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Hydrogenation of a Diene-Based Polymer Latex Hydrierung Eines Dien-Basierten Polymer-Latex Hydrogénation D’Un Latex Polymère À Base De Diène

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Hydrogenation of a Diene-Based Polymer Latex Hydrierung Eines Dien-Basierten Polymer-Latex Hydrogénation D’Un Latex Polymère À Base De Diène (19) TZZ __T (11) EP 2 676 971 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08C 19/02 (2006.01) C08F 36/04 (2006.01) 08.04.2015 Bulletin 2015/15 C08F 236/12 (2006.01) C08F 8/04 (2006.01) (21) Application number: 12173165.7 (22) Date of filing: 22.06.2012 (54) Hydrogenation of a diene-based polymer latex Hydrierung eines dien-basierten Polymer-Latex Hydrogénation d’un latex polymère à base de diène (84) Designated Contracting States: (56) References cited: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB EP-A1- 2 289 621 US-A1- 2006 211 827 GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR • DATABASE COMPENDEX [Online] ENGINEERING INFORMATION, INC., NEW YORK, (43) Date of publication of application: NY, US; 3 October 2011 (2011-10-03), 25.12.2013 Bulletin 2013/52 KONGPARAKUL S ET AL: "Metathesis hydrogenation of natural rubber latex", (73) Proprietor: UNIVERSITY OF WATERLOO XP002689385, Database accession no. Waterloo, Ontario N2L 3G1 (CA) E20113714322330 -& KONGPARAKUL S ET AL: "Metathesis hydrogenation of natural rubber (72) Inventors: latex", APPLIED CATALYSIS A: GENERAL, vol. • REMPEL, Garry L. 405, no. 1-2, 3 October 2011 (2011-10-03), pages Waterloo, Ontario N2T 2H4 (CA) 129-136, XP002690182, ELSEVIER NLD DOI: • PAN, Qinmin 10.1016/J.APCATA.2011.07.039 Waterloo, Ontario N2T 2W9 (CA) • DATABASE COMPENDEX [Online] • Wu, Jialong ENGINEERING INFORMATION, INC., NEW YORK, Waterloo, Ontario N2L 4N2 (CA) NY, US; 15 April 2008 (2008-04-15), MINGOTAUD •LIU,Yin A-F ET AL: "Characterization of the micellar ring Mississauga, Ontario L5B 0E8 (CA) opening metathesis polymerization in water of a norbornene derivative initiated by Hoveyda- (74) Representative: Hollah, Dorothee Grubbs’ catalyst", XP002689386, Database Isenbruck Bösl Hörschler LLP accession no. E20081511199730 -& MINGOTAUD Eastsite One A-F ET AL: "Characterization of the micellar ring Seckenheimer Landstrasse 4 opening metathesis polymerization in water of a 68163 Mannheim (DE) norbornene derivative initiated by Hoveyda- Grubbs’ catalyst", JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY, vol. 46, no. 8, 15 April 2008 (2008-04-15) , pages 2833-2844, XP002690183, JOHN WILEY AND SONS INC. US DOI: 10.1002/POLA.22617 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 676 971 B1 Printed by Jouve, 75001 PARIS (FR) EP 2 676 971 B1 Description FIELD OF THE INVENTION 5 [0001] The present invention relates to a process for selectively hydrogenating the carbon-carbon double bonds in diene-based polymers which are present in latex form, this means as a suspension of diene-based polymer particles in an aqueous medium, using a ruthenium- or osmium-based metathesis catalyst without any organic solvent. BACKGROUND OF THE INVENTION 10 [0002] It has been known that carbon-carbon double bonds in polymers may be successfully hydrogenated by treating the polymer in an organic solution with hydrogen in the presence of different catalysts. Such processes can be selective in the double bonds which are hydrogenated so that, for example, the double bonds in aromatic or naphthenic groups are not hydrogenated and double or triple bonds between carbon and other atoms such as nitrogen or oxygen are not 15 affected. This field of art contains many examples of catalysts suitable for such hydrogenations e.g. based on cobalt, nickel, rhodium, ruthenium, osmium, and iridium. The suitability of the catalyst depends on the extent of hydrogenation required, the rate of the hydrogenation reaction and the presence or absence of other groups, such as carboxyl and nitrile groups, in the polymers. [0003] Hydrogenation of diene-based polymers has been very successful, if the polymers were dissolved in an organic 20 solvent as e.g. disclosed in US-A-6,410,657 , US-A-6,020,439, US-A-5,705,571, US-A-5,057,581, and US-A-3,454,644. [0004] However, many diene-based polymers, -copolymers or -terpolymers are made by emulsion polymerization processes and are therefore obtained in latex form, i.a. as polymer particles suspended in the aqueous medium due to the stabilizing effect of emulsifiers, when they are discharged from polymerization reactors. Therefore it is very desirable to directly hydrogenate a diene-based polymer in said latex form and increasing efforts are spent on such direct hydro- 25 genation in the recent decade. [0005] So far significant attention has been paid to the hydrogenation of C=C bonds using hydrazine or a derivative of hydrazine as a reducing agent together with an oxidant like oxygen, air or hydrogen peroxide. The hydrogen source to saturate the C=C bonds is then generated in-situ as a result of the redox reactions in which diimide is also formed as intermediate. 30 [0006] In US-A-4,452,950 the latex hydrogenation is performed using the hydrazine hydrate/hydrogen peroxide (or oxygen) redox system to produce diimide in situ. CuSO4 or FeSO4 is used as a catalyst. [0007] US-A-5,039,737 and US-A-5,442,009 provide a more refined latex hydrogenation process which treats the hydrogenated latex with ozone to break the cross-linked polymer chains which form during or after the latex hydrogenation using the diimide approach. 35 [0008] US-A-6,552,132 discloses that specific compounds, if added before, during or after the latex hydrogenation serve to break cross-links formed during the hydrogenation using the diimide hydrogenation route. The specific compound can be chosen from primary or secondary amines, hydroxylamine, imines, azines, hydrazones and oximes. [0009] US-A-6,635,718 describes the process for hydrogenating C=C bonds of an unsaturated polymer in the form of an aqueous dispersion by using hydrazine and an oxidizing compound in the presence of a metal compound containing 40 a metal atom in an oxidation state of at least 4 (such as Ti(IV), V(V), Mo(VI) and W(VI)) as the catalyst. [0010] In Applied Catalysis A-General Vol. 276, no. 1-2, 2004, 123-128 and Journal of Applied Polymer Science Vol. 96, no. 4, 2005, 1122-1125 detailed investigations relating to the hydrogenation of nitrile butadiene rubber latex via the diimide hydrogenation route are presented which cover examining hydrogenation efficiency and degree of hydrogenation. It has been found that there are side reactions at the inter phase of the latex particles and within the polymer phase, 45 which generate radicals to initiate the cross-linking of polymers in the latex form. Using radical scavengers did not show any evidence in helping to suppress the degree of gel formation. [0011] Although there are methods developed to reduce the cross-linking, the aforementioned diimide route still en- counters gel formation problem, especially when high hydrogenation conversion is achieved. Therefore, the resulting hydrogenated rubber mass is difficult to process or is unsuitable for further use because of its macroscopic three dimen- 50 sional cross-linked structure. [0012] US-A-5,272,202 describes a process for the selective hydrogenation of the carbon-carbon double bonds of an unsaturated, nitrile-group-containing polymer with hydrogen in the presence of a hydrogenation catalyst being a palladium compound. In this process an aqueous emulsion of the unsaturated, nitrile-group-containing polymer is subjected to the hydrogenation and additionally an organic solvent capable of dissolving or swelling the polymer is used at a volume ratio 55 of the aqueous emulsion to the organic solvent in a range of from 1 : 1 to 1: 0.05. The aqueous emulsion is brought into contact with gaseous or dissolved hydrogen while maintaining an emulsified state. [0013] US-A-6,403,727 discloses a process for selectively hydrogenating ethylenically unsaturated double bonds in polymers. Said process involves reacting the polymers with hydrogen in the presence of at least one hydrogenation 2 EP 2 676 971 B1 catalyst selected from the salts and complex compounds of rhodium and/or of ruthenium, in an aqueous suspension of the polymers which comprises up to 20% by volume of an organic solvent. The suitable rhodium containing catalysts 3 4 5 are rhodium phosphine complexes of the formula RhXmL L (L )n wherein X is a halide, the anion of a carboxylic acid, acetylacetonate, aryl- or alkylsulfonate, hydride or the diphenyltriazine anion and L3, L4 and L5 independently are CO, 5 olefins, cycloolefins, dibenzophosphol, benzonitrile, PR3 or R2P-A-PR2, m is 1 or 2 and n is 0, 1 or 2, with the proviso 3 4 5 that at least one of L, L or L is one of the above mentioned phosphorus-containing ligands of the formula PR3 or PR2-A-PR2, wherein R is alkyl, alkyloxy, cycloalkyl, cycloalkyloxy, aryl or aryloxy. US-A-6,566,457 makes use of the same principal technology of hydrogenating a polymer in latex form in the presence of a ruthenium and/or rhodium containing catalyst in order to prepare graft polymers.. 10 [0014] JP 2001-288212 describes a further process for hydrogenating diene-based polymer latices. Latices of 2-chloro- 1,3-butadiene (co)polymers are mixed with solutions or dispersions of catalysts in organic solvents which dissolve or swell the (co)polymers, and then contacted with hydrogen.
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