(19) TZZ Z Z_T (11) EP 2 057 205 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08G 81/00 (2006.01) C08G 81/02 (2006.01) 08.02.2017 Bulletin 2017/06 C08F 299/00 (2006.01) C08F 299/04 (2006.01) C08F 299/06 (2006.01) C08L 53/00 (2006.01) (2006.01) (21) Application number: 07837260.4 B01J 31/00 (22) Date of filing: 23.08.2007 (86) International application number: PCT/US2007/018659 (87) International publication number: WO 2008/027283 (06.03.2008 Gazette 2008/10) (54) PRODUCTION OF META-BLOCK COPOLYMERS BY POLYMER SEGMENT INTERCHANGE HERSTELLUNG VON METABLOCK-COPOLYMEREN DURCH AUSTAUSCH AMORPHER POYLYMERSEGMENTE PRODUCTION DE COPOLYMÈRES MÉTABLOC PAR ÉCHANGE DE SEGMENTS POLYMÈRES (84) Designated Contracting States: (74) Representative: Beck Greener AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Fulwood House HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE 12 Fulwood Place SI SK TR London WC1V 6HR (GB) (30) Priority: 25.08.2006 US 840301 P (56) References cited: WO-A-01/44315 US-A- 3 821 328 (43) Date of publication of application: US-A- 3 860 675 13.05.2009 Bulletin 2009/20 • TINDALL D ET AL: "ACYCLIC DIENE (73) Proprietor: Dow Global Technologies LLC METATHESIS (ADMET) SEGMENTED Midland, MI 48674 (US) COPOLYMERS" MACROMOLECULES, ACS, WASHINGTON, DC, US, vol. 37, no. 9, 4 May 2004 (72) Inventors: (2004-05-04), pages 3328-3336, XP001196170 • ARRIOLA, Daniel, J. ISSN: 0024-9297 Midland, MI 48642 (US) • O’GARA J E ET AL: "Acyclic Diene Metathesis • TIMMERS, Francis, J. (ADMET) Polymerization. Synthesis of Midland, MI 48642 (US) unsaturated Polythioethers" • JAZDZEWSKI, Brian, A. MACROMOLECULES, ACS, WASHINGTON, DC, Midland, MI 48642 (US) US, vol. 26, no. 11, 1 January 1993 (1993-01-01), • VOSEJPKA, Paul, C. pages 2837-2841, XP002467200 ISSN: 0024-9297 Midland, MI 48640 (US) • WAGENER K B ET AL: "Well Phase Separated • WAGNER, Nicole, L. Segmented Copolymers via Acyclic Diene Midland, MI 48640 (US) Metathesis (ADMET) Polymerization" JOURNAL • LANDES, Brian, G. OF POLYMER SCIENCE - PART A - POLYMER Midland, MI 48640 (US) CHEMISTRY, WILEY & SONS, HOBOKEN, NJ, US, • JUEPTNER, Guenter vol. 35, 1 January 1997 (1997-01-01), pages 21714 Hammah (DE) 3441-3449, XP002466949 ISSN: 0887-624X • BANK, David, H. Midland, MI 48642 (US) • WENZEL, Timothy, T. Midland, MI 48642 (US) 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 2 057 205 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 2 057 205 B1 • DATABASE WPI Week 200542 Thomson Scientific, London, GB; AN 2005-410252 XP002498676 & JP 2005 139284 A (DOKURITSU GYOSEI HOJIN SANGYO GIJUTSU SO) 2 June 2005 (2005-06-02) 2 EP 2 057 205 B1 Description BACKGROUND OF THE INVENTION 5 [0001] The present invention relates in one aspect to a process for preparing block copolymers by metathesis of two or more polymers containing ethylenic unsaturation and in another aspect to meta-block copolymer compositions derived therefrom. Numerous olefin metathesis processes are previously known in the art. In general, olefin metathesis involves catalytic cleavage of one or more olefins at a point of unsaturation and recombination of the resulting cleavage products to form different olefin containing reaction products. Often, low molecular weight olefins and cyclic olefins are employed 10 as reagents in the foregoing reaction mixtures in order to provide low viscosity reaction mixtures, well defined reaction products, reduced polymer product molecular weight, and/or mixtures suitable for reaction injection molding (RIM) com- positions. Examples of the foregoing processes are disclosed in USP 5,731,383, 4,994,535, 4,049,616, 3,891,816, 3,692,872, and elsewhere. [0002] Metathesis involving polymeric olefins is also known. In Macromol., 33, 1494-1496 (2000), solid polymers were 15 depolymerized by surface contact with a metathesis catalyst. Reaction products of polymer metathesis can include random or block copolymers, functionalized polymers obtained through functionalization of resulting terminal unsatura- tion, ring opened metathesis products, and even cross-linked solids. Metathesis of two or more different olefins is referred to as a "cross-metathesis". Examples of such processes are disclosed by USP’s 6,867,274, 6,410,110, 5,603,985, 5,559,190, 5,446,102, 4,049,616, and other references. Suitable unsaturated polymers for the foregoing processes 20 include diene homopolymers and copolymers or partially hydrogenated derivatives thereof. Use of cyclic olefins can result in the formation of polymers having narrow molecular weight distributions. For example, preparations of linear polyethylene and poly(ethylidene-norbornene)/polycyclopentene diblock copolymers by ring opening metathesis of poly- cyclopentene or sequential polymerization of mixtures of ethylidene-norbornene and polycyclopentene were disclosed in Macromol., 33(25), 9215-9221 (2000). 25 [0003] In USP’s 3,692,872, 3,891,816 and 4,010,224 graft and block copolymers and interpolymers were prepared by metathesis of two polymers containing olefinic unsaturation, such as polybutadiene or polyisoprene. Monomers such as cyclooctene or dimers such as cyclooctadiene-cyclopentadiene dimer could be included in the polymerization as well. Similar processes involving the cross-metathesis of polybutadiene with polycyclooctene or polycyclododecene as well as grafting of EPDM polymers via metathesis were disclosed in DE 2,131,355 and DE 2,242,794. In the former process, 30 "thermoplastic properties were imparted to the elastomer". A summary of the work appeared in J. Mol. Catal., 15, 3-19 (1982). [0004] Similarly, in USP’s 3,692,872, 3,891,816 and 4,010,224 graft and block copolymers and interpolymers were prepared by metathesis of two polymers containing olefinic unsaturation, such as polybutadiene and polyisoprene. Monomers and dimers such as cyclooctene or cyclooctadiene-cyclopentadiene dimer could be included in the polym- 35 erization as well. Exemplified polymer pairs included partially polymerized cements of polycyclooctene and polycy- clooctadiene (Ex. I), EPDM/ polybutadiene (Ex. II and V), and two EPDM/ cyclooctadiene copolymers having differing cyclooctadiene contents (Ex. III). [0005] In Macromol., 36, 9675-96777 (2003) the ethenolysis of polypropylene/ 1,3-butadiene copolymers to prepare polymers having slightly increased melting temperature for the isotactic polymer segments due to improved packing of 40 shorter chain segments was disclosed. In German Democratic Republic patents DD 146,052 and DD 146,053, 1,4-cis- polybutadiene and copolymerssuch as ABS rubber or SBrubber were subjectedto metathetic depolymerization optionally in the presence of a functionalizing agent, especially an unsaturated carboxylic acid ester. According to USP 7,022,789, the products were polydisperse rubbers indicating the presence of cross-linking due to undesirable quantities of vinyl groups in the product. 45 [0006] In Macromol., 37, 3328-3336 (2004), a series of segmented copolymers was synthesized via acyclic diene metathesis (ADMET) chemistry by copolymerizing either an aliphatic carbonate hard segment diene or an aromatic ester hard segment diene with a telechelic oligomer soft segment diene of either poly(tetramethylene oxide) or polyisobutylene. [0007] In US3860675A, block polymers were prepared from at least two polymers which contain C=C double bonds. The at least two polymers containing C=C groups were treated in the liquid phase with a mixed catalysts of (a) a compound 50 of metals of group Vb or VIb of the periodic system, and (b) an organometallic compound of a metal of groups la to III a of the periodic system and a cocatalyst of epoxides of halogenated alcohols. [0008] Disadvantageously, the foregoing known polymeric olefin metathesis products are lacking in desirable physical properties due to the fact that at equilibrium, the individual block lengths, which approach the lengths of the unsaturated segments in the starting polymer reagents, are undesirably short and lacking in polymeric character. Moreover, the 55 individual blocks do not differ significantly from one another in chemical properties. For example, segment properties of polycyclooctene and polycyclododecene or of polybutadiene and polyisoprene, are nearly chemically equivalent. Co- polymers comprised of such polymer segments do not possess advantaged properties. Conventional block copolymers, such as those prepared by anionic polymerization techniques readily incorporate dissimilar, immiscible, lengthy segments 3 EP 2 057 205 B1 in the same polymer chain. Because the segments are of sufficient molecular weight to possess measurable physical properties, such as glass transition temperature (Tg), crystalline melting point (Tm), dielectric constant or solubility parameter the resulting polymers possess enhanced properties. For example, the presence of crystalline polymer seg- ments having a relatively high melting point and elastomeric polymer segments within the same polymer chain gives 5 thermoplastic materials having improved elastomeric and mechanical properties, such as high tensile strength, hyster- esis, and tear properties. [0009] The previously discussed processes utilized