phosphite, and methyl diphenyl phosphite.

the term" Included, for example, triphenyl Tricyclohexyl And trimethyl .

The term "sulfonate" includes, for example, triflate, tosylate, and mesylate.

The term "anthracene" includes, for example, (CH ₃ ) ₂ S(=O) and (C ₆ H ₅ ) ₂ S=O.

The term "thioether" includes, for example, CH ₃ SCH ₃ , C ₆ H ₅ SCH ₃ , CH ₃ OCH ₂ CH ₂ SCH ₃ and tetrahydrothiophene.

For the purposes of this application, the term "pyridine" is used as a collective term for all nitrogen-containing ligand bases, such as, for example, Grubbs as mentioned in WO-A-03/011455 . Examples are: pyridine, picoline (including α-, β- and γ-methylpyridine), lutidine (including 2,3-, 2,4-, 2,5-, 2,6-, 3 , 4- and 3,5-lutidine), trimethylpyridine (2,4,6-trimethylpyridine), trifluoromethylpyridine, phenylpyridine, 4-(dimethylamino)pyridine , chloropyridine, bromopyridine, nitropyridine, quinoline, pyrimidine, pyrrole, imidazole, and phenylimidazole.

In a preferred embodiment, a catalyst having the general formula (A) is used, wherein one or both of the ligands L represent an imidazoline or imidazolium ligand (also in this application) a structure which is collectively referred to as "Im"-ligand, unless otherwise indicated, having the formula (IIa) or (IIb) wherein the two ligands L have a basis according to (IIa) or (IIb) In the case of a structure, the meaning of L is the same or different,

Wherein R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are the same or different and represent hydrogen, straight or branched C ₁ -C ₃₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₂ -C ₂₀ - alkenyl, C ₂ -C ₂₀ - alkynyl, C ₆ -C ₂₄ - aryl, C ₇ -C ₂₅ - alkaryl, C ₂ -C ₂₀ heteroaryl, C ₂ -C ₂₀ heteroaryl Cyclo, C ₁ -C ₂₀ -alkoxy, C ₂ -C ₂₀ -alkenyloxy, C ₂ -C ₂₀ -alkynyloxy, C ₆ -C ₂₀ -aryloxy, C ₂ -C ₂₀ - Alkoxycarbonyl, C ₁ -C ₂₀ -alkylthio, C ₆ -C ₂₀ -arylthio, -Si(R) _3, -O-Si(R) ₃ , -OC(=O)R, C (=O)R, -C(=O)N(R) ₂ , -NR-C(=O)-N(R) ₂ , -SO ₂ N(R) _2, -S(=O)R, -S(=O) ₂ R, -OS(=O) ₂ R, halogen, nitro or cyano, wherein in the case where all of the above refers to the meaning of R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ Group R is the same or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or heteroaryl.

Where appropriate, one or more of R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ may be independent of each other, substituted with one or more substituents, preferably a straight or branched C ₁ -C ₁₀ -alkyl, C ₃ -C ₈ -cycloalkyl, C ₁ -C ₁₀ -alkoxy or C ₆ -C ₂₄ -aryl, C ₂ -C ₂₀ heteroaryl, C ₂ -C ₂₀ heterocyclic And substituted with a functional group selected from the group consisting of: a hydroxyl group, a thiol, a thioether, a ketone, an aldehyde, an ester, an ether, an amine, an imine, a guanamine, a nitro group, a carboxylic acid, a disulfide, a carbonic acid Esters, isocyanates, carbodiimides, alkoxycarbonyls, urethanes and halogens, wherein the above substituents may, in addition to the chemical extent, be further substituted by one or more substituents which are more Preferred is a group selected from the group consisting of halogen (particularly chlorine or bromine), C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy and phenyl.

For the sake of clarity only, it should be added that the structures of the imidazoline and imidazolium ligands depicted in the general formulae (IIa) and (IIb) in this patent application correspond to structures (IIa') and (IIb'. They are also frequently found in the literature on such imidazoline and imidazolium ligands and highlight the carbene characteristics of imidazolines and imidazolium. This applies analogously to the associated preferred structures (IIIa)-(IIIu) depicted below.

In a preferred embodiment of the catalyst having the general formula (A), R ⁸ and R ⁹ are each the same or different and represent hydrogen, C ₆ -C ₂₄ -aryl, linear or branched C ₁ -C _{The 10} -alkyl groups, or together with the carbon atoms to which they are attached, form a cycloalkyl or aryl structure.

More preferably, R ⁸ and R ⁹ are the same and are selected from the group consisting of hydrogen, methyl, propyl, butyl, and phenyl.

A preferred and more preferred meaning of R ⁸ and R ⁹ may be selected from a linear or branched C ₁ -C ₁₀ -alkyl or C ₁ -C ₁₀ -alkoxy group, C ₃ -C ₈ - Substituted by one or more additional substituents of the group consisting of a cycloalkyl group, a C ₆ -C ₂₄ -aryl group, and selected from the group consisting of a hydroxyl group, a thiol, a thioether, a ketone, an aldehyde, an ester, an ether, an amine, Substituted by a functional group of the group consisting of imine, decylamine, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, alkoxycarbonyl, urethane and halogen, all of which are The substituent may be further substituted by one or more substituents, preferably selected from halogen (specifically chlorine or bromine), C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy, and a group consisting of phenyl groups.

R ¹⁰ and R ¹¹ are the same or different and preferably represent a linear or branched C ₁ -C ₁₀ -alkyl group, a C ₃ -C ₁₀ -cycloalkyl group, a C ₆ -C ₂₄ -aryl group. Particularly preferred are phenyl, C ₁ -C ₁₀ -alkylsulfonate, C ₆ -C ₁₀ -arylsulfonate.

More preferably, R ¹⁰ and R ¹¹ are the same and are selected from the group consisting of isopropyl, neopentyl, adamantyl, phenyl, 2,6-diisopropylphenyl, 2, 6-Dimethylphenyl or 2,4,6-trimethylphenyl.

A preferred meaning of R ¹⁰ and R ¹¹ may be selected from a linear or branched C ₁ -C ₁₀ -alkyl or C ₁ -C ₁₀ -alkoxy group, a C ₃ -C ₈ -cycloalkyl group, Substituted by one or more additional substituents of the C ₆ -C ₂₄ -aryl group, and selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, hydrazine Substituting a functional group of a group consisting of an amine, a nitro group, a carboxylic acid, a disulfide, a carbonate, an isocyanate, a carbodiimide, an alkoxycarbonyl group, a urethane, and a halogen, wherein all of the substituents may be further Substituted by one or more substituents, preferably selected from the group consisting of halogen, specifically chlorine or bromine, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy, and phenyl .

Particularly preferred are catalysts of the general formula (A) in which one or both of the ligands L represent an imidazoline and an imidazolium ligand having the structures (IIIa) to (IIIu), Wherein "Ph" means phenyl in each case, "Bu" means butyl, "Mes" in each case means 2,4,6-trimethylphenyl, "Dipp" in all cases Bottom refers to 2,6-diisopropylphenyl and "Dimp" refers to 2,6-dimethylphenyl, and wherein the two ligands L in the formula (A) have according to (IIIa) In the case of the structure of (IIIu), the meaning of L may be the same or different,

In another preferred embodiment of the catalyst (A), one or both of the ligands may have the meaning of the formula (IIc) or (IId), wherein the two ligands L have According to the structure of (IIc) or (IId), the meaning of L may be the same or different,

Wherein R ⁸ , R ⁹ , and R ¹⁰ may have all of the general, preferred, better, and most preferred meanings of the formulae (IIa) and (IIb) as defined above, and R ¹⁵ , R ^And R ¹⁷ are the same or different and may represent an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, or a heterocyclic group.

In the general formulae (IIc) and (IId), R ⁸ , R ⁹ , R ¹⁰ , R ¹⁵ , R ¹⁶ and R ¹⁷ may also be selected from linear or branched C ₁ -C ₅ -alkyl groups, in particular Substituted by one or more additional, identical or different substituents of the group consisting of methyl, C ₁ -C ₅ -alkoxy, aryl, and selected from the group consisting of hydroxyl, thiol, thioether, ketone, a group consisting of an aldehyde, an ester, an ether, an amine, an imine, a guanamine, a nitro group, a carboxylic acid, a disulfide, a carbonate, an isocyanate, a carbodiimide, an alkoxycarbonyl group, a urethane, and a halogen Functional group substitution.

In a more preferred embodiment, the ligands L have the formula (IId) wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are the same or different, even more preferably the same, and can be represented C ₁ -C ₂₀ alkyl, C ₃ -C ₈ - cycloalkyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ aryloxy group, C ₂ -C ₂₀ heteroaryl An aryl group or a C ₂ -C ₂₀ heterocyclic group.

In an even more preferred embodiment, the ligand group L has the formula (IId) wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are the same and each is selected from the group consisting of : methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methyl Butyl, neopentyl, 1-ethylpropyl, n-hexyl, neophenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, biphenyl Base, naphthyl, phenanthryl, anthracenyl, tolyl, 2,6-dimethylphenyl, and trifluoromethyl.

In the case where one or both of the ligands L has the formula (IId), it is most preferably represented by PPh ₃ , P(p-Tol) ₃ , P(o-Tol) ₃ , PPh(CH). ₃ ) ₂ , P(CF ₃ ) ₃ , P(p-FC ₆ H ₄ ) ₃ , P(p-CF ₃ C ₆ H ₄ ) ₃ , P(C ₆ H ₄ -SO ₃ Na) ₃ , P( CH ₂ C ₆ H ₄ -SO ₃ Na) ₃ , P(isopropyl) ₃ , P(CHCH ₃ (CH ₂ CH ₃ )) ₃ , P(cyclopentyl) ₃ , P(cyclohexyl) ₃ , P (neopentyl) _3, or P (new phenyl) ₃ .

The following catalysts having structure (IV) (Grubbs I catalyst) and (V) (Grubbs II catalyst) should also be covered by component (1), wherein Cy is a cyclohexyl group.

Likewise, a catalyst having the formula (A1) should be covered by component (1), Wherein X ¹ , X ² and L may have the same general, preferred and particularly preferred meanings as in the formula (A), n is 0, 1 or 2, and m is 0, 1, 2, 3 or 4 And R ' are the same or different and are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkane a group of an amino group, an alkylthio group, an arylthio group, an alkylsulfonyl group or an alkylsulfinyl group, which in each case may be one or more alkyl groups, halogens, alkoxy groups, aromatic groups Substituted by a heteroaryl group.

Another catalyst having the formula (A1) has a catalyst of the following formula (VI) wherein, in each case, Mes is 2,4,6-trimethylphenyl, and Ph is a phenyl group.

Such a catalyst which is also known as "Nolan catalyst" in the literature is known, for example, from WO-A-2004/112951 .

The additional catalyst covered by component (1) has a catalyst of the formula (B), Wherein M is hydrazine or hydrazine, X ¹ and X ² are the same or different and are anionic ligands, R" are the same or different and are organic, Im is a substituted or unsubstituted imidazoline or Imidazolium ligands, and An is an anion. Catalysts of the formula (B) are known in principle (see, for example, Angew . Chem . Int . Ed . 2004 , 43 , 6161-6165 ).

X ¹ and X ² in the formula (B) may have the same general, preferred and particularly preferred meanings as in the formula (A).

The imidazoline or imidazolium ligand generally has a structure of the formula (IIa) or (IIb) (this has been carried out above for the catalyst of the formula (A) Mention) and may have all of the structures mentioned therein as preferred items, particularly those having the formulae (IIIa)-(IIIu).

In the general formula (B), R" are the same or different and each is a linear or branched C ₁ -C ₃₀ -alkyl group, a C ₅ -C ₃₀ -cycloalkyl group or an aryl group, wherein C ₁ - The _C30 -alkyl moiety can be blocked by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.

The aryl group is an aromatic group having 6 to 24 skeleton carbon atoms. As a preferred monocyclic, bicyclic or tricyclic carbocyclic aromatic moiety having 6 to 10 skeleton carbon atoms, a phenyl group, a diphenyl group, a naphthyl group, a phenanthryl group or an anthracenyl group can be mentioned by way of example.

Preferably, the groups R" in the formula (B) are the same and each is phenyl, cyclohexyl, cyclopentyl, isopropyl, o-tolyl, o-xylyl or 1,3 , 5-trimethylphenyl.

The additional catalyst covered by component (1) has a catalyst of the formula (C), Wherein M is ruthenium or osmium-based, R ¹³ and R ¹⁴ are each independently of one another hydrogen, C ₁ -C ₂₀ - alkyl, C ₂ -C ₂₀ - alkenyl, C ₂ -C ₂₀ - alkynyl, C ₆ -C ₂₄ -aryl, C ₁ -C ₂₀ -carboxylate, C ₁ -C ₂₀ -alkoxy, C ₂ -C ₂₀ -alkenyloxy, C ₂ -C ₂₀ -alkynyloxy, C ₆ -C ₂₄ -Aryloxy, C ₂ -C ₂₀ -alkoxycarbonyl, C ₁ -C ₂₀ -alkylthio, C ₁ -C ₂₀ -alkylsulfonyl or C ₁ -C ₂₀ -alkylsulfinium a group, an X ³ -based anionic ligand, an L ² -based uncharged π-bonded ligand, which may be either monocyclic or polycyclic, and the L ³ is selected from the group consisting of Site group: phosphine, sulfonated phosphine, fluorinated phosphine, having up to 3 aminoalkyl, ammonium alkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydroxyalkyl, hydroxyalkyl or Functionalized phosphines of ketoalkyl groups, phosphites, phosphinates, phosphonites, phosphonides, hydrazines, , ether, amine, decylamine, imine, hydrazine, thioether and pyridine, Y ^- line non-coordinating anion, and n is 0, 1, 2, 3, 4 or 5. The additional catalyst covered by component (1) has a catalyst of formula (D) , Wherein M is hydrazine or hydrazine, and X ¹ and X ² are the same or different and are anionic ligands, and the ligands may have X ¹ and X ² as mentioned in the general formulae (A) and (B) All of the meanings, the symbol L denotes the same or different ligands, which may have all the meanings of L mentioned in the general formulae (A) and (B), and R ¹⁹ and R ²⁰ are the same. Or different and each is hydrogen or a substituted or unsubstituted alkyl group.

The additional catalysts covered by component (1) have catalysts of the general formulae (E), (F) and (G) , Wherein M is hydrazine or hydrazine, and X ¹ and X ² are the same or different and are two ligands, preferably an anionic ligand, an L-former, preferably an uncharged electron. a precursor, Z ¹ and Z ² are the same or different and are uncharged electron donors, and R ²¹ and R ²² are each independently hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl a carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, alkylsulfonyl or alkylsulfinyl group, each of which The case is substituted by one or more substituents selected from alkyl, halogen, alkoxy, aryl or heteroaryl.

Catalysts of the general formulae (E), (F), and (G), for example, from WO 2003/011455 A1, WO 2003/087167 A2, Organometallics 2001, 20, 5314 and Angew. Chem. Int. Ed. 2002, 41 , 4038 is known in principle. These catalysts are commercially available or can be synthesized by the preparation methods specified in the above documents.

Catalysts having the general formulae (E), (F), and (G) wherein Z ¹ and Z ² are the same or different and are uncharged electron donors can be used. These ligands are usually weakly coordinated. The ligands are typically heterocyclic groups that are optionally substituted. They may be a five- or six-membered monocyclic group having from 1 to 4, preferably from 1 to 3, and particularly preferably one or two heteroatoms, or from two or three a bicyclic or polycyclic structure of four or five such five- or six-membered monocyclic groups of the type wherein all of the above groups are optionally substituted by one or more alkyl groups in each case, Preferred is a C ₁ -C ₁₀ -alkyl group, a cycloalkyl group, preferably a C ₃ -C ₈ -cycloalkyl group, an alkoxy group, preferably a C ₁ -C ₁₀ -alkoxy group, a halogen, Preferred is chlorine or bromine, an aryl group, preferably a C ₆ -C ₂₄ -aryl group, or a heteroaryl group, preferably a C ₅ -C ₂₃ -heteroaryl group, which groups may Each is substituted by one or more moieties, preferably selected from the group consisting of halogen (especially chlorine or bromine), C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy and phenyl.

Examples of Z ¹ and Z ² include nitrogen-containing heterocycles such as pyridines, Terpenoids, bipyridyls, pyrimidines, pyridyl Classes, pyrazoles, pyrrolidines, piperidines Classes, carbazoles, quinolines, anthraquinones, acridines, diimidazoles, mepyridyl imines, imidazolines, imidazolines and pyrroles.

Z ¹ and Z ² may also be bridged to each other to form a ring structure. In this case, Z ¹ and Z ² form a single bidentate ligand.

In the catalysts having the general formulae (E), (F), and (G), L may have the same general, preferred, and particularly preferred meanings as L in the general formulae (A) and (B). .

In the catalysts of the formulae (E), (F), and (G), R ²¹ and R ²² are the same or different and each is an alkyl group, preferably a C ₁ -C ₃₀ -alkyl group, particularly Preferred is a C ₁ -C ₂₀ -alkyl group, a cycloalkyl group, preferably a C ₃ -C ₂₀ -cycloalkyl group, particularly preferably a C ₃ -C ₈ -cycloalkyl group, an alkenyl group, preferably Is a C ₂ -C ₂₀ -alkenyl group, particularly preferably a C ₂ -C ₁₆ -alkenyl group, an alkynyl group, preferably a C ₂ -C ₂₀ -alkynyl group, particularly preferably a C ₂ -C ₁₆ -alkyne The aryl group is preferably a C ₆ -C ₂₄ -aryl group, a carboxylic acid ester, preferably a C ₁ -C ₂₀ -carboxylate, an alkoxy group, preferably a C ₁ -C ₂₀ - Alkoxy, alkenyloxy, preferably C ₂ -C ₂₀ -alkenyloxy, alkynyloxy, preferably C ₂ -C ₂₀ -alkynyloxy, aryloxy, preferably C ₆ -C ₂₄ -aryloxy, alkoxycarbonyl, preferably C ₂ -C ₂₀ -alkoxycarbonyl, alkylamino, preferably C ₁ -C ₃₀ -alkylamino, alkylthio, Preferred is a C ₁ -C ₃₀ -alkylthio group, an arylthio group, preferably a C ₆ -C ₂₄ -arylthio group, an alkylsulfonyl group, preferably a C ₁ -C ₂₀ -alkyl group. sulfo acyl, alkylsulfinyl or acyl, preferably a C ₁ -C ₂₀ - alkyl Sulfo acyl, wherein said substituents may be substituted with one or more portions of an alkyl, halo, alkoxy, aryl or heteroaryl group.

In the catalysts of the formulae (E), (F), and (G), X ¹ and X ² are the same or different and may have the same as indicated above for X ¹ and X ² in the formula (A) General, preferred, and particularly good meaning.

Further catalysts encompassed by component (1) have catalysts of the formulae (E), (F) and (G) wherein M is oxime, both X ¹ and X ² are halogen, in particular chlorine, R ¹ and R ² are the same or different and are a 5- or 6-membered monocyclic group having from 1 to 4, preferably from 1 to 3, and particularly preferably 1 or 2 heteroatoms. Or a bicyclic or polycyclic structure consisting of 2, 3, 4 or 5 such 5- or 6-membered monocyclic groups of this type, wherein all of the above groups may be one or more in each case alkyl, preferably a C ₁ -C ₁₀ - alkyl group, a cycloalkyl group, preferably a C ₃ -C ₈ - cycloalkyl group, an alkoxy group, preferably a C ₁ -C ₁₀ - alkoxy An oxy group, a halogen, preferably a chlorine or bromine group, an aryl group, preferably a C ₆ -C ₂₄ -aryl group, or a heteroaryl group, preferably a C ₅ -C ₂₃ -heteroaryl group Substituting, Z ¹ and Z ² are the same or different and have from 1 to 4, preferably from 1 to 3, and particularly preferably 5 or 6 of 1 or 2 heteroatoms. a monomonocyclic group, or a double consisting of two, three, four or five such five- or six-membered monocyclic groups of this type a cyclic or polycyclic structure wherein all of the above groups may be optionally substituted by one or more alkyl groups in each case, preferably a C ₁ -C ₁₀ -alkyl group, a cycloalkyl group, preferably C. _3- C ₈ -cycloalkyl, alkoxy, preferably C ₁ -C ₁₀ -alkoxy, halogen, preferably chlorine or bromine, aryl, preferably C ₆ -C ₂₄ - Aryl, or heteroaryl, preferably C ₅ -C ₂₃ -heteroaryl, which may in turn be each one or more moieties, preferably selected from halogen (especially chlorine or bromine), C Substituted by a moiety of the group consisting of ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy and phenyl, R ²¹ and R ²² are the same or different and are each C ₁ -C ₃₀ -alkane , C ₃ -C ₂₀ -cycloalkyl, C ₂ -C ₂₀ -alkenyl, C ₂ -C ₂₀ -alkynyl, C ₆ -C ₂₄ -aryl, C ₁ -C ₂₀ -carboxylate, C _1- C ₂₀ -alkoxy, C ₂ -C ₂₀ -alkenyloxy, C ₂ -C ₂₀ -alkynyloxy, C ₆ -C ₂₄ -aryloxy, C ₂ -C ₂₀ -alkoxycarbonyl, C ₁ -C ₃₀ -alkylamino, C ₁ -C ₃₀ -alkylthio, C ₆ -C ₂₄ -arylthio, C ₁ -C ₂₀ -alkylsulfonyl, C ₁ -C ₂₀ -alkyl Sulfosyl group, and LL has the above formula (IIa) or ( IIb), in particular a structure of one of the chemical formulae (IIIa) to (IIIu).

Another catalyst covered by component (1) has a structure (XIX),

Wherein R ²³ and R ²⁴ are the same or different and each is halogen, linear or branched C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -heteroalkyl, C ₁ -C ₁₀ -haloalkyl , C ₁ -C ₁₀ -alkoxy, C ₆ -C ₂₄ -aryl, preferably bromo, phenyl, decyl, nitro, nitrogen heterocycle, preferably pyridine, piperidine or pyridyl , carboxy, alkylcarbonyl, halocarbonyl, aminomethyl decyl, thiamine, carbamide, thiomethyl, amide, dialkylamino, trialkylcarbyl or tri Alkoxycarbenyl.

The above meanings for R ²³ and R ²⁴ are C ₁ -C ₂₀ -alkyl, C ₁ -C ₂₀ -heteroalkyl, C ₁ -C ₁₀ -haloalkyl, C ₁ -C ₁₀ -alkoxy, C ₆ -C ₂₄ -aryl, preferably phenyl, indolyl, nitro, nitrogen heterocycle, preferably pyridine, piperidine or pyridyl , carboxy, alkylcarbonyl, halocarbonyl, aminomethyl decyl, thiamine, carbamide, thiomethyl, amide, trialkylcarbenyl and trialkoxycarbenyl Each may in turn be substituted by a moiety of one or more halogens, preferably fluoro, chloro or bromo, C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy or phenyl.

The additional catalyst covered by component (1) has the structure (XIX a) or (XIX b) wherein R ²³ and R ²⁴ have the same meanings as indicated in the chemical formula (XIX).

When R ²³ and R ²⁴ are each bromine in the chemical formula (XIXa), this catalyst is referred to as " Grubbs III catalyst " in the literature.

Further catalysts encompassed by component (1) belonging to the general formulae (E), (F), and (G) have the following structural formulae (XX)-(XXXII), wherein Mes is 2 in each case, 4,6-trimethylphenyl.

The additional catalyst covered by component (1) contains a catalyst (N) of the formula (N1) in which a carbon atom indicated by "*" is bonded to a central metal having a ruthenium or osmium via one or more double bonds. Catalyst skeleton,

And wherein R ²⁵ -R ³² lines the same or different and each is hydrogen, halogen, hydroxy, aldehyde, ketone, thiol, CF _3, nitro, nitroso, cyano, thiocyanato, isocyanato Base, carbodiimide, urethane, thiocarbamate, dithiocarbamate, amine, decyl, imido, sulfhydryl, sulfonate (-SO ₃ ^- ) , -OSO ₃ ^- , -PO ₃ ^- or OPO ₃ ^- , or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylic acid ester, alkoxy, alkenyloxy, alkynyloxy, aryl An oxy group, an alkoxycarbonyl group, an alkylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an alkylsulfinyl group, a dialkylamino group, an alkyl fluorenyl group, or an alkoxy fluorenyl group, wherein Each of these groups may be optionally substituted by one or more substituents of an alkyl, halogen, alkoxy, aryl or heteroaryl group or, as an alternative, from R ²⁵ -R ³² The two directly adjacent substituents of the group formed form a cyclic group, preferably an aromatic system, by bridging together with the ring carbon to which they are attached, or as an alternative, R ⁸ can be selected Sexually bridged to 钌- or On the other ligand of the ruthenium-carbene miscible catalyst, m is 0 or 1, and A is oxygen, sulfur, C(R ³³ R ³⁴ ), NR ³⁵ , -C(R ³⁶ )=C(R ³⁷ -, -C(R ³⁶ )(R ³⁸ )-C(R ³⁷ )(R ³⁹ )-, wherein the R ³³ -R ³⁹ are the same or different and may each have the same R ²⁵ -R ³² The meaning.

In the catalyst having the structural element of the formula (N1), a carbon atom indicated by "*" is bonded to the catalyst skeleton via one or more double bonds. If the carbon atom indicated by "*" is attached to the catalyst skeleton by two or more double bonds, the double bonds may be cumulative or conjugated.

Such catalysts (N) have been described in US-A-2009/0076226 , which also discloses their preparation.

The catalyst (N) having the structural element of the formula (N1) includes, for example, a catalyst having the following general formulae (N2a) and (N2b) ,

Wherein M is hydrazine or hydrazine, X ¹ and X ² are the same or different, and are two ligands, preferably an anionic ligand, and L ¹ and L ² are the same or different ligands, Preferred are uncharged electron donors, wherein L ² may alternatively be bridged to the group R ⁸ , n is 0, 1, 2 or 3, preferably 0, 1 or 2, n ' 1 or 2, preferably 1, and R ^{25 -} R ³² , m and A have the same meanings as in the formula (N1).

In the catalyst of the formula (N2a), the structural element having the formula (N1) is represented by a double bond (n = 0) or by two, three or four cumulative double bonds (at n = 1) In the case of 2 or 3) is connected to the central metal of the miscible catalyst. In the catalyst of the formula (N2b) suitable for use in the catalyst system according to the invention, the structural element having the formula (N1) is bonded to the metal of the miscible catalyst via a conjugated double bond. In both cases, the carbon atom represented by "*" has a double bond in the direction of the central metal of the miscible catalyst.

Therefore, catalysts having the general formulae (N2a) and (N2b) include some catalysts in which the following general structural elements (N3)-(N9)

Binding to a catalyst skeleton having the general formula (N10a) or (N10b) by a carbon atom indicated by "*" via one or more double bonds

Wherein X ¹ and X ² , L ¹ and L ² , n, n' and R ^{25 -} R ³⁹ have the meanings given for the general formulae (N2a) and (N2b).

The Ru or Os-based carbene catalysts thus obtained typically have a fivefold coordination effect.

In the structural element having the formula (N1) , R ^{25 -} R ³² are the same or different and each is hydrogen, halogen, hydroxy, aldehyde, keto, thiol, CF ₃ , nitro, nitroso, Cyano, thiocyano, isocyanate, carbodiimide, urethane, thiocarbamate, dithiocarbamate, amine, decyl, imido, fluorenyl , sulfonate (-SO ₃ ^- ), -OSO ₃ -, -PO ₃ ^- or OPO ₃ ^- or alkyl, preferably C ₁ -C ₂₀ -alkyl, especially C ₁ -C ₆ -alkyl a cycloalkyl group, preferably a C ₃ -C ₂₀ -cycloalkyl group, especially a C ₃ -C ₈ -cycloalkyl group, an alkenyl group, preferably a C ₂ -C ₂₀ -alkenyl group, an alkynyl group, Preferred is C ₂ -C ₂₀ -alkynyl, aryl, preferably C ₆ -C ₂₄ -aryl, especially phenyl, carboxylic acid ester, preferably C ₁ -C ₂₀ -carboxylate The ester or alkoxy group is preferably a C ₁ -C ₂₀ -alkoxy group or an alkenyloxy group, preferably a C ₂ -C ₂₀ -alkenyloxy group, an alkynyloxy group, preferably a C ₂ group. -C ₂₀ -alkynyloxy, aryloxy, preferably C ₆ -C ₂₄ -aryloxy, alkoxycarbonyl, preferably C ₂ -C ₂₀ -alkoxycarbonyl, alkylamino , preferably C ₁ -C _{a 30} -alkylamino group, an alkylthio group, preferably a C ₁ -C ₃₀ -alkylthio group, an arylthio group, preferably a C ₆ -C ₂₄ -arylthio group, an alkylsulfonyl group, Preferred is a C ₁ -C ₂₀ -alkylsulfonyl group, an alkylsulfinyl group, preferably a C ₁ -C ₂₀ -alkylsulfinylene group, a dialkylamine group, preferably two (C ₁ -C ₂₀ -alkyl)amino group, alkyl formylalkyl group, preferably C ₁ -C ₂₀ -alkylindenyl group, or alkoxyfluorenyl group, preferably C ₁ -C ₂₀ a group of alkoxyfluorenyl groups, wherein the moieties may each be optionally substituted with one or more substituents of an alkyl, halogen, alkoxy, aryl or heteroaryl group, or alternatively each In this case, the two directly adjacent substituents in the group of free R ²⁵ -R ³² and the ring carbon to which they are bonded may also form a cyclic group by bridge, preferably an aromatic group. The family system, or alternatively R ^{8 ,} may be selectively bridged to another ligand of the rhodium- or ruthenium-carbene miscible catalyst, m system 0 or 1, and A is oxygen, sulfur, C (R ³³ (R ³⁴ ), NR ³⁵ , -C(R ³⁶ )=C(R ³⁷ )- or -C(R ³⁶ )(R ³⁸ )-C(R ³⁷ )(R ³⁹ )-, wherein R ³³ -R ³⁹ are the same or different and each may have the same preferred meaning as the groups R ¹ -R ⁸ .

a C ₁ -C ₆ -alkyl group in the structural element having the formula (N1), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tert-butyl Base, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl or n-hexyl.

A C ₃ -C ₈ -cycloalkyl group in the structural element having the formula (N1), for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group.

The C ₆ -C ₂₄ -aryl group in the structural element having the formula (N1) includes an aromatic group having 6 to 24 skeleton carbon atoms. As a preferred monocyclic, bicyclic or tricyclic carbocyclic aromatic group having 6 to 10 skeleton carbon atoms, a phenyl group, a diphenyl group, a naphthyl group, a phenanthryl group or an anthracenyl group can be mentioned by way of example.

X ¹ and X ² in the structural element having the general formula (N1) may have the same general, preferred and particularly preferred meanings as indicated for the catalyst in the general formula A.

In the general formulae (N2a) and (N2b) and similarly in the general formulae (N10a) and (N10b), L ¹ and L ² are the same or different ligands, preferably uncharged electrons. And may have the same general, preferred and particularly preferred meanings as indicated for the catalyst in Formula A.

The additional catalyst covered by component (1) is a catalyst of the general formula (N2a) or (N2b) having a general structural unit (N1) wherein M is 卤素, and both X ¹ and X ² are halogen, n 0, 1 or 2 in the general formula (N2a), or n ' is 1 L ¹ and L ² in the general formula (N2b) are the same or different and have the formula (N2a) and (N2b) The general and preferred meanings indicated, R ²⁵ -R ³² are the same or different and have the general and preferred meanings indicated for the formulae (N2a) and (N2b), m is 0 or 1, And, when m=1, A is oxygen, sulfur, C(C ₁ -C ₁₀ -alkyl) ₂ , -C(C ₁ -C ₁₀ -alkyl) ₂ -C(C ₁ -C ₁₀ -alkane ₂ ), -C(C ₁ -C ₁₀ -alkyl)=C(C ₁ -C ₁₀ -alkyl)- or -N(C ₁ -C ₁₀ -alkyl). The additional catalyst covered by component (1) is a catalyst of the general formula (N2a) or (N2b) having a general structural unit (N1) wherein M is oxime, and both X ¹ and X ² are chlorine, n Is 0, 1 or 2 in the formula (N2a), or n ' is 1 im 1 in the formula (N2b) is an imidazoline or imidazolium ligand having ^one of the formulae (IIIa) to (IIIf) , L ² is a sulfonated phosphine, a phosphate, a phosphinate, a phosphonite, an anthracene having one of the formulae (XIIa) to (XIIf), , ether, amine, decylamine, hydrazine, carboxyl, nitrosonopyl, pyridyl, imidazolidinyl or phosphine ligand, especially PPh ₃ , P(p-Tol) ₃ , P (o-Tol ₃ , PPh(CH ₃ ) ₂ , P(CF ₃ ) ₃ , P(p-FC ₆ H ₄ ) ₃ , P(p-CF ₃ C ₆ H ₄ ) ₃ , P(C ₆ H ₄ -SO ₃ Na) ₃ , P(CH ₂ C ₆ H ₄ -SO ₃ Na) ₃ , P(isopropyl) ₃ , P(CHCH ₃ (CH ₂ CH ₃ )) ₃ , P(cyclopentyl) ₃ , P ( Cyclohexyl) ₃ , P(neopentyl) ₃ and P(new phenyl) ₃ , R ²⁵ -R ³² have the general or preferred meanings indicated for the general formulae (N2a) and (N2b), m-system 0 or 1 and, when m=1, A is oxygen, sulfur, C(C ₁ -C ₁₀ -alkyl) ₂ , -C(C ₁ -C ₁₀ -alkyl) ₂ -C(C ₁ -C ₁₀ -alkyl) ₂ -, -C(C ₁ -C ₁₀ -alkyl)=C(C ₁ -C ₁₀ -alkyl)- or -N(C ₁ -C ₁₀ -alkyl).

When R ²⁵ is bridged to another ligand of the catalyst of formula N, for example for catalysts having the general formulae (N2a) and (N2b), this results in having the general formulae (N13a) and (N13b) The following structure, Wherein Y ¹ is oxygen, sulfur, NR ⁴¹ or PR ⁴¹ , wherein R ⁴¹ has the meaning indicated below, and R ⁴⁰ and R ⁴¹ are the same or different and each is alkyl, cycloalkyl, alkenyl, alkynyl, aryl Alkoxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl or alkylsulfinyl, each of which It may be optionally substituted by one or more substituents of an alkyl, halogen, alkoxy, aryl or heteroaryl group, p is 0 or 1, and Y ² is -(CH ₂ ) _r when p=1 -, where r = 1, 2 or 3, is -C(=O)-CH ₂ -, -C(=O)-, -N=CH-, -N(H)-C(=O)-, Or as an alternative, the monolithic structural unit "-Y ¹ (R ⁴⁰ )-(Y ² ) _p -" is (-N(R ⁴⁰ )=CH-CH ₂ -), (-N(R ⁴⁰ ,R ⁴¹ )=CH-CH ₂ -), and wherein M, X ¹ , X ² , L ¹ , R ²⁵ -R ³² , A, m and n have the same meanings as in the formulae (N2a) and (N2b) .

The additional catalyst covered by component (1) has a catalyst of the following structure:

Further catalysts encompassed by component (1) have catalysts of the general formula (Q) which are used for hydrogenation of nitrile rubber and/or molecular weight degradation during metathesis. Wherein M is hydrazine or hydrazine, X ¹ and X ² are the same or different ligands, and L is an electron donating ligand which may or may not be bonded to X ¹ to form a cyclic structure, R ¹ is hydrogen, An alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and R ² , R ³ , R ⁴ and R ⁵ are the same or different and each is a hydrogen or an organic or inorganic substituent, R ⁶ is H, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, -C(=O)R, -C(=O)OR, -C(=O)N(R ₂ , -C(=S)R, -C(=S)SR, -C(=S)OR, -C(=S)N(R) ₂ , -S(=O) ₂ N(R) ₂ , -S(=O) ₂ R, -S(=O)R or a group containing C=O or a C=S structural element adjacent to a carbon atom bonded to Y, n is 0 or 1 Where if n=1, then the element It should mean that Y and (E) _n are connected by a single bond or by a double bond, where (i) if Y and (E) _n are connected by a single bond, then Y is Oxygen (O), sulfur (S), NR or PR, and E is CH ₂ or (ii) If Y and (E) _n are linked by a double bond, then Y is N or PE is CH, if n=0, then Y is oxygen (O), sulfur (S), NR or PR and is directly bonded to the phenyl moiety depicted in the above formula (L) by a single bond and which has all of the above In the case of the formula (Q), R is hydrogen or an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

Catalysts of the general formula (Q) are known in principle. Representative of such compounds are, for example, those described by Hoveyda et al. in US 2002/0107138 A1 and in Angew . Chem . Int . Ed . 2003, 42, 4592, and by Grela in WO-A-2004/035596, Eur .J . Org. Chem 2003, 963-966 and Angew . Chem. Int . Ed . 2002, 41, 4038 , and J. Org. Chem. 2004 , 69, 6894-96 and Chem . Eur. J 2004, 10 , 777 Catalyst described in -784 . An additional representative of such catalysts is the catalyst described in EP-A-1 905 777.

The additional catalyst which falls within the general formula (Q) and which is covered by the component (1) has the following structure, wherein in each case, it is 2,4,6-trimethylphenyl

Component (2) which should be removed by the method of the present invention includes: an iron-containing residue and a degradation product thereof.

Such iron-containing residues can occur due to minimal corrosion or degradation that may occur in any metal vessel or pipe, or alternatively, because iron-containing compounds may have been used for activation in the polymerization of the nitrile rubber. The fact of the agent.

Component (III) which should be removed according to the invention comprises: fatty acids, antioxidants, and antidegradant stabilizers based on ionic and alkaline earth metal residues, in particular ionic residues based on Ca, Na, K, non-metal ions Residues, especially based on phosphorus.

Fatty acid, antioxidant, and anti-degradation stabilizers are used in the emulsion polymerization of the nitrile rubber and the emulsion latex and the resulting solid polymer are prevented from destabilizing.

Once the nitrile rubber is separated and the rubber is subsequently selectively hydrodegraded, it can occur by several mechanisms including thermal or photochemical degradation, oxidative degradation, and ozone degradation. In most mechanisms, degradation is initiated by the formation of a group species. The presence of an antioxidant or antidegradant stabilizer can inhibit such groups from "aging" the polymer prematurely. In general, the antioxidant or antidegradant stabilizer may be comprised of a hindered amine, a diamine, a phenylenediamine, a monophenol, and a bisphenol, which may include, but are not limited to, butylated hydroxytoluene ( BHT ^TM), octyl diphenylamine ^{(ODPA), Vulkanox TM 3100,} Vulkanox TM 4020, Naugard TM 446, Vulkanox TM HS (TMQ), Vulkanox TM BKF, Irganox TM MD 1024, Irganox TM 1010 and Vulkanox ^TM SKF. Although such antioxidants or antidegradant stabilizers are common knowledge that hinders degradation of the polymer by group inhibition, their benefits are actually a burden in the vulcanization process of the polymer, where it is desirable to Free radicals are produced for the purpose of crosslinking the polymer chains. For this reason, the ability to remove such antioxidants as well as anti-degradation stabilizers can be beneficial.

Purification parameters:

The purification of the present invention can be carried out in the presence of one or more organic solvents (rather than ionic liquids) which make it easier to separate the (H)NBR from the ionic liquid and the catalyst present therein. Contacting the (H)NBR with at least one ionic liquid results in the formation of a two phase system. If the components (1) to (3) to be removed have an ionic character, they are preferentially dissolved in the ionic liquid. Such an ionic phase comprising a catalyst, a catalyst degradation product together with all other compounds to be removed can be readily separated from the organic solvent and in the (H)NBR present therein. The catalyst in the ionic liquid can be recovered and used separately for further metathesis or hydrogenation, preferably after other impurities have been removed by distillation or washing steps. The method for recovering ionic liquids is known in principle from the prior art ( EP-A-1218890; Chem. Rev. 2002, 102, 3667-3692, US 2003/0085156 A ).

Typically, the solvent used is an organic solvent. Suitable organic solvents, in particular halogenated hydrocarbons such as dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane or trichloroethane; aromatic compounds such as benzene, toluene, xylene , cumene, or halogen-containing benzene; alkanes such as pentane, hexane, or cyclohexane; esters such as tertiary butyl methyl ester or acetate; ethers such as diethyl ether, tetrahydrofuran, And dimethoxyethane; guanamines such as dimethylformamide; antioxidants such as hydroquinone; acetone; dimethyl carbonate; or alcohols.

Preferred solvents for the system C used in the process of the present invention ₅ -C ₂₀ - alkoxy, ethers, and halogenated hydrocarbons. Acetone, toluene, or monochlorobenzene is very particularly preferred for use in the process of the present invention.

The process according to the invention can be carried out batchwise, i.e., discontinuously, or continuously. If the process is carried out batchwise, the selectively hydrogenated nitrile rubber (especially dissolved in an organic solvent) is contacted with at least one ionic liquid in a vessel which can be stirred. Typically, the selectively hydrogenated, selectively dissolved nitrile rubber dose is added to the vessel and thereafter the ionic liquid is added while the vessel is being agitated. In an alternative embodiment, the process can be performed continuously. In another example of the body, the process is carried out continuously. In particular, this continuous process is carried out in countercurrent. In another alternative embodiment, it is possible to bubble the ionic liquid through a solution of the selectively hydrogenated nitrile rubber. This is achievable for both batch and continuous processes.

After contacting, the ionic liquid can be removed from the selectively hydrogenated nitrile rubber, for example by known phase separation techniques. The selectively hydrogenated nitrile remaining in the organic solvent is then coagulated using a typical coagulation process.

In an alternative embodiment, a reaction mixture comprising a selectively hydrogenated nitrile rubber, at least one solvent, and at least one ionic liquid can be fed to the extruder or fed to a press, and Removing the ionic liquid And the solvent. The remaining selectively hydrogenated nitrile rubber can be subjected to one or more further washing and drying steps.

The process of the present invention is generally carried out at a temperature ranging from -20 ° C to 200 ° C, preferably from 0 ° C to 150 ° C, very particularly preferably from 20 ° C to 100 ° C.

Example:

The following examples describe the removal of cerium, lanthanum, iron, fatty acid emulsifiers, metal ions, non-metal ions, and polymeric stabilizers from nitrile rubber and from hydrogenated nitrile rubber. However, they in no way limit the scope of the invention in any way.

"phr" as referred to hereinafter means a weight fraction based on one hundred parts by weight of the corresponding rubber. The plasma liquid system was purchased from Polymer Laboratories Ltd. The following nitrile rubbers were used for metathesis and hydrogenation: Perbunan ^® T 3429 (nitrile rubber) is a commercially available statistical butadiene-acrylonitrile copolymer commercially available from LANXESS with an acrylonitrile content of 34 mol% and Nie viscosity (ML (1+4) at 100 ° C) is 29 MU.

Perbunan ^® T 4441 (nitrile rubber) a statistical butadiene-acrylonitrile copolymer having an acrylonitrile content of 44 mol% and a Mooney viscosity (ML (1+4), 41 MU at 100 °C.

The following commercially available ionic liquids were used:

Examples 1 and 2 Analysis of removal of Rh, Ru, and Fe metals from hydrogenated nitrile rubber

The decomposition of Perbunan ^® T 4441 was carried out using 4 phr of 1-hexene and 0.007 phr of Grubbs (II) generation catalyst. The low molecular weight nitrile rubber was then hydrogenated using 0,02 phr Wilkinson's catalyst (see Table 1). To a low molecular weight hydrogenated nitrile polymer solution in monochlorobenzene (100 g) was added 50 g of ionic liquid as shown in Table 1. The reaction was allowed to continue for a certain period of time (see Table 2) at the set temperature while stirring. After the set time allotment is completed, the reaction is allowed to undergo phase separation and the ion layer is separated from the rubber-containing organic solvent layer by using a separatory funnel. The organic layer is reacted with water to coagulate the rubber and then the rubber is separated. The Ru, Rh, and Fe contents in the rubber were then analyzed using ion phase chromatography and the results are shown in Table 2.

As can be observed from Table 2, nearly 100% of the ruthenium (Ru) metal was removed from the polymer, and 90% and 83% of the ruthenium (Rh) metal were removed, respectively, and 66% and 91 were removed, respectively. % of Fe.

Example 3-5: Removal of Rh, Fe, fatty acid emulsifiers and polymer antioxidant Vulkanox® BKF from HNBR (ie, 2-tris-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl) Analysis of methyl]-4-methyl-phenol)

The hydrogenated nitrile rubber was produced by hydrogenation at 138 ° C and a pressure of 85 bar of H ₂ using a solution of 0.05 phr of Wilkinson's catalyst and 1 phr of a solution of 15 wt.-% Perbunan ^® T 3429 in monochlorobenzene. The completion of the hydrogenation was monitored by 99+% hydrogenation of the carbon-carbon double bonds.

To 25 g of the hydrogenated nitrile rubber solution was added 25 g of an ionic liquid as shown in Table 3. The solution was stirred at a set time and temperature (see Table 3), and then the mixture was cooled and phase separated into an ionic liquid layer and an organic solvent layer. Analysis of the Rh and Fe contents of the hydrogenated nitrile rubber was then carried out using ion phase chromatography. Analysis of fatty acids and antioxidants and residues in the polymer was carried out by gas chromatography. All results are shown in Table 4.

Hydrogenated nitrile rubber (Therban ^® A 3406, available from LANXESS Deutschland GmbH) to obtain the comparison data, the hydrogenated nitrile rubber is based on a commercial scale by the use of Wilkinson's catalyst and triphenylphosphine to the principle of the embodiment Example 3-5 same manner as described for the hydrogenation of Perbunan ^® T 3429 manufactured.

Table 4 shows that increasing the temperature at which the reaction proceeds can improve the efficiency of the purification. When the temperature is increased from 22 ° C to 100 ° C and increased to 140 ° C, the efficiency of removing rhodium (Rh) is correspondingly increased from 83% to 90%. When moving from 22 ° C to 100 ° C, the temperature effect involving the efficiency of iron (Fe) removal is small, increasing only from 97% to 99+%. It was observed regardless of the antioxidant (Vulkanox ^® BKF) fatty acid, or emulsifier content is not dependent on the temperature, since the removal of 91% of each fatty acid from Example emulsifier embodiment, while removing 87% to 90% except BKF.

Example 6-9: Analysis of removal of Na, K, Mg, and Ca from nitrile rubber solution

To 75 g of Perbunan ^® T 3429 is added as a set amount specified in Table 5 in monochlorobenzene ionic liquid solution, and the mixture was stirred (see Table 5) at a set time and temperature. After the set time distribution was completed, the reaction was allowed to undergo phase separation and the ion layer was separated from the nitrile rubber-containing organic solvent layer by using a separatory funnel. The organic layer is then contacted with water to coagulate the nitrile rubber. Thereafter, the rubber was separated. The metal ion content of the nitrile rubber was then analyzed by ion phase chromatography (see Table 6).

The purification of the nitrile rubber using ionic liquids is shown in Table 6 to provide a reduction of more than 45% of the sodium (Na) content for Examples 8 and 9, and potassium (K) content for Examples 6 and 7. A reduction of more than 70%, a decrease of more than 50% of the calcium (Ca) content, and a decrease of more than 15% of the magnesium (Mg) ion content.

Example 10-11: Analysis of Removal of Na, K and Antioxidants from Nitrile Rubber Solutions

It was added to Perbunan ^® T 3429 100 g of monochlorobenzene was defined as a set amount of ionic liquid in Table 7, and then the mixture was stirred at a set time and temperature, as also shown in Table 7. After the set time distribution was completed, the reaction was allowed to undergo phase separation and the ion layer was separated from the nitrile rubber-containing organic solvent layer by using a separatory funnel. The organic layer is allowed to react with water to coagulate the nitrile rubber and thereafter the rubber is separated from the mixture.

The analysis of the resulting polymer is summarized in Table 8.

As can be seen from Table 8, purification using an ionic liquid provides a reduction of more than 50% of the antioxidant content of the polymer, a reduction of the sodium (Na) content of greater than 40%, and the potassium (K) A reduction in ion content above 45%.

Claims (15)

A method for purifying a selectively hydrogenated nitrile rubber, the method comprising contacting the selectively hydrogenated nitrile rubber with at least one ionic liquid. The method of claim 1, wherein the ionic liquid represents a quaternary ammonium cation, a quaternary phosphonium cation, a selectively substituted pyridinium cation, a selectively substituted imidazolium cation, and a selectively substituted pyridinium. A compound of an azole cation, and a selectively substituted pyrimidine cation. The method of claim 1, wherein the ionic liquid system is selected from the group consisting of ionic liquids having the general formulae (1) to (5): Wherein A ^n- shall mean an anion selected from the group consisting of hexafluorophosphate (PF ₆ ^- ), nitrate (NO ₃ ^- ), halide (preferably fluoride, chloride, bromide, Or iodide), sulfate, sulfonate, aluminate, carboxylate, phosphate, and borate, wherein n is 1, 2, or 3, depending on the negative charge of the anion above, and (1/n) It is 1 for an anion with a double negative charge, 1/2 for an anion with double negative charge, and 1/3 for an anion with a triple negative charge, X system nitrogen or phosphorus, R ¹ , R ² And R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different and represent hydrogen, halide, alkoxy, alkyl, substituted alkyl, aryl, preferably phenyl, substituted An aryl group, and Z ¹ , Z ² , Z ³ are the same or different and represent carbon (C) or nitrogen (N), the first condition of which is at least one of Z ¹ , Z ² and Z ³ is nitrogen And the second condition is that when any of Z ¹ , Z ² , and Z ³ is nitrogen, the group attached to R ¹ , R ² , or R ³ is null. The method of claim 1, wherein the ionic liquid system is selected from the group consisting of ionic liquids having the general formulae (1) to (5), wherein (1/n) A ^n- represents PF ₆ ^- , NO ₃ ^- , F ^- , Cl ^- , Br ^- , I ^- , R ⁷ SO ₃ ^- , R ⁷ OSO ₃ ^- , R ⁷ CO ₃ ^- , BF ₄ ^- , and B(R ⁷ ) ₄ ^- , wherein R ⁷ They are the same or different and represent an alkyl group, a substituted alkyl group, an aryl group, more preferably a phenyl group, a substituted aryl group, or an alkoxy group. The method of claim 1, wherein the ionic liquid system is selected from the group consisting of 1-ethyl-3-methyl-pyridine cation ethyl sulphate, 1-ethyl-3-methyl Base-imidazolium ionic ethyl sulfate, 1-methyl-3-butylimidazolium chloride, 1-methyl-3-ethylimidazolium chloride, N-butylpyridine cation chloride, Tetrabutylphosphonium chloride, ammonium hexafluorophosphate, ammonium tetrafluoroborate, ammonium toluenesulfonate, ammonium hydrogen sulfate, pyridine cation hexafluorophosphate, 1-methyl-3-butylimidazolium hexafluorophosphate A combination of two or more of pyridine cation tetrafluoroborate, pyridine cation hydrogen sulfate, n-butylpyridine cation hexafluorophosphate, and the above ionic liquid. The method of claim 1, wherein the nitrile rubber in contact with the ionic liquid represents a copolymer comprising repeating units of at least one α,β-unsaturated nitrile and at least one conjugated diene. The method of claim 6, wherein the nitrile rubber in contact with the ionic liquid comprises a repeating unit selected from the group consisting of 1,2-butadiene, 1,3-butadiene, isoprene, 2 At least one conjugated diene of the group consisting of 3-dimethylbutadiene, 1,3-pentadiene, and a mixture thereof, preferably 1,3-butadiene; and selected from acrylonitrile At least one α,β-unsaturated nitrile in the group consisting of methacrylonitrile, ethacrylonitrile and a mixture thereof is preferably acrylonitrile. The method of claim 6 or 7, wherein the nitrile rubber further comprises at least one repeating unit of a copolymerizable trimonomer, preferably selected from the group consisting of α,β-unsaturated monocarboxylic acids, and esters thereof. Groups of their classes, their guanamines, α,β-unsaturated dicarboxylic acids, their monoesters or diesters, or their corresponding anhydrides or guanamines. The method of claim 1, wherein the nitrile rubber has a Mooney viscosity (ML (1+4) at 100 ° C) determined according to DIN 53523/3 or ASTM D 1646 at 100 ° C. From 10 to 150, preferably from 20 to 100. The method of claim 1, wherein the nitrile rubber is prepared by emulsion polymerization. The method of claim 10, wherein the polymerization is followed by a metathesis reaction and/or a hydrogenation reaction before the obtained nitrile rubber or the partially or fully hydrogenated nitrile rubber is contacted with the at least one ionic liquid. The method of claim 11, wherein the component types (1) to (3) can be removed from the nitrile rubber which may be partially or completely hydrogenated: (1) for use in such or Metathesis reaction and/or hydrogenation reaction to catalyze ruthenium, osmium and ruthenium catalysts and any degradation products, (2) iron-containing residues and degradation products thereof, and (3) emulsion polymerization process and selectivity in nitrile rubber a metathesis reaction and a compound or any degradation product thereof used in the subsequent selective hydrogenation reaction, including but not limited to: fatty acid emulsifiers and salts thereof, salt complexes of Na, K, Mg, and Fe, residual nitrile rubber Molecular weight regulator, residual Acrylonitrile, defoamer, and anti-foaming agent. The method of claim 12, wherein the selectively hydrogenated nitrile rubber is first dissolved in one or more organic solvents other than the ionic liquid, and then the solution is contacted with the at least one ionic liquid, This produces a two-phase system in which the components (1) to (3) are preferentially dissolved in the ionic liquid and wherein the ionic liquid is separated from the organic solvent, the organic solvent comprising the selectively hydrogenated nitrile rubber. The method of claim 13, wherein the organic solvent is selected from the group consisting of halogenated hydrocarbons, preferably dichloromethane, chloroform, tetrachloromethane, 1, 2 - Dichloroethane and trichloroethane; aromatic compounds, preferably benzene, toluene, xylene, cumene and halobenzenes; alkanes, preferably pentane, hexane, and rings Hexane; esters, preferably tertiary butyl methyl esters and acetates; ethers such as diethyl ether, tetrahydrofuran, and dimethoxyethane; guanamines, preferably dimethylformamidine An amine; and an antioxidant, preferably hydroquinone; acetone; and dimethyl carbonate; and an alcohol. As in the method of claim 1, the method is carried out batchwise or continuously.