(12) United States Patent (10) Patent No.: US 8,349,977 B2 Koenig Et Al
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US008349977B2 (12) United States Patent (10) Patent No.: US 8,349,977 B2 Koenig et al. (45) Date of Patent: Jan. 8, 2013 (54) PROCESS FOR PREPARING W. W338 A .289 SETITY ISOBUTENE HOMO- OR WO WO 2010, 139684 A1 12/2010 OTHER PUBLICATIONS (75) Inventors: Hannah Maria Koenig, Mannheim (DE); Klaus Muellbach, Gruenstadt Edward C. Leonard. “High Polymers'. Wiley-Interscience, A Divi (DE); Matthias Kiefer, Ludwigshafen sion of John Wiley & Sons, Inc., vol. XXIV. (part 2), 1971, 1 front (DE); Sergei V. Kostjuk, Minsk (BY); page, pp. 713-733. 66/ - - - - - Irina Vasilenko, Minsk (BY): James D. Burrington, et al., Cationic polymerization using s s heteropolyacid salt catalysts'. Topics in Catalysis, vol. 23, Nos. 1-4. Alexander Frolov, Svisloch (BY) Aug. 2003, pp. 175-181. Sergei V. Kostjuk, et al., “Novel Initiating system based on AlCl (73) Assignee: BASFSE, Ludwigshafen (DE) etherate for quasiliving cationic polymerization of styrene'. Polymer Bulletin, vol. 52, 2004, pp. 227-234. (*) Notice: Subject to any disclaimer, the term of this Sergei V. Kostjuk, et al., “Cationic Polymerization of Styrene in patent is extended or adjusted under 35 Solution and Aqueous Suspension Using B(C6F5) as a Water-Toler U.S.C. 154(b) by 0 days. ant Lewis Acid', Macromolecules, vol.39, No. 9, Apr. 8, 2006, pp. 3110-3113. (21) Appl. No.: 13/029,413 U.S. Appl. No. 13/126,857, filed Apr. 29, 2011, Hildebrandt, et al. U.S. Appl. No. 13/305,132, filed Nov. 28, 2011, Koenig, et al. (22) Filed: Feb. 17, 2011 U.S. Appl. No. 13/305,283, filed Nov. 28, 2011, Koenig, et al. Y. Li et al.: “Electron-Pair-Donor Reaction Order in the Cationic (65) Prior Publication Data Polymerization of Isobutylene Coinitiated by AICI3” in: Journal of Polymer Science, Part A: Polymer Chemistry, vol. 45, No. 14, pp. US 2011 FO2O1772 A1 Aug. 18, 2011 3053-3061 (2007). L. Ambrozet al.: “Donor-Acceptor-Interactions in Cationic Polymer Related U.S. Application Data ization. II. Influence of Some Bases of Polymerization of Isobutylene' in: Journal of Polymer Science, vol. 30, pp. 381-389 (60) Provisional application No. 61/417,895, filed on Nov. (2003). 30, 2010, provisional application No. 61/315,431, M. Bahadur et al.: “Dimethylaluminium Chloride Catalyzed Living filed on Mar. 19, 2010, provisional application No. Isobutylene Polymerization” in: Macromolecules vol. 33, pp.9548 61/305,159, filed on Feb. 17, 2010. 9552 (2000). International Search Report of corresponding PCT/EP2011/051929. (51) Int. Cl. CSF 4/4 (2006.01) * cited by examiner CSF IO/TO (2006.01) (52) U.S. Cl. ..................... s26/27,526,3486,526,210. Primary Examiner Robert D. Harlan 526/212:526/290; 526/348.7 (74) Attorney, Agent, or Firm — Oblon, Spivak, (58) Field of Classification Search .................. sos, McClelland, Maier & Neustadt, L.L.P. 526/64, 210, 212, 290, 348.7 See application file for complete search history. (57) ABSTRACT Preparation of high-reactivity isobutene homo- or copoly (56) References Cited mers with a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol % and a polydis U.S. PATENT DOCUMENTS persity of preferably 1.05 to less than 3.5, by polymerizing 5,169,914 A 12/1992 Kaszas et al. isobutene or an isobutene-comprising monomer mixture in 5,324,878 A * 6/1994 Brunelli et al. ............... 585,508 the presence of an aluminum trihalide-donor complex effec 5,340,881 A 8/1994 Kennedy et al. tive as a polymerization catalyst or of an alkylaluminum 5,408,018 A 4, 1995 Rath halide-donor complex, especially of an aluminum trichlo FOREIGN PATENT DOCUMENTS ride-donor complex, said complex comprising, as the donor, DE 27 O2 604 A1 T 1978 an organic compound with at least one ether function or a EP O 145235 A1 6, 1985 carboxylic ester function. WO WO99,64482 * 12/1999 WO WO99,64482 A1 12/1999 25 Claims, No Drawings US 8,349,977 B2 1. 2 PROCESS FOR PREPARING In the literature article “Cationic polymerization using het HIGH-REACTIVITY ISOBUTENE HOMO- OR eropolyacid salt catalysts’ in Topics in Catalysis Vol. 23, p. COPOLYMERS 175-181 (2003), James D. Burrington et al. indicate that, with aluminum trichloride as a polymerization catalyst for The present invention relates to a novel process for prepar isobutene, only low-reactivity polyisobutenes with a low con ing high-reactivity isobutene homo- or copolymers with a tent of terminal vinylidene double bonds (C.-double bonds) content of terminal vinylidene double bonds per poly can be obtained. For instance, table 1 on page 178 of this isobutene chain end of at least 50 mol%. The present inven literature article cites an example of a polyisobutene prepared tion further relates to novel isobutene polymers. with AlCls, which has a number-average molecular weight In contrast to so-called low-reactivity polymers, high-re 10 Mn of 1000-2000, a polydispersity Mw/Mn of 2.5-3.5 and a activity isobutene homo- or copolymers are understood to content of vinylidene isomer (C.-double bond) of only 5% (in mean those polyisobutenes which comprise a high content of addition to 65% “tri", 5% “B” and 25% “tetra). terminal ethylenic double bonds (C.-double bonds), specifi In the literature article “Novel initiating system based on cally in practice usually of at least 80 mol %, based on the AlCletherate for quasiliving cationic polymerization of sty individual chain ends of the polyisobutene macromolecules. 15 rene' in Polymer Bulletin Vol. 52, p. 227-234 (2004), Sergei In the context of the present application, vinylidene groups V. Kostjuk et al. describe a catalyst system composed of are understood to mean those double bonds whose position in 2-phenyl-2-propanol and an aluminum trichloride/di-n-butyl the polyisobutene macromolecule is described by the general ether complex for polymerization of styrene. The polydisper formula sities M/M of the styrene polymers thus prepared are “-2.5” (see summary) or '-3' (see page 230). It was an object of the present invention to provide a pro cess for preparing high-reactivity isobutene homo- or copoly mers with a content of terminal vinylidene double bonds per polymer )- polyisobutene chain end of at least 80 mol % and simulta 25 neously with a narrow molecular weight distribution (i.e. low polydispersities) in acceptable yields. The catalyst system i.e. the double bond is present in an a position in the polymer should at the same time have sufficient activity and service chain. “Polymer represents the polyisobutene radical short life, the handling thereof should be unproblematic and it ened by one isobutene unit. The vinylidenegroups exhibit the should not be prone to failure. highest reactivity, for example in the thermal addition onto 30 The object was achieved by a process for preparing high sterically demanding reactants such as maleic anhydride, reactivity isobutene homo- or copolymers with a content of whereas a double bond further toward the interior of the terminal vinylidene double bonds per polyisobutene chain macromolecules in most cases exhibits lower reactivity, if end of at least 50 mol %, which comprises polymerizing any, in functionalization reactions. The uses of high-reactiv isobutene or an isobutene-comprising monomer mixture in ity polyisobutenes include use as intermediates for preparing 35 the presence of an aluminum trihalide-donor complex effec additives for lubricants and fuels, as described, for example, tive as a polymerization catalyst or of an alkylaluminum in DE-A 27 O2 604. halide-donor complex, said complex comprising, as the Such high-reactivity polyisobutenes are obtainable, for donor, an organic compound with at least one ether function example, by the process of DE-A 27 02 604 by cationic or a carboxylic ester function. polymerization of isobutene in the liquid phase in the pres 40 Isobutene homopolymers are understood in the context of ence of borontrifluoride as a catalyst. A disadvantage here is the present invention to mean those polymers which, based on that the polyisobutenes obtained have a relatively high poly the polymer, are formed from isobutene to an extent of at least dispersity. The polydispersity is a measure of the molecular 98 mol %, preferably to an extent of at least 99 mol %. weight distribution of the resulting polymer chains and cor Accordingly, isobutene copolymers are understood to mean responds to the quotient of weight-average molecular weight 45 those polymers which comprise more than 2 mol% of copo M, and number-average molecular weight M (PDI-M/ lymerized monomers other than isobutene, for example linear M). butenes. Polyisobutenes with a similarly high proportion of termi In the context of the present invention, the following defi nal double bonds but with a narrower molecular weight dis nitions apply to generically defined radicals: tribution are, for example, obtainable by the process of EP-A 50 A C- to Cs-alkyl radical is a linear or branched alkyl 145 235, U.S. Pat. No. 5,408,018 and WO 99/64482, the radical having 1 to 8 carbon atoms. Examples thereof are polymerization being effected in the presence of a deactivated methyl, ethyl, n-propyl, isopropyl. n-butyl, 2-butyl, isobutyl, catalyst, for example of a complex of boron trifluoride with tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbu alcohols and/or ethers. tyl, 2,2-dimethyl-propyl, 1-ethylpropyl, n-hexyl, 1,1-dimeth High-reactivity polyisobutenes are also obtainable by liv 55 ylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpen ing cationic polymerization of isobutene and Subsequent tyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1.2- dehydrohalogenation of the resulting polymerization prod dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2.3- uct, for example by the process from U.S.