Catalyst composition, selective hydrogenation method for conjugated diene latex, hydrogenated conjugated diene latex and use thereof

Abstract

The present invention belongs to the technical field of polymer hydrogenation modification, and particularly relates to a catalyst composition, a selective hydrogenation method for conjugated diene latex, a hydrogenated conjugated diene latex and the use thereof. The catalyst composition provided by the present invention comprises: a primary catalyst and a first cocatalyst, the primary catalyst being a ruthenium complex hydrogenation catalyst and / or an osmium complex hydrogenation catalyst, and the chemical structure of the first cocatalyst containing one or more of N, O, a carbon-carbon double bond and a carbon-carbon triple bond. The catalyst composition provided by the present invention allows for efficient selective hydrogenation of carbon-carbon double bonds of conjugated diene latex, can effectively reduce the amount of primary catalysts and cocatalysts used, involves mild hydrogenation conditions, achieves a lower residual amount of cocatalysts, achieves better properties of vulcanized rubber and high production efficiency, and eliminates gel problems.

Description

Catalyst composition, method for selective hydrogenation of conjugated diene latex, hydrogenated conjugated diene latex and use thereof

[0001] This application claims priority to the Chinese patent application filed with the Patent Office of China on March 27, 2024, with application number 202410361832.X and invention name “A catalyst composition, a method for selective hydrogenation of conjugated diene latex, hydrogenated conjugated diene latex and its application”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present invention belongs to the technical field of polymer hydrogenation modification, and in particular relates to a catalyst composition, a method for selective hydrogenation of conjugated diene latex, hydrogenated conjugated diene latex and applications thereof. Background Art

[0003] The research and development of hydrogenated diene-based rubber products primarily involves developing formulations and subsequent processing methods to achieve the desired performance based on the intended application environment. Currently, hydrogenated diene-based rubbers are primarily prepared in three ways, both in the laboratory and in industrial production. Hydrogenation of parent diene-based unsaturated polymers, such as nitrile rubber (also known as NBR) produced by the polymerization of acrylonitrile and butadiene, is well known. Using NBR as an example, the following are the specific methods:

[0004] (1) Acrylonitrile-ethylene copolymerization method:

[0005] In ethylene-acrylonitrile copolymerization, due to the significant difference in the reactivity ratios of acrylonitrile and ethylene (0.04 for acrylonitrile and 0.8 for ethylene), the input ratio of the reactants must be strictly controlled. Furthermore, group rearrangements are prone to occur during the copolymerization process, leading to numerous side reactions and resulting in poor chain segment randomness. This results in poor product performance and ultimately affects product processing. Therefore, this approach is currently under research.

[0006] (2) Solution hydrogenation method:

[0007] NBR solution hydrogenation methods include heterogeneous solution hydrogenation and homogeneous solution hydrogenation. During operation, NBR is crushed and dissolved in a suitable organic solvent, primarily cyclohexanone, chlorobenzene, xylene, and chloroform. It is then placed in a high-temperature, high-pressure reactor and reacted with hydrogen over a precious metal catalyst for selective hydrogenation to produce HNBR. Solution hydrogenation is currently the primary method for industrial production of HNBR. During hydrogenation, only the double bonds on the butadiene units are selectively hydrogenated to saturated single bonds, while the nitrile groups are not hydrogenated. The key to solution hydrogenation lies in the choice of catalyst. NBR solution hydrogenation methods can be categorized into heterogeneous hydrogenation, using a Group VIII metal coated on an inorganic support as a catalyst, and homogeneous hydrogenation, primarily using catalysts such as rhodium, ruthenium, and palladium. The heterogeneous solution hydrogenation method uses a supported catalyst containing palladium, rhodium, or ruthenium as the active component, supported by alumina, silica, activated carbon, carbon black, or alkaline earth metal carbonates. After the hydrogenation reaction, the hydrogenated product is separated from the catalyst by filtration or centrifugation. Japan's Zeon Corporation first used supported catalysts for NBR hydrogenation in the 1980s. These supported catalysts, based on carbon, offer high selectivity, with hydrogenation rates reaching up to 95.6%. However, during hydrogenation, the carbon readily adsorbs rubber molecules, leading to agglomeration and degradation of product performance. The primary advantage of heterogeneous supported catalysts is ease of catalyst separation, but their activity and selectivity are significantly affected by the environment. Furthermore, the active components of supported catalysts prepared using traditional methods are primarily distributed within the pores, requiring NBR molecules to diffuse into these pores for hydrogenation to proceed. To increase the reaction rate, the reaction must be conducted under high pressure and intense stirring, resulting in long reaction times and high energy consumption, which can easily deteriorate polymer properties.

[0008] Diolefin-based unsaturated polymers, for example, the acrylonitrile-butadiene rubber (also referred to as NBR) prepared by polymerization of acrylonitrile and butadiene, are well known in the art. For example, the copolymerization method of acrylonitrile and butadiene has been described in US3690349, US5770660 and CN102532414. According to the preparation conditions, this type of polymer can be obtained as the latex in the aqueous medium. Diolefin-based unsaturated polymers such as NBR are used for multiple industrial purposes, and the hydrogenation method of this type of unsaturated polymers is also well known in the art.

[0009] The technology of catalytic hydrogenation of polymers based on organic solutions is very mature, and related patents include US6410657, US6020439, US5705571, US5057581 and US3454644. It is known that carbon-carbon double bonds in diene-based polymers can be selectively hydrogenated by treating the polymer in an organic solution with hydrogen in the presence of a catalyst to produce saturated polymers thereof with significantly improved end-use properties. Such methods can be selective for the double bonds to be hydrogenated, such that, for example, double bonds in aromatic or cycloalkyl groups are not hydrogenated, and double or triple bonds between carbon and other atoms such as nitrogen or oxygen are not affected. This technical field includes many examples of catalysts suitable for such hydrogenations, including catalysts based on cobalt, nickel, rhodium, ruthenium, osmium and iridium. The suitability of the catalyst depends on the desired degree of hydrogenation, the hydrogenation reaction rate and the presence of other groups such as carboxyl and nitrile groups in the polymer.

[0010] US Pat. No. 6,410,657 teaches a method for selectively hydrogenating unsaturated double bonds within conjugated diene units of homopolymers or copolymers in the presence of a homogeneous organotitanium-based catalyst. The use of a catalyst mixture consisting of a substituted or unsubstituted monocyclopentadienyl titanium compound and lithium hydride derived from the reaction of an alkyl lithium with hydrogen in solution exhibits high hydrogenation degrees and reproducibility.

[0011] US6020439 describes a method for hydrogenating a living polymer primarily comprising a conjugated double bond monomer and an aromatic vinyl monomer. A polymer prepared from at least one conjugated diene compound is contacted with hydrogen in the presence of a catalyst. The catalyst is formed from a cyclopentadienyl titanium compound. A cocatalyst is provided in the form of an alkoxylithium compound. This catalyst system selectively hydrogenates unsaturated double bonds within the conjugated diene units of the living polymer in solution.

[0012] US Pat. No. 5,705,571 provides a method for the selective hydrogenation of conjugated diene polymers. The method comprises contacting the conjugated diene polymer with hydrogen in an inert organic solvent in the presence of a hydrogenation catalyst composition comprising a substituted or unsubstituted bis(cyclopentadienyl) Group VIII transition metal compound and an organolithium compound. The method claims that hydrogenation can be carried out under mild conditions in the presence of a small amount of the hydrogenation catalyst composition, and that both the hydrogenation conversion rate and the selectivity for conjugated diene units are high.

[0013] US Pat. No. 5,057,581 teaches a process for selectively hydrogenating carbon-carbon double bonds of conjugated diene copolymers in the presence of certain divalent ruthenium carbonyl complex catalysts containing phosphine ligands having bulky alkyl substituents in a homogeneous solution in an organic solvent.

[0014] US3454644 teaches the hydrogenation in solution of unsaturated organic compounds having 2 to 20 carbon atoms containing at least one moiety selected from ketones, formyls, nitriles, nonaromatic carbon double bonds and carbon-carbon triple bonds using as catalysts metal complexes of ruthenium or osmium bonded to two electronegative species selected from hydrogen and halogens and coordinated to at least two organic stabilizing ligands such as carbonyl groups or tertiary phosphines.

[0015] In summary, research in this area, namely the hydrogenation of diene-based polymers, has been very successful if the polymer is made soluble in an organic solvent, but dissolving the polymer in an organic solvent has many disadvantages and problems.

[0016] However, many diene-based polymers / copolymers are prepared by emulsion polymerization and are discharged from the polymerization reactor in the form of latex. It would be highly desirable to develop a process for the direct hydrogenation of diene-based polymer latexes.

[0017] (3) Emulsion hydrogenation method:

[0018] HNBR is produced by hydrogenating nitrile rubber latex with the addition of a heavy metal catalyst. Goodyear, a US company, first proposed a process for producing emulsion HNBR in 1984 using an imide as a reducing agent. NBR latex can be directly converted to HNBR using hydrazine, oxygen, or hydrogen peroxide as oxidants and iron or copper ion initiators (related US patent application: US4452950). However, this reduction method is prone to gelation, and the utilization rate of hydrazine or hydrogen peroxide is low, making it difficult to recycle. The advantages of emulsion hydrogenation are milder reaction conditions compared to solution hydrogenation, a simple process, and the absence of solvents, which can reduce costs and pollution. The product can also be recycled (the product, an emulsion, can be used as a specialty coating). Therefore, NBR emulsion hydrogenation is attracting increasing attention. A disadvantage is that unhydrogenated double bonds may undergo cross-linking reactions, resulting in increased system viscosity and compromising subsequent processing. Due to the complex process and the need for solvents during the reaction, solvent emissions can cause environmental pollution. The severe cross-linking reactions in NBR emulsion polymerization can easily cause the product to form gels, making product separation difficult. At the same time, the emulsion hydrogenation method has the problem of slow hydrogenation rate and is not suitable for large-scale production.

[0019] Yue Dongmei et al. from Beijing University of Chemical Technology improved the hydrogenation method of NBR latex, reduced the gel content of HNBR latex, and increased the degree of hydrogenation (related Chinese patent applications: CN101486775, CN101704909).

[0020] In recent years, direct hydrogenation of polymer latexes has attracted increasing attention. As described below, many efforts have been made to achieve this method.

[0021] US Pat. No. 6,552,132 claims a process for the hydrogenation of polymers composed of diene monomer units and monomer units containing nitrile groups, wherein the hydrogenation is carried out in the presence of hydrazine and an oxidizing compound in the form of an aqueous dispersion.

[0022] US Pat. No. 6,521,694 describes a process for hydrogenating carbon-carbon double bonds of unsaturated polymers in the form of an aqueous dispersion, to which are added a reducing agent selected from hydrazine and hydrazine-releasing compounds, an oxidizing compound and a catalyst, wherein the catalyst contains an element from Group 13 of the Periodic Table of the Elements.

[0023] US Pat. No. 5,272,202 describes a method for selectively hydrogenating carbon-carbon double bonds of unsaturated polymers containing nitrile groups using hydrogen in the presence of a hydrogenation catalyst. The method relates to an aqueous emulsion of the unsaturated polymer containing nitrile groups. Optionally, an organic solvent capable of dissolving or swelling the polymer is present in a volume ratio of aqueous emulsion to organic solvent ranging from 1:3 to 1:0. A palladium compound is used as the hydrogenation catalyst, and the aqueous emulsion is contacted with gaseous or dissolved hydrogen while maintaining an emulsified state.

[0024] US6403727 discloses a method for selectively hydrogenating ethylenically unsaturated double bonds in polymers. The method comprises reacting polymers with hydrogen in an aqueous suspension of the polymers in the presence of at least one hydrogenation catalyst selected from salts and complex compounds of rhodium and / or ruthenium. Suitable germanium-containing catalysts are of the formula RhX m L 3 L 4 (L 5 ) n Rhodium phosphine complexes wherein X is a halide, an anion of a carboxylic acid, acetylacetonate, an aryl or alkyl sulfonate, a hydride or a diphenyltriazine anion, and L 3 、,L 4 and L 5 are independently CO, alkene, cycloalkene, dibenzophosphol, benzonitrile, PR3 or R2P-A-PR2, m is 1 or 2 and n is 0, 1 or 2, provided that L 3 , L 4 or L 5 At least one of the above phosphorus-containing ligands is one of the formula PR3 or PR2-A-PR2, wherein R is alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl or aryloxy.

[0025] Research has disclosed a NBR latex hydrogenation technology, in which rubber latex is directly hydrogenated without pretreatment. Wilkinson's catalyst and its ligand, triphenylphosphine (TPP), serve as the catalyst and cocatalyst, respectively. In this study, the addition of excess TPP plays a crucial role in the catalyst's incorporation into the latex particles. A drawback of this system is the rather slow hydrogenation rate, which limits further development of this technology.

[0026] JP02178305 describes a method for hydrogenating nitrile rubber by contacting the emulsion with hydrogen in the presence of a palladium compound and optionally swelling the emulsion in an organic solvent. Thus, 100 ml of a 10% nitrile rubber emulsion (containing 39.4% units derived from acrylonitrile) was mixed with 63.3 mg of palladium benzoate in 50 ml of benzene and heated at 50° C. under a hydrogen pressure of 30 atm for 6 hours to give a 90.2% hydrogenated emulsion.

[0027] EP1705194A1 discloses a method for directly hydrogenating a diene-based polymer latex using an organometallic catalyst and high-pressure gaseous hydrogen. The organometallic catalyst is RhCl(PPh3)3. A 300 ml glass-lined stainless steel autoclave equipped with a temperature control device, an agitator, and a hydrogen addition point is used. A butadiene-acrylonitrile polymer latex having a limited acrylonitrile content of approximately 38% by weight and a Mooney viscosity (ML1+4@100°C) of approximately 29 is used. The solids content of the latex is 14.3% by weight. The average diameter of the polymer particles in the latex is approximately 75 nm. The reactor is charged with 50 ml of this latex, 100 ml of water, 0.0378 g of the catalyst RhCl(PPh3)3, and 0.594 g of PPh3. The latex is then degassed with hydrogen. The temperature is raised to 145°C and the hydrogen pressure is increased to 900 psi (6.1 MPa). After 87 hours, the degree of hydrogenation reaches 92%. No gel was produced and the obtained polymer was soluble in methyl ethyl ketone. The main problem of this technology is that the reaction rate is slow, resulting in a very long time, and the catalytic efficiency of the catalyst is low.

[0028] CN104428325, CN111019018 and CN111690080 provide methods for selective hydrogenation of carbon-carbon double bonds in butadiene-acrylonitrile latex by directly adding solid ruthenium or osmium hydrogenation catalysts to latex or mixing the catalysts with latex in batches. The main problem with this series of technologies is that solid ruthenium or osmium catalysts are non-water-soluble. When directly added to latex, the catalyst dispersion effect is poor and it is difficult for the catalyst to enter the micelles. The catalyst dosage is large and the catalytic effect is poor.

[0029] CN111479831, CN110627928, CN11303317, CN111905821, and CN112940185 employ solid ruthenium- or osmium-based hydrogenation catalysts with the aid of emulsifiers for selective hydrogenation of carbon-carbon double bonds in latexes. The main drawbacks of these technologies are that they either require reducing the solids content of the latex to improve catalyst dispersion, impacting production efficiency, or they require the addition of large amounts of emulsifiers to aid catalyst dispersion. However, such large amounts significantly impact post-processing of the latex, as residual emulsifier can affect solid latex performance. Furthermore, post-processing generates significant wastewater, polluting the environment.

[0030] In summary, there are two main approaches to research in this area: one approach, similar to traditional solution-catalyzed hydrogenation, hydrogenates polymers in latex form; the other involves the use of hydrazines, for example, where a hydrogen source is generated in situ as a result of a redox reaction. Currently, both approaches have encountered bottlenecks in achieving fast hydrogenation reaction rates, high conversions, and eliminating gel formation.

[0031] Currently, both ethylene-acrylonitrile copolymerization and NBR emulsion polymerization remain at the laboratory research stage, with no precedent for industrial application. The only industrialized method is NBR solution hydrogenation, which is employed by ARLANXEO, ZION Corporation of Japan, and ZANAN Technologies. Due to differences in the catalytic systems used in the hydrogenation reaction, ZION Corporation of Japan primarily uses a palladium / silica heterogeneous catalyst supported on silica to produce HNBR; ARLANXEO primarily uses a rhodium-based homogeneous catalyst, RhCl(P(C6H5)3)3; and ZANAN primarily uses a ruthenium-based catalyst to produce HNBR. Summary of the Invention

[0032] In view of this, the present invention aims to provide a catalyst composition, a method for selective hydrogenation of conjugated diene latex, a hydrogenated conjugated diene latex, and applications thereof. The catalyst composition provided by the present invention can efficiently and selectively hydrogenate the carbon-carbon double bonds of conjugated diene latex, effectively reducing the amount of the main catalyst and co-catalyst used, achieving mild hydrogenation conditions, lowering the amount of co-catalyst residual, improving the performance of the vulcanized rubber, and increasing production efficiency without any gelation problem.

[0033] The present invention provides a catalyst composition comprising: a main catalyst and a first co-catalyst, wherein the main catalyst is a ruthenium complex hydrogenation catalyst and / or an osmium complex hydrogenation catalyst, and the chemical structure of the first co-catalyst contains one or more of N, O, a carbon-carbon double bond and a carbon-carbon triple bond.

[0034] Preferably, the chemical structure of the main catalyst is at least one of formula (I), formula (II) and formula (III):

[0035] In formula (I), M is ruthenium or osmium; X 1 and X 2 are the same or different anionic ligands; L is an uncharged electron donor; two Rs are the same or different groups independently selected from alkyl, alkyl derivatives, cycloalkyl, cycloalkyl derivatives, alkenyl, alkenyl derivatives, alkynyl, alkynyl derivatives, aryl, aryl derivatives, carboxylate, carboxylate derivatives, alkoxy, alkoxy derivatives, alkenyloxy, alkenyloxy derivatives, alkynyloxy, alkynyloxy derivatives, aryloxy, aryloxy derivatives, alkoxycarbonyl, alkoxycarbonyl derivatives, alkylamino, alkylamino derivatives, thioamino, thioamino derivatives, thioaryl, thioaryl derivatives, alkylsulfonyl, alkylsulfonyl derivatives, alkylsulfinyl or alkylsulfinyl derivatives, wherein a derivative is a group formed by replacing the corresponding non-derivative group with one or more of alkyl, halogen, alkoxy, aryl and heteroaryl groups;

[0036] In formula (II), M is ruthenium or osmium; X 1 and X 2 are the same or different anionic ligands; L is an uncharged electron donor; Y is selected from O, S, NR 1 or PR 1 ; R 1 R is selected from alkyl, alkyl derivatives, cycloalkyl, cycloalkyl derivatives, alkenyl, alkenyl derivatives, alkynyl, alkynyl derivatives, aryl, aryl derivatives, alkoxy, alkoxy derivatives, alkenyloxy, alkenyloxy derivatives, alkynyloxy, alkynyloxy derivatives, aryloxy, aryloxy derivatives, alkoxycarbonyl, alkoxycarbonyl derivatives, alkylamino, alkylamino derivatives, alkylthio, alkylthio derivatives, arylthio, arylthio derivatives, alkylsulfonyl, alkylsulfonyl derivatives, alkylsulfinyl or alkylsulfinyl derivatives, wherein a derivative is a group formed by replacing the corresponding non-derivative group with one or more of alkyl, halogen, alkoxy, aryl and heteroaryl groups; 2 、R 3 、R 4 and R 5 Independently selected from hydrogen, halogen, nitro, CF3, C1-C 30 Alkyl, C3~C 20 Cycloalkyl, 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 20Alkylamino, C1~C 20 Alkylthio, C6~C 24 Arylthio, C1~C 20 Alkylsulfonyl or C1~C 20 Alkylsulfinyl; R 6 is selected from hydrogen, alkyl, alkenyl, alkynyl or aryl;

[0037] In formula (III), the dotted line represents a saturated bond or an unsaturated bond, and α and β cannot be unsaturated bonds at the same time; M is ruthenium or osmium; X 1 and X 2 are the same or different anionic ligands; L is an uncharged electron donor; when α is a saturated bond, L 2 NR 7 R 8 PR 7 R 8 、N=CR 7 R 8 or R 7 C=NR 8 , R 7 and R 8 independently selected from unsubstituted, substituted or heteroatom-containing C1-C 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl or C6~C 24 aryl, or R 7 and R 8 They are non-aromatic ring structures respectively; when α is a double bond, L 2 NR 7 or PR 7 , R 7 Selected from unsubstituted, substituted or heteroatom-containing C1-C 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl or C6~C 24 aryl, or R 7 A and B are independently selected from hydrocarbons, substituted hydrocarbons, hydrocarbons containing heteroatoms, or hydrocarbons with substituted groups and heteroatoms, or A and B are atoms in an aromatic ring; m represents 0 or 1; n represents 0 or 1; R 6 is selected from hydrogen, alkyl, alkenyl or aryl.

[0038] Preferably, in formula (I), formula (II) and formula (III), M is ruthenium; X 1 and X 2 independently selected from hydrogen, halogen, pseudohalogen, linear or branched C1-C 30Alkyl, 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 sulfonates, C1~C 20 Alkyl mercaptan, C6~C 24 Aryl thiols, C1~C 20 Alkylsulfonyl or C1-C 20 -alkylsulfinyl; L is selected from phosphine, sulfonated phosphine, phosphate, hypophosphorous acid, phosphite, phosphonate, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrite, pyridine, thioether or N-heterocyclic carbene ligand.

[0039] Preferably, in formula (I), formula (II) and formula (III), the X 1 and 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); L is at least one of the structures represented by formula (IV-a) to formula (IV-f):

[0040] Among them, R 9 、R 10 、R 11 and R 12 Independently selected from hydrogen, 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 Alkyl, 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 20Alkylthio, C6~C 20 R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; 13 、R 14 and R 15 Independently selected from C1 to C 20 of alkyl.

[0041] Preferably, the main catalyst comprises at least one of the following structural complexes:

[0042] Preferably, the first co-catalyst is one or more of esters, ethers, ketones, amines, carbamates, olefins and alkynes.

[0043] Preferably, the first co-catalyst is one or more of aliphatic monocarboxylic acid alkyl esters, aromatic monocarboxylic acid alkyl esters, aliphatic polycarboxylic acid alkyl esters, aromatic polycarboxylic acid alkyl esters, polyol alkyl esters, polyol cycloalkyl esters, polyol aryl esters, polyol alkylaryl esters, aliphatic ethers, cycloaliphatic ethers, aliphatic diethers, aliphatic ketones, aliphatic amines, aliphatic diamines, olefins and alkynes.

[0044] Preferably, the first co-catalyst is C1 to C 20 Saturated fatty acid alkyl esters, C7~C 24 Aromatic carboxylic acid alkyl esters, C2~C 20 -Diol aryl ester, C2~C 20 Fatty ethers, C3~C 20 Cyclic ethers, C5~C 20 Aliphatic diether, C3~C 20 Saturated fatty ketones, C3~C 20 Saturated fatty amines, C3~C 20 Saturated fatty diamines, C2~C 20 Olefins and C2~C 20 One or more of the alkynes.

[0045] Preferably, the molar ratio of the main catalyst to the first co-catalyst is 1:(20-100).

[0046] Preferably, the catalyst composition further comprises a second co-catalyst, and the second co-catalyst is one or more of carboxylate, sulfonate and phosphate.

[0047] Preferably, the second co-catalyst is one or more of non-emulsifier carboxylates, emulsifier carboxylates, non-emulsifier sulfonates, emulsifier sulfonates, non-emulsifier phosphates and emulsifier phosphates.

[0048] Preferably, the non-emulsified carboxylate is one or more of formates, acetates, propionates, butyrates, valerates, oxalates, malonates, succinates, glutarates, triacrylic acid salts, trisuccinates, triglutaric acid salts, maleates, tartrates, fumarates, malates, amino acid salts, cyclopentane salts, alginates, gluconates, crotonates, itaconates, citrates, mesaconic acid salts, aromatic carboxylates, heteroaromatic ring carboxylates, imidazoline carboxylates, pyruvates, epoxysuccinates, salicylates, fluorenedioates, hydroxypropionates, levulinates, furandicarboxylates, acrylates, methacrylates and trifluoroformates;

[0049] The emulsifier-type carboxylate is one or more of resinate, modified resinate, alkanoyl amino acid salt, fatty acid polypeptide condensate, acyl lactylate and long-chain alkyl carboxylate of C8 or above;

[0050] The non-emulsifier type sulfonate is methanesulfonate, trifluoromethanesulfonate, ethanesulfonate, perfluoroethanesulfonate, propanesulfonate, perfluoropropanesulfonate, hydroxypropanesulfonate, butylsulfonate, perfluorobutylsulfonate, hydroxybutylsulfonate, toluenesulfonate, dinitrotoluenesulfonate, styrenesulfonate, vinylsulfonate, allylsulfonate, methylallylsulfonate, perfluorosulfonic acid type polymer, aromatic sulfonate, heteroaromatic ring sulfonate, cycloalkanesulfonate, hydroxybenzoate, One or more of 2-(2-aminoethyl)aminoethanesulfonate, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonate, aminosulfonates, aminoaromaticsulfonates, ethylenediamineethanesulfonates, chrysinsulfonates, anthraquinonesulfonates, diaminoformylsulfonates, quinocetonesulfonates, thiazolesulfonates, imidazolinesulfonates, allylimidazolinesulfonates, triazolonesulfonates, triazinesulfonates, and flavonesulfonates;

[0051] The emulsifier-type sulfonate is one or more of alkyl aryl sulfonate, alkyl diphenyl oxide disulfonate, α-hydroxy sulfonate, α-olefin sulfonate, petroleum sulfonate, α-sulfomonocarboxylate, α-sulfomonocarboxylate derivatives, sulfoalkyl ester salt derivatives of fatty acids, sulfoalkyl amide salt derivatives of fatty acids, succinate sulfonate, lignin sulfonate, alkyl glyceryl ether sulfonate, 2-aminoethanesulfonate, 2-aminoethanesulfonate derivatives and long-chain alkyl sulfonates of C8 or above;

[0052] The non-emulsifier type phosphate salt is monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, monophenyl phosphate, diphenyl phosphate, triphenyl phosphate, mono-p-cresyl phosphate, di-p-cresyl phosphate, tri-p-cresyl phosphate, mono-o-cresyl phosphate, di-o-cresyl phosphate, tri-o-cresyl phosphate, mono-m-cresyl phosphate, di-m-cresyl phosphate, tri-m-cresyl phosphate, mono-p-isopropylphenyl phosphate, di-p-isopropylphenyl phosphate, tri-p-isopropylphenyl phosphate, mono-p-tert-butyl phosphate Phenyl ester salt, di-p-tert-butylphenyl phosphate salt, tri-p-tert-butylphenyl phosphate, mono-p-methoxyphenyl phosphate salt, di-p-methoxyphenyl phosphate salt, tri-p-methoxyphenyl phosphate, phenyl dimethyl phosphate, phenyl diethyl phosphate, phenyl dibutyl phosphate, diphenylmethyl phosphate, diphenylethyl phosphate, diphenylbutyl phosphate, p-tolyldimethyl phosphate, p-tolyldiethyl phosphate, p-tolyldibutyl phosphate, o-tolyldimethyl phosphate, o-tolyldiethyl phosphate, o-tolyldibutyl phosphate, m-tolyldimethyl phosphate, m-tolyldiethyl phosphate, m-tolyldibutyl phosphate, di-p-tolylmethyl phosphate Ester, di-p-tolyl ethyl phosphate, di-p-tolyl butyl phosphate, di-o-tolyl methyl phosphate, di-o-tolyl ethyl phosphate, di-o-tolyl butyl phosphate, di-m-tolyl methyl phosphate, di-m-tolyl ethyl phosphate, di-m-tolyl butyl phosphate, di-p-isopropylphenyl methyl phosphate, di-p-isopropylphenyl ethyl phosphate, di-p-isopropylphenyl butyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-isopropylphenyl dibutyl phosphate, p-tert-butylphenyl dimethyl phosphate, p-tert-butylphenyl diethyl phosphate, p-tert-butylphenyl dibutyl phosphate, di-p-tert-butylphenyl methyl phosphate, di-p-tert-butylphenyl ethyl phosphate, phosphorus One or more of di-p-tert-butylphenyl butyl phosphate, phenyl di-p-cresyl phosphate, phenyl di-p-isopropylphenyl phosphate, phenyl di-p-tert-butylphenyl phosphate, p-cresyl diphenyl phosphate, p-cresyl-p-diisopropylphenyl phosphate, p-cresyl-p-di-tert-butylphenyl phosphate, o-cresyl-p-diisopropylphenyl phosphate, o-cresyl-p-di-tert-butylphenyl phosphate, m-cresyl-p-diisopropylphenyl phosphate, m-cresyl-p-di-tert-butylphenyl phosphate, p-cumyl di-p-cresyl phosphate, p-cumyl di-o-cresyl phosphate, p-cumyl di-m-cresyl phosphate, p-cumyl di-p-phenyl phosphate and p-cumyl di-p-tert-butylphenyl phosphate;

[0053] The emulsifier-type phosphate salt is one or more of fatty alcohol polyvinyl ether phosphate monoester salt, fatty alcohol polyvinyl ether phosphate diester salt, alkylphenol polyoxyethylene ether phosphate monoester salt, alkylphenol polyoxyethylene ether phosphate diester salt, alcohol ether phosphate ester salt, phenol ether phosphate ester salt, long-chain alkyl phosphate monoester salt of C8 or above, and long-chain alkyl phosphate diester salt of C8 or above.

[0054] Preferably, the molar ratio of the main catalyst to the second co-catalyst is 1:(100-10000).

[0055] Preferably, the catalyst composition is in liquid form.

[0056] Preferably, the catalyst composition further comprises a solvent.

[0057] The present invention provides a method for selective hydrogenation of conjugated diene latex, comprising the following steps:

[0058] In the presence of the catalyst composition described in the above technical solution, the conjugated diene latex is selectively hydrogenated to obtain hydrogenated conjugated diene latex.

[0059] Preferably, the polymer in the conjugated diene latex contains at least one repeating unit of a C4-C6 conjugated diene.

[0060] Preferably, the polymer in the conjugated diene latex further contains repeating units of at least one other copolymerizable monomer.

[0061] Preferably, the polymer in the conjugated diene latex is a copolymer of 1,3-butadiene and acrylonitrile.

[0062] Preferably, the amount of the main catalyst is 0.001 to 5 wt% of the mass of the conjugated diene latex; the amount of the first co-catalyst is 0.01 to 5 wt% of the mass of the conjugated diene latex.

[0063] Preferably, when the catalyst composition includes a second co-catalyst, the amount of the second co-catalyst is 0.1 to 10 wt % based on the mass of the conjugated diene latex.

[0064] Preferably, the temperature of the selective hydrogenation is 35 to 200° C.; the time of the selective hydrogenation is 10 min to 24 h; and the hydrogen pressure of the selective hydrogenation is 0.5 to 35 MPa.

[0065] The present invention provides a hydrogenated conjugated diene latex, which is prepared according to the method described in the above technical solution.

[0066] The present invention provides an application of the hydrogenated conjugated diene latex described in the above technical solution in dipping, adhesives, coatings, film formation or preparation of composite materials.

[0067] The present invention provides a shaped product, wherein the components of the shaped product include the hydrogenated conjugated diene latex described in the above technical solution.

[0068] Preferably, the shaped article comprises one or more of a sealing strip, a sealing gasket, a belt, a hose, a bearing pad, a baffle, a wellhead seal, a valve seal, a cable jacket, a wheel, a roller, an in-situ gasket and a pipe seal.

[0069] Compared with the prior art, the present invention provides a catalyst composition, a method for selective hydrogenation of conjugated diene latex, hydrogenated conjugated diene latex and its application. The catalyst composition provided by the present invention comprises: a main catalyst and a first co-catalyst, preferably also comprising a second co-catalyst, the main catalyst being a ruthenium complex hydrogenation catalyst and / or an osmium complex hydrogenation catalyst, the chemical structure of the first co-catalyst containing one or more of N, O, a carbon-carbon double bond and a carbon-carbon triple bond, and the second co-catalyst being one or more of a carboxylate, a sulfonate and a phosphate. The catalyst composition provided by the present invention can efficiently carry out selective hydrogenation of carbon-carbon double bonds of conjugated diene latex, can effectively reduce the amount of the main catalyst and co-catalyst used, has mild hydrogenation conditions, has a lower amount of co-catalyst residue, has good vulcanizate performance, has high production efficiency, and does not have any gelation problems. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0071] FIG1 is an ultraviolet absorption spectrum of a catalyst composition provided in an embodiment of the present invention;

[0072] FIG2 is a sample photo of the catalyst composition provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0073] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0074] The present invention provides a catalyst composition, comprising: a main catalyst (a) and a first co-catalyst (b), preferably also comprising a second co-catalyst (c), wherein the main catalyst (a) is a ruthenium complex hydrogenation catalyst and / or an osmium complex hydrogenation catalyst, the chemical structure of the first co-catalyst contains one or more of N, O, a carbon-carbon double bond and a carbon-carbon triple bond, and the second co-catalyst is one or more of a carboxylate, a sulfonate and a phosphate.

[0075] In the present invention, the chemical structure of the main catalyst (a) is preferably at least one of formula (I), formula (II) and formula (III):

[0076] Wherein, M is a Group VIII metal element, preferably ruthenium or osmium.

[0077] X 1 and X 2 are the same or different anionic ligands, preferably, X 1 and X 2 independently selected from hydrogen, halogen, pseudohalogen, linear 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 sulfonates, C1~C 20 Alkyl mercaptan, C6~C 24 Aryl thiols, C1~C 20 Alkylsulfonyl or C1~C 20 The above-mentioned groups may also be further substituted by one or more groups, such as halogen (preferably fluorine), C1~C 10 Alkyl, C1~C 10 Alkoxy or C6~C 24 In addition, the above substituents may in turn be substituted to some extent chemically by one or more substituents, preferably comprising halogen (especially fluorine), C1~C5 alkyl, C1~C5 alkoxy or phenyl.

[0078] In a preferred embodiment of the present invention, X 1 and X 2 independently selected from halogen (especially fluorine, chlorine, bromine, iodine), benzoic acid, C1-C5 carboxylate, C1-C5 alkyl, phenoxy, C1-C5 alkoxy, C1-C5 alkylthiol, C6-C 14 Aromatic thiophenols, C6~C 14 Aryl or C1~C5 alkyl sulfonate.

[0079] In a particularly preferred embodiment, X 1 and X 2 independently selected from chlorine, CF3COO, CH3COO, CFH2COO, (CH3)3 CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, phenoxy, methoxy, ethoxy, toluenesulfonate (p-CH3-C6H4-SO3), methanesulfonic acid (CH3SO3) or trifluoromethanesulfonate (CF3SO3).

[0080] L represents a ligand, preferably an uncharged electron donor, and the ligand L is preferably selected from one or more of phosphine, sulfonated phosphine, phosphate, hypophosphorous acid, phosphite, phosphonate, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrite, pyridine, thioether and N-heterocyclic carbene ligands;

[0081] In the present invention, the term "hypophosphorous acid" includes phenyldiphenylphosphorous acid, cyclohexyldicyclohexylphosphorous acid, isopropyldiisopropylphosphorous acid and methyldiphenylphosphorous acid.

[0082] The term "phosphite" includes triphenylphosphite, tricyclohexylphosphite, tri-tert-butylphosphite, triisopropylphosphite and methyldiphenylphosphite.

[0083] The term "antimony" includes: triphenyl Tricyclohexyl and trimethyl

[0084] The term "sulfoxide" includes: (CH3)2S(=O) and (C6H5)2S=O.

[0085] The term "thioether" includes: CH3SCH3, C6H5SCH3, CH3OCH2CH2SCH3 and tetrahydrothiophene.

[0086] The term "pyridyl ligand" is used as a general term for all ligands based on pyridine or its derivatives.

[0087] 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.

[0088] In the present invention, L in the general expression (I) (II) or (II) represents phosphine as an electron donor, and its general expression is preferably:

[0089] Among them, R 13 、R14 and R 15 are the same or different, preferably the same, preferably C1 to C 20 The alkyl group is more preferably 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, neopentyl, C3 to C8 cycloalkyl; the most preferred are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, C1 to C8 20 Alkoxy, substituted or unsubstituted C6~C 20 Aryl; most preferably phenyl, biphenyl, naphthalene, phenanthrene, anthracene, tolyl, 2,6-dimethylphenyl, trifluoromethyl, C6~C 20 Aryloxy, C2~C 20 Heteroaryl, C2-C 20 The heterocyclic group may be halogen; the halogen is preferably fluorine.

[0090] If L represents a phosphine of the general formula (IV-f) and the structure shown in formula (I), (II) or formula (III) serves as an electron-donating ligand, such phosphine is preferably 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.

[0091] An n-heterocyclic carbene ligand is a cyclic carbene ligand containing at least one nitrogen heteroatom in the ring. The ring can be substituted in various ways. Preferably, the substitution pattern provides a certain degree of steric crowding.

[0092] In the present invention, the n-heterocyclic carbene ligands (hereinafter referred to as "NHC-ligands") are preferably based on imidazoline or imidazolinidine groups.

[0093] In the present invention, L is preferably an NHC-ligand, usually at least one of the structures represented by formula (IV-a) to formula (IV-e):

[0094] Among them, R 8 、R 9 、R 10 、R 11 Independently selected from hydrogen, linear or branched C1-C30 Alkyl, C3~C 20 Cycloalkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl, C6~C 24 Aryl, C7~C 25 Alkyl, 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 -S(=O)R', -S(=O)R', -OS(=O)R', halogen, nitro or cyano.

[0095] In the above R 8 、R 9 、R 10 and R 11 In the group, R' is the same or different and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl.

[0096] In the representative formulas (IV-a) to (IV-e), the carbon atom bonded to the ruthenium metal center is in the form of a carbene.

[0097] Optionally, R 9 、R 10 、R 11 and R 12 One or more of the can be independently substituted by one or more substituents, the substituents are preferably linear or branched C1~C 10 Alkyl, C3~C8 cycloalkyl, C1~C 10 Alkoxy, C6~C 24 Aryl, C2~C 20 Heteroaryl, C2~C 20or a group containing a hydroxyl group, a thiol group, a thioether group, a ketone group, an aldehyde group, an ester group, an ether group, an amine group, an imine group, an amide group, a nitro group, a carboxylic acid group, a disulfide group, a carbonate group, an isocyanate group, a carbodiimide group, an alkoxycarbonyl group, a carbamate group or a halogen group, wherein the above substituents may in turn be substituted to a certain extent chemically by one or more substituents, preferably containing halogen (especially chlorine or bromine groups), C1-C5 alkyl groups, C1-C5 alkoxy groups and phenyl groups.

[0098] For the sake of clarity, it should be noted that the NHC-ligand structures of the general formulae (IV-a) and (IV-b) depicted herein are identical to the structures (IVa-(i)) and (IVb-(i)) commonly encountered in the literature for such NHC-ligands, respectively, and emphasize the carbene nature of the NHC-ligands. This also applies to the further structures (IV-c) to (IV-e) and the preferred structures described below in relation to (IV-c) to (IV-e).

[0099] In a preferred NHC-ligand of the catalyst represented by the general expression, R 9 and R 10 are the same or different, they represent hydrogen, C6~C 24 Aryl (preferably phenyl), linear or branched C1-C 10 The alkyl group is more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, an i-butyl group or a tert-butyl group, or a cycloalkyl group or an aryl group bound to a carbon atom.

[0100] Preferably and more preferably, R 9 and R 10 One or more of the can be independently substituted by one or more substituents, the substituents are preferably linear or branched C1~C 10 Alkyl, straight chain or branched C1~C 10 Alkoxy, C3~C8 cycloalkyl, C6~C 24 or a group containing a hydroxyl group, a thiol group, a thioether group, a ketone group, an aldehyde group, an ester group, an ether group, an amine group, an imine group, an amide group, a nitro group, a carboxylic acid group, a disulfide group, a carbonate group, an isocyanate group, a carbodiimide group, an alkoxycarbonyl group, a carbamate group or a halogen group, wherein these substituents may in turn be substituted by one or more substituents, preferably containing halogen (especially chlorine or bromine), a C1-C5 alkyl group, a C1-C5 alkoxy group or a phenyl group.

[0101] In a further preferred NHC-ligand of the catalyst represented by the general expression, R 11 and R 12 are the same or different, preferably linear or branched C1~C 10Alkyl (preferably i-propyl or neopentyl), C3~C 10 cycloalkyl (preferably adamantyl), substituted or unsubstituted C6~C 24 Aryl (preferably phenyl, 2,6-isopropylbenzene, 2,6-xylyl or 2,4,6-trimethylphenyl), C1~C 10 Alkyl sulfonate or C6-C 10 -sulfonic acid.

[0102] Preferably, R 11 and R 12 It may be substituted by one or more substituents selected from linear or branched C1-C 10 Alkyl, straight chain or branched C1~C 10 Alkoxy, C3~C8 cycloalkyl, C6~C 24 or a group containing a hydroxyl group, a thiol group, a thioether group, a ketone group, an aldehyde group, an ester group, an ether group, an amine group, an imine group, an amide group, a nitro group, a carboxylic acid group, a disulfide group, a carbonate group, an isocyanate group, a carbodiimide group, an alkoxycarbonyl group, a carbamate group or a halogen group, wherein these substituents may in turn be substituted by one or more substituents, preferably containing halogen (especially chlorine or bromine), a C1-C5 alkyl group, a C1-C5 alkoxy group or a phenyl group.

[0103] In a further preferred NHC-ligand of the catalyst represented by the general expression, R 9 and R 10 are the same or different, they represent hydrogen, C6~C 24 Aryl (preferably phenyl), straight chain or branched C1~C 10 The alkyl group is more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, an i-butyl group, or a cycloalkyl group or an aryl group bound to a carbon atom.

[0104] R 11 and R 12 are the same or different, preferably linear or branched C1~C 10 Alkyl (preferably i-propyl or neopentyl), C3~C 10 cycloalkyl (preferably adamantyl), substituted or unsubstituted C6~C 24 Aryl (preferably phenyl, 2,6-isopropylphenyl, 2,6-xylyl or 2,4,6-trimethylphenyl), C1-C 10 Alkyl sulfonate or C6~C 10 of sulfonic acid.

[0105] Particularly preferably, the NHC ligand has the structures shown below (Va) to (Vu), 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 sec-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:

[0106] 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 degree of spatial crowding.

[0107] (i) For the procatalyst having formula (I):

[0108] Wherein, R is selected from one or more of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonic acid and alkylsulfinyl; these substituents may be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups.

[0109] Preferably, the substituent R is usually hydrogen, 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 These substituents may be optionally substituted with one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups.

[0110] (ii) For the procatalyst having formula (II):

[0111] Y is selected from O, S, NR1 or PR 1 group, where R 1 One or more substituents selected from alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonic acid and alkylsulfinyl; these substituents may be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups.

[0112] Preferably, the substituent R 1 Usually 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 These substituents may be optionally substituted with one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups.

[0113] R 1 More preferably, C3~C 20 Cycloalkyl, C6~C 24 aromatic, straight chain or branched C1~C 30 The alkyl radicals are, where appropriate, interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen. 1 Particularly preferred are linear or branched C1-C 12 of alkyl.

[0114] Among them, C3~C 20 The cycloalkyl group includes, for example, one or more of a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0115] A C1~C 12The alkyl group of can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-dodecyl. In particular, R 1 It is methyl or isopropyl.

[0116] C6~C 24 The aryl group is an aromatic group having 6 to 24 backbone carbon atoms. Preferred monocyclic, bicyclic or tricyclic carbocyclic aryl groups having 6 to 10 backbone carbon atoms can be synthesized using benzene, biphenyl, naphthalene, phenanthrene, anthracene or anthracene.

[0117] In the present invention, R 2 、R 3 、R 4 and R 5 independently selected from hydrogen groups, organic groups or inorganic groups;

[0118] In one suitable embodiment, R 2 、R 3 、R 4 、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 optionally substituted by one or more alkyl, alkoxy, halogen, aryl or heteroaryl groups.

[0119] Preferably, R 2 、R 3 、R 4 、R 5 They are usually the same or different, and each can be hydrogen, halogen (preferably chlorine or bromine), nitro, CF3, 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~C20 Alkylsulfonyl or C1~C 20 Alkylsulfinyl, these substituents may be replaced by one or more C1 to C 30 Alkyl, C1~C 20 Alkoxy, halogen, C6~C 24 The aryl or heteroaryl group is optionally substituted.

[0120] In a particularly preferred embodiment, R 2 、R 3 、R 4 、R 5 are the same or different, each can be nitro, straight chain or branched C1~C 30 Alkyl, C5~C 20 Cycloalkyl, straight chain or branched C1~C 20 Alkoxy or C6~C 24 Aryl (preferably phenyl or naphthyl), wherein C1 to C 30 Alkyl and C1~C 20 The alkoxy groups may be substituted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.

[0121] In addition, two or more groups R 2 、R 3 、R 4 or R 5 It can also be connected through aliphatic or aromatic structures. For example, R 3 、R 4 And by connecting their carbon atoms on the phenyl ring in the expression, a fused phenyl ring can be formed, and overall, a naphthyl structure is produced.

[0122] According to the present invention, R 6 One or more selected from hydrogen, alkyl, alkenyl, alkynyl and aryl; R 6 Preferably selected from hydrogen, C1-C 30 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl or C6~C 24 Aryl; R 6 Hydrogen is particularly preferred.

[0123] (iii) For the procatalyst having formula (III):

[0124] The dotted line represents a saturated bond or an unsaturated bond, for example, a double bond; α and β cannot be double bonds at the same time; A and B are independent linking groups, each derived from a hydrocarbon, such as C1~C 20 Alkyl, C2~C 20 Alkenyl, C2~C20 Alkynyl, C5~C 50 Aromatic groups, C6~C 24 Alkaryl, C6~C 24 or substituted hydrocarbons, such as C1~C 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl, C5~C 50 Aromatic groups, C6~C 24 Alkyl, C6~C 24 or hydrocarbons containing heteroatoms, such as C1~C 20 Heteroalkyl, C2~C 20 Heteroalkenyl, C2~C 20 Heteroalkynyl, C5~C 50 Heteroaromatic, C6~C 24 Heteroalkylaryl, C6~C 24 or heteroatom-containing hydrocarbons containing substituents, such as C1-C 20 Heteroalkyl, C2~C 20 Heteroalkenyl, C2~C 20 Heteroalkynyl, C5~C 50 Heteroaromatic groups, C6~C 24 Heteroalkylaryl, C6~C 24 Heteroalkene aryl; or -O-, -S-, -NR 8 -or-PR 8 -, R 8 Selected from hydrocarbons, such as C1~C 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl, C5~C 50 Aromatic groups, C6~C 24 Alkaryl, C6~C 24 or substituted hydrocarbons, such as C1~C 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl, C5~C 50 Aromatic groups, C6~C 24 Alkyl, C6~C 24 or hydrocarbons containing heteroatoms, such as C1~C 20 Heteroalkyl, C2~C 20Heteroalkenyl, C2~C 20 Heteroalkynyl, C5~C 50 Heteroaromatic, C6~C 24 Heteroalkylaryl, C6~C 24 or heteroatom-containing hydrocarbons containing substituents, such as C1-C 20 Heteroalkyl, C2~C 20 Heteroalkenyl, C2~C 20 Heteroalkynyl, C5~C 50 Heteroaromatic groups, C6~C 24 Heteroalkylaryl, C6~C 24 Heteroalkenyl aryl.

[0125] The overall structure composed of the organic groups A and B is preferably as shown in (A) to (G):

[0126] As a preferred embodiment, when α is a saturated bond, L 2 NR 7 R 8 PR 7 R 8 、N=CR 7 R 8 or R 7 C=NR 8 , R 7 、R 8 independently selected from unsubstituted, substituted or heteroatom-containing C1-C 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl or C5~C 24 aryl, or R 7 and R 8 They can be non-aromatic ring structures, such as piperidinyl (including substituted piperidinyl); m represents 0 or 1; n represents 0 or 1; R 6 Any one selected from hydrogen, alkyl, alkenyl or aryl.

[0127] As a preferred embodiment, the structural formula of the main catalyst is formula (VI) or formula (VII):

[0128] Among them, R 7 and R 8 Independently selected from C1 to C 12 Alkyl or C6~C 12Preferably, A is -CH2-, -CH2CH2-, or A is -CH2- or -CH2CH2- with a substituent.

[0129] In the main catalyst of the present invention, L, R 6 、R 7 、R 8 、X 1 、X 2 , β are as described above; more preferably R 7 、R 8 C1~C 12 Alkyl or C6~C 12 aryl, such as methyl, isopropyl, tert-butyl, cycloalkyl or phenyl, preferably A is -CH2-, -CH2CH2-, or A is a substituted group; when L2 is NR 7 R 8 or PR 7 R 8 When the main catalyst is a catalyst, the structural formula is formula (VI) or formula (VII).

[0130] As a preferred embodiment, the structural formula of the main catalyst is formula (VIII) or formula (IX):

[0131] In the main catalyst of the present invention, L 2 and B can be connected by an unsaturated bond, and the bond α at the dotted line can represent a double bond or a bond on an aromatic ring; when L 2 and B are connected by an unsaturated bond, L 2 Selected from NR 7 or PR 7 , more preferably NR 7 , R 7 Consistent with the above description; when α represents an unsaturated bond, the compound may contain an imine ligand, such as -B=NR 8 , or contains a pyridine ring, N and B are contained in a pyridine ring, and the structural formula of the catalyst is formula (VIII) or formula (IX).

[0132] In the present invention, R 1 、R 2 、R 3 、R 4 The optional organic group refers to a substituent group containing C atoms, such as alkyl, alkenyl, alkynyl, ester, alkoxy, alkenyloxy, cycloalkyl, aryl, heterocyclic, heteroaryl, alkylamino, etc. In the present invention, R 1 、R 2 、R 3 、R 4The optional inorganic group refers to a substituent group that does not contain a C atom, such as a hydroxyl group, a nitro group, a halogen group, a sulfonic acid group, an amino group, a cyano group, etc.; R 1 、R 2 、R 3 、R 4 Independently selected from hydrogen, halogen, nitro, CF3, C1-C 30 Alkyl, C3~C 30 Cycloalkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl, C6~C 24 Aryl, C2~C 20 Alkoxy, C2~C 20 Alkenyloxy, C2~C 20 Alkynyloxy, C6~C 24 Aryloxy, C2~C 20 Alkoxycarbonyl, C1~C 20 Alkylamino, C1-C2 alkylthio, C6-C 24 Arylthio, C1~C 20 Alkylsulfonyl or C1~C 20 of an alkylsulfinyl group.

[0133] In the present invention, R 1 、R 2 、R 3 、R 4 can be the same or different and are each selected from hydrogen or an organic group or an inorganic group; preferably, R 1 、R 2 、R 3 、R 4 Each is independently selected from hydrogen, halogen, nitro, CF3, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthioether, alkylsulfonyl or alkylsulfinyl.

[0134] More preferably, R 1 、R 2 、R 3 、R 4 Independently selected from hydrogen, fluorine, chlorine, bromine, nitro, straight or branched C1-C 30 Alkyl, C6~C 24 Cycloalkanes, straight or branched C1~C 20 Alkoxy or C6~C 24 aryl (preferably phenyl or naphthyl); wherein the C1~C 30 Alkyl and C1~C 20 The alkoxy group may be substituted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.

[0135] In addition, R 1 、R 2 、R 3 、R 4 Two or more of them may also be connected through an aliphatic or aromatic structure; for example, R 3 、R 4 And by connecting their carbon atoms on the phenyl ring in formula (VIII), a fused phenyl ring can be formed. Overall, a naphthyl structure is generated.

[0136] In the present invention, the above R 1 、R 2 、R 3 、R 4 It may be optionally substituted with one or more alkyl, alkoxy, halogen, aryl or heteroaryl groups or heteroaryl groups; more preferably, it may be substituted with one or more C1-C 30 Alkyl, C1~C 20 Alkoxy, halogen, C6~C 24 Aryl or C6~C 24 The heteroaryl group is optionally substituted.

[0137] In the present invention, R 6 Preferably, it is hydrogen, alkyl, alkenyl, alkynyl or aryl; More preferably, it is hydrogen, C1-C 30 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl or C6~C 24 further preferably, R 6 For hydrogen.

[0138] As a preferred embodiment, the structural formula of the main catalyst is at least one of the following structures:

[0139] As another preferred embodiment, the structural formula of the main catalyst is at least one of the following structures:

[0140] As another preferred embodiment, the structural formula of the main catalyst is at least one of the following structures:

[0141] The present invention does not limit the source of the Group VIII metal compound of formula (I), formula (II) or formula (III), and may be commercially available or prepared by methods disclosed in the prior art, such as those disclosed in US2002 / 0107138, US2008 / 0064882, US2009 / 0076226, J. Am. Chem. Soc, 2000, 122, 8168-8179, and CN111905821.

[0142] The main catalyst of the present invention is preferably selected from one or more of Grubbs II-III, Hoveyda-Grubbs II catalyst, and Grela catalyst, and has the following structural formula:

[0143] In the present invention, the main catalyst (a) may be water-soluble or water-insoluble. In the present invention, "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. 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 to be "water-soluble".

[0144] In the present invention, the first co-catalyst (b) is preferably one or more of aliphatic monocarboxylic acid alkyl esters, aromatic monocarboxylic acid alkyl esters, aliphatic polycarboxylic acid alkyl esters, aromatic polycarboxylic acid alkyl esters, polyol alkyl esters, polyol cycloalkyl esters, polyol aryl esters, polyol alkylaryl esters, aliphatic ethers, cycloaliphatic ethers, aliphatic diethers, aliphatic ketones, aliphatic amines, aliphatic diamines, olefins and alkynes.

[0145] More preferably, the first co-catalyst (b) is C1 to C 20 Alkyl esters of saturated fatty carboxylic acids, C7~C 24 Alkyl esters of aromatic carboxylic acids, C2~C 20 Aryl esters of diols, C2~C 20 Fatty ethers, C3~C 20 Cyclic ethers, C5~C 20 Aliphatic diether, C3~C 20 Saturated fatty ketones, C3~C 20 Saturated fatty amines, C3~C 20 Saturated fatty diamines, C3~C 20 Fatty amides, C7~C 24 Aromatic amides, C2~C 20 Olefins and C2~C 20 One or more of the alkynes.

[0146] Most preferably, the first co-catalyst (b) is one or more of methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, ethyl ether, hexyl ether, tetrahydrofuran, dioxane, acetone, butanone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone and N,N-dimethylformamide.

[0147] In the present invention, the second co-catalyst is preferably one or more of non-emulsifier carboxylates, emulsifier carboxylates, non-emulsifier sulfonates, emulsifier sulfonates, non-emulsifier phosphates and emulsifier phosphates.

[0148] In the present invention, "non-emulsifier carboxylate" refers to an organic small molecule carboxylate containing a carboxylate group that does not have an emulsifying effect, wherein "salt" can be hydrogen, an alkali metal cation, ammonium, an alkanolamine or other cations.

[0149] Preferably, the non-emulsifier carboxylate can be one or more of formates, acetates, propionates, butyrates, valerates, oxalates, malonates, succinates, glutarates, triacrylic acid salts, trisuccinates, glutaric acid salts, maleates, tartrates, fumarates, malates, amino acid salts, cyclopentane salts, alginate, gluconates, crotonates, itaconates, citrates, mesaconic acid salts, aromatic carboxylates, heteroaromatic carboxylates, imidazole (line) carboxylates, pyruvates, epoxysuccinates, salicylates, fluorenedioates, hydroxypropionates, levulinates, furandicarboxylates, acrylates, methacrylates and trifluoroformates.

[0150] In the present invention, "emulsifier-type carboxylate" is a surfactant containing a carboxylate group with an emulsifying effect, which can be one or more of long-chain alkyl carboxylates of C8 or above, resinates, modified resinates, alkanoyl amino acid salts, fatty acid polypeptide condensates and acyl lactylates.

[0151] In the present invention, the "long chain alkyl carboxylate of C8 or more" is represented by the general formula RCOOM (1 / n) , wherein R is hydrogen, C8~C 30 Alkyl, C8~C 20 Cycloalkyl, C8~C 20 Alkenyl, C8~C 20 Alkynyl, C8~C 24 Aryl, C8~C 20 Alkoxy, C8~C 20 Alkenyloxy, C8~C 20 Alkynyloxy, C8~C 24 Aryloxy, C8~C 20 Alkoxycarbonyl, C8~C 20Alkylamino, C8~C 20 Alkylthio, C8~C 24 Arylthio, C8~C 20 Alkylsulfonyl or C8~C 20 These substituents may be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; and n is the valence of the ion.

[0152] In the present invention, "resin salts" and "modified resin salts" are classified into (1) vinyl resin salts, (2) aliphatic resin salts, and (3) aromatic resin salts according to their chemical structures, with some typical examples being (disproportionated) pimarate, (disproportionated) neorosinate, (disproportionated) rosinate, (disproportionated) levosinate, and (disproportionated) palustine salt; and "salt" may be hydrogen, an alkali metal cation, ammonium, an alkanolamine, or other cations.

[0153] In the present invention, "alkanoyl amino acid salt" is mainly the condensation product of fatty acid and amino acid, such as alkanoyl amino acid salt, the typical types and general formula of which are as follows:

[0154] Alkanoyl aspartate: RCONHCH(CH2COO M (1 / n) )COO M (1 / n) ;

[0155] Alkanoyl-N-β-hydroxyethyl-glycine salt: RCON(CH2CH2OH ) )CH2COO M (1 / n) ;

[0156] N-fatty acyl sarcosinate (Medialan): RCON(CH3)CH2COO M (1 / n) ;

[0157] N-Alkanoyl peptide (Lamepon): RCONHR`(CONHR``)COO M (1 / n) ;

[0158] Among them, R is hydrogen, 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~C20 Alkoxycarbonyl, C1~C 20 Alkylamino, C1~C 20 Alkylthio, C6~C 24 Arylthio, C1~C 20 Alkylsulfonyl or C1~C 20 These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; and n is the valence of the ion.

[0159] In the present invention, "fatty acid polypeptide condensate" is obtained by condensing fatty acid chloride with amino acids of protein hydrolysate, and its general formula is RCONH(polypeptide)COOM (1 / n) ; Wherein, R is hydrogen, 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 groups, which may be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; n is the valence of the ion; the polypeptide chain length ranges from a molecular weight of 150 to 10,000, preferably a polypeptide with a molecular weight of 350 to 2,000.

[0160] In the present invention, "acyl lactate" is a salt obtained by esterification and polymerization of fatty acid (RCOOH) and lactic acid (H3CCH(OH)COOH) and neutralization, having the general formula RCO(OCH(CH3)CO) m OM (1 / n) ; Wherein, R is hydrogen, C1~C 30 Alkyl, C3~C 20 Cycloalkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl, C6~C 24 Aryl, C1~C20 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 These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; and n is the valence of the ion.

[0161] In the present invention, "non-emulsifier sulfonate" refers to an organic small molecule sulfonate containing a sulfonate group that does not have an emulsifying effect, wherein "salt" can be hydrogen, an alkali metal cation, ammonium, an alkanolamine or other cations.

[0162] Preferably, the non-emulsifier type sulfonic acid salt can be methanesulfonate, trifluoromethanesulfonate, ethanesulfonate, perfluoroethanesulfonate, propanesulfonate, perfluoropropanesulfonate, hydroxypropanesulfonate, butylsulfonate, perfluorobutylsulfonate, hydroxybutylsulfonate, toluenesulfonate, dinitrotoluenesulfonate, styrenesulfonate, vinylsulfonate, allylsulfonate, methylallylsulfonate, perfluorosulfonic acid type polymer, aromatic sulfonate, heteroaromatic ring sulfonate, cycloalkanesulfonate, hydroxybenzoate, One or more of sulfonates, 2-(2-aminoethyl)aminoethanesulfonate, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonate, aminosulfonates, aminoaromaticsulfonates, ethylenediamineethanesulfonates, chrysinsulfonates, anthraquinonesulfonates, diaminoformylsulfonates, quinocetonesulfonates, thiazolesulfonates, imidazolinesulfonates, allylimidazolinesulfonates, triazolonesulfonates, triazinesulfonates and flavonesulfonates.

[0163] In the present invention, the "emulsifier-type sulfonate" is a surfactant containing a sulfonate group with an emulsifying effect, which can be one or more of long-chain alkyl sulfonates of C8 or above, alkyl aryl sulfonates, alkyl diphenyl ether disulfonates, α-hydroxy sulfonates and α-olefin sulfonates, petroleum sulfonates, α-sulfomonocarboxylic acids and derivatives thereof, sulfoalkyl ester derivatives of fatty acids and sulfoalkyl amide derivatives of fatty acids, succinate sulfonates, lignin sulfonates, alkyl glycerol ether sulfonates, 2-aminoethanesulfonate and derivatives thereof.

[0164] In the present invention, "long-chain alkyl sulfonates of C8 or more" and "alkyl aryl sulfonates" have the general formula RSO3M (1 / n) , where R is C8~C 30 Alkyl, C8~C 20 Cycloalkyl, C8~C 20 Alkenyl, C8~C 20 Alkynyl, C6~C 24 Aryl, C8~C 20 Alkoxy, C8~C 20 Alkenyloxy, C8~C 20 Alkynyloxy, C6~C 24 Aryloxy, C8~C 20 Alkoxycarbonyl, C8~C 20 Alkylamino, C8~C 20 Alkylthio, C6~C 24 Arylthio, C8~C 20 Alkylsulfonyl or C8~C 20 These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; and n is the valence of the ion.

[0165] In the present invention, "alkyl diphenyl ether disulfonate" has the following general formula:

[0166] Among them, R is hydrogen, 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 These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; and n is the valence of the ion.

[0167] In the present invention, "α-hydroxysulfonate" has the following general formula:

[0168] In the present invention, "α-olefin sulfonate" has the following general formula:

[0169] In the above-mentioned general structure of "α-hydroxysulfonate" and "α-olefinsulfonate", R is hydrogen, 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 These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; n is the valence of the ion; m and p are 0 or positive integers.

[0170] In the present invention, "petroleum sulfonate" is a mixture, the main component of which is complex alkylbenzene sulfonate or alkylnaphthalene sulfonate, and the rest are sulfonates and oxides of aliphatic hydrocarbons and cyclic hydrocarbons; the "salt" therein can be hydrogen, alkali metal cations, ammonium, alkanolamine or other cations.

[0171] In the present invention, "α-sulfonated monocarboxylic acids and their derivatives" refer to various products obtained by replacing the H at the α-position of fatty acids or esters with a sulfonated group, mainly including the following types: (1) α-sulfonated fatty acid methyl ester mono (sodium) salt, which is a commercial product obtained by sulfonating and neutralizing fatty acid methyl ester as a raw material, referred to as MES (methyl ester sulfonate), with the general formula of RCH(SO3M (1 / n) )COOCH3, wherein R is hydrogen, C1~C 30 Alkyl, C3~C 20 Cycloalkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl, C6~C 24 Aryl, C1~C 20Alkoxy, 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 can be selectively substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M can be hydrogen, alkali metal cation, ammonium, alkanolamine or other cations; n is the valence of the ion. (2) α-sulfo-low carbon fatty acid high carbon alcohol esters, such compounds mainly include: ① sulfoacetic acid lauryl ester C 12 H 25 OOCCH2SO3Na, ② Esters formed by sulfoacetic acid and branched alcohols, long-chain alcohols or alcohol ethers.

[0172] In the present invention, the trade name of "sulfonalkyl ester salt derivative of fatty acid" is Igepon A, and its representative substance is sodium oleoyloxyethanesulfonate.

[0173] In the present invention, the trade name of "sulfonylamide salt derivative of fatty acid" is Igepon T, and the general formula is R 1 -CO-N(R 2 )-R 3 -SO3M (1 / n) , its representative is sodium N-oleoyl-N-methyl taurate; wherein, R 1 、R 2 、R 3 are the same or different and are each selected from hydrogen, C1 to 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 20These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; and n is the valence of the ion.

[0174] In the present invention, "succinate ester sulfonate" can be divided into succinate monoester sulfonate according to its structure, with the general formula ROOCCH2CH(SO3M (1 / n) COOM (1 / n) ), and succinic acid diester sulfonate, general formula ROOCCH2CH(SO3M (1 / n) COOR). According to the different hydroxyl-containing raw materials used in the esterification reaction, it can be divided into sulfosuccinic acid alkyl ester salts, sulfosuccinic acid fatty alcohol polyoxyethylene ether ester salts, sulfosuccinic acid fatty amide ethyl ester salts, etc. Among them, the typical one is sulfosuccinic acid fatty alcohol polyoxyethylene ether ester disodium salt, which has the general formula RO(CH2CH2O) m OCCH2CH(SO3Na)COONa, ethyl sulfosuccinamide disodium salt, has the general formula RCONH(CH2CH2O) m CH2CH2OOCCH2CH(SO3Na)COONa, disodium sulfosuccinate ethoxylated alkanolamide ester, RCONHCH2CH2OOCCH2CH(SO3Na)COONa, sulfosuccinate siloxane ester salt. Wherein, R is hydrogen, 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 These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; n is the valence of the ion; m is 0 or a positive integer.

[0175] In the present invention, "lignin sulfonate" is the main component of the wastewater produced during the sulfite pulping process of logs in the papermaking industry, and its general formula is as follows:

[0176] Lignin sulfonate is a mixture with a rather complex structure. It is generally believed to be a sulfonate of a polymer of guaiacylpropyl, syringylpropyl and p-hydroxyphenylpropyl. It can contain up to 8 sulfonic acid groups and 16 methoxy groups. The sulfonated carbon atom is at the α-position connected to the phenyl group. The molecular weight distribution range of lignin sulfonate is very wide, with a relative molecular mass ranging from 200 to 10,000. The average relative molecular mass of the most common lignin sulfonate is about 4,000.

[0177] In the present invention, "alkyl glyceryl ether sulfonate" has the general formula ROCH2CH(OH)CH2SO3M (1 / n) , wherein R is hydrogen, 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 These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, an alkanolamine, or another cation; and n is the valence of the ion.

[0178] In the present invention, "2-aminoethanesulfonate and its derivatives" are also called taurate and its derivatives, such as methyl taurate CH3NHCH2CH2SO3M (1 / n) Derivatives of N-acyl-N-alkyl taurates RCON(R`)CH2CH2SO3M (1 / n) Wherein, R and R' may be the same or different, each selected from hydrogen, 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 20Alkynyloxy, 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 These substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation; and n is the valence of the ion.

[0179] In the present invention, "non-emulsifier type phosphate salt" refers to an organic small molecule phosphate salt containing a phosphate group that does not have an emulsifying effect, wherein "salt" can be hydrogen, alkali metal cations, ammonium, alkanolamine or other cations.

[0180] Preferably, the non-emulsifier type phosphate salt can be monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, monophenyl phosphate, diphenyl phosphate, triphenyl phosphate, mono-p-cresyl phosphate, di-p-cresyl phosphate, tri-p-cresyl phosphate, mono-o-cresyl phosphate, di-o-cresyl phosphate, tri-o-cresyl phosphate, mono-m-cresyl phosphate, di-m-cresyl phosphate, tri-m-cresyl phosphate, mono-p-isopropylphenyl phosphate, di-p-isopropylphenyl phosphate, tri-p-isopropylphenyl phosphate, phosphate Mono-p-tert-butylphenyl phosphate, di-p-tert-butylphenyl phosphate, tri-p-tert-butylphenyl phosphate, mono-p-methoxyphenyl phosphate, di-p-methoxyphenyl phosphate, tri-p-methoxyphenyl phosphate, phenyl dimethyl phosphate, phenyl diethyl phosphate, phenyl dibutyl phosphate, diphenyl methyl phosphate, diphenyl ethyl phosphate, diphenyl butyl phosphate, p-tolyldimethyl phosphate, p-tolyldiethyl phosphate, p-tolyldibutyl phosphate, o-tolyldimethyl phosphate, o-tolyldiethyl phosphate, o-tolyldibutyl phosphate, m-tolyldimethyl phosphate, m-tolyldiethyl phosphate, m-tolyldibutyl phosphate, di-p-tolyl phosphate Phenyl methyl ester, di-p-tolyl ethyl phosphate, di-p-tolyl butyl phosphate, di-o-tolyl methyl phosphate, di-o-tolyl ethyl phosphate, di-o-tolyl butyl phosphate, di-m-tolyl methyl phosphate, di-m-tolyl ethyl phosphate, di-m-tolyl butyl phosphate, di-p-isopropylphenyl methyl phosphate, di-p-isopropylphenyl ethyl phosphate, di-p-isopropylphenyl butyl phosphate, di-p-isopropylphenyl dimethyl phosphate, di-p-isopropylphenyl diethyl phosphate, di-p-isopropylphenyl dibutyl phosphate, di-p-isopropylphenyl methyl phosphate, di-p-isopropylphenyl ethyl phosphate, One or more of di-p-tert-butylphenyl butyl phosphate, phenyl di-p-cresyl phosphate, phenyl di-p-isopropylphenyl phosphate, phenyl di-p-tert-butylphenyl phosphate, p-cresyl diphenyl phosphate, p-cresyl-p-diisopropylphenyl phosphate, p-cresyl-p-di-tert-butylphenyl phosphate, o-cresyl-p-diisopropylphenyl phosphate, o-cresyl-p-di-tert-butylphenyl phosphate, m-cresyl-p-diisopropylphenyl phosphate, m-cresyl-p-di-tert-butylphenyl phosphate, p-cumyl di-p-cresyl phosphate, p-cumyl di-o-cresyl phosphate, p-cumyl di-m-cresyl phosphate, p-cumyl di-p-phenyl phosphate and p-cumyl di-p-tert-butylphenyl phosphate.

[0181] In the present invention, the "emulsifier-type phosphate salt" is a surfactant containing a phosphate group with an emulsifying effect, and can be one or more of long-chain alkyl phosphate mono- or diester salts of C8 or greater, fatty alcohol polyvinyl ether phosphate mono- or distiller salts, alkylphenol polyoxyethylene ether phosphate mono- or distiller salts, and phosphate ester salts of alcohol ethers or phenol ethers. Particularly preferred are phosphate ester salts selected from the following chemical formulas:

[0182] Among them, R is usually 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 These substituents may be optionally substituted with one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups; M may be hydrogen, an alkali metal cation, ammonium, an alkanolamine or another cation.

[0183] In the present invention, the molar ratio of the main catalyst (a), the first co-catalyst (b) and the second co-catalyst (d) in the catalyst composition is preferably 1:(20-100):(100-10000).

[0184] In the present invention, the catalyst composition is preferably in liquid form. To achieve this, the catalyst composition may further include a solvent. The solvent may be appropriately selected based on the type of catalyst composition, so as to dissolve the catalyst composition. Generally, the solvent may be an organic solvent and / or water, preferably an aromatic hydrocarbon solvent and / or water, particularly preferably one or more of toluene, xylene, chlorobenzene, and water. The amount of the solvent used may be conventional in the art and will not be described in detail herein.

[0185] The present invention also provides a method for selective hydrogenation of conjugated diene latex, comprising the following steps:

[0186] In the presence of the catalyst composition described in the above technical solution, the conjugated diene latex is selectively hydrogenated to obtain hydrogenated conjugated diene latex.

[0187] In the present invention, the amount of the main catalyst (a) is preferably 0.001 to 5 wt % of the mass of the conjugated diene latex, more preferably 0.001 to 2 wt %, and most preferably 0.01 to 0.1 wt %.

[0188] In the present invention, the amount of the first cocatalyst (b) is preferably 0.01 to 5 wt % of the mass of the conjugated diene latex, more preferably 0.01 to 2 wt %, and most preferably 0.05 to 1 wt %.

[0189] In the present invention, the amount of the second cocatalyst (c) is preferably 0-10 wt % of the mass of the conjugated diene latex, more preferably 0.1-10 wt %, most preferably 0.5-2 wt %.

[0190] In the present invention, suitable substrates for hydrogenation are in principle all aqueous suspensions based on conjugated diene polymers, also referred to as "latexes". Such conjugated diene-based polymers contain carbon-carbon double bonds. These latexes include suspensions prepared by free radical polymerization of aqueous monomer latexes (primary suspensions) and those suspensions in which their polymers have been prepared by any method or approach and then converted into aqueous suspension form (secondary suspensions). The term "aqueous suspension" also includes, in principle, suspensions of microcapsules.

[0191] In the present invention, the polymer having carbon-carbon double bonds that can withstand the method of the present invention comprises repeating units based on at least one conjugated diene monomer. The conjugated diene monomer comprises at least one conjugated monomer (a); the conjugated diene monomer (a) is preferably selected from C4-C6 conjugated dienes, more preferably selected from one or more of 1,3-butadiene, isoprene, 1-methylbutadiene, 2,3-dimethylbutadiene, piperylene, and chloroprene, particularly preferably 1,3-butadiene and / or isoprene, and most preferably 1,3-butadiene.

[0192] In a further embodiment, a polymer having carbon-carbon double bonds can be subjected to the process of the invention, which comprises not only at least one conjugated diene as monomer (a), but also repeating units of at least one other copolymerizable monomer (b). Examples of suitable monomers (b) are olefins, such as ethylene or propylene. Further examples of suitable monomers (b) are vinyl aromatic monomers, such as styrene, α-methylstyrene, o-chlorostyrene or vinyltoluene, aliphatic or branched C1-C 18 Vinyl esters of monocarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl decanoate, vinyl laurate or vinyl stearate.

[0193] Preferred polymers to be used in the present invention are copolymers of 1,3-butadiene and styrene, or copolymers of 1,3-butadiene and α-methylstyrene, which copolymers may have a random or block-type structure.

[0194] Further suitable copolymers have repeating units derived from at least one conjugated diene and from at least one monomer (b) selected from the group consisting of ethylenically unsaturated mono- or dicarboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid, and typically C1-C 12 Alkanols, such as methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, n-hexanol, 2-ethylhexanol or C5~C 10 Esters of cycloalkanols, such as cyclopentanol or cyclohexanol, and preferably esters of acrylic acid and / or methacrylic acid; examples are methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, n-butyl acrylate, tert-butyl acrylate or 2-ethylhexyl acrylate.

[0195] Suitable other copolymerizable monomers (b) are α,β-unsaturated nitriles. It is possible to use any known α,β-unsaturated nitriles, preferably C3-C5 α,β-unsaturated nitriles, such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof, with acrylonitrile being particularly preferred.

[0196] Suitable copolymers to be used in the present invention are so-called nitrile rubbers (also referred to as "NBR"), which are copolymers having repeating units of at least one conjugated diene, preferably 1,3-butadiene, at least one α,β-unsaturated nitrile, preferably acrylonitrile, and optionally one or more other copolymerizable monomers.

[0197] Thus, particularly preferred nitrile rubbers are copolymers having repeating units derived from acrylonitrile and 1,3-butadiene.

[0198] In addition to the conjugated diene and the α,β-unsaturated nitrile, the nitrile rubber may include repeating units of one or more other copolymerizable monomers known in the art, for example, α,β-unsaturated (preferably monounsaturated) monocarboxylic acids, their esters or amides, α,β-unsaturated (preferably monounsaturated) dicarboxylic acids, their monoesters or diesters, and the corresponding anhydrides or amides of the α,β-unsaturated dicarboxylic acids.

[0199] As α,β-unsaturated monocarboxylic acids, acrylic acid and / or methacrylic acid are preferred third monomers for such nitrile rubbers.

[0200] Esters of α,β-unsaturated monocarboxylic acids may also be used, in particular alkyl esters, alkoxyalkyl esters, aryl esters, cycloalkyl esters, cyanoalkyl esters, hydroxyalkyl esters or fluoroalkyl esters.

[0201] As alkyl esters, C 1～ C 18 Alkyl esters of acrylic acid or methacrylic acid are preferably used, more preferably C l~C 18 alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate or 2-ethylhexyl methacrylate.

[0202] As alkoxyalkyl ester α, β-unsaturated monocarboxylic acid C2~C 18 Alkoxyalkyl esters are preferably used, more preferably alkoxyalkyl esters of acrylic acid or methacrylic acid, such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate or methoxyethyl (meth)acrylate.

[0203] It is also possible to use aromatic esters, preferably C6-C 14 Aryl esters, more preferably C6~C 10 The aryl esters are preferably aryl esters of acrylates and / or methacrylates, and most preferably the above aryl esters of acrylates and / or methacrylates.

[0204] In another embodiment, cycloalkyl esters, preferably C5 to C 12 Cycloalkyl esters, more preferably C6 to C 12 The cycloalkyl esters, and most preferably the above-mentioned cycloalkyl acrylates and / or methacrylates are used.

[0205] It is also possible to use cyanoalkyl esters, in particular cyanoalkyl acrylates or cyanoalkyl methacrylates, where the number of C atoms in the cyanoalkyl group is in the range from 2 to 12, preferably α-cyanoethyl acrylate, β-cyanoethyl acrylate or cyanobutyl methacrylate is used.

[0206] In another embodiment, hydrocarbon alkyl esters are used, in particular hydrocarbon alkyl acrylates and hydroxyalkyl methacrylates, wherein the number of C atoms in the hydroxyalkyl group is in the range of 1 to 12, preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate or 3-hydroxypropyl acrylate.

[0207] It is also possible to use fluorobenzyl esters, in particular fluorobenzyl acrylate or fluorobenzyl methacrylate, preferably trifluoroethyl acrylate and / or tetrafluoropropyl methacrylate. Acrylates and / or methacrylates containing substituted amino groups can also be used, such as dimethylaminomethacrylate and / or diethylaminoethylacrylate.

[0208] Various other esters of α,β-unsaturated carboxylic acids can also be used, such as, for example, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, epoxy (meth)acrylate, N-(2-hydroxyethyl)acrylamide, N-(2-hydroxymethyl)acrylamide or polyurethane (meth)acrylate.

[0209] It is also possible to use mixtures of all the above-mentioned esters of α,β-unsaturated carboxylic acids.

[0210] Further α,β-unsaturated dicarboxylic acids can be used, preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid or mesaconic acid (methylfumaric acid).

[0211] In another embodiment, anhydrides of α,β-unsaturated dicarboxylic acids are used, preferably maleic anhydride, itaconic anhydride, citraconic anhydride or mesaconic anhydride.

[0212] In a further embodiment, monoesters or diesters of α,β-unsaturated dicarboxylic acids may be used. Suitable alkyl esters are, for example, C1-C 10 Suitable alkoxyalkyl esters are, for example, C2 to C l2 Suitable hydroxyalkyl esters are, for example, C3 to C8 alkoxyalkyl monoesters or diesters. l ~C 12 Suitable cycloalkyl esters are, for example, C5-C l0 Cycloalkyl esters, preferably C6 to C 10 Suitable alkylcycloalkyl esters are, for example, C6 to C l0 Alkylcycloalkyl esters, preferably C7-C 10 -alkylcycloalkyl monoester or diester. Suitable aryl esters are, for example, C6-C l4 Aryl ester, preferably C6~C 10 Aryl monoesters or diesters.

[0213] Specific examples of α,β-ethylenically unsaturated dicarboxylic acid monoester monomers include:

[0214] "monoalkyl maleate", preferably monomethyl maleate, monoethyl maleate, monopropyl maleate or mono-n-butyl maleate;

[0215] "Monocycloalkyl maleate", preferably monocyclopentyl maleate, monocyclohexyl maleate or monocycloheptyl maleate;

[0216] "Monoalkylcycloalkyl maleate", preferably monomethylcyclopentyl maleate or monoethylcyclohexyl maleate;

[0217] "Maleic acid monoaryl ester", preferably monophenyl maleate;

[0218] "Monobenzyl maleate", preferably monobenzyl maleate;

[0219] "monoalkyl fumarate", preferably monomethyl fumarate, monoethyl fumarate, monopropyl fumarate or mono-n-butyl fumarate;

[0220] "monocycloalkyl fumarate", preferably monocyclopentyl fumarate, monocyclohexyl fumarate or monocycloheptyl fumarate;

[0221] "monoalkylcycloalkyl fumarate", preferably monomethylcyclopentyl fumarate or monoethylcyclohexyl fumarate;

[0222] "Monoaryl fumarate", preferably monophenyl fumarate;

[0223] "Monobenzyl fumarate", preferably monobenzyl fumarate;

[0224] "Citraconic acid monoalkyl ester", preferably monomethyl citraconate, monoethyl citraconate, monopropyl citraconate or mono-n-butyl citraconate;

[0225] "Citraconic acid monocycloalkyl ester", preferably citraconic acid monocyclopentyl ester, citraconic acid monocyclohexyl ester or citraconic acid monocycloheptyl ester;

[0226] "Monoalkylcycloalkyl citrate", preferably monomethylcyclopentyl citrate or monoethylcyclohexyl citrate;

[0227] "Citraconate monoaryl ester", preferably citraconate monophenyl ester;

[0228] "Monobenzyl citrate", preferably monobenzyl citrate;

[0229] "Itaconate monoalkyl ester", preferably itaconate monomethyl ester, itaconate monoethyl ester, itaconate monopropyl ester or itaconate mono-n-butyl ester;

[0230] "Itaconate monocycloalkyl ester", preferably itaconate monocyclopentyl ester;

[0231] "Monoalkylcycloalkyl itaconate", preferably monomethylcyclopentyl itaconate or monoethylcyclohexyl itaconate;

[0232] "Itaconate monoaryl ester", preferably itaconate monophenyl ester;

[0233] "Monobenzyl itaconate", preferably monobenzyl itaconate.

[0234] As α,β-ethylenically unsaturated dicarboxylic acid diester monomers, analogous diesters based on the monoester monomers explicitly mentioned above can be used, wherein, however, the two organic groups linked to the C═O group via the oxygen atom can be identical or different.

[0235] As further third monomers, vinyl aromatic monomers, like styrene, α-methylstyrene or vinylpyridine, and non-conjugated dienes, like 4-cyanocyclohexene and 4-vinylcyclohexene, and alkynes, like 1- or 2-butyne, can be used.

[0236] As an additional third monomer, a PEG acrylate monomer derived from a PEG acrylate of the general formula (X) may be used:

[0237] Wherein, R is hydrogen or a straight or branched C1~C 20 alkyl, preferably methyl, ethyl, butyl or ethylhexyl, n is 1 to 8, preferably 2 to 8, more preferably 2 to 5 and most preferably 3, and R 1 It is hydrogen or CH3-.

[0238] In the context of the present invention, the term "(meth)acrylate" means "acrylate" and "methacrylate". When R 1 When the group is CH3-, the molecule is a methacrylate. The term "polyethylene glycol" or abbreviation "PEG" refers to both monoethylene glycol segments having one repeating ethylene glycol unit (PEG-1, n=1) and polyethylene glycol segments having 2 to 8 repeating ethylene glycol units (PEG-2 to PEG-8; n=2 to 8). The term 'PEG acrylate' is also abbreviated as PEG-X-(M)A, where "X" represents the number of repeating ethylene glycol units, "MA" represents methacrylate and "A" represents acrylate. Acrylate monomers derived from PEG acrylate of the general formula (X) are referred to as "PEG acrylate monomers."

[0239] Preferred PEG acrylate monomers are selected from the following formulas No. 1 to No. 10, wherein n is 1, 2, 3, 4, 5, 6, 7 or 8, preferably 2, 3, 4, 5, 6, 7 or 8, more preferably 3, 4, 5, 6, 7 or 8 and most preferably 3:

[0240] Other common names for methoxypolyethylene glycol acrylate (Formula 3) are, for example, poly(ethylene glycol) methyl ether acrylate, acryloyl-PEG, methoxy-PEG acrylate, methoxypoly(ethylene glycol) monoacrylate, poly(ethylene glycol) monomethyl ether monoacrylate or mPEG acrylate.

[0241] Particularly preferred is a third monomer selected from the following chemical formula:

[0242] Among them, R 1 is hydrogen or a methyl group, and R 2 、R 3 、R 4 、R 5 are the same or different and can represent H, C1~C 12 alkyl, cycloalkyl, alkoxyalkyl, hydroxyalkyl, epoxyalkyl, aryl or heteroaryl.

[0243] Particularly preferred as the PEG acrylate termonomer are methoxy-PEG-1-acrylate (MEA), butyl diglycol methacrylate (butoxy-PEG-2-MA, BDGMA) or ethyl diglycol methacrylate (ethoxy-PEG-3-MA).

[0244] In the present invention, in the case where the polymer to be subjected to the process of the present invention comprises not only repeating units of one or more conjugated dienes but also repeating units of one or more other copolymerizable monomers, the ratio of the conjugated dienes to the other copolymerizable monomers may vary within a wide range, specifically:

[0245] When NBR polymers are used in the process of the present invention, the proportion or total proportion of conjugated dienes is generally in the range of 40% to 90% by weight, preferably in the range of 50% to 85% by weight, based on the total polymer. The proportion or total proportion of α,β-unsaturated nitrile is generally in the range of 10% to 60% by weight, preferably 15% to 50% by weight, based on the total polymer. In each case, the proportions of the monomers add up to 100% by weight. Additional third monomers may optionally be present. If used, they are generally present in an amount of greater than 0% to 40% by weight, preferably 0.1% to 40% by weight, and particularly preferably 1% to 30% by weight, based on the total polymer. In this case, the corresponding proportions of conjugated dienes and / or α,β-unsaturated nitrile are replaced by the proportions of the additional third monomer, with the proportions of all monomers adding up to 100% by weight.

[0246] The preparation of nitrile rubbers by polymerizing the abovementioned monomers is sufficiently known to the person skilled in the art and is comprehensively described in the polymer literature.

[0247] The nitrile rubber used according to the present invention has a Mooney viscosity (ML1+4 at 100° C.) in the range of 25 to 70, preferably in the range of 30 to 50. This corresponds to a weight average molecular weight M in the range of 100,000 to 500,000, preferably in the range of 200,000 to 400,000. w .

[0248] A nitrile rubber having a Mooney viscosity of about 34, for example, has an intrinsic viscosity of about 1.1 dL / g measured in chlorobenzene at 35° C. The nitrile rubber used also has a polydispersity PDI=M w / M n , where M w is the weight average molecular weight, and M n is the number average molecular weight, ranging from 2.0 to 10.0, and preferably ranging from 2.0 to 4.0. The Mooney viscosity is measured according to ASTM standard D1646.

[0249] If the polymer used in the present invention contains repeating units of one or more conjugated dienes and optionally one or more other copolymerizable monomers such as, for example, styrene or α-methylstyrene, the proportion of the conjugated diene is generally between 15% bw (by weight) and 100% bw, and the proportion or total proportion of the copolymerizable termonomers is between 0% bw and 85% bw. If, as other copolymerizable monomers, styrene or α-methylstyrene is used, the proportion of styrene and / or methylstyrene is preferably between 15% bw and 60% bw, with the remainder to 100% bw being represented by the conjugated diene.

[0250] The carbon-carbon double bond-containing polymers useful in the present invention in latex form can be prepared by any method known to those skilled in the art, such as latex polymerization, solution polymerization, or bulk polymerization. Preferably, the carbon-carbon double bond-containing polymers useful in the present invention are prepared by an aqueous latex polymerization method because this method directly produces the polymer in latex form.

[0251] Preferably, according to the present invention, the polymer solid content in the aqueous latex lies in the range of 1 to 75% by weight, more preferably 5 to 50% by weight, based on the total weight of the aqueous latex.

[0252] The preparation of such polymers, which are subjected to the process according to the invention, is known to the person skilled in the art and can in principle be carried out by anionic, free-radical or Ziegler-Natta polymerization in solution, in bulk, in suspension or in latex. Depending on the type of reaction, the conjugated dienes are 1,4- and / or 1,2-polymerized. For the hydrogenation process according to the invention, preference is given to using polymers prepared by free-radical aqueous latex polymerization of the above-mentioned monomers (a) and (b). These techniques are well known to the person skilled in the art and are described in detail in the literature, for example in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A 21, pp 373-393. Typically, such polymers are prepared in the presence of free radical initiators and, if desired, surface-active substances such as emulsifiers and protective colloids (see, for example, Houben Weyl, Methoden der organischen Chemie, Volumen XIV / 1, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, pp 192-208).

[0253] Suitable free-radical polymerization initiators include organic peroxides, such as tert-butyl hydroperoxide, benzoyl hydroperoxide or diisopropylbenzoyl peroxide, inorganic peroxides, such as hydrogen peroxide, salts of peroxomono and / or peroxodisulfuric acid, in particular ammonium and / or alkali metal peroxodisulfates (persulfates), and azo compounds, particularly preferred are persulfates. Also preferred are combined systems consisting of at least one organic reducing agent and at least one peroxide and / or hydroperoxide, such as tert-butyl hydroperoxide and the sodium salt of hydroxymethanesulfonic acid, or hydrogen peroxide and ascorbic acid (as an electrolyte-free redox initiator system), in combination with a system which additionally comprises small amounts of metal compounds which are soluble in the polymerization medium and whose metal components can be present in multiple valence states, for example ascorbic acid / iron(II) sulfate / hydrogen peroxide. It is also possible to replace ascorbic acid with hydroxymethanesulfinic acid, sodium sulfite, sodium hydrogensulfate or the sodium salt of sodium hydrogensulfite, and to replace hydrogen peroxide with tert-butyl hydroperoxide, alkali metal peroxodisulfates and / or ammonium peroxodisulfates. Instead of water-soluble iron(II) salts, it is also possible to use combinations of water-soluble Fe / V salts.

[0254] These polymerization initiators are employed in customary amounts, for example in amounts of 0.01% bw to 5% bw, preferably 0.1% bw to 2.0% bw, based on the monomers to be polymerized.

[0255] The monomer mixture can, if desired, be polymerized in the presence of customary regulators such as mercaptans, for example tert-dodecyl mercaptan. These regulators are then used in amounts of 0.01% bw to 5% bw, based on the total amount of the mixture.

[0256] There are no particular restrictions on the emulsifiers that can be used. Preferred are neutral emulsifiers such as ethoxylated mono-, di- and tri-alkylphenols (ethylene oxide degree: 3 to 50, alkyl group C4 to C9) or ethoxylated fatty alcohols (ethylene oxide degree: 3 to 50, alkyl group C4 to C9), and / or anionic emulsifiers such as alkali metal and ammonium salts of fatty acids (alkyl group: C 12 to C 24 ), alkyl sulfate (alkyl group: C8 to C 22 ), ethoxylated alkanol (ethylene oxide degree: 4 to 30, alkyl group: C8 to C 22 ) or ethoxylated alkylphenol (ethylene oxide degree: 3 to 50, alkyl: C4 to C 20 ) sulfuric acid monoesters, alkyl sulfonic acid (alkyl: C8 to C 22 ) or alkyl aryl sulfonic acid (alkyl group: C4 to C 18 ). Further suitable anionic emulsifiers are mono- or di-C4 ... 24 Alkali metal or ammonium salts of alkyl derivatives.

[0257] Particularly preferred are the alkali metal and / or ammonium salts, especially the sodium salts, of: alkylarylsulfonic acids, alkylsulfonic acids (e.g., sulfonated C 12 ~C 18 Suitable emulsifiers include paraffin waxes, alkyl sulfates (e.g. sodium lauryl sulfate) and sulfate monoesters of ethoxylated alkanols (e.g. sulfoxylated ethoxylates of lauryl alcohol with 2 to 3 ethylene oxide units). Further suitable emulsifiers are fatty acids (C 12 -C 23 Suitable emulsifiers include sodium or potassium salts of alkyl groups (e.g., alkyl groups in the presence of hydroxybenzoate), such as potassium oleate. Other suitable emulsifiers are listed in Houben-Weyl, Loc. Cit., pp. 192-208. Instead of emulsifiers or in admixture with emulsifiers, it is also possible to employ conventional protective colloids, such as polyvinyl alcohol, polyvinylpyrrolidone, or amphiphilic block polymers with short hydrophobic blocks, for co-stabilization purposes. Typically, the amount of emulsifier used will not exceed 5% by weight, based on the monomers to be polymerized.

[0258] The free radical polymerization reaction can be carried out by the full batch initial charge (batch) technique, but is preferably operated according to the feed technique, especially on an industrial scale. In this technique, the major amount (usually 50% to 100% by weight) of the monomers to be polymerized is added to the polymerization vessel according to the progress of the polymerization of the monomers already in the polymerization vessel. In this context, the free radical initiator system can either be included entirely in the initial charge to the polymerization vessel or be added to the polymerization reaction continuously or in stages, the addition rate being the rate at which it is consumed during the free radical aqueous latex polymerization. In each individual case, this will depend, as is well known, on the chemical nature of the initiator system and the polymerization temperature. The initiator system is preferably supplied to the polymerization zone at the rate at which it is consumed.

[0259] Polymerization reaction also can be carried out in the presence of aqueous polymer suspension as polymer (seed latex (seed latex)).This type of technology is known to those skilled in the art at all, and is described in for example DE-A 42 13967, DE-A 4213968, EP567811, EP 567812 or EP 567819, which are all incorporated herein by reference. In principle, according to desired characteristics, it is possible to include the seed in the initial charge, or to add it continuously or in stages during the polymerization. Polymerization is preferably carried out with the seed in the initial charge. Preferably, the amount of seed polymer is based on monomer a) to monomer d) by weight 0.05% to 5%, preferably 0.1% to 2%, and specifically in the scope of 0.2% to 1%. The polymer particles of the seed latex preferably used have a weight average particle size (weight average diameter) ranging from 10 nm to 100 nm, preferably from 20 nm to 60 nm, and in particular about 30 nm. It is preferred to use polystyrene seeds.

[0260] The polymerization reaction is preferably carried out above atmospheric pressure. The polymerization time can vary within a wide range and is generally from 1 hour to 15 hours, preferably from 3 hours to 10 hours. The polymerization temperature is also variable within a wide range and depends on the initiator used, from about 0°C to 110°C.

[0261] The polymer suspension prepared in this manner typically has a solids content of up to 75% by weight. For use in the hydrogenation process of the present invention, it is possible to employ suspensions having these solids contents. However, in some cases, it may be advisable to pre-dilute the suspension to an appropriate solids content. The solids content of the suspension employed is preferably in the range of 5% to 50% by weight, based on the total weight of the suspension.

[0262] Typically, surface-active substances are still present in the polymer suspension, and further substances, such as customary polymerization aids used in latex polymerization, do not have a destructive effect on the hydrogenation process according to the invention. However, it is advisable that the polymer suspension is subjected to a chemical or physical deodorization before hydrogenation. Physical deodorization by stripping residual monomers with steam is known, for example, from EP 584 458. EP 327 006, for its part, recommends the use of conventional distillation methods. Chemical deodorization is preferably carried out by a post-polymerization process after the main polymerization. Such methods are described, for example, in DE-A 3834 734, EP 379 892, EP 327 006, DE-A 4419 518, DE-A 4435 422 and DE-A 4435 423.

[0263] Preferably, according to the invention, the content of diene-based polymer in the aqueous suspension lies in the range from 1% to 75% by weight, more preferably from 5% to 50% by weight, based on the total weight of the latex.

[0264] According to the method of the present invention:

[0265] In the present invention, hydrogenated is understood to mean that preferably at least 50% of the residual double bonds (RDB) present in the starting diene-based polymer are hydrogenated, preferably 70-100%, more preferably 80-100%, even more preferably 90-100%, and most preferably 95-100%.

[0266] In the present invention, the temperature of the selective hydrogenation is preferably 35 to 200° C., more preferably 60 to 200° C., most preferably 80 to 180° C., and most preferably 90 to 160° C.; the reaction time of the selective hydrogenation is preferably 10 min to 24 h, more preferably 15 min to 20 h, and most preferably 1 to 8 h; the hydrogen pressure of the selective hydrogenation is preferably 0.5 to 35 MPa, more preferably 3 to 10 MPa; and the atmosphere of the selective hydrogenation is preferably pure hydrogen.

[0267] In the present invention, prior to the hydrogenation, the latex system is preferably degassed using a gas; wherein the gas is preferably nitrogen; the degassing pressure is preferably 0.1 to 6 MPa; the degassing time is preferably 10 to 300 minutes, more preferably 20 to 240 minutes, and most preferably 30 to 120 minutes; the degassing temperature is preferably 0 to 50°C, more preferably 10 to 30°C, and most preferably 25°C. After degassing, stirring is preferably continued for 30 minutes to 12 hours; the stirring speed is preferably 50 to 800 r / min, more preferably 200 to 500 r / min.

[0268] Generally, the selective hydrogenation process provided by the present invention can be carried out in a suitable reactor equipped with a temperature regulator and a stirring device. According to the present invention, the polymer latex can be fed into the reactor and degassed as needed, and then the catalyst composition can be added in pure form or, in some cases, as a solution with a small amount of organic solvent, and then the reactor can be pressurized with hydrogen. Alternatively, in another alternative embodiment, the reactor can be pressurized with hydrogen and the catalyst composition can be added in pure form or as a solution. Alternatively, according to the present invention, the catalyst composition can be added to the reactor in pure form, and then the polymer latex can be fed into the reactor and degassed as needed.

[0269] Typically, when the hydrogenation reaction is complete to the desired extent, the reaction vessel is cooled and vented. The resulting hydrogenated latex can be used as a latex if desired or coagulated and washed to obtain a hydrogenated polymer in solid form.

[0270] The procatalyst (a) used in the inventive method is very effective, so that the catalyst residue in the final hydrogenated polymer product can be low enough to make the catalyst metal removal or recovery step alleviate or even unnecessary. However, when reaching the desired degree, the procatalyst (a) used in the method process of the present invention can be removed. Such removal can be carried out, for example, by using ion exchange resins, as described in EP2072532 A1 and EPA2072533 A1. The reaction mixture obtained after the hydrogenation is completed can be obtained and treated with ion exchange resins at, for example, 100 ℃ under nitrogen for 48 hours, which causes the combination of the procatalyst (a) and the resin, and the reaction mixture can be processed using common final treatment method simultaneously.

[0271] For the purpose of greater clarity, the present invention is described in detail with reference to the following examples and comparative examples.

[0272] In the following examples and comparative examples provided by the present invention, the materials used in the hydrogenation reaction are listed in Table 1.

[0273] Table 1 Basic raw materials of embodiment

[0274] In the following examples and comparative examples provided by the present invention, the analysis and testing involved are as follows:

[0275] FT-IR is tested: the spectrum of the acrylonitrile-butadiene rubber before, during and after the hydrogenation reaction is recorded on the TENSOR II infrared spectrometer of Bruker.The solution of acrylonitrile-butadiene rubber in chlorobenzene is cast on a KBr disk and the dry film that is formed is used for test.Analyze degree of hydrogenation by FT-IR according to the ASTM D5670 method.

[0276] UV Testing: UV spectra of the Hoveyda-Grubbs II catalyst solution and catalyst composition were recorded using a TU-1901 UV-visible spectrophotometer from Beijing Puxi General Instrument Co., Ltd. The formation of the catalyst composition was determined by changes in the peak position of the UV absorption spectrum.

[0277] Catalyst composition preparation example:

[0278] Example 1

[0279] 0.03 g of Hoveyda-Grubbs II catalyst was dissolved in 10 g of butanone and 2.5 g of water at room temperature to form a light green solution.

[0280] Example 2

[0281] 0.03 g of Hoveyda-Grubbs II catalyst and 2 g of potassium oleate were dissolved in 10 g of butanone and 2.5 g of water at room temperature to form a light green solution which then slowly turned purple.

[0282] Example 3

[0283] 0.03 g of Hoveyda-Grubbs II catalyst and 2 g of sodium dodecylbenzenesulfonate were dissolved in 10 g of butanone and 2.5 g of water at room temperature to form a light green solution which then slowly turned yellow.

[0284] Example 4

[0285] 0.03 g of Hoveyda-Grubbs II catalyst and 2 g of potassium lauryl phosphate monoester were dissolved in 10 g of butanone and 2.5 g of water at room temperature to form a light green solution which then slowly turned white.

[0286] The products of Examples 1 to 4 were subjected to ultraviolet absorption spectrum testing. The results are shown in Table 2 and Figure 1. Figure 1 is an ultraviolet absorption spectrum of the catalyst composition provided in an embodiment of the present invention, where 1, 2, 3, and 4 correspond to Example 1, Example 2, Example 3, and Example 4, respectively.

[0287] Table 2 UV absorption spectrum results

[0288] The products of Examples 1 to 4 were photographed, and the results are shown in FIG2 . FIG2 is a sample photograph of the catalyst composition provided in an embodiment of the present invention, wherein (a), (b), (c), and (d) correspond to Example 1 (light green), Example 2 (purple), Example 3 (yellow), and Example 4 (white), respectively.

[0289] 1 and 2 , it can be seen that the number and position of the absorption peaks of the sample shifted, and the color of the dispersion changed, confirming the formation of the catalyst composition.

[0290] Emulsion hydrogenation example

[0291] Example 5

[0292] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.02 g of Grubbs II, 1 g of tetrahydrofuran, and 2 g of sodium butanesulfonate were premixed at room temperature, and the mixture changed color from red to yellow before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0293] The results showed that after 5 hours, the degree of hydrogenation reached 98.0%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0294] Example 6

[0295] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.03 g of Grubbs III, 1 g of tetrahydrofuran, and 2 g of sodium butanesulfonate were premixed at room temperature. The mixture changed color from brown to yellow before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0296] The results showed that after 5 hours, the degree of hydrogenation reached 98.2%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0297] Example 7

[0298] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.02 g of Hoveyda-Grubbs II, 1 g of tetrahydrofuran, and 2 g of sodium butanesulfonate were premixed, and the mixture changed color from green to yellow before being added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0299] The results showed that after 5 hours, the degree of hydrogenation reached 99.1%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0300] Example 8

[0301] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.02 g of Grubbs II, 1 g of tetrahydrofuran, and 2 g of sodium toluenesulfonate were premixed at room temperature until the mixture changed color from red to yellow. The mixture was then added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0302] The results showed that after 5 hours, the degree of hydrogenation reached 98.5%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0303] Example 9

[0304] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.02 g of Hoveyda-Grubbs II, 1 g of tetrahydrofuran, and 2 g of sodium toluenesulfonate were premixed, and the mixture was changed from green to yellow before being added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0305] The results showed that after 5 hours, the degree of hydrogenation reached 99.0%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0306] Example 10

[0307] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.02 g of Hoveyda-Grubbs II, 1 g of tetrahydrofuran, 2 g of sodium toluenesulfonate, and 20 g of toluene were premixed, and the mixture changed color from green to yellow before being added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0308] The results showed that after 5 hours, the degree of hydrogenation reached 99.1%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0309] Example 11

[0310] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged into the reactor. 0.03 g of Hoveda-Grubbs II, 1 g of butanone, and 2 g of sodium allylsulfonate were premixed, and the mixture was changed from green to yellow before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0311] The results showed that after 5 hours, the degree of hydrogenation reached 99.5%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0312] Example 12

[0313] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.03 g of Grubbs II, 1 g of ethyl acetate, and 2 g of sodium acetate were premixed at room temperature, the mixture changing color from red to purple, and then added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0314] The results showed that after 5 hours, the degree of hydrogenation reached 97.6%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0315] Example 13

[0316] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.03 g of Grubbs III, 1 g of ethyl acetate, and 2 g of sodium acetate were premixed at room temperature until the mixture changed color from brown to purple. The mixture was then added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0317] The results showed that after 5 hours, the degree of hydrogenation reached 97.8%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0318] Example 14

[0319] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.01 g of Hoveyda-Grubbs II, 1 g of ethyl acetate, and 2 g of sodium acetate were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0320] The results showed that after 5 hours, the degree of hydrogenation reached 98.0%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0321] Example 15

[0322] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.02 g of Grubbs II, 1 g of ethyl acetate, and 1 g of disodium maleate were premixed at room temperature until the mixture changed color from red to purple. The mixture was then added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0323] The results showed that after 5 hours, the degree of hydrogenation reached 98.2%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0324] Example 16

[0325] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.01 g of Hoveyda-Grubbs II, 1 g of ethyl acetate, and 1 g of disodium maleate were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0326] The results showed that after 5 hours, the degree of hydrogenation reached 98.6%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0327] Example 17

[0328] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.01 g of Hoveyda-Grubbs II, 1 g of ethyl acetate, 1 g of disodium maleate, and 20 g of toluene were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0329] The results showed that after 5 hours, the degree of hydrogenation reached 98.8%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0330] Example 18

[0331] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.02 g of Hoveda-Grubbs II, 1 g of butanone, and 2 g of sodium acrylate were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0332] The results showed that after 5 hours, the degree of hydrogenation reached 99.2%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0333] Example 19

[0334] A 1L stainless steel high-pressure reactor equipped with a temperature control system, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged into the reactor. 0.01 g of Grubbs II, 1 g of diisobutyl phthalate, and 1 g of monoethyl phosphate were pre-mixed at room temperature, and the mixture changed color from red to white before being added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was completed, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0335] The results showed that after 5 hours, the degree of hydrogenation reached 97.4%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0336] Example 20

[0337] A 1L stainless steel high-pressure reactor equipped with a temperature control system, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged into the reactor. 0.03 g of Grubbs III, 1 g of diisobutyl phthalate, and 1 g of monoethyl phosphate were pre-mixed at room temperature. The mixture changed color from brown to white and was then added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was completed, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0338] The results showed that after 5 hours, the degree of hydrogenation reached 97.8%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0339] Example 21

[0340] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.01 g of Hoveda-Grubbs II, 1 g of diisobutyl phthalate, and 1 g of monoethyl phosphate were premixed, and the mixture changed color from green to white before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0341] The results showed that after 5 hours, the degree of hydrogenation reached 97.9%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0342] Example 22

[0343] A 1L stainless steel high-pressure reactor equipped with a temperature control system, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged into the reactor. 0.01 g of Grubbs II, 1 g of diisobutyl phthalate, and 1 g of dibutyl phosphate were pre-mixed at room temperature until the mixture changed color from red to white, and then added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was completed, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0344] The results showed that after 5 hours, the degree of hydrogenation reached 97.7%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0345] Example 23

[0346] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.01 g of Hoveda-Grubbs II, 1 g of diisobutyl phthalate, and 1 g of dibutyl phosphate were premixed, and the mixture was changed from green to white before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0347] The results showed that after 5 hours, the degree of hydrogenation reached 98.3%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0348] Example 24

[0349] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.01 g of Hoveyda-Grubbs II, 1 g of diisobutyl phthalate, 1 g of dibutyl phosphate, and 20 g of toluene were premixed, and the mixture changed color from green to white before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The agitator speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, and the agitator speed was increased to 500 rpm. The reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0350] The results showed that after 5 hours, the degree of hydrogenation reached 98.8%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0351] Example 25

[0352] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.03 g of Hoveda-Grubbs II, 1 g of butanone, and 1 g of triphenyl phosphate were premixed, and the mixture changed color from green to white before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0353] The results showed that after 5 hours, the degree of hydrogenation reached 98.7%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0354] Example 26

[0355] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.03 g of Hoveda-Grubbs II, 1 g of butanone, 20 g of water, and 2 g of sodium dodecylbenzenesulfonate were premixed, and the mixture was changed from green to yellow before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0356] The results showed that after 5 hours, the degree of hydrogenation reached 99.3%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0357] Example 27

[0358] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.03 g of Hoveyda-Grubbs II, 1 g of butanone, 20 g of water, and 2 g of potassium oleate were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0359] The results showed that after 5 hours, the degree of hydrogenation reached 99.2%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0360] Example 28

[0361] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged into the reactor. 0.03 g of Hoveda-Grubbs II, 1 g of butanone, 20 g of water, and 2 g of potassium lauryl monophosphate were premixed, and the mixture was changed from green to white before being added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0362] The results showed that after 5 hours, the degree of hydrogenation reached 99.0%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0363] Example 29

[0364] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.03 g of Hoveda-Grubbs II, 1 g of N,N-dimethylformamide, and 2 g of sodium acrylate were pre-mixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0365] The results showed that after 5 hours, the degree of hydrogenation reached 99.6%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0366] Example 30

[0367] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.03 g of Hoveda-Grubbs II, 1 g of N-methylpyrrolidone, and 2 g of sodium acrylate were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0368] The results showed that after 5 hours, the degree of hydrogenation reached 99.5%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0369] Example 31

[0370] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.03 g of Hoveda-Grubbs II, 1 g of 1-hexene, and 2 g of sodium acrylate were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0371] The results showed that after 5 hours, the degree of hydrogenation reached 99.5%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0372] Example 32

[0373] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.03 g of Hoveda-Grubbs II and 1 g of butanone were premixed and then added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0374] The results showed that after 5 hours, the degree of hydrogenation reached 96.8%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0375] Example 33

[0376] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.03 g of Hoveda-Grubbs II and 1 g of tetrahydrofuran were premixed and then added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0377] The results showed that after 5 hours, the degree of hydrogenation reached 96.9%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0378] Example 34

[0379] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.03 g of Hoveda-Grubbs II and 1 g of N-methylpyrrolidone were premixed and then added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0380] The results showed that after 5 hours, the degree of hydrogenation reached 95.6%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0381] Example 35

[0382] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. The reactor was charged with 500 g of latex, 0.03 g of Hoveda-Grubbs II, and 1 g of N,N-dimethylformamide, which were premixed and then added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0383] The results showed that after 5 hours, the degree of hydrogenation reached 96.1%. No gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0384] Example 36

[0385] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of the latex was charged to the reactor. 0.03 g of Hoveyda-Grubbs II, 1 g of butanone, 20 g of water, 0.5 g of sodium acetate, and 0.5 g of sodium dodecylbenzenesulfonate were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, and the stirring speed was increased to 500 rpm. The reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0386] The results showed that the degree of hydrogenation reached 100% after 5 hours, no gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0387] Example 37

[0388] A 1L stainless steel high-pressure reactor equipped with temperature control, a stirrer, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The latex had a solids content of 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex was charged to the reactor. 0.03 g of Hoveyda-Grubbs II, 1 g of butanone, 20 g of water, 0.5 g of sodium butanesulfonate, and 0.5 g of potassium oleate were premixed, and the mixture changed color from green to purple before being added to the latex. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, and the stirring speed was increased to 500 rpm. The reaction was continued for 5 hours. A small amount of latex was precipitated with ethanol and then dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0389] The results showed that the degree of hydrogenation reached 100% after 5 hours, no gel was produced during the reaction, and the obtained polymer was soluble in xylene.

[0390] Comparative Example 1

[0391] A 1L stainless steel high-pressure reactor equipped with a temperature control device, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4@100°C) of 55 was used. The solid content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex and 0.03 g of Grubbs II were loaded into the reactor. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was completed, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the speed was increased to 500 rpm, and the reaction was allowed to proceed for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0392] The results showed that after 5 hours, the degree of hydrogenation reached 65.9%, and the reaction produced about 0.1% gel.

[0393] Comparative Example 2

[0394] A 1L stainless steel high-pressure reactor equipped with a temperature control device, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4@100°C) of 55 was used. The solid content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. 500 g of latex and 0.03 g of Grubbs III were loaded into the reactor. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was completed, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the speed was increased to 500 rpm, and the reaction was allowed to proceed for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0395] The results showed that after 5 hours, the degree of hydrogenation reached 70.5%, and the reaction produced about 0.1% gel.

[0396] Comparative Example 3

[0397] A 1L stainless steel high-pressure reactor equipped with a temperature control device, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. The reactor was charged with 500 g of latex and 0.03 g of Hoveda-Grubbs II. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0398] The results showed that after 5 hours, the degree of hydrogenation reached 76.8%, and the reaction produced about 0.3% gel.

[0399] Comparative Example 4

[0400] A 1L stainless steel high-pressure reactor equipped with temperature control, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. The reactor was charged with 500 g of latex, 0.03 g of Hoveda-Grubbs II, and 2 g of sodium dodecylbenzenesulfonate. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0401] The results showed that after 5 hours, the degree of hydrogenation reached 99.2% and no gel was produced during the reaction.

[0402] Comparative Example 5

[0403] A 1L stainless steel high-pressure reactor equipped with a temperature control system, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. The reactor was charged with 500 g of latex, 0.03 g of Hoveda-Grubbs II, and 2 g of potassium oleate. The latex was then degassed with nitrogen at a temperature of 25°C, a pressure of 0.1 MPa, and a time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0404] The results showed that after 5 hours, the degree of hydrogenation reached 99.3% and no gel was produced during the reaction.

[0405] Comparative Example 6

[0406] A 1L stainless steel high-pressure reactor equipped with a temperature control system, an agitator, and a hydrogen addition point was used. A butadiene-acrylonitrile polymer latex with an acrylonitrile content of approximately 33 wt% and a Mooney viscosity (ML1+4 @ 100°C) of 55 was used. The solids content of the latex was 20 wt%. The average diameter of the polymer particles in the latex was approximately 80 nm. The reactor was charged with 500 g of latex, 0.03 g of Hoveda-Grubbs II, and 2 g of potassium lauryl monophosphate. The latex was then degassed with nitrogen at a degassing temperature of 25°C, a degassing pressure of 0.1 MPa, and a degassing time of 30 minutes. The stirring speed during degassing was 200 rpm. After degassing was complete, the temperature was raised to 120°C, the hydrogen pressure was increased to 1200 psi, the rotation speed was increased to 500 rpm, and the reaction was continued for 5 hours. A small amount of the latex was precipitated with ethanol, and the precipitate was dissolved in chlorobenzene for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument and calculated using standard methods.

[0407] The results showed that after 5 hours, the degree of hydrogenation reached 99.0% and no gel was produced during the reaction.

[0408] The hydrogenation conditions and results of Examples 5 to 37 and Comparative Examples 1 to 6 are summarized in Table 3:

[0409] Table 3 Comparison of hydrogenation effects of catalysts according to the present invention Note: phr is the mass of solid content in latex, which is 100 phr.

[0410] From the comparison of the examples and comparative examples, it can be seen that in the presence of cocatalyst (b) and optional cocatalyst (c), the catalyst composition has no gelation problem and uses less cocatalyst than the catalyst alone or the mixture of the catalyst and the emulsifier.

[0411] Evaluation of basic physical properties of latex and vulcanized rubber after treatment with polyvalent inorganic salts:

[0412] Solid synthetic rubber is prepared by emulsion polymerization. In industry, polyvalent inorganic salts, such as calcium chloride, magnesium chloride, calcium sulfate, aluminum sulfate, etc., are usually used as flocculants to demulsify and flocculate the polymer latex. The flocculated particles are then washed with water to remove the emulsifier.

[0413] The present invention uses calcium chloride as a flocculant to flocculate and demulsify the latexes of Example 16, Example 27, Example 34 and Comparative Example 5, and then washes with water to obtain a solid rubber, which is then vulcanized and tested for basic physical properties. The specific implementation method and data are as follows:

[0414] Flocculation and post-treatment process:

[0415] Prepare a 2% aqueous solution of calcium chloride, take a calcium chloride aqueous solution 1 to 2 times the volume of the latex, drop the latex into it at a certain speed, continue stirring and heating to prevent the latex from agglomerating during the flocculation process, stir for a certain period of time, and repeatedly wash with a large amount of hot water until the washing liquid is transparent and does not bubble, control the moisture of the rubber particles, and dry them at 60-80℃ to constant weight.

[0416] Emulsifier residual test:

[0417] Because the residue after flocculation of the emulsifier calcium chloride is dissolved in ethanol, according to the national standard GB / T3516-2006 for the determination of rubber solvent extracts, ethanol is used for reflux and the weight loss after 48 hours is measured to evaluate the residual amount of emulsifier.

[0418] Vulcanized rubber formula, see Table 4:

[0419] Table 4 Vulcanized rubber formula

[0420] Preparation and vulcanization process:

[0421] (1) The mixing process is divided into four parts: the first stage of internal mixing to add the active agent, carbon black and plasticizer, the thin sheet is passed through the open mill, the second stage of internal mixing to add the vulcanization system, and the thin sheet is passed through the open mill.

[0422] The first stage mixing of the rubber compound was carried out in a Harp torque meter with a starting temperature of 60°C and a rotor speed of 50 rpm. The mixing process was as follows: HNBR → 2 min to add zinc oxide + stearic acid + magnesium oxide-75 → 3 min to add half of N550 → 4.5 min to add the other half of N550 and TOTM → 6 min to add F-40 + TAIC → 8 min to clean → 10 min to drain the rubber; the rubber compound was triangular-wrapped six times with a 0.3 mm roller spacing on the mixing mill and unrolled with a 2.0 mm roller spacing, and then parked at room temperature.

[0423] (2) Vulcanization process: The rubber mix was vulcanized on a flat vulcanizer. The vulcanization conditions for the test piece were 180°C × 10 min × 10 MPa, and the vulcanization conditions for the type A compression test specimen were 180°C × 15 min × 10 MPa.

[0424] Physical property test:

[0425] The Shore A hardness of the vulcanized rubber was tested in accordance with GB / T531.1-2008, with three parallel measurements taken and the median value calculated. The tensile properties were tested in accordance with GB / T528-2009 at a tensile rate of 500 mm / min, with five parallel measurements taken and the median value calculated. The tear strength was tested in accordance with GB / T529-2008 at a tensile rate of 500 mm / min, with three parallel measurements taken and the average value calculated.

[0426] Compression set: The compression set of vulcanized rubber was tested in accordance with GB / T7759.1-2015, using a blast oven at 150°C for 72 hours.

[0427] Oil resistance: The oil resistance of the vulcanized rubber was tested in accordance with GB / T1690-2010. The test conditions were 150°C for 168 hours. The test contents included mass change rate, volume change rate, hardness change, and tensile property change.

[0428] The test results are shown in Table 5 and Table 6:

[0429] Table 5 Ethanol extraction weight loss and vulcanized rubber physical properties data

[0430] Table 6 Physical and mechanical properties of vulcanized rubber after resistant to 3# oil

[0431] From the comparison of the examples and comparative examples, it can be seen that the catalyst composition has less emulsifier residue, higher hardness, tensile strength and modulus, better compression deformation performance and 3# oil resistance than the method using only a mixture of catalyst and emulsifier.

[0432] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A catalyst composition, characterized in that include: A main catalyst and a first co-catalyst, wherein the main catalyst is a ruthenium complex hydrogenation catalyst and / or an osmium complex hydrogenation catalyst, and the chemical structure of the first co-catalyst contains one or more of N, O, a carbon-carbon double bond and a carbon-carbon triple bond.

2. The catalyst composition according to claim 1, characterized in that The chemical structure of the main catalyst is at least one of formula (I), formula (II) and formula (III): In formula (I), M is ruthenium or osmium; X 1 and X 2 are the same or different anionic ligands; L is an uncharged electron donor; two Rs are the same or different groups independently selected from alkyl, alkyl derivatives, cycloalkyl, cycloalkyl derivatives, alkenyl, alkenyl derivatives, alkynyl, alkynyl derivatives, aryl, aryl derivatives, carboxylate, carboxylate derivatives, alkoxy, alkoxy derivatives, alkenyloxy, alkenyloxy derivatives, alkynyloxy, alkynyloxy derivatives, aryloxy, aryloxy derivatives, alkoxycarbonyl, alkoxycarbonyl derivatives, alkylamino, alkylamino derivatives, thioamino, thioamino derivatives, thioaryl, thioaryl derivatives, alkylsulfonyl, alkylsulfonyl derivatives, alkylsulfinyl or alkylsulfinyl derivatives, wherein a derivative is a group formed by replacing the corresponding non-derivative group with one or more of alkyl, halogen, alkoxy, aryl and heteroaryl groups; In formula (II), M is ruthenium or osmium; X 1 and X 2 are the same or different anionic ligands; L is an uncharged electron donor; Y is selected from O, S, NR 1 or PR 1 ; R 1 R is selected from alkyl, alkyl derivatives, cycloalkyl, cycloalkyl derivatives, alkenyl, alkenyl derivatives, alkynyl, alkynyl derivatives, aryl, aryl derivatives, alkoxy, alkoxy derivatives, alkenyloxy, alkenyloxy derivatives, alkynyloxy, alkynyloxy derivatives, aryloxy, aryloxy derivatives, alkoxycarbonyl, alkoxycarbonyl derivatives, alkylamino, alkylamino derivatives, alkylthio, alkylthio derivatives, arylthio, arylthio derivatives, alkylsulfonyl, alkylsulfonyl derivatives, alkylsulfinyl or alkylsulfinyl derivatives, wherein a derivative is a group formed by replacing the corresponding non-derivative group with one or more of alkyl, halogen, alkoxy, aryl and heteroaryl groups; 2 、R 3 、R 4 and R 5 Independently selected from hydrogen, halogen, nitro, CF3, C1-C 30 Alkyl, C3~C 20 Cycloalkyl, 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; R 6 is selected from hydrogen, alkyl, alkenyl, alkynyl or aryl; In formula (III), the dotted line represents a saturated bond or an unsaturated bond, and α and β cannot be unsaturated bonds at the same time; M is ruthenium or osmium; X 1 and X 2 are the same or different anionic ligands; L is an uncharged electron donor; when α is a saturated bond, L 2 NR 7 R 8 PR 7 R 8 、N=CR 7 R 8 or R 7 C=NR 8 , R 7 and R 8 independently selected from unsubstituted, substituted or heteroatom-containing C1-C 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl or C6~C 24 aryl, or R 7 and R 8 They are non-aromatic ring structures respectively; when α is a double bond, L 2 NR 7 or PR 7 , R 7 Selected from unsubstituted, substituted or heteroatom-containing C1-C 20 Alkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl or C6~C 24 aryl, or R 7 A and B are independently selected from hydrocarbons, substituted hydrocarbons, hydrocarbons containing heteroatoms, or hydrocarbons with substituted groups and heteroatoms, or A and B are atoms in an aromatic ring; m represents 0 or 1; n represents 0 or 1; R 6 is selected from hydrogen, alkyl, alkenyl or aryl.

3. The catalyst composition according to claim 2, characterized in that In formula (I), formula (II) and formula (III), M is ruthenium; X 1 and X 2 independently selected from hydrogen, halogen, pseudohalogen, 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 sulfonates, C1~C 20 Alkyl mercaptan, C6~C 24 Aryl thiols, C1~C 20 Alkylsulfonyl or C1-C 20 -alkylsulfinyl; L is selected from phosphine, sulfonated phosphine, phosphate, hypophosphorous acid, phosphite, phosphonate, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrite, pyridine, thioether or N-heterocyclic carbene ligand.

4. The catalyst composition according to claim 3, characterized in that In formula (I), formula (II) and formula (III), the X 1 and X 2 is independently selected from chlorine, CF3COO, CH3COO, CFH2COO, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, phenoxy, methoxy, ethoxy, toluenesulfonate, methanesulfonic acid or trifluoromethanesulfonate; L is at least one of the structures represented by formula (IV-a) to formula (IV-f): Among them, R 9 、R 10 、R 11 and R 12 independently selected from hydrogen, C1-C 30 Alkyl, C3~C 20 Cycloalkyl, C2~C 20 Alkenyl, C2~C 20 Alkynyl, C6~C 24 Aryl, C7~C 25 Alkyl, 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 R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; R is selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heteroaryl; 13 、R 14 and R 15 Independently selected from C1 to C 20 of alkyl.

5. The catalyst composition according to claim 1, characterized in that The main catalyst includes at least one of the following structural complexes:

6. The catalyst composition according to claim 1, characterized in that The first co-catalyst is one or more of esters, ethers, ketones, amines, carbamates, olefins and alkynes.

7. The catalyst composition according to claim 6, characterized in that The first co-catalyst is one or more of aliphatic monocarboxylic acid alkyl esters, aromatic monocarboxylic acid alkyl esters, aliphatic polycarboxylic acid alkyl esters, aromatic polycarboxylic acid alkyl esters, polyol alkyl esters, polyol cycloalkyl esters, polyol aryl esters, polyol alkylaryl esters, aliphatic ethers, cycloaliphatic ethers, aliphatic diethers, aliphatic ketones, aliphatic amines, aliphatic diamines, olefins and alkynes.

8. The catalyst composition according to claim 7, characterized in that The first co-catalyst is C1~C 20 Saturated fatty acid alkyl esters, C7~C 24 Aromatic carboxylic acid alkyl esters, C2~C 20 -Diol aryl ester, C2~C 20 Fatty ethers, C3~C 20 Cyclic ethers, C5~C 20 Aliphatic diether, C3~C 20 Saturated fatty ketones, C3~C 20 Saturated fatty amines, C3~C 20 Saturated fatty diamines, C2~C 20 Olefins and C2~C 20 One or more of the alkynes.

9. The catalyst composition according to claim 1, characterized in that The molar ratio of the main catalyst to the first co-catalyst is 1:(20-100).

10. The catalyst composition according to claim 1, characterized in that The catalyst composition further includes a second co-catalyst, which is one or more of carboxylate, sulfonate and phosphate.

11. The catalyst composition according to claim 10, characterized in that The second co-catalyst is one or more of non-emulsifier carboxylates, emulsifier carboxylates, non-emulsifier sulfonates, emulsifier sulfonates, non-emulsifier phosphates and emulsifier phosphates.

12. The catalyst composition according to claim 11, characterized in that The non-emulsified formulation carboxylate is one or more of formates, acetates, propionates, butyrates, valerates, oxalates, malonates, succinates, glutarates, triacrylic acid salts, trisuccinates, triglutarates, maleates, tartrates, fumarates, malates, amino acid salts, naphthenates, alginates, gluconates, crotonates, itaconates, citrates, mesaconic acid salts, aromatic carboxylates, heteroaromatic ring carboxylates, imidazoline carboxylates, pyruvates, epoxysuccinates, salicylates, fluorenedioates, hydroxypropionates, levulinates, furandicarboxylates, acrylates, methacrylates, and trifluoroformates; The emulsifier-type carboxylate is one or more of resinate, modified resinate, alkanoyl amino acid salt, fatty acid polypeptide condensate, acyl lactylate and long-chain alkyl carboxylate of C8 or above; The non-emulsifier type sulfonate is methanesulfonate, trifluoromethanesulfonate, ethanesulfonate, perfluoroethanesulfonate, propanesulfonate, perfluoropropanesulfonate, hydroxypropanesulfonate, butylsulfonate, perfluorobutylsulfonate, hydroxybutylsulfonate, toluenesulfonate, dinitrotoluenesulfonate, styrenesulfonate, vinylsulfonate, allylsulfonate, methylallylsulfonate, perfluorosulfonic acid type polymer, aromatic sulfonate, heteroaromatic ring sulfonate, cycloalkanesulfonate, hydroxybenzoate, One or more of 2-(2-aminoethyl)aminoethanesulfonate, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonate, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonate, aminosulfonates, aminoaromaticsulfonates, ethylenediamineethanesulfonates, chrysinsulfonates, anthraquinonesulfonates, diaminoformylsulfonates, quinocetonesulfonates, thiazolesulfonates, imidazolinesulfonates, allylimidazolinesulfonates, triazolonesulfonates, triazinesulfonates, and flavonesulfonates; The emulsifier-type sulfonate is one or more of alkyl aryl sulfonate, alkyl diphenyl oxide disulfonate, α-hydroxy sulfonate, α-olefin sulfonate, petroleum sulfonate, α-sulfomonocarboxylate, α-sulfomonocarboxylate derivatives, sulfoalkyl ester salt derivatives of fatty acids, sulfoalkyl amide salt derivatives of fatty acids, succinate sulfonate, lignin sulfonate, alkyl glyceryl ether sulfonate, 2-aminoethanesulfonate, 2-aminoethanesulfonate derivatives and long-chain alkyl sulfonates of C8 or above; The non-emulsifier type phosphate salt is monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, monophenyl phosphate, diphenyl phosphate, triphenyl phosphate, mono-p-cresyl phosphate, di-p-cresyl phosphate, tri-p-cresyl phosphate, mono-o-cresyl phosphate, di-o-cresyl phosphate, tri-o-cresyl phosphate, mono-m-cresyl phosphate, di-m-cresyl phosphate, tri-m-cresyl phosphate, mono-p-isopropylphenyl phosphate, di-p-isopropylphenyl phosphate, tri-p-isopropylphenyl phosphate, mono-p-tert-butyl phosphate Phenyl ester salt, di-p-tert-butylphenyl phosphate salt, tri-p-tert-butylphenyl phosphate, mono-p-methoxyphenyl phosphate salt, di-p-methoxyphenyl phosphate salt, tri-p-methoxyphenyl phosphate, phenyl dimethyl phosphate, phenyl diethyl phosphate, phenyl dibutyl phosphate, diphenylmethyl phosphate, diphenylethyl phosphate, diphenylbutyl phosphate, p-tolyldimethyl phosphate, p-tolyldiethyl phosphate, p-tolyldibutyl phosphate, o-tolyldimethyl phosphate, o-tolyldiethyl phosphate, o-tolyldibutyl phosphate, m-tolyldimethyl phosphate, m-tolyldiethyl phosphate, m-tolyldibutyl phosphate, di-p-tolylmethyl phosphate Ester, di-p-tolyl ethyl phosphate, di-p-tolyl butyl phosphate, di-o-tolyl methyl phosphate, di-o-tolyl ethyl phosphate, di-o-tolyl butyl phosphate, di-m-tolyl methyl phosphate, di-m-tolyl ethyl phosphate, di-m-tolyl butyl phosphate, di-p-isopropylphenyl methyl phosphate, di-p-isopropylphenyl ethyl phosphate, di-p-isopropylphenyl butyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-isopropylphenyl dibutyl phosphate, p-tert-butylphenyl dimethyl phosphate, p-tert-butylphenyl diethyl phosphate, p-tert-butylphenyl dibutyl phosphate, di-p-tert-butylphenyl methyl phosphate, di-p-tert-butylphenyl ethyl phosphate, phosphorus One or more of di-p-tert-butylphenyl butyl phosphate, phenyl di-p-cresyl phosphate, phenyl di-p-isopropylphenyl phosphate, phenyl di-p-tert-butylphenyl phosphate, p-cresyl diphenyl phosphate, p-cresyl-p-diisopropylphenyl phosphate, p-cresyl-p-di-tert-butylphenyl phosphate, o-cresyl-p-diisopropylphenyl phosphate, o-cresyl-p-di-tert-butylphenyl phosphate, m-cresyl-p-diisopropylphenyl phosphate, m-cresyl-p-di-tert-butylphenyl phosphate, p-cumyl di-p-cresyl phosphate, p-cumyl di-o-cresyl phosphate, p-cumyl di-m-cresyl phosphate, p-cumyl di-p-phenyl phosphate and p-cumyl di-p-tert-butylphenyl phosphate; The emulsifier-type phosphate salt is one or more of fatty alcohol polyvinyl ether phosphate monoester salt, fatty alcohol polyvinyl ether phosphate diester salt, alkylphenol polyoxyethylene ether phosphate monoester salt, alkylphenol polyoxyethylene ether phosphate diester salt, alcohol ether phosphate ester salt, phenol ether phosphate ester salt, long-chain alkyl phosphate monoester salt of C8 or above, and long-chain alkyl phosphate diester salt of C8 or above.

13. The catalyst composition according to claim 10, characterized in that The molar ratio of the main catalyst to the second co-catalyst is 1:(100-10000).

14. The catalyst composition according to claim 1, characterized in that The catalyst composition is in liquid form.

15. The catalyst composition according to claim 1, characterized in that The catalyst composition also includes a solvent.

16. A method for selective hydrogenation of conjugated diene latex, characterized in that: The following steps are involved: In the presence of the catalyst composition according to any one of claims 1 to 15, the conjugated diene latex is selectively hydrogenated to obtain hydrogenated conjugated diene latex.

17. The method according to claim 16, characterized in that The polymer in the conjugated diene latex contains at least one repeating unit of a C4-C6 conjugated diene.

18. The method according to claim 17, characterized in that The polymer in the conjugated diene latex further contains repeating units of at least one other copolymerizable monomer.

19. The method according to claim 18, characterized in that The polymer in the conjugated diene latex is a copolymer of 1,3-butadiene and acrylonitrile.

20. The method according to claim 16, wherein The amount of the main catalyst is 0.001 to 5 wt% of the mass of the conjugated diene latex; the amount of the first co-catalyst is 0.01 to 5 wt% of the mass of the conjugated diene latex.

21. The method according to claim 20, characterized in that When the catalyst composition includes a second co-catalyst, the amount of the second co-catalyst used is 0.1 to 10 wt % based on the mass of the conjugated diene latex.

22. The method according to claim 16, wherein The temperature of the selective hydrogenation is 35 to 200° C.; the time of the selective hydrogenation is 10 minutes to 24 hours; and the hydrogen pressure of the selective hydrogenation is 0.5 to 35 MPa.

23. A hydrogenated conjugated diene latex, characterized in that: It is prepared according to the method according to any one of claims 16 to 22.

24. Use of the hydrogenated conjugated diene latex according to claim 23 in impregnation, adhesives, coatings, film formation or preparation of composite materials.

25. A molded product, characterized in that The components of the molded article include the hydrogenated conjugated diene latex according to claim 23.

26. The molded article according to claim 25, characterized in that The shaped articles include one or more of sealing strips, gaskets, belts, hoses, bearing pads, baffles, wellhead seals, valve seals, cable jackets, wheels, rollers, in-situ gaskets, and pipe seals.

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