Hydrogenated nitrile rubber with reduced catalyst impurities

Abstract

To recover a residual catalyst from a hydrogenated nitrile rubber solution.SOLUTION: The residual hydrogenation catalyst from the hydrogenated nitrile rubber solution is recovered by using two steps such as (1) the catalyst extraction step with an ammonium salt and water (optionally including an oxidation step) to extract catalyst from the HNBR polymer chain to the solvent and then (2) the separation / column recovery step with the column packed with functional ion exchange resins for the separation of ammonia-catalyst complex from hydrogenated nitrile rubber solution and the column recovery for the high catalyst recovery with functional groups of resins. The ammonium salt for the catalyst extraction step is selected from ammonium chloride, ammonium bromide, ammonium iodide, and ammonium acetate. The functional groups in the functional ion exchange resins for packing the column is selected from thiourea, thiouronium, thiol, amine, diamine, triamine, TMT, dithiocarbamate, and carbodithioate.SELECTED DRAWING: Figure 1

Description

Disclosure Contents

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application hereby claims the benefit of Provisional Patent Application No. 63 / 134,980 of the same title, filed January 8, 2021, the disclosure of which is incorporated herein by reference in its entirety.

[0002] 〔background〕 The present disclosure relates to a method for recovering residual catalyst from a hydrogenated nitrile rubber solution.

[0003] Acrylonitrile-butadiene copolymer (NBR) is widely used in the rubber industry, but its use is limited by its heat resistance, oil resistance, and weather resistance. To improve NBR, it is hydrogenated in an organic solvent using a homogeneous catalyst, such as a Rh catalyst, or a heterogeneous catalyst, such as a silica-supported palladium catalyst. Partially or highly saturated acrylonitrile-butadiene copolymer or hydrogenated nitrile rubber is called HNBR.

[0004] After the hydrogenation of NBR with homogeneous or heterogeneous catalysts in organic solvents, there are several problems associated with residual catalysts in HNBR. The first is the high price of the catalyst compared to the price of HNBR. The second is unfavorable properties such as dark color and heat- or light-initiated degradation. The third is the limited amount of transition metals in the earth. The last is a potential environmental issue.

[0005] 〔overview〕 The process for recovering the residual hydrogenation catalyst from the hydrogenated nitrile rubber solution includes (1) a catalyst extraction step with ammonium salt and water (optionally including an oxidation step) to extract the catalyst from the HNBR polymer chains into a solvent, followed by (2) a separation / column recovery step using a column packed with a functionalized ion exchange resin that is not subjected to a pressure drop to separate the ammonia-catalyst complex from the hydrogenated nitrile rubber solution.

[0006] The ammonium salt for the catalyst extraction step is selected from ammonium chloride, ammonium bromide, ammonium iodide, and ammonium acetate.

[0007] The functional groups in the functional ion exchange resin for packing the column are selected from thiourea, thiouronium, thiol, amine, diamine, triamine, trimercaptotriazine (TMT), dithiocarbamate, and carbodithioate.

[0008] This method for recovering hydrogenation catalyst residues from hydrogenated nitrile rubber solutions uses two steps: (1) a catalyst extraction step with ammonium salt and water (optionally including an oxidation step), followed by (2) a separation / column recovery step using a column packed with functionalized ion exchange resin, providing an economical and practical process that leaves little residual catalyst in the hydrogenated nitrile rubber. This process overcomes the problem of impurities in hydrogenated nitrile rubber as well as the high cost of recovering the residual hydrogenation catalyst by regenerating the used ion exchange resin several times due to the limited functional groups on the surface of the ion exchange resin.

[0009] These and other objects and advantages will become apparent from the accompanying drawings and description thereof.

[0010] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments and, together with the general description given above and the detailed description of the embodiments given below, serve to explain the principles of the disclosure. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 illustrates the concept of catalyst extraction from polymer chains by chelating agents and column recovery packed ion exchange resin. [Figure 2] FIG. 1 shows a catalytic extraction step and column recovery using two columns packed with ion exchange resin. [Figure 3]FIG. 1 shows a catalytic extraction step and column recovery using one column packed ion exchange resin. [Figure 4] FIG. 1 shows the effect of temperature and water in the catalyst extraction step using an ammonium salt (Examples 1 to 4). [Figure 5] 1 is a graph of local residual palladium in hydrogenated nitrile rubber passed through a column at flow rates of 0.5 to 2.0 BV / hr at 50° C. after a Pd extraction step with 4 to 10% HNBR solution (Examples 41 to 45). [Figure 6] 1 is a graph of local residual palladium in hydrogenated nitrile rubber passed through a column without a Pd extraction step (Comparative Examples 1 and 2) and after a Pd extraction step (Examples 54 and 55).

[0012] Detailed Description In order to solve the above-mentioned problems, the present inventors have tackled high catalyst recovery from hydrogenated nitrile rubber solution without contaminating the polymer with impurities by two steps, namely, a catalyst extraction step using ammonium salt and water from HNBR polymer chains, followed by a separation / column recovery step using a column packed with functional ion exchange resin without pressure reduction, which has a high catalyst recovery efficiency without regenerating used resin, with a resin efficiency of over 75%.

[0013] The process for recovering residual hydrogenation catalyst from a hydrogenated nitrile rubber solution involves (1) a catalyst extraction step using ammonium salt and water (optionally including an oxidation step) to extract the catalyst from the HNBR polymer chain into a solvent, followed by (2) a separation / column recovery step using a column packed with functionalized ion exchange resin without pressure reduction to separate the ammonia-catalyst complex from the hydrogenated nitrile rubber solution. The resulting HNBR has less than 50 ppm of residual catalyst by weight of HNBR. Residual catalyst (Pd) is measured by using ICP (inductively coupled plasma argon emission spectroscopy) on the solid polymer.

[0014] The efficiency of catalyst extraction from HNBR polymer chains in the catalyst extraction step (1) can be affected by the amount of ammonium salt, water, extraction temperature, and extraction time. Factors include the state of the hydrogenated nitrile rubber solution, such as the degree of oxidation, viscosity, and catalyst amount, for effectively extracting the catalyst in the form of an ammonia-catalyst complex from the hydrogenated nitrile rubber in a dissolved state. The state of the hydrogenated nitrile rubber solution in the catalyst extraction step (1) is controlled by using the degree of oxidation, extraction temperature, extraction time, and solids content of the HNBR solution.

[0015] Acrylonitrile-butadiene copolymer (NBR) can be hydrogenated in the presence of a hydrogen source using a heterogeneous or homogeneous catalyst. In some embodiments, the catalyst is a heterogeneous catalyst, which has a different phase from the reactants and can be on a solid support. Examples include catalysts containing ruthenium, rhodium, palladium, osmium, iridium, and platinum. In some embodiments, the heterogeneous catalyst is selected from Pd / SiO2, Pd / Al2O3, Pd / TiO2, Pd / CeO2, and Pd / ZrO2. In some embodiments, the heterogeneous catalyst contains palladium or platinum. In some embodiments, the heterogeneous catalyst contains palladium. In some embodiments, the catalyst is a homogeneous catalyst in the same phase as the reactants. Examples include catalysts containing rhodium, iridium, and nickel, such as Wilkinson's catalyst, Lindlar's catalyst, and Raney nickel.

[0016] Acrylonitrile-butadiene copolymer (NBR) is hydrogenated to form hydrogenated nitrile rubber (HNBR). The saturation level (iodine value) of HNBR is reduced to less than 45 mg / 100 mg. In some embodiments, the iodine value (IV) is less than 40 mg / 100 mg, e.g., less than 35 mg / 100 mg, 30 mg / 100 mg, 20 mg / 100 mg, and 10 mg / 100 mg. The Wijs procedure is used to measure the unsaturation (iodine value) in hydrogenated nitrile rubber (HNBR) by adding iodine monochloride. This test method measures unsaturation as the iodine value by adding an iodine / chlorine reagent. The amount of absorbed reagent is determined by back-titrating excess reagent and comparing it to a blank determination. Iodine number is reported in centigrams of iodine per gram of HNBR [cg(I2) / g]. A higher iodine number indicates a higher level of unsaturation. This test method is suitable for calculating the residual unsaturation of hydrogenated nitrile rubber when the iodine number of the base polymer before hydrogenation has been measured.

[0017] In some embodiments, a process for recovering hydrogenation catalyst residue from a hydrogenated nitrile rubber solution can obtain more than 80% of the residual catalyst from a highly saturated hydrogenated nitrile rubber using an extraction step to remove the catalyst from the HNBR polymer chains, followed by a step of separating the chelating agent-catalyst complex from the hydrogenated nitrile rubber solution. This process overcomes the problems of having impurities in the hydrogenated nitrile rubber, the commercial problem of separating the chelating agent-catalyst complex from the catalyst extraction solvent-hydrogenated nitrile rubber solution, and the high cost of regenerating used resin to recover the residual hydrogenation catalyst from the hydrogenated nitrile rubber solution.

[0018] Hydrogenated nitrile rubber solutions can be prepared using heterogeneous or homogeneous catalysts in solution under a hydrogenation atmosphere. The hydrogenation reaction of nitrile rubber in solution results in at least 80% reduction of the original carbon-carbon double bonds contained in the unsaturated nitrile rubber. The nitrile rubber content in solution is typically 2-50%, depending on the catalyst type, mixing efficiency, and target saturation. The catalysts used for hydrogenating nitrile rubber are either homogeneous or heterogeneous. Hydrogenated nitrile rubber solutions are contained in hydrogenated acrylonitrile-butadiene copolymer solutions, hydrogenated acrylonitrile-acrylate-butadiene terpolymer solutions, and hydrogenated acrylonitrile-butadiene-methacrylic acid terpolymer solutions. When heterogeneous catalysts are used in solution, a portion of the catalyst can be separated by prior filtration or centrifugation.

[0019] Catalyst Extraction Step The catalyst extraction step is the formation of an ammonia-catalyst complex from free catalyst in solution or immobilized catalyst attached to the hydrogenated nitrile rubber by using less than 2% by weight of ammonium salt of the hydrogenated nitrile rubber in solution which is oxidized by an optional oxidizing agent prior to and / or during the catalyst extraction step.

[0020] The concept of catalyst extraction from polymer chains in HNBR solution is shown in Figure 1.

[0021] In some embodiments, the oxidation state of the dissolved hydrogenated nitrile rubber is controlled by contact with an oxygen (air) / nitrogen mixture or an oxidizing agent, such as iron (III) chloride, iodine, hydrogen peroxide, copper (II) chloride, copper (II) acetate, benzoquinone, tert-butyl hydroperoxide, manganese dioxide, nitric acid, or sodium chlorate. In some embodiments, the oxidizing agent for dissolved hydrogenated nitrile rubber is oxygen (air), iron (III) chloride, copper (II) chloride, benzoquinone, or hydrogen peroxide. Two or three co-oxidizing agents may be used simultaneously to improve oxidation efficiency. When oxygen is used as an oxidizing agent in this process, a safe oxygen concentration with nitrogen should be used at less than 10% by volume, which is below the flammable limit. In some embodiments, the oxygen concentration is less than 8% by volume, e.g., less than 3% by volume.

[0022] The general chemical structure of the ammonium salt for forming the chelating agent-catalyst complex from the hydrogenated nitrile rubber solution is shown below: [ka]

[0023] wherein R1, R2, R3, and R4 are hydrogen or alkyl, and X is an anion. The anion (X) is chloride, bromide, iodide, or acetate. Examples of ammonium salts in the chemical structure are ammonium chloride, ammonium bromide, ammonium iodide, and ammonium acetate. In some embodiments, the ammonium salt is ammonium chloride.

[0024] The ammonium salt for the catalyst extraction step may be used alone or in combination of two or three ammonium salts selected from the aforementioned ammonium salts. The ammonium salt may be used in a solid state or in a solution state, for example, with the ammonium salt concentration in the solution being less than 25 wt%. The amount of ammonium salt for the catalyst extraction step depends on the residual catalyst level in the hydrogenated nitrile rubber, the type of ammonium salt, the hydrogenated nitrile rubber content in the solution, the amount of residual metal in the solution, the extraction time, the mixing efficiency, the type of solvent for the catalyst extraction step, and the type of hydrogenated nitrile rubber. A typical amount of ammonium salt used is about 4 moles per mole of catalyst in the hydrogenated nitrile rubber. In some embodiments, this amount is 5 moles per mole of catalyst, 6 moles per mole of catalyst, or 10 moles per mole of catalyst. The amount of ammonium salt used in the solution is based on the amount of residual catalyst, but the efficiency of the ammonium salt depends on the solid content, acrylonitrile content, reaction time, reaction temperature, mixing method, and type of solvent. Other residual metals can form complexes with ammonium salts, which can reduce the efficiency of catalyst extraction efficiency and require more ammonium salts.

[0025] In the catalyst extraction step, the ammonium salt can be added alone or in a mixture with a solvent such as water, alcohol, methanol, or glycerol. In some embodiments, the solvent is water. A small amount of water containing the ammonium salt can help the ammonium salt migrate from the solution to the hydrogenated nitrile rubber because the ammonium salt has better solubility in water than acetone. The amount of water containing the ammonium salt must be less than the amount that would cause phase separation. If the amount of water containing the ammonium salt is greater than the amount that causes phase separation, the catalyst-extracted HNBR solution will not pass through the column packed with the functionalized resin due to gel formation.

[0026] In some embodiments, the amount of water used in the catalyst extraction step is related to the total solids content (TSC) of the HNBR solution, the composition of the hydrogenated nitrile rubber, and the polymer type of the base nitrile rubber, such as copolymer or terpolymer. Typical amounts of water for the catalyst extraction step can be about 0% to about 5% by weight, e.g., about 0.05% to 2% by weight, or 0.1% to 1.5% by weight, based on the hydrogenated nitrile rubber solution. If less than 0.05% by weight of water is used based on the hydrogenated nitrile rubber solution, a small amount of catalyst is extracted from the hydrogenated nitrile rubber. If more than 2% by weight of water is used based on the hydrogenated nitrile rubber, polymer separation from the hydrogenated nitrile rubber solution occurs.

[0027] In the catalytic extraction step using ammonium salt, the content of hydrogenated nitrile rubber in the solution is directly related to the extraction efficiency. The appropriate hydrogenated nitrile rubber content in the solution is 1% to 20% by weight, for example, 2% to 16% by weight, and 4% to 14% by weight. A hydrogenated nitrile rubber content of less than 1% is not good for an economical process. A hydrogenated nitrile rubber content of more than 20% is difficult to mix with ammonium salt, resulting in low extraction efficiency.

[0028] Another important factor in mixing efficiency is the mixing method, such as shaking or stirring with a stirrer. Depending on the mixing method, extraction efficiency can be improved. A typical stirrer stirring is very effective. High temperature can also affect extraction efficiency by increasing the mobility of polymer chains and decreasing the viscosity of the solution, so that the ammonium salt can more easily access the polymer chains.

[0029] In the catalytic extraction step with ammonium salt, the organic solvent for dissolving the hydrogenated nitrile rubber may be the same solvent as that used in the hydrogenation process of nitrile rubber, or may be a solvent that is partially or completely miscible with water. Suitable organic solvents include ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isopropyl ketone; and ethers such as dioxane and tetrahydrofuran, with acetone being a particularly preferred organic solvent.

[0030] Separation / column recovery step using a column packed with functionalized ion exchange resin After the catalyst is extracted from the HNBR polymer chains into a solution of ammonium salt and solvent, a separation / column recovery step using a column packed with functionalized ion exchange resin is required to separate the ammonia-platinum complex from the hydrogenated nitrile rubber solution. The functional groups of the ion exchange resin used to pack the column can bind to the platinum-ammonia complex or platinum-ammonium chloride complex as it passes through the column.

[0031] In some embodiments, two columns are used after the catalyst extraction step, as shown in Figure 2. Each column has dimensions of 1.02 cm diameter and 12 cm length, with an L / D of 12.2. In some embodiments, one column after the catalyst extraction step, as shown in Figure 3. In this column, the column dimensions are 1.02 cm diameter and 29 cm length, with an L / D of 28.8.

[0032] In some embodiments, the functional group in the functional ion exchange resin for packing the column is selected from thiourea, thiouronium, thiol, amine, diamine, triamine, TMT, dithiocarbamate, carbodithioate, and combinations thereof. In some embodiments, the functional group in the functional ion exchange resin is thiourea.

[0033] The type and shape of the functional ion exchange resin are not limited. Examples include spherical PS-DVB copolymer, fibrous olefin copolymer, or spherical silica.

[0034] The average particle size of the functionalized ion exchange resin is not limited. Examples of average particle sizes of the functionalized ion exchange resin for this process are in the range of at least 0.07 mm on a dry basis to a maximum of less than 1.50 mm, e.g., at least 0.15 mm to less than 1.20 mm on a dry basis, or at least 0.42 mm to less than 0.85 mm on a dry basis. If the average particle size of the functionalized ion exchange resin is less than 0.07 mm, the pressure drop through the resin-packed column increases dramatically, making the resin unusable even if the catalyst recovery efficiency is high. If the average particle size of the functionalized ion exchange resin is more than 1.50 mm, the catalyst recovery efficiency decreases even if the pressure drop through the resin-packed column is very small.

[0035] The temperature of the catalyst-extracted HNBR solution is not limited. The viscosity of the catalyst-extracted HNBR solution is desirable so that it can flow through the resin-packed column with an acceptable pressure drop. The temperature of the catalyst-extracted HNBR solution must be lower than the boiling point of the solvent used. If the temperature of the catalyst-extracted HNBR solution is higher than the temperature of the solvent used during passage through the resin-packed column, the catalyst recovery efficiency will decrease due to the formation of numerous bubbles.

[0036] After the ion exchange resin is loaded into the column, the amount of effluent discharged from the column packed with ion exchange resin is expressed as a relative value based on the resin bed volume (BV), which is the volume of ion exchange resin used in the column. The flow rate of the effluent is directly related to the catalyst recovery efficiency, which is called the space velocity (SV = Q / V: effluent flow rate / bed volume) and is expressed in bed volumes per hour (BV / hr). The flow rate (BV / hr) is controlled based on the solids content of the HNBR polymer in the HNBR solution, the residual catalyst concentration, the number of columns, and the viscosity of the HNBR solution.

[0037] Typical flow rates (BV / hr) of the Pd-extracted HNBR solution having 1-20 wt% HNBR polymer are 0.01 BV / hr to 10.0 BV / hr, preferably 0.1 BV / hr to 5.0 BV / hr, and more preferably 0.2 BV / hr to 3.0 BV / hr.

[0038] The catalyst recovery efficiency is the volume of the effluent before breakthrough. The effluent volume is measured in terms of bed volume numbers (BV), the total volume of solids and liquid in the column. Breakthrough occurs when the concentration of exchange ions (catalyst ions or palladium complexes) in the effluent increases to a predetermined limit. Once breakthrough is reached, the column no longer has the desired effectiveness. The target catalyst recovery efficiency for this process is greater than 100 BV, preferably greater than 1000 BV, and more preferably 5000 BV; more than 60% of the residual catalyst in the HNBR solution is removed.

[0039] Typical ion exchange resins have functional groups on the resin surface. As the BV increases, catalyst recovery efficiency reaches a critical point. At that point, the concentration of exchange ions removed decreases. The critical point occurs when the readily available functional groups on the resin are used.

[0040] After the catalyst-extracted HNBR solution has been completely passed through the resin-packed column, the hydrogenated nitrile rubber can be separated from the catalyst-separated HNBR solution by coagulation with a polar solvent. The coagulation method with a polar solvent can be a typical coagulation method, such as when the polar solvent is water, methanol, ethanol, or other alcohol. In some embodiments, water is the polar solvent.

[0041] After solidification of the catalyst-separated HNBR solution, the final product (catalyst-separated HNBR) is obtained by a typical drying method.

[0042] Residual catalyst in the final hydrogenated nitrile rubber can be measured by using ICP (Inductively Coupled Plasma Argon Emission Spectroscopy).

[0043] The catalyst extracted and separated from the hydrogenated nitrile rubber solution can be recovered from the spent resin after separating the spent resin from the spent resin column. The spent resin can be further purified by calcination to obtain purified palladium. The recovery efficiency of purified palladium depends on the capacity of the catalyst recovery process.

[0044] While the present disclosure has been illustrated by the description of several embodiments, and exemplary embodiments have been described in considerable detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such details. Additional advantages and modifications will be readily apparent to those skilled in the art. Furthermore, features from separate listings may be combined; features from examples may be generalized throughout the disclosure. [Example]

[0045] Example 1 A fully hydrogenated acrylonitrile-butadiene rubber solution (ZETPOL 2000L cement from Zeon Chemicals LP) was produced using a heterogeneous catalyst (silica-supported palladium) in acetone. After completing the heterogeneous hydrogenation under high pressure hydrogen, most of the palladium was recovered by using silica-supported palladium. To measure the residual palladium in the ZETPOL 2000L cement after recovering most of the silica-supported palladium, the ZETPOL 2000L cement was completely coagulated with excess water and dried. The dried ZETPOL 2000L was shown to have 166.9 ppm residual palladium using ICP. 46 g of Zetpol 2000L cement, with 166.9 ppm residual palladium and 13.1% solids by weight, was placed in a 1-liter glass jar equipped with a stirrer. 104 g of acetone was added to the Zetpol 2000L binder and stirred until a homogeneous mixture was formed. The total solids content was 4 wt%. 0.10 g of ammonium chloride was added to the 4% Zetpol 2000L binder at 23°C. After the ammonium chloride addition, the catalyst extraction step was carried out for 5 hours. At the end of the catalyst extraction step, an excess amount of water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 5.44 g of dried polymer was obtained. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP) with an Agilent 5110 ICP. The residual palladium content of the dried HNBR polymer (Zetpol 2000L) was 74.4 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 55.4%. The results are shown in Table 1 and Figure 4.

[0046] Examples 2 to 4 Example 2 was prepared according to the same procedure as Example 1, except for the temperature during the catalyst extraction step. The catalyst extraction step was carried out at 50°C using 0.10 g of ammonium chloride in 150 g of 4% Zetpol 2000L binder with stirring for 5 hours. After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 5.48 g of dry polymer was obtained. The dried polymer was measured for residual palladium using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 39.0 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 76.6%. The results are shown in Table 1 and Figure 4.

[0047] Example 3 was prepared according to the same procedure as Example 1, except that 25% aqueous ammonium chloride solution was added at 50°C for 5 hours for the catalyst extraction step. The catalyst extraction step was carried out at 50°C using 0.4 g of 25% (by weight) aqueous ammonium chloride solution after mixing 0.1 g of ammonium chloride and 0.3 g of water in 150 g of 4% Zetpol 2000L binder with stirring for 5 hours. After the catalyst extraction step, excess water was added to coagulate the polymer. The completely coagulated polymer was filtered and dried to obtain 5.49 g of dried polymer. The dried polymer was measured for residual palladium using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium of the dried HNBR polymer (Zetpol 2000L) was 29.3 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 82.4%. The results are shown in Table 1 and Figure 4.

[0048] Example 4 was prepared according to the same procedure as Example 1, except that 16.7% aqueous ammonium chloride solution was added at 50°C for 5 hours for the catalyst extraction step. The catalyst extraction step was carried out at 50°C using 0.6 g of 16.7% (by weight) aqueous ammonium chloride solution after mixing 0.1 g of ammonium chloride and 0.5 g of water in 150 g of 4% Zetpol 2000L binder with stirring for 5 hours. After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the completely coagulated polymer, 5.22 g of dried polymer was obtained. The dried polymer was measured for residual palladium using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium of the dried HNBR polymer (Zetpol 2000L) was 27.0 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 83.8%. The results are shown in Table 1 and Figure 4. [Table 1] a Zetpol 2000L bonding agent: Hydrogenated nitrile rubber-acetone solution with 13.1% solids, 36% acrylonitrile, and 99% hydrogenation (Zeon Chemicals LP) b AC: Ammonium chloride: NH4Cl - insoluble in acetone, soluble in water (26.7 wt% at room temperature) c DW: deionized water d AC / DW solution (wt%): ammonium chloride in aqueous ammonium chloride solution (%) by weight e TSC (%): total solids in the catalyst extraction step

[0049] Example 5 In Example 5, a fully hydrogenated acrylonitrile-butadiene rubber solution (ZETPOL 2000L binder from Zeon Chemicals LP) was produced using a heterogeneous catalyst (palladium on silica) in acetone. After completing the heterogeneous catalyst hydrogenation under high pressure hydrogen, most of the palladium was recovered by using a silica-supported catalyst. After complete coagulation with excess water and drying, 166.90 ppm of residual palladium was present in the fully hydrogenated acrylonitrile-butadiene rubber. 46 g of Zetpol 2000L binder, having 166.90 ppm of residual palladium and 13.1% solids by weight, was placed in a 1-liter glass jar equipped with a stirrer. 104 g of acetone was added to the Zetpol 2000L binder and stirred until homogeneous. The total solids content was 4% by weight. In a separate beaker, 0.009 g of ammonium chloride and 0.30 g of deionized water were mixed to produce a 2.8% ammonium chloride / water solution (AC / DW solution). 0.3009 g of the 2.8% AC / DW solution was added to 4% Zetpol 2000L binder at room temperature, which was then heated to 50°C. After the reactor temperature reached 50°C, the catalyst extraction step was carried out for 5 hours. At the end of the catalyst extraction step, the reactor was cooled to room temperature, and an excess amount of water was added to produce a complete coagulation. The completely coagulated polymer was filtered and dried, yielding 5.34 g of dried polymer. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium content of the dried HNBR polymer (Zetpol 2000L) was 38.5 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 76.9%. The results are shown in Table 2.

[0050] Examples 6 to 15 Example 6 was prepared according to the same procedure as Example 5, except for the total solids and ammonium chloride content. 69 g of Zetpol 2000L binder, containing 166.90 ppm of residual palladium and 13.1% solids by weight, was placed in a 1-liter glass jar equipped with a stirrer. 81 g of acetone was added to the Zetpol 2000L binder and stirred until homogeneous. The total solids content was 6 wt%. In a separate beaker, 0.026 g of ammonium chloride and 0.30 g of deionized water were mixed to produce a 7.9% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, yielding 8.65 g of dried polymer. The dried polymer was measured for residual palladium using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 34.3 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 79.4%. The results are shown in Table 2.

[0051] Example 7 was prepared according to the same procedure as Example 5, except for the total solids content, the amount of ammonium chloride, and the amount of deionized water. 92 g of Zetpol 2000L binder, having 166.90 ppm of residual palladium and 13.1% solids by weight, was placed in a 1-liter glass jar equipped with a stirrer. 58 g of acetone was added to the Zetpol 2000L binder and stirred until homogeneous. The total solids content was 8 wt%. In a separate beaker, 0.04 g of ammonium chloride and 0.50 g of deionized water were mixed to produce a 7.4% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, yielding 11.58 g of dried polymer. The dried polymer was measured for residual palladium using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 30.4 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 81.8%. The results are shown in Table 2.

[0052] Example 8 was prepared according to the same procedure as Example 7, except for the amount of ammonium chloride. The amount of ammonium chloride used was 0.03 g instead of 0.04 g, and together with 0.5 g of deionized water, a 5.7% ammonium chloride / water solution (AC / DW solution) was produced. After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 11.65 g of dried polymer was obtained. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 40.6 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 75.7%. The results are shown in Table 2.

[0053] Example 9 was prepared according to the same procedure as Example 7, except for the amount of ammonium chloride. The amount of ammonium chloride used was 0.02 g instead of 0.04 g, and together with 0.5 g of deionized water, a 3.8% ammonium chloride / water solution (AC / DW solution) was produced. After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 11.68 g of dried polymer was obtained. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 45.5 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 72.7%. The results are shown in Table 2.

[0054] Example 10 was prepared according to the same procedure as Example 5, except for the total solids content, amount of ammonium chloride, and amount of deionized water. 115 g of Zetpol 2000L binder, having 136.0 ppm residual palladium and 13.1% solids by weight, was placed in a 1-liter glass jar equipped with a stirrer. 36 g of acetone was added to the Zetpol 2000L binder and stirred until homogeneous. The total solids content was 10 wt%. In a separate beaker, 0.04 g of ammonium chloride and 0.50 g of deionized water were mixed to produce a 7.4% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, yielding 14.87 g of dried polymer. The dried polymer was measured for residual palladium using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 28.0 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 79.4%. The results are shown in Table 2.

[0055] Example 11 was prepared according to the same procedure as Example 10, except for the amount of ammonium chloride. The amount of ammonium chloride used was 0.03 g instead of 0.04 g, and together with 0.5 g of deionized water, a 5.7% ammonium chloride / water solution (AC / DW solution) was produced. After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 14.95 g of dried polymer was obtained. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 29.1 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 78.6%. The results are shown in Table 2.

[0056] Example 12 was prepared according to the same procedure as Example 11, except for the amount of deionized water. Instead of 0.50 g, 0.40 g of deionized water was used, along with 0.03 g of ammonium chloride, to produce a 7.0% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 14.94 g of dry polymer was obtained. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 30.1 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 77.9%. The results are shown in Table 2.

[0057] Example 13 was prepared according to the same procedure as Example 10, except for the amounts of ammonium chloride and deionized water. The amount of ammonium chloride used was 0.02 g instead of 0.04 g, and the amount of deionized water was 0.75 g instead of 0.50 g, producing a 2.6% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 14.97 g of dried polymer was obtained. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium content of the dried HNBR polymer (Zetpol 2000L) was 30.7 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 77.4%. The results are shown in Table 2.

[0058] Example 14 was prepared according to the same procedure as Example 10, except for the amounts of ammonium chloride and deionized water. The amount of ammonium chloride used was 0.015 g instead of 0.04 g, and the amount of deionized water was 1.00 g instead of 0.50 g, producing a 1.5% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 14.97 g of dried polymer was obtained. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium content of the dried HNBR polymer (Zetpol 2000L) was 34.1 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 74.9%. The results are shown in Table 2.

[0059] Example 15 was prepared according to the same procedure as Example 5, except for the total solids content, the amount of ammonium chloride, and the amount of deionized water. 150 g of Zetpol 2000L binder, containing 166.90 ppm of residual palladium and 13.1% solids by weight, was placed in a 1-liter glass jar equipped with a stirrer. In a separate beaker, 0.030 g of ammonium chloride and 0.75 g of deionized water were mixed to produce a 3.8% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, 19.82 g of dried polymer was obtained. The dried polymer was measured for residual palladium using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium content of the dried HNBR polymer (Zetpol 2000L) was 49.2 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 65.7%. The results are shown in Table 2. [Table 2] a Zetpol 2000L bonding agent: Hydrogenated nitrile rubber-acetone solution with 13.1% solids, 36% acrylonitrile, and 99% hydrogenation (Zeon Chemicals LP) b AC: Ammonium chloride: NH4Cl - insoluble in acetone, soluble in water (26.7 wt% at room temperature) c DW: deionized water d AC / DW solution (wt%): ammonium chloride in aqueous ammonium chloride solution (%) by weight e TSC (%): total solids in the catalyst extraction step

[0060] Example 16 In Example 16, a fully hydrogenated acrylonitrile-butadiene rubber solution (ZETPOL 2000L binder from Zeon Chemicals LP) was produced using a heterogeneous catalyst (palladium on silica) in acetone. After completing the heterogeneous catalyst hydrogenation under high pressure hydrogen, most of the palladium was recovered by using silica-supported catalyst. After complete coagulation with excess water and drying, 124.60 ppm of residual palladium was present in the fully hydrogenated acrylonitrile-butadiene rubber. 1000 g of Zetpol 2000L binder, containing 124.60 ppm of residual palladium and 13.5% solids by weight, was placed in a 2.5-liter glass jar equipped with a stirrer. In a separate beaker, 0.20 g of ammonium chloride and 6.67 g of deionized water were mixed to produce a 2.9% ammonium chloride / water solution (AC / DW solution). 6.87 g of a 2.9% AC / DW solution was added to 13.5% Zetpol 2000L binder at room temperature, which was then heated to 50°C. After the reactor temperature was raised to 50°C, the catalyst extraction step was carried out for 5 hours. At the end of the catalyst extraction step, the reactor was cooled to room temperature, and an excess amount of water was added to produce a complete coagulation. The completely coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 40.8 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 67.3%. The results are shown in Table 3.

[0061] Example 17 was prepared according to the same procedure as Example 16, except for the amount of deionized water. Instead of 6.67 g, 5.00 g of deionized water was used, along with 0.20 g of ammonium chloride, to produce a 3.8% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 50.2 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 59.7%. The results are shown in Table 3.

[0062] Example 18 was prepared according to the same procedure as Example 16, except for the amount of deionized water. Instead of 6.67 g, 3.33 g of deionized water was used, along with 0.20 g of ammonium chloride, to produce a 5.7% ammonium chloride / water solution (AC / DW solution). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 57.1 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 54.2%. The results are shown in Table 3. [Table 3] a Zetpol 2000L bonding agent: Hydrogenated nitrile rubber-acetone solution with 13.1% solids, 36% acrylonitrile, and 99% hydrogenation (Zeon Chemicals LP) b AC: Ammonium chloride: NH4Cl - insoluble in acetone, soluble in water (26.7 wt% at room temperature) c DW: deionized water d AC / DW solution (wt%): ammonium chloride in aqueous ammonium chloride solution (%) by weight e TSC (%): total solids in the catalyst extraction step

[0063] Example 19 In Example 19, a partially hydrogenated acrylonitrile-butadiene rubber solution (ZETPOL 2010 binder from Zeon Chemicals LP) was prepared using a heterogeneous catalyst (palladium on silica) in acetone. After completing the heterogeneous catalyst hydrogenation under high pressure hydrogen, most of the palladium was recovered by using silica-supported catalyst. After complete coagulation with excess water and drying, 42.30 ppm of residual palladium was present in the partially hydrogenated acrylonitrile-butadiene rubber. 1000 g of Zetpol 2010 binder, containing 42.30 ppm of residual palladium and 12.7% solids by weight, was placed in a 2.5-liter glass jar equipped with a stirrer. In a separate beaker, 0.20 g of ammonium chloride and 6.67 g of deionized water were mixed to produce a 2.9% ammonium chloride / water solution (AC / DW solution). 6.87 g of a 2.9% AC / DW solution was added to 12.7% Zetpol 2010 binder at room temperature under atmospheric conditions with air in the headspace (closed system), and then heated to 50°C. After heating the reactor to 50°C, the catalyst extraction step was carried out for 5 hours. At the end of the catalyst extraction step, the reactor was cooled to room temperature and an excess amount of water was added to produce a complete coagulation. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium in the dried HNBR polymer (Zetpol 2010) was 17.3 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 59.1%. The results are shown in Table 4.

[0064] Example 20 was prepared according to the same procedure as Example 19, except that nitrogen was used in the headspace instead of air. After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2010) was 24.1 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 43.0%. The results are shown in Table 4.

[0065] Example 21 was prepared according to the same procedure as Example 19, except that the TSC was 10.0% instead of 12.7%. 213 g of acetone was added to 788 g of 12.7% Zetpol 2010 binder to produce 1,000 g of 10.0% Zetpol 2010 binder. After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2010) was 17.0 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 59.8%. The results are shown in Table 4.

[0066] Example 22 was prepared according to the same procedure as Example 19, except that the TSC was 10.0% instead of 12.7%. 64 g of acetone was added to 256 g of 12.7% Zetpol 2010 binder to produce 300 g of 10.0% Zetpol 2010 binder. After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2010) was 16.2 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 61.7%. The results are shown in Table 4. [Table 4] a Zetpol 2010 bonding agent: Hydrogenated nitrile rubber-acetone solution with 12.7% solids, 36% acrylonitrile, and 95% hydrogenation (Zeon Chemicals LP) b AC: Ammonium chloride: NH4Cl - insoluble in acetone, soluble in water (26.7 wt% at room temperature) c DW: deionized water d AC / DW solution (wt%): ammonium chloride in aqueous ammonium chloride solution (%) by weight e TSC (%): total solids in the catalyst extraction step

[0067] Example 23 In Example 23, a fully hydrogenated acrylonitrile-acrylate-butadiene rubber solution (ZETPOL 4300 binder from Zeon Chemicals LP) was produced using a heterogeneous catalyst (palladium on silica) in acetone. After completing the heterogeneous catalyst hydrogenation under high pressure hydrogen, most of the palladium was recovered by using a silica-supported catalyst. After complete coagulation with excess water and drying, 140.30 ppm of residual palladium was present in the fully hydrogenated acrylonitrile-butadiene rubber. 984 g of Zetpol 4300 binder, having 140.30 ppm of residual palladium and 12.2% solids by weight, was placed in a 2.5-liter glass jar equipped with a stirrer. 516 g of acetone was added to produce an 8.0% TSC and mixed to produce a homogeneous solution. In a separate beaker, 0.30 g of ammonium chloride and 5.0 g of deionized water were mixed to produce a 5.7% ammonium chloride / water solution (AC / DW solution). 5.30 g of the 5.7% AC / DW solution was added to 8.0% Zetpol 4300 binder at room temperature under atmospheric conditions with air in the headspace (closed system), and then heated to 50°C. After heating the reactor to 50°C, the catalyst extraction step was carried out for 5 hours. At the end of the catalyst extraction step, the reactor was cooled to room temperature and an excess amount of water was added to produce a complete coagulation. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using inductively coupled plasma argon emission spectroscopy (ICP). The residual palladium in the dried HNBR polymer (Zetpol 4300) was 44.4 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 68.4%. The results are shown in Table 4.

[0068] Example 24 was prepared according to the same procedure as Example 23, except that the amounts of ammonium chloride and water were different. After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 4300) was 43.2 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 69.2%. The results are shown in Table 5. [Table 5] a Zetpol 4300 adhesive: Hydrogenated nitrile rubber-acetone solution with 13.1% solids, 17% acrylonitrile, and 99% hydrogenation (Zeon Chemicals LP) b AC: Ammonium chloride: NH4Cl - insoluble in acetone, soluble in water (26.7 wt% at room temperature) c DW: deionized water d AC / DW solution (wt%): ammonium chloride in aqueous ammonium chloride solution (%) by weight e TSC (%): total solids in the catalyst extraction step

[0069] Example 25 In Example 25, a fully hydrogenated acrylonitrile-butadiene rubber solution (ZETPOL 2000L binder from Zeon Chemicals LP) was produced using a heterogeneous catalyst (palladium on silica) in acetone. After completing the heterogeneous catalyst hydrogenation under high pressure hydrogen, most of the palladium was recovered by using silica-supported catalyst. After complete coagulation with excess water and drying, 124.60 ppm of residual palladium was present in the fully hydrogenated acrylonitrile-butadiene rubber. 1000 g of Zetpol 2000L binder, containing 124.60 ppm of residual palladium and 13.5% solids by weight, was placed in a 2.5-liter glass jar equipped with a stirrer. In a separate beaker, 0.20 g of ammonium chloride and 6.67 g of deionized water were mixed to produce a 2.9% ammonium chloride / water solution (AC / DW solution). 6.87 g of a 2.9% AC / DW solution was added to 13.5% Zetpol 2000L binder at room temperature, which was then heated to 60°C under nitrogen. After the reactor temperature was raised to 60°C, the catalyst extraction step was carried out for 5 hours. At the end of the catalyst extraction step, the reactor was cooled to room temperature, and an excess amount of water was added to produce a complete coagulation. The completely coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 55.9 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 55.1%. The results are shown in Table 6.

[0070] Example 26 was prepared according to the same procedure as Example 25, except that the temperature was 40°C under air. After the catalyst extraction step, excess water was added to coagulate the polymer. The completely coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 62.1 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 50.2%. The results are shown in Table 6.

[0071] Example 27 was prepared according to the same procedure as Example 25, except that the mixture was extracted under air instead of nitrogen. After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 41.6 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 66.6%. The results are shown in Table 6.

[0072] Example 28 was prepared according to the same procedure as Example 25, except that ferric chloride was used as the co-oxidant and the temperature was 50°C under air. 0.0097 g of ferric chloride hexahydrate was mixed with 6.87 g of a 2.9% aqueous AC / DW solution and then added to 1000 g of Zetpol 2000L binder. After the oxidation / catalytic extraction step at 50°C under air for 5 hours, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 47.2 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 62.1%. The results are shown in Table 6.

[0073] Examples 29-33 were prepared according to the same procedure as Example 25, except that the temperature was 50°C under nitrogen or 2 vol% oxygen using ferric chloride hexahydrate or cupric chloride dihydrate depending on the amount of co-oxidant. After the catalyst extraction step, excess water was added to coagulate the polymer. After the fully coagulated polymer was filtered and dried, the residual palladium was measured using inductively coupled plasma (ICP) argon emission spectroscopy. The residual palladium in the dried HNBR polymer (Zetpol 2000L) and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 6. [Table 6] aZetpol 2000L bonding agent: Hydrogenated nitrile rubber-acetone solution with 13.1% solids, 36% acrylonitrile, and 99% hydrogenation (Zeon Chemicals LP) b AC: Ammonium chloride: NH4Cl - insoluble in acetone, soluble in water (26.7 wt% at room temperature) c DW: deionized water d AC / DW solution (wt%): ammonium chloride in aqueous ammonium chloride solution (%) by weight e TSC (%): total solids in the catalyst extraction step

[0074] Example 34 In Example 34, a partially hydrogenated acrylonitrile-butadiene rubber solution (ZETPOL 2010 binder from Zeon Chemicals LP) was prepared using a heterogeneous catalyst (palladium on silica) in acetone. After completing the heterogeneous catalyst hydrogenation under high pressure hydrogen, most of the palladium was recovered by using silica-supported catalyst. After complete coagulation with excess water and drying, 42.30 ppm of residual palladium was present in the partially hydrogenated acrylonitrile-butadiene rubber. 1000 g of Zetpol 2010 binder, having 42.30 ppm of residual palladium and 12.7% solids by weight, was placed in a 2.5-liter glass jar equipped with a stirrer. In a separate beaker, 0.20 g of ammonium chloride and 6.67 g of deionized water were mixed to produce a 2.9% ammonium chloride / water solution (AC / DW solution). 6.87 g of a 2.9% AC / DW solution was added to 12.7% Zetpol 2010 binder at room temperature under nitrogen in the headspace (closed system), and then heated to 50°C. After heating the reactor to 50°C, the catalyst extraction step was carried out for 5 hours. At the end of the catalyst extraction step, the reactor was cooled to room temperature and an excess amount of water was added to produce a complete coagulation. The completely coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2010) was 24.1 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 43.0%. The results are shown in Table 7.

[0075] Example 35 was prepared according to the same procedure as Example 34, except that the headspace was under air conditions instead of nitrogen conditions. After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2010) was 17.3 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 59.1%. The results are shown in Table 7.

[0076] Examples 36-40 were prepared according to the same procedure as Example 34, except for the use of different co-oxidants, such as ferric chloride hexahydrate or cupric chloride dihydrate, under different headspace conditions. After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using inductively coupled plasma (ICP) argon emission spectroscopy. The residual palladium in the dried HNBR polymer (Zetpol 2010) and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 7. [Table 7] a Zetpol 2010 bonding agent: Hydrogenated nitrile rubber-acetone solution with 12.7% solids, 36% acrylonitrile, and 95% hydrogenation (Zeon Chemicals LP) b AC: Ammonium chloride: NH4Cl - insoluble in acetone, soluble in water (26.7 wt% at room temperature) c DW: deionized water d AC / DW solution (wt%): ammonium chloride in aqueous ammonium chloride solution (%) by weight e TSC (%): total solids in the catalyst extraction step

[0077] Examples 41 to 45 In Examples 41-45, two columns with a diameter of 1.02 cm and a length of 12 cm (L / D = 12) were packed with Lewatit Monoplus TP214 (thiourea-functional PS-DVB microporous ion-exchange resin, bead size = 0.55 ± 0.05 mm) manufactured by Lanxess and then connected to separate the palladium-ammonia complex and extract palladium with the thiourea functional groups located within the pores and surface of the ion-exchange resin beads. The temperature was maintained at 50°C to reduce the viscosity of the HNBR-acetone solution and improve the separation and extraction of the palladium complex. The flow rate was varied from 2.0 BV / hr to 0.5 BV / hr to maximize the separation / extraction efficiency of the palladium complexes using 4% Zetpol 2000L binder, 8% Zetpol 2000L binder, 10% Zetpol 2000L binder, and 8% Zetpol 4300 binder. Figure 2 shows the column conditions and connections to the Pd extraction section. The Pd extraction Zetpol binders used were 4% Zetpol 2000L from Example 5, 8% Zetpol 2000L from Example 8, 10% Zetpol 2000L from Example 11, and Zetpol 4300 binder from Example 23. After passing through the two columns, the polymer was coagulated by adding an excess amount of water. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 8 and Figure 5. The residual palladium in the HNBR polymer after Pd extraction was reduced by 19.7 ppm at 1 bed volume (BV) / hr for 1330 BV of 4% Zetpol 2000L binder, 17.6 ppm at 2 BV / hr for 160 BV of 4% Zetpol 2000L binder, 29.0 ppm at 0.5 BV / hr for 1078 BV of 8% Zetpol 2000L binder, 14.2 ppm at 0.5 BV / hr for 1000 BV of 10% Zetpol 2000L binder, and 32.0 ppm at 0.5 BV / hr for 875 BV of Zetpol 4300 binder.The Pd extraction efficiency after column passage was 88.7% at 1 BV / h for the 4% Zetpol 2000L binder, 87.5% at 2 BV / h for the 4% Zetpol 2000L binder, 91.5% at 0.5 BV / h for the 8% Zetpol 2000L binder, 89.0% at 0.5 BV / h for the 10% Zetpol 2000L binder, and 91.2% at 0.5 BV / h for the 8% Zetpol 4300 binder. The overall Pd extraction efficiency of the Zetpol binder without ion-exchange resin washing for 4443 BV was 89.9%. After separating the Pd-extracted TP214 resin from the column, the separated and extracted palladium in the resin was 26,283.6 ppm. The resin efficiency of the thiourea functional groups in the ion-exchange resin was 74.7%. [Table 8]

[0078] Example 46 In Example 46, a column with a diameter of 1.02 cm and a length of 29 cm (L / D = 28.8) was packed with Lewatit Monoplus TP214 (thiourea-functional PS-DVB microporous ion exchange resin, bead size = 0.55 ± 0.05 mm) manufactured by Lanxess and then connected to separate the palladium-ammonia complex and extract palladium through the thiourea functional groups located within the pores and surface of the ion exchange resin beads. The temperature was maintained at 40 °C to reduce the viscosity of the HNBR-acetone solution and improve the separation and extraction of the palladium complex. The flow rate was fixed at 0.5 BV / h to maximize the separation / extraction efficiency of the palladium complex with a 13.5% Zetpol 2000L binder. Figure 3 shows the column conditions and connection to the Pd extraction section. The Pd extraction Zetpol binder from Example 16 was used, 13.5% Zetpol 2000L. After passing through one column, excess water was added to coagulate the polymer. The completely coagulated polymer was filtered and dried, and then the residual palladium was measured using ICP (Inductively Coupled Plasma-Argon Emission Spectroscopy). The residual palladium in the dried HNBR polymer and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 9. The residual palladium in the HNBR polymer after Pd extraction was reduced by 25.8 ppm at 0.5 BV / hr for 30 bed volumes (BV) of 13.5% Zetpol 2000L binder. The Pd extraction efficiency after passing through the column was 88.0%. [Table 9]

[0079] Examples 47 to 53 In Examples 47-53, a column with a diameter of 1.02 cm and a length of 29 cm (L / D = 28.8) was packed with Lewatit Monoplus TP214 (thiourea-functional PS-DVB microporous ion exchange resin, bead size = 0.55 ± 0.05 mm) manufactured by Lanxess and then connected to separate the palladium-ammonia complex and extract palladium through the thiourea functional groups located within the pores and surface of the ion exchange resin beads. The temperature was maintained at 40 °C to reduce the viscosity of the HNBR-acetone solution and improve the separation and extraction of the palladium complex. The flow rate was fixed at 0.5 BV / h to maximize the separation / extraction efficiency of the palladium complex with 13.5% Zetpol 2000L binder. Figure 3 shows the column conditions and connection to the Pd extraction section. The Pd extraction Zetpol binder used was 13.5% Zetpol 2000L from Examples 27-33. After passing through one column, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 10. The residual palladium in the HNBR polymer after Pd extraction was reduced by 20.8-43.7 ppm at 0.5 BV / hr for 16-30 bed volumes (BV) of 13.5% Zetpol 2000L binder, depending on the oxidation / Pd extraction conditions. The Pd extraction efficiency after passing through the column was 80.9-93.8%. [Table 10]

[0080] Comparative Example 1 In Comparative Example 1, two columns with a diameter of 1.02 cm and a length of 12 cm (L / D = 12) were packed with MP-Thiourea-Fine (thiourea-functionalized PS-DVB microporous ion exchange resin, bead size = 100-200 mesh) manufactured by Supra Sciences and then used without the Pd extraction step. The temperature was maintained at 50 °C to reduce the viscosity of the HNBR-acetone solution and improve the separation and extraction of the palladium complex. The flow rate was fixed at 1.0 BV / h to maximize the separation / extraction efficiency of palladium for 4% Zetpol 2000L binder. Figure 2 shows the column conditions, excluding the Pd extraction step. After passing through the two columns, excess water was added to coagulate the polymer. The completely coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 11 and Figure 6. The residual palladium in the HNBR polymer without Pd extraction increased from 14.4 ppm to 87.3 ppm after 637 BV and remained at 88.0 ppm until 874 BV. The Pd extraction efficiency after passing through the column decreased from 91.4% to 47.3% depending on the time and the number of bed volumes (BV). [Table 11]

[0081] Comparative Example 2 and Example 54 In Comparative Example 2 and Example 54, two columns with a diameter of 1.02 cm and a length of 12 cm (L / D = 12) were used. The first column was packed with MP-Thiourea-Fine (thiourea-functionalized PS-DVB microporous ion-exchange resin, bead size = 100-200 mesh) manufactured by Supra Sciences, and the second column was packed with A501P (type I, macroporous polystyrene ion-exchange resin, bead size = 300-1200 μm) manufactured by Purolite. The temperature was maintained at 50°C to reduce the viscosity of the HNBR-acetone solution and improve the separation and extraction of palladium. The flow rate was fixed at 1.0 BV / h to maximize the separation / extraction efficiency of palladium with 4% Zetpol 2000L binder. The column conditions, excluding the Pd extraction step for Comparative Example 2 and the Pd extraction step (Example 5) for Example 54, are shown in Figure 2. In Comparative Example 2, 4% Zetpol 2000L binder was passed through the column up to 341 BV, followed by 4% Pd-extracted Zetpol 2000L binder (Example 5) from 342 BV to 388 BV. After passing through the two columns, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 12 and Figure 6. The residual palladium in the HNBR polymer without Pd extraction (Comparative Example 2) increased from 62.9 ppm to 126.0 ppm after 314 BV. The residual palladium in the HNBR polymer after the Pd extraction step (Example 54) suddenly decreased to 33.7 ppm at 21 BV and then continuously decreased to 28.8 ppm at 26 BV. The Pd extraction efficiency after passing through the column changed from 62.3% to 24.5% for 314 BV of Comparative Example 2, and then changed from 79.8% to 82.7% for 47 BV of Example 54. [Table 12]

[0082] Example 55 In Example 55, two columns with a diameter of 1.02 cm and a length of 12 cm (L / D = 12) were used. The first column was packed with MP-Thiourea-Fine (thiourea-functionalized PS-DVB microporous ion-exchange resin, bead size = 100-200 mesh) manufactured by Supra Sciences, and the second column was packed with A501P (type I, macroporous polystyrene ion-exchange resin, bead size = 300-1200 μm) manufactured by Purolite. The temperature was maintained at 50°C to reduce the viscosity of the HNBR-acetone solution and improve the separation and extraction of the palladium complex. The flow rate was fixed at 1.0 BV / h to maximize the separation / extraction efficiency of the palladium complex with 4% Zetpol 2000L binder. Figure 2 shows the column conditions and the connection to the Pd extraction section. The Pd-extracted Zetpol binder used in Example 5 was 4% Zetpol 2000L. After passing through two columns, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 13 and Figure 6. The residual palladium in the HNBR polymer after Pd extraction slightly decreased from 20.0 ppm to 16.9 ppm with 4% Zetpol 2000L binder 868BV. The Pd extraction efficiency after passing through the columns ranged from 88.0% to 89.9% with 4% Pd-extracted Zetpol 2000L binder 868BV, with no change in Pd extraction efficiency depending on the BV. [Table 13]

[0083] Example 56 In Example 56, a fully hydrogenated acrylonitrile-butadiene rubber solution (ZETPOL 2000L binder from Zeon Chemicals LP) was produced using a heterogeneous catalyst (palladium on silica) in acetone. After completing the heterogeneous catalyst hydrogenation under high pressure hydrogen, most of the palladium was recovered by using a silica-supported catalyst. After complete coagulation with excess water and drying, 162.40 ppm of residual palladium was present in the fully hydrogenated acrylonitrile-butadiene rubber. 1000 g of Zetpol 2000L binder, having 162.40 ppm of residual palladium and 13.5% solids by weight, was placed in a 2.5 liter glass jar equipped with a stirrer. In a separate beaker, 0.20 g of ammonium chloride, 6.59 g of deionized water, and 0.078 g of 3% aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to palladium in rubber = 0.34) were mixed to produce 6.87 g of hydrogen peroxide / ammonium chloride / water solution (HP / AC / DW solution). The 6.87 g of HP / AC / DW solution was added to 13.5% Zetpol 2000L binder at room temperature, which was then heated to 50°C under nitrogen. After the reactor temperature reached 50°C, the oxidation / catalyst extraction step was carried out for 5 hours. At the end of the oxidation / catalyst extraction step, the reactor was cooled to room temperature and excess water was added to produce a complete coagulation. The fully coagulated polymer was filtered and dried, after which the residual palladium was measured using inductively coupled plasma (ICP) argon emission spectroscopy. The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 71.7 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 55.8%. The results are shown in Table 14.

[0084] Example 57 was prepared according to the same procedure as Example 56, except that the amount of aqueous hydrogen peroxide solution was different. The amount of 0.3% aqueous hydrogen peroxide solution was 0.39 g instead of 0.34 g (molar ratio of hydrogen peroxide to palladium in rubber = 1.7). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 52.2 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 67.9%. The results are shown in Table 14.

[0085] Example 58 was prepared according to the same procedure as Example 56, except that the amount of aqueous hydrogen peroxide solution was different. The amount of 0.3% aqueous hydrogen peroxide solution was 0.78 g instead of 0.34 g (molar ratio of hydrogen peroxide to palladium in rubber = 3.4). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 49.0 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 69.8%. The results are shown in Table 14.

[0086] Example 59 was prepared according to the same procedure as Example 56, except that the amount of aqueous hydrogen peroxide solution was different. The amount of 0.3% aqueous hydrogen peroxide solution was 1.16 g instead of 0.34 g (molar ratio of hydrogen peroxide to palladium in rubber = 5.1). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 51.5 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 68.3%. The results are shown in Table 14.

[0087] Example 60 was prepared according to the same procedure as Example 56, except that the amount of aqueous hydrogen peroxide solution was different. The amount of 0.3% aqueous hydrogen peroxide solution was 1.55 g instead of 0.34 g (molar ratio of hydrogen peroxide to palladium in rubber = 6.8). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 48.8 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 70.0%. The results are shown in Table 14.

[0088] Example 61 was prepared according to the same procedure as Example 56, except that the amount of aqueous hydrogen peroxide solution was different. The amount of 0.3% aqueous hydrogen peroxide solution was 1.94 g instead of 0.34 g (molar ratio of hydrogen peroxide to palladium in rubber = 8.4). After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 42.5 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 73.8%. The results are shown in Table 14.

[0089] Example 62 was prepared according to the same procedure as Example 56, except for the total solids content of the Zetpol 2000L binder and the amount of aqueous hydrogen peroxide solution. 741 g of Zetpol 2000L binder, having 162.4 ppm residual palladium and 13.5% solids by weight, was placed in a 2.5-liter glass jar equipped with a stirrer. 259 g of acetone was added to the Zetpol 2000L binder and stirred until homogeneous. The total solids content was 10 wt%. The amount of 0.3% aqueous hydrogen peroxide solution was 0.78 g (hydrogen peroxide / palladium molar ratio in rubber = 4.6) instead of 0.34 g. After the catalyst extraction step, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, after which the residual palladium was measured using ICP (inductively coupled plasma argon emission spectroscopy). The residual palladium in the dried HNBR polymer (Zetpol 2000L) was 27.5 ppm, and the palladium extraction efficiency of the dried HNBR polymer was 83.1%. The results are shown in Table 14. [Table 14] a Zetpol 2000L bonding agent: Hydrogenated nitrile rubber-acetone solution with 13.1% solids, 36% acrylonitrile, and 99% hydrogenation (Zeon Chemicals LP) b AC: Ammonium chloride: NH4Cl - insoluble in acetone, soluble in water (26.7 wt% at room temperature) c DW: deionized water d HP solution: 3% by weight hydrogen peroxide in aqueous solution e HP / Pd: Palladium-based hydrogen peroxide molar ratio f HP / AC / DW solution: A solution of hydrogen peroxide, ammonium chloride, and deionized water. g TSC (%): total solids in the catalyst extraction step

[0090] Examples 63 to 69 In Examples 63-69, a column with a diameter of 1.02 cm and a length of 29 cm (L / D = 28.8) was packed with Lewatit Monoplus TP214 (thiourea-functional PS-DVB microporous ion exchange resin, bead size = 0.55 ± 0.05 mm) manufactured by Lanxess, and then connected to separate the palladium-ammonia complex and extract palladium via the thiourea functional groups located within the pores and surface of the ion exchange resin beads. The temperature was maintained at 40 °C to reduce the viscosity of the HNBR-acetone solution and improve the separation and extraction of the palladium complex. The flow rate was fixed at 0.5 BV / h to maximize the separation / extraction efficiency of the palladium complex for 13.5% and 10% Zetpol 2000L binders. The column conditions and connection to the Pd extraction section are shown in Figure 3. The Pd extraction Zetpol binders used were the 13.5% and 10% Zetpol 2000L binders from Examples 56-62. After passing through one column, excess water was added to coagulate the polymer. The fully coagulated polymer was filtered and dried, and the residual palladium was measured using inductively coupled plasma (ICP) spectroscopy. The residual palladium in the dried HNBR polymer and the palladium extraction efficiency of the dried HNBR polymer are shown in Table 15. Depending on the oxidation / Pd extraction conditions, the residual palladium in the HNBR polymer after Pd extraction was reduced to 9.2-17.6 ppm at 0.5 BV / hr with 9-15 bed volumes (BV) of 13.5% Zetpol 2000L binder, and to 11.2 ppm at 0.5 BV / hr with 14 bed volumes of 10% Zetpol 2000L binder. The Pd extraction efficiency after passing through the column was 89.2-94.3%. [Table 15]

[0091] Example 70 Partially hydrogenated acrylonitrile-butadiene rubber (HNBR) solutions were produced using a homogeneous catalyst (palladium acetate) in acetone, reduced at 15°C for 1 hour, and then hydrogenated at 55°C for 6 hours under a hydrogen pressure of 4950.44 kPa (718 psi). The hydrogenation degree of the HNBR was 87% at 10% TSC and 90% at 5% TSC. After complete coagulation with excess water and drying, the residual palladium in the partially hydrogenated acrylonitrile-butadiene rubber was 480.9 ppm at 10% TSC and 575.7 ppm at 5% TSC. 252 g of 10% solids by weight of HNBR binder with 480.9 ppm residual palladium was placed in a 1-liter glass jar equipped with a stirrer. In a separate beaker, 0.025 g of ammonium chloride, 0.87 g of deionized water, and 0.40 g of 3% aqueous hydrogen peroxide (molar ratio of hydrogen peroxide to palladium in rubber = 3.10 for 10% TSC and 5.18 for 5% TSC) were mixed to produce 1.30 g of hydrogen peroxide / ammonium chloride / water solution (HP / AC / DW solution). The 1.30 g of HP / AC / DW solution was added to the HNBR binder at room temperature, which was then heated to 55°C under nitrogen. After the reactor temperature reached 55°C, the oxidation / catalyst extraction step was carried out for 6 hours. At the end of the oxidation / catalyst extraction step, the reactor was cooled to room temperature and an excess amount of water was added to produce a complete coagulation. The fully coagulated polymer was filtered and dried, after which the residual palladium was measured using inductively coupled plasma (ICP) argon emission spectroscopy. The residual palladium in the dried HNBR polymer was 130.8 ppm at 10% TSC and 53.1 ppm at 5% TSC, and the palladium extraction efficiency in the dried HNBR polymer was 72.8% at 10% TSC and 90.8% at 5% TSC.

[0092] A column with a diameter of 1.02 cm and a length of 29 cm (L / D = 28.8) was packed with Lewatit Monoplus TP214 (thiourea-functional PS-DVB microporous ion exchange resin, bead size = 0.55 ± 0.05 mm) manufactured by Lanxess, and then connected to separate the palladium-ammonia complex. Palladium was extracted via the thiourea functional groups located within the pores and surface of the ion exchange resin beads. The temperature was maintained at 40 °C to reduce the viscosity of the HNBR-acetone solution and improve the separation and extraction of the palladium complex. The flow rate was fixed at 0.5 BV / h to maximize the separation / extraction efficiency of the palladium complex for the 10% HNBR binder. Figure 3 shows the column conditions and the connection to the Pd extraction section. After passing through one column, excess water was added to coagulate the polymer. After filtering and drying the fully coagulated polymer, residual palladium was measured using inductively coupled plasma (ICP) argon emission spectroscopy. Residual palladium in the HNBR polymer after Pd extraction was reduced to 40.6-45.4 ppm at 0.5 BV / hr for 8 bed volumes (BV) of 10% HNBR binder and to 19.3-22.9 ppm at 0.5 BV / hr for 8 bed volumes of 5% HNBR binder. The Pd extraction efficiency after column passage was 90.6-91.6% at 10% TSC and 96.0-96.6% at 5% TSC.

[0093] [Embodiment] (1) Hydrogenated nitrile rubber (HNBR), a) hydrogenating nitrile rubber to HNBR by heterogeneous or homogeneous catalysis; b) mixing the hydrogenation product with an aqueous ammonium salt solution; c) passing the mixture through a column packed with a functionalized ion exchange resin; and The resulting hydrogenated nitrile rubber (HNBR) has a residual heterogeneous or homogeneous catalyst content of less than 50 ppm by dry weight of said HNBR. (2) The HNBR according to embodiment 1, wherein the heterogeneous or homogeneous catalyst is a heterogeneous catalyst comprising a metal selected from platinum, palladium, ruthenium, or nickel. 3. The HNBR of claim 1, wherein the heterogeneous catalyst comprises palladium. (4) The HNBR of claim 1, wherein the HNBR has a saturation level (iodine value) of less than 45 mg / 100 mg. (5) The ammonium salt is [ka] and 2. The HNBR of embodiment 1, wherein R1, R2, R3, and R4 are independently selected from hydrogen or alkyl, and X is selected from chloride, bromide, iodide, or acetate.

[0094] (6) The HNBR of embodiment 5, wherein the ammonium salt is selected from ammonium chloride, ammonium bromide, ammonium iodide, ammonium acetate, and combinations thereof. (7) The HNBR of embodiment 1, further comprising adding an oxidizing agent selected from air, oxygen gas, iron(III) chloride, iodine, hydrogen peroxide, copper(II) chloride, copper(II) acetate, benzoquinone, tert-butyl hydroperoxide, manganese dioxide, nitric acid, sodium chlorate, and combinations thereof. (8) The HNBR of embodiment 1, wherein the functional ion exchange resin comprises functional groups selected from thiourea, thiouronium, thiol, amine, diamine, triamine, TMT, dithiocarbamate, carbodithioate, and combinations thereof. (9) The HNBR according to embodiment 1, wherein the functionalized ion exchange resin has an average particle size ranging from about 0.07 mm to about 1.50 mm. 10. The HNBR of claim 1, wherein the nitrile rubber is selected from acrylonitrile-butadiene copolymers, acrylonitrile-acrylate-butadiene terpolymers, and combinations thereof.

[0095] (11) The HNBR of claim 1, wherein the dry weight of the resulting HNBR has less than 50 ppm of residual heterogeneous or homogeneous catalyst, and the HNBR has a saturation level (iodine number) of less than 45 mg / 100 mg. (12) A process for recovering residual heterogeneous or homogeneous catalyst from a hydrogenated nitrile rubber solution, comprising: (1) a catalyst extraction step with ammonium salt and water, optionally including an oxidation step; (2) A separation / column recovery step using a column packed with a functional ion exchange resin for catalyst recovery of the extracted catalyst; The process includes: 13. The process of claim 12, wherein the residual heterogeneous or homogeneous catalyst in the hydrogenated nitrile rubber comprises a metal selected from palladium, platinum, rhodium, and ruthenium. (14) The process of claim 12, wherein the hydrogenated nitrile rubber solution in the extraction step with ammonium salt and water has about 1% to about 20% by weight of hydrogenated nitrile rubber. 15. The process of claim 12, wherein the hydrogenated nitrile rubber solution in the extraction step with ammonium salt and water has about 4% to about 15% by weight of hydrogenated nitrile rubber.

[0096] 16. The process of claim 12, wherein the oxidizing agent for the oxidation step prior to and / or during the catalyst extraction step is oxygen mixed with an inert gas. 17. The process of claim 12, wherein the oxidizing agent for oxidizing the catalyst prior to and / or during the catalyst extraction step is selected from iron(III) chloride, iodine, hydrogen peroxide, copper(II) chloride, copper(II) acetate, benzoquinone, tert-butyl hydroperoxide, and combinations thereof. (18) The ammonium salt in the catalyst extraction step is [ka] and 13. The process of embodiment 12, wherein R1, R2, R3, and R4 are independently selected from hydrogen and alkyl, and X is selected from chloride, bromide, iodide, and acetate. 19. The process of claim 18, wherein the ammonium salt is selected from ammonium chloride, ammonium bromide, ammonium iodide, ammonium acetate, and combinations thereof. 20. The process of claim 12, wherein the amount of ammonium salt in the catalyst extraction step is less than 2% by weight of the hydrogenated nitrile rubber.

[0097] 21. The process of claim 12, wherein the amount of water in the extraction step is less than 5% by weight of the hydrogenated nitrile rubber solution. 22. The process of claim 12, wherein the functional groups in the functionalized ion exchange resin for packing the column are selected from thiourea, thiouronium, thiol, amine, diamine, triamine, TMT, dithiocarbamate, carbodithioate, and combinations thereof. 23. The process of claim 12, wherein the average particle size of the functionalized ion exchange resin ranges from about 0.07 mm to about 1.50 mm. 24. The process of claim 12, wherein the nitrile rubber is selected from acrylonitrile-butadiene copolymers, acrylonitrile-acrylate-butadiene terpolymers, and combinations thereof.

Claims

1. 1. A process for producing hydrogenated nitrile rubber (HNBR), said process comprising: a) heterogeneously or homogeneously catalyzed hydrogenation of nitrile rubber to HNBR as a hydrogenated product; b) mixing the hydrogenation product with an aqueous solution of an ammonium salt to form a mixture; c) passing the mixture through a column packed with a functionalized ion exchange resin; Including, The dry weight of the resulting HNBR has less than 50 ppm of residual heterogeneous or homogeneous catalyst.

2. 10. The method of claim 1, wherein the heterogeneous or homogeneous catalyst is a heterogeneous catalyst comprising a metal selected from platinum, palladium, ruthenium, or nickel.

3. The method of claim 1 , wherein the heterogeneous catalyst comprises palladium.

4. 2. The method of claim 1, wherein the saturation level (iodine value) of the HNBR is less than 45 mg / 100 mg.

5. The ammonium salt is 【Chemical 1】 and In the formula, R １ , R ２ , R ３ , and R ４ 10. The method of claim 1, wherein X is independently selected from hydrogen or alkyl, and X is selected from chloride, bromide, iodide, or acetate.

6. 6. The method of claim 5, wherein the ammonium salt is selected from ammonium chloride, ammonium bromide, ammonium iodide, ammonium acetate, and combinations thereof.

7. 10. The method of claim 1, further comprising adding an oxidizing agent selected from air, oxygen gas, iron (III) chloride, iodine, hydrogen peroxide, copper (II) chloride, copper (II) acetate, benzoquinone, tert-butyl hydroperoxide, manganese dioxide, nitric acid, sodium chlorate, and combinations thereof.

8. 10. The method of claim 1, wherein the average particle size of the functionalized ion exchange resin ranges from 0.07 mm to 1.50 mm.

9. 10. The method of claim 1, wherein the nitrile rubber is selected from acrylonitrile-butadiene copolymers, acrylonitrile-acrylate-butadiene terpolymers, and combinations thereof.

10. The method described in claim 1, wherein the dry weight of the obtained HNBR has a residual heterogeneous or homogeneous catalyst of less than 50 ppm and the saturation level (iodine value) of the HNBR is less than 45 mg / 100 mg.

11. 1. A process for recovering residual heterogeneous or homogeneous catalyst from a hydrogenated nitrile rubber solution, comprising: (1) a catalytic extraction step with ammonium salt and water, optionally including an oxidation step; (2) a separation / column recovery step using a column packed with a functionalized ion exchange resin for catalyst recovery of the extracted catalyst; The process includes:

12. 12. The process of claim 11, wherein the residual heterogeneous or homogeneous catalyst in the hydrogenated nitrile rubber comprises a metal selected from palladium, platinum, rhodium, and ruthenium.

13. 12. The process of claim 11, wherein the hydrogenated nitrile rubber solution in the extraction step with ammonium salt and water has 1% to 20% by weight of hydrogenated nitrile rubber.

14. 12. The process of claim 11, wherein the hydrogenated nitrile rubber solution in the extraction step with ammonium salt and water has 4% to 15% by weight of hydrogenated nitrile rubber.

15. 12. The process of claim 11, wherein the oxidizing agent for the oxidation step prior to and / or during the catalyst extraction step is oxygen mixed with an inert gas.

16. 12. The process of claim 11, wherein an oxidizing agent for oxidation of the catalyst prior to and / or during the catalyst extraction step is selected from iron(III) chloride, iodine, hydrogen peroxide, copper(II) chloride, copper(II) acetate, benzoquinone, tert-butyl hydroperoxide, and combinations thereof.

17. The ammonium salt in the catalyst extraction step is 【Chemistry 2】 and In the formula, R １ , R ２ , R ３ , and R ４ 12. The process of claim 11, wherein is independently selected from hydrogen and alkyl, and X is selected from chloride, bromide, iodide, and acetate.

18. 18. The process of claim 17, wherein the ammonium salt is selected from ammonium chloride, ammonium bromide, ammonium iodide, ammonium acetate, and combinations thereof.

19. 12. The process of claim 11, wherein the amount of said ammonium salt in said catalyst extraction step is less than 2% by weight of said hydrogenated nitrile rubber.

20. 12. The process of claim 11, wherein the amount of water in the catalyst extraction step is less than 5% by weight of the hydrogenated nitrile rubber solution.

21. 12. The process of claim 11, wherein the average particle size of the functionalized ion exchange resin ranges from 0.07 mm to 1.50 mm.

22. The process of claim 11, wherein the nitrile rubber is selected from acrylonitrile-butadiene copolymers, acrylonitrile-acrylate-butadiene terpolymers, and combinations thereof.

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