EP2798001A1 - Procede pour la production de caoutchoucs nitrile épurés - Google Patents

Procede pour la production de caoutchoucs nitrile épurés

Info

Publication number
EP2798001A1
EP2798001A1 EP12799185.9A EP12799185A EP2798001A1 EP 2798001 A1 EP2798001 A1 EP 2798001A1 EP 12799185 A EP12799185 A EP 12799185A EP 2798001 A1 EP2798001 A1 EP 2798001A1
Authority
EP
European Patent Office
Prior art keywords
nitrile rubber
radical
nitrile
mono
ultrafiltration
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP12799185.9A
Other languages
German (de)
English (en)
Inventor
Sven Brandau
Sarah DAVID
Florian Forner
Stefan HUESGEN
Andreas Kaiser
Julia Maria JESCHKO
Peter Schwan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP12799185.9A priority Critical patent/EP2798001A1/fr
Publication of EP2798001A1 publication Critical patent/EP2798001A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the invention relates to a process for the preparation of purified nitrile rubbers, which have a significantly reduced proportion of special by-products compared with the nitrile rubber used for the purification, furthermore the purified nitrile rubbers obtainable by this process, their use for the preparation of vulcanizates and also these vulcanizates.
  • Nitrile rubbers also abbreviated to "NBR” are rubbers which are copolymers or terpolymers of at least one ⁇ , ⁇ -unsaturated nitrile, at least one conjugated diene and optionally one or more further copolymerizable monomers
  • NBR Nitrile rubbers
  • NBR and HNBR have been firmly established in the field of specialty elastomers for many years. They have an excellent property profile in terms of excellent oil resistance, good heat resistance and excellent resistance to ozone and chemicals, the latter being even more pronounced in the case of HNBR than NBR. NBR and HNBR also have very good mechanical and performance properties. For this reason, they are widely used in a variety of applications and are used, for example, for the production of seals, hoses, belts and damping elements in the automotive sector, also for stators, borehole seals and valve seals in the field of oil production and also for many parts of the electrical industry, the machine industry. and shipbuilding.
  • nitrile rubbers have hitherto been produced almost exclusively by so-called emulsion polymerization.
  • dodecylmercaptans in particular tertiary dodecylmercaptans (abbreviated to "TDDM” or "TDM"), are frequently used.
  • TDDM tertiary dodecylmercaptans
  • TDM tertiary dodecylmercaptans
  • the NBR latex obtained is coagulated in a first step and the NBR solid is isolated therefrom.
  • the metathesis is carried out using special metathesis-active metal complex catalysts and the hydrogenation can be carried out, for example, using homogeneous or else heterogeneous hydrogenation catalysts.
  • the hydrogenation catalysts are usually based on rhodium, ruthenium or titanium. However, it is also possible to use platinum, iridium, palladium, rhenium, ruthenium, osmium, cobalt or copper either as metal or else preferably in the form of metal compounds
  • Emulsion polymerisation of nitrile rubbers produced in the aforementioned applications are preferred impurity fractions, which are significantly less than 2 wt .-%.
  • the use of molded parts made of nitrile rubbers with a too large proportion of foreign substances in electronic applications is also only possible to a limited extent. This is especially true when the rubbers contain water and / or ions as foreign substances, as these strongly influence the corrosion and conductivity behavior of electronic products and can not always be removed without residue by thermal influence.
  • the use of nitrile rubbers having a relatively high level of impurity (greater than 3% by weight) can also result in reduced surface quality of the articles as well as mold soils or efflorescence in many applications such as injection molded articles or extrusion articles.
  • Nitrile rubbers with an impurity content of greater than 4 wt .-%, based on the nitrile rubber, for reactions such as metatheses and / or hydrogenation, which must be carried out in the presence of sensitive transition metal catalysts, are often not used, since the impurities complicate the reaction control, extend turnover times and lower the catalyst efficiency. Furthermore, in the case of hydrogenation, the foreign substances can contribute significantly to the corrosion and thus to the wear of the systems required for the hydrogenation.
  • emulsifiers include, for example, emulsifiers, fatty acids, fatty acid salts and esters from the emulsion polymerization of the nitrile rubber. Due to the processing and purification processes known in the prior art, these foreign substances could not be separated for a long time and if only with considerable economic effort, since they are enclosed by the nitrile rubber during the latex coagulation and thus are difficult or impossible to access to the washing processes. Possible is a fractional precipitation of the nitrile rubbers from solution for the separation of low molecular weight compounds. Suitable organic solvents are used as precipitants, in which the polymer is insoluble (eg methanol), while certain foreign substances such as the emulsifiers, fatty acids, fatty acid esters and fatty acid salts remain dissolved.
  • EP-A-1 524 277 a process for the purification of elastomers and in particular nitrile rubbers is known in which elastomers produced by free-radical emulsion polymerization are worked up by ultrafiltration. The process reclaims the up to 99% removal of the by-products and foreign substances resulting from the emulsion polymerization, in particular the emulsifiers used in large quantities in the polymerization.
  • the two examples of EP-A-1 524 277 show the removal of fatty acids from a nitrile rubber or a hydrogenated nitrile rubber dissolved in monochlorobenzene as organic solvent.
  • Diels-Alder by-products include by-products derived from Diels-Alder Reaction of two molecules of the same monomer arise, as well as those arising from the Diels-Alder reaction of two molecules of different monomers. This means, for example, that in the case of a butadiene-acrylonitrile copolymer, 4-vinylcyclohexene (“VCH”) and 4-cyanocyclohexene (“CCH”) can arise as Diels-Alder by-products.
  • VCH is formed by Diels- Alder reaction from 2 molecules of 1,3-butadiene, CCH by Diels-Alder reaction of 1,3-butadiene and acrylonitrile.
  • the object of the present invention was thus to provide a process for purifying Diels-Alder by-products containing nitrile rubbers, with which the proportion of Diels-Alder by-products in the nitrile rubber can be reduced so clearly and in a controlled manner that applications in which It depends on special purity, and subsequent reactions such as metathesis and hydrogenation are not adversely affected.
  • a process for producing a purified nitrile rubber which is characterized in that a nitrile rubber having repeating units of at least one conjugated diene monomer and at least one ⁇ , ⁇ -unsaturated nitrile monomer and Diels-Alder by-products of these monomers is subjected to an ultrafiltration, by passing the dissolved in at least one organic solvent nitrile rubber one or more times over an ultrafiltration membrane, thereby not flowing through the ultrafiltration membrane, the and a permeate stream containing the ultrafiltration membrane containing Diels-Alder by-products, with the provisos that
  • the ultrafiltration membrane has one or more porous layers and the layer having the smallest pores has a pore diameter in the range of 1 to 200 nm,
  • the ultrafiltration is carried out at a temperature in the range of 10 to 150 ° C and using a pressure in the range of 1 to 80 bar, and
  • the flow rate of the retentate stream during the ultrafiltration is set to a value greater than 0.2 m / sec
  • Another object of the invention is the preparation of vulcanizates by subjecting the purified nitrile rubber to vulcanization.
  • Another object of the invention are the vulcanizates based on the purified nitrile rubbers.
  • purified nitrile rubbers corresponding to unreacted nitrile rubbers having repeating units of at least one conjugated diene monomer and at least one ⁇ , ⁇ -unsaturated nitrile monomer can be prepared which have a content reduced by at least 50% by weight compared to the original unpurified state Diels-Alder by-products.
  • Purified nitrile rubbers containing Diels-Alder by-products which have been reduced by at least 80% by weight, based on the content in the originally used nitrile rubber, are preferably obtained by the process according to the invention.
  • nitrile rubbers purified by the process according to the invention having a content of Diels-Alder by-products which has been reduced by at least 90% by weight and up to 99.9% by weight, based on the content in the originally used nitrile rubber.
  • the non-purified nitrile rubbers used in the process according to the invention are usually nitrile rubbers which have a content of Diels-Alder by-products of the monomers in the range from 0.1 to 120% by weight, based on 100% by weight of the nitrile rubber.
  • purified nitrile rubbers are nitrile rubbers whose content of Diels-Alder by-products of the monomers is at least 50% by weight, preferably at least 80% by weight and more preferably at least 90% by weight. > And up to 99.9 wt.% O, based on the content in the originally used nitrile rubber, was reduced.
  • nitrile rubber containing Diels-Alder by-products of the monomers of e.g. 10% by weight, based on 100% by weight of the nitrile rubber
  • a purified nitrile rubber with a content of Diels-Alder by-products of the monomers of 5% by weight or less, based on 100 wt.%> Of the nitrile rubber.
  • the process according to the invention is characterized in that this relative purification of a nitrile rubber used succeeds independently of the absolute degree of impurity of the nitrile rubber used.
  • the process according to the invention not only enables the removal of the Diels-Alder by-products, but also the removal of other substances.
  • the method according to the invention it is also possible, for example, to remove substances which are selected from the group consisting of unreacted monomers, unreacted initiator, initiator decomposition products, polymerization stoppers, stabilizers used as antioxidants, molecular weight regulators, and fragments or decomposition products of these molecular weight regulators, and of oligomeric constituents.
  • the nitrile rubbers used in the process according to the invention have repeating units of at least one conjugated diene and at least one ⁇ , ⁇ -unsaturated nitrile and contain Diels-Alder by-products of these monomers;
  • the nitrile rubber may additionally comprise repeating units of one or more copolymerizable termonomers.
  • Diels-Alder by-products containing nitrile rubbers are typically prepared by free radical polymerization in at least one organic solvent.
  • the conjugated diene monomer in the nitrile rubber may be of any nature. Preference is given to using (C 4 -C 10 ) conjugated dienes. Particular preference is given to 1,2-butadiene, 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof. Particular preference is given to 1,3-butadiene and isoprene or mixtures thereof. Very particular preference is 1, 3-butadiene.
  • any known ⁇ , ⁇ -unsaturated nitrile can be used, preferably (C 3 -C 5 ) - ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Particularly preferred is acrylonitrile.
  • a preferred nitrile rubber to be used in the process according to the invention is a copolymer of acrylonitrile and 1,3-butadiene.
  • the nitrile rubber to be used in the process of the present invention may optionally contain recurring units of one or more copolymerizable termonomers, for example, aromatic vinyl monomers, preferably styrene, ⁇ -methylstyrene and vinylpyridine, fluorine-containing vinyl monomers, preferably fluoroethylvinylether, fluo ⁇ ropylvinylether, o-fluoromethylstyrene, vinylpenta-fluorobenzoate, difluoroethylene and Tetrafluoroethylene, or copolymerizable Antiageing monomers, preferably N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamide, N- (4-anilinophenyl) crotonamid, N-phenyl-4 - (3-vinylbenzyloxy) aniline and N-phenyl-4- (4
  • the nitrile rubber to be used according to the invention may also contain repeating units of carboxy group-containing, copolymerizable termonomers, for example ⁇ , ⁇ -unsaturated monocarboxylic acids, their esters, their amides, ⁇ , ⁇ -unsaturated dicarboxylic acids, their mono- or diesters, their corresponding anhydrides or amides ,
  • ⁇ -unsaturated monocarboxylic acids are preferably acrylic acid and methacrylic acid in question.
  • esters of ⁇ , ⁇ -unsaturated monocarboxylic acids preferably their alkyl esters and alkoxyalkyl esters. Preference is given to the alkyl esters, in particular CpCig alkyl esters of ⁇ , ⁇ -unsaturated monocarboxylic acids.
  • alkyl esters in particular CpCig alkyl esters of acrylic acid or of methacrylic acid, in particular methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate.
  • alkoxyalkyl esters of ⁇ , ⁇ -unsaturated monocarboxylic acids particularly preferably alkoxyalkyl esters of acrylic acid or of methacrylic acid, in particular C 2 -C 12 -alkoxyalkyl esters of acrylic acid or of methacrylic acid, very particularly preferably methoxymethyl acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and methoxymethyl (meth) acrylate.
  • alkyl esters such as e.g. the foregoing, with alkoxyalkyl esters, e.g. in the form of the aforementioned.
  • cyanoalkyl acrylates and cyanoalkyl methacrylates in which the C atom number of the cyanoalkyl group is 2-12, preferably ⁇ -cyanoethyl acrylate, ⁇ -cyanoethyl acrylate and cyano-butyl methacrylate.
  • hydroxyalkyl acrylates and hydroxyalkyl methacrylates in which the C atom number of the hydroxyalkyl groups is 1 to 12, preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl acrylate; It is also possible to use fluorine-substituted benzyl-containing acrylates or methacrylates, preferably fluorobenzyl acrylates, and fluorobenzyl methacrylate. It is also possible to use fluoroalkyl-containing acrylates and methacrylates, preferably trifluoroethyl acrylate and tetrafluoropropyl methacrylate.
  • amino-group-containing ⁇ , ⁇ -unsaturated carboxylic acid esters such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate.
  • Further copolymerizable monomers which can also be used are ⁇ , ⁇ -unsaturated dicarboxylic acids, preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.
  • ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides preferably maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride.
  • ⁇ , ⁇ -unsaturated dicarboxylic acid mono- or diesters may, for example, be alkyl, preferably C 1 -C 10 -alkyl, in particular ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-
  • alkyl esters of ⁇ , ⁇ -unsaturated monocarboxylic acids are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth ) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 2-propylheptyl acrylate and lauryl
  • (Meth) acrylate In particular, n-butyl acrylate is used.
  • alkoxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and methoxymethyl (meth) acrylate.
  • methoxyethyl acrylate is used.
  • Particularly preferred hydroxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.
  • Particularly preferred epoxyalkyl esters of the ⁇ , ⁇ -unsaturated monocarboxylic acids are 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate, 2- (n-propyl) glycidyl acrylate, 2- (n-propyl) glycidyl methacrylate, 2- (n-butyl) glycidyl acrylate, 2- (n-butyl) glycidyl methacrylate, glycidyl methyl acrylate, glycidyl methyl methacrylate, glycidyl acrylate, (3 ', 4'-epoxyheptyl) -2-ethyl acrylate, (3', 4'-epoxyheptyl) -2-ethyl methacrylate, (6 ' , 7'-epoxyheptyl) acrylate, (6 ', 7'-epoxyheptyl) me
  • esters of ⁇ for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, N- (2-hydroxyethyl) acrylamides, N- (2-hydroxymethyl) acrylamides and urethane (meth) acrylate are used.
  • ⁇ , ⁇ -unsaturated dicarboxylic acid monoesters include Maleic monoalkyl esters, preferably monomethyl maleate, monoethyl maleate, monopropyl maleate and mono-n-butyl maleate;
  • Malemic monocycloalkyl ester preferably monocyclopentyl maleate, monocyclohexyl maleate and monocycloheptyl maleate;
  • Maleic acid monoalkylcycloalkyl ester preferably monomethylcyclopentyl maleate and monoethylcyclohexylmaleate;
  • Maleic monoaryl ester preferably monophenylmaleate
  • Fumaric acid monoalkyl esters preferably monomethyl fumarate, monoethyl fumarate, monopropyl fumarate and mono-n-butyl fumarate;
  • Fumaric monocycloalkyl ester preferably monocyclopentylium tartrate, monocyclohexyl fumarate and monocycloheptyl fumarate;
  • Fumarcic Acidmonoalkylcycloalkylester preferably Monomethylcyclopentylfumarat and mono ethylcyclohexylfumarat;
  • Fumaric monoaryl ester preferably monophenyl fumarate
  • Fumaric acid monobenzyl ester preferably monobenzyl fumarate
  • Citracon Acidmonoalkylester preferably Monomethylcitraconat, Monoethylcitraconat, Monopropylcitraconat and mono-n-butyl citraconate;
  • Citraconic monocycloalkyl esters preferably monocyclopentylcitraconate, monocyclohexyl citraconate and monocycloheptylcitraconate;
  • Citracon Acidmonoalkylcycloalkylester preferably Monomethylcyclopentylcitraconat and Monoethylcyclohexylcitraconat;
  • Citracon Acidmonoarylester preferably Monophenylcitraconat
  • Citraconic acid monobenzyl ester preferably monobenzyl citraconate
  • Itaconic acid monoalkyl ester preferably monomethyl itaconate, monoethyl itaconate, monopropyl itaconate and mono-n-butyl itaconate;
  • Itaconic acid monocycloalkyl ester preferably monocyclopentyl itaconate, monocyclohexyl itaconate and monocycloheptyl itaconate;
  • Itaconic acid monoalkylcycloalkyl ester preferably monomethylcyclopentyl itaconate and monoethylcyclohexyl itaconate;
  • Itaconic acid monoaryl ester preferably monophenyl itaconate
  • Itaconic acid monobenzyl ester preferably monobenzyl itaconate.
  • the analog diesters can be used based on the aforementioned monoester groups, wherein the ester groups may also be chemically different. It is also possible to use, as further copolymerizable monomers, free-radically polymerizable compounds which contain two or more olefinic double bonds per molecule.
  • di- or polyunsaturated compounds are di- or polyunsaturated acrylates, methacrylates or itaconates of polyols such as 1,6-hexanediol diacrylate (HDODA), 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate, triethylene glycol diacrylate, butanediol -l, 4-diacrylate, propanediol-1,2-diacrylate, butanediol-1,3-dimethacrylate, neopentylglycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate,
  • polyols such as 1,6-hexanediol diacrylate (HDODA), 1,6-hexan
  • Trimethylolpropane triacrylate Trimethylolpropane trimethacrylate (TMPTMA), glycerol di- and triacrylate, pentaerythritol di-, tri- and tetraacrylate or methacrylate, dipentaerythritol tetra, penta- and hexaacrylate or methacrylate or itaconate, sorbitol tetraacrylate, sorbitol hexamethacrylate, diacrylates or
  • polyunsaturated monomers it is also possible to use acrylamides, e.g. Methylenebisacrylamide, hexamethylene-1, 6-bisacrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamido-propoxy) ethane or 2-acrylamido-ethyl acrylate. Examples of polyunsaturated
  • Vinyl and allyl compounds are divinylbenzene, ethylene glycol divinyl ether, diallyl phthalate, allyl methacrylate, diallyl maleate, triallyl isocyanurate or triallyl phosphate.
  • the proportions of the at least one conjugated diene monomer and the at least one ⁇ , ⁇ -unsaturated nitrile monomer in the nitrile rubber can vary within wide limits.
  • the proportion of or the sum of the conjugated dienes is usually in the range of 40 to 90 wt .-%, preferably in the range of 50 to 85 wt.%, Based on the total polymer.
  • the proportion of or the sum of the ⁇ , ⁇ -unsaturated nitriles is usually from 10 to 60 wt .-%, preferably from 15 to 50 wt .-%, based on the total polymer.
  • the proportions of the monomers add up to 100% by weight in each case.
  • the additional monomers can be used in amounts from 0 to
  • the glass transition temperatures of the unpurified and also the correspondingly purified nitrile rubbers used are usually in the range from -70.degree. C. to + 20.degree. C., preferably in the range from -60.degree. C. to 10.degree.
  • the nitrile rubbers which can be used in the process according to the invention usually have a polydispersity index in the range from 1.1 to 6.0, preferably from 1.3 to 5.0, particularly preferably from 1.4 to 4.5.
  • a polydispersity index in the range from 1.1 to 6.0, preferably from 1.3 to 5.0, particularly preferably from 1.4 to 4.5.
  • the nitrile rubbers used in the process according to the invention are usually prepared by free-radical polymerization of the corresponding monomers in at least one organic solvent. Large amounts of water, as in the case of emulsion polymerization, are not present in the reaction system. Lower amounts of water, of the order of magnitude of up to 5% by weight, preferably up to 1% by weight (based on the amount of the organic solvent), may well be present during the polymerization. The decisive factor is that the amount of water present must be kept so low that precipitation of the nitriding rubber that forms does not occur. It should be made clear at this point that the polymerization in solution is not an emulsion polymerization.
  • Suitable organic solvents are, for example, dimethylacetamide, monochlorobenzene, toluene, ethyl acetate, 1,4-dioxane, t-butanol, isobutyronitrile, 3-propanone, dimethyl carbonate, 4-methylbutan-2-one, acetone, acetonitrile and methyl ethyl ketone.
  • radical polymerization in solution for the preparation of the nitrile rubbers used in the process according to the invention can be carried out in various variants,
  • Z is H, a linear or branched, saturated, mono- or polyunsaturated alkyl radical, a saturated, mono- or polyunsaturated carbo- or heterocyclyl radical, aryl,
  • M represents repeat units of one or more monounsaturated or polyunsaturated monomers, comprising conjugated or nonconjugated dienes, alkynes and vinyl compounds, or a structural element which derives polymers comprising polyethers, in particular polyalkylene glycol ethers and polyalkylene oxides, polysiloxanes, polyols,
  • Polycarbonates, polyurethanes, polyisocyanates, polysaccharides, polyesters and polyamides, n and m are the same or different and are each in the range from 0 to 10,000,
  • Embodiment (1) of radical polymerization in solution is a radical polymerization in solution:
  • At least one molecular weight regulator (“regulator") of the general formula (VI) is used, those mentioned in the radicals Z and R of the general formula (VI) Meanings can each be mono- or polysubstituted.
  • the following radicals have a single or multiple substitution: alkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, aryloxy, alkylthio, arylthio, amino, amido, carbamoyl, phosphonato, phosphinato, sulfanyl, thiocarboxy, sulfinyl , Sulfono, sulfino, sulfeno, sulfamoyl, silyl, silyloxy, carbonyl, carboxy, oxycarbonyl, oxysulfonyl, oxo, thioxo, borates, selenates and epoxy.
  • substituents in turn, as far as chemically stable compounds result, all meanings in question, which Z can assume.
  • Particularly suitable substituents are halogen, preferably fluorine, chlorine, bromine or iodine, nitrile (CN) and carboxy.
  • Z and R in the general formula (VI) also explicitly include salts of said radicals, as far as they are chemically possible and stable. These may be, for example, ammonium salts, alkali metal salts, alkaline earth metal salts, aluminum salts or protonated forms of the regulators of the general formula (VI).
  • Z and R in the general formula (VI) also include organometallic radicals, for example those which give the regulator a Grignard function.
  • Z and R may further represent a carbanion with lithium, zinc, tin, aluminum, lead and boron as the counterion.
  • the regulator is coupled via the radical R via a linker to a solid phase or carrier substance.
  • the linker may be Wang, Sasrin, Rink acid, 2-chlorotrityl, Mannich, Safety-Catch, Traceless or photolabile linker known to those skilled in the art.
  • solid phases or carriers examples include silica, ion exchange resins, clays, montmorillonites, crosslinked polystyrene, polyethylene glycol grafted onto polystyrene, polyacrylamides ("pepsyn"), polyethylene glycol-acrylamide copolymers (PEGA), cellulose, cotton and granular porous glass (CPG, controlled pore glass) in question.
  • pepsyn polyacrylamides
  • PEGA polyethylene glycol-acrylamide copolymers
  • CPG controlled pore glass
  • regulators of general formula (VI) act as ligands for organometallic complex compounds, e.g. for those based on the central metals rhodium, ruthenium, titanium, platinum, iridium, palladium, rhenium, ruthenium, osmium, cobalt, iron or copper.
  • M can be monosubstituted or polysubstituted, meaning that M can be repeating units of one or more mono- or polyunsaturated monomers, preferably optionally an or multiply substituted conjugated or non-conjugated dienes, optionally mono- or polysubstituted alkynes or optionally mono- or polysubstituted vinyl compounds, for example fluorinated mono- or polyunsaturated vinyl compounds, or else a divalent structural element which is derived from substituted or unsubstituted polymers comprising polyethers, in particular polyalkylene glycol ethers and polyalkylene oxides, polysiloxanes, polyols, polycarbonates, polyurethanes, polyisocyanates, Polysaccharides, polyesters and polyamides. Behind these residues "M” can thus hide a monomeric or polymeric residue.
  • n, m and t are all zero.
  • This preferred controller thus has the general structure (via):
  • radicals Z and R may have all the meanings given above for the general formula (VI).
  • This particularly preferred regulator of the general formula (VIb) is obtained from the regulator of the general formula (VI) by
  • These particularly preferred regulators of the general formula (VIb) are thus, depending on whether Z and R are identical or not within the given meanings, symmetrical or asymmetric trithiocarbonates.
  • alkyl radical is a linear or branched, saturated or mono- or polyunsaturated, optionally mono- or polysubstituted alkyl radical, preferably a corresponding C 3 -C 20 -alkyl radical, in particular sec-butyl, tert-butyl, isopropyl, 1-buten-3-yl, 2-chloro-l-buten-2-yl, propionic acid-2-yl, propionitrile-2-yl, 2-methylpropanenitril-2-yl, 2-methylpropionic acid-2-yl or 1H, 1H, 2-keto-3-oxo-4H, 4H, 5H, 5H-perfluoroundecanyl, or
  • aryl radical represents a (hetero) aryl radical, very particularly preferably a C 6 -C 24- (hetero) aryl radical, in particular phenyl, pyridinyl or anthracenyl,
  • - represents a (hetero) aralkyl radical, very particularly preferably benzyl, phenylethyl or 1-methyl-1-phenyleth-2-yl, or
  • Z has the meanings previously given for the general formula (VI), but also with the additional restriction to such meanings that Z forms after homolytic cleavage of the Z-S bond either a secondary, tertiary or aromatic stabilized radical.
  • Alkyl radical in particular sec-butyl, tert-butyl, isopropyl, 1-buten-3-yl, 2-chloro-1-buten-2-yl, propionic acid-2-yl, propionitrile-2-yl, 2-methylpropanenitril-2-yl, 2-methylpropionic acid-2-yl or 1H, 1H, 2-keto-3-oxo-4H, 4H, 5H, 5H-perfluoroundecanyl, or
  • aryl radical represents a (hetero) aryl radical, very particularly preferably a C 6 -C 24- (hetero) aryl radical, in particular phenyl, pyridinyl or anthracenyl,
  • - represents a (hetero) aralkyl radical, very particularly preferably benzyl, phenylethyl or 1-methyl-1-phenyleth-2-yl, or
  • radicals R and Z which upon homolytic cleavage of the R-S (or Z-S) linkage lead to a radical which may be termed "tertiary", are e.g. tert. Butyl, cyclohexane-1-nitril-1-yl and 2-methylpropanenitril-2-yl.
  • radicals R and Z which upon homolytic cleavage of the R-S (or Z-S) bond lead to a radical which is to be termed "secondary", are e.g. sec-butyl, iso-propyl and cycloalkyl, preferably cyclohexyl.
  • radicals Z which lead upon homolytic cleavage of the ZS bond to as "primary" to be designated radical therefore include H, straight-chain C 1 -C 20 alkyl, OH, SH, SR and C 2 - C 20 alkyl groups with branches beyond the C atom that binds to S.
  • X is C (Z) 2 ,
  • - represents a linear or branched, saturated or mono- or polyunsaturated, optionally mono- or polysubstituted alkyl radical, preferably a corresponding C3-C20-alkyl radical, in particular sec-butyl, tert-butyl, isopropyl, l Butan-3-yl, 2-chloro-l-buten-2-yl, propionic acid-2-yl, propionitril-2-yl, 2-methylpropanenitril-2-yl, 2-methylpropionic acid-2-yl or 1H, 1H , 2-keto-3-oxo-4H, 4H, 5H, 5H-perfluoroundecanyl, or
  • aryl radical represents a (hetero) aryl radical, very particularly preferably a C 6 -C 24- (hetero) aryl radical, in particular phenyl, pyridinyl or anthracenyl,
  • - represents a (hetero) arylalkyl radical, very particularly preferably a C7-C25- (hetero) arylalkyl radical, in particular benzyl, phenylethyl or 1-methyl-1-phenyleth-2-yl, or
  • At least one regulator of the general formula (VId) is used, wherein
  • Z has the meanings given above for the general formula (VI), but with the restriction that Z forms a primary radical after homolytic cleavage of the S-Z bond, and
  • R may have the same meanings as Z in the general formula (VI), but with the proviso that R after homolytic cleavage of the S-R bond forms either a secondary, tertiary or aromatic stabilized radical, and
  • Z has the meanings given above for the general formula (VI), but with the restriction that Z forms a primary radical after homolytic cleavage of the S-Z bond, and
  • R may have the same meanings as Z in the general formula (VI), but with the proviso that R forms after homolytic cleavage of the S-R bond either a secondary, tertiary or aromatic stabilized radical.
  • Z with the proviso that Z forms a primary radical after homolytic cleavage of the SZ bond, H, a linear or branched, saturated or mono- or polyunsaturated, optionally mono- or polysubstituted alkyl radical, very particularly preferably a corresponding Ci-Ciö alkyl radical , in particular methyl, ethyl, n-prop-1-yl, but-2-en-1-yl, n-pent-1-yl, n-hex-1-yl or n-dodecan-1-yl, aralkyl, most preferably C 7 -C 25 aralkyl, in particular benzyl, amino, amido, carbamoyl, hydroxyimino, alkoxy, aryloxy, F, Cl, Br, I, hydroxy, alkylthio, arylthio, carbonyl, carboxy, oxo, thioxo, cyanates, thiocyanates , Isocyanates
  • R with the proviso that after homolytic cleavage of the SR bond R forms either a secondary, tertiary or aromatically stabilized radical is a linear, branched or cyclic, saturated or mono- or polyunsaturated, optionally mono- or polysubstituted alkyl radical, preferably a corresponding C 3 -C 20 -alkyl radical, in particular sec-butyl, tert-butyl, isobutyl, Propyl, 1-buten-3-yl, 2-chloro-l-buten-2-yl, propionic acid-2-yl, propionitril-2-yl, 2-methylpropanenitril-2-yl, 2-methylpropionic acid-2-yl or 1H, 1H, 2-keto-3-oxo-4H, 4H, 5H, 5H-perfluoroundecanyl, or
  • aryl radical or heteroaryl radical is an aryl radical or heteroaryl radical, very particularly preferably a C 6 -C 24 -aryl radical, in particular phenyl, pyridinyl or anthracenyl,
  • - represents an aralkyl radical, very particularly preferably benzyl, phenylethyl or 1-methyl-1-phenyleth-2-yl, or
  • dithioester stands for thiocarboxy, carbonyl, carboxy, oxo, thioxo, epoxy, as well as salts of the aforementioned compounds.
  • At least one regulator of the general formula (VIe) is used,
  • R may have the same meanings as Z in the general formula (VI), but with the proviso that R forms after homolytic cleavage of the S-R bond either a secondary, tertiary or aromatic stabilized radical.
  • This preferred regulator of the general formula (VIe) results from the regulator of the general formula (VI), wherein
  • X is CH 2 ,
  • R may have the same meanings as Z in the general formula (VI), but with the proviso that R after homolytic cleavage of the SR bond forms either a secondary, tertiary or aromatic stabilized radical.
  • Particular preference is given to a regulator of the abovementioned general formula (VIe), in which R, with the proviso that R forms either a secondary, tertiary or aromatically stabilized radical after homolytic cleavage of the SR bond,
  • - represents a linear or branched, saturated or mono- or polyunsaturated, optionally mono- or polysubstituted alkyl radical, preferably a corresponding C3-C20-alkyl radical, in particular sec-butyl, tert-butyl, isopropyl, l Butan-3-yl, 2-chloro-l-buten-2-yl, propionic acid-2-yl, propionitril-2-yl, 2-methylpropanenitril-2-yl, 2-methylpropionic acid-2-yl or 1H, 1H , 2-keto-3-oxo-4H, 4H, 5H, 5H-perfluoroundecanyl, or
  • Heterocyclyl radical in particular cyclohexyl, cumyl or cyclohexane-1-nitril-1-yl,
  • aryl radical represents a (hetero) aryl radical, very particularly preferably a C 6 -C 24- (hetero) aryl radical, in particular phenyl, pyridinyl or anthracenyl,
  • - represents a (hetero) arylalkyl radical, very particularly preferably a C7-C25- (hetero) arylalkyl radical, in particular benzyl, phenylethyl or 1-methyl-1-phenyleth-2-yl, or
  • Nitrile rubber dodecylpropanoic acid trithiocarbonate DoPAT
  • dibenzoyl trithiocarbonate DiBenT
  • cumylphenyl dithioacetate CPDA
  • cumyl dithiobenzoate phenylethyl dithiobenzoate
  • cyanoisopropyl dithiobenzoate CPDB
  • 2-cyanopropyldodecyltrithiocarbonate 2-cyanoethyldithiobenzoate, 2-cyano-2-propyl-2-yl-dithiophenylacetate
  • 2-cyanoprop 2-yl-dithiobenzoate S-thiobenzoyl-1H, 1H, 2-keto-3-oxa-4H, 4H, 5H, 5H-perfluoroundecanethiol and S-thiobenzoyl-1-phenyl-2-keto-3-oxa-4H , 4H, 5H, 5H-perfluorounde
  • variant (1) of the radical polymerization to the nitrile rubber 5 to 2000 mol% of the regulator based on 1 mol of the initiator are used. Preferably, 20 to 1000 mol% of the regulator are used based on 1 mol of the initiator.
  • the compounds of the general formula (VIb) which can be used in the export process (1) of free-radical polymerization to form the nitrile rubber are known from the so-called RAFT technology.
  • variant (2) which is the subject of a not yet published European patent application with the file number 10174654.3, at least one compound selected from the group consisting of the above-mentioned.
  • Preferred mercaptans (i) are alkylmercaptans, particularly preferred are C 1 -C 6 -alkyl mercaptans, which may be branched or unbranched.
  • methylmercaptan ethylmercaptan, n-butylmercaptan, n-hexylmercaptan, n-octylmercaptan, n-dodecylmercaptan and tert-dodecylmercaptans.
  • Tert-dodecyl mercaptans can be used both in the form of individual isomers and in the form of mixtures of two or more isomers.
  • Preferred mercaptoalcohols (ii) are aliphatic or cycloaliphatic mercaptoalcohols, in particular
  • mercapto-1-ethanol 3-mercapto-1-propanol, 3-mercaptopropan-1, 2-diol (also known as thioglycerol), 4-mercapto-1-butanol and 2-mercaptocyclohexanol.
  • Preferred mercaptocarboxylic acids (iii) are mercaptoacetic acid (also called sulfanylacetic acid),
  • 3-mercaptopropionic acid mercaptobutanedioic acid (also known as mercaptosuccinic acid), cysteine and N-acetylcysteine.
  • Preferred mercapto-carboxylic acid esters (iii) are alkyl thioglycolates, in particular ethylhexyl thioglycolate.
  • a preferred thiocarboxylic acid (iv) is thioacetic acid.
  • Preferred disulphides (v) are xanthogen disulphides, particularly preferred is diisopropylxanthogen disulphide.
  • Preferred allyl compounds (vii) are allyl alcohol or allyl chloride.
  • a preferred aldehyde (viii) is crotonaldehyde.
  • Preferred aliphatic or araliphatic halogenated hydrocarbons are chloroform, carbon tetrachloride, iodoform or benzyl bromide.
  • the aforementioned molecular weight regulators are in principle known from the literature (see KC Berger and G. Brandrup in J. Brandrup, EH Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, p 11/81 - 11/141) and commercially available or alternatively can be prepared by methods known to those skilled in the literature (see, for example, Chimie & Industrie, Vol 90 (1963), No. 4, 358-368, US Pat. No. 2,531,602, DD 137 307, DD 160 222, US-A-3,137,735, WO-A-2005/082846, GB 823,824, GB 823,823,
  • Molecular weight regulators are characterized in that they accelerate chain transfer reactions in the context of the polymerization reaction and thus cause the reduction of the degree of polymerization of the resulting polymers.
  • the aforementioned regulators comprise mono-, bi- or polyfunctional regulators, depending on the number of functional groups in the molecule which can lead to one or more chain transfer reactions.
  • the molecular weight regulator to be used in the process according to the invention is particularly preferably tert-dodecylmercaptans, both in the form of individual isomers and in the form of mixtures of two or more isomers.
  • Ci2-01efin starting material also referred to as "Ci2 feed stock” are predominantly oligomer mixtures based on tetramerized propene (also called “tetrapropene” or “tetrapropylene”), trimerized isobutene (also “triisobutene” or “triisobutylene “called), trimerized n-butene and dimerized hexene used.
  • molecular weight regulator one or more tert-dodecyl mercaptans selected from the group consisting of 2,2,4,6,6-pentamethylheptane thiol-4, 2,4,4,6,6-pentamethylheptane thiol-2,2 , 3,4,6,6-Pentamethylheptanthiol-2, 2,3,4,6,6-Pentamethylheptanthiol- 3 and any mixtures of two or more of the aforementioned isomers used.
  • Pentamethylheptanthiol-2 and 2,3,4,6,6-pentamethylheptanethiol-3 contains.
  • the preparation of this mixture is described in EP-A-2,162,430.
  • variant (2) of the process according to the invention from 1 to 5000 mol% of the molecular weight regulator (i) to (ix) are used, based on 1 mol of initiator. Preference is given to using 5 to 2000 mol% of the molecular weight regulator, based on 1 mol of the initiator.
  • Variant (3) of Radical Polymerization to Nitrile Rubber
  • the polymerization to nitrile rubber can be carried out in at least one solvent even in the absence of any compounds defined as compounds for embodiments (1) and (2) (i) to (xi) are used.
  • the manner in which the radical polymerization is initiated to the nitrile rubber is not critical. It is possible initiation by peroxide initiators, azo initiators, redox systems or photochemically. Azo initiators are preferred.
  • azo initiators for example, the following compounds can be used:
  • 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-cyano-2-butane), dimethyl 2,2'-azobisdimethylisobutyrate, 4,4'-azobis (4-cyanopentanoic acid) , 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1, 1) -bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2 'azobis [2-methyl-N-hydroxyethyl] -propionamide, 2,2'-azobis (N, N-dimethyleneisobutyr-amidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis ( N, N'-dimethyleneisobutyramine), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide), 2,2'-azo
  • the azo initiators are used in an amount of 10 to 10 "1 mol / 1, preferably 10" 3 to 10 "2 mol / 1 is used.
  • the ratio of the amount of initiator used to the amount of controller used it is possible, both the reaction kinetics as well as to influence the molecular structure (molecular weight, polydispersity).
  • peroxidic initiators which can be used are the following peroxo compounds which have an OOO unit: hydrogen peroxide, peroxodisulfates, peroxodiphosphates, hydroperoxides, peracids, peracid esters, peracid anhydrides and peroxides with two organic radicals.
  • As salts of Peroxodisulfuric acid and peroxodiphosphoric acid sodium, potassium and ammonium salts can be used.
  • Suitable hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide and p-menthane hydroperoxide.
  • Suitable peroxides with two organic radicals are dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethylhexane-2,5-di-tert-butyl peroxide, bis (t-butylperoxy-isopropyl) benzene, t-butyl cumyl peroxide, di-tert-butyl butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, t-butyl peracetate, 2,5-dimethylhexane-2,5-diperbenzoate, t-butyl per-3,5,5-trimethylhexanoate and 1,1-bis (tert-butylperoxy) -3 , 5,5-trimethyl.
  • Preference is given to using p-menthane hydroperoxide, cumene hydroperoxide, pinane hydroperoxide or 1,1-bis (tert-butylperoxy)
  • the half-life of the respective initiator in the selected solvent is 10 hours or more than 10 hours.
  • azoinitators of the following structural formulas (Ini-1) to (Ini-6) are used:
  • the aforementioned azo initiators of the structural formulas (Ini-1) to (Ini-6) are commercially available, for example, from Wako Pure Chemical Industries, Ltd.
  • half-life is familiar to the skilled person in connection with initiators.
  • a half-life of 10 hours in a solvent at a certain temperature means concretely that under these conditions half of the initiator has decomposed after 10 hours.
  • oxidizing agent As redox systems, the following systems of an oxidizing agent and a reducing agent can be used.
  • the choice of suitable amounts of oxidizing and reducing agents is sufficiently familiar to the person skilled in the art.
  • salts of transition metal compounds such as iron, cobalt or nickel are frequently used in addition in combination with suitable complexing agents such as sodium ethylenediaminetetraacetate, sodium nitrilotriacetate and trisodium phosphate or tetrapotassium diphosphate.
  • reducing agents which may be used in the process according to the invention are sodium formaldehyde sulfoxylate, sodium benzaldehydesulfoxylate, reducing sugars, ascorbic acid, sulfenates, sulfinates, sulfoxylates, dithionite, sulfite, metabisulfite, disulfite, sugar, urea, thiourea, xanthates, thioxanthogenates, hydrazinium salts, amines and
  • Amine derivatives such as aniline, dimethylaniline, monoethanolamine, diethanolamine or triethanolamine. Preference is given to using sodium formaldehyde sulfoxylate.
  • the initiation of the radical polymerization can also be carried out photochemically as described below:
  • a photoinitiator is added to the reaction mixture, which is excited by irradiation by means of light of suitable wavelength and initiates a free-radical polymerization.
  • the irradiation time depends on the power of the radiator, on the distance between the radiator and the reaction vessel and on the irradiation surface.
  • the choice of the appropriate amount of initiation is possible for the expert without any problems and serves to influence the time-turnover behavior of the polymerization.
  • photochemical initiators for example, the following may be used: benzophenone, 2-methylbenzophenone, 3,4-dimethylbenzophenone, 3-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-dihydroxybenzophenone, 4, 4'-bis [2- (1-propenyl) phenoxy] benzophenone, 4- (diethylamino) benzophenone, 4- (dimethylamino) benzophenone, 4-benzoylbiphenyl, 4-hydroxybenzophenone, 4-methylbenzophenone, benzophenone-3, 3 ' , 4,4'-tetracarboxylic dianhydride, 4,4'-
  • Benzoin isopropyl ether benzoin isobutyl ether, 4,4'-dimethylbenzil, hexachlorocyclopentadienes, or combinations thereof.
  • the radical polymerization is usually carried out at a temperature in a range of 5 ° C to 150 ° C, preferably in a range of 8 ° C to 130 ° C, more preferably in a range of 9 ° C to 120 ° C and completely more preferably in a range of 10 ° C to 110 ° C.
  • a temperature in the range of 40 ° C to 110 ° C and even more pronounced in the range of 60 to 110 ° C a significant formation of Diels-Alder by-products of the monomers is observed.
  • the radical polymerization of the nitrile rubber usually takes place in such a way that the ⁇ , ⁇ -unsaturated nitrile and the optionally used further copolymerizable monomers, the solvent, the initiator and the regulator (s) in a reaction vessel are submitted and then the one or more conjugated dienes is / are added. The polymerization is then started by increasing the temperature.
  • the oxidizing agent is typically metered into the reaction vessel together with one of the monomers.
  • the polymerization is then started by addition of the reducing agent.
  • the nitrile rubbers obtained are distinguished by one or more structural elements of the general formulas (I), (II), (III), (IV) or (V) either in the polymer main chain or as end groups.
  • Such nitrile rubbers can be subjected to follow-up reactions with other polymerizable monomers due to these structural elements / end groups, since the Structural elements / end groups can act as RAFT agents via further fragmentation. In this way, the targeted construction of various polymer architectures is possible.
  • these nitrile rubbers can also later crosslink more easily than conventional nitrile rubbers, since the structural elements / end groups are structurally similar to the usual crosslinking agents, especially those based on sulfur.
  • crosslinking density can be achieved with the nitrile rubbers already with a smaller amount of crosslinker.
  • crosslinking via the end groups reduces the number of loose polymer chain ends in the vulcanizate, which leads to improved properties, such as dynamic properties.
  • H is H, a linear or branched, saturated, mono- or polyunsaturated alkyl radical, a saturated, mono- or polyunsaturated carbo- or heterocyclyl radical, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, aryloxy, heteroaryloxy, amino, amido, hydroxyirnino, Carbamoyl, alkoxycarbonyl, F, Cl, Br, I, hydroxy, phosphonato, phosphinato, alkylthio, arylthio, sulfanyl, thiocarboxy, sulfinyl, sulfono, sulfino, sulfeno, sulfonic acids, sulfamoyl, silyl, silyloxy, nitrile, carbonyl, carboxy, oxycarbonyl, Oxysulfonyl, oxo, thioxo,
  • n and m are the same or different and are each in the range of 0 to 10,000,
  • R (a) for the case that m ⁇ 0, may have the same meanings as the radical Z and
  • m 0, H, a linear or branched, saturated, mono- or polyunsaturated alkyl radical, a saturated, mono- or polyunsaturated carbo- or heterocyclyl radical, aryl, heteroaryl, arylalkyl, heteroarylalkyl , Alkoxy, aryloxy, heteroaryloxy, amino, amido, carbamoyl, alkoxy, aryloxy, alkylthio, arylthio, sulfanyl, thiocarboxy, sulfinyl, sulfono, sulfmo, sulfeno, sulfonic acids, sulfamoyl, carbonyl, carboxy, oxycarbonyl, oxysulfonyl, oxo, thioxo, epoxy , Cyanates, thiocyanates, isocyanates, thioisocyanates or isocyanides.
  • radicals Z and R can each be mono- or polysubstituted.
  • the remarks made on the general formula (VI) with regard to the inclusion of some meanings for Z and R apply identically for Z and R in the general structural elements (I) - (V).
  • the comments on the general formula (VI) with regard to the optional substitution of the meanings concealing the M behind are identical for the general structural element (I), (II), (IV) and (V).
  • Hydrogenated nitrile rubbers which have structural elements (ii) of the general formulas (VIb-1) and (VIb-2) can preferably be obtained via variant (2), and - R (Vlb-2) wherein
  • Z has previously mentioned meanings for the general formula (I) and R has the meanings given above for the general formula (I), but with the proviso that R after homolytic cleavage of the bond to the next bonded atom in the nitrile rubber forms either a secondary, tertiary or aromatic stabilized radical. It has proven especially that Z and R are different here.
  • nitrile rubbers are contained in the nitrile rubbers as end groups and result when using the preferred regulators of the general formula (VIb).
  • nitrile rubbers are obtained, which are used as general
  • Structural elements (ii) contain the end groups n (VIb-1) and (VIb-2), in which R, with the proviso that R forms either a secondary, tertiary or aromatically stabilized radical after homolytic cleavage of the bond to the next bonded atom,
  • alkyl radical is a linear or branched, saturated or mono- or polyunsaturated, optionally mono- or polysubstituted alkyl radical, preferably a corresponding C 3 -C 20 -alkyl radical, in particular sec-butyl, tert-butyl, isopropyl, 1-buten-3-yl, 2-chloro-1-buten-2-yl, propionic acid-2-yl, propionitrile-2-yl, 2-methylpropanenitril-2-yl, 2-methylpropionic acid-2-yl or 1H, 1H, 2-keto-3-oxo-4H, 4H, 5H, 5H-perfluoroundecanyl, or
  • aryl radical represents a (hetero) aryl radical, very particularly preferably a C 6 -C 24- (hetero) aryl radical, in particular phenyl, pyridinyl or anthracenyl,
  • - represents a (hetero) aralkyl radical, very particularly preferably benzyl, phenylethyl or 1-methyl-1-phenyleth-2-yl, or
  • optionally hydrogenated nitrile rubbers are obtained which are used as general structural elements (ii)
  • nitrile rubbers which contain as general structural elements (ii) the elements ( ⁇ ) and ( ⁇ ) and / or ( ⁇ ), wherein R and Z are the same or different and with the Provided that R and Z after homolytic cleavage of
  • alkyl radical preferably a corresponding C 3 -C 20 -alkyl radical, in particular sec-butyl, tert-butyl, isopropyl, 1-buten-3-yl, 2-chloro-1-butene
  • aryl radical very particularly preferably a C 6 -C 24- (hetero) aryl radical, in particular phenyl, pyridinyl or anthracenyl,
  • aralkyl radical very particularly preferably benzyl, phenylethyl or 1-methyl-1-phenyleth-2-yl, or
  • nitrile rubbers are obtained which are used as general structural elements (ii)
  • R has the meanings given above for the general formula (II), but with the
  • optionally hydrogenated nitrile rubbers are obtained which contain as structural elements (ii) the structural elements (VIc-1) and (VIc-2), wherein
  • R with the proviso that after homolytic cleavage of the bond to the next atom in the optionally hydrogenated nitrile rubber, R forms a secondary, tertiary or aromatically stabilized radical
  • alkyl radical is a linear or branched, saturated or mono- or polyunsaturated, optionally mono- or polysubstituted alkyl radical, preferably an appropriate C3-C20-alkyl radical, in particular sec-butyl, tert-butyl, isopropyl , 1-buten-3-yl, 2-chloro-l-buten-2-yl, propionic acid-2-yl, propionitril-2-yl, 2-methylpropan-2-nitryl, 2-methylpropionic acid-2-yl or 1H , 1H, 2-keto-3-oxo-4H, 4H, 5H, 5H-perfluoroundecanyl, or
  • aryl radical is a (hetero) aryl radical, very particularly preferably a C 6 -C 24 (hetero) aryl radical, in particular phenyl, pyridinyl or anthracenyl,
  • aralkyl radical represents a (hetero) aralkyl radical, very particularly preferably benzyl, phenylethyl or 1-methyl-1-phenyleth-2-yl, or
  • the nitrile rubbers obtained are distinguished by one or more structural elements either in the polymer main chain or as end groups, which are prepared by incorporation and / or Reaction of one of the variant (2) defined molecular weight regulator (i) to (x) arise with the polymer chains formed.
  • the nitrile rubbers obtained are characterized in that, in contrast to corresponding rubbers which are obtained according to the prior art via the emulsion polymerization, they are completely emulsifier-free and also contain no salts, such as Usually used for the coagulation of the latices after the emulsion polymerization for the precipitation of the nitrile rubber. However, they contain the Diels-Alder by-products already described earlier in this application.
  • a solution of the unpurified nitrile rubber in an organic solvent is used.
  • organic solvents various organic solvents or mixtures of two or more solvents can be used.
  • the nitrile rubber to be purified should dissolve at> 90% by weight at the process conditions selected in each case.
  • Preferred solvents are aromatic, aliphatic and / or chlorinated solvents and ketones and cyclic ethers.
  • the process according to the invention makes it possible to subject the nitrile rubber contaminated by free-radical polymerization in at least one organic solvent, contaminated by Diels-Alder by-products, directly to ultrafiltration without further isolation.
  • Solvent should be carried out as the previous solution polymerization. It may also be useful to subject the nitrile rubber to be used before the ultrafiltration of a filtration.
  • the solution of the crude nitrile rubber is at a temperature in the range of 10 to 150 ° C and using a pressure in the range of 1 to 80 bar or a passed several times through an ultrafiltration membrane.
  • a retentate stream which does not flow through the ultrafiltration membrane and contains the purified nitrile rubber is obtained, as well as a permeate stream containing the ultrafiltration membrane containing Diels-Alder by-products, the flow rate of the retentate stream being adjusted to a value greater than 0.2 m / sec during the ultrafiltration ,
  • the one or more times passing the solution over an ultrafiltration membrane is also referred to as single or multiple "overflow" of the membrane.
  • the ultrafiltration membrane must have at least one semipermeable membrane which is permeable to the solvent (s) and the Diels-Alder by-products contained therein but impermeable to the nitrile rubber.
  • the residual concentration of the Diels-Alder by-products in the purified nitrile rubber can be adjusted.
  • the depletion of the Diels-Alder by-products is determined under these conditions by their retention and the Diafiltrationskostoryen (ratio of permeate to retentate).
  • the process according to the invention can be carried out both batchwise and continuously.
  • the process according to the invention is carried out batchwise.
  • Batchwise means that the originally used solution of the unpurified nitrile rubber is subjected to ultrafiltration by means of the desired number of overflows, without adding a further amount of solution of the unpurified nitrile rubber to the retentate stream in the course of the passages.
  • the ultrafiltration in the process according to the invention at a temperature in the range of 10 ° C to 150 ° C, preferably in the range of 20 ° C to 130 ° C and at a pressure in the range 1 to 80 bar, preferably in the range of 2 bar to 50 bar performed.
  • the flow rate of the retentate stream past the membrane should not fall below 0.2 m / sec, since otherwise at higher concentrations of the nitrile rubber in the solvent, in particular a concentration greater than 3 wt Concentration polarization can occur, whereby the permeate flow rate decreases.
  • the concentration of the nitrile rubber in the ultrafiltration solution of nitrile rubber, Diels-Alder by-products and optionally other interfering substances is typically up to 40% by weight, based on the sum of solvent (s), nitrile rubber, Diels-Alder By-products and optionally other interfering substances. If a higher concentration is chosen, the viscosity increases too much. This in turn depends on the molecular weight and the monomer composition of the nitrile rubber. Some reduction of the viscosity of the nitrile rubber solution is possible by heating the polymer solution.
  • the concentration of the nitrile rubber in the solution to be treated by ultrafiltration is preferably in the range of 5 to 20% by weight.
  • the ultrafiltration membrane to be used in the process according to the invention has one or more
  • Layers wherein the layer with the smallest pores must have a pore diameter in the range of 1-200 nm.
  • Preferred is an ultrafiltration membrane having at least one highly porous, permeable outer layer and one or more fine porous inner layers, of which the one with the smallest pores has a pore diameter in the range of 1 to 200 nm.
  • the highly porous outer layer (s) mainly act as a backing layer and may constitute a woven or nonwoven fabric or a ceramic base. By high porosity is meant a pore diameter of the outer layer (s) in the range of usually greater than 500 nm.
  • the inner layer (s) is / are usually finer porous than the respective outer layer (s).
  • the inner layers are symmetrical or asymmetric membranes applied to the outer layers, e.g. may be constructed of suitable polymers or another fine porous ceramic layer.
  • the pore diameters of the inner layers can also become continuously smaller from the outside to the inside.
  • the pore size of the finest porous layer is in the range of 1 nm to 200 nm, preferably in the range of 1 to 100 nm and particularly preferably in the range of 1 to 50 nm.
  • the pore sizes can be determined by methods known to the person skilled in the art.
  • the separation limit of such an ultrafiltration membrane used is thus in the range of 1 to 200 nm, preferably in the range of 1 to 100 nm and particularly preferably in the range of 1 to 50 nm.
  • the ultrafiltration membrane may have a thin layer on the surface, optionally ionic Contains groups.
  • Suitable membrane polymers for both the outer and the inner layer (s) are polysulfones, polyethersulfones, polyamides, polyether ketones, polyureas, polyurethanes, polyvinylidene difluoride, cellulose acetates, cellulose nitrates, polycarbonates, polyacrylonitrile and polyepoxides. Ceramic building materials can also be used as membranes, for example based on partly mixed oxides, carbonates, carbides and nitrides of the elements aluminum, antimony, barium, beryllium, bismuth,
  • the ultrafiltration membrane is usually part of a membrane module.
  • all commercial types come into consideration, which are known in the art. Preference is given to plate modules, winding modules, tube modules, capillary modules and multi-channel modules, which can optionally be supported by integrated flow breakers.
  • the Diels-Alder by-products can be removed step by step, but also different concentrations of these Diels-Alder by-products in the nitrile rubber solution can be adjusted.
  • the solution of the nitrile rubber (retentate) treated by the process according to the invention can be marketed as such or by the workup methods known to the person skilled in the art, such as degassing and spray drying or coagulation in water, optionally with salt addition or using other suitable polar solvents followed by Drying as powder, crumb or bale-forming Other drying methods such as evaporation, thin-film evaporation or freeze-drying are also possible. It is also possible to use dry-finishing, which is described for nitrile rubbers in EP-A-2 368 916.
  • a purified nitrile rubber whose content of Diels-Alder by-products has been reduced by the ultrafiltration can be hydrogenated in a further step with a transition metal catalyst.
  • This solution of the hydrogenated nitrile rubber, which has a transition metal catalyst and / or constituents, can again be subjected to an ultrafiltration process.
  • hydrogenated nitrile rubber can be produced, but also the cost-intensive transition metal catalyst can be recovered.
  • the process according to the invention can be used to prepare purified nitrile rubbers or their hydrogenated secondary products in which the content of Diels-Alder by-products is at least 50 wt .-% is reduced compared to the content in the originally used, unrefined nitrile rubber.
  • the purified nitrile rubbers or their hydrogenated secondary products obtained by the process according to the invention are distinguished by a number of advantages. They show less mold contamination in injection molding applications and can be used in food contact, in the cosmetic and medical sector as well as in the electronics sector.
  • a decisive advantage of the purified nitrile rubbers obtained is that in subsequent finishing processes such as, for example, hydrogenation or metathesis by side reactions, corrosion effects or catalyst deactivations, disadvantages to be expected are minimized.
  • ultrafiltration is readily feasible even on an industrial scale.
  • nitrile rubbers were used in the form of copolymers of acrylonitrile and butadiene:
  • VCH 4-vinylcyclohexene
  • NBR type A and B were prepared by polymerization of acyl nitrile and butadiene in monochlorobenzene as an organic solvent according to the examples of WO 2012/028503 A, wherein tert as a molecular weight regulator. Dodecylmercaptan was used.
  • NBR type C was prepared by polymerization of acrylonitrile and butadiene in monochlorobenzene as the organic solvent according to the examples of WO 2011/032832 A, using DoPAT (dodecylpropanoic acid trithiocarbonate) as molecular weight regulator.
  • DoPAT dodecylpropanoic acid trithiocarbonate
  • the purification of the solution of this nitrile rubber was carried out batchwise by ultrafiltration.
  • the original solution and analogously the retentate obtained at each overflow was pumped through the membrane module under pressure.
  • the desired amount of permeate was separated and replaced by an equal amount of monochlorobenzene continuously fed to the retentate. This ensured that the concentration of nitrile rubber in the solution did not change during the cleaning process.
  • In front of the membrane was a feed pressure of 10 bar set.
  • the flow rate of the retentate stream was 2.5 m / s.
  • the differential pressure at the membrane was 1.5 bar and the permeate flow 24 kg / m 2 h.
  • the temperature of the solution of nitrile rubber was 90 ° C.
  • This multi-channel element contained 7 channels with an inner diameter of 6 mm each and a membrane area of 0.133 m 2 .
  • the separation limit of the membrane was 5 nm.
  • Table 2 The results of ultrafiltration are given in Table 2 below, the diafiltration coefficient corresponding to the number of overflows through the ultrafiltration membrane.
  • a 5.2% by weight solution of NBR type C in monochlorobenzene was used.
  • the purification of the solution of this nitrile rubber was carried out as described in Example 2, with the following parameters being set:
  • the flow rate of the retentate stream was 4.8 m / s.
  • the differential pressure at the membrane was 3.5 bar and the permeate flow 25.3 kg / m 2 h.
  • the temperature of the solution of nitrile rubber was 25 ° C.

Abstract

L'invention concerne un nouveau procédé de production d'un caoutchouc nitrile épuré, selon lequel le caoutchouc nitrile qui contient des impuretés spéciales, est soumis à une ultrafiltration définie. Cela permet de réduire de manière substantielle la teneur en impuretés spéciales du caoutchouc nitrile.
EP12799185.9A 2011-12-29 2012-12-11 Procede pour la production de caoutchoucs nitrile épurés Withdrawn EP2798001A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12799185.9A EP2798001A1 (fr) 2011-12-29 2012-12-11 Procede pour la production de caoutchoucs nitrile épurés

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11196044.9A EP2610296A1 (fr) 2011-12-29 2011-12-29 Procédé de fabrication de caoutchoucs nitriles purifiés
PCT/EP2012/075092 WO2013098073A1 (fr) 2011-12-29 2012-12-11 Procede pour la production de caoutchoucs nitrile épurés
EP12799185.9A EP2798001A1 (fr) 2011-12-29 2012-12-11 Procede pour la production de caoutchoucs nitrile épurés

Publications (1)

Publication Number Publication Date
EP2798001A1 true EP2798001A1 (fr) 2014-11-05

Family

ID=47351665

Family Applications (2)

Application Number Title Priority Date Filing Date
EP11196044.9A Withdrawn EP2610296A1 (fr) 2011-12-29 2011-12-29 Procédé de fabrication de caoutchoucs nitriles purifiés
EP12799185.9A Withdrawn EP2798001A1 (fr) 2011-12-29 2012-12-11 Procede pour la production de caoutchoucs nitrile épurés

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP11196044.9A Withdrawn EP2610296A1 (fr) 2011-12-29 2011-12-29 Procédé de fabrication de caoutchoucs nitriles purifiés

Country Status (5)

Country Link
US (1) US20140329982A1 (fr)
EP (2) EP2610296A1 (fr)
KR (1) KR20140098200A (fr)
CN (1) CN104024322A (fr)
WO (1) WO2013098073A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150044559A1 (en) 2012-03-26 2015-02-12 Zeon Corporation Composite particles for negative electrodes of secondary batteries, use of same, method for producing same, and binder composition
EP2966097A1 (fr) * 2014-07-07 2016-01-13 Lanxess Inc. Ultrafiltration de copolymères de poly(isooléfine)
US20170174795A1 (en) * 2014-07-24 2017-06-22 Arlanxeo Singapore Pte. Ltd. Ultrapure copolymers
US10766974B2 (en) 2014-12-19 2020-09-08 Arlanxeo Singapore Pte. Ltd. Ultrafiltration of polyisoolefin copolymers and polyisoolefin copolymers with reduced oligomer content
JPWO2017170250A1 (ja) * 2016-03-31 2019-02-14 日本ゼオン株式会社 共重合体の製造方法、及びラテックスの製造方法
KR20210044623A (ko) 2019-10-15 2021-04-23 광주과학기술원 에너지관리시스템 및 에너지관리방법
CN116003711B (zh) * 2021-10-21 2023-06-20 中国石油化工股份有限公司 丁腈橡胶及其制备方法、氢化丁腈橡胶、丁腈橡胶组合物和丁腈橡胶硫化胶

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2531602A (en) 1946-12-28 1950-11-28 Pure Oil Co Production of thioethers and/or mercaptans
GB823823A (en) 1957-07-05 1959-11-18 Ici Ltd Process for the preparation of mercaptans
GB823824A (en) 1957-07-05 1959-11-18 Ici Ltd Process for the preparation of mercaptans
US3137735A (en) 1961-10-20 1964-06-16 Phillips Petroleum Co Process for synthesis for mercaptans
DD137307A3 (de) 1970-04-07 1979-08-29 Wolfgang Cleve Verfahren zur herstellung von tertiaeren mercaptanen
DD160222A3 (de) 1970-04-07 1983-05-18 Wolfgang Cleve Verfahren zur herstellung von tertiaeren mercaptanen
JP3558096B2 (ja) 1993-12-29 2004-08-25 日本ゼオン株式会社 ２，２，４，６，６−ペンタメチルヘプタン−４−チオールの製造法
JPH07316127A (ja) 1994-03-31 1995-12-05 Nippon Zeon Co Ltd ２，２，４，６，６−ペンタメチルヘプタン−４−チオールの製造方法
JP3587215B2 (ja) 1994-03-31 2004-11-10 日本ゼオン株式会社 ２，２，４，６，６−ペンタメチルヘプタン−４−チオールの製法
JP2002506426A (ja) 1997-04-25 2002-02-26 トランスジエノミツク・インコーポレーテツド 非多孔質ポリマービーズ上でのポリヌクレオチド分離
MY129174A (en) 1997-07-02 2007-03-30 Shell Int Research Removing a gaseous component from a fluid
DE10347704A1 (de) * 2003-10-14 2005-05-12 Bayer Ag Verfahren zur Herstellung von gereinigten Elastomeren aus Lösung
FR2866024A1 (fr) 2004-02-06 2005-08-12 Arkema Procede de fabrication de dodecylmercaptans.
DE102007024009A1 (de) 2007-05-22 2008-11-27 Lanxess Deutschland Gmbh Mercaptangemisch
WO2011032832A1 (fr) 2009-09-17 2011-03-24 Lanxess Deutschland Gmbh Caoutchouc de nitrile et sa fabrication dans des solvants organiques
PL2368916T3 (pl) 2010-03-25 2013-03-29 Lanxess Int Sa Sposób wytwarzania kauczuków nitrylowych wolnych od wody i rozpuszczalników
EP2423235A1 (fr) 2010-08-31 2012-02-29 LANXESS Deutschland GmbH Procédé de fabrication de caoutchoucs nitriles dans des solvants organiques
EP2423238A1 (fr) 2010-08-31 2012-02-29 LANXESS Deutschland GmbH Procédé de fabrication de caoutchoucs nitriles dans des solvants organiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013098073A1 *

Also Published As

Publication number Publication date
EP2610296A1 (fr) 2013-07-03
CN104024322A (zh) 2014-09-03
US20140329982A1 (en) 2014-11-06
WO2013098073A1 (fr) 2013-07-04
KR20140098200A (ko) 2014-08-07

Similar Documents

Publication Publication Date Title
WO2013098073A1 (fr) Procede pour la production de caoutchoucs nitrile épurés
EP2478021B1 (fr) Caoutchouc nitrile et sa fabrication dans des solvants organiques
EP2316860B1 (fr) Caoutchouc de nitrile
EP2611837B1 (fr) Procédé pour produire des caoutchoucs nitriles dans des solvants organiques
EP2554558A1 (fr) Procédé de fabrication de caoutchoucs nitriles dans des solvants organiques
EP2152759A1 (fr) Caoutchoucs nitrile
WO2012089804A1 (fr) Compositions vulcanisables à base de caoutchoucs nitriles contenant des groupes époxy
WO2012028506A1 (fr) Mélanges de caoutchoucs constitués de différents caoutchoucs nitriles
EP2298824A1 (fr) Caoutchouc nitrile et sa fabrication dans des solvants organiques
EP2810957A1 (fr) Caoutchoucs nitriles couplés par groupes bisdihydropyrazol, leur fabrication et leur utilisation
EP2385074A1 (fr) Caoutchouc nitrile et sa fabrication dans des solvants organiques
WO2012028501A1 (fr) Procédé pour produire des caoutchoucs nitriles dans des solvants organiques
DE10060222A1 (de) Quaterpolymere mit funktionellen Hydroxyl- oder Epoxy-Gruppen
DE19643035A1 (de) Terpolymere bestehend aus konjugiertem Diolefin, vinylsubstituiertem Aromat und olefinisch ungesättigtem Nitril
EP2623518A1 (fr) Caoutchoucs nitriles couplés par groupes bistriazolyl, leur fabrication et leur utilisation
WO2002020632A1 (fr) Polymeres quaternaires comportants des groupes fonctionnels aminiques
DE2613051C2 (de) Verfahren zur Herstellung eines synthetischen Kautschuks mit verbesserter Grünfestigkeit
TW201341407A (zh) 用於製備純化腈橡膠之方法
DD150213B1 (de) Verfahren zur herstellung von synthesekautschuk-polyvinylchlorid-verschnitten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140729

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20150219