WO2003080681A1 - Latex polymere a base de diene conjugue hydrogene et procede de production de celui-ci, et caoutchouc polymere a base de diene conjugue hydrogene - Google Patents

Latex polymere a base de diene conjugue hydrogene et procede de production de celui-ci, et caoutchouc polymere a base de diene conjugue hydrogene Download PDF

Info

Publication number
WO2003080681A1
WO2003080681A1 PCT/JP2003/003718 JP0303718W WO03080681A1 WO 2003080681 A1 WO2003080681 A1 WO 2003080681A1 JP 0303718 W JP0303718 W JP 0303718W WO 03080681 A1 WO03080681 A1 WO 03080681A1
Authority
WO
WIPO (PCT)
Prior art keywords
latex
polymer
hydrogenated
based polymer
platinum group
Prior art date
Application number
PCT/JP2003/003718
Other languages
English (en)
Japanese (ja)
Inventor
Takafumi Kawanaka
Kozo Mitani
Kiyomori Ooura
Kazuhiro Takahashi
Tatsuo Usui
Original Assignee
Zeon Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002201609A external-priority patent/JP4123848B2/ja
Priority claimed from JP2002209156A external-priority patent/JP4123852B2/ja
Application filed by Zeon Corporation filed Critical Zeon Corporation
Publication of WO2003080681A1 publication Critical patent/WO2003080681A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
    • C08C1/04—Purifying; Deproteinising
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C2/00—Treatment of rubber solutions
    • C08C2/02—Purification
    • C08C2/04—Removal of catalyst residues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium

Definitions

  • the present invention relates to a hydrogenated conjugated polymer latex, a method for producing the same, and a hydrogenated conjugated polymer rubber.
  • the hydrogenated conjugated polymer latex of the present invention is characterized in that the amount of residual hydrogenation catalyst contained in the hydrogenated conjugated polymer constituting the latex is extremely low.
  • a useful means of modifying conjugated polymers is to selectively or partially hydrogenate carbon-carbon unsaturated bonds of the polymer, such as hydrogenated acrylonitrile butadiene copolymer. Is often adopted. Hydrogenated conjugated polymer rubbers are used in a wide range of industrial applications because of their excellent properties such as oil resistance, weather resistance, ozone resistance, heat resistance, and cold resistance.
  • the raw material polymer once recovered from the latex of the conjugated gen-based polymer was pulverized with a crusher or the like and dissolved again in an organic solvent.
  • the organic solvent used in the hydrogenation reaction was distilled off after the reaction. It requires complicated operations such as squatting, and it is hard to say that it is too roundabout and efficient.
  • the process J cannot directly produce a hydrogenated polymer in such a state.
  • Still another object is to provide a simplified method for producing a hydrogenated conjugated polymer latex in which the carbon-carbon unsaturated bond of the conjugated polymer is hydrogenated in the form of a latex.
  • An object of the present invention is to provide a method for producing a hydrogenated conjugated polymer latex which is easy to separate and is industrially advantageous.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, dissolve or disperse a hydrogenation catalyst containing a platinum group element compound in a conjugated gen-based polymer latex.
  • the carbon-carbon unsaturated bond is hydrogenated, and the precipitate formed by adding a complexing agent that forms a water-insoluble complex with the platinum group element to the resulting hydrogenated polymer latex is then filtered, for example. It has been found that by separation by means, a hydrogenated conjugated polymer latex containing a small amount of metal derived from the hydrogenation catalyst can be produced extremely efficiently.
  • the improved method as described above has the following problems. (1) Since the unsupported catalyst dissolved or dispersed in the latex, the catalyst for the conjugated gen-based polymer in the latex can be used. (2) Since the used hydrogenation catalyst can be easily recovered and reused, there is a problem in economical efficiency even if a large amount of catalyst is used. (3) The present invention has been completed by confirming that it has the following advantages: (3) the amount of residual catalyst in the obtained latex is extremely small, so there is no adverse effect on the quality of latex products or rubber products; I came to.
  • a latex of a hydrogenated conjugated gen-based polymer having a content of a platinum group element per polymer of 100 ppm or less is provided.
  • a hydrogenated conjugated gen-based polymer rubber having a platinum group element content of 100 ppm or less which is obtained by separating from the above latex.
  • a hydrogenation catalyst containing a platinum group element compound is dissolved or dispersed in a latex of a conjugated gen-based polymer to hydrogenate carbon-carbon unsaturated bonds of the polymer, and then to form A method for producing a hydrogenated conjugated polymer-based latex, comprising separating a precipitate formed by adding a complexing agent that forms a water-insoluble complex with a platinum group element to a hydrogenated polymer latex.
  • FIG. 1 is a cross-sectional view showing an example of a part of a filter of a filtration device for separating a precipitate formed by adding a complexing agent to a latex of a hydrogenated polymer.
  • the latex of the hydrogenated conjugated diene polymer of the present invention is characterized in that the content of the platinum group element per polymer is 100 ppm or less.
  • the content of the platinum group element per polymer is preferably 80 ppm or less, more preferably 50 ppm or less.
  • the hydrogenated conjugated gen-based polymer rubber of the present invention is a rubber obtained by separation from the latex, wherein the content of the platinum group element per polymer rubber is 100 ppm. It is characterized by the following.
  • the content of the platinum group element per polymer rubber is preferably at most 80 ppm, more preferably at most 50 ppm.
  • the hydrogenated conjugated polymer rubber and latex of the present invention in which the content of the platinum group element derived from the hydrogenation catalyst is extremely low as described above does not have any quality problems such as coloring.
  • a hydrogenated conjugated polymer rubber having a content per polymer rubber of about 5 ppm or less is produced industrially advantageously. It is difficult to do.
  • the weight average molecular weight (gel permeation 'chromatography method, standard polystyrene conversion) of the hydrogenated conjugated gen-based polymer constituting the latex is not particularly limited, but is usually 50,000 to 500,000. Range.
  • the solid content concentration of the conjugated polymer latex as described above is not particularly limited, but is usually 2 to 70% by weight, preferably 5 to 60% by weight.
  • the solid concentration can be appropriately adjusted by a known method such as a blending method, a dilution method, and a concentration method.
  • the latex containing the hydrogenated conjugated polymer having a reduced platinum group element content as described above is useful as an adhesive, a coating agent, a paint, a raw material for dip-formed gloves, and the like.
  • the latex of the hydrogenated conjugated polymer of the present invention is obtained by dissolving or dispersing a hydrogenation catalyst containing a platinum group element compound in a conjugated polymer polymer latex to form a carbon-carbon unsaturated bond of the polymer. Is hydrogenated, and then a precipitate formed by adding a complexing agent that forms a water-insoluble complex with a platinum group element to the latex of the hydrogenated polymer to be produced is produced.
  • the latex of a conjugated gen-based polymer to which the present method can be applied is a latex composed of a homopolymer or a copolymer of a conjugated gen monomer, and one or more conjugated gen monomers or a conjugated gen monomer It is produced by a conventionally known emulsion polymerization method by combining at least one kind of monomer copolymerizable with ⁇ and at least one kind of conjugated monomer.
  • the conjugated diene monomer is not particularly limited as long as it is a polymerizable monomer having a conjugated diene structure.
  • Monomers copolymerizable with the conjugated diene monomer include, for example, ⁇ , ⁇ —: L thylene unsaturated monotriles such as acrylonitrile, methacrylonitrile, crotonditrile, and vinylidene cyanide.
  • ⁇ , 8-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid and itaconic acid; methyl acrylate, ⁇ -butyl acrylate, 2-ethylhexyl acrylate, Q !, such as trifluoroethyl acrylate, methyl methacrylate and methyl crotonate; ethylenically unsaturated carboxylic acid esters; ⁇ , 8-ethylenically unsaturated carboxylic acid amides such as acrylamide and methacrylamide; Styrene, vinyl acetate such as methylstyrene, p-methylstyrene, divinylbenzene, vinylpyridine Aromatic compounds; vinyl ether compounds such as full old Roe chill ethers; vinyl acetate, vinyl ester le such as propylene Sainsan vinyl and like et be.
  • carboxylic acids such as acrylic acid
  • monomers having an electron-withdrawing functional group are preferable from the viewpoint that the hydrogenation reaction in the present invention proceeds slowly, and ⁇ , monoethylenically unsaturated ditrimethyl monomers are preferred.
  • acrylonitrile is preferably used.
  • a preferred conjugated diene polymer is a copolymer of a conjugated diene monomer and an ⁇ , / 3-ethylenically unsaturated nitrile monomer, in particular, 1,3-butadiene 30 to 95% by weight More preferably, it is a copolymer of 45 to 85% by weight and acrylonitrile of 5 to 70% by weight, more preferably 15 to 55% by weight.
  • Emulsion polymerization is generally performed in an aqueous medium using a radical polymerization initiator.
  • Known polymerization initiators may be used.
  • the polymerization reaction may be a batch system, a semi-batch system, or a continuous system, and the polymerization temperature and pressure are not particularly limited.
  • the emulsifier to be used is also not particularly limited, and may be an anionic surfactant, a surfactant, an amphoteric surfactant, Nonionic surfactants and the like can be used, but anionic surfactants are preferred. These emulsifiers may be used alone or in combination of two or more. The amount used is not particularly limited.
  • the monomer composition ratio in the conjugated gen-based polymer is not particularly limited, it is usually 5 to 100% by weight of the conjugated gen monomer and 95 to 0% by weight of a monomer copolymerizable therewith. It is preferably 10 to 90% by weight of a conjugated diene monomer and 90 to 10% by weight of a monomer copolymerizable therewith.
  • the hydrogenation catalyst used in the production method of the present invention is a water-soluble or water-dispersible compound of a platinum group element (ruthenium, rhodium, palladium, osmium, iridium, platinum). Such a hydrogenation catalyst is dissolved or dispersed in the above-mentioned latex without being supported on a carrier and subjected to a hydrogenation reaction.
  • a platinum group element ruthenium, rhodium, palladium, osmium, iridium, platinum.
  • platinum group element ruthenium, rhodium, palladium, osmium, iridium, platinum.
  • the palladium compound is not particularly limited as long as it is water-soluble or water-dispersible, preferably water-soluble, and has hydrogenation catalytic activity.
  • a palladium compound having a valence of II or IV is used, and its form is a salt / complex.
  • the palladium compound examples include organic acid salts such as palladium acetate and palladium cyanide; halides such as palladium fluoride, palladium chloride, palladium bromide, and palladium iodide; oxyacid salts such as palladium nitrate and palladium sulfate; Palladium oxide; Palladium hydroxide; Palladium compounds such as dichloro (cyclopentadiene) palladium, dichloro (norbornadiene) palladium, dichlorobis (triphenylphosphine) palladium, sodium palladium tetradecarate, ammonium hexahexaparadiadate; tetra Complex salts such as potassium cyanopalladate; and the like.
  • organic acid salts such as palladium acetate and palladium cyanide
  • halides such as palladium fluoride, palladium chloride, palladium bromide, and palladium io
  • palladium acetate, palladium nitrate, palladium sulfate, palladium chloride, sodium tetrachloropalladium, and ammonium hexachloropalladate are preferred, and palladium acetate, palladium nitrate and palladium chloride are more preferred.
  • Rhodium compounds include halides such as rhodium chloride, rhodium bromide and rhodium iodide; inorganic acid salts such as rhodium nitrate and rhodium sulfate; rhodium acetate, rhodium formate, rhodium propionate, rhodium butyrate, rhodium valerate, Organic acid salts such as rhodium naphthenate and rhodium acetylacetonate; rhodium oxide; rhodium trihydroxide; and the like.
  • Such a compound of the platinum group element can be obtained from a commercially available product, or can be used after being prepared by a known method.
  • the method of dissolving or dispersing the compound of the platinum group element in the latex is not particularly limited, and examples thereof include a method of directly adding the compound to the latex and a method of dissolving or dispersing the compound in water. .
  • inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, bromic acid, perchloric acid, and phosphoric acid
  • organic acids such as acetic acid
  • the solubility in water is improved, which may be preferable.
  • the hydrogenation catalyst is dissolved or dispersed in the conjugated polymer latex, and the hydrogenation reaction in the latex state is efficiently performed. Let it proceed.
  • the hydrogenation reaction is performed under basic conditions, the reaction efficiency is further improved and the amount of catalyst used can be reduced.
  • Such basic conditions are not particularly limited as long as the pH of the hydrogenation reaction solution (latex) measured by a pH meter is more than 7, and is preferably 7.2 to 13 and more preferably. Is in the range of 7.5 to 12.5, more preferably 8.0 to 12.
  • the basic compound for making the hydrogenation reaction solution basic is not particularly limited, and examples thereof include an alkali metal compound, an alkaline earth metal compound, ammonia, ammonium chloride, and an organic amine compound. Preferably, they are an alkali metal compound and an alkaline earth metal compound.
  • alkali metal compound examples include hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonate compounds such as lithium carbonate, sodium carbonate, and potassium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, and hydrogen carbonate power.
  • Bicarbonate compounds such as lithium; oxides such as lithium oxide, potassium oxide and sodium oxide; organic acid salt compounds such as potassium acetate and sodium acetate; lithium methoxide, lithium ethoxide, sodium methoxide; Sodium ethoxide, Alkoxides such as potassium tert-butoxide; phenoxides such as sodium phenoxide and potassium phenoxide; and the like.
  • alkali metal hydroxides, carbonate compounds and bicarbonate compounds and more preferred are hydroxides.
  • alkaline earth metal compound examples include hydroxides, carbonate compounds, hydrogen carbonate compounds, oxides, organic acid salt compounds, alkoxides of alkaline earth metals such as magnesium, calcium, strontium, and barium. Phenoxides and the like. Preferred are hydroxides, carbonate compounds, and hydrogen carbonate compounds of alkaline earth metals, and more preferred are hydroxides.
  • ammonium salt compound examples include ammonium carbonate and ammonium hydrogen carbonate.
  • organic amine compound examples include aliphatic, alicyclic, and aromatic mono- and polyamino compounds, such as triethylamine, ethanolamine, morpholine, N-methylmorpholine, pyridine, hexamethylenediamine, and dodecamethylenediamine. And xylylenediamine.
  • These basic compounds can be used as they are, or can be used by diluting or dissolving with an organic solvent such as water or alcohol.
  • the basic compounds may be used alone or in combination of two or more, and the amount used may be appropriately selected so that the hydrogenation reaction solution exhibits basicity.
  • the method and timing of adding the basic compound to the hydrogenation reaction solution are not particularly limited.For example, before adding the hydrogenation catalyst to the hydrogenation reaction solution, the basic compound is added to the latex in advance. And a method of adding a basic compound after the start of the hydrogenation reaction.
  • the latex is preferably soluble or dispersible in the latex and has a weight average molecular weight of preferably from 1,000 to 100.
  • a polymer compound having a molecular weight of 0.000 can be used.
  • Hydrogenation catalyst stabilizers are soluble or dispersible in latex (meaning that they are in a stable dispersed state such as colloidal form), and are aggregated in latex. Any material can be used as long as it can maintain the hydrogenation catalyst in a dissolved or dispersed state without causing leaching.
  • Specific examples of the hydrogenation catalyst stabilizer include polymers of a vinyl compound having a polar group in a side chain such as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal, and polyalkyl vinyl ether; sodium polyacrylate, and polyacrylic acid.
  • Metal salts of polyacrylic acid such as realm; polyethers such as polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer; cellulose derivatives such as carboxymethylcellulose and hydroxypropylcellulose; gelatin, albumin And natural polymers; and the like.
  • polyethers such as polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer
  • cellulose derivatives such as carboxymethylcellulose and hydroxypropylcellulose
  • gelatin, albumin And natural polymers and the like.
  • a polymer or polyether of a vinyl compound having a polar group in a side chain is preferable.
  • polymers of a vinyl compound having a polar group in the side chain polyvinyl pyrrolidone and polyalkyl vinyl ether are particularly preferred.
  • the molecular weight of these polymer compounds is represented by the following formula: weight average molecular weight (M w), ⁇ , 0000 to 100, 000, preferably 2, 000 to 500, 000. It is.
  • Mw weight average molecular weight
  • ⁇ weight average molecular weight
  • the hydrogenation catalyst stabilizer can be dissolved or dispersed in latex together with the hydrogenation catalyst and used for the hydrogenation reaction.
  • the concentration of the hydrogenation catalyst stabilizer in the latex is preferably 0.5 to 20 times, more preferably 1 to 10 times, the weight of the metal element in the hydrogenation catalyst. .
  • the hydrogenation catalyst stabilizer of the present invention can be dissolved or dispersed in water or an organic solvent together with the hydrogenation catalyst, prepared in advance as a hydrogenation catalyst solution, and supplied to the hydrogenation reaction.
  • the catalyst solution is an aqueous solution, for example, an inorganic acid such as nitric acid, sulfuric acid, hydrochloric acid, bromic acid, perchloric acid, or phosphoric acid; a metal salt such as a sodium salt or a potassium salt of such an inorganic acid; an organic acid such as acetic acid An acid; etc., which may increase the solubility of the hydrogenation catalyst in water.
  • the concentration of the acid in the aqueous catalyst solution is preferably 1 to 20 times, more preferably 1 to 10 times the molar amount of the metal element in the hydrogenation catalyst.
  • the method for preparing the catalyst aqueous solution includes a step of preparing an acidic aqueous solution of the hydrogenation catalyst. Next, it is preferable to include a step of adding the hydrogenation catalyst stabilizer of the present invention to the aqueous solution.
  • the catalyst aqueous solution does not cause aggregation or precipitation of the hydrogenation catalyst even after standing at 25 ° C for 1 hour or more, preferably 1 day or more, more preferably 14 days or more.
  • the temperature of the hydrogenation reaction is usually 0 to 200, preferably 5 ° C to 150 ° C, more preferably 10 ° to 100 ° C. An excessively high reaction temperature is not desirable because side reactions such as hydrogenation of a nitrile group may occur. On the other hand, if the reaction temperature is too low, the reaction rate is reduced, which is not practical.
  • the pressure of the hydrogen is usually from atmospheric pressure to 20 MPa, preferably from atmospheric pressure to 15 MPa, more preferably from atmospheric pressure to 10 MPa.
  • the reaction time is not particularly limited, but is usually 30 minutes to 50 hours.
  • the hydrogenation reaction proceeds rapidly despite the reaction in the latex state.
  • the hydrogenation rate (the ratio of hydrogenated carbon-carbon double bonds to the total number of carbon-carbon double bonds present in the polymer before the reaction) of the obtained hydrogenated conjugated polymer is determined by the above-mentioned various types. By appropriately changing the reaction conditions, it can be arbitrarily controlled in the range of 1 to 100%.
  • the hydrogenation rate expressed as iodine value, is preferably less than 120.
  • the greatest feature of the method for producing a conjugated gen-based polymer latex according to the present invention is that a platinum group element present in an aqueous medium and a polymer particle of the latex after completion of the hydrogenation reaction is replaced with a platinum group element. It is a post-treatment and recovery of a catalyst that uses a complex forming ability to precipitate in a latex in a separable shape larger than polymer particles or to separate by precipitation and aggregation. That is, it is essential to separate a precipitate formed in the latex by hydrogenating the conjugated gen-based polymer in a latex state and then adding a complexing agent that forms a water-insoluble complex with the platinum group element.
  • a complexing agent treatment the hydrogenation catalyst can be efficiently separated.
  • an oxidizing agent is added to the reaction mixture containing the hydrogenated polymer, and the catalyst (catalyst residue) contained in the reaction mixture is contacted with the oxidizing agent.
  • the catalyst in the system after the completion of the hydrogenation reaction is in a reduced state, and is oxidized by bringing it into contact with an oxidizing agent.
  • the oxidation treatment allows the hydrogenation catalyst to be separated more efficiently.
  • the oxidizing agent is not particularly limited as long as it has catalytic oxidizing ability, and examples thereof include air (oxygen); and peroxides such as hydrogen peroxide, peracetic acid, and perbenzoic acid; and the like. Air, hydrogen peroxide, more preferably hydrogen peroxide.
  • the use amount of these oxidizing agents is not particularly limited, and is 1 to 100 times, preferably 3 to 50 times the mol of the platinum group element contained in the catalyst used for the hydrogenation reaction.
  • the contact temperature is usually 0 to 100 ° C, preferably 50 to 95 ° C, and more preferably 70 to 90 ° C.
  • the contact time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours.
  • the method of contact between the catalyst and the oxidizing agent is not uniform depending on the type of the oxidizing agent.
  • a method of continuously blowing air into the reaction mixture in an open state a method of continuously blowing air into the reaction mixture in an open state; open or closed
  • a method in which the atmosphere of the gaseous part of the reaction mixture container in the state is air, and the reaction mixture is stirred.
  • hydrogen peroxide it may be added to the reaction mixture and stirred.
  • a complexing agent is added in the form of a powder or a solution, with or without the above-mentioned oxidizing agent treatment.
  • the complexing agent is brought into contact with the platinum group element to form a complex, which is deposited in the latex and grown or aggregated to a particle size larger than the polymer particles. It is preferable to take the steps of standing still and cooling.
  • the latex pH at the time of complex formation is preferably adjusted to about 8 to 10.5.
  • the complexing agent is not particularly limited as long as it forms a water-insoluble complex with the platinum group element, but a water-insoluble complex having a strong self-aggregating property is preferable.
  • a compound of the formula x, and a compound of the formula x is preferable in view of the strength of the complex-forming ability, and ⁇ , j8-alkanedione such as dimethyl dali xylene, cyclohexanedi x dixylene, etc. Zhiximum is more preferred. Among them, dimethyl dalioxime is most preferred.
  • the amount of the complexing agent to be used is generally 1 to 50 times, preferably 2 to 30 times, mol per mol of the platinum group element of the catalyst used.
  • Precipitates that precipitate in latex by adding a complexing agent and have a particle size larger than the polymer particles are removed from the latex by a known simple separation operation such as filtration or eccentric separation, and recovered. Is done.
  • the filtration device and the filtration method are not limited except that a filter medium that passes only the latex but does not pass the precipitate is used. Both vacuum filtration and pressure filtration can be employed.
  • the catalyst thus recovered as a precipitate can be subjected to a regeneration treatment as needed, and then used for a hydrogenation reaction.
  • the reaction mixture containing the complex can be contacted with the adsorbent after completion of the complexing treatment in order to further increase the separation efficiency.
  • the adsorbent include activated carbon; silicon-containing inorganic compounds such as diatomaceous earth, talc, clay, activated clay, and silica; activated alumina; synthetic zeolites such as radiolite; and ion-exchange resins. Of these, activated carbon and silicon-containing inorganic compounds are preferred.
  • the adsorption treatment can be carried out by adding an adsorbent to the reaction mixture containing the complex, stirring and mixing the mixture, or passing the reaction mixture through a column filled with these adsorbents.
  • the adsorbent that has adsorbed the complex can be removed from the reaction mixture by a known separation operation such as filtration or centrifugation.
  • the filtration device As the filtration device, a filtration device having a structure in which a plurality of filter elements are housed in a sealable housing is usually used.
  • the “filter element” includes a filter element alone or a combination of a filter medium and a filter plate, and refers to the entire member having the “filtration J function” of the filtration device.
  • the filter device preferably has a filter element having a cylindrical or hollow disk shape, and the number thereof is preferably 5 or more, and more preferably 10 or more.
  • the filter element of the filtration device has a structure that allows passage of the hydrogenated conjugated polymer latex but does not allow passage of the water-insoluble complex.
  • a filter medium having pores of such a size is used.
  • Materials include natural fibers, synthetic fibers, metals, synthetic resins, and ceramics. These filter media may be used in combination.
  • the filter plate of the filter element is made of metal or synthetic resin from the viewpoint of strength etc. Is preferred.
  • the metal is preferably stainless steel
  • the synthetic resin is preferably reinforced polypropylene resin, polyvinylidene fluoride resin, polyphenylene sulfide, or the like.
  • the housing of the filtration device is of a closed type that is connected to the outside only by a housing hole for introducing a substance to be filtered and for extracting a filtrate.
  • the reaction mixture as the substance to be filtered is filled into the housing through the housing hole through the pipe.
  • the inside of the housing is pressurized by filling the reaction mixture, the reaction mixture is filtered as it passes through the filter element, and the filtrate (latex) is taken out. Then, the water-insoluble complex of the platinum group element is captured on the filter element.
  • Examples of the above-mentioned filtration device include those generally known as a pressurized filter which is called a funda-back filter or a leaf filter.
  • FIG. 1 An example of a leaf filter provided with a hollow disk-shaped filter element is shown in FIG.
  • the housing 1 has a sealed structure in which the inlet 2 for the reaction mixture containing the complex and the filtered latex communicates with the outside only through the outlet 3.
  • the reaction mixture containing the complex flows in the direction of the arrow. That is, the reaction mixture is introduced from the inlet 2, and the latex passes through the leaf filter 4, passes through the core 6 through the core hole 5, and is discharged from the outlet 3.
  • the insoluble complex of the platinum group element captured on the filter element is washed off from the filter element by passing air or the like through the filter element in the direction opposite to the filtration direction, and collected together with the filter aid. Can be.
  • the filter element can be pre-coated with a filter aid such as diatomaceous earth.
  • a filter aid such as diatomaceous earth.
  • the suspension of the filter aid is filled in the housing before the supply of the substance to be filtered, and the suspension is filtered to form a pre-coat layer of the filter aid on the filter element.
  • a hydrogenated conjugated gen-based polymer latex from which the platinum group element catalyst can be almost removed is obtained.
  • the recovery rate of the platinum group element is at least 70% based on the platinum group element used in the hydrogenation reaction, and about 95% or less depending on the conditions selected. Can be on.
  • the content (remaining amount) of the platinum group element in the latex is usually 300 ppm or less. If the conditions are properly selected, the amount of catalyst can be significantly reduced, and the content of the platinum group element per polymer is 100 ppm or less, preferably 80 ppm or less, more preferably 5 ppm or less.
  • a hydrogenated conjugated gen-based polymer latex of 0 ppm or less can be obtained.
  • a method generally used in industry may be appropriately employed.
  • a coagulant such as aluminum sulfate, magnesium sulfate, calcium chloride, etc.
  • a coagulant such as aluminum sulfate, magnesium sulfate, calcium chloride, etc.
  • the separated platinum group element-containing catalyst and its complex can be recovered and reused by dissolving, decomposing, reacting, etc.
  • the hydrogenation rate of the hydrogenated conjugated polymer was measured by proton NMR.
  • the amount of palladium in the hydrogenated conjugated polymer rubber was determined by atomic absorption analysis after dissolving a part of the hydrogenated polymer rubber in sulfuric acid after carbonizing it at 600 ° C. It was measured.
  • the hydrogenated polymer rubber whose palladium amount was measured was obtained by concentrating and drying the entire amount of the hydrogenated polymer latex using a rotary evaporator. Are the same.
  • Palladium acetate (the amount used is 800 ppm in the ratio of Pd metal / NBR described above) and nitric acid in an amount of 5 times the molar equivalent of palladium are added to an acidic aqueous palladium solution (300 mI) to obtain a weight-average solution.
  • Polyvinylpyrrolidone having a molecular weight of 500,000 was added at 5 times the weight of palladium.
  • a potassium hydroxide aqueous solution was added to prepare a catalyst aqueous solution A having a pH of 9.0.
  • the pH of the above reaction mixture (latex) was adjusted to 9.5, and dimethyldalioxime corresponding to 5 times the molar amount of palladium contained in the aqueous catalyst solution A was added in powder form. Then, the mixture was heated to 80 ° C and stirred for 5 hours. As a result, insolubles were precipitated in the latex. The whole latex was subjected to suction filtration to separate a precipitate. The obtained white filtrate was concentrated under reduced pressure by a rotary evaporator to obtain solid hydrogenated NBR. Hydrogenation The hydrogenation rate of NBR was 93%. The amount of palladium in the hydrogenated NBR was 65 ppm. This amount of palladium was equivalent to 8.1% of the palladium charged to the hydrogenation reaction, and the remaining palladium had been removed from the hydrogenated NBR.
  • Example 2 The same operation as in Example 1 was performed except that the hydroxylating power used in preparing the aqueous catalyst solution A of Example 1 was not used.
  • the hydrogenation rate of the obtained hydrogenated NBR was 65%.
  • the amount of palladium in the hydrogenated NBR was 68 ppm. Equivalent to 8.5% of the palladium charged to the hydrogenation reaction, the remaining palladium had been removed from the hydrogenated NBR.
  • Palladium acetate (the amount of Pd metal used was 700 ppm based on the NBR ratio) was added to water, and nitric acid was added at a molar equivalent of 5 times the amount of palladium to prepare 300 parts of a palladium acidic aqueous solution. .
  • polyvinyl viridone having a weight average molecular weight of 50,000 was added 5 times by weight with respect to palladium.
  • an aqueous potassium hydroxide solution was added to prepare an aqueous catalyst solution A having a pH of 9.0.
  • the hydrogenation rate of NBR was 93%.
  • the amount of palladium in the hydrogenated NBR was 37 ppm. This amount of palladium corresponded to 5.2% of the palladium charged in the hydrogenation reaction, and the remaining palladium had been removed from the hydrogenated NBR.
  • Example 3 In the method of Example 3 above, a comparative experiment was conducted as described below to examine the effect of the hydrogenation catalyst stabilizer (polyvinylpyrrolidone) added prior to the hydrogenation.
  • the storage stability was 25 ° C. No aggregation or precipitation was observed at all even after standing for a day.
  • Example 3 For comparison, the hydrogenation reaction and the recovery of the hydrogenated polymer were performed in the same manner as in Example 3 except that polyvinylpyrrolidone was not added to the aqueous hydrogenation catalyst solution A used in the method of Example 3 above. Was performed. Hydrogenation The hydrogenation rate of NBR reached only 70%. As a result of evaluating the storage stability of the catalyst aqueous solution A to which polyvinylpyrrolidone was not added, a slight precipitate was observed when the catalyst aqueous solution A was allowed to stand at 25 ° C for 1 hour.
  • the reaction mixture containing the insolubles was filtered using a FUNDABAC filter (trade name: FUNDABAC, manufactured by Ishikawajima-Harima Heavy Industries, Ltd.).
  • the fundaback filter has a large number of cylindrical filter elements (16 to 18 depending on the model) in a sealable housing. Each filter element has a tubular filter plate covered with a filter cloth.
  • the tubular filter plate consists of a candle piece through which the filtrate flows and a riser pipe in the center where the filtrate collects. After filtering the radiolite into the filter element with the radiolite (diatomaceous earth) suspension, pressure filtration was performed.
  • the obtained white filtrate was concentrated under reduced pressure by a rotary evaporator to obtain solid hydrogenated NBR.
  • Hydrogenation The hydrogenation rate of NBR was 93%.
  • the amount of palladium in the hydrogenated NBR was 40 ppm. Also, the amount of palladium lost due to leakage during filtration and attachment to the housing wall was only 1% of the amount used for the hydrogenation reaction.
  • Example 4 The same operation as in Example 4 was performed except that the filtration was performed using a leaf filter (Ishikawajima-Harima Heavy Industries, Ltd., see FIG. 1).
  • the leaf filter has one or two disc-shaped filter elements (three in Fig. 1), which are attached to a cylindrical core passing through the center. One end of the cylindrical core is closed, and the other end is opened to the outside through the wall of the housing. At least one core hole is provided in each of the filter element mounting portions, and the filter element is filtered. The collected filtrate is collected and taken out.
  • the filter media of each filter element is a stainless steel wire mesh. Precoating with a radio light was performed in the same manner as in Example 4. The time required to obtain the same amount of filtrate as in Example 4 was the same as in Example 4.
  • the amount of palladium in the obtained hydrogenated NBR was 40 ppm.
  • the amount of palladium lost due to leakage during filtration and adhesion to the housing wall was 3% of the amount used for the hydrogenation reaction.
  • Example 4 In order to investigate the effect of the filtration device having a plurality of filter elements used in Example 4 and Example 5, the following comparative experiment was performed using a filtration device having a single filter element.
  • Example 4 the same operation as in Example 4 was performed except that the filtration was performed using a membrane filter (manufactured by Millipore) having only one filter element covered with a polytetrafluoroethylene membrane as a filtration device. Pre-recording by radio was not performed.
  • a membrane filter manufactured by Millipore
  • Pre-recording by radio was not performed.
  • the amount of palladium in the obtained hydrogenated NBR was 40 ppm. Due to clogging, the filter element was replaced once. In addition, the time required to obtain the same amount of filtrate as in Example 4 was twice as long as that in Example 4. As a result, the loss of palladium was 15% of the amount used in the hydrogenation reaction.
  • the latex of a hydrogenated conjugated diene polymer produced by the method of the present invention and having a reduced content of a platinum group element is useful as an adhesive, a coating agent, a paint, a raw material for dip-molded bag, and the like. Since the amount of residual platinum group elements in latex is significantly reduced, when used as an adhesive, coating agent, paint, etc., the corrosion resistance of the adhered or coated metal material is high, and the residual platinum group elements Since there is no darkening caused by paint, coatings and paints have a high degree of freedom in coloring. Further, gloves obtained by dip-forming latex are suitable for work such as a semiconductor device manufacturing process.
  • the hydrogenated conjugated polymer rubber obtained from the hydrogenated conjugated polymer latex is derived from the platinum group element because the content of the platinum group element per polymer is 100 ppm or less. It has no fear of darkening or coloring and can be used in a wide range of industrial applications that make use of various properties such as oil resistance, weather resistance, ozone resistance, heat resistance, and cold resistance.
  • the separated platinum group element-containing catalyst and its complex can be recovered by dissolution, decomposition, reaction treatment, etc., and reused.

Abstract

L'invention concerne un latex constitué de polymère à base de diène conjugué hydrogéné, qui contient 100 ppm, par rapport au polymère, d'un élément appartenant au groupe des platines ; un caoutchouc polymère à base de diène conjugué hydrogéné, qui est préparé par séparation dudit latex ; et un procédé de production de ce latex, qui comporte les étapes consistant à dissoudre ou disperser un catalyseur d'hydrogénation contenant un composé d'un élément du groupe des platines dans un latex de polymère à base de diène conjugué, à mettre en oeuvre l'hydrogénation d'une liaison insaturée carbone-carbone, à ajouter un agent complexant pouvant former un complexe insoluble dans l'eau avec le métal du groupe des platines dans le latex polymère hydrogéné obtenu afin de former un précipité, et à séparer le précipité.
PCT/JP2003/003718 2002-03-26 2003-03-26 Latex polymere a base de diene conjugue hydrogene et procede de production de celui-ci, et caoutchouc polymere a base de diene conjugue hydrogene WO2003080681A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2002-85087 2002-03-26
JP2002085087 2002-03-26
JP2002087735 2002-03-27
JP2002-87735 2002-03-27
JP2002-201609 2002-07-10
JP2002201609A JP4123848B2 (ja) 2002-07-10 2002-07-10 水素化共役ジエン系重合体ラテックスの製造方法
JP2002-209156 2002-07-18
JP2002209156A JP4123852B2 (ja) 2002-07-18 2002-07-18 水素化触媒安定化剤、水素化触媒溶液及びその調製方法、水素化反応方法

Publications (1)

Publication Number Publication Date
WO2003080681A1 true WO2003080681A1 (fr) 2003-10-02

Family

ID=28457866

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/003718 WO2003080681A1 (fr) 2002-03-26 2003-03-26 Latex polymere a base de diene conjugue hydrogene et procede de production de celui-ci, et caoutchouc polymere a base de diene conjugue hydrogene

Country Status (1)

Country Link
WO (1) WO2003080681A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8044147B2 (en) 2005-02-23 2011-10-25 Zeon Corporation Nitrile group-containing copolymer rubber and a vulcanizable nitrile group-containing copolymer rubber composition
US20190202943A1 (en) * 2017-10-13 2019-07-04 Zeon Corporation Method for producing hydrogenated conjugated diene polymer latex
TWI732092B (zh) 2017-01-20 2021-07-01 日商日本瑞翁股份有限公司 氫化共軛二烯系聚合物乳膠的製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03210304A (ja) * 1989-11-20 1991-09-13 Polysar Rubber Corp ポリマーの処理工程
WO1999020662A1 (fr) * 1997-10-16 1999-04-29 Teijin Limited Polymere olefinique cyclique a teneur reduite en reste de catalyseur, utilisation d'un tel polymere et procede de production correspondant
EP0964005A1 (fr) * 1998-06-10 1999-12-15 Teijin Limited Procédé de préparation de copolymères hydrogénés d'alpha-oléfines et de dicyclopentadiène, procédé de moulage de ces copolymères et matériau optique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03210304A (ja) * 1989-11-20 1991-09-13 Polysar Rubber Corp ポリマーの処理工程
WO1999020662A1 (fr) * 1997-10-16 1999-04-29 Teijin Limited Polymere olefinique cyclique a teneur reduite en reste de catalyseur, utilisation d'un tel polymere et procede de production correspondant
EP0964005A1 (fr) * 1998-06-10 1999-12-15 Teijin Limited Procédé de préparation de copolymères hydrogénés d'alpha-oléfines et de dicyclopentadiène, procédé de moulage de ces copolymères et matériau optique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8044147B2 (en) 2005-02-23 2011-10-25 Zeon Corporation Nitrile group-containing copolymer rubber and a vulcanizable nitrile group-containing copolymer rubber composition
TWI732092B (zh) 2017-01-20 2021-07-01 日商日本瑞翁股份有限公司 氫化共軛二烯系聚合物乳膠的製造方法
US20190202943A1 (en) * 2017-10-13 2019-07-04 Zeon Corporation Method for producing hydrogenated conjugated diene polymer latex

Similar Documents

Publication Publication Date Title
EP2470576B1 (fr) Particules nanométriques de latex hydrogéné à base de diènes
CN107708860B (zh) 催化剂回收方法
JP4124004B2 (ja) 水素化共役ジエン系重合体ラテックスおよびその製造方法、ならびに水素化共役ジエン系重合体ゴム
US8563622B2 (en) Picolylamine resins
WO2003080681A1 (fr) Latex polymere a base de diene conjugue hydrogene et procede de production de celui-ci, et caoutchouc polymere a base de diene conjugue hydrogene
JP4107129B2 (ja) 水素化共役ジエン系重合体の製造方法
JP4123848B2 (ja) 水素化共役ジエン系重合体ラテックスの製造方法
JP2011005365A (ja) 触媒分離方法、回収方法及び触媒再利用方法
JP6981431B2 (ja) 水素化共役ジエン系重合体ラテックスの製造方法
WO2003085008A1 (fr) Recuperation d'un catalyseur dans un melange de reaction d'hyrogenation et production d'un polymere diene conjugue hydrogene
CN108889342A (zh) 一种用于丁腈橡胶非均相加氢催化剂的再生及回收再利用方法
JPWO2019188708A1 (ja) 白金族元素の回収方法
JP4175082B2 (ja) 水素化触媒回収方法、及び共役ジエン系重合体水素化物の製造方法
EP3666799B1 (fr) Procédé de production d'un latex de polymère de diène conjugué hydrogéné
JP4123852B2 (ja) 水素化触媒安定化剤、水素化触媒溶液及びその調製方法、水素化反応方法
WO2023190768A1 (fr) Procédé de récupération d'un élément du groupe platine
CN111566132B (zh) 氢化共轭二烯系聚合物胶乳的制造方法
JP4461655B2 (ja) 共役ジエン系重合体の水素化方法および水素化触媒
JP4239490B2 (ja) 水素化重合体の製造方法
JP2004026998A (ja) 触媒回収方法
JP7373160B2 (ja) 触媒成分の分離方法
KR20160058164A (ko) 팔라듐의 회수 방법
JP2003277431A (ja) 共重合体及びその製造方法、並びに水素化共重合体の製造方法
JPWO2017204154A1 (ja) 触媒回収方法
JP2004162099A (ja) 金属粉の洗浄方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase