Method for preparing hydrogenated rubber latex by one-step method

Abstract

The invention provides a method for preparing hydrogenated rubber latex by a one-step method, 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, lowering the temperature, adding an initiator, and introducing hydrogen with certain pressure to carry out prepolymerization reaction, and raising the temperature to carry out polymerization and hydrogenation reactions to obtain the hydrogenated rubber latex. According to the hydrogenated rubber latex prepared by prepolymerizing the diene monomer and the copolymerizable monomer at low temperature and certain hydrogen pressure and then raising the temperature to continue the reaction, nano-particle micelles in the latex are stable in performance, the nano-micelles are good in size uniformity, small in particle size distribution range, small in particle size and not prone to demulsification, and the preparation method is simple, convenient to operate and suitable for industrial production. The industrialization is easy to realize.

Description

Technical Field

[0001] The present invention belongs to the technical field of special rubber latex synthesis, and relates to a one-step method for preparing hydrogenated rubber latex, and specifically relates to a method for producing hydrogenated rubber latex by prepolymerizing a diene monomer and a copolymerizable monomer using a ruthenium (or osmium, iron, molybdenum, tungsten, titanium, rhenium, copper, chromium, manganese, rhodium, vanadium, zinc, gold, iridium, palladium, silver, nickel and cobalt) hydrogenation catalyst, at least one surfactant and an initiator at low temperature and a certain hydrogen pressure, and then raising the temperature to continue the reaction. Background Art

[0002] The hydrogenation of unsaturated polymers is an important process in polymer chemical modification. It not only provides a targeted approach to improve the mechanical, chemical, physical, and thermal properties of unsaturated polymers, but also provides a convenient route to synthesize polymers with desired microstructures and unique stereochemical properties.

[0003] Selective hydrogenation of unsaturated olefin groups in nitrile rubber (NBR) is an industrially successful commercial hydrogenation process. Hydrogenated nitrile rubber (HNBR) maintains the elastomeric properties of nitrile rubber, has excellent resistance to thermal oxidative degradation, and has significant improvements in mechanical properties such as tensile strength, elongation, wear resistance and hardness. Due to these superior physical and chemical properties, HNBR has been used in 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 the main force in high-performance elastomer applications.

[0004] The traditional HNBR preparation process is divided into two steps: 1. Preparation of NBR latex by acrylonitrile-butadiene emulsion copolymerization; 2. Preparation of HNBR by hydrogenation of NBR.

[0005] The preparation of NBR latex is usually carried out by adding acrylonitrile-butadiene emulsion monomers and initiators, surfactants and other additives to an aqueous medium to react to generate NBR. This method has major technical defects. The prepared NBR latex contains a large amount of unreacted monomers, resulting in a high VOC (volatile organic compounds) content 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 of preparing HNBR using NBR latex is divided into catalytic hydrogenation and non-catalytic hydrogenation, wherein 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 that NBR latex is directly converted into HNBR latex under the action of hydrazine hydrate, oxygen or hydrogen peroxide and other oxidants 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, the reaction conditions are mild, and the equipment is simple. The disadvantage is that cross-linking side reactions are easily generated on the unhydrogenated double bonds. If the cross-linking is serious, it will lead to difficulty in plasticization. Therefore, there is no industrial production at present.

[0008] (2) NBR solution hydrogenation method: NBR solution hydrogenation method is currently the main method for industrial production of HNBR. During the operation, the NBR latex needs to be flocculated into a solid glue, and then crushed and dissolved in a large amount of organic solvents. The organic solvents used mainly include cyclohexanone, xylene and chloroform. It not only causes environmental pollution, but also has a long reaction time, high reaction temperature, high energy consumption, and requires a large amount of raw materials 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 of the homogeneous solution hydrogenation method includes an inorganic carrier and a Group VIII metal coated on the inorganic carrier. The catalyst of the heterogeneous solution hydrogenation method includes an inorganic carrier and a rhodium, ruthenium and / or palladium metal coated on the inorganic carrier. The inorganic carrier includes alumina, silicon oxide, activated carbon, carbon black, alkaline earth metal carbonate, etc. After the heterogeneous solution hydrogenation reaction is completed, the hydrogenation product is usually directly separated from the catalyst by filtering or centrifugal separation. For example, Japan's Zeon Company first used supported catalysts for NBR hydrogenation reactions in the 1980s. The heterogeneous support catalyst used was a palladium / carbon catalyst with carbon as the carrier. The catalyst had high selectivity and a hydrogenation rate of up to 95.6%. However, in the hydrogenation reaction, carbon easily adsorbed rubber molecules and caused agglomeration, which affected the performance of the product.

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

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

[0012] Compared with the organic solution catalytic hydrogenation method, the aqueous phase-based NBR emulsion catalytic hydrogenation has very obvious advantages: milder reaction conditions, fewer reaction processes, no need to use organic solvents, energy saving and pollution reduction. The emulsion catalytic hydrogenation method greatly reduces the preparation cost of HNBR, and the hydrogenated product can be directly applied to the HNBR emulsion demand industry. In this field, Professor Garry L. Rempel's research group has carried out a lot of work and achieved quite outstanding research results. However, due to the fact that the existing polymerization technology can achieve emulsion hydrogenation of NBR latex brands is relatively small, and the hydrogenation process needs to further introduce a large number of surfactants and other factors, 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, which have the disadvantages of long reaction time, high cost, high energy consumption, environmental pollution, etc., and it is necessary to further improve the technology for producing HNBR. Summary of the invention

[0014] The purpose of the present invention is to provide a one-step method for preparing hydrogenated rubber latex (HR latex) and its application, integrating the existing unsaturated rubber emulsion polymerization and emulsion hydrogenation into one step, aiming to solve the shortcomings of the prior art such as cumbersome process flow, low efficiency, high energy consumption and large pollution. The present invention adopts the design of low-temperature prepolymerization and high-temperature polymerization / hydrogenation, with excellent performance, fast hydrogenation rate and lower energy consumption. Specifically, the present invention provides the following technical solutions:

[0015] A one-step method for preparing hydrogenated rubber latex comprises the following steps:

[0016] The comonomer and diene monomer are emulsified in the presence of a surfactant, a hydrogenation catalyst, other additives and water, the temperature is lowered, an initiator is added and a certain pressure of hydrogen is introduced to carry out a prepolymerization reaction, and then the temperature is increased to carry out polymerization and hydrogenation reactions to obtain hydrogenated rubber latex.

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

[0018] S1. The surfactant, hydrogenation catalyst, comonomer, diene monomer, optional additives and water are mixed and emulsified at room temperature;

[0019] S2. Lowering the temperature to the prepolymerization temperature, adding an initiator and introducing high pressure hydrogen to carry out the prepolymerization reaction;

[0020] S3. Raise the temperature to carry out polymerization and hydrogenation reaction to obtain hydrogenated rubber latex.

[0021] The invention also provides hydrogenated rubber latex prepared by the method.

[0022] Specifically, the hydrogenation degree of the hydrogenated rubber latex is 70-100%, the content of the comonomer is 10-60 mol%, the content of the diene monomer is 40%-90%, and the solid content of the hydrogenated rubber latex is 10-70 wt%.

[0023] The present invention achieves the following beneficial effects:

[0024] The hydrogenated rubber latex prepared by prepolymerizing diene monomers and comonomers at low temperature and a certain hydrogen pressure and then raising the temperature to continue the reaction has stable nanoparticle micelle performance in the latex, good size uniformity of the nano micelles, a small particle size distribution range, a small particle size, and is not easy to demulsify.

[0025] In addition, the preparation method of the present invention is simple, easy to operate and easy to realize industrialization.

[0026] Secondly, the method of the present invention designs the steps of low-temperature prepolymerization and high-temperature polymerization / hydrogenation, with a fast hydrogenation rate, excellent product performance and lower energy consumption.

[0027] Furthermore, in the synthesis process of the present invention, polymerization and hydrogenation are carried out simultaneously, the hydrogenation efficiency is high, and the degree of hydrogenation is high; the conversion rate of the monomer is extremely high, which reduces all the steps required from the post-treatment of the unsaturated rubber latex to the hydrogenation of the unsaturated rubber latex, avoids the use of organic solvents, and prevents the pollution of the environment by the volatilization of unreacted monomers. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a transmission electron microscope (TEM) image of the HNBR latex prepared in Example 2 of the present invention;

[0029] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the HNBR latex prepared in Example 2 of the present invention;

[0030] Figure 3 The present invention is a flow chart for preparing hydrogenated nitrile rubber. DETAILED DESCRIPTION

[0031] [One-step method for preparing hydrogenated rubber latex]

[0032] A one-step method for preparing hydrogenated rubber latex comprises the following steps:

[0033] The comonomer and diene monomer are emulsified in the presence of a surfactant, a hydrogenation catalyst, other additives and water, the temperature is lowered, an initiator is added and a certain pressure of hydrogen is introduced to carry out a prepolymerization reaction, and then the temperature is increased to carry out polymerization and hydrogenation reactions to obtain hydrogenated rubber latex.

[0034] According to an embodiment of the present invention, the method specifically comprises the following steps:

[0035] S1. The surfactant, hydrogenation catalyst, comonomer, diene monomer, optional additives and water are mixed and emulsified at room temperature;

[0036] S2. Lowering the temperature to the prepolymerization temperature, adding an initiator and introducing high pressure hydrogen to carry out the prepolymerization reaction;

[0037] S3. Raise the temperature to carry out polymerization and hydrogenation reaction to obtain hydrogenated rubber latex.

[0038] According to an embodiment of the present invention, the method specifically comprises the following steps:

[0039] 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;

[0040] S2. lowering the temperature to the prepolymerization temperature, adding 0.001 to 1 part of an initiator to the emulsified product, and conducting a prepolymerization reaction under high pressure hydrogen;

[0041] S3. The prepolymer product is polymerized and hydrogenated at a temperature of 60 to 180° C. for 0.5 to 10 hours to obtain hydrogenated rubber latex.

[0042] According to an embodiment of the present invention, the amount of the surfactant is preferably 3 to 8 parts, the amount of water is preferably 600 to 1000 parts, and the amount of the initiator is preferably 0.005 to 1 part.

[0043] According to an embodiment of the present invention, the amount of the hydrogenation catalyst is preferably 0.02 to 0.1 parts, for example 0.05 parts.

[0044] According to an embodiment of the present invention, the auxiliary agent includes a chain transfer agent and / or a pH adjuster.

[0045] According to an embodiment of the present invention, the amount of the chain transfer agent is 0.25 to 2 parts, preferably 0.5 to 1.5 parts.

[0046] According to an embodiment of the present invention, the pH adjuster is used in an amount of 0.05 to 1.5 parts, preferably 0.1 to 0.6 parts.

[0047] According to an embodiment of the present invention, the emulsification temperature is room temperature.

[0048] According to an embodiment of the present invention, the emulsification time is 0.2 to 2 hours, preferably 0.5 to 1 hour.

[0049] According to an embodiment of the present invention, step S1 comprises the following steps:

[0050] S1-a, first dissolving 2 to 15 parts of a surfactant in a portion of water to obtain a surfactant solution;

[0051] S1-b, adding 10-60 parts of copolymerizable monomers, 0.01-0.2 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;

[0052] 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.

[0053] According to the embodiment of the present invention, in step S1-a, dissolving the surfactant in a portion of the water can effectively maintain the stability of the emulsion interface, thereby significantly improving the particle stability of the polymer nanoemulsion. In addition, using an excess of surfactant can also prepare a nanoemulsion with a smaller particle size to increase the micelle specific surface area.

[0054] According to the embodiment of the present invention, in step S1-b, the pH value in the system cannot be automatically maintained constant during the reaction, but is in dynamic change. The addition of a pH regulator can effectively maintain the pH in the system within a smaller range, so that the surfactant can effectively maintain the stability of the liquid surface, which is conducive to the reaction in a stable micelle; 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 glue. In the present invention, the hydrogenation catalyst used is compatible with the gemini surfactant, and can effectively catalyze hydrogenation, the hydrogenation rate is greatly accelerated, and the gemini surfactant activity also greatly reduces the amount of catalyst used, further reducing the cost.

[0055] According to an embodiment of the present invention, in step S1-c, an inert gas is introduced to replace the air in the reactor to ensure the purity of the gas in the reactor 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 emulsified, and under the action of the surfactant, the surface tension of water is reduced, and the comonomer and the diene monomer are encapsulated in micelles to form oily monomer droplets of uniform size, thereby ensuring sufficient monomer concentration in the system during the reaction and the stability of the monomer droplets.

[0056] 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.

[0057] According to an embodiment of the present invention, the degassing in step S1-c is performed under stirring conditions, and the stirring speed is 100 to 600 rpm, preferably 160 to 360 rpm, and more preferably, the stirring speed is constant.

[0058] According to an embodiment of the present invention, step S2 is specifically:

[0059] S2. Lower the temperature to the prepolymerization temperature, add 0.001 to 1 part of initiator to the emulsified product, and introduce high-pressure hydrogen into the reactor to carry out a prepolymerization reaction.

[0060] According to an embodiment of the present invention, the temperature of the prepolymerization reaction in step S2 is 2-40°C, preferably the temperature of the prepolymerization reaction is 5-20°C, and further preferably, the temperature of the prepolymerization reaction is 6-12°C, for example, 5°C, 6°C, 7°C, 8°C, 9°C.

[0061] According to an embodiment of the present invention, the pressure of the high-pressure hydrogen in step S2 is 3 to 15 MPa, and preferably the pressure of the high-pressure hydrogen is 5 to 12 MPa.

[0062] According to an embodiment of the present invention, the stirring speed in step S2 is 300 to 900 rpm, preferably the stirring speed is 450 to 650 rpm, and preferably the stirring speed is constant.

[0063] According to an embodiment of the present invention, the prepolymerization reaction time in step S2 is 0.5 to 6 hours, preferably the prepolymerization reaction time is 2 to 4 hours.

[0064] According to an embodiment of the present invention, step S3 comprises the following steps: heating the reactor to 60-180° C. and continuing polymerization and hydrogenation reaction for 0.5-10 hours to obtain HNBR latex.

[0065] According to an embodiment of the present invention, the reaction temperature in step S3 is 70-150°C, preferably 80-100°C.

[0066] According to an embodiment of the present invention, the reaction in step S3 is carried out under stirring conditions, and the stirring speed is 300-900 rpm, preferably the stirring speed is 450-650 rpm, for example, 450 rpm.

[0067] According to an embodiment of the present invention, the reaction time in step S3 is 2 to 10 hours, preferably the reaction time is 3 to 6 hours, for example, 5 hours.

[0068] [Comonomer and Diene Monomer]

[0069] 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 of methacrylic acid.

[0070] 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 C4-C6 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.

[0071] [Surfactant]

[0072] 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 or ammonium salts of alkylsulfonic acids, alkali metal or ammonium salts of alkylarylsulfonic acids, ethoxylated monoalkylphenols, dialkylphenols, trialkylphenols, ethoxylated fatty alcohols, mono C4-C4 of bis(benzenesulfonic acid) ethers. 24 Alkali metal or ammonium salts of alkyl derivatives, di-C4-C 24 At least one of an alkali metal salt or ammonium salt of an alkyl derivative, an alkylarylsulfonic acid, an alkali metal salt or ammonium salt of a sulfuric acid monoester of an ethoxylated alkanol, and a gemini surfactant.

[0073] According to an embodiment of the present invention, the fatty acid surfactant is selected from 12 -C 23 The alkali metal salt or ammonium salt of a fatty acid is preferably sodium oleate (NaO) or potassium oleate (KO).

[0074] According to an embodiment of the present invention, the alkyl sulfate, ethoxylated alkanol sulfate monoester, ethoxylated alkylphenol, alkali metal salt or ammonium salt of alkyl sulfonic acid, alkali metal salt or ammonium salt of alkyl aryl sulfonic acid surfactant is the following emulsifier: such as alkyl sulfate (alkyl: C8 to C 22 ), ethoxylated alkanol (ethylene oxide degree: 4 to 30, alkyl group: C8 to C 22 ), ethoxylated alkylphenol (ethylene oxide degree: 3 to 50, alkyl group: C4 to C 20 ) sulfonic acid monoesters, alkyl sulfonic acids (alkyl groups: C8 to C 22 ) alkali metal salt or ammonium salt, alkyl aryl sulfonic acid (alkyl: C4 to C 18 ) alkali metal salt or ammonium salt. For example, the surfactant is sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS).

[0075] According to an embodiment of the present invention, the ethoxylated monoalkylphenol, dialkylphenol, trialkylphenol, ethoxylated fatty alcohol surfactant is the following emulsifier: ethoxylated mono-, di- or tri-alkylphenol (ethylene oxide degree: 3 to 50; alkyl C4 to C9) or ethoxylated fatty alcohol (ethylene oxide degree: 3 to 50; alkyl C4 to C9).

[0076] According to an embodiment of the present invention, the alkali metal salt or ammonium salt surfactant of alkyl aryl sulfonic acid, alkyl sulfonic acid, ethoxylated alkanol sulfuric acid monoester is an alkali metal salt or ammonium salt, especially a sodium salt, of alkyl aryl sulfonic acid, alkyl sulfonic acid (e.g. sulfonated C 12 To C 18 paraffins), alkyl sulfates such as sodium lauryl sulfonate, and sulfuric acid monoesters of ethoxylated alkanols such as the sulfoxylated ethoxylates of lauryl alcohol having 2 to 3 ethylene oxide units.

[0077] According to an embodiment of the present invention, the gemini surfactant is at least one selected from a cationic gemini surfactant, an anionic gemini surfactant, a nonionic gemini surfactant and an asymmetric gemini surfactant.

[0078] According to an embodiment of the present invention, the anionic gemini surfactant is at least one anionic gemini surfactant selected from the group consisting of phosphate type, sulfonate type, carboxylate type and sulfate type.

[0079] In some embodiments of the present invention, the cationic gemini surfactant has a structure as shown in formula (I):

[0080]

[0081] In formula (I), R1, R2, Y, x, and y have the definitions described in A1-A8:

[0082] A1:R1=R2=C m H 2m+1 ;Y=CH2;x+y+1=s;msm surfactants;

[0083] A2: R1=R2=C m H 2m+1 ;Y=CH2,O,S,N(CH3),x=y=2;

[0084] A2: R1=R2=C m H 2m+1 ;Y=CHOH,(CHOH)2;x=y=1;

[0085] A3:R1=R2=C m H 2m+1; Y=(OCH2CH2) z ,x=2;y=0;m-EOz-m surfactants;

[0086] A4: R1=R2=C m H 2m+1 ; Y = C ≡ C; x = y = 1;

[0087] A5:R1=R2=C m H 2m+1 ;Y=a phenylene group;x=y=1;

[0088] A6: R1=R2=C m H 2m+1 OC(O)CH2; no Y; x=y=1; counterion=chloride;

[0089] A7: R1=R2=C m F 2m C4H8; no Y; x = y = 1;

[0090] A8:R1=C m H 2m+1 ; R2=C n H 2n+1 ; no Y; x = y = 1; s; m-2-n surfactants (m is not equal to n);

[0091] wherein, in A1-A8, m, n, and z are independently 1-60;

[0092] Br - Can be replaced by any other anion, preferably F from Group VIIA elements - , Cl - ,I - 、At - , Ts - .

[0093] In some embodiments of the present invention, the gemini surfactant is selected from at least one of the following:

[0094] C 12 H 25 N + (CH3)2-(CH2) n -N + (CH3)2C 12 H 25 2Br – (n=3–8),

[0095] C 12 H25 N + (CH3)2-(CH2) 16 -N + (CH3)2C 12 H 25 2Br – 、

[0096] C 16 H 33 N + (CH3)2-(CH2)2-N + (CH3)2C 16 H 33 2Br – 、

[0097] C8H 17 N + (CH3)2-(CH2)3-N + (CH3)2C8H 17 2Br – 、

[0098] C 12 H 25 N + (CH3)2-(CH2)2-O-(CH2)2-N + (CH3)2C 12 H 25 2Cl – 、

[0099] C 16 H 33 N + (CH3)2-(CH2)5-N + (CH3)2C 16 H 33 2Br – 、

[0100] C 16 H 33 N + (CH3)2-(CH2)2-O-(CH2)2-N + (CH3)2C 16 H 33 2Br – 、

[0101] C 16 H 33 N + (CH3)2-CH2-(CH2-O-CH2)3-CH2-N + (CH3)2C 16 H 33 2Br– 、

[0102] C 12 H 25 N + (CH3)2-CH2-CH(OH)-CH2-N + (CH3)2C 12 H 25 2Br – 、

[0103] C 12 H 25 N + (CH3)2-CH2-C6H4-CH2-N + (CH3)2C 12 H 25 2Br – 、

[0104] C 12 H 25 N + (CH3)2-CH2-CH(OH)-CH(OH)-CH2-N + (CH3)2C 12 H 25 2Br – 、

[0105] C 12 H 25 N + (CH3)2-CH2-CH(OH)-CH2-N + (CH3)2-CH2-CH(OH)-CH2-N + (CH3)2C 12 H 25 3Cl – 、

[0106] C 12 H 25 OPO2 – -O-(CH2)6-OPO2 – -OC 12 H 25 2Na + 、

[0107] C 10 H 21 O-CH2-CH(OSO3 – )-CH2-O-(CH2)2-O-CH2-CH(OSO3 – )-CH2-OC 10 H 21 2Na +

[0108] According to an embodiment of the present invention, the surfactant is selected from at least one of potassium oleate (KO), sodium dodecylbenzene sulfonate (SDBS), and didodecyldimethylammonium bromide.

[0109] [Initiator]

[0110] 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 a peroxide initiator, an azo initiator, and a redox initiator.

[0111] According to an embodiment of the present invention, the peroxide initiator is an organic peroxide and / or an inorganic peroxide.

[0112] According to an embodiment of the present invention, the azo initiator includes azobisisobutyronitrile, azobisisoheptanenitrile and the like.

[0113] According to an embodiment of the present invention, the redox initiator includes benzoyl peroxide / sucrose, tert-butyl hydroperoxide / rongalite, tert-butyl hydroperoxide / sodium metabisulfite, benzoyl peroxide / N,N-dimethylaniline, etc.

[0114] 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 / bleaching agent, ammonium persulfate / ferrous sulfate, hydrogen peroxide / ferrous sulfate, benzoyl peroxide / / N,N-diethylaniline, benzoyl peroxide / ferrous pyrophosphate, potassium persulfate / silver nitrate, persulfate / thiol, isopropylbenzene hydroperoxide / ferrous chloride, potassium persulfate / ferrous chloride, hydrogen peroxide / ferrous chloride, isopropylbenzene hydroperoxide / tetraethyleneimine, isopropylbenzene hydroperoxide / ferrous sulfate, etc.

[0115] According to an embodiment of the present invention, the initiator is selected from any one of redox initiators. The use of redox initiators can initiate polymerization at a relatively low temperature (0-50° C.), increase the reaction rate, reduce energy consumption, and produce a small latex particle size with a narrow particle size distribution range.

[0116] [Additives]

[0117] 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, for example, dodecyl mercaptan, which has good performance and can effectively reduce the molecular weight of latex.

[0118] According to an embodiment of the present invention, the pH adjuster is selected from at least one of sodium phosphate, tetrasodium diphosphate, trisodium phosphate, sodium hexametaphosphate, and sodium bicarbonate.

[0119] [Hydrogenation catalyst]

[0120] According to an embodiment of the present invention, 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.

[0121] According to an embodiment of the present invention, the hydrogenation catalyst has a structure as shown in formula (A):

[0122]

[0123] 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 or iridium;

[0124] L is a ligand; uncharged electron donors are preferred;

[0125] Y is O, S, Se, N-R1 or P-R1 or AsR or SbR radical;

[0126] X 1 , X 2 are independently selected from anionic ligands;

[0127] 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;

[0128] R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen radicals, organic free radicals or inorganic free radicals;

[0129] R 6 is selected from H, alkyl, alkenyl, alkynyl or aryl.

[0130] According to an embodiment of the present invention, the hydrogenation catalyst is added to the diene-based polymer aqueous medium suspension in a solid form.

[0131] Such catalysts as shown in general expression (A) are usually insoluble in water. In the present application, "water-insoluble" means that at 24 + / - 2 degrees Celsius, 0.001 or less of the weight content of the substance can be completely dissolved in 100 equivalents of water, and 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 to be "water-soluble".

[0132] According to an embodiment of the present invention, R 2 , R 3 , R 4 and R 5 the same or different, independently selected from hydrogen, halogen, nitro, CF3, C1-C 30 -alkyl, C3-C 20 -Alkynyloxy, C2-C 20 -alkenyl, C2-C 20 -Alkynyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C2-C 20 -Alkenyloxy, C2-C 20 -Alkynyloxy, C6-C 24 -Aryloxy, C2-C 20 -Alkoxycarbonyl, C1-C 20 -Alkylamino, C1-C 20 -alkylthio, C6-C 24 -Arylthio, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl, the H in these substituents may be replaced by one or more C1-C 30 -alkyl, C1-C 20 -alkoxy, halogen, C6-C 24 - aryl or heteroaryl optionally substituted.

[0133] According to an embodiment of the present invention, R 2 , R 3 , R 4 and R 5 The same or different, independently selected from nitro, linear or branched C1-C 30 -alkyl, C5-C 20 -Cycloalkanes, straight or branched C1-C 20 -alkoxy or C6-C 24 -aryl radical, preferably the C6-C 24 The -aryl radical is selected from phenyl or naphthyl.

[0134] Preferably, C1-C 30 -alkyl radical, C1-C20 The -alkoxy radical may be interrupted by one or more double or triple bonds or by one or more heteroatoms, preferably oxygen or nitrogen.

[0135] According to an embodiment of the present invention, two or more free radicals R 2 , R 3 , R 4 or R 5 Linkage can also be via aliphatic or aromatic structures.

[0136] According to an embodiment of the present invention, R 6 Selected from hydrogen, C1-C 30 -alkyl radical, C2-C 20 -Alkenyl radical, C2-C 20 -Alkynyl radical or C6-C 24 -Aryl radical, R 6 Hydrogen is particularly preferred.

[0137] According to an embodiment of the present invention, the X 1 , X 2 are the same or different anionic ligands.

[0138] According to an embodiment of the present invention, the X 1 , X 2 independently selected from H, halogen, pseudohalogen, straight or branched C1-C 30 -alkyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C6-C 24 -Aryloxy, C3-C 20 -Alkyl diketone, C6-C 24 -Aryl diketone, C1-C 20 -Carboxylates, C6-C 24 -Alkyl sulfonate, C6-C 24 -Aryl sulfonate, C1-C 20 -Alkyl mercaptan, C6-C 24 -Aryl thiols, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl.

[0139] According to an embodiment of the present invention, the X 1 , X 2 The H on the 10 -alkyl, C1-C 10 -alkoxy or C6-C- 24The aryl group is substituted, further preferably, by fluorine, C1-C5-alkyl, C1-C5-alkoxy or phenyl. Preferably, the H on the substituent group can be further substituted by one or more halogens.

[0140] As an example, the X 1 , X 2 Independently selected from chlorine, CF3COO, CH3COO, CFH2COO, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, phenoxy, methoxy, ethoxy, toluenesulfonate (p-CH3-C6H4-SO3), methanesulfonic acid (CH3SO3) or trifluoromethanesulfonate (CF3SO3).

[0141] 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.

[0142] According to an embodiment of the present invention, the hypophosphorous acid is selected from phenyldiphenylphosphorous acid, cyclohexyldicyclohexylphosphorous acid, isopropyldiisopropylphosphorous acid or methyldiphenylphosphorous acid.

[0143] According to an embodiment of the present invention, the phosphite is selected from triphenylphosphite, tricyclohexylphosphite, tri-tert-butylphosphite, triisopropylphosphite or methyldiphenylphosphite.

[0144] According to an embodiment of the present invention, the antimonide is selected from triphenyl Tricyclohexyl or trimethyl

[0145] According to an embodiment of the present invention, the sulfonate is selected from trifluoromethylsulfonate, toluenesulfonate or methanesulfonate.

[0146] According to an embodiment of the present invention, the sulfoxide is selected from (CH3)2S(=O) or (C6H5)2S=O.

[0147] According to an embodiment of the present invention, the thioether is selected from CH3SCH3, C6H5SCH3, CH3OCH2CH2SCH3 or tetrahydrothiophene.

[0148] 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.

[0149] 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):

[0150]

[0151] Among them, R 12 , R 13 and R 14 The same or different, preferably the same, are independently selected from C1-C 20- Alkyl, C3-C8-cycloalkyl, C1-C 20- Alkoxy, substituted or unsubstituted C6-C 20- Aryl, C2-C 20- Heteroaryl, C2-C 20- heterocyclic group or halogen.

[0152] According to an embodiment of the present invention, the C1-C 20- The alkyl group is methyl, ethyl, n-n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl or neopentyl.

[0153] According to an embodiment of the present invention, the C3-C8-cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

[0154] According to an embodiment of the present invention, the C1-C 20- The alkoxy group is phenyl, biphenyl, naphthalene, phenanthrene, anthracene, tolyl or 2,6-dimethylphenyl.

[0155] As an example, if L represents a phosphine of general formula (IIf) and as an electron donating ligand in general formula (A), such phosphine is preferably selected from PPh3, P(p-Tol)3, P(o-Tol)3, PPh(CH3)2, P(CF3)3, P(p-FC6H4)3, P(p-CF3C6H4)3, P(C6H4-SO3Na)3, P(CH2C6H4-SO3Na)3, P(isopropyl)3, P(CHCH3(CH2CH3))3, P(cyclopentyl)3, P(cyclohexyl)3, P(neopentyl)3 or P(neopentyl)3, wherein Ph represents phenyl and Tol represents tolyl.

[0156] According to an embodiment of the present invention, the catalyst is selected from a complex of M and an n-heterocyclic carbene ligand, wherein the n-heterocyclic carbene ligand is a cyclic carbene ligand having at least one nitrogen as a heteroatom in the ring. The ring may have different substitution patterns. Preferably, this substitution pattern can provide a certain degree of stereo growth.

[0157] 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 imidazolinidine group.

[0158] According to an embodiment of the present invention, the NHC-ligand has a structure as shown in formula (IIa)-(IIe):

[0159]

[0160] Among them, R 8 , R 9 , R 10 and R 11 are the same or different and are independently selected from hydrogen, a linear or branched C1-C 30 -alkyl, C3-C 20 -cycloalkyl, C2-C 20 -alkenyl, C2-C 20 -Alkynyl, C6-C 24 -Aryl, C7-C 25 -Alkaryl, C2-C 20 Heterocyclic aromatic group, C2-C 20 Heterocyclic, C1-C 20 -alkoxy, C2-C 20 -alkenyl, C2-C 20 -Alkynyloxy, C6-C 20 -Aryloxy, C2-C 20 -Alkoxycarbonyl, C1-C 20 -alkylthio, C6-C 20-arylthio, -Si(R)3, -O-Si(R)3, -OC(=O)R, C(=O)R, -C(=O)N(R)2, -NR-C(=O)-N(R)2, -SO2N(R)2, -S(=O)R, -S(=O)2R, -OS(=O)2R, halogen, nitro or cyano.

[0161] According to an embodiment of the present invention, in the representative formulas of formulae (IIa) to (IIe), the carbon atom that forms a bond with the ruthenium metal center is present in the form of a carbene.

[0162] According to an embodiment of the present invention, R 8 , R 9 , R 10 and R 11 The H in the formula (a) may be independently substituted by one or more substituents selected from linear or branched C1-C 10 -alkyl, C3-C8-cycloalkyl, C1-C 10 -alkoxy, C6-C 24 -Aryl, C2-C 20 Heteroaryl, C2-C 20 Heterocycle, hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, alkoxycarbonyl, carbamate or halogen.

[0163] Wherein, H in the above substituents may be further substituted by one or more substituents to a certain extent chemically, wherein the substituents are selected from halogen, C1-C5-alkyl, C1-C5-alkoxy or phenyl, and the halogen is preferably chlorine or bromine.

[0164] It should be added that the NHC-ligand structures of the general formula (IIa) and (IIb) depicted in the present invention are identical to the structures (IIa-(i)) and (IIb-(i)) respectively frequently encountered in the literature regarding such NHC-ligands, and the carbene character of the NHC-ligands should be emphasized, which also applies to the further structures (IIc) to (IIe) as well as the preferred structures related to (IIc)-(IIe) described below.

[0165]

[0166] In a preferred NHC-ligand of the catalyst represented by the general formula (A), R 8 and R 9 are the same or different, they represent hydrogen, C6-C 24 - aryl, preferably benzene, straight chain or branched C1-C 10-alkyl, more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl or tert-butyl, or forms a cycloalkyl or aryl structure bound to a carbon atom.

[0167] According to an embodiment of the present invention, R 8 and R 9 It can be composed of one or more linear or branched C1-C 10 -alkyl or C1-C 10 -alkoxy, C3-C8-cycloalkyl, C6-C 24 - aryl, and a functional group selected from the group consisting of hydroxy, 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 comprising halogen, in particular chlorine or bromine, C1-C5-alkyl, C1-C5-alkoxy and benzene.

[0168] 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 C1-C 10 -alkyl, more preferably i-propyl or neopentyl, C3-C 10 -cycloalkyl, more preferably adamantyl, substituted or unsubstituted C6-C 24 -aryl, more preferably phenyl, 2,6-isopropylbenzene, 2,6-xylyl, or 2,4,6-trimethylphenyl, C1-C 10 --Alkyl sulfonate or C6-C 10 -sulfonic acid.

[0169] Preferably, R 10 and R 11 It may be substituted with one or more substituents selected from the group consisting of linear or branched C1-C 10 --Alkyl or C1-C 10 --Alkoxy, C3-C8-cycloalkyl, C6-C 24 - aryl, and a functional group selected from the group consisting of hydroxy, 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 comprising halogen, in particular chlorine or bromine, C1-C5-alkyl, C1-C5-alkoxy and benzene.

[0170] In a further preferred NHC-ligand of the catalyst represented by the general formula (A), R 8 and R 9 are the same or different, they represent hydrogen, C6-C 24 -aryl, more preferably benzene, straight or branched C1-C 10 -alkyl, more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, or forms a cycloalkyl or aryl structure bound to a carbon atom.

[0171] R 10 and R 11 are the same or different, preferably straight chain or branched C1-C 10 -alkyl, more preferably i-propyl or neopentyl, C3-C 10 -cycloalkyl, more preferably adamantyl, substituted or unsubstituted C6-C 24 -aryl, more preferably phenyl, 2,6-isopropylbenzene, 2,6-xylyl or 2,4,6-trimethylphenyl, C1-C 10 -Alkyl sulfonate or C6-C 10 -sulfonic acid.

[0172] Particularly preferably, the NHC-ligand has the structures shown below (IIIa) to (IIIu), wherein "Ph" represents a phenyl group in each case, "Bu" represents a butyl group in each case, i.e., any of n-butyl, tert-butyl, isobutyl, or tert-butyl. "Mes" represents a 2,4,6-trimethylphenyl group in each case, "Dipp" represents a 2,6-diisopropylbenzene in all cases, and "Dimp" refers to a 2,6-dimethylphenyl group in each case.

[0173]

[0174] NHC-ligands contain not only an "N" (nitrogen) but also an "O" (oxygen) in the ring, which makes R 8 , R 9 , R 10 and / or R 11 The replacement pattern tends to provide a certain amount of spatial crowding.

[0175] 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, which substituents may be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.

[0176] Substituent R 1Usually C1-C 30 -alkyl, C3-C 20 -cycloalkyl, C2-C 20 -alkenyl, C2-C 20 -Alkynyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C2-C 20 -Alkenyloxy, C2-C 20 -Alkynyloxy, C6-C 24 -Aryloxy, C2-C 20 -Alkoxycarbonyl, C1-C 20 -Alkylamino, C1-C 20 -alkylthio, C6-C 24 -Arylthio, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl, these substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.

[0177] According to an embodiment of the present invention, R 1 C3-C is preferred 20 -cycloalkyl, C6-C 24 -aryl or straight or branched C1-C 30 - alkyl radicals, the latter being interrupted, where appropriate, by one or more double or triple bonds or by one or more heteroatoms, preferably oxygen or nitrogen. 1 Particularly preferred are straight-chain or branched C1-C 12 -alkyl radical.

[0178] Preferably, C3-C 20 -Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0179] According to an embodiment of the present invention, R 1 Preferably C1-C 12 -alkyl radical, C1-C 12 -alkyl radical is 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 It is methyl or isopropyl.

[0180] C6-C 24 -Aryl is an aromatic free radical having 6 to 24 backbone carbon atoms, preferably a monocyclic, bicyclic or tricyclic carbocyclic aromatic radical having 6 to 10 backbone carbon atoms, which can be synthesized from benzene, biphenyl, naphthalene, phenanthrene, anthracene or anthracene.

[0181] In the general expression (A), the free radical R 2 , R 3 , R 4 and R 5 are the same or different, they can be hydrogen, organic or inorganic radicals.

[0182] In one suitable embodiment, R 2 , R 3 , R 4 and R 5 are the same or different and each can be hydrogen, halogen, nitro, CF3, 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.

[0183] R 2 , R 3 , R 4 and R 5 are usually the same or different, and each may be hydrogen, halogen, preferably chlorine or bromine, nitro, CF3, C1-C 30 -alkyl, C3-C 20 -Alkynyloxy, C2-C 20 -alkenyl, C2-C 20 -Alkynyl, C6-C 24 -Aryl, C1-C 20 -alkoxy, C2-C 20 -Alkenyloxy, C2-C 20 -Alkynyloxy, C6-C 24 -Aryloxy, C2-C 20 -Alkoxycarbonyl, C1-C 20 -Alkylamino, C1-C 20 -alkylthio, C6-C 24 -Arylthio, C1-C 20 -alkylsulfonyl or C1-C 20 -alkylsulfinyl, these substituents may be replaced by one or more C1-C 30 -alkyl, C1-C 20 -alkoxy, halogen, C6-C 24 - aryl or heteroaryl optionally substituted.

[0184] In one particularly useful embodiment, R 2 , R 3 , R 4 and R 5can be the same or different, each can be nitro, straight or branched C1-C 30 -alkyl, C5-C 20 -cylcoalkyl, linear or branched C1-C 20 -alkoxy or C6-C 24 - an aryl radical, preferably a phenyl or naphthyl radical. 30 -alkyl radicals and C1-C 20 The -alkoxy radical may be interrupted by one or more double or triple bonds or by one or more heteroatoms, preferably oxygen or nitrogen.

[0185] In addition, two or more free radicals R 2 , R 3 , R 4 or R 5 It can also be linked via aliphatic or aromatic structures. 3 , R 4 And by connecting their carbon atoms on the phenyl ring in the expression (B), a fused phenyl ring can be formed, and overall, a naphthyl structure is produced.

[0186] In the general expression (A), R 6 The free radical is hydrogen or an alkyl, alkenyl, alkynyl or aryl group. 6 Preferably hydrogen, C1-C 30 -alkyl radical, C2-C 20 -Alkenyl radical, C2-C 20 -Alkynyl radical or C6-C 24 -Aryl radical. 6 Hydrogen is particularly preferred.

[0187] The most preferred ones are catalysts having the structure of formula (IV) (so-called Hoveyda-Grubbs second generation catalysts), catalysts having the structure of formula (V) (so-called Grubbs second generation catalysts), and catalysts having the structure of formula (VI) (so-called Grubbs third generation catalysts).

[0188]

[0189] According to an embodiment of the present invention, the reactor is selected from a high-pressure reactor, for example, a high-temperature and high-pressure stainless steel reactor.

[0190] According to an embodiment of the present invention, the high-temperature and high-pressure stainless steel reactor comprises a reactor body and at least two high-pressure hoses, one end of which is connected to the reactor body and the other end is connected to a high-pressure gas, such as an inert gas and hydrogen.

[0191] According to an embodiment of the present invention, the high temperature resistant hose comprises 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.

[0192] According to an embodiment of the present invention, the kettle body is further provided with an exhaust port.

[0193] According to an embodiment of the present invention, a pressure sensor is further provided in the kettle, and the measuring range of the pressure sensor is -1 to 30 MPa.

[0194] According to an embodiment of the present invention, a temperature sensor is further provided in the kettle, and the measuring range of the temperature sensor is 0-180°C.

[0195] 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.

[0196] [Hydrogenated rubber latex]

[0197] The present invention also provides a hydrogenated rubber latex prepared by the above method, wherein the hydrogenation degree of the hydrogenated rubber latex is 50-100%, the content of the comonomer is 10-60 mol%, the content of the diene monomer is 40%-90%, and the solid content of the hydrogenated rubber latex is 10-70wt%.

[0198] According to the embodiment of the present invention, the hydrogenated rubber molecules exist in numerous nanoparticles in the form of latex. Meanwhile, the hydrogenated rubber solid glue can also be obtained by flocculating the hydrogenated rubber latex, and then washing and drying.

[0199] According to an embodiment of the present invention, the degree of hydrogenation of the hydrogenated rubber latex is greater than or equal to 90%, preferably the degree of hydrogenation of the hydrogenated rubber latex is 95%, and further preferably, the degree of hydrogenation of the hydrogenated rubber latex is 97%, for example, 89.1%, 96.9%, 76.5%, 97.9%, 98.8%, 99.3%.

[0200] According to an embodiment of the present invention, the content of the comonomer is 20-50 mol%, for example 30 mol%.

[0201] According to an embodiment of the present invention, the particle size of the hydrogenated rubber latex is 50 to 80 nm, preferably the particle size of the hydrogenated rubber latex is 50 to 70 nm, for example, 55 nm, 61 nm, 62 nm, 63 nm, 69 nm, or 70 nm.

[0202] 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.

[0203] According to an embodiment of the present invention, the hydrogenated rubber solid gum can be obtained by first flocculating the hydrogenated rubber latex and then subjecting the flocculated product to post-treatments such as washing and drying.

[0204] The preparation method of the present invention will be described in further detail below in conjunction with specific examples. It should be understood that the following examples are only exemplary illustrations and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0205] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0206] See Table 1 for the raw materials and their sources used in the following examples.

[0207] Table 1 Reaction materials and sources

[0208]

[0209]

[0210] Example 1

[0211] 1) Dissolve 7 g of surfactant didodecyl dimethyl ammonium bromide in 300 g of deionized water to obtain a surfactant aqueous solution and add it into a reactor.

[0212] 2) 30 g of acrylonitrile, 0.05 g of a hydrogenation catalyst Hoveyda-Grubbs second generation catalyst, 0.3 g of a chain transfer agent tert-dodecyl mercaptan, and 0.05 g of a pH adjuster sodium phosphate were added to the reactor.

[0213] 3) 0.5 MPa of inert gas (nitrogen) was introduced into the reactor, and degassing was performed for 0.5 hour while stirring at 200 rpm. Then 70 g of butadiene was added in liquid form to the degassed reactor, mixed, and emulsified at room temperature for 1 hour.

[0214] 4) The temperature of the reactor was lowered to the prepolymerization temperature of 7° C., 0.05 g of initiator cumene hydroperoxide and 0.05 g of initiator ferrous sulfate were added to the reactor through a feed tank, 5 MPa high-pressure hydrogen was introduced into the reactor, and prepolymerization was carried out for 4 hours.

[0215] 5) The system temperature after the prepolymerization reaction was raised to 70° C., the reactor was kept at a constant temperature and pressure (maintaining a hydrogen environment of 70° C. and 5 MPa), the stirring was maintained at a constant speed of 450 rpm, and the polymerization and hydrogenation reaction were carried out for 5 hours to obtain HNBR latex.

[0216] Example 2

[0217] 1) Dissolve 7 g of surfactant potassium oleate in 300 g of deionized water to obtain a surfactant aqueous solution and add it into a reactor.

[0218] 2) 30 g of acrylonitrile, 0.05 g of a hydrogenation catalyst Hoveyda-Grubbs second generation catalyst, 0.3 g of a chain transfer agent tert-dodecyl mercaptan, and 0.05 g of a pH adjuster sodium phosphate were added to the reactor.

[0219] 3) 0.5 MPa of inert gas (nitrogen) was introduced into the reactor, and degassing was performed for 0.5 hour while stirring at 200 rpm. Then 70 g of butadiene was added in liquid form to the degassed reactor, mixed, and emulsified at room temperature for 1 hour.

[0220] 4) The temperature of the reactor was lowered to the prepolymerization temperature of 7° C., 0.05 g of initiator cumene hydroperoxide and 0.05 g of initiator ferrous sulfate were added to the reactor through a feed tank, 5 MPa high-pressure hydrogen was introduced into the reactor, and prepolymerization was carried out for 4 hours.

[0221] 5) The system temperature after the prepolymerization reaction was raised to 70° C., the reactor was kept at a constant temperature and pressure (maintaining a hydrogen environment of 70° C. and 5 MPa), the stirring was maintained at a constant speed of 450 rpm, and the polymerization and hydrogenation reaction were carried out for 5 hours to obtain HNBR latex.

[0222] See also Figure 1 As shown in FIG. 1 , it is a TEM image of the HNBR latex prepared in this embodiment. As can be seen from the figure, the latex prepared in this embodiment has a small particle size and is evenly distributed. Figure 2 As shown, it is the hydrogen nuclear magnetic resonance spectrum of the HNBR latex prepared in this embodiment. It can be seen from the figure that the signal displayed by the proton of the saturated structure is between 0.32 and 2.8 ppm; the peak at 2.6 ppm indicates the presence of -CH(CN)- units; a very small amount of peaks remain between 4.9 and 5.7 ppm, the 4.9-5.3 ppm region is attributed to the hydrogen on the 1,2-vinyl terminal bond, and the hydrogen appearing in the 5.3-5.7 ppm region is attributed to the 1,4-trans olefin unit; it means that the HNBR is successfully synthesized and the degree of hydrogenation is very high.

[0223] Example 3

[0224] 1) Dissolve 7 g of the surfactant sodium dodecylbenzene sulfonate in 300 g of deionized water to obtain a surfactant aqueous solution and add it into a reactor.

[0225] 2) 30 g of acrylonitrile, 0.05 g of a hydrogenation catalyst Hoveyda-Grubbs second generation catalyst, 0.3 g of a chain transfer agent tert-dodecyl mercaptan, and 0.05 g of a pH adjuster sodium phosphate were added to the reactor.

[0226] 3) 0.5 MPa of inert gas (nitrogen) was introduced into the reactor, and degassing was performed for 0.5 hour while stirring at 200 rpm. Then 70 g of butadiene was added in liquid form to the degassed reactor, mixed, and emulsified at room temperature for 1 hour.

[0227] 4) The temperature of the reactor was lowered to the prepolymerization temperature of 7° C., 0.05 g of initiator cumene hydroperoxide and 0.05 g of initiator ferrous sulfate were added to the reactor through a feed tank, 5 MPa high-pressure hydrogen was introduced into the reactor, and prepolymerization was carried out for 4 hours.

[0228] 5) The system temperature after the prepolymerization reaction was raised to 70° C., the reactor was kept at a constant temperature and pressure (maintaining a hydrogen environment of 70° C. and 5 MPa), the stirring was maintained at a constant speed of 450 rpm, and the polymerization and hydrogenation reaction were carried out for 5 hours to obtain HNBR latex.

[0229] Example 4

[0230] 1) Dissolve 7 g of surfactant potassium oleate in 300 g of deionized water to obtain a surfactant aqueous solution and add it into a reactor.

[0231] 2) 30 g of acrylonitrile, 0.05 g of a hydrogenation catalyst Hoveyda-Grubbs second generation catalyst, 0.3 g of a chain transfer agent tert-dodecyl mercaptan, and 0.05 g of a pH adjuster sodium phosphate were added to the reactor.

[0232] 3) 0.5 MPa of inert gas (nitrogen) was introduced into the reactor, and degassing was performed for 0.5 hour while stirring at 200 rpm. Then 70 g of butadiene was added in liquid form to the degassed reactor, mixed, and emulsified at room temperature for 1 hour.

[0233] 4) The temperature of the reactor was lowered to the prepolymerization temperature of 7° C., 0.05 g of initiator potassium persulfate and 0.05 g of initiator ferrous chloride were added to the reactor through a feed tank, and 5 MPa high-pressure hydrogen was introduced into the reactor to carry out prepolymerization for 4 hours.

[0234] 5) The system temperature after the prepolymerization reaction was raised to 70° C., the reactor was kept at a constant temperature and pressure (maintaining a hydrogen environment of 70° C. and 5 MPa), the stirring was maintained at a constant speed of 450 rpm, and the polymerization and hydrogenation reaction were carried out for 5 hours to obtain HNBR latex.

[0235] Example 5

[0236] 1) Dissolve 7 g of surfactant potassium oleate in 300 g of deionized water to obtain a surfactant aqueous solution and add it into a reactor.

[0237] 2) 30 g of acrylonitrile, 0.07 g of a hydrogenation catalyst Hoveyda-Grubbs second generation catalyst, 0.3 g of a chain transfer agent tert-dodecyl mercaptan, and 0.05 g of a pH regulator sodium phosphate were added to the reactor.

[0238] 3) 0.5 MPa of inert gas (nitrogen) was introduced into the reactor, and degassing was performed for 0.5 hour while stirring at 200 rpm. Then 70 g of butadiene was added in liquid form to the degassed reactor, mixed, and emulsified at room temperature for 1 hour.

[0239] 4) The temperature of the reactor was lowered to the prepolymerization temperature of 7° C., 0.05 g of initiator cumene hydroperoxide and 0.05 g of initiator ferrous sulfate were added to the reactor through a feed tank, 5 MPa high-pressure hydrogen was introduced into the reactor, and prepolymerization was carried out for 4 hours.

[0240] 5) The system temperature after the prepolymerization reaction was raised to 70° C., the reactor was kept at a constant temperature and pressure (maintaining a hydrogen environment of 70° C. and 5 MPa), the stirring was maintained at a constant speed of 450 rpm, and the polymerization and hydrogenation reaction were carried out for 5 hours to obtain HNBR latex.

[0241] Example 6

[0242] 1) Dissolve 7 g of surfactant potassium oleate in 300 g of deionized water to obtain a surfactant aqueous solution and add it into a reactor.

[0243] 2) 30 g of acrylonitrile, 0.05 g of a hydrogenation catalyst Hoveyda-Grubbs second generation catalyst, 0.3 g of a chain transfer agent tert-dodecyl mercaptan, and 0.05 g of a pH adjuster sodium phosphate were added to the reactor.

[0244] 3) 0.5 MPa of inert gas (nitrogen) was introduced into the reactor, and degassing was performed for 0.5 hour while stirring at 200 rpm. Then 70 g of butadiene was added in liquid form to the degassed reactor, and mixed and emulsified at room temperature for 1 hour.

[0245] 4) The temperature of the reactor was lowered to the prepolymerization temperature of 7° C., 0.05 g of initiator cumene hydroperoxide and 0.05 g of initiator ferrous sulfate were added to the reactor through a feed tank, 5 MPa high-pressure hydrogen was introduced into the reactor, and prepolymerization was carried out for 4 hours.

[0246] 5) The system temperature after the prepolymerization reaction was raised to 90° C., the reactor was kept at a constant temperature and pressure (maintaining a hydrogen environment of 90° C. and 5 MPa), the stirring speed was kept constant at 450 rpm, and the polymerization and hydrogenation reaction were carried out for 5 hours to obtain HNBR latex.

[0247] Example 7

[0248] 1) Dissolve 7 g of surfactant potassium oleate in 300 g of deionized water to obtain a surfactant aqueous solution and add it into a reactor.

[0249] 2) 30 g of acrylonitrile, 0.05 g of a hydrogenation catalyst Grubbs second generation catalyst, 0.3 g of a chain transfer agent tert-dodecyl mercaptan, and 0.05 g of a pH adjuster sodium phosphate were added to the reactor.

[0250] 3) 0.5 MPa of inert gas (nitrogen) was introduced into the reactor, and degassing was performed for 0.5 hour while stirring at 200 rpm. Then 70 g of butadiene was added in liquid form to the degassed reactor, mixed, and emulsified at room temperature for 1 hour.

[0251] 4) The temperature of the reactor was lowered to the prepolymerization temperature of 7° C., 0.05 g of initiator cumene hydroperoxide and 0.05 g of initiator ferrous sulfate were added to the reactor through a feed tank, 5 MPa high-pressure hydrogen was introduced into the reactor, and prepolymerization was carried out for 4 hours.

[0252] 5) The system temperature after the prepolymerization reaction was raised to 70° C., the reactor was kept at a constant temperature and pressure (maintaining a hydrogen environment of 70° C. and 5 MPa), the stirring was maintained at a constant speed of 450 rpm, and the polymerization and hydrogenation reaction were carried out for 5 hours to obtain HNBR latex.

[0253] Example 8

[0254] 1) Dissolve 7 g of surfactant potassium oleate in 300 g of deionized water to obtain a surfactant aqueous solution and add it into a reactor.

[0255] 2) 30 g of acrylonitrile, 0.05 g of a hydrogenation catalyst Grubbs third generation catalyst, 0.3 g of a chain transfer agent tert-dodecyl mercaptan, and 0.05 g of a pH adjuster sodium phosphate were added to the reactor.

[0256] 3) 0.5 MPa of inert gas (nitrogen) was introduced into the reactor, and degassing was performed for 0.5 hour while stirring at 200 rpm. Then 70 g of butadiene was added in liquid form to the degassed reactor, mixed, and emulsified at room temperature for 1 hour.

[0257] 4) The temperature of the reactor was lowered to the prepolymerization temperature of 7° C., 0.05 g of initiator cumene hydroperoxide and 0.05 g of initiator ferrous sulfate were added to the reactor through a feed tank, 5 MPa high-pressure hydrogen was introduced into the reactor, and prepolymerization was carried out for 4 hours.

[0258] 5) The system temperature after the prepolymerization reaction was raised to 70° C., the reactor was kept at a constant temperature and pressure (maintaining a hydrogen environment of 70° C. and 5 MPa), the stirring was maintained at a constant speed of 450 rpm, and the polymerization and hydrogenation reaction were carried out for 5 hours to obtain HNBR latex.

[0259] Table 2 Experimental conditions of Examples 1-8

[0260]

[0261] Table 3 Test results of HNBR latex prepared in Examples 1-8

[0262] Particle size (nm) Particle size distribution Acrylonitrile content (%) Degree of hydrogenation (%) Example 1 62 0.021 33 89.1 Example 2 55 0.011 32 95.4 Example 3 63 0.009 30 76.5 Example 4 67 0.014 33 96.2 Example 5 60 0.013 32 98.8 Example 6 61 0.023 33 99.3 Example 7 62 0.012 32 95.6 Example 8 59 0.005 33 96.8

[0263] As shown in Table 3, the performance test results of the HNBR latex prepared in Examples 1-9 of the present invention are shown. It can be seen that the HNBR latex prepared in the present invention has a small particle size (mostly equal to 60nm, the lowest can reach 55nm), a small particle size distribution range (mostly less than 0.023), is not easy to demulsify, the preparation method is simple, the operation is convenient, and it is easy to realize industrialization; in the synthesis process, the degree of hydrogenation is about 80%, and the highest can reach 99.3%, the hydrogenation effect is good, and the degree of hydrogenation is high.

[0264] The above examples are used to illustrate the specific implementation of the present invention. However, the protection scope of the present invention is not limited to the above exemplary implementation. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A one-step method for preparing hydrogenated rubber latex, characterized in that: The method comprises the following steps: The comonomer and diene monomer are emulsified in the presence of a surfactant, a hydrogenation catalyst, other additives and water, the temperature is lowered, an initiator is added and a certain pressure of hydrogen is introduced to carry out a prepolymerization reaction, and then the temperature is increased to carry out polymerization and hydrogenation reactions to obtain hydrogenated rubber latex.

2. The method for preparing hydrogenated rubber latex by one step 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. Lowering the temperature to the prepolymerization temperature, adding an initiator and introducing high pressure hydrogen to carry out the prepolymerization reaction; S3. Raise the temperature to carry out polymerization and hydrogenation reaction to obtain hydrogenated rubber latex.

3. The method for preparing hydrogenated rubber latex by one step according to claim 2, characterized in that: 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. lowering the temperature to the prepolymerization temperature, adding 0.001 to 1 part of an initiator to the emulsified product, and conducting a prepolymerization reaction under high pressure hydrogen; S3. The prepolymer product is polymerized and hydrogenated at a temperature of 60 to 180° C. for 0.5 to 10 hours to obtain hydrogenated rubber latex.

4. The method for preparing hydrogenated rubber latex by one step according to any one of claims 1 to 3, characterized in that: The auxiliary agent includes a chain transfer agent and / or a pH adjuster. The amount of the chain transfer agent is 0.25 to 2 parts, and the amount of the pH adjuster is 0.05 to 1.5 parts.

5. The method for preparing hydrogenated rubber latex by one step according to any one of claims 1 to 3, characterized in that: Step S1 includes 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, 0.01-0.2 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.

6. The method for preparing hydrogenated rubber latex by one step according to any one of claims 1 to 3, characterized in that: Step S3 comprises the following steps: heating the reactor to 60-180° C. and continuing polymerization and hydrogenation reaction for 0.5-10 hours to obtain hydrogenated rubber latex.

7. The method for preparing hydrogenated rubber latex by one step according to any one of claims 1 to 3, 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.

8. The method for preparing hydrogenated rubber latex by one step according to any one of claims 1 to 3, 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, vanadium, zinc, rhodium, 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.

9. The method for preparing hydrogenated rubber latex by one step according to claim 8, characterized in that: The hydrogenation catalyst has a structure as shown in formula (A): 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; 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.

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 70-100%, the content of the comonomer is 10-60 mol%, the content of the diene monomer is 40%-90%, and the solid content of the hydrogenated rubber latex is 10-70 wt%.

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