Method for preparing hydrogenated butadiene-acrylonitrile rubber latex through high-temperature emulsion polymerization hydrogenation method

Abstract

The invention belongs to the technical field of special rubber latex synthesis, and relates to a method for preparing hydrogenated butadiene-acrylonitrile rubber latex by a high-temperature emulsion polymerization hydrogenation method, which comprises the following steps: emulsifying a comonomer and a diene monomer in the presence of a surfactant and a hydrogenation catalyst, optionally adding or not adding other assistants and water; raising the temperature, adding an initiator to perform polymerization reaction, adding a terminator after the reaction is finished, and then performing hydrogenation reaction under high-pressure hydrogen and high-temperature conditions to obtain the hydrogenated rubber latex. The invention integrates and simplifies the existing NBR emulsion polymerization and emulsion hydrogenation, and aims to overcome the defects of complicated process flow, low efficiency, high energy consumption, serious pollution and the like in the prior art.

Description

Technical Field

[0001] The present invention belongs to the technical field of the synthesis of special rubber latex, and relates to a method for preparing hydrogenated nitrile rubber latex by high-temperature emulsion polymerization hydrogenation, in particular to a method in which at least one metal catalyst of ruthenium (or osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, iridium, palladium, silver, nickel) and at least one surfactant first carry out a polymerization reaction on a diene monomer and a copolymerizable monomer at a high temperature, and after the polymerization is completed, a terminator is added, and then hydrogen gas under a certain pressure is directly introduced and the temperature is raised to hydrogenate the nitrile rubber latex to produce a new method for HNBR latex. Background Art

[0002] The hydrogenation of unsaturated polymers is an important process for the chemical modification of polymers. 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] The 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 nitrile rubber, has excellent thermal oxidative degradation resistance, 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. Copolymerization of acrylonitrile-butadiene emulsion to prepare NBR latex; 2. Hydrogenation of NBR to prepare HNBR.

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

[0006] At present, the process for preparing HNBR using NBR latex is 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, it is necessary to first flocculate NBR latex into solid rubber, then crush it and dissolve it in a large amount of organic solvents. The main organic solvents used are 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 requires a large amount of raw material and time costs.

[0009] According to 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 of Japan first used 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, since carbon is prone to adsorb rubber molecules and cause agglomeration, the performance of the product is affected.

[0010] In addition, most of the active components of the supported catalyst prepared by the traditional method are distributed inside the pores. 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. Not only is the reaction time long and the process energy consumption high, but it is also easy to cause deterioration of the polymer performance.

[0011] (3) Emulsion hydrogenation method: In order to avoid the cumbersome hydrogenation steps in solution hydrogenation and avoid the use of a large amount of organic solvents, the emulsion hydrogenation method was proposed. The emulsion hydrogenation method is a method of directly adding a catalyst to NBR emulsion and then preparing HNBR emulsion 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, and organic solvents do not need to be used, 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: that is, in the first step, NBR latex is generated by emulsion polymerization, and then NBR is hydrogenated to obtain HNBR. Currently, the emulsion polymerization process is generally used to manufacture NBR, that is, monomers, initiators, surfactants and other additives are added in an aqueous medium for reaction to generate NBR; in the second step of the hydrogenation process, it includes: 1. Traditional catalytic hydrogenation, including catalytic emulsion hydrogenation and catalytic solution hydrogenation; for catalytic emulsion hydrogenation, the NBR prepared by emulsion polymerization needs to be post-treated, and then a catalyst and other additives are added in another container for reaction, with complex operations and prone to demulsification and gel formation; catalytic solution hydrogenation is to flocculate the NBR prepared by emulsion polymerization to obtain NBR solid, and then use a solvent to dissolve NBR and add a catalyst to prepare hydrogenated nitrile rubber. Solution hydrogenation requires post-treatment, uses a large amount of organic solvents causing pollution, and requires more catalyst dosage for preparing the same hydrogenated nitrile rubber, with a low solution solid content and far lower production efficiency than emulsion hydrogenation. 2. Non-catalytic hydrogenation, which also requires preparing NBR latex first, and then using non-catalytic means, with diimide participating in the redox reaction to generate a hydrogen source. Currently, in order to obtain a fast hydrogenation reaction rate, high conversion rate, eliminate the formation of gel, and save a large amount of time, cost and reduce environmental pollution, great obstacles have been encountered in this two-step hydrogenation method. Therefore, the existing HNBR production technology needs to be further improved. Summary of the Invention

[0014] To improve the deficiencies of the existing technology, the purpose of the present invention is to provide a method and application for preparing hydrogenated nitrile rubber latex by high-temperature emulsion polymerization hydrogenation, integrating and simplifying the existing NBR emulsion polymerization and emulsion hydrogenation, aiming to solve the disadvantages of the existing technology such as cumbersome process flow, low efficiency, high energy consumption and large pollution.

[0015] In the first aspect, the present invention provides a method for preparing hydrogenated rubber latex by high-temperature emulsion polymerization hydrogenation, including the following steps:

[0016] The comonomer and the diene monomer are emulsified in the presence of a surfactant, a hydrogenation catalyst, optionally with or without other additives and water. The temperature is raised and an initiator is added to carry out a polymerization reaction. After the reaction is completed, a terminator is added, and then a hydrogenation reaction is carried out under high-pressure hydrogen and high-temperature conditions to obtain a hydrogenated rubber latex.

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

[0018] S1. Mix a surfactant, a hydrogenation catalyst, a comonomer, a diene monomer, optionally added or not added additives with water, and emulsify at room temperature;

[0019] S2. Raise the temperature to the polymerization temperature and then add an initiator to carry out a polymerization reaction. After the polymerization is completed, add a terminator;

[0020] S3. Raise the temperature to the hydrogenation reaction temperature and then introduce high hydrogen pressure to carry out a hydrogenation reaction to obtain a hydrogenated 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 unsaturated carboxylic acids such as methacrylic acid.

[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(phenylsulfonic acid) ethers, alkali metal salts or ammonium salts of di-C 4 to C 24 alkyl derivatives of bis(phenylsulfonic 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.

[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, azobisisobutyramidine hydrochloride, azobisisobimidazoline 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 as 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 is selected;

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

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

[0032] R 1 are independently selected from hydrogen, halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups, aryloxy groups, alkoxycarbonyl groups, alkylamino groups, alkylthio groups, arylthio groups, alkyl-alkoxysilyl groups, alkyl-aryloxysilyl groups, alkyl-cycloalkoxysilyl groups, arylammonium groups, alkyl sulfonates, aryl sulfonates, alkyl phosphonates, aryl phosphonates, carboxylate esters, alkylsulfonic acid groups or alkylsulfinyl groups. 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;

[0033] R 2 、R 3 、R 4 and R 5 are independently selected from hydrogen groups, organic radicals or inorganic radicals;

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

[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 also provides a hydrogenated rubber latex prepared by the above method. The hydrogenation degree of the hydrogenated rubber latex is 75-100%, the content of the comonomer is 25-40 mol%, and the conversion rate is 60-95 wt%.

[0038] Beneficial effects

[0039] 1) In the present invention, a diene monomer and a comonomer are synthesized into HNBR. Before polymerization, a hydrogenation catalyst is added. After the polymerization reaction is completed, hydrogen is directly introduced for hydrogenation, reducing the post-treatment of NBR latex, removing the process of adding the hydrogenation catalyst, discharging toxic gases of butadiene, and removing the deoxygenation process before hydrogenation. The conversion rate of rubber is high, and the gel is less, which has the advantages of saving time, cost, and being green and environmentally friendly.

[0040] 2) The HNBR prepared by the present invention has a smaller particle size distribution, a higher hydrogenation degree, a faster hydrogenation rate, and high stability, is not easily demulsified, and has a very low gel content compared with the HNBR synthesized by the traditional hydrogenation method; the conversion rate of the latex synthesized by the present invention is higher than that of the traditional method. Moreover, the ruthenium (or osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, iridium, palladium, silver, nickel) metal catalyst used in the present invention has high hydrogenation activity and does not use any organic solvents and cocatalysts, which is helpful for green chemical industry. Description of the drawings

[0041] Figure 1 It is a particle size distribution diagram of the latexes prepared in Example 1 and Example 2 of the present invention;

[0042] Figure 2 It is an infrared spectrum diagram of Example 7. Detailed implementation manners

[0043] [Method for preparing hydrogenated rubber latex by high-temperature emulsion polymerization hydrogenation method]

[0044] A method for preparing hydrogenated rubber latex by high-temperature emulsion polymerization hydrogenation method includes the following steps:

[0045] Emulsify a comonomer and a diene monomer in the presence of a surfactant, a hydrogenation catalyst, optionally adding or not adding other additives and water, raise the temperature and add an initiator for polymerization reaction. After the reaction is completed, add a terminator, and then carry out a hydrogenation reaction under high-pressure hydrogen and high-temperature conditions to obtain a hydrogenated rubber latex.

[0046] According to an embodiment of the present invention, the method specifically includes the following steps:

[0047] S1. Mix a surfactant, a hydrogenation catalyst, a comonomer, a diene monomer, and optionally an additive with water, and emulsify at room temperature.

[0048] S2. Raise the temperature to the polymerization temperature, add an initiator to carry out a polymerization reaction, and add a terminator after the polymerization is completed.

[0049] S3. Raise the temperature to the hydrogenation reaction temperature, introduce high hydrogen pressure to carry out a hydrogenation reaction, and obtain a hydrogenated rubber latex.

[0050] According to an embodiment of the present invention, the method specifically includes the following steps:

[0051] S1. By mass, mix 2-15 parts of a surfactant, 0.01-0.1 part of a hydrogenation catalyst, 10-60 parts of a comonomer, 40-90 parts of a diene monomer, 0.3-3 parts of an additive with 150-1500 parts of water, and emulsify at room temperature for 0.2-1 h.

[0052] S2. Raise the temperature to 40-100 °C, add 0.5-3 parts of an initiator to carry out a polymerization reaction for 0.5-10 h, and then add a terminator to stop the reaction.

[0053] S3. Raise the temperature of the polymerization product to 70-180 °C, then introduce hydrogen to a pressure of 6-15 Mpa to carry out a hydrogenation reaction for 0.5-10 h, and obtain a hydrogenated rubber latex.

[0054] According to an embodiment of the present invention, the dosage of the surfactant is preferably 3-8 parts, the dosage of the water is preferably 150-500 parts, and the dosage of the initiator is preferably 0.5-1 part.

[0055] According to an embodiment of the present invention, the dosage of the initiator is preferably 1-3 parts, for example, 1.5 parts.

[0056] According to an embodiment of the present invention, the dosage of the hydrogenation catalyst is preferably 0.02-0.1 part, for example, 0.02 part.

[0057] According to an embodiment of the present invention, the additive includes a chain transfer agent and / or a pH regulator.

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

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

[0060] According to an embodiment of the present invention, the temperature of the emulsification is room temperature.

[0061] According to an embodiment of the present invention, the emulsification time is 0.2 to 1 h, preferably 0.5 to 1 h.

[0062] According to an embodiment of the present invention, step S1 includes the following steps:

[0063] S1-a. First, dissolve 2 to 15 parts of a surfactant in a part of water to obtain a surfactant solution;

[0064] S1-b. Add 10 - 60 parts of a copolymerizable monomer, 0.01 - 0.1 part of a hydrogenation catalyst, 0.25 - 2 parts of a chain transfer agent, 0.01 - 0.6 part of a pH regulator, and the balance of water to the surfactant solution and mix;

[0065] S1-c. Introduce an inert gas into the reaction kettle for degassing, add 40 - 90 parts of a diene monomer, and emulsify for 0.2 to 2 h at room temperature to obtain an emulsified product.

[0066] 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 particle stability 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.

[0067] According to an embodiment of the present invention, in step S1-b, during the reaction process, the acidity and alkalinity in the system cannot be automatically maintained constant but are 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 a 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.

[0068] According to an embodiment of the present invention, in step S1-c, introducing an inert gas replaces 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, first emulsify the copolymerizable monomer and the diene monomer. Under the action of the surfactant, the surface tension of water decreases, and the copolymerizable monomer and the diene monomer are wrapped in the micelles, forming uniform-sized oily monomer droplets, thereby ensuring sufficient monomer concentration in the system during the reaction and the stability of the monomer droplets.

[0069] 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 to 1 MPa, for example, 0.5 MPa.

[0070] 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 to 600 rpm, preferably 160 to 360 rpm. Further preferably, the stirring speed is constant.

[0071] According to an embodiment of the present invention, the dosage of the initiator in step S2 is 0.5 - 3 parts, and the temperature of the polymerization reaction is 40 to 100 °C. Preferably, the temperature of the polymerization reaction is 40 to 70 °C.

[0072] According to an embodiment of the present invention, the stirring speed in step S2 is 200 to 900 rpm. Preferably, the stirring speed is 200 to 650 rpm. Preferably, the stirring speed is constant.

[0073] According to an embodiment of the present invention, the time of the polymerization reaction in step S2 is 0.5 to 8 h. Preferably, the time of the polymerization reaction is 2 to 6 h.

[0074] According to an embodiment of the present invention, the temperature of the reaction in step S3 is 70 to 180 °C. Preferably, it is 80 to 100 °C.

[0075] 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, 500 rpm.

[0076] According to an embodiment of the present invention, the time of the hydrogenation reaction in step S3 is 2 to 10 h. Preferably, the time of the hydrogenation reaction is 3 to 6 h, for example, 5 h.

[0077] [Comonomer and diene monomer]

[0078] 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.

[0079] According to an embodiment of the present invention, the diene monomer is a conjugated monomer, and the conjugated monomer is selected from at least one of C 4 -C 6 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.

[0080] [Surfactant]

[0081] 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) ethers, alkali metal salts or ammonium salts of di C 4 to 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.

[0082] According to an exemplary 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 to C 23 , preferably sodium oleate (NaO) or potassium oleate (KO).

[0083] According to an exemplary 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 ), sulfonic 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) or sodium dodecylbenzenesulfonate (SDBS).

[0084] According to an exemplary embodiment of the present invention, the ethoxylated monoalkylphenol, dialkylphenol, trialkylphenol or ethoxylated fatty alcohol surfactants are the following emulsifiers: ethoxylated mono-, di- or trialkylphenols (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 ).

[0085] According to an exemplary embodiment of the present invention, the alkali metal salt or ammonium salt surfactant of alkylaryl 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: alkylaryl 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 the sulfated ethoxylate of lauryl alcohol with 2 to 3 ethylene oxide units).

[0086] 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.

[0087] According to an exemplary 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.

[0088] In some embodiments of the present invention, the cationic gemini surfactant has the structure shown in formula (1):

[0089]

[0090] In formula (1), R 1 , R 2 , Y, x, and y have the definitions described in A1 - A8:

[0091] A1: R 1 = R 2 = C m H 2m+1 ; Y = CH 2 ; x + y + 1 = s; m - s - m surfactants;

[0092] A2: R 1 = R 2 = C m H 2m+1 ; Y = CH 2 , O, S, N(CH 3 ), x = y = 2;

[0093] A2: R 1 = R 2 = C m H 2m+1 ; Y = CHOH, (CHOH) 2 ; x = y = 1;

[0094] A3: R 1 = R2 = C m H 2m+1 ; Y = (OCH 2 CH 2 ) z , x = 2; y = 0; m-EOz-m surfactants;

[0095] A4: R 1 = R 2 = C m H 2m+1 ; Y = C≡C; x = y = 1;

[0096] A5: R 1 = R 2 = C m H 2m+1 ; Y = a pHenylene group; x = y = 1;

[0097] A6: R 1 = R 2 = C m H 2m+1 OC(O)CH 2 ; no Y; x = y = 1; counterion = chloride;

[0098] A7: R 1 = R 2 = C m F 2m C 4 H 8 ; no Y; x = y = 1;

[0099] 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),

[0100] Among A1 - A8, m, n, z are independently 1 - 60,

[0101] Br - can be replaced by any other anion, preferably F in Group VIIA of the periodic system - , Cl - , I - , At - , Ts - . In some embodiments of the present invention, the gemini surfactant is selected from at least one of the following:

[0102] C 12 H 25 N + (CH 3 ) 2 -(CH 2 ) n -N + (CH 3 ) 2 C 12 H 25 2Br – (n = 3–8),

[0103] C 12 H 25 N + (CH 3 ) 2 -(CH 2 ) 16 -N + (CH 3 ) 2 C 12 H 25 2Br – 、

[0104] C 16 H 33 N + (CH 3 ) 2 -(CH 2 ) 2 -N + (CH 3 ) 2 C 16 H 33 2Br – 、

[0105] C 8 H 17 N + (CH 3 ) 2 -(CH 2 ) 3 -N + (CH 3 ) 2 C 8 H 17 2Br – 、

[0106] C 12 H 25 N + (CH 3 ) 2 -(CH 2 ) 2-O-(CH 2 ) 2 -N + (CH 3 ) 2 C 12 H 25 2Cl – 、

[0107] C 16 H 33 N + (CH 3 ) 2 -(CH 2 ) 5 -N + (CH 3 ) 2 C 16 H 33 2Br – 、

[0108] C 16 H 33 N + (CH 3 ) 2 -(CH 2 ) 2 -O-(CH 2 ) 2 -N + (CH 3 ) 2 C 16 H 33 2Br – 、

[0109] 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 – 、C 12 H 25 N + (CH 3 ) 2 -CH 2 -CH(OH)-CH 2 -N + (CH3 ) 2 C 12 H 25 2Br – 、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 – 、

[0110] 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 – 、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 – 、C 12 H 25 OPO 2 – -O-(CH 2 ) 6 -OPO 2 – -OC 12 H 25 2Na + 、

[0111] 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 + 。

[0112] 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.

[0113] In the examples of the present invention, the surfactants used include: anionic surfactants and gemini surfactants. The anionic surfactants produce latex particles with smaller particle sizes, good latex stability, and are not prone to generating agglomerates during the polymerization process, enabling the production of a latex with a high solid content and stability; the gemini surfactants have good chemical stability to electrolytes, but the polymerization reaction rate is gentle, the particle size of the resulting latex particles is larger, and agglomerates are easily generated during the polymerization process.

[0114] [Polymerization initiator]

[0115] According to an embodiment of the present invention, the polymerization initiator of the hydrogenated rubber latex is at least one free radical initiator, including oil-soluble initiators: azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, etc.; water-soluble initiators: potassium persulfate, azodiisobutyramidine hydrochloride, azodiisobimidazoline hydrochloride, ammonium persulfate, etc.

[0116] According to an exemplary embodiment of the present invention, the initiator is any one or several of ammonium persulfate, potassium persulfate, and sodium persulfate. The persulfide initiator has strong thermal decomposition ability, fast reaction speed, and the concentration of free radicals generated can reach the highest concentration for the reaction at room temperature.

[0117] [Auxiliary agent]

[0118] 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, and n-butyl mercaptan.

[0119] In the examples of the present invention, the chain transfer agent is selected from dodecyl mercaptan, and dodecyl mercaptan has good performance and can effectively reduce the molecular weight of the latex.

[0120] 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, and sodium bicarbonate.

[0121] [Terminator]

[0122] Substances having the following structure or capable of forming the following structure can all be used as terminators: quinones, nitro groups, nitroso groups, aryl polyhydroxy compounds, and many sulfur-containing compounds.

[0123] According to an embodiment of the present invention, the terminator is selected from N,N-diethylhydroxylamine.

[0124] [Hydrogenation catalyst]

[0125] 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.

[0126] According to an embodiment of the present invention, the hydrogenation catalyst has the structure shown in formula (A):

[0127]

[0128] 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;

[0129] L is a ligand; preferably an uncharged electron donor is selected;

[0130] Y is a radical of O, S, Se, N-R1, P-R1, AsR, or SbR;

[0131] X 1 、X 2 are independently selected from anionic ligands;

[0132] R 1 are independently selected from hydrogen, halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups, aryloxy groups, alkoxycarbonyl groups, alkylamino groups, alkylthio groups, arylthio groups, alkyl-alkoxysilyl groups, alkyl-aryloxysilyl groups, alkyl-cycloalkoxysilyl groups, arylammonium groups, alkyl sulfonates, aryl sulfonates, alkyl phosphonates, aryl phosphonates, carboxylates, alkylsulfonyl groups, or alkylsulfinyl groups. Optionally, each of the above R1 can be selectively substituted by one or more alkyl groups, halogen groups, alkoxy groups, aryl groups, or heteroaryl groups;

[0133] R 2 、R 3 、R 4 and R 5 are each independently selected from a hydrogen group, an organic radical or an inorganic radical;

[0134] R 6 is selected from H, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0135] According to an embodiment of the present invention, the hydrogenation catalyst is added to the diolefin-based polymer aqueous medium suspension in a solid form.

[0136] This type of catalyst represented by the general formula (A) is generally insoluble in water. In this application, "water-insoluble" means that at 24 ± 2 °C, 0.001 or less weight content of the substance can be completely dissolved in 100 equivalents of water, while at 24 ± 2 °C, 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".

[0137] 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 -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 the H in these substituents may be replaced by one or more C 1 -C 30 -alkyl, C 1 -C 20 -alkoxy, halogen, C 6 -C 24 -aryl or heteroaryl are selectively substituted.

[0138] 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, linear or branched C 1 -C 30 -alkyl, C 5 -C 20 -cycloalkane, linear 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.

[0139] Preferably, the C 1 -C 30 -alkyl radical, C 1 -C 20 -alkoxy radical may be interrupted by one or more double bonds or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.

[0140] According to an embodiment of the present invention, 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.

[0141] According to an embodiment of the present invention, R 6 is selected from hydrogen, C 1 -C 30 -alkyl radical, C 2 -C 20 -alkenyl radical, C 2 -C 20 -alkynyl radical or C 6 -C 24 -aryl radical, and R 6 is particularly preferably hydrogen.

[0142] According to an embodiment of the present invention, the X 1 , X 2are the same or different anionic ligands.

[0143] According to an embodiment of the present invention, said X 1 , X 2 are independently selected from H, halogen, pseudohalogen, linear or branched C 1 -C 30 -alkyl, C 6 -C 24 -aryl, C 1 -C 20 -alkoxy, C 6 -C 24 -aryloxy, C 3 -C 20 -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 C 1 -C 20 -alkylsulfinyl.

[0144] According to an embodiment of the present invention, the H on said X 1 , X 2 can be further substituted by other groups, preferably substituted by halogen, C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy or C 6 -C- 24 aryl, and further preferably substituted by fluorine, C 1 -C 5 -alkyl, C 1 -C 5 -alkoxy or phenyl, and preferably, the H on the substituent can be further substituted by one or more halogens.

[0145] As an example, said X 1 , X 2 are independently selected from chlorine, CF 3 COO, CH 3 COO, CFH 2 COO, (CH3 ) 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 ).

[0146] According to an embodiment of the present invention, L is selected from an uncharged electron donor, preferably L is selected from a phosphine, phosphine, sulfonated phosphine, phosphate, hypophosphite, phosphite, sulfonate, sulfoxide, carboxyl, nitrosyl, nitrile, isonitrile, sulfonated phosphine, phosphate, hypophosphite, phosphite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrite, pyridine, thioether or N-heterocyclic carbene ligand.

[0147] According to an embodiment of the present invention, the hypophosphorous acid is selected from phenyldiphenylphosphorous acid, cyclohexyldicyclohexylphosphorous acid, isopropyldiisopropylphosphorous acid or methyldiphenylphosphorous acid.

[0148] According to an embodiment of the present invention, the phosphite is selected from triphenylphosphite, tricyclohexylphosphite, tri-tert-butylphosphite, triisopropylphosphite or methyldiphenylphosphite.

[0149] According to an embodiment of the present invention, the antimonide is selected from triphenyl Tricyclohexyl or trimethyl

[0150] According to an embodiment of the present invention, the sulfonate is selected from trifluoromethylsulfonate, toluenesulfonate or methanesulfonate.

[0151] 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.

[0152] According to an embodiment of the present invention, the thioether is selected from CH 3 SCH 3 , C 6 H 5SCH 3 、CH 3 OCH 2 CH 2 SCH 3 or tetrahydrothiophene.

[0153] According to an embodiment of the present invention, the term "pyridyl ligand" is used as a general term for all pyridine-based ligands or their derivatives, as is the case, for example, in WO-A-03 / 011455. The term "pyridyl ligand" includes pyridine itself, methylpyridine (such as α-, β- and γ-methylpyridine), dimethylpyridine (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.

[0154] According to an embodiment of the present invention, L is selected from electron-donating phosphines having the structure shown in formula (IIf):

[0155]

[0156] wherein R 12 、R 13 and R 14 are the same or different, preferably the same, and are 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.

[0157] 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.

[0158] According to an embodiment of the present invention, the C 3 -C 8 -cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

[0159] According to an embodiment of the present invention, the C 1 -C 20- alkoxy group is phenyl, biphenyl, naphthalene, phenanthrene, anthracene, tolyl or 2,6-dimethylphenyl.

[0160] 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(CH 2 C 6 H 4 -SO 3 Na) 3 , P(isopropyl) 3 , P(CHCH 3 (CH 2 CH 3 )) 3 , P(cyclopentyl) 3 , P(cyclohexyl) 3 , P(neopentyl) 3 or P(neopentyl) 3 , where Ph represents phenyl and Tol represents tolyl.

[0161] 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.

[0162] 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.

[0163] According to an embodiment of the present invention, the NHC-ligand has a structure as shown in formulas (IIa)-(IIe):

[0164]

[0165] 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 heterocyclic aryl, C 2 -C 20 heterocycle, C 1 -C 20 -alkoxy, C 2 -C 20 -alkenyl, 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.

[0166] 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.

[0167] According to an embodiment of the present invention, R 8 、R 9, R 10 and R 11 The H in can be independently substituted by one or more substituents selected from linear 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.

[0168] Among them, the H in the above substituents can, to a certain extent in chemistry, 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.

[0169] It should be added that the NHC-ligand structures of the general formulas (IIa) and (IIb) depicted in the present invention are the same as 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.

[0170]

[0171] In a preferred NHC-ligand in 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, linear 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.

[0172] According to an embodiment of the present invention, R 8 and R9 can be one or more 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.

[0173] In a further preferred NHC-ligand in 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 -C 10 --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 --alkylsulfonate or C 6 -C 10 -sulfonic acid.

[0174] 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.

[0175] 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 represent hydrogen, C 6 -C 24 -aryl, more preferably benzene, linear 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 forming a bond to a carbon atom.

[0176] R 10 and R 11 are the same or different, preferably linear or branched C 1 -C 10 -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 -alkylsulfonate or C 6 -C 10 -sulfonic acid.

[0177] 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 sec-butyl. "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.

[0178]

[0179] 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 degree of steric crowding.

[0180] 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.

[0181] 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 -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 can be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.

[0182] 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 C1 -C 30 – The alkyl radical, in appropriate cases, can be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen. R 1 Straight-chain or branched C 1 -C 12 -alkyl radicals are particularly preferred.

[0183] Preferably, C 3 -C 20 -cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0184] According to an embodiment of the present invention, R 1 is preferably a C 1 -C 12 -alkyl radical, C 1 -C 12 -alkyl radicals are 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.

[0185] 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 acenaphthene.

[0186] In the general formula (A), the radicals R 2 , R 3 , R 4 and R 5 are the same or different and can be hydrogen, organic, or inorganic radicals.

[0187] 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, alkenoxy, alkynoxy, 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.

[0188] R 2 , R3 , R 4 and R 5 are usually the same or different, and each may be hydrogen, halogen, preferably chlorine or bromine, nitro, CF 3 , C 1 -C 30 -alkyl, C 3 -C 20 -alkoxy, 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.

[0189] In one particularly useful embodiment, R 2 , R 3 , R 4 and R 5 are the same or different, and each may be nitro, straight-chain or branched C 1 -C 30 -alkyl, C 5 -C 20 -cylcoalkyl, straight-chain 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 can be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.

[0190] In addition, two or more radicals R 2 , R 3 , R 4 or R 5 can also be connected 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) can form a fused phenyl ring, and overall, a naphthyl structure is produced.

[0191] In the general expression (A), the radical R 6 is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical. R 6 is preferably hydrogen, C 1 -C 30 -alkyl radical, C 2 -C 20 -alkenyl radical, C 2 -C 20 -alkynyl radical or C 6 -C 24 -aryl radical. R 6 is particularly preferably hydrogen.

[0192] 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).

[0193]

[0194] According to an embodiment of the present invention, the reaction kettle is selected from high-pressure reaction kettles, such as a high-temperature and high-pressure stainless steel reaction kettle.

[0195] 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, and the high-pressure gas is, for example, inert gas and hydrogen.

[0196] 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.

[0197] According to an embodiment of the present invention, an exhaust port is further provided on the kettle body.

[0198] According to an embodiment of the present invention, a pressure sensor is further provided in the kettle body, and the range of the pressure sensor is -1 to 30 MPa.

[0199] According to an embodiment of the present invention, a temperature sensor is further provided in the kettle body, and the range of the temperature sensor is 0 to 180 °C.

[0200] 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, and the stirring speed of the stirring device is 0 to 800 rpm.

[0201] [Hydrogenated rubber latex]

[0202] The present invention also provides a hydrogenated rubber latex prepared by the above method. The hydrogenation degree of the hydrogenated rubber latex is 75-100%, the content of the comonomer is 25-40 mol%, and the conversion rate is 60-95 wt%.

[0203] According to an embodiment of the present invention, the hydrogenation degree of the hydrogenated rubber latex is greater than or equal to 85%, preferably the hydrogenation degree of the hydrogenated rubber latex is greater than or equal to 95%, and further preferably, the hydrogenation degree of the hydrogenated rubber latex is greater than or equal to 97%, for example, 86.5%, 98.5%, 87.5%, 99.2%, 99.5%, 98.6%, 99.6%, 99.1.

[0204] According to an embodiment of the present invention, the content of the comonomer is 30-35 mol%, for example, 32 mol%, 33 mol%, 34 mol%, 35 mol%.

[0205] According to an embodiment of the present invention, the particle size of the hydrogenated rubber latex is 80-140 nm, preferably the particle size of the hydrogenated rubber latex is 90-120 nm, for example, 87.7 nm, 107.8 nm, 82 nm, 96 nm, 86 nm, 84 nm, 97 nm, 98 nm, 89 nm.

[0206] According to an embodiment of the present invention, the conversion rate of the hydrogenated rubber latex is 65 - 85 wt%, for example, the conversion rate of the hydrogenated rubber latex is 63.6 wt%, 76.5 wt%, 70.3 wt%, 75.5 wt%, 75.3 wt%, 81.3 wt%, 83.2 wt%, 73.2 wt%, 76.2 wt%.

[0207] According to an embodiment of the present invention, in the hydrogenated rubber latex, the hydrogenated rubber molecules are distributed in nano - micelles and exist in the form of latex.

[0208] According to an embodiment of the present invention, the hydrogenated rubber solid rubber can be obtained by first flocculating the hydrogenated rubber latex and then performing post - treatments such as washing and drying on the flocculated product.

[0209] The preparation method of the HNBR latex by high - temperature emulsion polymerization hydrogenation method of the present invention will be further described in detail below 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.

[0210] 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.

[0211] A preparation method for preparing HNBR latex by high - temperature emulsion polymerization hydrogenation method of the present invention, the examples include:

[0212] Example 1

[0213] 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.

[0214] 2) Add 30 g of acrylonitrile, 0.05 g of the hydrogenation catalyst Hoveyda - Grubbs second - generation 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.

[0215] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, perform a 0.5 - hour degassing treatment while stirring at a speed of 200 rpm, and then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and emulsify the monomers by stirring at room temperature for 1 hour.

[0216] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of initiator potassium persulfate to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed; then adjust the rotation speed to 450 rpm and raise the temperature of the reaction kettle to 90 °C, and introduce 6 MPa of high-pressure hydrogen for the hydrogenation reaction. After reacting for 5 h, HNBR latex is obtained.

[0217] Example 2

[0218] 1) Dissolve 7 g of surfactant oleic acid potassium in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0219] 2) Add 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst Hoveyda-Grubbs second-generation catalyst, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate to the reaction kettle.

[0220] 3) Introduce 0.5 Mpa of inert gas (nitrogen) into the reaction kettle, perform degassing treatment for 0.5 h while stirring at a rotation speed of 200 rpm, then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir and emulsify the monomers at room temperature for 1 h.

[0221] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of initiator potassium persulfate to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed; then adjust the rotation speed to 450 rpm and raise the temperature of the reaction kettle to 90 °C, and introduce 6 MPa of high-pressure hydrogen for the hydrogenation reaction. After reacting for 5 h, HNBR latex is obtained.

[0222] Example 3

[0223] 1) Dissolve 7 g of surfactant sodium dodecylbenzenesulfonate in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0224] 2) Add 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst Hoveyda-Grubbs second-generation catalyst, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate to the reaction kettle.

[0225] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, perform degassing treatment for 0.5 h while stirring at a rotation speed of 200 rpm, then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir and emulsify the monomers at room temperature for 1 h.

[0226] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of the initiator potassium persulfate to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed; then adjust the rotation speed to 450 rpm and raise the temperature of the reaction kettle to 90 °C, and introduce 6 MPa of high-pressure hydrogen for the hydrogenation reaction. After reacting for 5 h, HNBR latex is obtained.

[0227] Example 4

[0228] 1) Dissolve 10 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 30 g of acrylonitrile, 0.05 g of the hydrogenation catalyst Hoveyda-Grubbs second-generation 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.

[0230] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, perform a degassing treatment for 0.5 h while stirring at a rotation speed of 200 rpm, and then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir and emulsify the monomers at room temperature for 1 h.

[0231] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of the initiator benzoyl peroxide to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed; then adjust the rotation speed to 450 rpm and raise the temperature of the reaction kettle to 90 °C, and introduce 6 MPa of high-pressure hydrogen for the hydrogenation reaction. After reacting for 5 h, HNBR latex is obtained.

[0232] Example 5

[0233] 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.

[0234] 2) Add 30 g of acrylonitrile, 0.07 g of the hydrogenation catalyst Hoveyda-Grubbs second-generation 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.

[0235] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, perform a degassing treatment for 0.5 h while stirring at a rotation speed of 200 rpm, and then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir and emulsify the monomers at room temperature for 1 h.

[0236] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of initiator potassium persulfate to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed; then adjust the rotation speed to 450 rpm and raise the temperature of the reaction kettle to 90 °C, and introduce 6 MPa of high-pressure hydrogen for the hydrogenation reaction. After reacting for 5 h, HNBR latex is obtained.

[0237] Example 6

[0238] 1) Dissolve 7 g of surfactant oleic acid potassium in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0239] 2) Add 30 g of acrylonitrile, 0.1 g of hydrogenation catalyst Hoveyda-Grubbs second-generation catalyst, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate to the reaction kettle.

[0240] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, perform a degassing treatment for 0.5 h while stirring at a rotation speed of 200 rpm, and then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir and emulsify the monomers at room temperature for 1 h.

[0241] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of initiator potassium persulfate to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed; then adjust the rotation speed to 450 rpm and raise the temperature of the reaction kettle to 90 °C, and introduce 6 MPa of high-pressure hydrogen for the hydrogenation reaction. After reacting for 5 h, HNBR latex is obtained.

[0242] Example 7

[0243] 1) Dissolve 7 g of surfactant oleic acid potassium in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0244] 2) Add 30 g of acrylonitrile, 0.05 g of hydrogenation catalyst Hoveyda-Grubbs second-generation catalyst HG2, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate to the reaction kettle.

[0245] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, perform a degassing treatment for 0.5 h while stirring at a rotation speed of 200 rpm, and then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir and emulsify the monomers at room temperature for 1 h.

[0246] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of initiator potassium persulfate to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed; then adjust the rotation speed to 450 rpm and raise the temperature of the reaction kettle to 90 °C, and introduce high-pressure hydrogen gas of 6 MPa for the hydrogenation reaction. After reacting for 5 h, HNBR latex is obtained.

[0247] Comparative Example 1

[0248] 1) Dissolve 7 g of surfactant oleic acid potassium in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0249] 2) Add 30 g of acrylonitrile, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate to the reaction kettle.

[0250] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, and perform degassing treatment for 0.5 h while stirring at a rotation speed of 200 rpm. Then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir and emulsify the monomers at room temperature for 1 h.

[0251] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of initiator potassium persulfate to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed;

[0252] 5) After the polymerization reaction is completed; perform monomer removal treatment on the emulsion, then add a small amount of surfactant and catalyst, and then perform degassing. After raising the temperature to 90 °C, introduce high-pressure hydrogen gas of 6 MPa for the hydrogenation reaction. After reacting for 5 h, HNBR is obtained.

[0253] Comparative Example 2

[0254] 1) Dissolve 7 g of surfactant oleic acid potassium in 300 g of deionized water to obtain an aqueous surfactant solution and add it to the reaction kettle.

[0255] 2) Add 30 g of acrylonitrile, 0.3 g of chain transfer agent tert-dodecyl mercaptan, and 0.05 g of pH regulator sodium phosphate to the reaction kettle.

[0256] 3) Introduce 0.5 MPa of inert gas (nitrogen) into the reaction kettle, and perform degassing treatment for 0.5 h while stirring at a rotation speed of 200 rpm. Then add 70 g of butadiene in liquid form to the degassed reaction kettle, mix, and stir and emulsify the monomers at room temperature for 1 h.

[0257] 4) After the emulsification is completed, raise the temperature to 40 °C, add 1.5 g of initiator potassium persulfate to the reaction kettle to start the polymerization reaction, and add a terminator after the polymerization is completed;

[0258] 5) After the polymerization reaction is completed, the emulsion is subjected to de - monomer treatment, then flocculated and washed, and finally dried.

[0259] 6) The solid NBR after drying is shredded, solubilized with chlorobenzene to prepare a rubber concentration of about 10%, then added to a reaction kettle. After heating to 90 °C, high - pressure hydrogen of 6 MPa is introduced for hydrogenation reaction. After reacting for 5 h, HNBR is obtained.

[0260] Table 1 Conditions for preparing NBR latex in Examples 1 - 7 and Comparative Examples 1 - 2

[0261]

[0262]

[0263] In Table 1, Gemini represents didodecyldimethylammonium bromide, SDBS represents sodium dodecylbenzenesulfonate, and KO represents potassium oleate.

[0264] The following methods are used to calculate or measure the properties of the NBR latex prepared in Examples 1 - 7 and Comparative Examples 1 - 2:

[0265] Calculation of hydrogenation degree: Based on the corresponding absorbances of the characteristic peaks at 2236 cm -1 , 970 cm -1 and 723 cm -1 in the FT - IR spectrum.

[0266] 2236 cm -1 is the characteristic peak of cyano (-C≡N), 970 cm -1 is the characteristic peak of -C=C-(trans 1,4 structure), and 723 cm -1 is the characteristic peak of (-CH2)n, n > 4.

[0267]

[0268] K(723)=0.255, K(970)=2.3 are the specific constants of HNBR.

[0269] Then the relative amount of -C=C- in HNBR is:

[0270]

[0271] The relative amount of methylene formed by hydrogenation of -C=C- in NBR is:

[0272]

[0273] The hydrogenation degree calculation formula is:

[0274]

[0275] Acrylonitrile content: It is obtained by measuring the N atom content using elemental analysis to obtain the acrylonitrile content.

[0276] Determination of polymer conversion rate: The solid content of the latex is measured using a moisture meter, and the conversion rate of the monomer in the polymerization reaction is calculated.

[0277] The polymer conversion rate is calculated by Equation (7).

[0278]

[0279] Wherein, W1 is the weight of the solid in the NBR latex, W2 is the weight of the added solid (such as surfactant and initiator), W3 is the weight of all monomers, and x is the reading on the moisture meter.

[0280] Polymer particle size: The particle size of the nanoparticles was measured by dynamic light scattering (DLS) using a Nano ZS 3500 nanosizer.

[0281] Table 2 Performance test results of NBR latexes prepared in Examples 1-7 and Comparative Examples 1-2

[0282] Particle size (nm) Acrylonitrile content (%) Conversion rate (%) Hydrogenation degree (%) Example 1 87.7 32 63.6 86.5 Example 2 107.8 32 76.5 98.5 Example 3 82 33 70.3 87.5 Example 4 96 33 75.5 99.2 Example 5 86 34 75.3 99.5 Example 6 84 34 81.3 98.6 Example 7 97 35 83.2 99.6 Comparative Example 1 98 33 73.2 98.6 Comparative Example 2 89 34 76.2 99.1

[0283] As can be seen from Table 2, the hydrogenated nitrile butadiene latex prepared by the one-step high-temperature emulsion polymerization hydrogenation method of the present invention has stable latex properties, good size uniformity of nano-micelles, a small particle size distribution range, is not easily demulsified, has a simple preparation method, is easy to operate, and is easy to industrialize; the hydrogenation effect is good and the hydrogenation degree is high during the synthesis process. Compared with Comparative Example 1, emulsion hydrogenation saves a large number of steps, reduces investment and energy consumption; compared with Comparative Example 2, flocculation washing and many steps of shearing the sol before hydrogenation are omitted, the use of organic solvents is reduced, it is more environmentally friendly, and the latex produced by emulsion hydrogenation will increase an application range.

[0284] 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 substitutions, 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 rubber latex by high temperature emulsion polymerization hydrogenation method, characterized in that: The steps include: The comonomer and the diene monomer are emulsified in the presence of a surfactant, a hydrogenation catalyst, optionally with or without other additives and water, the temperature is raised and an initiator is added to carry out a polymerization reaction, after the reaction is completed, a terminator is added, and then a hydrogenation reaction is carried out under high pressure hydrogen and high temperature conditions to obtain a hydrogenated rubber latex.

2. The method for preparing hydrogenated rubber latex by high temperature emulsion polymerization hydrogenation method according to claim 1, characterized in that: The method comprises the following steps: S1. The surfactant, hydrogenation catalyst, comonomer, diene monomer, optional additives and water are mixed and emulsified at room temperature; S2. After raising the temperature to the polymerization temperature, an initiator is added to carry out the polymerization reaction, and after the polymerization is completed, a terminator is added; S3. After raising the temperature to the hydrogenation reaction temperature, high hydrogen pressure is introduced to carry out hydrogenation reaction to obtain hydrogenated rubber latex. Preferably, the method specifically comprises the following steps: S1. Mix 2 to 15 parts of a surfactant, 0.01 to 0.1 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 150 to 1500 parts of water by mass, and emulsify at room temperature for 0.2 to 1 hour; S2. Raise the temperature to 40-100°C, add 0.5-3 parts of initiator to carry out polymerization for 0.5-10h, then add terminator to stop the reaction; S3. Raise the temperature and keep the polymerization product at 70 to 180°C, then introduce hydrogen to a pressure of 6 to 15 MPa for a hydrogenation reaction for 0.5 to 10 hours to obtain hydrogenated rubber latex. Preferably, step S1 comprises the following steps: S1-a, first dissolving 2 to 15 parts of a surfactant in a portion of water to obtain a surfactant solution; S1-b, adding 10-60 parts of copolymerizable monomers, 0.01-0.1 parts of hydrogenation catalysts, 0.25-2 parts of chain transfer agents, 0.01-0.6 parts of pH regulators and the balance of water into a surfactant solution and mixing; S1-c, introducing inert gas into the reaction kettle for degassing, adding 40-90 parts of diene monomer, and emulsifying at room temperature for 0.2-2 hours to obtain an emulsified product.

3. The method for preparing hydrogenated rubber latex by high temperature emulsion polymerization hydrogenation method 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 rubber latex by high temperature emulsion polymerization hydrogenation method 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 rubber latex by high temperature emulsion polymerization hydrogenation method according to claim 1, characterized in that: The surfactant is selected from fatty acids, alkyl sulfates, sulfuric acid monoesters of ethoxylated alkanols, ethoxylated alkylphenols, alkali metal salts or ammonium salts of alkylsulfonic acids and alkylarylsulfonic acids, ethoxylated monoalkylphenols, dialkylphenols and trialkylphenols, ethoxylated fatty alcohols, mono C4 to C5 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 rubber latex by high temperature emulsion polymerization hydrogenation 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 rubber latex by high temperature emulsion polymerization hydrogenation 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 rubber latex by high temperature emulsion polymerization hydrogenation method 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 rubber latex by high temperature emulsion polymerization hydrogenation method 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 rubber latex prepared by the method according to any one of claims 1 to 9, characterized in that: The hydrogenation degree of the hydrogenated rubber latex is 75-100%, the content of the comonomer is 25-40 mol%, and the conversion rate is 60-95 wt%; Preferably, the degree of hydrogenation of the hydrogenated rubber latex is greater than or equal to 85%, the content of the comonomer is 30-35 mol%, and the conversion rate of the hydrogenated rubber latex is 65-85 wt%.

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