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A Surgical Clip For Clipping A Tubular Structure In Vivo

Abstract: A polyether composition comprised of a polyether, a functionalizing catalyst and a metal cyanide catalyst is formed by forming a functionalized initiator compound by reacting a precursor initiator compound with a functionalizing compound and a functionalizing catalyst to form the functionalized initiator compound, forming a mixture of the functionalized initiator compound containing at least a portion of the functionalizing catalyst, an alkylene oxide and a metal cyanide catalyst complex, and subjecting the mixture to conditions sufficient to activate the catalyst complex and to alkoxylate the functionalized initiator compound to form the polyether. The functionalized initiator compound may be of a vegetable oil, animal fat or modified vegetable oil or modified animal fat. The functionalizing catalyst may be a tin, titanium, iodine, rhodium, nickel, acid or enzyme catalyst.

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Patent Information

Application #
Filing Date
28 July 2005
Publication Number
27/2007
Publication Type
INA
Invention Field
METALLURGY
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2008-10-30
Renewal Date

Applicants

UNIVERSITY OF LONDON
GOWER STREET LONDON WC1E 6BT, GREAT BRITAIN

Inventors

1. BARKER STEPHEN
THE ACADEMIC VASCULAR UNIT THE MIDDLESEX HOSPITAL MORTIMER STREET LONDON WIN8AA UK
2. HOLLINGSWORTH
THE ACADEMIC VASCULAR UNIT THE MIDDLESEX HOSPITAL MORTIMER STREET LONDON WIN 8AA UK

Specification

IMPROVED METHOD FOR ALKOXYLATING ACTIVE HYDROGEN CONTAINING COMPOUNDS AND THE ALKOXYLATED COMPOUNDS MADE THEREFROM This application claims benefit of United States Provisional Patent Application No. 60/622,298, filed October 26, 2004. This invention relates to processes for preparing poly(oxyalkylene) polymers and to methods for preparing same. Polyethers made from alkylene oxides are well known and useful in a number of applications such as detergent and cleaner compositions, oil well drilling fluids, inks, metal working fluids, lubricants in paper coating compositions, ceramics manufacturing, chemical intermediates for nonionic surfactants which in turn are used in cosmetics, textiles and chemical processing, polyurethanes which are used as flexible foams and elastomers, chemical intermediates for esters which are used in textile spin finishes, cosmetic agents, and as foam control agents for a wide variety of processes. These polymers may have no more than one oxyalkylene group in succession, or be a higher molecular weight polymer containing one or more long chains of consecutive oxyalkylene groups. Polyethers of this type are commonly made through an anionic polymerization process, whereby the alkylene oxide is combined with an initiator compound and a strongly basic catalyst such as potassium hydroxide or certain organic amines. The initiator compound contains one or more oxyalkylatable groups such as hydroxyl, thiol, carboxylic acid and the like. The initiator compound determines the functionality (i.e., number of hydroxyl groups/molecule of product) and in some cases may introduce some desired functional group into the product. There are some disadvantages of polymerizing alkylene oxides using these strongly basic catalysts. One problem is that the strongly basic catalysts do not produce a low polydispersity product when a tertiary alcohol initiator compound is used. In addition, the basic catalyst usually must be removed from the product before it is used, which increases manulacturing costs. In addition, some kinds of initiator compounds cannot be alkoxylated using strongly basic catalysts, because they contain base-sensitive functional groups. For example, initiators containing certain types of alkenyl or alkynyl groups undergo a side reaction in which the alkenyl or alkynyl group will "migrate" along the molecular chain, so that the unsaturation in the polyether is at a different place than it was on "the initiator. This is of particular concern when terminal unsaturation is desired. Ofben, unsaturation that is in a terminal position on the initiator migrates to a non-terrnLnal position during the alkoxylation reaction. Unsaturated compounds in which a triple bond is adjacent to a hydroxyl-substituted carbon atom, are prone to decomposing during the alkoxylation reaction. Many compounds of this type are reaction products of acetylene with a ketone sucfai as acetone or an aldehyde such as acetaldehyde. Alkali metal or alkaline earth bases can cause these initiators to decompose to regenerate acetylene. Acetylene is an explosion hazard. In order to try to avoid these problems, Lewis acids such as boron trifluoride-diethyl etherate and organic amines such as triethylamine have been tried. However, some of these catalysts tend to promote the formation of large amounts of by-prodixcts, especially when it is attempted to add three or more moles of alkylene oxide per equivalent of initiator compound. The Lewis acid catalysts tend to catalyze 'backbiting" reactions where tlie growing polymer chain reacts with itself. The reactions form cyclic ethers such as dioxane, dimethyldioxane and various crown ethers. These cannot be removed easily from the desired product, and so the product cannot be used in nxany applications. To solve some of the problems described, a metal cyanide catalyst complex has been employed, but the use of such metal cyanide catalysts has been limited due to tleir sensitivity to catalysts needed to form the initiator compounds containing active hydrogen initiating groups (e.g., hydroxyl, anhydride, primary and secondary amino groups). Consequently, the use of metal cyanide catalysts have required initiators free from catalysts (e.g., bases and acids) used to form the initiators, which has required extensive purification of such initiators. Thus, it would be desirable to provide a method whereby polyethers made using certain initiator compounds could be produced in good yield with low levels of byproducts without having to purify the initiator compounds. In one aspect, this invention is a process for preparing a polyether comprising; (i) forming a fiinctionalized initiator by reacting a precursor initiator compound with a functionalizing compound and a functionalizing catalyst to form the fiinctionalized initiator, (ii) forming a mixture, of the functionalized initiator containing at least a poxrtion of the functionalizing catalyst from step (i), an alkylene oxide and a metal cyanide catalyst complex, and, (iii) subjecting the mixture to conditions sufficient to activate the catalyst complex and to alkoxylate the initiator compound to form the polyethear. The functionalizing catalyst is a catalyst that is used to incorporate into the initiator compound groups that are reactive with the alkylene oxide such that the polye~ther can be formed using a metal cyanide complex. In a second aspect, this invention is a polyether, i.e., poly(alkylene oxide), polymer containing a functionalizing catalyst and metal cyanide catalyst. This invention permits the ready formation of polymers of initiators that have been fimctionalized (chemical groups that react with the alkylene oxide, for example, hydroxyls, carboxylic acids, and amines) without having to scrupulously remove the catalyst or catalysts used to form such initiators to avoid poisoning of the metal cyanide catalyst. In this invention, fimctionalized initiators that have been formed using a. catalyst are alkoxylated by reaction with one or more alkylene oxides in the presence of a catalytically effective amount of a metal cyanide catalyst. The alkoxylation is conducted by combining the fimctionalized initiator, metal cyanide catalyst and alkyleme oxide. The catalyst is then allowed to become activated in the presence of the alkyleaie oxide. Once the catalyst has become activated, the mixture is subjected to conditions sufficient to polymerize the alkylene oxide. In this manner, the fimctionalized initiator becomes alkoxylated until poly(oxyalkylene) chains of a desired length are introduced. As discussed below, once polymerization has begun, other iypes of monomers that are copolymerizable with alkylene oxides can be polymerized as well. The fimctionalized initiator may be any organic compound (precursor initiator compound) that has been reacted using a catalyst to incorporate groups thai; may be alkoxylated using a metal cyanide catalyst. Preferably, the precursor initiator compound is a vegetable oil, animal fat, modified vegetable oil, modified fat or combination thereof. Modified herein means altering the vegetable oil or fat in some way but not functionalizing the oil or fat. It is understood herein that fatty acids from the fat or oil (i.e., simple saponification) are not fimctionalized initiators. The precursor initiator compound may be any animal fat or vegetable oil that is comprised of triglycerides that upon saponification with a base such as aqueoixs sodium hydroxide yields a fatty acid and glycerol, where at least a portion of the fatty acids are unsaturated fatty acids (i.e., contain at least one carbon-carbon double bond). Preferred vegetable oils are those that yield at least about 70 percent unsaturated fatty acids weight. More preferably, the vegetable oil yields at least about 85 percent, more preferably at least 87 percent, and most preferably at least about 90 percent by weight unsaturated fatty acids. It is understood that specific fatty acids derived from a vegetable oil, animal fat or any other source may be used. That is to say, for example, palmitoleic, oleic, linoleic, linolenic and arachidonic fatty acids or their alkyl esters m_ay be used to form the precursor initiator compound that is used to form the functionalized initiator. It is preferred, however, to use a vegetable oil as previously described. Preferred vegetable oils include, for example, soy, safflower, cotton, linseed, peamut, olive, sunflower, canola., rapeseed, corn, palm oil or combination thereof. More preferably, the vegetable oil is a soy, sunflower, canola, corn, rapeseed oil, or combination thereof. Most preferably, the vegetable oil is soy, sunflower, canola oil or combination thereof. It is understood that the vegetable oil may be obtained from a genetically modified organism, such as genetically modified soybean, sunflower or canola. The functionalized initiator may then be formed by taking the fatty acid alkyl esters of the fatty acid, the fatty acid of a vegetable oil or fat, or the vegetable oil or fat itself and by any suitable process such as those known in the art to form, for example, a "hydroxymethylated" animal fat or vegetable oil, or their corresponding fatty acid or alkyl ester functionalized initiator. The hydroxymethyl group may be introduced by a hydroformylation process using a cobalt, nickel or rhodium catalyst, followed by the hydrogenation of the foirmyl group to obtain the hydroxymethyl group by catalytic or by chemical reduction. Procedures to form such compounds are described in U.S. Pat. Mos. 4,216,343; 4216,344; 4,304,945 and 4,229,562 and in particular 4,083,816. Other known processes to form hydroxymethylesters from fatty acids may also be used such as described by U.S. Pat. Nos. 2,332,849 and 3,787,459. These hydroxymethylester initiator compounds may then be further transesterified as described by US. Patent Nos. 4,423,162; 4,496,487 and 4,543,369 and copending International application WO 2004/012427 designating the U.S using a catalyst such as a tin or titanium catalyst, enzyme catalyst or combination thereof, each of the above patents or applications for patent being incorporated herein by reference. Exemplary tin and titanium catalysts for the transesterification include tin (II) octanoate, tin (II) 2-ethylheptanoate, dibutyl tin (TV) dilaurate, and otlier tin catalysts that are similarly functionalized, titanium tetraisopropoxide, titanium tetraisobutoxide, or any appropriately functionalized titanium (IV) alkoxide or combination thereof. An exemplary enzyme catalyst is lipase. Preferably, the functionalized initiator from the just described process is a modified vegetable oil that is a polyol comprised of where R is a residue of a polyol, polyamine or aminoalcohol initiator; X and X' may the same or different and is O, N or NH; p is an integer from 1 to 5; q is an integer from. 1 to 5 wherein p + q is from 3 to 8, t is an integer from 3 to 8 and A may be the same or different and is selected from the group consisting of Al, A2 and A3 where where m, n, v, r, s, a, b and c are integers and m is greater than 3, n greater tlaan or equal to zero and m+n is fiom 11 to 19, v is greater than 3, r is greater than or eqoial to zero, s is greater than or equal to zero and v+r4-s is from 10 to 18, a is from 0 to 35, b is from 0 to 35 and c is from 0 to 35, so long as that all a's, b's and c's in any molecule of the vegetable oil based polyol are not all zero and (a+b+c)/(p+q+t) is greater than 0 to about 100. These preferred polyols generally are formed using a titanium, tin or enzyme catalyst described above. The residue of the polyol, polyamine or aminoalcohol initiator may be any of those described in WO 04/096882. The vegetable oil (triglyceride), fatty acid alkyl ester (e.g., methyl ester) or fatty acid may be functionalized by epoxidizing the carbon-carbon double bonds by oxidizing using a suitable method, such as those known in the art using a peracid, alkyl peroxide or hydroperoxide or compound that forms these in situ. Preferred acids that epoxidize the fatty acid, seed oil or alkyl ester include peracetic acid, peirformic acid or combination thereof. The peracid for the epoxidation may be generated in situ, for example, by using stoichiometric amounts of hydrogen peroxide in conjunction with catalytic amounts of a carboxylic acid such as acetic acid or formic acid. The ring opening of the epoxy, preferably uses a hydroxyl-containing nucleophile such as water, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerine, trimethylolpropane, and an acid catalyst such as mineral acid (e.g., perchloric acid, sulfuric acid or hydrochloric acid), an acidic sulfonated polystyrene ion. exchange resin (e.g., DOWEX* MSC-1, *Trademark of The Dow Chemical Company, Midland, MI), or sulfonated organic acids (e.g., methanesul&nic acid or other alkylsulfbnic acid or aromatic sulfonic acid such as p-toluenesulfbnic acid). The nucleophile may also be, for example, an organic acid such as formic acid, acetic acid, propionic acid, saturated fatty acids as well as polyfanctional saturated and unsaturated carboxylic acids such as adipic acid, succinic acid, maleic acid, fumaric acid, etc.. Alternately, tke carboxylic acid form of an unsaturated fatty acid can be used, which would create an oligomerized initiator via epoxidation of the unsaturated functionality in conjunction -with subsequent ring-opening oligomerization. Other known nucleophiles may also be used such as certain amines, mercaptans and multi-functional analogs such as hydroxycarboxylic acids, mercaptocarboxylic acids, hydroxylamines, and combination thereof. Exemplary methods and conditions such as those described in Biermann, XL; Friedt, W.; Lang, S.; Liihs, W.; Machmiiller, G.; Metzger, J.; Klaas, M.R.; Schafer, H.J.; Schneider, M.P. Angew. Chem. Int. Ed. Engl 39, 2206-2224 (2000), Baumann, H.; BiihJer, M.; Fochem, H.; Hirsinger, F.; Zoelelein, H.; Falbe, J. Angew. Chem. Int. Ed. Engl 27, 41-62 (1988), Swern, D.; Billen, G.N. Findley, T.W.; Scanlan, J.T. J. Am. Chem. Soc. & 7, 1786-9 (1945), US Pat. Nos. 2,485,160; 2,774,774; 6,121,398; 3,169,139; 4,508,853; 4,742,087; and 6,107,433 and WO 03/029182 Al may be used. The vegetable oil, fatty acid or fatty acid methyl ester may be functionalized by formoxylation or acetoxylation, for example, by addition reactions of acetic acid or formic acid (functionalizing compounds) to the carbon-carbon double bond of the vegetable oil, fatty acid or fatty acid alkyl ester (e.g., methyl ester) using a strong acid catalyst followed by ester cleavage using an acid catalyst to form a hydroxyl group in the vegetable oil, fatty acid or fatty acid alkyl ester. The strong acid catalysts are the same as those described above. Exemplary methods and conditions include those described in Knight, H.B.; Koos, R.E.; Swern, D. J. Am. Chem. Soc. 75, 6212-6215 (1953), and US Patent 2,759,953. The vegetable oil, fatty acid, or fatty acid alkyl ester may be functionalized by a Diels-Alder reaction meclianism using a catalyst that is non-basic such as an iodine or sulfur containing catalyst. Preferably, iodine is used as the catalyst to cause the required double bond conjugation and Diels-Alder reaction. Exemplary methods and conditions include those described by British Pat. Nos. 1,032,363; 762,122; 1,039,787; and 1,046,207, US Pat. Nos. 5,053,534; 5,194,640; 5,731,450; 4,740,367; 4,081,462; 4,196,134; 2,452,029; 3,753,968; and 3,890,259. The dienophile (functionalizing compound) may be any suitable to react with the vegetable oil or the like such as those known in the art. Preferably, the dienophile is maleic anhydride, maleic acid, fumaric acid, acrylic acid, metliacrylic acid, and other a,B-unsaturated carboxylic acids or corresponding esters, half-esters, or groups that can be readily converted to carboxylic acid functionality such as carboxylic acid chlorides or combination thereof. More preferably the dienophile is maleic anhydride, acrylic acid, or combination thereof. After the Diels-Alder adduct h.as been added into the vegetable oil or the like, if "the dienophile is an acyclic anhydride the adduct is ring opened to add in the reactive group necessary for alkoxylation using a metal cyanide catalyst. When a ring is present, thie ring may be opened by known metlxods and compounds such as water, an alcohol, aminoalcohol, polyol or combination thereof. Examples of such compounds include water, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerine, trimethylolpropane, aminoethanol, aminopropanol or combination thereof. Exemplary methods and conditions are described by US Pat. Nos. 2,444,328, 3,412,056 and 4,376,789. Even though the particular catalysts described above used to functionalize the initiator need not be removed, because they have surprisingly been found not to impede the alkoxylation using a metal cyanide catalyst, they may at least be partially removed for other reasons sucfci as side reactions that may be catalyzed by sixch catalysts during alkoxylation. Preferably, at most about 75%, more preferably at most about 50%, even more preferably at most about 25%, and most preferably at most; about 10% of the fiinctionalizing catalyst is removed prior to alkoxylating. Generally, the amount of functionalizing catalyst remaining in the resultant polyether is at least about 5 parts per million by weight- Preferably, the amount of the fiinctionalizing catalyst remaining in the resultant polyether is at least about 10 parts per million by weight (ppm), more preferably at least about 25 ppm, even more preferably at least about 50 ppm, and most preferably at least about 100 ppm. After the functionalized initiator has been formed, the alkoxylation is performed by first mixing the functionalized initiator, DMC catalyst and an alkylene oxide and allowing the mixture to sit for a period of time at room or an elevated temperature. When these materials are mixed, a so-called induction period occurs, during which the oxyalkylene reaction occurs very slowly. The induction period may range from a few minutes to several hoiirs, depending on the particular DMC catalyst that is used and the temperature. During this induction period, the DMC catalyst becomes activated, and rapid polymerization of the alkylene oxide then commences. The starting mixture of DMC catalyst, functionalized initiator and alkylene oxide is conveniently made by combining the DMC catalyst and functionalized initiator in a pressure reactor (or by forming the catalyst in the initiator), and tben pressurizing the reactor with an initial quantity of alkylene oxide. The induction period follows, as indicated by a nearly" constant or slowly decreasing pressure in the reactor. The onset of rapid polymerization that follows the induction period is evidenced by a drop in pressure as the alkylene oxide is consumed. The starting mixture of DMC catalyst, functionalized initiator and alkylene oxide may be brought to any convenient temperature to activate the ca_talyst, such as from about 20oC, preferably from about 50°C, more preferably from about 70°C, even more preferably from aboxit 80°C to about 150°C, most preferably to about 100°C. These temperatures are also suitable for conducting the polymerization once the DMC catalyst is activated. Depending on the desired degree of alkoxylation, all the necessary alkylene oxide may be added to the reactor at the outset. It is usually preferred to add more alkylene oxide to the reactor once the DMC catalyst has become activated, especially when making higher moleexdar weight polyethers. A convenient way of adding the alkylene oxide is to pressurize the reactor with alkylene oxide and allow alkylene oxide to feed to the reactor on demand, maintaining a more or less constant pressure inside the reactor. Alternatively, any additional alkylene oxide may be fed in one or more discrete increments. The total amount of alkylene oxide that is fed will depend on the desired equivalent weight of the product. As few as one mole of alkylene oxide per equivalent of initiator compound can be added. This invention is particularly suited for polymerizing at least about 1 mole of alkylene oxide per equivalent of initiator compound. Sufficient alkylene oxide can be added to make any desirable molecular weight polyether, such as one having a weight average molecular weight of 200,000 daltons or more. However, in most cases the intended end-use of the product will dictate its molecular or equivalent weight. Thus, for example, for making polyols for polyurethane applications, polyether equivalent weights of from about 75-500 are of particular interest for arigid polyurethane foams, equivalent weights of from about 300-1300 are of particular interest for making molded foams and high resiliency slabstock foams, and equivalent weights of from about 800-3000 are of particular interest for making conventional slabstock foam and reaction injection molded elastomers. For surfactant applications, molecular weights of from about 350 to about 6000 are of particular interest. In most applications, it is desirable that the product be a liquid. Poly(oxyethylene) homopolymers tend to form solids when their weight average molecular weights exceed about 700 daltons. All weights reported above are number average molecular weights. Similarly, the selection of alkylene oxide will depend to a large extent on the intended end-use of the product. Among the alkylene oxides that can be polymerized with the catalyst complex of the invention are ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, and mixtures thereof. Mixtures of these can be used, and two or more of them can be polymerized sequentially to make block copolymers. For polyurethanes applications, preferred alkylene oxides are propylene oxide alone, mixtures of at least 50 weight % propylene oxide and up to about 50 weight % ethylene oxide (to form a random copolymer), and propylene oxide followed lay ethylene oxide, so as to form terminal poly(oxyethylene) chains constituting up to aboxit 30% of the total weight of the product. For other applications, ethylene oxide alone, 1,2-butylene oxide, ethylene oxide/l,2-butylene oxide mixtures, ethylene oxide followed lay propylene oxide or butylene oxide, bxxtylene oxide followed by ethylene and/or propylene oxide, propylene oxide alone, mixtures of propylene oxide and ethylene and/or butylene oxide, and propylene oxide followed by ethylene and/or butylene oxide are preferred alkylene oxides. In addition, monomers that will copolymerize with the alkylene oxide in the presence of the DMC catalyst complex can be used to prepare modified polyether polyols, after the DMC catalyst has become activated. Such comonomers include oxetanes as described in U. S. Patent Nos. 3,278,457 and 3,404,109 and anhydrides as described in U. S. Patent Nos. 5,145,883 and 3,538,043, which yield polyethers and polyester or polyetherester polyols, respectively. Lactones as described in U. S. Patent No. 5,525,702 and carbon dioxide are examples of other suitable monomers that can be polymerized in accordance with the invention. The polymerization reaction may be performed continuously or batchwise. In such continuous processes, the initiator/catalyst mixture is continuoxisly fed into a continuous reactor such as a continuously stirred tank reactor (CSTR) or a tubular reactor. A feed of alkylene oxide is introduced into the reactor and the product continuously removed. The concentration of the DMC catalyst is selected to polymerize the alkylene oxide at a desired rate or within a desired period of time. Generally, a suitable amount of DMC catalyst is from about 5 to about 10,000 parts by weight metal cyanide catalyst complex per million parts of the product. For determining the amount of catalyst complex to use, the weight of the product is generally considered to equal the combined weight of alkylene oxide and initiator, plus any comonomers that majr be used. More preferred catalyst complex levels are from about 10, especially from about 25, to about 5000, more preferably about 3000 ppm, on the same basis. The metal cyanide catalyst can be represented by the general formula: Mb[MKCN)r(X)t]c[M2(X)6]d • zL nM3*Ay, wherein M is a metal ion that forms an insoluble precipitate with the ML1(CN)r(X)t group and which has at least one water soluble salt; M1 and M2 are transition metal ions that may be the same or different; each X independently represents a group other than cyanide that coordinates with an M1 or M2 ion; L represents an organic complexing agent; M3xAy represents a water-soluble salt of metal ion M3 and anion A, wlierein M3 is the same as or different than M; b and c are positive numbers that, together with d, reflect an electrostatically neutral complex; d is zero or a positive number; x and y are ivumbers that reflect an electrostatically neutral salt; r is from 4 to 6; t is from 0 to 2; z is zero or a positive number and n is a positive number indicating the relative quantities of the complexing agent and MxAy, respectively, z and n may be fractions. The X groups in any M2(X)6 do not have to be all the same. The molar ratio of is advantageously from about 100:0 to about 20:80, more preferably from about 100:0 to about 50:50, and even more preferably from about 100:0 to about 80:20. Similarly, the catalyst may contain two or more types of Ma(CN)r(X)t groups and two or more types of M2(X)6 groups. M and M3 are preferably metal ions selected from the getup consisting of Zn+2, Fe+2, Co+2, NTi+2, Mo+4, Mo+6, Al+3, V+4, V+5, Sr*2, W+4, W+6, Mn+2, Sn+2, Sn+4, Pb+2, Cu+2? La+3 and Cr*"3. M and M3 are more preferably Zn+2, Fe+2, Co+2, NTi+2, La+3 and Cr+3. M is most preferably Zn+2. Suita"ble anions A include halides such as chloride and hromide, nitrate, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, perchlorate, isothiocyanate, and a Ci-4 carboxylate. Chloride ion is especially preferred. M1 and M2 are preferably Fe+3, Fe+2, Co+3, Co+2, Cr*2, Cr*3, Mn+2, Mn+3, Ir+3, Ni+2, Rh+3, Ru+2, V+4 and V+5. Among the foregoing, those in the plus-tlree oxidation state are more preferred. Co+3 and Fe+3 are even more preferred and Co+3 is most preferred. Preferred groups X include anions such as halide (especially chloride), hydroxide, sulfate, Ci-4 carbonate, oxalate, thiocyanate, isocyanate, isothiocyanate, C1-4 carboxylate and nitrite (NO2-), and uncharged species such as CO, H2O and NO. Particularly preferred groups X are NO, N02~and CO. The catalyst is usually complexed with an organic complexing agent. A great number of complexing agents are potentially useful, although ca_talyst activity may vary according to the selection of a particular complexing agent. Examples of such complexing agents include alcohols, aldehydes, ketones, ethers, amides, nitriles, sulfides, and. the like. Suitable alcohols include monoalcohols and polyalcohols. Suitable monoalcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, octanol, octadecanol, 3-butyn-l-ol, 3-butene-l-ol, propargyl alcohol, 2-naethyl-2-propanol, 2-methyl-3-bu±yn-2-ol, 2-methyl-3-butene-2-ol, 3-butyn-l-ol, 3-butene-l-ol, l-t-butoxy-2-propanol and the like. Suitable monoalcohols also include halogenated. alcohols such as 2-chloroethanol, 2-bromoethanol, 2-chloro-l-propanol, 3-chloro-l-propanol, 3-bromo-l-propanol, l,3-dichloro-2-propanol, l-chloro-2-methyl-2-propanol as well as nitroalcohols, keto-alcohols, ester-alcohols, cyanoalcohols, and other inertly substituted alcohols. Suitable polyalcohols include ethylene glycol, propylene glycol, glycerine, 1,1,1-trimethylol propane, 1,1,1-trimethylol ethane, 1,2,3-trihydroxybutane, pentaerythritol, xylitol, arabitol, mannitol, 2,5-dimethyl-3-hexyn-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, sucrose, sorbitol, alkyl glucosides such as methyl glucoside and ethyl glucoside, and the like. Low molecular weight polyether polyols, particular those having an equivalent weight of about 350 or less, more preferably about 125-250, are also useful complexing agents. Suitable aldehydes include formaldehyde, acetaldehyde, butjrxaldehyde, valeric aldehyde, glyoxal, benzaldehyde, toluic aldehyde and the like. Suitable ketones include acetone, methyl ethyl ketone, 3-pentanone, 2-hexanone and the like. Suitable ethers include cyclic ethers such as dioxane, trioxymethylene and paraformaldehyde as well as acyclic ethers such as diethyl ether, 1-ethoxy pentane, bis(betachloro ethyl) ether, methyl propyl ether, diethoxy methane, dialkyl ethers of alkylene or polyalkylene glycols (such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and octaethylene glycol dimethyl ether), and tb.e like. Amides such as formamide, acetamide, propionamide, butyramide and valeramide are useful complexing agents. Esters such as amyl formate, ethyl formate, hexyl formate, propyl formate, ethyl acetate, methyl acetate, triethylene glycol diacetate and the like can be used as well. Suitable nitriles include acetonitrile, proprionitrile and the like. Suitable sulfides include dimethyl sulfide, diethyl sulfide, dibutyl sulfide, diamyl sulfide and the like. Preferred complexing agents are t-butanol, l-t-butoxy-2-pxopanol, polyether polyols having an equivalent weight of about 75-350 and dialkyl ethers of alkylene and polyalkylene glycols. Especially preferred complexing agents are t-butanol, 1-t-butoxy-2-propanol, polyether polyols having an equivalent weight of 125-250 and a dimethyl ether of mono-, di- or triethylene glycol. t-Butanol and glyme (1,2-dimethoxy ethane) are especially preferred. A silane-functional complexing agent, as described in U.S. Patent No. 6,348,565, may be used instead of or in additino to the aforementioned complexing agents. As described therein, the silane-functional complexing agent may be polymerized to form a film or polymer, optionally on a support, or may function as a coupling agent to attach the catalyst complex to a support material. In addition, the catalyst complex often contains a quantity of water that is bound into the crystalline lattice of the complex. Although the amoxxnt of bound water is difficult to determine, it is believed that this amount is typically from about 0.25 to about 3 moles of water per mole of M1 and M2 ions. Exemplary catalysts include: Zinc hexacyanocobaltate • zL • aEfeO • nZnCb; Zn[Co(CN)5NTO] • zL • alfcO • nZnCls; Zna[Co(CN)e]o[Fe(CN)5NO]p • zL • aH2O - nZnCla (o, p = positive numbers, s=1.5o + p); ZnB[Co(CN)e]o[Co(NO2)6]p[Fe(CN)5NO]q • zL • aBkO • nZnCh (o, p„ q = positive numbers, s=L5(o+p)+q); Zinc hexacyanocobaltate • zL • aEbO • nLaCk; Zn[Co(CN)5NO] * zL • aH20 • nLaCls; Zn[Co(CN)6]o[Fe(CN)5NO]p • zL • aHzO • nLaCls (o, p = positive n.xunbers, s=1.5o + p); Zns[Co(CN)6]o[Co(N02)6]p[Fe(C^D5NO]q • zL • aEfeO • nLaCls (o, p, q = positive numbers, s=1.5(o+p)+q); Zinc hexacyanocobaltate • zL • aBbO • nCrCk; Zn[Co(CN)sNO] • zL • aHaO • nCrCls; Zns[Co(CN)6]o[Fe(CN)5NO]p • zL • aH20 • nCrCla (o, p = positive numbers, s=1.5o + p); Zns[Co(CN)6]o[Co(N02)6]P[Fe(C]SD5NO]q • zL • aBbO • nCrCl3(o, p, q = positive numbers, s=1.5(o+p)+q); Magnesium hexacyanocobaltate • zL • aH20 • nZnCk; Mg[Co(CN)5NO] • zL • aH20 • nZnClz; Mgs[Co(CN)6]o[Fe(CN)5NO]p • zL • aH20 • nZnCl2 (o, p = positive numbers,s=1.5o + p); Mg8[Co(CN)6]o[Co(N02)6]p[Fe(CN)5NO]q • zL • aBkO • nZnClj (o, p, q = positive numbers, s=1.5(o+p)+q); Magnesium hexacyanocobaltate • zL • aEfeO • riLaCla; Mg[Co(CN)5]SFO] • zL • aH2O • nLaCk; Mg3[Co(CN)6]o[Fe(CN)6NO]p • zL • aHsiO • nLaCk (o, p = positive numbers, s=1.5o + p); MgstCo(CN)6]o[Co(N02)6]p[Fe(CN)5NO]q • zL - aH2O • nLaCls (o, p, q = positive numbers, s=L5(o+p)+q); Magnesium hexacyanocobaltate • zL • alfcO • nCrCk; Mg[Co(CN>NO] • zL • alfcO • nCrCla; Mgs[Co(CN)6]o[Fe(CN)BNO]P • zL * aBjO • nCrCk (o, p = positive nvunbers, s=1.5o + p); Mg8[Co(CN)6]o[Co(NO2)6]p[Fe(CN)5NO]q • zL * aHaO • nCrCla (o, p, q = positive numbers, s=1.5(o+p)+q); as well as the various complexes such as are described at column 3 of U. S. Patent No. 3,404,109. Preferred metal cyanide catalysts include those described in WO 03/080239 and WO O3/080240. The DMC catalyst complex may be supported. One method of making a supported DMC catalyst is by precipitating the catalyst in the presence of a polycarboxyl or polycarboxylate compound, as described in WO 01/04180. Supported DMC catalysts as described in WO 99/44379 are also useful. In addition, supported DMC catalysts can be prepared as described in the U.S. Pat. No. 6,348,565. The DMC catalyst complex is conveniently made using standard precipitation methods as are described, for example, in U. S. Patent Nos. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3,427,256, 3,427,334, 3,427,335, 5,470,813, 5,482,908, 5,536,883, 5,589,431, 5,627,120, 5,627,122, 5,639,705, 5,714,428, 5,731,407, 5,780,584, 5,783,513, all incorporated herein by reference. In addition, the DMC catalyst may be formed directly as a dispersion in an initiator compound, as described in U.S. Pat. No. 6,429,166, or through an incipient wetness technique as described in U.S. Pat. No. 6,423,662. Thie product polyether contains one or more chains of oxyalkylene groups that are bonded to the functionalized initiator through a heteroatom. The heteroatom is preferably oxygen and the linkage is most preferably an ether linkage. Ttie product polyether is typically prepared in good yield with only small amounts of undesired by-products. In some instances, the product may contain a high moleculaar weight fraction that has a weight average molecular weight of 1.5X or more of that of th.e desired product. Typically, when this fraction is present, it constitutes about 20% or less, more typically less than about 10% of the total weight of the product. The product polyether is generally characterized by having a good polydispersity, typically less than about 2.0, more typically less than about 1.6 and preferably less than about 1.2, as crude products before purification to remove high molecular weight species. The following examples are provided to illustrate the invention, but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated. For all of the Examples, the DMC catalyst is a catalyst prepared in the same way as described by Example 15 of published WO patent application WO 03/080239. Example 1. DMC Catalyzed Propoxvlation of Methyl Hvclroxvmethvlstearate (HMS^ Starting Reagents: Methyl Hydroxymethylstearate (0.1223 g) (from methyl oleate) containing rhodium catalyst (the functionalizing catalyst) is produced according to the procedure described in WO 04/096744 Propylene Oxide (0.5895 g) 3 wt% DMC slurry catalyst composition in 20 rl wt/wt Voranol* 2070 (a 700 molecular weight glycerine propoxylate) polyol/trimethylolpropane (0.0122 g, to provide, 505 ppm of DMC catalyst in the product based upon total mass of reactants charged). Voranol* is a Trademark of the Dow Chemical Company - All reagents are charged into the sealed reactox- vial in a nitrogen atmosphere drybox and the polymerization is performed at 90°C for- 21 h. After devolatilization for 30 min at 90°C under a nitrogen sweep to remove any xinreacted propylene oxide (PO), the final fluid product mass is 0.7228 g. This corresponds to about 100% yield in the propoxylation reaction. Examnle 2: DMC Propoxvlation of a PolvhYdroxv Polyester Functionalized Initiator Compound A polyhydroxy polyester functionalized initiator compound is formed as follows. Methyl hydroxymethyl stearate (HMS), made in a lOse manner as described in the previous example, (76.66 g) and 400 molecular weight ethoxylated glycerine (23.34 g) are added to a tared 250-mL, three-necked round bottom flask fitted with a magnetic stirbar, heating mantle, thermocouple attached to an electronic temperature controller, Dean-Stark trap fitted with a chilled condenser and attached house-vacuum inlet, and nitrogen sweep via a needle insert though a rubber septum. The reactor and contents are alternately evacuated then refilled with nitrogen several times to remove air. The mixture of HMS and ethoxylated glycerine is slowly heated to 140°C over 45 min under vacuum (100-125 torr) with a slight nitrogen sweep to remove water and other volatiles. The clear, essentially colorless mixture is maintained a_t 140°C for an additional 25 min with vacuum and nitrogen applied. Tin(II) 2-ethylhexanoate (0.0171 g) is then added at 140°C under nitrogen padding with no vacuum applied. The temperature is increased to 150°C and additional -tin(II) 2-ethylhexanoate is added in three separate portions over 35 min. A total of O.H46 g of tin(II) 2-ethylhexanoate is added during the time the reaction mixture is in the 140-150°C operating temperature range. Only very slight bubbling and volatiles evolution are observed at these catalyst charges and reaction conditions. The reaction mixture is heated incrementally to 160°C, then to 170°C over 30 min. During this heating period, bubbling and overhead distillate collection rate increases. The mixture is then heated to 180°C, at which the bubbling and overhead distillate collection rate increases to approximately 1 mL per 10 min. After 30 min, a slow nitrogen gas sweep is introduced via the needle inserted in the septum with the gas exiting thorough the open condenser. The mixture is maintained at 180°C for a total of 70 min, providing approximately 6 mL of collected distillate over this time period. The bubbling and distillate collection rate diminishes toward the end of the reaction period at 180°C. The pale yellow, clear reaction mixture is then heated to 190°C while still maintaining a slight nitrogen sweep over the head space. The bubbling and distillate collection rates increase slightly during the initial heating stage at 190°C. The mixture is maintained at 190°C for approximately 1 h. A total of approximately 8-8.5 mL of distillate is collected over the various heating stages from 160-190°C using a nitrogen sweep. The mixture is heated to 200°C, at which a slight initial increase in bubbling is observed in the liquid. Vacuum (100-125 torr) and a slight nitrogen sweep is then applied to the 200°C reaction mixture to further remove methanol from the reaction mixture and drive the transesterification to form the functionalized initiator compound. The mixture is maintained at 200°C under vacuum with a nitrogen sweep for a total of 3 h. The reactor and functionalized initiator compound are cooled to ambient temperature. The functionalized initiator compound is a. viscous, pale yellow fluid having a product mass (92.33 g) as determined by mass difference. This functionalized initiator compound is propoxylated as follows. Starting Reagents: Functionalized initiator compound (0.1203 g) Propylene Oxide (0.5935 g) 3 wt% DMC slurry catalyst composition in 20:1 wt/wt Voranol* 2070 polyol/trimethylolpropane (0.0120 g, to provide 495 ppm of DMC catalyst in the product based upon total mass of reactants charged). All reagents are charged into the reactor vial in a nitrogen atmosphere drybox and the polymerization is performed at 90°C for 21 h. After devolatilization for 30 min at 90°C under a nitrogen sweep to remove any ixnreacted PO, the final fluid product mass is 0.7255 g. This corresponds to about 100% yield in the propoxylation reaction. Example 3. Propoxvlation of Ring Opened Epoxidized Soybean Oil FLEXOL™ EPO plasticizer, an epoxidized soy bean oil, available from The Dow Chemical Company, Midland MI, (250.0 g, 7.0 wt% epoxide O, approximately 1.09 mol epoxide) and methanol (250 g, 7.80 mol) axe added to a 1-liter, three-necked round bottom flask equipped with a mechanical stirrer, condenser topped with nitrogen/vacuum inlet, heating mantle, and a tliermocouple probe connected to an electronic temperature controller. While stirring at 300 rpm, the two-phase mixture is evacuated and back-filled with nitrogen several times to remove air. The mixture is then heated to 65°C while stirring at 300 rpm. At approximately 50°C, the mixture becomes a clear, pale yellow, homogeneous solution. DOWEX* MSC-1 (*Trademark of the Dow Chemical Company, Midland, Michigan) ion exchange resin beads (50 g) are thoroughly rinsed with warm methanol, then water, then extensively with warm methanol to remove color bodies and water. The beads are then briefly air-dried under vacuuin, providing 38.1 g of rinsed and dried DOWEX* MSC-1 ion exchange resin beads. The dLried beads are then added to the 65°C reaction mixture under a pad of nitrogen and the stirring rate is increased to 500 rpm. The 65°C reaction mixture is allowed to stir at 50O rpm for 18 h. Upon cooling to room temperature (24°C), the reaction mixture consists of a clear, homogeneous, pale yellow solution plus resin beads. The mixture is vacuum filtered to remove the DOWEX* MSC-1 ion exchange resin beads and the beads are rinsed several times with methanol. The air-dried beads are briefly air-dried, providing a recovered mass of 46.2 g. The combined filtrates are vacuum distilled with a slight nitxogen sweep on a rotary evaporator at 60°C bath temperature while gradually decreasing the pressure to 10-15 torr. After 1 h at 60°C / 10-15 torr, the bath temperature is increased to 70°C and the mixture is further distilled for 2 h at 70°C /10-15 torr with a slight vacuum sweep. The final fuxictionalized initiator compound (262.7 g) is a clear, light golden-yellow oil with 5.158% hydroxyl by titration and an acid number of 0.006 meq/g. The fiinctionalized initiator compound (light golden yellow oil) is propoxylated as follows. Starting Reagents; Functionalized initiator compound (0.1246 g) Propylene Oxide (0.5895 g) 3 wt% DMC slurry catalyst composition in 20:1 wt/wt Voranol* 2070 polyol/trimethylolpropane (0.0120 g to provide 496 ppm of DMC catalyst in the product fcased upon total mass of reactants charged). All reagents are charged into the reactor vial in a nitrogen atmosphere drybox and the polymerization is performed at 90°C for 21 h. After devolatiUzation for 30 min at 90°C under a nitrogen sweep to remove any uioreacted PO, the final fluid product mass is 0.7262 g. This corresponds to about 100% yield in the propoxylation reaction. Example 4: Pronoxvlation of Ring Opened Epoxidized Soybean Oil Soybean oil (200 g) is added to a 500-mILi, three-necked round bottom flask equipped with a mechanical stirrer, chilled condenser, heating mantle, and a thermocouple probe connected to an electronic temperature controller. The mixture is heated to 50°C and stirred at 700 rpm. Aqueous 50% hydrogen peroxide (74.8 g total) and 90% formic acid (16.9 g total) are each added sequentially in four portions to the reaction mixture at 50 °C and 700 rpm stirring over a 2 h 15 min addition period with 30-70 min between additions. In each addition, one-fourth of the total hydrogen peroxide charge is added followed by one-fourth of the total formic acid charge. A slow exotlierm is typically observed after each hydrogen peroxide/formic acid addition with a maximmn temperature of 60°C observed during the four addition steps. The reaction is allowed to stir at a 50°C setpoint with periodic heating provided, as required, by the heating mantle and cooling provided, as required, by cool air from a heat gun. The mixture maintains a reaction temperature between 50-65°C by the exothermic heat of reaction over an additional 45 rain of stirring. At this time, the light orange colored resection mixture is heated to a 60 °C setpoint and the stirring is increased to 800 rpm. Again, the exothermic heat of reaction maintains the reaction temperature at 60-65°C "with only periodic external heating and/or air cooling for the next 1 h of reaction. The mixture is allowed to stir at 800 rpm and 60-65°C reaction temperature for a total of 8 h, then is allowed to cool to ambient temperature (25°C) with stirring. At 25°C, the mixture is a very faint yellow, opaque emulsion. Ethyl acetate (100 mL) is added and the mixture is reheated to 60°C while stirring at 800 rpm. The warm solution is then transferred to a separately funnel. Additional ethyl acetate (100 mL, 200 mL total) is used to rinse the reactor and further dilute the reaction mixture. The lower aqueous layer (5-4 g, pH = 1) is removed from the pale yellow organic layer. The organic layer is then washed four times with 100 mL portions of water for each wash. A small portion of ethyl acetate is added during each wash to aid in phase separation and to help clarify the layers. A very small emulsified rag layer is removed with each water wash separation. The final (fourth) water wash is approximately pH = 2. The organic layer is then distilled using a rotary evaporator with the water bath temperature set at 60°C. The pressure is slowly reduced to 10-15 torr during the distillation until the bulk of the solvent removal is complete. The oil is further devolatilized at 60°C / 10-15 torr for 2 h, providing an epoxidized soyhean product (217.8 g) as a light yellow oil. The epoxidized soybean oil (200.0 g, approximately 7 wt% epoxide oxygen, approximately 0.875 mol epoxide) and glacial acetic acid (105 g, 1.75 mol) are added to a 500-mL round bottomed flask. The mixture is swirled to provide a clear solution. DOWEX* MSC-1 ion exchange resin beads (50 g) are thoroughly rinsed sequentially with methylene chloride, methanol, water, methanol, then finally with methylene chloride. The beads are then briefly air-dried under vacuum, providing 37 g of rinsed and dried DOWEX* MSC-1 ion exchange resin beads. The ion exchange beads are added to the reaction mixture containing the epoxidized soybean oil and acetic acid. "Water (31.3 g) is then added to the mixture, providing a. slightly turbid liquid phase. The flask is placed into a water bath at 70°C and the contents are mixed by rotation with an electric rotary evaporator motor. Witiiin 3 h the initially turbid liquid phase becomes essentially clear. The reaction is allowed to stir at 70°C for 4.5 h, then is cooled to room temperature (25°C) and stirred an additional 16 h. The mixture is reheated to 70°C and vacuum filtered through a fritted glass funnel to remove the ion exchange beads. The beads and filter are rinsed with ethyl acetate then rinsed extensively with water. The resultant filtrate is distilled on a rotary evaporator at 90°G bath temperature and <10 torr final vacuum over 3 h to provide 207.3 g of oil. The oil is redissolved in glacial acetic acid (200 mL) and the recovered (rinsed and air dried) DOWEX* MSC-1 ion exchange resin beads are added. The mixture is allowed to react for 2.5 h at 90°C in a water bath using the same rotary mixing method as before. The beads are separated from the liquid product by vacuum filtration and the beads are rinsed with ethyl acetate and watex. The resultant filtrate is distilled on a rotary evaporator at 90°C bath temperature and <10 torr final vacuum over 2-3 h to provide 203.6 g of clear, orange oil. The functionalized initiator compouixd (clear orange oil) is propoxylated as follows. Starting Reagents: Functionalized Initiator compound (clear orange oil) (0.1212 g) Propylene Oxide (0.5914 g) 3 wt% DMC slurry catalyst composition in 20:1 wt/wt Voranol* 2070 polyol/trimethylolpropane (0.0121 g, to provide 501 ppm of DMC catalyst in the product based upon total mass of reactants charged). All reagents are charged into the reactor vial in a nitrogen atmosphere drybox and the polymerization is performed at 90°C for 21 h. After devolatilization for 30 min at 90 °C under a nitrogen sweep to remove any unreacted PO, the final fluid product mass is 0.7240 g. This corresponds to about lO0% yield in the propoxylation reaction.. Example 5. Propoxvlation of Ring-opened Enoxidized Methvl Oleate 70% Methyl oleate (Sigma-Aldrich, Milwaukee, WI) (395 g) is added to a 1-liter Erlenmeyer flask with a magnetic stirbar. The flask containing the methyl oleate is heated to 50°C while stirring in a heated water bath. Aqueous 50% hydrogen peroxide solution (113.2 g) and 90% formic acid (25.6 g) are each added sequentially in four equal portions to the well-stirred reaction mixture over 90 min. For each addition, one-fourth of the total hydrogen peroxide charge is added., followed by one-fourth of the total formic acid charge. A slight exotherm (typically 4-6°C) is observed after each addition of hydrogen peroxide/formic acid. After the final hydrogen peroxide/formic acid charge, the reaction temperature continues to slowly increase to 65°C within tlxe 50°C water bath. The mixture is allowed to stir within the 50°C water bath for an. additional 8 h after the final hydrogen peroxide/formic acid addition, then the mixture is allowed to cool to room temperature and stir for 8 h. The two-phase reaction mixture is slowly heated to 60°C over 3 h using a water bath. Ethyl acetate (200 mL) is added to the 60°C mixture and the warm solution is poured into a separatory funnel. Additional ethyl acetate (200 mL) and water (50 mL) are added and the organic and aqueous phases are allowed to separate. A slight emulsion (rag) layer is present at the organic/aqueous interface. The lower aqueous layer is separated along with rag layer. The organic layer is washed six times with water (100 mL each wash). The organic layer is then distilled on a rotary evaporator at 60°C bath temperature while gradually increasing the vacuum to 20 torr. After the bulk of the solvent has been distilled, the resultant oil is further devolatilized at 60°C / 10-15 torr for 2.5 h. The final epoxidized methyl oleate product (417.3 g) is a clear, pale yellow oil. The epoxidized methyl oleate (250 g) and methanol (250 g) are added to a 1-liter, three-necked round bottom flask equipped wrfch a mechanical stirrer, condenser topped with nitrogen/vacuum inlet, heating mantle, and a thermocouple probe connected to an electronic temperature controller. DOWEX* MSC-1 ion exchange resin beads (50.0 g) are thoroughly soaked and rinsed with methanol, then vacuum filtered and briefly air-dried under vacuum, providing 44.3 g of rinsed and dried DOWEX* MSC-1 ion exchange resin beads. The methanol treated beads are added to the reactor containing the epoxidized methyl oleate and methanol. While stirring at 300 rpm, the mixture is evacuated and back-filled with nitrogen six times to remove air. The mixture is then heated to 65°C and the stirring rate is increased to 500 rpm. The 65°C reaction mixture is allowed to stir at 500 rpm for 12 h. The mixture is then allowed to cool to 25°C and continue stirring at 500 rpm for an additional 5 h. At room temperature (25°C), the reaction mixture consists of a clear, homogeneous, pale yellow solution plus resin beads. The mixture is vacuum filtered to remove the DOWEX* MSC-1 ion exchange resin beads and the beads are rinsed several times with methanol to remove entrained product. The combined filtrates are vacuum distilled with a slight nitrogen sweep on a rotary evaporator at 60°C bath temperature while gradually decreasing the pressure to 20 torr. After removal of the main methanol distillate, the mixture is further devolatilized for 3 h at 60°C / 10-15 torr with a slight vacuum sweep. The functionalized initiator compound (ring opened epoxidized methyl oleate) (261.6 g) is a clear, light golden-yellow oil with 4.374% hydroxyl by titration and an acid number of 0.02 meq/g. The functionalized initiator compound (light golden-yellow oil) is propoxylated as follows. Starting Reagents: Functionalized initiator compound (0.1234 g) Propylene Oxide (0.5934 g) 3 wt% DMC slurry catalyst composition in 20:1 wt/wt Voranol*2070 polyol/trimethylolpropane (0.0125 g, to provide 514 ppm of DMC catalyst in the product: based upon total mass of reactants charged). All reagents are charged into the reactor vial in a nitrogen atmosphere drybosc and the polymerization is performed at 90° C for 21 h. After devolatilization for 30 min at 90°C under a nitrogen sweep to remove any unreacted PO, the final fluid product mass is 0.7288 g. This corresponds to about 100% yield in the propoxylation reaction. Example 6. Pronoxvlation of Epoxidized-Bing Opened Oligomer of Oleic Acid Oleic acid (Sigma-Aldrich, tech grade) (20 g) and acetic acid (1.42 g) are added to a 250-mL Erlenmeyer flask containing a magnetic stirbar. While stirring the mixture a_t 25°C, 96% sulfuric acid (1.6 g), the acid catalyst, is added slowly dropwise to the oleic acid/acetic acid mixture. The mixture turns slightly darker orange color upon adding the sulfuric acid. The reaction mixture is placed into a water bath at 40°C. While stirring in the 40°C water bath, aqueous 30% hydrogen peroxide (8.20 g) Ls added in small portions over 15 min. The temperature of the mixture rises to 55CC and becomes light yellow during the early stages of hydrogen peroxide addition. Thje resultant light yellow emulsion is allowed to stir for 16.5 h within the 40°C water batfci. During this additional reaction time, the mixture becomes an unstirrable cream-colore

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# Name Date
1 1729-chenp-2005-pct.pdf 2011-09-03
2 1729-chenp-2005-form 5.pdf 2011-09-03
3 1729-chenp-2005-form 3.pdf 2011-09-03
4 1729-chenp-2005-form 18.pdf 2011-09-03
5 1729-chenp-2005-form 1.pdf 2011-09-03
6 1729-chenp-2005-drawings.pdf 2011-09-03
7 1729-chenp-2005-description(complete).pdf 2011-09-03
8 1729-chenp-2005-correspondnece-po.pdf 2011-09-03
9 1729-chenp-2005-correspondnece-others.pdf 2011-09-03
10 1729-chenp-2005-claims.pdf 2011-09-03
11 1729-chenp-2005-abstract.pdf 2011-09-03
12 1729-chenp-2005 drawings-duplicate.pdf 2011-09-03
13 1729-chenp-2005 drawings granted.pdf 2011-09-03
14 1729-chenp-2005 description(complete)-duplicate.pdf 2011-09-03
15 1729-chenp-2005 description(complete) granted.pdf 2011-09-03
16 1729-chenp-2005 claims-duplciate.pdf 2011-09-03
17 1729-chenp-2005 claims granted.pdf 2011-09-03
18 1729-chenp-2005 abstract-duplicate.pdf 2011-09-03
19 1729-chenp-2005 abstract granted.pdf 2011-09-03

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