CN112876610A - Method for preparing conjugated diene latex capable of being selectively hydrogenated - Google Patents

Method for preparing conjugated diene latex capable of being selectively hydrogenated Download PDF

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CN112876610A
CN112876610A CN202011558758.9A CN202011558758A CN112876610A CN 112876610 A CN112876610 A CN 112876610A CN 202011558758 A CN202011558758 A CN 202011558758A CN 112876610 A CN112876610 A CN 112876610A
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conjugated diene
latex
hydrogenation
gemini surfactant
selectively hydrogenated
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王辉
杜庆之
王英超
蔡颖辉
王传齐
刘振学
王勇
曹峰
李泽珊
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Qingdao University of Science and Technology
Chambroad Chemical Industry Research Institute Co Ltd
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Chambroad Chemical Industry Research Institute Co Ltd
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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Abstract

The invention provides a preparation method of conjugated diene rubber latex capable of being selectively hydrogenated, which comprises the following steps: A) carrying out polymerization reaction on a conjugated diene monomer and a comonomer in the presence of a gemini surfactant and a polymerization initiator to obtain a conjugated diene polymer emulsion; B) and distilling the conjugated diene latex under reduced pressure to remove unreacted monomers to obtain the selectively hydrogenated conjugated diene latex. The conjugated diene latex prepared by the method can be directly used for selective hydrogenation reaction of osmium metal and/or ruthenium metal catalysts, and hydrogenation is only carried out on residual double bonds of the conjugated diene. The conjugated diene latex prepared by the method can be used for catalytic hydrogenation under the combined action of an osmium metal catalyst and/or a ruthenium metal catalyst, residual double bonds of the conjugated diene can be selectively hydrogenated under the condition of not using any organic solvent and cocatalyst, functional group double bonds in a comonomer are not influenced, no gel problem exists, and the cold and hot stability of the hydrogenated emulsion is particularly high.

Description

Method for preparing conjugated diene latex capable of being selectively hydrogenated
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to a conjugated diolefin latex capable of being selectively hydrogenated, a preparation method thereof and a preparation method of a diene main chain saturated polymer emulsion.
Background
The development of hydrogenated diene-based rubber products mainly refers to obtaining rubber products with required properties through formula design and subsequent processing methods according to the application environment of rubber parts. At present, hydrogenated diene-based rubbers, diene-based unsaturated polymers such as nitrile rubber (also referred to as NBR) prepared by polymerization of acrylonitrile and butadiene, are prepared mainly by three ways in both laboratory and industrial production, and NBR is exemplified specifically as follows.
(1) Acrylonitrile-ethylene copolymerization. In the copolymerization of ethylene and acrylonitrile, since reactivity ratios of acrylonitrile and ethylene are greatly different (0.04 for acrylonitrile and 0.8 for ethylene), the charge ratio of the reaction raw materials must be strictly controlled. In addition, radical rearrangement is easy to occur in the copolymerization reaction process, side reactions are more, the randomness of chain segments is poor, the performance of the obtained product is poor, and the processing performance of the product is finally influenced, so the method is still in the research stage at present.
(2) Emulsion hydrogenation: adding a heavy metal catalyst into the butyronitrile latex for hydrogenation to prepare HNBR. The first process of using diimide as reducing agent to prepare HNBR emulsion was proposed in 1984 by the American Guest-specific company, and the NBR latex can directly generate HNBR under the action of hydrazine hydrate, oxygen or hydrogen peroxide as oxidant and iron and copper metal ion initiator (related U.S. patent application: US 4452950A). The emulsion hydrogenation has the advantages of mild reaction conditions compared with solution hydrogenation, simple process, no need of solvent, reduced cost and pollution, and the product can be recycled (the product is emulsion and can be used as special coating). Therefore, NBR emulsion hydrogenation processes are receiving increasing attention. The disadvantage is that the unhydrogenated double bonds can undergo crosslinking reactions, which leads to an increase in the viscosity of the system and can impair the subsequent processing. The NBR solution hydrogenation method has complex process, needs a solvent in the reaction process, and causes environmental pollution due to the discharge of the solvent. The emulsion polymerization of NBR results in difficult product separation due to the presence of severe crosslinking reactions which make the product gel-forming easily. Meanwhile, the emulsion hydrogenation method has the problem of slow hydrogenation rate, and is not suitable for large-scale production. In recent years, Yuandong plum in Beijing chemical industry and the like have improved the hydrogenation method of NBR latex, reduce the gel content of HNBR latex and improve the hydrogenation degree (related Chinese patent applications: CN101486775A and CN 101704909A).
At present, both an ethylene-acrylonitrile copolymerization method and an NBR emulsion polymerization method are in a laboratory research stage, and no prior case exists for industrial application. The only industrialization is the NBR solution hydrogenation process, which is used by both german langerhans, japanese swizzen and dutyman. Due to the difference of catalytic systems used in hydrogenation reactions, the Japan Rui Wen corporation mainly adopts palladium/white carbon black heterogeneous catalyst with white carbon black as a carrier to prepare HNBR; the Langshan company mainly adopts a rhodium-based homogeneous catalyst RhCl (P (C)6H5)3)3Preparation ofHNBR。
(3) Solution hydrogenation process
The NBR solution hydrogenation method comprises a heterogeneous solution hydrogenation method and a homogeneous solution hydrogenation method, wherein during operation, NBR is crushed and dissolved in a proper organic solvent, and the used solvent mainly comprises cyclohexanone, xylene, chloroform and the like. And placing the mixture in a high-temperature high-pressure reactor, and reacting the mixture with hydrogen under the action of a noble metal catalyst to selectively hydrogenate to prepare HNBR. The solution hydrogenation method is the main method for industrially producing HNBR at present. In the hydrogenation, only the double bonds of the butadiene units are selectively hydrogenated to reduce them to saturated single bonds, without hydrogenating the nitrile groups. The key to the solution hydrogenation process is the choice of catalyst. The NBR solution hydrogenation method can be classified into heterogeneous hydrogenation using a group viii metal coated on an inorganic carrier as a catalyst and homogeneous hydrogenation mainly using a catalyst such as a rhodium-based, ruthenium-based, or palladium-based catalyst. The heterogeneous catalyst adopted by the heterogeneous solution hydrogenation method is a supported catalyst which takes palladium, rhodium, ruthenium and the like as active components and takes alumina, silica, active carbon, carbon black, alkaline earth metal carbonate and the like as carriers, and a hydrogenation product is directly separated from the catalyst by adopting a filtration or centrifugal separation method after the hydrogenation reaction is finished. In the 80 th century of the Japan Ruizui company, a supported catalyst is used for NBR hydrogenation reaction at the earliest, a heterogeneous carrier catalyst is a palladium/carbon catalyst taking carbon as a carrier, the catalyst has high selectivity, the hydrogenation rate can reach as high as 95.6%, but in the hydrogenation reaction, the carbon is easy to adsorb rubber molecules, so that the agglomeration is caused, and the product performance is influenced. The main advantage of the heterogeneous supported catalysts is that the catalysts are easy to separate, but the hydrogenation catalyst activity and selectivity are greatly influenced by the environment. In addition, most of the active components of the supported catalyst prepared by the traditional method are distributed in the pore channel, NBR molecules must diffuse into the pore channel to carry out hydrogenation reaction, in order to improve the reaction rate, the reaction must be carried out under the conditions of high pressure and strong stirring, the reaction time is long, the energy consumption of the process is high, and the performance of the polymer is easy to deteriorate.
In summary, there are two main approaches to research in this area: one approach is similar to conventional solution catalytic hydrogenation, which hydrogenates the polymer in latex form; another approach involves the use of diimides, where the hydrogen source is generated in situ as a result of an oxidation-reduction reaction. Currently, both approaches suffer from deficiencies in order to achieve rapid hydrogenation reaction rates, high conversion rates and eliminate gel formation. And thus, still further improvements are desired.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a selectively hydrogenated conjugated diene latex, which can be hydrogenated under the combined action of a gemini surfactant and an osmium metal catalyst and/or a ruthenium metal catalyst, can selectively hydrogenate residual double bonds of conjugated diene under the condition of not using any organic solvent and cocatalyst, has no influence on double bonds of functional groups in a comonomer, has no gel problem, and has particularly high cold and hot stability of the obtained hydrogenated emulsion.
The invention provides a preparation method of conjugated diene rubber latex capable of being selectively hydrogenated, which comprises the following steps:
A) carrying out polymerization reaction on a conjugated diene monomer and a comonomer in the presence of a gemini surfactant and a polymerization initiator to obtain a conjugated diene polymer emulsion;
B) and distilling the conjugated diene latex under reduced pressure to remove unreacted monomers to obtain the selectively hydrogenated conjugated diene latex.
Preferably, the conjugated diene monomer is a conjugated diene of C4-C6; preferably, the conjugated diene monomer is at least one selected from the group consisting of 1, 3-butadiene, isoprene, 1-methylbutadiene, 2, 3-dimethylbutadiene, piperylene and chloroprene.
Preferably, the comonomer is selected from one or more of acrylonitrile, methacrylonitrile, styrene, alpha-methyl styrene, propyl acrylate, butyl acrylate, propyl methacrylate, butyl methacrylate or unsaturated carboxylic acid;
the polymerization initiator is one or more selected from potassium persulfate, ammonium persulfate, dialkyl peroxide, azo compounds or alkyl hydroperoxide.
Preferably, the gemini surfactant is one or more selected from cationic gemini surfactants, anionic gemini surfactants, nonionic gemini surfactants and asymmetric gemini surfactants.
Preferably, the anionic gemini surfactant is selected from one or more of phosphate type, sulfonate type, carboxylate type and sulfate type;
the cationic gemini surfactant has a structure shown in a formula (I):
Figure BDA0002859643750000031
wherein, A1: R1＝R2＝CmH2m+1；Y＝CH2；
A2:R1＝R2＝CmH2m+1；Y＝CH2,O,S,N(CH3),x＝y＝2；
A2:R1＝R2＝CmH2m+1；Y＝CHOH,(CHOH)2；x＝y＝1；
A3:R1＝R2＝CmH2m+1；Y＝(OCH2CH2) z, x is 2; y is 0; z is any integer;
A4:R1＝R2＝CmH2m+1；Y＝C≡C；x＝y＝1；
A5:R1＝R2＝CmH2m+1(ii) a Y ═ phenylene; x-y-1;
A6:R1＝R2＝CmH2m+1OC(O)CH2(ii) a Does not contain Y; x-y-1;
A7:R1＝R2＝CmF2mC4H8；does not contain Y; x-y-1;
A8:R1＝CmH2m+1；R2＝CnH2n+1(ii) a m is not equal to n and does not contain Y; x-y-1;
wherein in A1-A8, m, n and z are each independently 1-60,
br-may be replaced by any other anion, preferably F-, Cl-, I-, At-, Ts-in the elements of group VIIA of the periodic System.
Preferably, the gemini surfactant
At least one selected from the group consisting of:
C12H25N+(CH3)2-(CH2)n-N+(CH3)2C12H25 2Br–(n＝3–8)、
C12H25N+(CH3)2-(CH2)16-N+(CH3)2C12H25 2Br–、
C16H33N+(CH3)2-(CH2)2-N+(CH3)2C16H33 2Br–、
C8H17N+(CH3)2-(CH2)3-N+(CH3)2C8H17 2Br–、
C12H25N+(CH3)2-(CH2)2-O-(CH2)2-N+(CH3)2C12H25 2Cl–、
C16H33N+(CH3)2-(CH2)5-N+(CH3)2C16H33 2Br–、
C16H33N+(CH3)2-(CH2)2-O-(CH2)2-N+(CH3)2C16H33 2Br–、
C16H33N+(CH3)2-CH2-(CH2-O-CH2)3-CH2-N+(CH3)2C16H33 2Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2C12H25 2Br–、
C12H25N+(CH3)2-CH2-C6H4-CH2-N+(CH3)2C12H25 2Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH(OH)-CH2-N+(CH3)2C12H25 2Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2C 12H25 3Cl–、
C12H25OPO2 –-O-(CH2)6-OPO2 –-OC12H25 2Na+、
C10H21O-CH2-CH(OSO3 –)-CH2-O-(CH2)2-O-CH2-CH(OSO3 –)-CH2-OC10H21 2Na+。
preferably, the temperature of the reduced pressure distillation is 20-80 ℃;
the solid content of the selectively hydrogenated conjugated diene rubber latex is 1-60 wt%;
the gemini surfactant accounts for 0.01-10 wt% of the total mass of the conjugated diene monomer and the copolymerizable monomer;
the polymerization initiator accounts for 0.01-5 wt% of the total mass of the conjugated diene monomer and the copolymerizable monomer;
the polymerization reaction temperature of the conjugated diene monomer and the comonomer is 0-100 ℃; the time is 0.25 to 100 hours.
The invention provides a conjugated diene latex capable of being selectively hydrogenated, which is prepared by the preparation method in any one of the technical schemes.
The invention provides a preparation method of a diene-based main chain saturated polymer emulsion, which comprises the following steps:
the conjugated diene rubber latex which can be selectively hydrogenated and is prepared by the preparation method in any one of the technical schemes is obtained by hydrogenation reaction under the action of osmium metal and/or ruthenium metal catalyst and gemini surfactant.
Preferably, the osmium metal catalyst or ruthenium metal catalyst has the formula:
Figure BDA0002859643750000051
wherein M is osmium or ruthenium,
X1and X2Are the same or different anionic ligands and are,
l is a ligand, preferably an uncharged electron donor,
y is O, S, N-R1Or P-R1The free radical(s) is (are),
R1is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonic acid or alkylsulfinyl, optionally, each R above1May be optionally substituted with one or more alkyl, halo, alkoxy, aryl or heteroaryl groups,
R2、R3、R4and R5Are identical or different hydrogen radicals, organic radicals or inorganic radicals,
R6is hydrogen, alkyl, alkenyl, alkynyl or aryl.
Preferably, the temperature of the hydrogenation reaction is 60-200 ℃; the time is 10min to 24 hours; the hydrogenation reaction pressure is 0.5-35 Mpa;
the mass of the osmium metal and/or ruthenium metal catalyst is 0.011 to 5.0 wt% based on the solid content of the selectively hydrogenatable conjugated diene rubber latex.
Compared with the prior art, the invention provides a preparation method of conjugated diene rubber latex capable of being selectively hydrogenated, which comprises the following steps: A) carrying out polymerization reaction on a conjugated diene monomer and a comonomer in the presence of a gemini surfactant and a polymerization initiator to obtain a conjugated diene polymer emulsion; B) and distilling the conjugated diene latex under reduced pressure to remove unreacted monomers to obtain the selectively hydrogenated conjugated diene latex. The conjugated diene latex prepared by the method can be directly used for selective hydrogenation reaction of osmium metal and/or ruthenium metal catalysts, and hydrogenation is only carried out on residual double bonds of the conjugated diene. The conjugated diene latex prepared by the method can be used for catalytic hydrogenation under the combined action of an osmium metal catalyst and/or a ruthenium metal catalyst, residual double bonds of the conjugated diene can be selectively hydrogenated under the condition of not using any organic solvent and cocatalyst, functional group double bonds in a comonomer are not influenced, no gel problem exists, and the cold and hot stability of the hydrogenated emulsion is particularly high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic representation of the structure of a gemini surfactant according to one embodiment of the present invention;
fig. 2 is a schematic structural view of a gemini surfactant according to another embodiment of the present invention.
Detailed Description
The invention provides a conjugated diene latex capable of being selectively hydrogenated, a preparation method thereof and a preparation method of a diene main chain saturated polymer emulsion, and a person skilled in the art can use the contents for reference and appropriately improve the process parameters to realize the purpose. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the method and application of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the method and application, as well as other suitable variations and combinations, may be made to implement and use the techniques of the present invention without departing from the spirit and scope of the invention.
The invention provides a preparation method of conjugated diene rubber latex capable of being selectively hydrogenated, which comprises the following steps:
A) carrying out polymerization reaction on a conjugated diene monomer and a comonomer in the presence of a gemini surfactant and a polymerization initiator to obtain a conjugated diene polymer emulsion;
B) and distilling the conjugated diene latex under reduced pressure to remove unreacted monomers to obtain the selectively hydrogenated conjugated diene latex.
The invention provides a preparation method of selectively hydrogenated conjugated diene rubber latex, which comprises the following step of carrying out polymerization reaction on a conjugated diene monomer and a comonomer in the presence of a gemini surfactant and a polymerization initiator to obtain a conjugated diene polymer emulsion.
The inventor finds that the gemini surfactant can effectively maintain the stability of the interface of the emulsion in the process of preparing the conjugated diene rubber latex, and further remarkably improves the particle stability of the emulsion.
The gemini surfactant can keep the emulsion stability in the concentration or dilution process of the conjugated diene latex, and can obtain latexes with different solid content.
The conjugated monomer of the present invention may be selected from (C)4-C6) At least one of conjugated dienes. According to an embodiment of the present invention, the twoThe ethylenic monomer is preferably at least one selected from the group consisting of 1, 3-butadiene, isoprene, 1-methylbutadiene, 2, 3-dimethylbutadiene, piperylene and chloroprene.
In addition, the copolymerizable monomer may be selected from acrylonitrile, methacrylonitrile, styrene, α -methylstyrene, propyl acrylate, butyl acrylate, propyl methacrylate, butyl methacrylate, and unsaturated carboxylic acids selected from fumaric acid, maleic acid, acrylic acid, and methacrylic acid.
Specifically, the conjugated diene monomer constitutes 15 to 100% by weight of the polymer. If a copolymerizable monomer is used and is selected from styrene and alpha-methylstyrene, the styrene and/or alpha-methylstyrene monomers preferably constitute from 15 to 60 weight percent of the polymer. If other copolymerizable monomers are used and are selected from acrylonitrile and methacrylonitrile, the acrylonitrile and/or methacrylonitrile monomers preferably constitute from 15 to 60 wt% of the polymer and the conjugated diene constitutes from 40 to 85 wt% of the polymer.
If other copolymerizable monomers are used and are selected from acrylonitrile and methacrylonitrile and additionally from unsaturated carboxylic acids, the acrylonitrile or methacrylonitrile constitutes from 15% to 60% by weight of the polymer, the unsaturated carboxylic acids constitute from 1% to 20% by weight of the polymer and the conjugated dienes constitute from 40% to 84% by weight of the polymer.
Preferably, the products include random or block type styrene-butadiene polymers, butadiene-acrylonitrile polymers and butadiene-acrylonitrile-methacrylic acid polymers. The preferred butadiene-acrylonitrile polymers have an acrylonitrile content of about 15 wt% to about 49 wt%.
Particularly suitable copolymers are nitrile rubbers (nitrile rubbers), which are copolymers of α, β -unsaturated nitriles, preferably acrylonitrile, and conjugated dienes, particularly preferably 1, 3-butadiene, and optionally one or more other copolymerizable monomers, for example α, β -unsaturated monocarboxylic or dicarboxylic acids, their esters or amides.
As the α, β -unsaturated monocarboxylic or dicarboxylic acid in such a nitrile rubber, fumaric acid, maleic acid, acrylic acid and methacrylic acid are preferable.
As the esters of α, β -unsaturated carboxylic acids in such nitrile rubbers, it is preferred to use alkyl esters or alkoxyalkyl esters thereof. Particularly preferred alkyl esters of α, β -unsaturated carboxylic acids are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and octyl acrylate. Particularly preferred alkoxyalkyl esters of α, β -unsaturated carboxylic acids are methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and methoxyethyl (meth) acrylate. Mixtures of alkyl esters (such as those described above) with alkoxyalkyl esters (such as those of the form described above) may also be used.
Preferred terpolymers are those of acrylonitrile, 1, 3-butadiene and a third monomer selected from fumaric acid, maleic acid, acrylic acid, methacrylic acid, n-butyl acrylate and t-butyl acrylate.
According to an embodiment of the present invention, in step (1), a polymerization initiator, such as potassium persulfate (KPS), may be used to perform the synthesis process. Other polymerization initiators may also be employed, including thermal initiators such as Ammonium Persulfate (APS), dialkyl peroxides or azo compounds, and redox initiators such as alkyl hydroperoxides, e.g., the hydroperoxides of cumene, diisopropylbenzene, p-menthane and pinane, optionally in combination with chelating salts and suitable reducing agents.
Specifically, the polymerization initiator may be used in a small amount. Such as potassium sulfate (KPS), is used in an amount of 0.01 wt% to 5 wt%, preferably 0.02 wt% to 1 wt%, based on the total amount of monomers, relative to the total amount of monomers.
According to a specific embodiment of the present invention, the synthesis process of step (1) is preferably performed using a gemini surfactant.
Specifically, gemini surfactants refer to surfactants in which two single-chain surfactants (Chains) are linked by spacers (spacers) of different properties and lengths at or near the Head group (Head groups).
According to the specific embodiment of the present invention, the gemini surfactant employed in the present invention has the structure as shown in fig. 1 and 2. Figure 2 shows a typical structure of a non-gemini surfactant.
According to a specific embodiment of the present invention, unlike the molecular structure of the classical surfactants, the molecular structure of the gemini surfactant comprises at least two hydrophilic groups (ionic or polar groups) and two hydrophobic chains, which are linked together by a linking group (spacer) through a chemical bond (covalent bond or ionic bond) at or near the hydrophilic group, as shown in fig. 1-2. In fig. 2, R is a hydrophobic group; i is a hydrophilic group; y is a linking group. From the synthesized gemini surfactant, both R and I can be more than 2, and Y can be more than 1. The hydrophilic group constituting the gemini surfactant may be a cation (e.g., quaternary ammonium salt), an anion (e.g., phosphate, sulfate, sulfonate, carboxylate, etc.), a zwitterion, a nonionic and a cationic (cationic) or ionic pair (ion-paired), etc. The hydrophobic moiety is typically a CH chain (about 8-20C atoms in length, sometimes containing oxygen or phenyl groups), and more recently a CF chain. The linking group is various in variety and can be short-chain (2 atoms) or long-chain (more than 20 atoms); a rigid chain (e.g., diphenylethylene) or a flexible chain (e.g., a plurality of methylene groups); polar chains (e.g., polyethers) or nonpolar chains (e.g., aliphatic and aromatic), and the like. The overall structure of the gemini surfactant molecule may also be asymmetric, i.e. I in FIG. 21≠I2，R1≠R2. In the molecular structure of gemini surfactants, two (or more) hydrophilic groups are linked by chemical bonds depending on the linking group, thereby resulting in a rather intimate association of the two (or more) surfactant monomers. On one hand, the structure enhances the hydrophobic effect of the hydrocarbon chain, and increases the escape tendency of hydrophobic groups from the aqueous solution; on the other hand, the tendency of the ionic head groups to separate from each other due to electrical repulsion is greatly diminished by the restriction of chemical bonds. Therefore, the change of factors such as the linking group and the chemical structure thereof, the lateral degree of the linking position, the chain length and the like enables the structure of the gemini surfactant to have diversified characteristics, and further generates properties such as the solution and aggregate behaviors and the likeThe influence is generated, so that the material has more excellent physicochemical characteristics, such as: the capability and efficiency of reducing the surface tension of the aqueous solution are more outstanding; very low Krafft point; good foam stability, Ca soap dispersing power, wetting and solubilization. Antibacterial and detergent power, etc.
According to a specific embodiment of the present invention, the gemini surfactant employed in the steps (1) and (2) may be at least one selected from the group consisting of a cationic gemini surfactant, an anionic gemini surfactant, a nonionic gemini surfactant and an asymmetric gemini surfactant. Specifically, the anionic gemini surfactant is at least one anionic gemini surfactant selected from the group consisting of a phosphate type, a sulfonate type, a carboxylate type and a sulfate type. Therefore, the gemini surfactant can remarkably improve the loading amount of the catalyst, and further remarkably improve the hydrogenation reaction rate.
According to a particular embodiment of the invention, preference is given to using cationic gemini surfactants, in particular
Figure BDA0002859643750000101
Wherein, A1: R1＝R2＝CmH2m+1；Y＝CH2；
A2:R1＝R2＝CmH2m+1；Y＝CH2,O,S,N(CH3),x＝y＝2；
A2:R1＝R2＝CmH2m+1；Y＝CHOH,(CHOH)2；x＝y＝1；
A3:R1＝R2＝CmH2m+1；Y＝(OCH2CH2) z, x is 2; y is 0; z is any integer;
A4:R1＝R2＝CmH2m+1；Y＝C≡C；x＝y＝1；
A5:R1＝R2＝CmH2m+1(ii) a Y ═ phenylene; x-y-1;
A6:R1＝R2＝CmH2m+1OC(O)CH2(ii) a Does not contain Y; x-y-1;
A7:R1＝R2＝CmF2mC4H8；does not contain Y; x-y-1;
A8:R1＝CmH2m+1；R2＝CnH2n+1(ii) a m is not equal to n and does not contain Y; x-y-1;
wherein in A1-A8, m, n and z are each independently 1-60,
Br-can be replaced by any other anion, preferably F-, Cl-in the elements of group VIIA of the periodic system-、I-、 At-、Ts-。
Therefore, the cationic gemini surfactant with the structure has more outstanding effect of reducing the surface tension of an aqueous solution, so that the stability of an interface of emulsion polymerization can be effectively maintained, and stable polymer particles with smaller particle size are synthesized. The inventors have found that the combined action of a suitable amount and a small amount of cationic gemini surfactant with the water-insoluble rhodium metal catalyst and the promoter can also achieve the effect of significantly improving the hydrogenation reaction efficiency.
Specifically, gemini surfactants with a large number of different structures can be prepared by linking any two identical or different single-headed surfactants via a spacer. The spacer may be hydrophilic or hydrophobic, flexible or rigid, a heteroatom or an aromatic ring. Thus, the structure and properties of the gemini surfactant may be tailored to its particular use.
For example, the gemini surfactant employed in the present invention may be at least one selected from the group consisting of:
C12H25N+(CH3)2-(CH2)n-N+(CH3)2C12H25 2Br–(n＝3–8)、
C12H25N+(CH3)2-(CH2)16-N+(CH3)2C12H25 2Br–、
C16H33N+(CH3)2-(CH2)2-N+(CH3)2C16H33 2Br–、
C8H17N+(CH3)2-(CH2)3-N+(CH3)2C8H17 2Br–、
C12H25N+(CH3)2-(CH2)2-O-(CH2)2-N+(CH3)2C12H25 2Cl–、
C16H33N+(CH3)2-(CH2)5-N+(CH3)2C16H33 2Br–、
C16H33N+(CH3)2-(CH2)2-O-(CH2)2-N+(CH3)2C16H33 2Br–、
C16H33N+(CH3)2-CH2-(CH2-O-CH2)3-CH2-N+(CH3)2C16H33 2Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2C12H25 2Br–、
C12H25N+(CH3)2-CH2-C6H4-CH2-N+(CH3)2C12H25 2Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH(OH)-CH2-N+(CH3)2C12H25 2Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2C 12H25 3Cl–、
C12H25OPO2 –-O-(CH2)6-OPO2 –-OC12H25 2Na+、
C10H21O-CH2-CH(OSO3 –)-CH2-O-(CH2)2-O-CH2-CH(OSO3 –)-CH2-OC10H21 2Na+。
the gemini surfactants have the advantages of simple preparation process, easily obtained raw materials and low critical micelle concentration relative to other gemini surfactants. And the conjugated diene rubber latex can be prepared by adopting the conjugated diene rubber latex as an emulsifier, and the rubber latex is more stable and has longer storage period. In addition, the hydrogenation efficiency of the conjugated diene rubber latex can be remarkably improved particularly by adopting the gemini surfactants, and the hydrogenation rate can reach 99 percent of hydrogenation degree within 2 hours.
According to a specific embodiment of the present invention, the gemini surfactant is preferably one of the following:
C12H25N+(CH3)2-(CH2)n-N+(CH3)2C12H25 2Br–(n＝3-8)；
C12H25N+(CH3)2-(CH2)2-O-(CH2)2-N+(CH3)2C12H25 2Cl–；
C12H25OPO2 –-O-(CH2)6-OPO2 –-OC12H25 2Na+。
according to a specific embodiment of the present invention, the above gemini surfactant may be used in an amount of 0.01 to 10% by weight, preferably 0.02 to 1% by weight, based on the total mass of the conjugated diene monomer and the copolymerizable monomer. Therefore, by adopting the gemini surfactant, compared with the single-chain-head surfactant used at present, the consumption is obviously reduced, the cost is further reduced, and meanwhile, the small amount of gemini surfactant can also obviously improve the hydrogenation efficiency of the subsequent hydrogenation reaction step.
According to a particular embodiment of the invention, the polymerization reaction of step A) can be carried out using water as the reaction medium for the monomers, the amount of water being from about 1 to 30 times, preferably from 1.5 to 10 times, the weight of the monomers used.
The polymerization process can be carried out in a suitable reactor equipped with temperature regulation means and with monomer feeding and stirring means.
In general, suitable temperatures for the polymerization of the invention are from 0 ℃ to 100 ℃ and preferably from about 5 ℃ to 70 ℃.
According to a preferred embodiment, the reaction time during the polymerization process is 0.25 to 100 hours, preferably 1 to 10 hours, more preferably 2 to 8 hours, which may be determined according to the operation conditions. The conversion rate of the monomer is controlled to be less than 75 percent, the redox initiator system is preferably controlled to be 65 to 75 percent, and the peroxide initiator system is preferably controlled to be 50 to 70 percent
According to a preferred embodiment, the aging time during the polymerization process after the completion of the monomer feed is from 0.25 to 50 hours, preferably from 1 to 15 hours, depending on the operating conditions.
According to a preferred embodiment, when the polymerization reaction is completed to a desired extent, a terminator, which may be sodium dimethyldithiocarbamate (sodium ferbamate), hydroquinone, diethylhydroxylamine, hydroxylamine sulfate, etc., may be added to stop the reaction, and a polymer latex is obtained.
The polymers containing carbon-carbon double bonds used in the present invention are preferably prepared in an aqueous emulsion polymerization process, since this process gives the polymer directly in the form of a latex. According to the invention, the polymer content of the preferred latex may be in the range of from 1 to 45% by weight, more preferably from 5 to 30% by weight, based on the total weight of the latex.
And distilling the conjugated diene latex under reduced pressure to remove unreacted monomers to obtain the selectively hydrogenated conjugated diene latex.
And removing unreacted monomers from the obtained emulsion by adopting a reduced pressure distillation method, and further concentrating or diluting to obtain the conjugated diene rubber latex with different solid content contents.
Specifically, the reduced pressure distillation method can adopt a rotary evaporator or other reduced pressure distillation equipment, and a defoaming agent can be added to reduce the generation of foams.
According to the specific embodiment of the invention, the gemini surfactant is used to improve the stability of the emulsion, the emulsion is not broken in a high solid content state, and the reduced pressure distillation temperature is 20-80 ℃, preferably 30-60 ℃.
According to a preferred embodiment, the emulsion obtained can be further concentrated by means of distillation under reduced pressure, in order to increase the polymer content, or diluted in order to reduce the polymer content. Increasing the polymer content of the emulsion can increase the yield of the hydrogenation process, and decreasing the polymer content can achieve a faster hydrogenation rate. The latex with high solid content can be directly applied to various fields such as coating, water paint, dipped products, paper and fiber treatment and the like.
The solid content of the selectively hydrogenated conjugated diene rubber latex is 1-60 wt%; preferably 10 to 55 wt%.
The invention provides a conjugated diene latex capable of being selectively hydrogenated, which is prepared by the preparation method in any one of the technical schemes.
The present invention has been described above clearly for the specific preparation method, and is not described herein redundantly.
The invention provides a preparation method of a diene-based main chain saturated polymer emulsion, which comprises the following steps:
the conjugated diene rubber latex which can be selectively hydrogenated and is prepared by the preparation method in any one of the technical schemes is obtained by hydrogenation reaction under the action of osmium metal and/or ruthenium metal catalyst and gemini surfactant.
The invention carries out hydrogenation reaction on the conjugated diene latex and hydrogen in an aqueous medium in the presence of gemini surfactant, osmium metal catalyst and/or ruthenium metal catalyst so as to obtain hydrogenated diene-based polymer emulsion.
Therefore, the catalytic hydrogenation reaction of the diene-based unsaturated polymer emulsion provided by the embodiment of the invention can achieve the effect of rapid hydrogenation only by adopting a gemini surfactant, an osmium metal catalyst and/or a ruthenium metal catalyst, without a cocatalyst, and in an aqueous medium without any organic solvent.
According to the present invention, the osmium metal catalyst or ruthenium metal catalyst has the following formula:
Figure BDA0002859643750000131
wherein M is osmium or ruthenium,
X1and X2Are the same or different anionic ligands and are,
l is a ligand, preferably an uncharged electron donor,
y is O, S, N-R1Or P-R1The free radical(s) is (are),
R1is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonic acid or alkylsulfinyl, optionally, each R above1May be optionally substituted with one or more alkyl, halo, alkoxy, aryl or heteroaryl groups,
R2、R3、R4and R5Are identical or different hydrogen radicals, organic radicals or inorganic radicals,
R6is hydrogen, alkyl, alkenyl, alkynyl or aryl.
Such catalysts, represented by the general formula (A), are added in solid form to the aqueous suspension of the diene-based polymer.
Such catalysts as shown by the general expression (A) are generally insoluble in water. In this application, "water insoluble" means that at 24+/-2 degrees Celsius, a material in an amount of 0.001 or less by weight can be completely dissolved in 100 equivalents of water, whereas at 24+/-2 degrees Celsius, a catalyst is considered "water soluble" if more than 0.5 weight percent of the catalyst can be completely dissolved in 100 equivalents of water.
X1And X2：
In the catalyst shown by the general expression (A), X1And X2Are the same or different anionic ligands.
In one embodiment of the catalyst shown by the general expression (A), X1Represents hydrogen, halogen, pseudohalogen, straight or branched C1-C30Alkyl radical, C6-C24-aryl, C1-C20-alkoxy, C6-C24Aryloxy group, C3-C20-alkyldione, C6-C24Aryl diketones, C1-C20-carboxylic acid salt, C6-C24-alkylsulfonic acid salt, C6-C24Aryl sulfonates, C1-C20Alkyl mercaptans, C6-C24Aryl thiols, C1-C20-alkylsulfonyl or C1-C20-an alkylsulfinyl group.
X listed above1The radicals may also be further substituted by one or more radicals, e.g. halogen, preferably fluorine, C1-C10Alkyl radical, C1-C10-alkoxy or C6-C-24And (4) an aryl group. Conversely, these radicals may also be composed ofSubstituted by one or more halogen-containing groups, preferably fluorine, C1-C5Alkyl radical, C1-C5-alkoxy and phenyl.
In a preferred embodiment, X1Is halogen, especially fluorine, chlorine, bromine, iodine, benzoic acid, C1-C5-carboxylic acid salt, C1-C5Alkyl, phenoxy, C1-C5Alkoxy radical, C1-C5Alkyl mercaptans, C6-C14-aromatic thiophenols, C6-C14Aryl or C1-C5-alkyl sulfonates.
In a particularly preferred embodiment, X1Represents chlorine, CF3COO、CH3COO、CFH2COO、 (CH3)3CO、(CF3)2(CH3)CO、(CF3)(CH3)2CO, phenoxy, methoxy, ethoxy, tosylate (p-CH)3-C6H4-SO3) Methanesulfonic acid (CH)3SO3) Or trifluoromethanesulfonate (CF)3SO3)。
L：
In the general expression (A), the symbol L represents a ligand, preferably an uncharged electron donor.
The ligand L may be, for example, a phosphine, sulfonated phosphine, phosphate, phosphonate, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrite, pyridine, thioether or N-heterocyclic carbene ligand.
The term "hypophosphorous acid" includes: phenyl diphenyl hypophosphorous acid, cyclohexyl dicyclohexyl hypophosphorous acid, isopropyl diisopropyl hypophosphorous acid and methyl diphenyl hypophosphorous acid.
The term "phosphite" includes: triphenyl phosphite, tricyclohexyl phosphite, tri-tert-butyl phosphite, triisopropyl phosphite and methyl diphenyl phosphite.
The term "stibine" includes: triphenyl radical
Figure BDA0002859643750000155
Tricyclohexyl radical
Figure BDA0002859643750000153
And trimethyl
Figure BDA0002859643750000154
。
The term "sulfonate" includes: triflate, tosylate and mesylate salts.
The term "sulfoxide" includes: (CH)3)2S (═ O) and (C)6H5)2S＝O。
The term "thioether" includes: CH (CH)3SCH3、C6H5SCH3、CH3OCH2CH2SCH3And tetrahydrothiophene.
For the present application, the term "pyridyl ligand" is used as A generic term for all pyridine-based ligands or derivatives thereof, as is the case, for example, in WO-A-03/011455. The term "pyridyl ligand" includes pyridine itself, picolines (e.g., alpha-, beta-, and gamma-picolines), lutidines (e.g., 2,3-,2,4-, 2,5-,2,6-,3,4-, and 3, 5-lutidines), collidines (2,4, 6-collidines), trifluoromethylpyridines, phenylpyridines, 4- (dimethylamino) -pyridines, chloropyridines, bromopyridines, nitropyridines, quinolines, pyrimidines, pyrroles, imidazoles, and phenylimidazoles.
If L represents phosphine as electron donor in the general expression (A), then its general expression is preferably (IIf).
Figure BDA0002859643750000151
Wherein R is12、R13And R14Are identical or different, preferably identical, and may be C1-C20Alkyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutylCyclobutyl, neopentyl, 1-ethylpropyl, n-hexyl, or neopentyl, C3-C8Cycloalkyl, preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, C1-C20Alkoxy, substituted or unsubstituted C6-C20Aryl, preferably phenyl, biphenyl, naphthalene, phenanthrene, anthracene, tolyl, 2, 6-dimethylphenyl, or trifluoromethyl, C6-C20Aryloxy radical, C having at least one hetero atom in the ring2-C20Heteroaryl, C having at least one hetero atom in the ring2-C20Heterocyclyl, or is halogen, preferably fluorine;
if L represents a phosphine of the general formula (IIf) and is present as electron-donating ligand in the general formula (A) or (B), such a 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)3P (isopropyl)3、P(CHCH3(CH2CH3))3P (cyclopentyl)3P (cyclohexyl)3P (neopentyl)3Or P (neopentyl)3Wherein Ph represents a phenyl group and Tol represents a tolyl group.
The n-heterocyclic carbene ligand is a cyclic carbene ligand having at least one nitrogen as a heteroatom in the ring. The rings may have different substitution patterns. Preferably, this substitution pattern provides a degree of spatial crowning.
In this invention, the n-heterocyclic carbene ligands (hereinafter referred to as "NHC-ligands") are preferably based on imidazoline or imidazolidine groups.
NHC-ligands usually have a structure corresponding to the general expressions (IIa) to (IIe).
Figure BDA0002859643750000161
Wherein R is8、R9、R10And R11Are identical or different and represent hydrogen, a linear or branched C1-C30-alkyl radical, C3-C20-cycloalkyl, C2-C20-alkenyl, C2-C20-alkynyl, C6-C24-aryl, C7-C25-alkylaryl, C2-C20Heterocyclic aryl radicals, C2-C20Heterocycle, C1-C20-alkoxy, C2-C20-alkenyl, C2-C20-alkynyloxy, C6-C20Aryloxy group, C2-C20-alkoxycarbonyl, C1-C20Alkylthio radical, C6-C20-arylthio, -Si (R)3、 -O-Si(R)3、-O-C(＝O)R、C(＝O)R、-C(＝O)N(R)2、-NR-C(＝O)-N(R)2、-SO2N(R)2、 -S(＝O)R、-S(＝O)2R、-O-S(＝O)2R, halogen, nitro or cyano; in relation to R appearing above8、 R9、R10And R11In the radicals, R are identical or different and represent hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl or heterocycloaryl.
In the representative formulae (IIa) to (IIe), the carbon atom bonded to the ruthenium metal center is present in the form of carbene.
Optionally, R8、R9、R10And R11May be substituted independently of each other by one or more substituents, preferably straight-chain or branched C1-C10Alkyl radical, C3-C8-cycloalkyl, C1-C10-alkoxy, C6-C24-aryl, C2-C20Heteroaryl, C2-C20Heterocyclic ring, and one selected from the group consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, aminoFormate and halogen, wherein the above substituents may in turn be chemically substituted to some extent by one or more substituents, preferably halogen, especially chlorine or bromine, containing groups C1-C5Alkyl radical, C1-C5-alkoxy and benzene. For the sake of clarity, it is added that the NHC-ligand structures of the general expressions (IIa) and (IIb) depicted in the examples of the present invention and the structures (IIa- (i)) and (IIb- (i)) frequently encountered in the literature for such NHC-ligands, respectively, are the same and the carbene character of the NHC-ligand is to be emphasized. The same applies to the further structures (IIc) to (IIe) and also to the preferred structures described below in connection with (IIc) - (IIe).
Figure BDA0002859643750000171
Among the preferred NHC-ligands in the catalyst represented by the general expression (A)
R8And R9Are identical or different and represent hydrogen, C6-C24Aryl, preferably benzene, straight or branched C1-C10-alkyl, more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl or tert-butyl, or forms a cycloalkyl or aryl structure bound to a carbon atom.
Preferably and more preferably, R8And R9May be substituted by one or more groups comprising a straight or branched chain C1-C10-alkyl or C1-C10-alkoxy, C3-C8-cycloalkyl, C6-C24Aryl, and a functional group chosen from the group comprising hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherein these substituents may in turn be substituted by one or more substituents, preferably comprising halogen, in particular chlorine or bromine, C1-C5Alkyl radical, C1-C5-alkoxy and benzene.
R in a further preferred NHC-ligand in the catalyst represented by the general formula (A)10And R11Are identical or different, preferably straight-chain or branched C1-C10- -alkyl, more preferably i-propyl or neopentyl, C3-C10Cycloalkyl, more preferably adamantyl, substituted or unsubstituted C6-C24Aryl, more preferably phenyl, 2, 6-isopropylbenzene, 2, 6-xylyl, or 2,4, 6-trimethylphenyl, C1-C10- - -alkylsulfonic acid salts or C6-C10-sulfonic acid.
Preferably, R10And R11May be substituted by one or more substituents selected from the group consisting of straight or branched C1-C10- -alkyl or C1-C10- -alkoxy radical, C3-C8-cycloalkyl, C6-C24Aryl, and a functional group chosen from the group comprising hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate and halogen, wherein these substituents may in turn be substituted by one or more substituents, preferably comprising halogen, in particular chlorine or bromine, C1-C5Alkyl radical, C1-C5-alkoxy and benzene.
R in a further preferred NHC-ligand in the catalyst represented by the general formula (A)8And R9Are the same or different and represent hydrogen, C6-C24Aryl, more preferably benzene, straight or branched C1-C10-alkyl, more preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, or is a cycloalkyl or aryl structure forming a bond to a carbon atom.
R10And R11Are identical or different, preferably straight-chain or branched C1-C10Alkyl, more preferably i-propyl or neopentyl, C3-C10-cycloalkyl, more preferably goldAlkyl, substituted or unsubstituted C6-C24Aryl, more preferably phenyl, 2, 6-isopropylbenzene, 2, 6-xylyl or 2,4, 6-trimethylphenyl, C1-C10Alkyl sulfonates or C6-C10-sulfonic acid.
Particularly preferably, the NHC-ligand has the structure shown below in (IIIa) to (IIIu), wherein "Ph" represents phenyl in each case and "Bu" represents butyl in each case, i.e. any of n-butyl, tert-butyl, isobutyl, or tert-butyl. "Mes" stands for 2,4, 6-trimethylphenyl in each case, "Dipp" for 2, 6-diisopropylbenzene in each case and "Dimp" for 2, 6-dimethylphenyl in each case.
Figure BDA0002859643750000181
NHC-ligands contain not only one "N" (nitrogen) but also one "O" (oxygen) in the ring, which makes R8、R9、R10And/or R11The substitution pattern of (2) is more likely to provide a certain spatial crowning.
In the general expression (A), the substituent R1Is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, hydroxyethylaryl sulfide, alkylsulfonyl, or alkylsulfinyl, which substituents may be optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.
Substituent R1In general C1-C30Alkyl radical, C3-C20-cycloalkyl, C2-C20-alkenyl, C2-C20-alkynyl, C6-C24-aryl, C1-C20-alkoxy, C2-C20-alkenyloxy, C2-C20-alkynyloxy, C6-C24Aryloxy group, C2-C20-alkoxycarbonyl, C1-C20Alkylamino radical, C1-C20Alkylthio radical, C6-C24-arylthio group, C1-C20-alkylsulfonyl or C1-C20-alkylsulfinyl, these substituents being optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals.
R1Preferably C3-C20-cylcoalkyl，C6-C24Aryl or straight or branched C1-C30Alkyl radicals, the latter being able to be interrupted, where appropriate, by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen. R1Particular preference is given to straight-chain or branched C1-C12-alkyl radicals.
C3-C20Cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
A C1-C12The alkyl radical may 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-hexane, n-heptyl, n-octyl, n-decyl, n-dodecyl. In particular, R1Is methyl or isopropyl.
C6-C24Aryl is an aromatic radical having from 6 to 24 skeletal carbon atoms. As preferred monocyclic, bicyclic or tricyclic carbocyclic aryl groups containing from 6 to 10 skeletal carbon atoms, can be synthesized from benzene, biphenyl, naphthalene, phenanthrene, anthracene or anthracene.
In the general expression (A), the radical R2，R3，R4And R5Are identical or different and can be hydrogen, organic or inorganic radicals.
In one suitable embodiment, R2，R3，R4And R5Are the same or different and may each be hydrogen, halogen, nitro, CF3Alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxyCarbonyl, alkylamino, alkylthio, hydroxyethylaryl sulfide, alkylsulfonyl, or alkylsulfinyl, which substituents may be optionally substituted with one or more alkyl, alkoxy, halogen, aryl, or heteroaryl radicals.
R2，R3，R4And R5Are generally the same or different and may each be hydrogen, halogen, preferably chlorine or bromine, nitro, CF3、C1-C30Alkyl radical, C3-C20-alkynyloxy, C2-C20-alkenyl, C2-C20-alkynyl, C6-C24-aryl, C1-C20-alkoxy, C2-C20-alkenyloxy, C2-C20-alkynyloxy, C6-C24Aryloxy group, C2-C20-alkoxycarbonyl, C1-C20Alkylamino radical, C1-C20Alkylthio radical, C6-C24-arylthio group, C1-C20-alkylsulfonyl or C1-C20Alkylsulfinyl radicals, these substituents being able to be interrupted by one or more C1-C30Alkyl radical, C1-C20Alkoxy, halogen, C6-C24-aryl or heteroaryl is optionally substituted.
In one particularly useful embodiment, R2，R3，R4And R5Are identical or different and may each be nitro, straight-chain or branched C1-C30Alkyl radical, C5-C20-cylcopakyl, linear or branched C1-C20-alkoxy or C6-C24Aryl radicals, preferably phenyl or naphthyl. C1-C30Alkyl radicals and C1-C20The alkoxy radical may be interrupted by one or more double or triple bonds or one or more heteroatoms, preferably oxygen or nitrogen.
In addition, two or more radicals R2，R3，R4Or R5They may also be linked by aliphatic or aromatic structures. For example, R3、R4And the carbon atoms to which they are attached on the phenyl ring in the formula (B), may form a fused phenyl ring, and in general, a naphthyl structure is produced.
In the general expression (A), R6The radical is hydrogen or an alkyl, alkenyl, alkynyl or aryl radical. R6Preferably hydrogen, C1-C30Alkyl radicals, C2-C20-alkenyl radical, C2-C20-alkynyl radical or C6-C24-aryl radicals. R6Hydrogen is particularly preferred.
Most preferred are catalysts having the structure (IV) (so-called Hoveyda-Grubbs catalysts) wherein Mes represents mesityl.
The hydrogenation reaction of the present invention is carried out under a hydrogen pressure of 0.5 to 35MPa, preferably 3 to 10 MPa.
The above-described hydrogenation reaction of the present invention may be carried out in a suitable reactor equipped with a temperature regulator and a stirring device. According to the invention, the polymer latex can be fed to the reactor, optionally degassed, and the catalyst can then be added in pure raw material form or in some cases in solution with a small amount of organic solvent, and the reactor is then pressurized with hydrogen, or in an alternative embodiment the reactor can be pressurized with hydrogen and the catalyst can be added in pure raw material or solution. Alternatively, according to the invention, the catalyst can be introduced into the reactor in pure form, and the polymer latex can then be fed into the reactor and, if desired, degassed. The hydrogenation method of the invention does not use any catalyst auxiliary agent and is carried out in an aqueous medium without organic solvent.
According to the specific embodiment of the invention, the temperature of the hydrogenation reaction is 60-200 ℃, preferably 80-180 ℃, and more preferably 90-150 ℃.
According to a specific embodiment of the present invention, the time of the hydrogenation reaction in step (3) is 10 minutes to 24 hours, preferably 15 minutes to 20 hours, more preferably 30 minutes to 10 hours, and still more preferably 1 hour to 4 hours. Thus, the hydrogenated polymer of the present invention has a degree of hydrogenation of carbon-carbon double bonds of at least 50%, preferably from about 70 to 100%, more preferably from 80 to 100%, still more preferably from 90 to 100%, most preferably from 95 to 100%.
Preferably, the present invention can increase the hydrogenation efficiency to a hydrogenation degree of 99% in 1 hour by subjecting the conjugated diene latex to a hydrogenation reaction with hydrogen in an aqueous medium in the presence of a gemini surfactant and an osmium metal catalyst and/or a ruthenium metal catalyst. The hydrogenation efficiency far exceeds the hydrogenation rate of the prior diene-based emulsion, and can represent the most advanced hydrogenation technology at present.
According to the specific embodiment of the invention, in the step (3), the gemini surfactant is adopted to remarkably improve the hydrogenation reaction efficiency, so that the use amount of the osmium metal catalyst and/or the ruthenium metal catalyst can be greatly reduced, the catalyst cost is reduced, and the catalyst recovery rate can be improved. Specifically, in the hydrogenation reaction process, the gemini surfactant is obtained from the step A), namely, the hydrogenation reaction is carried out by directly using the mixture containing the gemini surfactant and the conjugated diene polymer obtained in the step A) as a raw material.
Therefore, the gemini surfactant may be used in an amount of 0.01 to 15% by weight, preferably 0.02 to 1% by weight, based on the total mass of the conjugated diene monomer and the copolymerizable monomer. And the amount of the catalyst is 0.01 to 5.0 wt%, preferably 0.02 to 2.0 wt%, based on the total mass of the contents of the solids in the conjugated diene latex. Therefore, the use amount of the catalyst is obviously reduced by adopting the gemini surfactant disclosed by the embodiment of the invention, so that the cost of the catalyst is reduced, and meanwhile, the recovery rate of the catalyst is indirectly improved.
Finally, when the hydrogenation reaction is complete to the desired extent, the reaction vessel may be cooled and vented. The hydrogenated latex obtained may be used in the form of a latex or coagulated and washed as necessary to obtain a hydrogenated polymer in a solid form.
According to a second aspect of the invention, the invention also proposes the use of a gemini surfactant in the preparation of a conjugated diolefin latex. The inventor finds that the gemini surfactant can effectively maintain the stability of an emulsion interface in the process of preparing the emulsion of the diene unsaturated polymer, and further remarkably improves the particle stability of the emulsion.
The conjugated diene latex is hydrogenated. By adopting the gemini surfactant, the osmium metal catalyst and/or the ruthenium metal catalyst which cannot be used for catalytic hydrogenation of the diene unsaturated rubber emulsion can be effectively used, and the osmium metal catalyst and/or the ruthenium metal catalyst have higher catalytic activity, so that the using amount of the catalyst is reduced. Furthermore, the gemini surfactant and the osmium metal catalyst and/or the ruthenium metal catalyst are adopted to carry out catalytic hydrogenation under the coaction, so that the selective hydrogenation of the conjugated diene rubber latex can be obviously improved under the condition of not using any organic solvent and cocatalyst, and the problem of gel is avoided, so that the cost is further reduced, the reaction condition is milder, and the method is more favorable for green chemical industry.
According to a third aspect of the present invention, the present invention also proposes the use of a gemini surfactant in combination with an osmium metal catalyst and/or a ruthenium metal catalyst for the preparation of hydrogenated diene-based nanoemulsions. Therefore, the gemini surfactant is adopted, and is compatible with the osmium metal catalyst and/or the ruthenium metal catalyst, so that the hydrogenation can be effectively catalyzed, the hydrogenation rate is greatly accelerated, the use amount of the catalyst is greatly reduced through the gemini surfactant, and the cost is further reduced. Moreover, the gemini surfactant is adopted for hydrogenation reaction, any cocatalyst and organic solvent are not used, the reaction condition is milder, the industrial cost is reduced, and the method is beneficial to green chemical industry.
Therefore, the method for preparing a conjugated diene rubber latex according to the above embodiment of the present invention can not only prepare diene rubber emulsions having different solid content contents, but also significantly improve the hydrogenation reaction efficiency. The preparation method of the embodiment of the invention can reach the hydrogenation rate of 99% in 2 hours, does not produce gel, and can represent the most advanced hydrogenation technology at present. The solid content of the hydrogenated emulsion can reach more than 45 percent, and the hydrogenated emulsion can be directly applied to various fields of coatings, water-based paints, dipped products, paper, fiber treatment and the like.
In addition, the hydrogenated emulsion has excellent cold and hot stability. Under the condition of filling steam for heating, the emulsion is kept stable after heating for 24 hours. And (3) placing the hydrogenated emulsion into liquid nitrogen, quickly freezing, then recovering the liquid state at room temperature, and repeating the operation for 3 times to keep the emulsion stable. The emulsion can be stored at room temperature and can be kept for one year without demulsification.
According to the invention, the mass of the osmium metal and/or ruthenium metal catalyst is 0.011 to 5.0 wt% based on the solid content of the selectively hydrogenated conjugated diene rubber latex.
The invention provides a preparation method of conjugated diene rubber latex capable of being selectively hydrogenated, which comprises the following steps: A) carrying out polymerization reaction on a conjugated diene monomer and a comonomer in the presence of a gemini surfactant and a polymerization initiator to obtain a conjugated diene polymer emulsion; B) and distilling the conjugated diene latex under reduced pressure to remove unreacted monomers to obtain the selectively hydrogenated conjugated diene latex. The conjugated diene latex prepared by the method can be directly used for selective hydrogenation reaction of osmium metal and/or ruthenium metal catalysts, and hydrogenation is only carried out on residual double bonds of conjugated diene. The conjugated diene latex prepared by the method can be subjected to catalytic hydrogenation under the combined action of an osmium metal catalyst and/or a ruthenium metal catalyst, residual double bonds of the conjugated diene can be selectively hydrogenated under the condition of not using any organic solvent and cocatalyst, functional group double bonds in a comonomer are not influenced, no gel problem exists, and the cold and hot stability of the hydrogenated emulsion is particularly high.
To further illustrate the present invention, the following examples are provided to describe in detail a selectively hydrogenatable conjugated diene latex, a method for preparing the same, and a method for preparing an emulsion of a diene-based unsaturated polymer. All parts and percentages are by weight. The raw materials used in the examples are as follows:
Figure BDA0002859643750000231
Figure BDA0002859643750000241
example 1
NBR preparation
5 parts of gemini surfactant C12H25N+(CH3)2-(CH2)n-N+(CH3)2C12H25 2Br–(n-3-8) and 200 parts of water were placed in a 1000mL stainless steel autoclave (Parr Instruments) equipped with a stirrer, a feed tank, an internal cooling coil and a thermostatic water bath, cooled to 10 ℃ and purged with nitrogen to remove oxygen. 35 parts of acrylonitrile, 65 parts of butadiene and 0.6 part of tert-butyl mercaptan are added and stirred for 1 hour. Adding 0.02 part of redox system activator solution into a charging tank, wherein the redox initiator solution comprises 1.5 parts of ferrous sulfate, 3 parts of EDTA, 4 parts of sodium formaldehyde sulfoxylate and 91.5 parts of pure water; a redox initiator solution and 0.03 part of cumene hydroperoxide suspension are added. Stirring and reacting for 7 hours at the temperature of 5 ℃, adding 1 part of diethylhydroxylamine serving as a terminator after the reaction is finished, and removing unreacted monomers in vacuum by a rotary evaporator. The monomer conversion was 71% and the resulting emulsion had a solids content of 25%. Molecular structure was characterized using FT-IR, 1 HNMR.
Hydrogenation operation
A300 mL stainless steel high pressure reactor (Parr Instruments) with a temperature control device, a stirrer, and a hydrogen addition valve was used. The NBR emulsion obtained in the previous step was used. 50ml of this latex (containing gemini surfactant C) was charged into a reactor12H25N+(CH3)2-(CH2)n-N+(CH3)2C12H25 2Br–(n-3-8)), 50ml of water, 25mg of Hoveyda-Grubbs' second generation catalyst, and then removing oxygen from the system with nitrogen. The temperature was raised to 100 ℃ and the hydrogen pressure was increased to 1000psi (6.89 MPa). After the reaction is finished, the hydrogenated NBR latex is coagulated with ethanolAn HNBR copolymer is obtained. The coagulum was then dissolved in MEK for analysis of the degree of hydrogenation. The degree of hydrogenation was measured using an FT-IR instrument.
The results show that after 1 hour, the degree of hydrogenation reached 99%. No gel was produced and the resulting polymer was soluble in methyl ethyl ketone.
Example 2
NBR preparation
The conditions and procedure were the same as described in example 1, except that a peroxide initiator system was used. The peroxide was 0.5 part of KPS instead of the redox system activator and initiator solution of example 1. The reaction temperature was 50 ℃, the 4-hour monomer conversion was 58%, and the latex solids content was 22%.
Hydrogenation operation
The hydrogenation procedure was identical to that of example 1, with 22mg of the Hoveyda-Grubbs secondary catalyst, and the results were identical.
Example 3
NBR preparation
The conditions and procedure were the same as described in example 1, except that the monomer addition was reduced to 7 parts acrylonitrile, 13 parts butadiene concentration, 200 parts water, and the remaining additive make-up monomer amount was reduced proportionally. The 7 hour monomer conversion was 69% and the latex solids content was 6%.
Hydrogenation operation
The hydrogenation operation was identical to that of example 1, except that 100ml of the emulsion was added, no water was added, and 12mg of Hoveyda-Grubbs secondary catalyst was added, and it was shown that the degree of hydrogenation reached 99% after 1 hour. No gel was produced and the resulting polymer was soluble in methyl ethyl ketone.
Example 4
NBR preparation
The conditions and procedure were the same as described in example 2, except that the monomer addition was reduced to 7 parts acrylonitrile, 13 parts butadiene concentration, 200 parts water, and the remaining additive make-up monomer amount was reduced proportionally. The 4.5 hour monomer conversion was 56% and the latex solids content was 6%.
Hydrogenation operation
The hydrogenation operation was identical to that of example 2, except that 100ml of the emulsion was added, no water was added, and 12mg of Hoveyda-Grubbs secondary catalyst was added, and it was shown that the degree of hydrogenation reached 99% after 1 hour. No gel was produced and the resulting polymer was soluble in methyl ethyl ketone.
Example 5
NBR preparation
The conditions and procedure were the same as described in example 1, except that the monomer addition was 15 parts of acrylonitrile, 85 parts of butadiene concentration. The 7 hour monomer conversion was 66% and the latex solids content was 24%.
Hydrogenation operation
The hydrogenation operation was identical to that of example 1, with the addition of 24mg of Hoveyda-Grubbs' secondary catalyst, and it was shown that after 2 hours, the degree of hydrogenation reached 99%. No gel was produced and the resulting polymer was soluble in methyl ethyl ketone.
Example 6
NBR preparation
The conditions and procedure were the same as described in example 2, except that the monomer addition was 15 parts of acrylonitrile, 85 parts of butadiene concentration. The 4 hour monomer conversion was 61% and the latex solids content was 23%.
Hydrogenation operation
The hydrogenation operation was identical to that of example 1, with the addition of 23mg of Hoveyda-Grubbs' secondary catalyst, and it was found that the degree of hydrogenation reached 99% after 2.5 hours. No gel was produced and the resulting polymer was soluble in methyl ethyl ketone.
Example 7
NBR preparation
The conditions and procedure were the same as described in example 1, with a monomer conversion of 69%. Except that after removal of the monomers, the latex was further concentrated using distillation under reduced pressure to a solid content of 45.8%.
Hydrogenation operation
The hydrogenation operation was identical to that of example 1, except that 100ml of latex were added, no water was added and 50mg of Hoveyda-Grubbs secondary catalyst were added. The results show that after 4 hours, the degree of hydrogenation reached 99%. No gel was produced and the resulting polymer was soluble in methyl ethyl ketone. .
Example 8
NBR preparation
The conditions and procedure were the same as described in example 1, with the difference that gemini surfactant C was used12H25N+(CH3)2-(CH2)2-O-(CH2)2-N+(CH3)2C12H25·2Cl–. The monomer conversion was 68% and the resulting emulsion had a solids content of 26%.
Hydrogenation operation
The hydrogenation operation was identical to that in example 1, and the results were identical.
Example 9
NBR preparation
The conditions and procedures were the same as described in example 1. The monomer conversion was 68% and the resulting emulsion had a solids content of 25%.
Hydrogenation operation
The hydrogenation operation was identical to that of example 1, except that 25mg of Grubbs's third-generation catalyst was used, and the results showed that the degree of hydrogenation reached 99% after 3 hours. No gel was produced and the resulting polymer was soluble in methyl ethyl ketone.
Example 10
NBR preparation
The conditions and procedures were the same as described in example 1. The monomer conversion was 70% and the resulting emulsion had a solids content of 25%.
Hydrogenation operation
The hydrogenation operation was identical to that of example 1, except that 25mg of Grubbs's secondary catalyst was used, and the results showed that the degree of hydrogenation reached 99% after 3 hours. No gel was produced and the resulting polymer was soluble in methyl ethyl ketone.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (11)

1. A preparation method of a conjugated diene latex capable of being selectively hydrogenated is characterized by comprising the following steps:
A) carrying out polymerization reaction on a conjugated diene monomer and a comonomer in the presence of a gemini surfactant and a polymerization initiator to obtain a conjugated diene polymer emulsion;
B) and distilling the conjugated diene latex under reduced pressure to remove unreacted monomers to obtain the selectively hydrogenated conjugated diene latex.
2. The method of claim 1, wherein the conjugated diene monomer is a conjugated diene of C4 to C6; preferably, the conjugated diene monomer is at least one selected from the group consisting of 1, 3-butadiene, isoprene, 1-methylbutadiene, 2, 3-dimethylbutadiene, piperylene and chloroprene.
3. The preparation method according to claim 1, wherein the comonomer is selected from one or more of acrylonitrile, methacrylonitrile, styrene, alpha-methyl styrene, propyl acrylate, butyl acrylate, propyl methacrylate, butyl methacrylate or unsaturated carboxylic acid;
the polymerization initiator is selected from one or more of potassium persulfate, ammonium persulfate, dialkyl peroxide, azo compounds or alkyl hydroperoxide.
4. The preparation method according to claim 1, wherein the gemini surfactant is one or more selected from the group consisting of cationic gemini surfactants, anionic gemini surfactants, nonionic gemini surfactants and asymmetric gemini surfactants.
5. The preparation method according to claim 4, wherein the anionic gemini surfactant is selected from one or more of a phosphate type, a sulfonate type, a carboxylate type and a sulfate type;
the cationic gemini surfactant has a structure shown in a formula (I):
Figure FDA0002859643740000011
wherein, A1: R1＝R2＝CmH2m+1；Y＝CH2；
A2:R1＝R2＝CmH2m+1；Y＝CH2,O,S,N(CH3),x＝y＝2；
A2:R1＝R2＝CmH2m+1；Y＝CHOH,(CHOH)2；x＝y＝1；
A3:R1＝R2＝CmH2m+1；Y＝(OCH2CH2) z, x is 2; y is 0; z is any integer;
A4:R1＝R2＝CmH2m+1；Y＝C≡C；x＝y＝1；
A5:R1＝R2＝CmH2m+1(ii) a Y ═ phenylene; x-y-1;
A6:R1＝R2＝CmH2m+1OC(O)CH2(ii) a Does not contain Y; x-y-1;
A7:R1＝R2＝CmF2mC4H8(ii) a Does not contain Y; x-y-1;
A8:R1＝CmH2m+1；R2＝CnH2n+1(ii) a m is not equal to n and does not contain Y; x-y-1;
wherein in A1-A8, m, n and z are each independently 1-60,
br-may be replaced by any other anion, preferably F-, Cl-, I-, At-, Ts-in the elements of group VIIA of the periodic System.
6. The method of claim 5, wherein the gemini surfactant is selected from at least one of the following:
C12H25N+(CH3)2-(CH2)n-N+(CH3)2C12H252Br–(n＝3–8)、
C12H25N+(CH3)2-(CH2)16-N+(CH3)2C12H252Br–、
C16H33N+(CH3)2-(CH2)2-N+(CH3)2C16H332Br–、
C8H17N+(CH3)2-(CH2)3-N+(CH3)2C8H172Br–、
C12H25N+(CH3)2-(CH2)2-O-(CH2)2-N+(CH3)2C12H252Cl–、
C16H33N+(CH3)2-(CH2)5-N+(CH3)2C16H332Br–、
C16H33N+(CH3)2-(CH2)2-O-(CH2)2-N+(CH3)2C16H332Br–、
C16H33N+(CH3)2-CH2-(CH2-O-CH2)3-CH2-N+(CH3)2C16H332Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2C12H252Br–、
C12H25N+(CH3)2-CH2-C6H4-CH2-N+(CH3)2C12H252Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH(OH)-CH2-N+(CH3)2C12H252Br–、
C12H25N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2-CH2-CH(OH)-CH2-N+(CH3)2C12H253Cl–、
C12H25OPO2 –-O-(CH2)6-OPO2 –-OC12H252Na+、
C10H21O-CH2-CH(OSO3 –)-CH2-O-(CH2)2-O-CH2-CH(OSO3 –)-CH2-OC10H212Na+。
7. the preparation method according to claim 1, wherein the temperature of the reduced pressure distillation is 20-80 ℃;
the solid content of the selectively hydrogenated conjugated diene rubber latex is 1-60 wt%;
the gemini surfactant accounts for 0.01-10 wt% of the total mass of the conjugated diene monomer and the copolymerizable monomer;
the polymerization initiator accounts for 0.01-5 wt% of the total mass of the conjugated diene monomer and the copolymerizable monomer;
the polymerization reaction temperature of the conjugated diene monomer and the comonomer is 0-100 ℃; the time is 0.25 to 100 hours.
8. A conjugated diene latex capable of being selectively hydrogenated, which is obtained by the production method according to any one of claims 1 to 7.
9. A method for preparing an emulsion of a diene-based backbone saturated polymer, comprising:
the conjugated diene rubber latex capable of being selectively hydrogenated, which is prepared by the preparation method of any one of claims 1 to 7, is obtained by hydrogenation reaction under the action of an osmium metal and/or ruthenium metal catalyst and a gemini surfactant.
10. The method of claim 9, wherein the osmium or ruthenium metal catalyst has the formula:
Figure FDA0002859643740000031
wherein M is osmium or ruthenium,
X1and X2Are the same or different anionic ligands and are,
l is a ligand, preferably an uncharged electron donor,
y is O, S, N-R1Or P-R1The free radical(s) is (are),
R1is alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonate or alkylsulfinyl, optionally, each R above1May be optionally substituted with one or more alkyl, halo, alkoxy, aryl or heteroaryl groups,
R2、R3、R4and R5Are identical or different hydrogen radicals, organic radicals or inorganic radicals,
R6is hydrogen, alkyl, alkenyl, alkynyl or aryl.
11. The method according to claim 9, wherein the temperature of the hydrogenation reaction is 60 to 200 ℃; the time is 10min to 24 hours; the hydrogenation reaction pressure is 0.5-35 Mpa;
the mass of the osmium metal and/or ruthenium metal catalyst is 0.011 to 5.0 wt% based on the solid content of the selectively hydrogenatable conjugated diene rubber latex.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN110540617A (en) * 2018-05-28 2019-12-06 王辉 Method for preparing hydrogenated diene based nanoemulsions and use of gemini surfactants
CN110540609A (en) * 2018-05-28 2019-12-06 王辉 Method for preparing hydrogenated diene based nanoemulsions and use of gemini surfactants
CN110540608A (en) * 2018-05-28 2019-12-06 王辉 Method for preparing hydrogenated diene based nanoemulsions and use of gemini surfactants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110540617A (en) * 2018-05-28 2019-12-06 王辉 Method for preparing hydrogenated diene based nanoemulsions and use of gemini surfactants
CN110540609A (en) * 2018-05-28 2019-12-06 王辉 Method for preparing hydrogenated diene based nanoemulsions and use of gemini surfactants
CN110540608A (en) * 2018-05-28 2019-12-06 王辉 Method for preparing hydrogenated diene based nanoemulsions and use of gemini surfactants

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