Method for preparing hydrogenated butadiene-acrylonitrile rubber latex through emulsion polymerization and hydrogenation of ruthenium metal catalyst

Abstract

The invention belongs to the field of synthesis of special rubber latex, and particularly relates to a method for preparing hydrogenated butadiene-acrylonitrile rubber latex through emulsion polymerization and hydrogenation of a ruthenium metal catalyst, which comprises the following steps: emulsifying a comonomer and a diene monomer in the presence of a surfactant, a hydrogenation catalyst, other auxiliaries and water; adding an initiator, carrying out polymerization reaction at a polymerization temperature, adding a terminator, raising the temperature, and carrying out hydrogenation reaction under high-pressure hydrogen to obtain the hydrogenated butadiene-acrylonitrile rubber latex. According to the method disclosed by the invention, the processes of post-treatment of the NBR latex, deoxygenation before hydrogenation and removal of hydrogenation catalyst addition are reduced, the pollution to the environment after volatilization of unreacted monomers is prevented, and the performance of the flocculated latex material is excellent.

Description

Technical Field

[0001] The present invention belongs to the field of synthesis of special rubber latex, and particularly relates to a method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst, specifically to a method for preparing HNBR latex by first polymerizing a ruthenium-based (or osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, iridium, palladium, gold, silver, nickel, and cobalt or osmium or palladium or iridium) metal catalyst and at least one surfactant at low temperature, adding a terminator, and then directly raising the temperature and introducing hydrogen for hydrogenation to polymerize diene monomers and copolymerizable monomers. Background Art

[0002] Hydrogenation of unsaturated polymers is an important process in polymer chemical modification. It not only provides a targeted method for improving the mechanical, chemical, physical, and thermal properties of unsaturated polymers, but also provides a convenient way to synthesize polymers with desired microstructures and unique stereochemical properties.

[0003] Selective hydrogenation of unsaturated olefin groups in nitrile rubber (NBR) is a commercially successful hydrogenation process in the industry. Hydrogenated nitrile rubber (HNBR) retains the elastomeric properties of NBR, has excellent resistance to thermal oxidative degradation, and has significant improvements in mechanical properties such as tensile strength, elongation at break, abrasion resistance, and hardness. Due to these superior physicochemical properties, HNBR has important applications in the fields of automobiles, oil wells, aerospace, and various fields with high performance requirements. Since 1977, hydrogenated nitrile rubber has become the most important member of hydrogenated elastomers and is the main force in the application of high-performance elastomers.

[0004] The traditional process for preparing HNBR is divided into two steps: 1. Emulsion copolymerization of acrylonitrile-butadiene to prepare NBR latex; 2. Hydrogenation of NBR to prepare HNBR.

[0005] Preparing NBR latex usually involves reacting acrylonitrile-butadiene emulsion monomers, initiators, surfactants, and other additives in an aqueous medium to produce NBR. This method has significant defects in the process. The prepared NBR latex contains a large amount of unreacted monomers, resulting in a high content of VOC (volatile organic compounds) in the product, which is harmful to the environment. At the same time, the content of residual monomers also affects the subsequent hydrogenation process.

[0006] Currently, the processes for preparing HNBR using NBR latex are divided into catalytic hydrogenation and non-catalytic hydrogenation. Among them, catalytic hydrogenation is further divided into emulsion hydrogenation and solution hydrogenation, and non-catalytic hydrogenation refers to the hydrazine hydrate hydrogenation method.

[0007] (1) The hydrazine hydrate hydrogenation method is a process where NBR latex directly forms HNBR latex under the action of hydrazine hydrate, oxidants such as oxygen or hydrogen peroxide, and metal ion initiators such as copper and iron. The main advantage of the hydrazine hydrate hydrogenation method is that the hydrogenation reaction is carried out under normal pressure, with mild reaction conditions and simple equipment. The disadvantage is that cross-linking side reactions are likely to occur on the unhydrogenated double bonds. If the cross-linking is severe, it will lead to difficulties in plasticizing, so there is currently no industrial production.

[0008] (2) NBR solution hydrogenation method: The NBR solution hydrogenation method is currently the main method for industrial production of HNBR. During operation, the NBR latex needs to be first flocculated into solid rubber, then crushed and dissolved in a large amount of organic solvents. The organic solvents mainly include cyclohexanone, xylene, chloroform, etc. This not only causes environmental pollution but also has a long reaction time, requires a relatively high reaction temperature, consumes a large amount of energy, and incurs high raw material and time costs.

[0009] According to the different catalysts, the NBR solution hydrogenation method is divided into heterogeneous solution hydrogenation method and homogeneous solution hydrogenation method. The catalyst for the homogeneous solution hydrogenation method includes an inorganic carrier and a Group VIII metal coated on the inorganic carrier. The catalyst for the heterogeneous solution hydrogenation method includes an inorganic carrier and a rhodium-based, ruthenium-based, and / or palladium-based metal coated on the inorganic carrier. The inorganic carrier includes alumina, silica, activated carbon, carbon black, alkaline earth metal carbonates, etc. After the heterogeneous solution hydrogenation reaction is completed, the hydrogenated product and the catalyst are usually separated directly by filtration or centrifugation. For example, in the 1980s, Zeon Corporation in Japan was the first to use a supported catalyst for the NBR hydrogenation reaction. The heterogeneous carrier catalyst it used was a palladium / carbon catalyst with carbon as the carrier. This catalyst has high selectivity, and the highest hydrogenation rate can reach 95.6%. However, in the hydrogenation reaction, due to the easy adsorption of rubber molecules by carbon, it leads to agglomeration and caking, thus affecting the product performance.

[0010] In addition, most of the active components of the supported catalyst prepared by the traditional method are distributed inside the pores. The NBR molecules must diffuse into the pores to carry out the hydrogenation reaction. To increase the reaction rate, the reaction must be carried out under the conditions of high-pressure stirring. This not only results in a long reaction time and high process energy consumption but also easily leads to deterioration of the polymer performance.

[0011] (3) Emulsion hydrogenation method: To avoid the cumbersome hydrogenation steps in solution hydrogenation and the use of a large amount of organic solvents, the emulsion hydrogenation method was proposed. The emulsion hydrogenation method is a process where the catalyst is directly added to the NBR emulsion, and then the HNBR emulsion is prepared through a hydrogen reduction reaction.

[0012] Compared with the catalytic hydrogenation method in organic solution, the catalytic hydrogenation of NBR emulsion based on aqueous phase has very obvious advantages: the reaction conditions are milder, the reaction process is less, organic solvents are not required, which can save energy and reduce pollution. The emulsion catalytic hydrogenation method greatly reduces the preparation cost of HNBR, and the hydrogenated product can be directly applied to the industries demanding HNBR emulsion. In this field, the research group led by Professor Garry L. Rempel has carried out a lot of work and achieved quite excellent research results. However, due to factors such as fewer NBR latex grades that can achieve emulsion hydrogenation with existing polymerization technologies, and the need to further introduce a large amount of surfactants during the hydrogenation process, the emulsion catalytic hydrogenation technology has not yet met the requirements of industrial production.

[0013] In summary, the existing methods for producing HNBR are all carried out in two steps, with defects such as longer reaction time, higher cost, greater energy consumption, and environmental pollution, and the technology for producing HNBR needs to be further improved. Summary of the Invention

[0014] To improve the deficiencies of the existing technology, the present invention provides a method for preparing hydrogenated nitrile rubber latex by ruthenium-based metal catalyst emulsion polymerization hydrogenation, which can reduce the reaction cost and energy consumption.

[0015] In the first aspect, the present invention provides a method for preparing hydrogenated nitrile rubber latex by ruthenium-based metal catalyst emulsion polymerization hydrogenation, comprising the following steps:

[0016] Emulsify the comonomer and diene monomer in the presence of a surfactant, hydrogenation catalyst, other additives and water, add an initiator and carry out a polymerization reaction at the polymerization temperature, add a terminator, then raise the temperature and carry out a hydrogenation reaction under high-pressure hydrogen to obtain hydrogenated nitrile rubber latex.

[0017] According to an embodiment of the present invention, the method specifically comprises the following steps:

[0018] S1. Mix the surfactant, comonomer, hydrogenation catalyst, diene monomer, additives that may or may not be added, and water, and emulsify at room temperature;

[0019] S2. Add an initiator and carry out a polymerization reaction at the polymerization temperature, and add a terminator after the polymerization is completed;

[0020] S3. Raise the temperature, introduce high-pressure hydrogen and carry out a hydrogenation reaction to obtain hydrogenated nitrile rubber latex.

[0021] According to an embodiment of the present invention, the comonomer is selected from at least one of acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, propyl acrylate, butyl acrylate, propyl methacrylate, butyl methacrylate, fumaric acid, maleic acid, acrylic acid and methacrylic acid, which are unsaturated carboxylic acids.

[0022] According to an embodiment of the present invention, the diene monomer is a conjugated monomer, and the conjugated monomer is selected from C 4 -C 6 at least one of conjugated dienes. Preferably, the diene monomer is selected from at least one of 1,3-butadiene, isoprene, 1-methylbutadiene, 2,3-dimethylbutadiene, piperylene, and chloroprene.

[0023] According to an embodiment of the present invention, the surfactant is selected from fatty acids, alkyl sulfates, sulfuric acid monoesters of ethoxylated alkanols, ethoxylated alkylphenols, alkali metal salts or ammonium salts of alkyl sulfonic acids and alkyl aryl sulfonic acids, ethoxylated monoalkylphenols, dialkylphenols and trialkylphenols, ethoxylated fatty alcohols, alkali metal salts or ammonium salts of mono-C 4 to C 24 alkyl derivatives of bis(benzenesulfonic acid) ether, alkali metal salts or ammonium salts of di-C 4 to C 24 alkyl derivatives of bis(benzenesulfonic acid) ether, alkyl aryl sulfonic acids, alkyl sulfonic acids, alkali metal salts or ammonium salts of sulfuric acid monoesters of ethoxylated alkanols, and at least one of gemini surfactants.

[0024] According to an embodiment of the present invention, the polymerization initiator is at least one free radical initiator, including oil-soluble initiators: azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, etc.; water-soluble initiators: potassium persulfate, azobis(isobutyramidine) hydrochloride, azobis(2-methylimidazoline) hydrochloride, ammonium persulfate, etc.

[0025] According to an embodiment of the present invention, the hydrogenation catalyst is selected from noble metal complex catalysts, and the noble metal is selected from at least one of ruthenium, osmium, palladium, iridium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, nickel or cobalt. Preferably, the hydrogenation catalyst is selected from at least one of ruthenium complexes, osmium complexes, palladium complexes, and iridium complexes.

[0026] According to an embodiment of the present invention, the hydrogenation catalyst has a structure shown in formula (A):

[0027]

[0028] wherein, M is selected from ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, iridium, palladium, silver, nickel, and cobalt; preferably, M is selected from ruthenium, osmium, palladium, and iridium;

[0029] L is a ligand; preferably an uncharged electron donor;

[0030] Y is a radical of O, S, Se, N-R1 or P-R1 or AsR or SbR;

[0031] X 1 and X 2 are each independently selected from anionic ligands;

[0032] R 1 are each independently selected from hydrogen, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, an alkylamino group, an alkylthio group, an arylthio group, an alkyl-alkoxysilyl group, an alkyl-aryloxysilyl group, an alkyl-cycloalkoxysilyl group, an arylammonium group, an alkyl sulfonate, an aryl sulfonate, an alkyl phosphonate, an aryl phosphonate, a carboxylate, an alkylsulfonyl group or an alkylsulfinyl group. Optionally, each of the above R1 may be selectively substituted by one or more alkyl groups, halogen groups, alkoxy groups, aryl groups or heteroaryl groups;

[0033] R 2 and R 3 and R 4 and R 5 are each independently selected from a hydrogen group, an organic radical or an inorganic radical;

[0034] R 6 is selected from H, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0035] According to an embodiment of the present invention, the hydrogenation catalyst has a structure represented by formula (IV), formula (V) or formula (VI):

[0036]

[0037] In a second aspect, the present invention provides a hydrogenated nitrile rubber latex prepared by the above method. The hydrogenation degree of the hydrogenated nitrile rubber latex is 50-100%, the content of the comonomer is 10-60 mol%, and the conversion rate is 60-80 wt%.

[0038] Beneficial effects

[0039] 1) The hydrogenated nitrile rubber latex prepared by emulsion polymerization hydrogenation of the ruthenium-based metal catalyst of the present invention has stable nanoparticle micelle properties in the latex, good uniformity of the size of the nanomicelles, a small particle size distribution range, is not easily demulsified, the preparation method is simple, the operation is convenient, and it is easy to realize industrialization; during the synthesis process, a hydrogenation catalyst (ruthenium-based metal catalyst) is added before polymerization, and hydrogen is directly introduced for hydrogenation reaction after polymerization at a lower temperature, with high hydrogenation efficiency and high hydrogenation degree; the conversion rate of the monomer is extremely high; the post-treatment of the NBR latex and the processes of deoxygenation before hydrogenation and removal of the added hydrogenation catalyst are reduced, preventing environmental pollution caused by the volatilization of unreacted monomers, and the properties of the flocculated rubber compound are excellent.

[0040] 2) The preparation method of the present invention has a high hydrogenation degree while achieving a conversion rate as high as 80%, and the hydrogenation degree is greater than 99%, which is significantly higher than the existing preparation methods. Description of the Drawings

[0041] Figure 1 1H NMR spectrum of the HNBR latex prepared in Example 9. Detailed Description of the Invention

[0042] [Method for Preparing Hydrogenated Nitrile-Butadiene Rubber Latex by Emulsion Polymerization with Ruthenium-Based Metal Catalyst]

[0043] A method for preparing hydrogenated nitrile-butadiene rubber latex by emulsion polymerization with a ruthenium-based metal catalyst includes the following steps:

[0044] Emulsify the comonomer and the diene monomer in the presence of a surfactant, a hydrogenation catalyst, other additives and water, add an initiator and carry out a polymerization reaction at the polymerization temperature, add a terminator, then raise the temperature and carry out a hydrogenation reaction under high-pressure hydrogen to obtain the hydrogenated nitrile-butadiene rubber latex.

[0045] According to the embodiment of the present invention, the method specifically includes the following steps:

[0046] S1. Mix the surfactant, the hydrogenation catalyst, the comonomer, the diene monomer, the additive (optionally added or not added) and water, and emulsify at room temperature;

[0047] S2. Add an initiator and carry out a polymerization reaction at the polymerization temperature, and add a terminator after the polymerization is completed;

[0048] S3. Raise the temperature and introduce high-pressure hydrogen to carry out a hydrogenation reaction to obtain the hydrogenated nitrile-butadiene rubber latex.

[0049] According to the embodiment of the present invention, the method specifically includes the following steps:

[0050] S1. Mix 2-15 parts by mass of the surfactant, 0.01-0.1 part of the hydrogenation catalyst, 10-60 parts of the comonomer, 40-90 parts of the diene monomer, 0.3-3 parts of the additive and 300-1500 parts of water, and emulsify at room temperature for 0.2-2 h;

[0051] S2. Add 0.01-1 part of the initiator and carry out a polymerization reaction at the polymerization temperature, and add a terminator after the reaction is completed;

[0052] S3. Carry out a hydrogenation reaction on the polymerization product at a temperature of 60-180 °C and a hydrogen pressure of 5-15 Mpa for 0.5-10 h to obtain the hydrogenated nitrile-butadiene rubber latex.

[0053] According to an embodiment of the present invention, the end of the reaction in step S2 means reaching the expected conversion rate, preferably the conversion rate is greater than or equal to 70%, for example, the conversion rate reaches 80%.

[0054] According to an embodiment of the present invention, the dosage of the surfactant is preferably 3 to 8 parts, the dosage of the water is preferably 150 to 1500 parts, and the dosage of the initiator is preferably 0.05 to 1 part.

[0055] According to an embodiment of the present invention, the dosage of the hydrogenation catalyst is preferably 0.02 to 0.1 part, for example, 0.05 part.

[0056] According to an embodiment of the present invention, the dosage of the initiator is 0.05 to 1 part, for example, 0.05 part.

[0057] According to an embodiment of the present invention, the auxiliary agent includes at least one of a chain transfer agent, a pH regulator, or a reducing agent.

[0058] According to an embodiment of the present invention, the dosage of the chain transfer agent is 0.25 to 2 parts, preferably 0.5 to 1.5 parts.

[0059] According to an embodiment of the present invention, the dosage of the pH regulator is 0.05 to 1.5 parts, preferably 0.1 to 0.6 parts.

[0060] According to an embodiment of the present invention, the dosage of the reducing agent is 0.001 to 0.05 part, preferably 0.005 to 0.01 part.

[0061] According to an embodiment of the present invention, the temperature of the emulsification is room temperature.

[0062] According to an embodiment of the present invention, the emulsification time is 0.2 to 2 h, preferably 0.5 to 1 h.

[0063] According to an embodiment of the present invention, step S1 includes the following steps:

[0064] S1-a. First, dissolve 2 to 15 parts of the surfactant in a part of the water to obtain a surfactant solution;

[0065] S1-b. Add 0.001 to 0.05 part of the reducing agent, 10 - 60 parts of the copolymerizable monomer, 0.01 - 0.2 part of the hydrogenation catalyst, 0.25 - 2 parts of the chain transfer agent, 0.01 - 0.6 part of the pH regulator and the remaining water to the surfactant solution and mix;

[0066] S1-c. Introduce an inert gas into the reaction kettle for degassing, add 40 - 90 parts of the diene monomer, and emulsify for 0.2 to 2 h at room temperature to obtain an emulsified product.

[0067] According to an embodiment of the present invention, in step S1-a, dissolving the surfactant in a part of water can effectively maintain the stability of the emulsion interface, thereby significantly improving the stability of the particles of the polymer nanoemulsion. Moreover, using an excessive amount of surfactant can also prepare a nanoemulsion with a smaller particle size to increase the specific surface area of the micelles.

[0068] According to an embodiment of the present invention, in step S1-b, during the reaction, the pH value in the system cannot be automatically maintained constant but is in a dynamic change. Adding a pH regulator can effectively maintain the pH in the system within a small range, so that the surfactant can effectively maintain the liquid surface stability, which is beneficial for the reaction to proceed in stable micelles; in step S1-b, adding an appropriate amount of chain transfer agent can effectively control the degree of polymerization and molecular weight, thereby ensuring the chemical and physical properties of the latex or dry rubber. In the present invention, the hydrogenation catalyst used is compatible with the gemini surfactant, and thus can effectively catalyze hydrogenation, greatly accelerating the hydrogenation rate. Moreover, the gemini surfactant also greatly reduces the amount of catalyst used, further reducing the cost.

[0069] According to an embodiment of the present invention, in step S1-c, an inert gas is introduced to displace the air in the reaction kettle to ensure the purity of the gas in the kettle and eliminate the influence of air on the polymerization and hydrogenation effects of the system; before the reaction, the comonomer and the diene monomer are first emulsified. Under the action of the surfactant, the surface tension of water is reduced, and the comonomer and the diene monomer are wrapped in the micelles, forming oil-like monomer droplets with uniform size, thereby ensuring sufficient monomer concentration in the system during the reaction and the stability of the monomer droplets.

[0070] According to an embodiment of the present invention, the inert gas in step S1-c is selected from at least one of helium, argon, and nitrogen. Preferably, the pressure of the inert gas is 0.1-1 MPa, for example, 0.5 MPa.

[0071] According to an embodiment of the present invention, the degassing in step S1-c is carried out under stirring conditions, and the stirring speed is 100-600 rpm, preferably 160-360 rpm. Further preferably, the stirring speed is constant.

[0072] According to an embodiment of the present invention, step S2 is specifically as follows:

[0073] S2. Add 0.01-1 part of initiator to the emulsified product, raise the temperature to the polymerization reaction temperature, and carry out the polymerization reaction.

[0074] According to an embodiment of the present invention, the temperature of the polymerization reaction in step S2 is 2 to 40 °C, preferably the temperature of the polymerization reaction is 5 to 20 °C, and further preferably, the temperature of the polymerization reaction is 6 to 12 °C, for example, 5 °C, 6 °C, 7 °C, 8 °C, 9 °C.

[0075] According to an embodiment of the present invention, the time of the polymerization reaction in step S2 is 0.5 to 6 h, preferably the time of the prepolymerization reaction is 2 to 4 h.

[0076] According to an embodiment of the present invention, step S3 includes the following steps: heating the reaction kettle to 60 to 180 °C and performing a hydrogenation reaction for 0.5 to 10 h in a hydrogen atmosphere under a pressure of 5 to 15 Mpa to obtain HNBR latex.

[0077] According to an embodiment of the present invention, the temperature of the reaction in step S3 is 70 to 150 °C, preferably 80 to 100 °C.

[0078] According to an embodiment of the present invention, the reaction in step S3 is carried out under stirring conditions, and the stirring speed is 300 to 900 rpm, preferably the stirring speed is 450 to 650 rpm, for example, 450 rpm.

[0079] According to an embodiment of the present invention, the time of the reaction in step S3 is 2 to 10 h, preferably the time of the reaction is 3 to 6 h, for example, 5 h.

[0080] According to an embodiment of the present invention, the hydrogen pressure in step S3 is 6 to 10 Mpa, for example, 8 Mpa.

[0081] [Comonomer and diene monomer]

[0082] According to an embodiment of the present invention, the comonomer is selected from at least one of acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, propyl acrylate, butyl acrylate, propyl methacrylate, butyl methacrylate, fumaric acid, maleic acid, acrylic acid, and unsaturated carboxylic acids such as methacrylic acid.

[0083] According to an embodiment of the present invention, the diene monomer is a conjugated monomer, and the conjugated monomer is selected from C 4 -C 6 at least one of conjugated dienes, and preferably the diene monomer is selected from at least one of 1,3-butadiene, isoprene, 1-methylbutadiene, 2,3-dimethylbutadiene, piperylene, and chloroprene.

[0084] [Surfactant]

[0085] According to an embodiment of the present invention, the surfactant is selected from fatty acids, alkyl sulfates, sulfuric acid monoesters of ethoxylated alkanols, ethoxylated alkylphenols, alkali metal salts or ammonium salts of alkyl sulfonic acids, alkali metal salts or ammonium salts of alkyl aryl sulfonic acids, ethoxylated monoalkylphenols, dialkylphenols, trialkylphenols, ethoxylated fatty alcohols, alkali metal salts or ammonium salts of mono C 4 -C 24 alkyl derivatives of bis(benzenesulfonic acid) ethers, alkali metal salts or ammonium salts of di C 4 -C 24 alkyl derivatives of bis(benzenesulfonic acid) ethers, alkyl aryl sulfonic acids, alkyl sulfonic acids, alkali metal salts or ammonium salts of sulfuric acid monoesters of ethoxylated alkanols, and at least one of gemini surfactants.

[0086] According to an embodiment of the present invention, the fatty acid surfactant is selected from alkali metal salts or ammonium salts of fatty acids having an alkyl group of C 12 -C 23 , preferably sodium oleate (NaO) or potassium oleate (KO).

[0087] According to an embodiment of the present invention, the alkyl sulfate, sulfuric acid monoesters of ethoxylated alkanols, ethoxylated alkylphenols, alkali metal salts or ammonium salts of alkyl sulfonic acids, and alkali metal salts or ammonium salts of alkyl aryl sulfonic acids surfactants are the following emulsifiers: such as alkyl sulfates (alkyl: C 8 to C 22 ), ethoxylated alkanols (degree of ethylene oxide: 4 to 30, alkyl: C 8 to C 22 ), sulfuric acid monoesters of ethoxylated alkylphenols (degree of ethylene oxide: 3 to 50, alkyl: C 4 to C 20 ), alkali metal salts or ammonium salts of alkyl sulfonic acids (alkyl: C 8 to C 22 ), and alkali metal salts or ammonium salts of alkyl aryl sulfonic acids (alkyl: C 4 to C 18 ). For example, the surfactant is sodium dodecyl sulfate (SDS) and sodium dodecylbenzenesulfonate (SDBS).

[0088] According to an embodiment of the present invention, the ethoxylated monoalkylphenols, dialkylphenols, trialkylphenols, and ethoxylated fatty alcohol surfactants are the following emulsifiers: ethoxylated mono-, di- or tri-alkylphenols (degree of ethylene oxide: 3 to 50; alkyl C 4 to C 9 ) or ethoxylated fatty alcohols (degree of ethylene oxide: 3 to 50; alkyl C 4 to C 9 ).

[0089] According to an embodiment of the present invention, the alkali metal salt or ammonium salt surfactant of alkyl aryl sulfonic acid, alkyl sulfonic acid, or sulfuric acid monoester of ethoxylated alkanol is the alkali metal salt or ammonium salt, especially the sodium salt, of the following: alkyl aryl sulfonic acid, alkyl sulfonic acid (such as sulfonated C 12 to C 18 paraffin), alkyl sulfate (such as sodium lauryl sulfate), and sulfuric acid monoester of ethoxylated alkanol (such as subsulfated ethoxylate of lauryl alcohol with 2 to 3 ethylene oxide units).

[0090] According to an embodiment of the present invention, the gemini surfactant is at least one selected from cationic gemini surfactants, anionic gemini surfactants, nonionic gemini surfactants, and asymmetric gemini surfactants.

[0091] According to an embodiment of the present invention, the anionic gemini surfactant is at least one anionic gemini surfactant selected from phosphate ester salt type, sulfonate type, carboxylate type, and sulfate ester salt type.

[0092] In some embodiments of the present invention, the cationic gemini surfactant has a structure shown in formula (I):

[0093]

[0094] In formula (I), R 1 , R 2 , Y, x, and y have the definitions described in A1 - A8:

[0095] A1: R 1 = R 2 = C m H 2m+1 ; Y = CH 2 ; x + y + 1 = s; m - s - m surfactants;

[0096] A2: R 1 = R 2 = C m H 2m+1 ; Y = CH 2 , O, S, N(CH 3 ), x = y = 2;

[0097] A2: R 1 = R 2 = C m H 2m+1 ; Y = CHOH, (CHOH) 2 ; x = y = 1;

[0098] A3: R 1 = R 2=C m H 2m+1 ; Y = (OCH 2 CH 2 ) z , x = 2; y = 0; m-EOz-m surfactants;

[0099] A4: R 1 = R 2 = C m H 2m+1 ; Y = C≡C; x = y = 1;

[0100] A5: R 1 = R 2 = C m H 2m+1 ; Y = a phenylene group; x = y = 1;

[0101] A6: R 1 = R 2 = C m H 2m+1 OC(O)CH 2 ; no Y; x = y = 1; counterion = chloride;

[0102] A7: R 1 = R 2 = C m F 2m C 4 H 8 ; no Y; x = y = 1;

[0103] A8: R 1 = C m H 2m+1 ; R 2 = C n H 2n+1 ; no Y; x = y = 1; s; m-2-n surfactants (m is not equal to n);

[0104] Among A1 - A8, m, n, and z are independently 1 - 60 respectively;

[0105] Br - can be replaced by any other anion, preferably F in Group VIIA elements - , Cl - , I - , At - , Ts - .

[0106] In some embodiments of the present invention, the gemini surfactant is selected from at least one of the following:

[0107] C 12 H 25 N + (CH 3 ) 2 -(CH 2 ) n -N + (CH 3 ) 2 C 12 H 25 2Br – (n = 3–8),

[0108] C 12 H 25 N + (CH 3 ) 2 -(CH 2 ) 16 -N + (CH 3 ) 2 C 12 H 25 2Br – 、

[0109] C 16 H 33 N + (CH 3 ) 2 -(CH 2 ) 2 -N + (CH 3 ) 2 C 16 H 33 2Br – 、

[0110] C 8 H 17 N + (CH 3 ) 2 -(CH 2 ) 3 -N + (CH 3 ) 2 C 8 H 17 2Br – 、

[0111] C 12 H 25 N + (CH 3 ) 2 -(CH 2 )2 -O-(CH 2 ) 2 -N + (CH 3 ) 2 C 12 H 25 2Cl – 、

[0112] C 16 H 33 N + (CH 3 ) 2 -(CH 2 ) 5 -N + (CH 3 ) 2 C 16 H 33 2Br – 、

[0113] C 16 H 33 N + (CH 3 ) 2 -(CH 2 ) 2 -O-(CH 2 ) 2 -N + (CH 3 ) 2 C 16 H 33 2Br – 、

[0114] C 16 H 33 N + (CH 3 ) 2 -CH 2 -(CH 2 -O-CH 2 ) 3 -CH 2 -N + (CH 3 ) 2 C 16 H 33 2Br – 、

[0115] C 12 H 25 N + (CH 3 ) 2 -CH 2-CH(OH)-CH 2 -N + (CH 3 ) 2 C 12 H 25 2Br – 、

[0116] C 12 H 25 N + (CH 3 ) 2 -CH 2 -C 6 H 4 -CH 2 -N + (CH 3 ) 2 C 12 H 25 2Br – 、

[0117] C 12 H 25 N + (CH 3 ) 2 -CH 2 -CH(OH)-CH(OH)-CH 2 -N + (CH 3 ) 2 C 12 H 25 2Br – 、

[0118] C 12 H 25 N + (CH 3 ) 2 -CH 2 -CH(OH)-CH 2 -N + (CH 3 ) 2 -CH 2 -CH(OH)-CH 2 -N + (CH 3 ) 2 C 12 H 25 3Cl – 、

[0119] C 12 H 25 OPO 2 – -O-(CH2 ) 6 -OPO 2 – -OC 12 H 25 2Na + 、

[0120] C 10 H 21 O-CH 2 -CH(OSO 3 – )-CH 2 -O-(CH 2 ) 2 -O-CH 2 -CH(OSO 3 – )-CH 2 -OC 10 H 21 2Na +

[0121] According to an embodiment of the present invention, the surfactant is selected from at least one of potassium oleate (KO), sodium dodecylbenzenesulfonate (SDBS), and didodecyldimethylammonium bromide.

[0122] [Initiator]

[0123] According to an embodiment of the present invention, the initiator of the HNBR latex is at least one free radical initiator, including at least one of peroxide initiators, azo initiators, and redox initiators.

[0124] According to an embodiment of the present invention, the peroxide initiator is an organic peroxide and / or an inorganic peroxide.

[0125] According to an embodiment of the present invention, the azo initiators include azodiisobutyronitrile, azodiisoheptonitrile, etc.

[0126] According to an embodiment of the present invention, the redox initiators include benzoyl peroxide / sucrose, tert-butyl hydroperoxide / Rongalite, tert-butyl hydroperoxide / sodium metabisulfite, benzoyl peroxide / N,N-dimethylaniline, etc.

[0127] According to an embodiment of the present invention, the redox initiator is selected from at least one of ammonium persulfate / sodium bisulfite, potassium persulfate / sodium bisulfite, hydrogen peroxide / tartaric acid, hydrogen peroxide / formaldehyde sodium sulfoxylate, ammonium persulfate / ferrous sulfate, hydrogen peroxide / ferrous sulfate, benzoyl peroxide / / N,N-diethylaniline, benzoyl peroxide / ferrous pyrophosphate, potassium persulfate / silver nitrate, persulfate / thiol, cumene hydroperoxide / ferrous chloride, potassium persulfate / ferrous chloride, hydrogen peroxide / ferrous chloride, cumene hydroperoxide / tetraethylenimine, cumene hydroperoxide / ferrous sulfate, etc.

[0128] According to an embodiment of the present invention, the initiator is selected from any one of redox initiators. Using a redox initiator can initiate a polymerization reaction at a relatively low temperature (0 - 50 °C), and can increase the reaction rate, reduce energy consumption, and the prepared latex has small particle size and a narrow particle size distribution range.

[0129] [Auxiliary agent]

[0130] According to an embodiment of the present invention, the chain transfer agent is selected from at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan, tert-butyl mercaptan, n-butyl mercaptan. For example, it is dodecyl mercaptan, and dodecyl mercaptan has good performance and can effectively reduce the molecular weight of the latex.

[0131] According to an embodiment of the present invention, the pH regulator is selected from at least one of sodium phosphate, tetrasodium diphosphate, trisodium phosphate, sodium hexametaphosphate, sodium bicarbonate.

[0132] [Terminator]

[0133] According to an embodiment of the present invention, the terminator is selected from at least one of quinone, nitro, nitroso, aryl polyhydroxy compounds, and sulfur-containing compounds.

[0134] According to an embodiment of the present invention, N,N-diethylhydroxylamine is used as the terminator for the polymerization reaction.

[0135] [Hydrogenation catalyst]

[0136] According to an embodiment of the present invention, the hydrogenation catalyst is selected from noble metal complex catalysts, and the noble metal is selected from at least one of ruthenium, osmium, palladium, iridium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, nickel or cobalt. Preferably, the hydrogenation catalyst is selected from at least one of ruthenium complexes, osmium complexes, palladium complexes, and iridium complexes.

[0137] According to an embodiment of the present invention, the hydrogenation catalyst has a structure shown in formula (A):

[0138]

[0139] Among them, M is selected from ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, iridium, palladium, silver, nickel, and cobalt; preferably, M is selected from ruthenium, osmium, palladium, or iridium;

[0140] L is a ligand; preferably an uncharged electron donor is selected;

[0141] Y is a radical of O, S, Se, N-R1, P-R1, AsR, or SbR;

[0142] X 1 、X 2 are each independently selected from anionic ligands;

[0143] R 1 are each independently selected from hydrogen, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, an alkylamino group, an alkylthio group, an arylthio group, an alkyl-alkoxysilyl group, an alkyl-aryloxysilyl group, an alkyl-cycloalkoxysilyl group, an arylammonium group, an alkyl sulfonate, an aryl sulfonate, an alkyl phosphonate, an aryl phosphonate, a carboxylate, an alkylsulfonyl group, or an alkylsulfinyl group. Optionally, each of the above R1s can be selectively substituted by one or more alkyl groups, halogen groups, alkoxy groups, aryl groups, or heteroaryl groups;

[0144] R 2 、R 3 、R 4 and R 5 are each independently selected from a hydrogen group, an organic radical, or an inorganic radical;

[0145] R 6 is selected from H, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group.

[0146] According to an embodiment of the present invention, the hydrogenation catalyst is added to the diene-based polymer aqueous medium suspension in solid form.

[0147] This type of catalyst represented by the general formula (A) is usually insoluble in water. In this application, "water-insoluble" means that at 24 + / - 2 degrees Celsius, 0.001 or less weight content of the substance can be completely dissolved in 100 equivalents of water, while at 24 + / - 2 degrees Celsius, if more than 0.5 weight content of the catalyst can be completely dissolved in 100 equivalents of water, the catalyst is considered "water-soluble".

[0148] According to an embodiment of the present invention, R 2 ,R 3 ,R 4 and R 5 are the same or different and are each independently selected from hydrogen, halogen, nitro, CF 3 、C 1 -C30 -alkyl, C 3 -C 20 -alkynyloxy, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, 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 -alkylamino, C 1 -C 20 -alkylthio, C 6 -C 24 -arylthio, C 1 -C 20 -alkylsulfonyl or C 1 -C 20 -alkylsulfinyl, and the H in these substituents may be selectively substituted by one or more C 1 -C 30 -alkyl, C 1 -C 20 -alkoxy, halogen, C 6 -C 24 -aryl or heteroaryl.

[0149] According to an embodiment of the present invention, R 2 , R 3 , R 4 and R 5 are the same or different and are independently selected from nitro, straight-chain or branched C 1 -C 30 -alkyl, C 5 -C 20 -cycloalkane, straight-chain or branched C 1 -C 20 -alkoxy or C 6 -C 24 -aryl radical, preferably the C 6 -C 24 -aryl radical is selected from phenyl or naphthyl.

[0150] Preferably, C 1 -C 30 -alkyl radical, C1 -C 20 -alkoxy radicals can be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.

[0151] According to an embodiment of the present invention, two or more radicals R 2 , R 3 , R 4 or R 5 can also be linked by an aliphatic or aromatic structure.

[0152] According to an embodiment of the present invention, R 6 is selected from hydrogen, C 1 -C 30 -alkyl radicals, C 2 -C 20 -alkenyl radicals, C 2 -C 20 -alkynyl radicals or C 6 -C 24 -aryl radicals, R 6 Particularly preferably hydrogen.

[0153] According to an embodiment of the present invention, the X 1 , X 2 are the same or different anionic ligands.

[0154] According to an embodiment of the present invention, the X 1 , X 2 are each independently selected from H, halogen, pseudohalogen, straight-chain 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 -alkyl diketone, C 6 -C 24 -aryl diketone, C 1 -C 20 -carboxylate, C 6 -C 24 -alkyl sulfonate, C 6 -C 24 -aryl sulfonate, C 1 -C 20 -alkyl mercaptan, C 6 -C 24 -aryl mercaptan, C 1 -C 20 -alkyl sulfonyl or C1 -C 20 -alkylsulfinyl.

[0155] According to an embodiment of the present invention, the H on the X 1 , X 2 may be further substituted by other groups, preferably by halogen, C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy or C 6 -C- 24 -aryl, and further preferably, it is substituted by fluorine, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy or phenyl, and preferably, the H on the substituent may be further substituted by one or more halogens.

[0156] As an example, the X 1 , X 2 are independently selected from 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, phenoxy, methoxy, ethoxy, toluenesulfonate (p-CH 3 -C 6 H 4 -SO 3 ), methanesulfonic acid (CH 3 SO 3 ), or trifluoromethanesulfonate (CF 3 SO 3 ).

[0157] According to an embodiment of the present invention, the L is selected from uncharged electron donors, preferably the L is selected from a phosphine, phosphine, sulfonated phosphine, phosphate ester, phosphinate, phosphite, sulfonate, sulfoxide, carboxyl, nitrosyl, nitrile, isonitrile, sulfonated phosphine, phosphate, hypophosphorous acid, phosphite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitroso, pyridine, thioether or N-heterocyclic carbene ligand.

[0158] According to an embodiment of the present invention, the hypophosphorous acid is selected from phenyldiphenylphosphorous acid, cyclohexyldicyclohexylphosphorous acid, isopropyldiisopropylphosphorous acid or methyldiphenylphosphorous acid.

[0159] According to an embodiment of the present invention, the phosphite is selected from triphenylphosphite, tricyclohexylphosphite, tri-tert-butylphosphite, triisopropylphosphite or methyldiphenylphosphite.

[0160] According to an embodiment of the present invention, the antimonide is selected from triphenyl Tricyclohexyl or trimethyl

[0161] According to an embodiment of the present invention, the sulfonate is selected from trifluoromethylsulfonate, toluenesulfonate or methanesulfonate.

[0162] According to an embodiment of the present invention, the sulfoxide is selected from (CH 3 ) 2 S(=O) or (C 6 H 5 )2S=O.

[0163] According to an embodiment of the present invention, the thioether is selected from CH 3 SCH 3 , C 6 H 5 SCH 3 , CH 3 OCH 2 CH 2 SCH 3 or tetrahydrothiophene.

[0164] According to an embodiment of the present invention, the term "pyridyl ligand" is used as a generic term for all pyridine-based ligands or derivatives thereof, for example, as in WO-A-03 / 011455. The term "pyridyl ligand" includes pyridine itself, methylpyridines (such as α-, β- and γ-methylpyridine), dimethylpyridines (such as 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dimethylpyridine), trimethylpyridine (2,4,6-trimethylpyridine), trifluoromethylpyridine, phenylpyridine, 4-(dimethylamino)-pyridine, chloropyridine, bromopyridine, nitropyridine, quinoline, pyrimidine, pyrrole, imidazole and phenylimidazole.

[0165] According to an embodiment of the present invention, L is selected from electron donor phosphine, and the electron donor phosphine has a structure shown in formula (IIf):

[0166]

[0167] Among them, R12 , R 13 and R 14 are the same or different, preferably the same, and are each independently selected from C 1 -C 20- alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 20- alkoxy, substituted or unsubstituted C 6 -C 20- aryl, C 2 -C 20- heteroaryl, C 2 -C 20- heterocyclic group or halogen.

[0168] According to an embodiment of the present invention, the C 1 -C 20- alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl or neopentyl.

[0169] According to an embodiment of the present invention, the C 3 -C 8 -cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

[0170] According to an embodiment of the present invention, the C 1 -C 20- alkoxy is phenyl, biphenyl, naphthalene, phenanthrene, anthracene, tolyl or 2,6-dimethylphenyl.

[0171] As an example, if L represents a phosphine of the general formula (IIf) and is used as an electron-donating ligand in the general formula (A), such a phosphine is preferably selected from 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(CH2 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(neopentyl) 3 wherein, Ph represents phenyl and Tol represents tolyl.

[0172] According to an embodiment of the present invention, the catalyst is selected from complexes of M with n - heterocyclic carbene ligands, and the n - heterocyclic carbene ligand is a cyclic carbene ligand having at least one nitrogen as a heteroatom in the ring. The ring can have different substitution patterns. Preferably, such a substitution pattern provides a certain degree of steric hindrance.

[0173] According to an embodiment of the present invention, the n - heterocyclic carbene ligand (hereinafter referred to as "NHC - ligand") is preferably based on an imidazoline or imidazolidine group.

[0174] According to an embodiment of the present invention, the NHC - ligand has a structure as shown in formulas (IIa) - (IIe):

[0175]

[0176] wherein, R 8 、R 9 、R 10 and R 11 are the same or different and are independently selected from hydrogen, linear 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 heterocycle, C 1 -C 20 -alkoxy, C 2 -C20 -enyl, 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 、-O-C(=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、-O-S(=O) 2 R, halogen, nitro or cyano.

[0177] According to an embodiment of the present invention, in the representative formulas of formulas (IIa)-(IIe), the carbon atom bonded to the ruthenium metal center exists in the form of a carbene.

[0178] According to an embodiment of the present invention, H in R 8 、R 9 、R 10 and R 11 can be independently substituted by one or more substituents selected from straight-chain or branched C 1 -C 10 -alkyl, C 3 -C 8 -cycloalkyl, C 1 -C 10 -alkoxy, C 6 -C 24 -aryl, C 2 -C 20 heteroaryl, C 2 -C 20 heterocycle, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, alkoxycarbonyl, carbamate or halogen.

[0179] Among them, H in the above substituents can also be further substituted by one or more substituents selected from halogen, C 1 -C 5 -alkyl, C 1 -C 5-alkoxy or phenyl, and the halogen is preferably chlorine or bromine.

[0180] It should be added that the NHC-ligand structures of the general formulas (IIa) and (IIb) depicted in the present invention are identical to the structures (IIa-(i)) and (IIb-(i)) of such NHC-ligands often encountered in the literature, and the carbene characteristics of the NHC-ligands are emphasized, which also applies to the further structures of (IIc) to (IIe) and the preferred structures related to (IIc)-(IIe) described below.

[0181]

[0182] In a preferred NHC-ligand of the catalyst represented by the general formula (A), R 8 and R 9 are the same or different and represent hydrogen, C 6 -C 24 -aryl, preferably benzene, straight-chain or branched C 1 -C 10 -alkyl, more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl or tert-butyl, or a cycloalkyl or aryl structure forming a bond to a carbon atom.

[0183] According to an embodiment of the present invention, R 8 and R 9 can be substituted by one or more groups containing straight-chain or branched C 1 -C 10 -alkyl or C 1 -C 10 -alkoxy, C 3 -C 8 -cycloalkyl, C 6 -C 24 -aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, alkoxycarbonyl, carbamate and halogen, wherein these substituents in turn may be substituted by one or more substituents, preferably including halogen, especially chlorine or bromine, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy and benzene.

[0184] In a further preferred NHC-ligand of the catalyst represented by the general formula (A), R 10 and R 11 are the same or different, preferably straight-chain or branched C 1 -C10 -- alkyl, more preferably i - propyl or neopentyl, C 3 -C 10 - cycloalkyl, more preferably adamantyl, substituted or unsubstituted C 6 -C 24 - aryl, more preferably phenyl, 2,6 - diisopropylbenzene, 2,6 - dimethylphenyl, or 2,4,6 - trimethylphenyl, C 1 -C 10 -- alkyl sulfonate or C 6 -C 10 - sulfonic acid.

[0185] Preferably, R 10 and R 11 can be substituted by one or more substituents selected from the group consisting of straight - chain or branched C 1 -C 10 -- alkyl or C 1 -C 10 -- alkoxy, C 3 -C 8 - cycloalkyl, C 6 -C 24 - aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, alkoxycarbonyl, carbamate, and halogen, wherein these substituents in turn may be substituted by one or more substituents, preferably including halogen, especially chlorine or bromine, C 1 -C 5 - alkyl, C 1 -C 5 - alkoxy and benzene.

[0186] In a further preferred NHC - ligand in the catalyst represented by the general formula (A), R 8 and R 9 are the same or different and they represent hydrogen, C 6 -C 24 - aryl, more preferably benzene, straight - chain or branched C 1 -C 10 - alkyl, more preferably methyl, ethyl, n - propyl, i - propyl, n - butyl, sec - butyl, i - butyl, or a cycloalkyl or aryl structure that forms a bond to a carbon atom.

[0187] R 10 and R 11 are the same or different, preferably straight - chain or branched C 1 -C 10 - alkyl, more preferably i - propyl or neopentyl, C 3 -C10 -cycloalkyl, more preferably adamantyl, substituted or unsubstituted C 6 -C 24 -aryl, more preferably phenyl, 2,6 - diisopropylbenzene, 2,6 - dimethylbenzene or 2,4,6 - trimethylphenyl, C 1 -C 10 -alkyl sulfonate or C 6 -C 10 -sulfonic acid.

[0188] Particularly preferably, the NHC - ligand has the structures shown in the following (IIIa) to (IIIu), where "Ph" represents phenyl in each case, "Bu" represents butyl in each case, i.e., n - butyl, tert - butyl, isobutyl, or any one of them. "Mes" represents 2,4,6 - trimethylphenyl in each case, "Dipp" represents 2,6 - diisopropylbenzene in all cases, and "Dimp" refers to 2,6 - dimethylphenyl in each case.

[0189]

[0190] The NHC - ligand contains not only one "N" (nitrogen), but also one "O" (oxygen) in the ring, which makes the substitution pattern of R 8 , R 9 , R 10 and / or R 11 more likely to provide a certain steric crowding.

[0191] In the general formula (A), the substituent R 1 is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, hydroxyethyl aryl sulfide, alkylsulfonyl, or alkylsulfinyl, and these substituents can be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.

[0192] The substituent R 1 is usually 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 1 -C 20 -alkoxy, C 2 -C 20 -alkenyloxy, C 2 -C20 -alkoxy, C 6 -C 24 -aryloxy, C 2 -C 20 -alkoxycarbonyl, C 1 -C 20 -alkylamino, C 1 -C 20 -alkylthio, C 6 -C 24 -arylthio, C 1 -C 20 -alkylsulfonyl or C 1 -C 20 -alkylsulfinyl, and these substituents may be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.

[0193] According to an embodiment of the present invention, R 1 is preferably C 3 -C 20 -cycloalkyl, C 6 -C 24 -aryl or straight-chain or branched C 1 -C 30 –alkyl radical, and in appropriate cases, the latter can be interrupted by one or more double bonds or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen. R 1 Particularly preferably a straight-chain or branched C 1 -C 12 -alkyl radical.

[0194] Preferably, C 3 -C 20 -cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0195] According to an embodiment of the present invention, R 1 is preferably C 1 -C 12 -alkyl radical, C 1 -C 12 -alkyl radical selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexane, n-heptyl, n-octyl, n-decyl, or n-dodecyl. In particular, R 1 is methyl or isopropyl.

[0196] C 6 -C 24-Aryl is an aromatic radical having 6 to 24 skeletal carbon atoms, preferably a monocyclic, bicyclic or tricyclic carbocyclic aryl containing 6 to 10 skeletal carbon atoms, and can be synthesized from benzene, biphenyl, naphthalene, phenanthrene, anthracene or pyrene.

[0197] In the general formula (A), the radical R 2 , R 3 , R 4 and R 5 are the same or different and can be hydrogen, organic or inorganic radicals.

[0198] In a suitable embodiment, R 2 , R 3 , R 4 and R 5 are the same or different and each can be hydrogen, halogen, nitro, CF 3 , alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, hydroxyethyl aryl sulfide, alkylsulfonyl, or alkylsulfinyl, and these substituents can be selectively substituted by one or more alkyl, alkoxy, halogen, aryl or heteroaryl radicals.

[0199] R 2 , R 3 , R 4 and R 5 are generally the same or different and each can be hydrogen, halogen, preferably chlorine or bromine, nitro, CF 3 , C 1 -C 30 -alkyl, C 3 -C 20 -alkynyloxy, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 6 -C 24 -aryl, 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 -alkylamino, C 1 -C 20 -alkylthio, C 6 -C 24-arylthio, C 1 -C 20 -alkylsulfonyl or C 1 -C 20 -alkylsulfinyl, and these substituents may be selectively substituted by one or more C 1 -C 30 -alkyl, C 1 -C 20 -alkoxy, halogen, C 6 -C 24 -aryl or heteroaryl.

[0200] In one particularly useful embodiment, R 2 , R 3 , R 4 and R 5 are the same or different and each may be nitro, a straight or branched C 1 -C 30 -alkyl, C 5 -C 20 -cylcoalkyl, a straight or branched C 1 -C 20 -alkoxy or C 6 -C 24 -aryl radical, preferably phenyl or naphthyl. C 1 -C 30 -alkyl radical and C 1 -C 20 -alkoxy radical may be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.

[0201] In addition, two or more of the radicals R 2 , R 3 , R 4 or R 5 may also be linked by an aliphatic or aromatic structure. For example, R 3 , R 4 and the carbon atoms connecting them on the phenyl ring in the expression (B) may form a fused phenyl ring, and overall, a naphthyl structure is produced.

[0202] In the general expression (A), the R 6 radical is hydrogen or alkyl, alkenyl, alkynyl or aryl. R 6 is preferably hydrogen, a C 1 -C 30 -alkyl radical, a C 2 -C 20 -alkenyl radical, a C 2 -C 20 -alkynyl radical or a C 6 -C24 -aryl radical. R 6 Particularly preferably hydrogen.

[0203] Most preferably, the catalyst has the structure of formula (IV) (i.e., the so-called second-generation Hoveyda-Grubbs catalyst), the catalyst of formula (V) (i.e., the so-called second-generation Grubbs catalyst), and the catalyst of formula (VI) (i.e., the so-called third-generation Grubbs catalyst).

[0204]

[0205] According to an embodiment of the present invention, the reaction kettle is selected from high-pressure reaction kettles, such as high-temperature and high-pressure stainless steel reaction kettles.

[0206] According to an embodiment of the present invention, the high-temperature and high-pressure stainless steel reaction kettle includes a kettle body and at least two high-pressure resistant hoses. One end of the high-pressure resistant hose is connected to the kettle body, and the other end is connected to high-pressure gas. The high-pressure gas is, for example, inert gas and hydrogen.

[0207] According to an embodiment of the present invention, the high-temperature resistant hose includes a stainless steel high-temperature resistant hose and a plastic high-temperature resistant hose. The stainless steel high-temperature resistant hose is used to introduce hydrogen into the kettle body, and the plastic high-temperature resistant hose is used to introduce inert gas into the kettle body.

[0208] According to an embodiment of the present invention, an exhaust port is further provided on the kettle body.

[0209] According to an embodiment of the present invention, a pressure sensor is further provided in the kettle body. The measuring range of the pressure sensor is -1 to 30 MPa.

[0210] According to an embodiment of the present invention, a temperature sensor is further provided in the kettle body. The measuring range of the temperature sensor is 0 to 180 °C.

[0211] According to an embodiment of the present invention, a stirring device is further provided in the kettle body for fully mixing the materials in the system. The stirring speed of the stirring device is 0 to 800 rpm.

[0212] [Hydrogenated nitrile rubber latex]

[0213] The present invention also provides a hydrogenated nitrile rubber latex prepared by the above method. The hydrogenation degree of the hydrogenated nitrile rubber latex is 50-100%, the content of the comonomer is 10-60 mol%, and the conversion rate is 60-80 wt%.

[0214] According to an embodiment of the present invention, hydrogenated nitrile rubber molecules exist in numerous nanoparticles and are in the form of latex. At the same time, solid hydrogenated nitrile rubber can also be obtained by flocculating the hydrogenated nitrile rubber latex and then performing post-treatment methods such as washing and drying.

[0215] According to an embodiment of the present invention, the hydrogenation degree of the hydrogenated nitrile rubber latex is greater than or equal to 90%, preferably the hydrogenation degree of the hydrogenated nitrile rubber latex is 95%, and further preferably, the hydrogenation degree of the hydrogenated nitrile rubber latex is 97%, for example, 89.1%, 96.9%, 97.9%, 99.4%, 99.6%, 98.8%, 99.8%, 95.6%.

[0216] According to an embodiment of the present invention, the content of the comonomer is 30-40 mol%, for example, 31 mol%, 32 mol%, 33 mol%, 34 mol%.

[0217] According to an embodiment of the present invention, in the hydrogenated nitrile rubber latex, the hydrogenated nitrile rubber molecules are distributed in nano-micelles and exist in the form of latex.

[0218] According to an embodiment of the present invention, solid hydrogenated nitrile rubber can be obtained by first flocculating the hydrogenated nitrile rubber latex and then performing post-treatment such as washing and drying on the flocculated product.

[0219] The preparation method and application of the present invention will be further described in detail below in conjunction with specific examples. It should be understood that the following examples are only for illustrative explanation of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection of the present invention.

[0220] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

[0221] Example 1

[0222] 1) Dissolve 7 g of the surfactant didodecyldimethylammonium bromide in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0223] 2) Add 0.005 g of the reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of the hydrogenation catalyst, 0.3 g of the chain transfer agent tert-dodecyl mercaptan, and 0.05 g of the pH regulator sodium phosphate to the reaction kettle.

[0224] 3) Introduce 0.5 Mpa of inert gas (nitrogen) into the reaction kettle, and conduct degassing treatment for 0.5 hours while stirring at a speed of 200 rpm. Then add 70 g of butadiene in liquid form into the degassed reaction kettle, mix, and use a high and low temperature cooling circulation machine to cool down the reaction kettle, and emulsify at room temperature for 1 hour.

[0225] 4) Add 0.05 g of the emulsion polymerization initiator cumene hydroperoxide into the reaction kettle through the feeding tank; introduce 5 Mpa of high-pressure hydrogen into the kettle, and raise the temperature of the reaction kettle to the polymerization reaction temperature of 7 °C for polymerization. After reaching 80% conversion rate, add the terminator N,N-diethylhydroxylamine.

[0226] 5) Raise the temperature of the system to 70 °C and introduce hydrogen at a pressure of 8 Mpa. At this time, start the hydrogenation reaction. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, obtain HNBR latex.

[0227] Example 2

[0228] 1) Dissolve 7 g of the surfactant oleic acid potassium in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0229] 2) Add 0.005 g of the reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst, 0.3 g of the chain transfer agent tert-dodecyl mercaptan, and 0.05 g of the pH regulator sodium phosphate into the reaction kettle.

[0230] 3) Introduce 0.5 Mpa of inert gas (nitrogen) into the reaction kettle, and conduct degassing treatment for 0.5 hours while stirring at a speed of 200 rpm. Then add 70 g of butadiene in liquid form into the degassed reaction kettle, mix, and use a high and low temperature cooling circulation machine to cool down the reaction kettle, and emulsify at room temperature for 1 hour.

[0231] 4) Add 0.05 g of the emulsion polymerization initiator cumene hydroperoxide into the reaction kettle through the feeding tank; and raise the temperature of the reaction kettle to the polymerization reaction temperature of 7 °C for polymerization. After reaching 80% conversion rate, add the terminator N,N-diethylhydroxylamine.

[0232] 5) Raise the temperature of the system to 70 °C and introduce hydrogen at a pressure of 8 Mpa. At this time, start the hydrogenation reaction. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, obtain HNBR latex.

[0233] Example 3

[0234] 1) Dissolve 7 g of the surfactant sodium dodecylbenzenesulfonate in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle;

[0235] 2) Add 0.005 g of reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate into the reaction kettle.

[0236] 3) Introduce 0.5 Mpa of inert gas (nitrogen) into the reaction kettle. While stirring at a speed of 200 rpm, conduct degassing treatment for 0.5 hour. Then add 70 g of butadiene in liquid form into the degassed reaction kettle, mix, and use a high and low temperature cooling circulation machine to cool down the reaction kettle, and conduct emulsification at room temperature for 1 hour.

[0237] 4) Add 0.05 g of emulsion polymerization initiator cumene hydroperoxide into the reaction kettle through the feeding tank; and raise the temperature of the reaction kettle to the polymerization reaction temperature of 7 °C, conduct polymerization, and add terminator N,N-diethylhydroxylamine after reaching 80% conversion rate.

[0238] 5) Raise the system temperature to 70 °C and introduce hydrogen at a pressure of 8 Mpa. At this time, start the hydrogenation reaction. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, obtain HNBR latex.

[0239] Example 4

[0240] 1) Dissolve 10 g of surfactant oleic acid potassium in 300 g of deionized water to obtain an aqueous surfactant solution and add it into the reaction kettle.

[0241] 2) Add 0.005 g of reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate into the reaction kettle.

[0242] 3) Introduce 0.5 Mpa of inert gas (nitrogen) into the reaction kettle. While stirring at a speed of 200 rpm, conduct degassing treatment for 0.5 hour. Then add 70 g of butadiene in liquid form into the degassed reaction kettle, mix, and use a high and low temperature cooling circulation machine to cool down the reaction kettle, and conduct emulsification at room temperature for 1 hour.

[0243] 4) Add 0.05 g of emulsion polymerization initiator cumene hydroperoxide into the reaction kettle through the feeding tank; and raise the temperature of the reaction kettle to the polymerization reaction temperature of 7 °C, conduct polymerization, and add terminator N,N-diethylhydroxylamine after reaching 80% conversion rate.

[0244] 5) Raise the system temperature to 70 °C and introduce hydrogen at a pressure of 8 Mpa. At this time, start the hydrogenation reaction. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, obtain HNBR latex.

[0245] Example 5

[0246] 1) Dissolve 7 g of surfactant potassium oleate in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle;

[0247] 2) Add 0.005 g of reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.07 g of hydrogenation catalyst, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate to the reaction kettle;

[0248] 3) Introduce 0.5 Mpa of inert gas (nitrogen) into the reaction kettle, conduct degassing treatment for 0.5 hours while stirring at a speed of 200 rpm, then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, use a high and low temperature cooling circulation machine to cool the reaction kettle, and emulsify at room temperature for 1 hour.

[0249] 4) Add 0.05 g of emulsion polymerization initiator cumene hydroperoxide to the reaction kettle through a feeding tank; raise the temperature of the reaction kettle to the polymerization reaction temperature of 7 °C, conduct polymerization, and add terminator N,N-diethylhydroxylamine after reaching 80% conversion rate.

[0250] 5) Raise the temperature of the system to 70 °C and introduce hydrogen at a pressure of 8 Mpa. At this time, start the hydrogenation reaction. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, obtain HNBR latex.

[0251] Example 6

[0252] 1) Dissolve 7 g of surfactant potassium oleate in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle;

[0253] 2) Add 0.005 g of reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate to the reaction kettle;

[0254] 3) Introduce 0.5 Mpa of inert gas (nitrogen) into the reaction kettle, conduct degassing treatment for 0.5 hours while stirring at a speed of 200 rpm, then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, use a high and low temperature cooling circulation machine to cool the reaction kettle, and emulsify at room temperature for 1 hour.

[0255] 4) Add 0.05 g of emulsion polymerization initiator cumene hydroperoxide to the reaction kettle through a feeding tank; raise the temperature of the reaction kettle to the polymerization reaction temperature of 7 °C, conduct polymerization, and add terminator N,N-diethylhydroxylamine after reaching 80% conversion rate.

[0256] 5) Raise the system temperature to 90 °C and introduce hydrogen at a pressure of 8 MPa. At this time, the hydrogenation reaction begins. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, HNBR latex is obtained.

[0257] Example 7

[0258] 1) Dissolve 7 g of the surfactant sodium dodecylbenzenesulfonate in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle;

[0259] 2) Add 0.005 g of the reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst, 0.3 g of the chain transfer agent tert-dodecyl mercaptan, and 0.05 g of the pH regulator sodium phosphate to the reaction kettle;

[0260] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, perform degassing treatment for 0.5 hours while stirring at a speed of 200 rpm, then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and use a high and low temperature cooling circulation machine to cool the reaction kettle. Emulsify at room temperature for 1 hour.

[0261] 4) Add 0.05 g of the emulsion polymerization initiator cumene hydroperoxide to the reaction kettle through a feeding tank; raise the temperature of the reaction kettle to the polymerization reaction temperature of 7 °C, carry out polymerization, and add the terminator N,N-diethylhydroxylamine after reaching 80% conversion.

[0262] 5) Raise the system temperature to 90 °C and introduce hydrogen at a pressure of 8 MPa. At this time, the hydrogenation reaction begins. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, HNBR latex is obtained.

[0263] Example 8

[0264] 1) Dissolve 7 g of the surfactant sodium dodecylbenzenesulfonate in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle;

[0265] 2) Add 0.005 g of the reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst, 0.3 g of the chain transfer agent tert-dodecyl mercaptan, and 0.05 g of the pH regulator sodium phosphate to the reaction kettle;

[0266] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, perform degassing treatment for 0.5 hours while stirring at a speed of 200 rpm, then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and use a high and low temperature cooling circulation machine to cool the reaction kettle. Emulsify at room temperature for 1 hour.

[0267] 4) Add 0.05 g of the emulsion polymerization initiator cumene hydroperoxide to the reaction kettle through the feed tank; raise the temperature of the reaction kettle to the polymerization reaction temperature of 12 °C and carry out the polymerization. After reaching 80% conversion, add the terminator N,N - diethylhydroxylamine.

[0268] 5) Raise the temperature of the system to 90 °C and introduce hydrogen at a pressure of 8 Mpa. At this time, start the hydrogenation reaction. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, obtain HNBR latex.

[0269] Example 9

[0270] 1) Dissolve 7 g of the surfactant sodium dodecylbenzenesulfonate in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle;

[0271] 2) Add 0.005 g of the reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of the hydrogenation catalyst, 0.3 g of the chain transfer agent tert - dodecyl mercaptan, and 0.05 g of the pH regulator sodium phosphate to the reaction kettle;

[0272] 3) Introduce 0.5 Mpa of inert gas (nitrogen) into the reaction kettle, carry out degassing treatment for 0.5 hours while stirring at a speed of 200 rpm, then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and use a high - low temperature cooling circulator to cool the reaction kettle. Emulsify at room temperature for 1 hour.

[0273] 4) Add 0.05 g of the emulsion polymerization initiator cumene hydroperoxide to the reaction kettle through the feed tank; raise the temperature of the reaction kettle to the polymerization reaction temperature of 5 °C and carry out the polymerization. After reaching 80% conversion, add the terminator N,N - diethylhydroxylamine.

[0274] 5) Raise the temperature of the system to 80 °C and introduce hydrogen at a pressure of 8 Mpa. At this time, start the hydrogenation reaction. Keep the temperature and pressure constant in the reaction kettle, and keep the stirring speed constant at 450 rpm. After reacting for 5 hours, obtain HNBR latex.

[0275] Comparative Example 1

[0276] 1) Dissolve 7 g of the surfactant sodium dodecylbenzenesulfonate in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0277] 2) Add 0.005 g of the reducing agent ferrous sulfate, 30 g of acrylonitrile, 0.05 g of the hydrogenation catalyst, 0.3 g of the chain transfer agent tert - dodecyl mercaptan, and 0.05 g of the pH regulator sodium phosphate to the reaction kettle.

[0278] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, conduct degassing treatment for 0.5 hours while stirring at a speed of 200 rpm, then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir the emulsified monomer at room temperature for 1 hour.

[0279] 4) Add 0.05 g of the emulsion polymerization initiator cumene hydroperoxide to the reaction kettle through the feeding tank; raise the temperature of the reaction kettle to the polymerization reaction temperature of 5 °C, conduct polymerization, and add the terminator N,N - diethylhydroxylamine after reaching 80% conversion rate;

[0280] 5) After the polymerization reaction ends; conduct monomer removal treatment on the emulsion, then add a small amount of surfactant and catalyst, and then conduct degassing. After heating up to 90 °C, introduce 6 MPa of high - pressure hydrogen for hydrogenation reaction. After reacting for 5 h, HNBR is obtained.

[0281] Table 1 Performance test results of different HNBR latexes

[0282]

[0283] In Table 1, Gemini represents didodecyldimethylammonium bromide, SDBS represents sodium dodecylbenzenesulfonate, and KO represents potassium oleate.

[0284] Rubber mixing: Prepare the mixed rubber with the HNBR prepared in Example 6 and the competitor Arlanxeo HNBR3406 using the same mixing formula (Table 2).

[0285] Table 2 Rubber compound formula of hydrogenated nitrile rubber

[0286]

[0287] The experiment uses a Harp torque rheometer to conduct two - stage internal mixing on the mixed rubber compound:

[0288] In the first - stage internal mixing, first add HNBR, then add SA (stearic acid), ZnO and 445, then add N550 (carbon black) and TOTM (once); then conduct cleaning and finally discharge the rubber compound. In the first - stage internal mixing, a total of 6 times of making triangular packages are carried out, and the roll gap of the open mill is set to 1.0 mm for sheet - making. After completion, place the obtained rubber compound at room temperature for storage.

[0289] In the second - stage internal mixing, add BIPB (bis - tert - butylperoxyisopropylbenzene) and TAIC (triallyl isocyanurate) to the above - mentioned rubber compound and then discharge the rubber compound. The roll gap is set to 0.3 mm, and 6 times of triangular packages are also carried out. Set the roll gap to 1.5 mm for sheet - making. After completion, place the rubber compound at room temperature for storage.

[0290] Vulcanization characteristics

[0291] In this experiment, a non-rotor rheometer was used to test the mixed rubber according to the standard of GB / T16584-1996. The experimental conditions were set at 180 °C to test the vulcanization characteristics of the rubber compound. During vulcanization, the scorch time T10, the processing optimum vulcanization time T90, the maximum torque MH, and the minimum torque ML were recorded.

[0292] Mechanical properties

[0293] For the test of vulcanized rubber, the Shore A hardness was carried out according to the standard of GB / T531.1-2008, and three parallel measurements were made, and the median was selected as the result. The tensile property test was carried out according to the standard of GB / T528-2009, with a tensile rate of 500 mm / min, and five parallel tests were carried out, and the median was selected as the result. The tear strength test was carried out according to the standard of GB / T529-2008, with a tensile rate of 500 mm / min, and three parallel tests were carried out, and the average value was calculated as the result. The rebound value test was carried out according to the standard of GB / T1681-2009, using Type A specimens, and three tests were carried out after adjusting three times, and the median was selected as the result.

[0294] Heat-resistant air aging performance

[0295] The HNBR under the conditions of Example 6 and the competing HNBR were placed in a vacuum oven, the temperature was set at 150 °C, and the samples were taken out after 72 h. After the experiment, the hardness, tensile strength, and elongation at break of the samples were tested to analyze the changes in the properties of the rubber compound before and after aging.

[0296] Compression set resistance performance

[0297] Put the Type A specimen into the compression fixture of the instrument, adjust the height of the limiter to 9.4 mm, and lock the fixture. After placing the fixture at 150 °C for 72 h, immediately take out the fixture from the oven and remove the specimen, and quickly measure the thickness after compression deformation.

[0298] The calculation method of compression set is as follows:

[0299] Compression deformation rate = (thickness before compression - thickness after compression) / (thickness before compression - limiter) × 100 (%)

[0300] Oil resistance performance

[0301] After the HNBR prepared in Example 6 and the competing HNBR were placed at 150 °C for 72 h, their performance tests for No. 3 standard oil were carried out, and the changes in their hardness, tensile strength, and elongation at break were observed.

[0302] Table 3 Performance comparison of HNBR prepared in Example 6 and competing HNBR

[0303]

[0304] The hydrogenated nitrile rubber latex prepared by the one-step ruthenium-based metal catalyst emulsion polymerization hydrogenation method of the present invention has stable latex properties, good uniformity of the size of nano-micelles, a small particle size distribution range, is not easily demulsified, the preparation method is simple, the operation is convenient, and it is easy to realize industrialization; during the synthesis process, the hydrogenation effect is good and the hydrogenation degree is high. The HNBR prepared by the present invention has hardness, property change rate, etc. equivalent to those of competing HNBRs.

[0305] The specific embodiments of the present invention have been exemplarily described above through examples. However, the protection scope of the present invention is not limited to the above exemplary embodiments. Any modifications, equivalent replacements, improvements, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. A method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst, characterized in that: The steps include: The copolymer monomer and the diene monomer are emulsified in the presence of a surfactant, a hydrogenation catalyst, other additives and water, an initiator is added to carry out a polymerization reaction at a polymerization temperature, a terminator is added, the temperature is increased, and a hydrogenation reaction is carried out under high-pressure hydrogen to obtain a hydrogenated nitrile rubber latex.

2. The method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst according to claim 1, characterized in that: The method specifically comprises the following steps: S1. The surfactant, hydrogenation catalyst, comonomer, diene monomer, optional additives and water are mixed and emulsified at room temperature; S2. Adding an initiator to carry out polymerization at a polymerization temperature, wherein the polymerization temperature is 2 to 40 ° C. After the polymerization is completed, a terminator is added; S3. Raise the temperature and introduce high-pressure hydrogen to carry out hydrogenation reaction to obtain hydrogenated nitrile rubber latex. Preferably, the method specifically comprises the following steps: S1. Mix 2 to 15 parts of a surfactant, 0.01 to 0.2 parts of a hydrogenation catalyst, 10 to 60 parts of a comonomer, 40 to 90 parts of a diene monomer, 0.3 to 3 parts of an additive and 300 to 1500 parts of water by mass, and emulsify at room temperature for 0.2 to 2 hours; S2. Add 0.01-1 parts of initiator, carry out polymerization reaction at polymerization temperature, and add terminator after the reaction is completed; S3. The polymerization product is subjected to hydrogenation reaction at a temperature of 60 to 180° C. and a hydrogen pressure of 5 to 15 MPa for 0.5 to 10 hours to obtain hydrogenated nitrile rubber latex.

3. The method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst according to claim 1, characterized in that: The comonomer is selected from at least one of acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, propyl acrylate, butyl acrylate, propyl methacrylate, butyl methacrylate, fumaric acid, maleic acid, acrylic acid and unsaturated carboxylic acids of methacrylic acid.

4. The method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst according to claim 1, characterized in that: The diene monomer is a conjugated monomer, and the conjugated monomer is selected from at least one of C4-C6 conjugated dienes. Preferably, the diene monomer is selected from at least one of 1,3-butadiene, isoprene, 1-methylbutadiene, 2,3-dimethylbutadiene, piperylene and chloroprene.

5. The method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst according to claim 1, characterized in that: The surfactant is selected from fatty acids, alkyl sulfates, ethoxylated alkanol sulfate monoesters, ethoxylated alkylphenols, alkali metal salts or ammonium salts of alkyl sulfonic acids and alkyl aryl sulfonic acids, ethoxylated monoalkylphenols, dialkylphenols and trialkylphenols, ethoxylated fatty alcohols, mono C4 to C 24 Alkali metal or ammonium salts of alkyl derivatives, di-C4 to C 24 At least one of an alkali metal salt or ammonium salt of an alkyl derivative, an alkali metal salt or ammonium salt of an alkylarylsulfonic acid, an alkylsulfonic acid, an alkali metal salt or ammonium salt of a sulfuric acid monoester of an ethoxylated alkanol, and a gemini surfactant.

6. The method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst according to any one of claims 1 to 5, characterized in that: The polymerization initiator is at least one free radical initiator, including oil-soluble initiators: azobisisobutyronitrile, dibenzoyl peroxide, isopropylbenzene hydroperoxide, etc.; water-soluble initiators: potassium persulfate, azobisisobutyramidine hydrochloride, azobisisobutylimidazoline hydrochloride, ammonium persulfate, etc.

7. The method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst according to any one of claims 1 to 5, characterized in that: The hydrogenation catalyst is selected from a noble metal complex catalyst, and the noble metal is selected from at least one of ruthenium, osmium, palladium, iridium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, silver, nickel or cobalt. Preferably, the hydrogenation catalyst is selected from at least one of a ruthenium complex, an osmium complex, a palladium complex and an iridium complex.

8. The method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst according to claim 7, characterized in that: The hydrogenation catalyst has a structure as shown in formula (A): Wherein, M is selected from ruthenium, osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, iridium, palladium, silver, nickel and cobalt; preferably, M is selected from ruthenium, osmium, palladium and iridium; L is a ligand; uncharged electron donors are preferred; Y is O, S, Se, N-R1 or P-R1 or AsR or SbR radical; X 1 , X 2 are independently selected from anionic ligands; R 1 are independently selected from hydrogen, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryloxy group, an alkoxycarbonyl group, an alkylamino group, an alkylthio group, an arylthio group, an alkyl-alkoxysilyl group, an alkyl-aryloxysilyl group, an alkyl-cycloalkoxysilyl group, an arylammonium group, an alkyl sulfonate group, an aryl sulfonate group, an alkyl phosphonate group, an aryl phosphonate group, a carboxylate group, an alkyl sulfonic acid group or an alkyl sulfinyl group, and optionally, each of the above R1 can be selectively replaced by one or more alkyl groups, halogen groups, alkoxy groups, aryl groups or heteroaryl groups; R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen radicals, organic free radicals or inorganic free radicals; R 6 is selected from H, alkyl, alkenyl, alkynyl or aryl.

9. The method for preparing hydrogenated nitrile rubber latex by emulsion polymerization hydrogenation using a ruthenium-based metal catalyst according to claim 8, characterized in that: The hydrogenation catalyst has a structure shown in formula (IV), formula (V) or formula (VI):

10. A hydrogenated nitrile rubber latex prepared by the method according to any one of claims 1 to 9, characterized in that: The hydrogenation degree of the hydrogenated nitrile rubber latex is 50-100%, the content of the comonomer is 10-60 mol%, and the conversion rate is 60-80 wt%. Preferably, the degree of hydrogenation of the hydrogenated nitrile rubber latex is greater than or equal to 90%, and the content of the comonomer is 30-40 mol%.

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