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United States Patent [191 [11] Patent Number: 5,055,536 Dubois [45] Date of Patent: Oct

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United States Patent [191 [11] Patent Number: 5,055,536 Dubois [45] Date of Patent: Oct United States Patent [191 [11] Patent Number: 5,055,536 Dubois [45] Date of Patent: Oct. 8, 1991 [54] PROCESS TO PREPARE VINYL ETHER tem for Living Cationic . ”, Sawamoto et al., Macro POLYMERS molecules, 1987, 20, 2693-2697. [75] Inventor: Donn A. Dubois, Houston, Tex. “Mechanism of Living Polymerization of Vinyl Ethers by the Hydrogen Iodide . ", I'Iigashimura et al., Mac [73] Assignee: Shell Oil Company, Houston, Tex; romolecules, 1985, 18, 611-616. [21] Appl. No.: 564,523 “Synthesis of Monodisperse Living Poly(vinyl ethers) and Block Copolymers . ", Miyamoto et al., Macro [22] Filed: ' Aug. 9, 1990 molecules, 1984, 17, 2228-2230. [51] Int. Cl.5 ....................... .. C08F 4/16; CO8F 12/24; “Synthesis of P-Mcthoxystyrene-Isobutyl Vinyl Ether C08F 16/16 Block Copolymers by Living Cationic . ", I-Iiga [52] US. Cl. ................................. .. 526/194; 526/313; shimura et al., Macromolecules, 1979. 526/332; 526/292.9; 526/273; 526/312; Hawley’s Condensed Chemical Dictionary, 11th Ed., 526/ 279 VanNostrand, New York, 1987, pp. 697-698, 792-793, [58] Field of Search ....................................... .. 526/ 194 1248-1249. [56] References Cited R. Szostak, “Molecular Sieves”, Van Nostrand, New York, 1989, pp. 2-3, 26-27. U.S. PATENT DOCUMENTS Kirk Othmer Encyclopedia of Chemical Technology, 2,104,000 12/1937 Reppe ................................. .. 526/90 3rd Ed. (1981), pp. 638-669, “Molecular Sieves". 2,882,244 4/1959 Milton . .. 252/455 O. W. Webster et al., (1983) J. Am. Chem. Soc. 105, 3,228,923 1/1966 Scott et a1. 260/9l.1 5706-5708. 3,365,433 1/1968 Manson et al. 260/9l.l 3,394,116 7/1968 Sorkin ........... .. 260/91.1 Primary Examiner-Joseph L. Schofer 3,461,075 8/1969 Manson et a1. .... .. 252/301 3 Assistant Examiner-M. Nagumo 3,819,596 6/1974 Gross ........ .. 260/91.1 M Attorney, Agent, or Firm-James O. Okorafor 4,866,145 9/1989 Dicker ....................... .. 526/ 190 [57] ABSTRACT FOREIGN PATENT DOCUMENTS A method of preparing vinyl ether polymers is pro 74004055 1/ 1974 Japan . 096195/13 2/1989 Japan . vided. The process utilizes as a catalyst an iodine con 1561968 3/1980 United Kingdom . taining electrophile and a zeolite. The vinyl ethers cat ionically polymerize to polymers having narrow molec OTHER PUBLICATIONS ular weight distributions. The vinyl ether may be copo “Living Cationic Polymerization of P-Methoxystyrene lymerized with styrene, alkyl-substituted styrenes, al by Hydrogen . ", I-Iigashimura et al., Polymer Bulle koxy-substituted styrenes and mixtures thereof. tin, 19, 7-11, 1988. “Hydrogen Iodide/ Zinc Iodide: A New Initiating Sys 15 Claims, No Drawings 5,055,536 1 2 It is therefore an object of this invention to provide a PROCESS TO PREPARE VINYL ETHER process to polymerize vinyl ethers which results in POLYMERS polymer compositions having narrow molecular weight distributions and wherein soluble cocatalyst is not re FIELD OF THE INVENTION quiretL This invention relates to a process to polymerize SUMMARY OF THE INVENTION vinyl ethers. The objects of the present invention are achieved by BACKGROUND OF THE INVENTION providing a process‘ to polymerize vinyl ether utilizing Polymers of vinyl ether and processes to prepare 10 an iodine containing electrophile as an initiator and a these polymers by cationic polymerization are known. zeolite as a coinitiator. This initiator system, when uti For example, Higashimura describes a process for poly lized under favorable solvent and temperature condi merizing vinyl ether and para-methoxy styrenes tions, can result in high molecular weight polymers wherein a catalyst obtained by combining HI and I; or with narrow molecular weight distributions, and can be 15 ZnXz wherein X is a halogen such as iodine, chlorine or utilized to produce block copolymers by sequential bromine is used, Higashimura et al., Macromolecules, monomer addition. A preferred iodine containing elec Vol. 12, p. 178 (1979). This system is effective in the trophile is trimethylsilyliodide. Other iodine containing preparation of these polymers, but the zinc halides are electrophiles which may be utilized include HI. toxic and a process which utilizes a non-toxic catalyst is 20 DETAILED DESCRIPTION OF THE desirable. The zinc catalysts are also soluble in the poly‘ INVENTION mer solutions and will contaminate the polymer requir ing a costly catalyst extraction procedure. Without The vinyl ether useful in the present invention may be removing the catalyst the polymer will be highly dis of the general formula: clored and the polymer generally has an undesirable 25 color even after catalyst extraction. Alternative processes to prepare vinyl ether poly wherein R’ is an alkyl, cycloalkyl or alkyl substituted mers include utilization of zeolites as catalysts. Exem cycloalkyl, aromatic or alkyl substituted aromatic hav plary processes are described in, for example, U.S. Pat. ing from about 1 to about 20 carbon atoms R’ may Nos. 3,228,923; 3,365,433; 3,394,116; 3,461,075; and optionally be substituted with such groups as halogen, 3,819,596. Although the mechanism for this polymeriza epoxy, tertiary amine, vinyl, siloxy and the like. tion is not clear, it does not appear to be a cationic The catalyst useful in the process of the present in polymerization. The resultant polymers may have high vention is prepared by combining trimethylsilyliodide, molecular weights, but have an extremely wide molecu hydrogen iodide or another iodine-containing electro lar weight distribution. The polymer made by the pro 35 phile with a zeolite to produce an initiator system. cess of U.S. Pat. No. 3,819,596 is touted as an excellent The amount of iodine utilized is determined by the plasticizer due to the broad molecular weight distribu desired polymer molecular weight. In general, the tion. The index of dispersity (ratio of highest molecular moles of iodine provided will be equal to the grams of weight to peak molecular weight) for these polymers monomer divided by the desired weight average poly exceeds 20. The polymer produced by this method is mer molecular weight. said to have a molecular weight distribution which Zeolites which have acid sites are effective as the extends from 180 to 800,000. This wide molecular cocatalysts of this invention. Acidity can be introduced weight distribution is bene?cial for some properties and by the decomposition of the NH4+ ion-exchanged end uses, such as tacki?ers and plasticizers. For other form, by hydrogen-ion exchange, and by hydrolysis of end uses, a narrow molecular weight distribution is 45 zeolite containing multivalent cations during hydroge preferred. For molding compositions, ?lms and ex nation. truded products, having a high tensile strength with a A wide variety of acid site containing zeolites may be low melt viscosity is desirable. Compositions which utilized as the cocatalysts of this invention. The zeolites have a wide variety molecular weights generally have a can include both synthetic and naturally occurring zeo of high melt viscosity due to the high molecular weight 50 lites. Illustrative of the synthetic zeolites are Zeolite X, constituents, and a relatively low tensile strength due to U.S. Pat. Nos. 2,882,244; Zeolite Y, 3,130,007; Zeolite the low molecular weight constituents. A’ polymer with A, 2,882,243; Zeolite L, Bel. 575,117; Zeolite D, Can. a narrow molecular weight distribution is therefore 611,981; Zeolite R, 3,030,181; Zeolite S, 3,054,657; Zeo preferred for many applications. lite T, 2,950,952; Zeolite Z, Can. 614,995; Zeolite E, Polymers which have narrow molecular weight dis 55 Can. 636,931; Zeolite F, 2,995,358; Zeolite 0, 3,140,252; tributions are also preferred as lubricating oil additives Zeolite W, 3,008,803; Zeolite Q, 2,991,151; Zeolite M, viscosity index improvers. Polymers that are high in 2,995,423; Zeolite H, 3,010,789; Zeolite J, 3,001,869; molecular weight are degraded by mechanical shear Zeolite W, 3,012,853; Zeolite KG, 3,056,654; Zeolite while in lubricating oil service. High molecular weight SL, ‘Dutch 6,710,729; Zeolite Omega, Can. 817,915; polymers also contribute disproportionately to the Zeolite ZK-S, 3,247,195; Zeolite Beta, 3,308,069; Zeo thickening effect, or change in viscosity for a constant lite EU-l, 4,537,754; Zeolite ZK-4, 3,314,752; Zeolite amount of polymer added. The shearing of these high ZSM-5, 3,702,886; Zeolite ZSM-ll, 3,709,979; Zeolite molecular weight polymers therefore drastically affects ZSM-12, 3,832,449; Zeolite ZSM-ZO, 3,972,983; Zeolite the viscosity of the lubricating oil composition. Having ZSM-35, 4,016,245; Zeolite ZSM-SO, 4,640,829; syn a narrow molecular weight distribution therefore re 65 thetic mordenite; the so-called ultrastable zeolites of sults in a viscosity index improver with a minimal U.S. Pat. Nos. 3,293,192 and 3,449,070; and the refer change in viscosity over time for a similar initial thick ences cited therein, incorporated herein by reference. ening effect. Other acceptable synthetic zeolites are described in the 5,055,536 3 book “'Zeolite Molecular sieves-Structure, Chemistry and Use,” by Donald W. Breck, 1974, John Wiley & Sons, incorporated by reference herein. Illustrative of the acceptable naturally occurring zeolites are anal cime, bikitaite, edingtonite, epistilbite, levynite, dachi ardite, erionite, faujasite, analcite, paulingite, noselite, ferrierite, heulandite, scolecite, stilbite, clinoptilolite, harmotone, phillipsite, brewsterite, flakite, datolite, wherein: chabazite, gmelinite, cancrinite, leucite, lazurite, scole R is a hydrogen or an alkyl group, and cite, mesolite, ptilolite, mordenite, nepheline, natrolite, R’ is a hydrogen, alkyl, or alkyloxy. scapolite, thomsonite, gismondine, garronite, gonnar A particularly preferred alkoxy substituted styrene is dite, heulandite, laumontite, levynite, offretite, and methyloxystyrene. Styrene is also a preferred comono yugawaralite. Descriptions of certain acceptable natu mer.
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