text:
|Publication number
|Publication type
|Application number
|PCT number
|Publication date
|Nov 4, 1997
|Filing date
|Dec 8, 1993
|Priority date
|Dec 8, 1992
|Fee status
|Also published as
|Publication number
|Robert Dryden Tack, Jacob Isaac Emert, Alan R Katritzky, Irina V Shcherbakova
|Original Assignee
|Exxon Chemical Patents Inc
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (19), Non-Patent Citations (30), Referenced by (3), Classifications (48), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
The invention relates to an improved method for the manufacture of nitrogen-containing compounds. More particularly, the invention relates to an improved method for the manufacture of functionalised polymers suitable for use as lubricating or fuel oil additives or as intermediates suitable for use in the manufacture of such additives, to functionalised polymers obtainable by the said method and to their use. The invention also relates to the manufacture of dihydrooxazines.
For the past 30 to 50 years, lubricating oils used as crankcase lubricants in internal combustion engines in automobiles and trucks have normally contained ashless dispersants. Dispersants maintain oil-insoluble substances, resulting from oxidation during use, in suspension in the fluid, thus preventing sludge flocculation and precipitation or deposition on metal parts. So-called ashless dispersants are organic materials which form substantially no ash on combustion, in contrast to metal-containing (and thus ash-forming) detergent. Examples of ashless disperants are the reaction products of amines and/or alcohols, including amino-alcohols, with hydrocarbyl-substituted mono- or dicarboxylic acids, long chain aliphatic hydrocarbons having one or more polyamine molecules attached directly thereto, and Mannich condensation products containing a long chain hydrocarbyl group, far example, as a substituent of a phenol. Crankcase lubricants may in addition, or alternatively, contain viscosity index modifier dispersants (sometimes called multifunctional viscosity modifiers), which have both viscosity index-modifying and dispersant properties. Ashless dispersants and/or viscosity index modifier dispersants are frequently also used in other lubricating oil compositions, an ashless dispersants may also be used in fuels.
One advantageous class of the ashless dispersants mentioned above comprises the hydrocarbyl-substituted dicarboxylic acids or anhydrides and derivatives thereof, the hydrocarbyl substituents of the said acids or anhydrides containing, for example, from 50 to 400 carbon atoms. That class includes especially succinic acid or anhydride having a side chain derived from polyisobutene, the last-mentioned compounds commonly being known as PIBSAs, and their reaction products with alcohols and/or amines, for example, polyamines (PAMs). A previously known process for the manufacture of hydrocarbyl-substituted dicarboxylic acids or anhydrides involves a chlorination step, in which a polyalkene is reacted with chlorine, and an "acidification" step, in which the chlorinated polyalkene is reacted with maleic anhydride. The chlorination and acidification steps may be carried out either simultaneously or sequentially.
The polymer functionalisation step in the above-mentioned process involves the use of chlorine gas, and requires suitable precautions to be taken in handling and disposal.
Other methods known in the art for functionalizing polyolefins involve hydroformylation, iminomethylation, reductive amination and alkylation, each of which require catalysts which necessitate handling precautions.
Amidoalkylation of olefinically-unsaturated compounds has been described in relation to non-polymeric olefins in U.S. Pat. No. 3,190,882, GB-A-1 231 409, GB-A-1 147 888, Perchec et al (Revue de L'Institut Francais du Petrole, Vol. 41, No. 2, 275 to 295) and Zaugg (Synthesis, 1970, 49 to 73), but these documents do not describe the amidoalkylation of olefinically unsaturated polymers to form products which may be useful as a dispersant for lubricants or fuels.
The present invention provides a method of preparing a functionalised polymer, particularly a functionalised polymer suitable for use as a dispersant or as an intermediate for use in the preparation of a dispersant, comprising reacting, in the presence of an acid catalyst,
(i) an olefinically unsaturated polymer of number average molecular weight from 350 to 100,000 and
(ii) an acid amide or acid imide of which the amido or imido nitrogen atom, respectively, is substituted by a group --CHX R2 in which X is a group that, under the reaction conditions, acts as a leaving group, and R2 is a hydrogen atom or a hydrocarbyl radical having from 1 to 11 carbon atoms.
The imido or amido group advantageously contains a carbon--carbon double bond in the α,β-position relative to the carbonyl of the said group.
As acid amide there may advantageously be used a compound of general formula I
in which R1 is a hydrogen atom or a hydrocarbyl radical having from 1 to 12 carbon atoms.
The invention also provides a functionalised polymer comprising a compound of the general formula II' or II" ##STR1## or a compound of the general formula III' ##STR2## in which R1 is a hydrogen atom or a hydrocarbyl radical having from 1 to 12 carbon atoms, R3 and R4, which may be the same or different, are each hydrogen atoms or hydrocarbyl radicals and Polymer--represents a polymer chain derived from an olefinically unsaturated polymer of number average molecular weight 350 to 100,000.
The invention further provides an oleaginous composition comprising a base oil and, a functionalised polymer obtainable according to a method of the invention.
The product of the reaction of a polymer and an N-substituted amide or imide (referred to hereafter as the "amidoalkylation product" that term being used herein to include those products obtained in accordance with the invention by reaction of an N-substituted imide with an olefinically unsaturated polymer) and derivatives thereof are functionalised polymers which may be useful as additives in lubricating or fuel oil compositions. For use as dispersants in lubricating oil compositions there are preferred functionalised polymers obtained from olefinically unsaturated polymers of Mn at least 700 and preferably from 2,000 to 6,000.
Functionalised polymers of the invention for use as dispersants in lubricating oils are preferably those obtainable by reacting the amidoalkylation product with an amine, an aminoalcohol or a thiol.
Functionalised polymers of the invention obtainable from olefinically unsaturated polymers having a Mn of from 10,000 to 50,000 may be used as viscosity index-modifying dispersants in lubricating oil compositions. Although functionalised polymers of Mn 2,000 to 10,000 useful as dispersants will generally exhibit viscosity index-modifying properties, the amounts of such compounds required to effect the necessary modifications of viscosity index may be appreciable. Accordingly, where functionalised polymers of Mn less than 10,000 are included in a lubricating oil composition, an additional viscosity index-improver will generally be desirable.
For use as dispersants in fuels, there are preferred functionalised polymers (which may be either the amidoalkylation product or the derivatives obtainable by reacting that product with an amine, an aminoalcohol or a thiol) obtainable from olefinically unsaturated polymers of Mn from 350 to 2,000.
Thus, the invention further provides the use of a functionalised polymer obtainable in accordance with the method of the invention as a dispersant in a lubricating oil or fuel composition.
The invention also provides the use of a functionalised polymer obtainable in accordance with the method of the invention as a viscosity index modifier in a lubricating oil composition.
Number average molecular weights may be determined by available techniques such as gel permeation chromatography. Except where otherwise stated, number average molecular weights referred to herein are measured by gel permeation chromatography.
Whilst the invention is not to be construed as limited by the following explanation, it is thought that the product of the reaction of the olefinically unsaturated polymer and the N-substituted amide or imide contains a major proportion of an amino alcohol. For example, the reaction product of a polymer
Polymer-CR3 ═CHR4
and the N-(hydroxymethyl) amide
is believed to be an amino alcohol of general formula ##STR3## R3 and R4, which may be the same or different, each being hydrogen atoms or hydrocarbyl radicals, for example, C1 to C6 hydrocarbyl radicals. It is believed that the product may also contain a polymer-substituted dihydrooxazine, which in the case of the reactants just mentioned might be of general formula III ##STR4## in which R3 and R4 have the meanings given above. The polymer-substituted dihydrooxazine, if present, is believed to constitute a minor proportion of the reaction product. The actual proportion may depend on the conditions and, in particular, on the nature, for example, the chain length and/or structure, of the olefinically unsaturated polymer used, and the nature of the acid catalyst used. Other species that might be present are compounds obtainable by elimination of water from the amino alcohol. The invention extends to compounds of the general formula II' or II" ##STR5## in which R1 is a hydrogen atom or a hydrocarbyl radical having from 1 to 12 carbon atoms, R3 and R4, which may be the same or different, are each hydrogen atoms or hydrocarbyl radicals and Polymer--represents a polymer chain derived from an olefinically unsaturated polymer of number average molecular weight 350 to 100,000; and compounds of general formula III' ##STR6## in which R1, R3, R4 and Polymer--have the meanings given in connection with general formula II'; either individually or in combination.
The term "hydrocarbyl" as used herein means that the radical concerned is primarily composed of hydrogen and carbon atoms but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the radical concerned. Such radicals include:
(i) Hydrocarbon groups, for example, aliphatic (eg. alkyl or alkenyl), alicyclic (eg. cycloalkyl or cycloalkenyl) and aromatic groups, aromatic groups having aliphatic or alicyclic substituents, and aliphatic and alicyclic groups having aromatic substituents. Examples of hydrocarbon groups include methyl, ethyl, ethenyl, propyl, propenyl, butenyl, cyclohexyl, t-butylphenyl, 2-benzethyl and phenyl groups;
(ii) Substituted hydrocarbon groups, that is, groups having one or more non-hydrocarbon substituents which do not detract from the substantially hydrocarbon characteristics of the group. Examples of suitable non-hydrocarbon substituents include hydroxy, nitrile, nitro, oxo, chloro groups, and groups having ether or thioether linkages; and
(iii) Hetero groups, that is, groups containing an atom other than carbon in a chain or ring otherwise composed of carbon atoms, the said atom not detracting from the substantially hydrocarbon characteristics of the group. Nitrogen, oxygen and sulphur may be mentioned as suitable hetero atoms.
The hydrocarbyl radicals preferably contain only one non-hydrocarbon substituent or one non-carbon hetero atom if such substituents or atoms are present.
The olefinically unsaturated polymers that may be used in accordance with the invention preferably include a backbone chain of carbon atoms. They may, if desired, have pendant hydrocarbyl side chains provided that the side chains do not contain nitrogen. The polymers have at least one carbon--carbon double bond, which is adjacent to, or more preferably in, a terminal position of the backbone chain or of a pendant side chain but any pendant side chains are preferable free of other reactive double bonds. The polymers may include one or more substituents or hetero atoms as defined above in relation to the term "hydrocarbyl" on or in the polymer chain that do not interfere with the reaction--thus they should not contain nitrogen.
Suitable polymers include those obtainable by polymerisation (including copolymerisation) of lower molecular weight olefins, for example, olefins having up to eight carbon atoms, or derivatives of such olefins. For example, the polymer may be one obtainable by polymerisation of an olefin selected from ethene, propene, n-butene, isobutene, butadiene, and 1-hexene or by copolymerisation of two or more olefins, for example, by copolymerisation of ethene and an α-olefin. The polymer is advantageously one that is obtainable by polymerisation of n-butene or isobutene. Suitable copolymers include, for example, those obtainable by copolymerisation of ethene and propene. A suitable diene may be used as a copolymer in a molar proportion that is so chosen that the polymer has a desired proportion of pendant double bonds with which the N-substituted amide or imide may react. For example, when Ziegler-Natta catalysis, is used to prepare the polymer, ethylidene-norbornene may be used. Other suitable dienes are well-known to those skilled in the art.
The polymers may especially be obtainable by Ziegler-Natta catalysis, for example using a vanadium/aluminium Ziegler-Natta catalyst system, metallocene catalysis, cationic catalysis, anionic catalysis or free radical polymerisation. Suitable methods, having regard to the monomers to be used and the desired chain length, will be immediately apparent to those skilled in the art.
The group R1 of the amide of general formula I is advantageously a hydrocarbyl group having from 1 to 12, and preferably from 2 to 8, carbon atoms. Preferably, R1 is a hydrocarbyl group that has a carbon--carbon double bond in the α,βposition with respect to the carbonyl group of the amide I, as that results in the presence of the carbonyl group and an adjacent C═C group (--C═C--CO--) in the reaction product. That is advantageous in that it facilitates the introduction in a subsequent reaction step of other groups at the double bond, for example, by means of Michael addition. R1 may advantageously be an aliphatic hydrocarbyl group. In an especially preferred embodiment of the invention, R1 is an alkenyl group having a carbon--carbon double bond adjacent to the carbonyl group.
R1 may be an aromatic group, for example a phenyl group.
As suitable N-substituted amides there may be mentioned N-substituted acrylamides, methacrylamides, crotonamides, benzamides, and cinnamamides.
Suitable N-substituted imides for use in the method of the invention include in particular those having a carbon--carbon double bond adjacent to the carbonyl of the imido group. Examples of suitable N-substituted imides are maleimide and methylmaleimide.
In its broadest aspect, the invention also includes the use of amides of dicarboxylic acids, for example, fumaric amide or diamide and itaconamide.
As already mentioned, R2 of the amide of general formula I is a hydrogen atom or a hydrocarbyl group having from 1 to 11 carbon atoms. Preferably, R2 is a hydrogen atom.
The group X is any group which, under the reaction conditions, may act as a leaving group. For example, the group X may be selected from hydroxy, hydrocarbyloxy (preferably alkoxy, aryloxy, aralkyloxy or alkaryloxy) and amido groups which do not contain any aliphatic unsaturation. Preferably, X is a hydroxy, aryloxy or amido group. If the reaction is to be carried out in an anhydrous medium, X is preferably an amido group.
While the amide of general formula I is preferably prepared in a separate step before it is mixed with the polymer, it may, if desired, be prepared in situ by reacting two or more precursor compounds to form the amide. For example, in an aqueous acidic environment, formaldehyde reacts with a nitrile or an amide to form an N-(hydroxymethyl)amide. An N-(hydroxymethyl)amide may, be generated in situ by hydrolysis of an N, N", N"'-triacyl triazine of which the acyl groups are of the formula R1 CO--, in which R1 has the meaning given above.
The imido or amido compound is advantageously present in molar excess, for example, from two- to ten-fold and, preferably, up to a five-fold molar excess, with respect to the olefinically unsaturated polymer.
The acid catalyst used in the method of the invention preferably has a pKa of 3 or less, most preferably 0 or less and may be a mineral acid, an organic acid or a Lewis acid. Examples of suitable mineral acids are sulphuric acid and phosphotungstic acid. Acid clay may also be used. Preferably, very strong acids are avoided as they may lead to undesirable side reactions. Thus Lewis acids are preferably used in combination with weaker acids.
Examples of suitable organic acids are acetic acid, trifluoroacetic acid, p-toluenesulphonic acid and methanesulphonic acid and acidic ion exchange resins, for example, Amberlyst 15 (obtainable from Rohm and Haas).
The acid catalyst may be present in a catalytic amount. It may be desirable in some cases for the acid catalyst to be present in an amount greater than that required merely to catalyse the reaction, for example, where the acid acts also as a solvent or is required to form a salt with the reaction product. In such cases, the acid may be present in a stoichiometric amount or in molar excess, with respect to the olefinically unsaturated polymer.
In one preferred method of the invention, the olefinically unsaturated polymer is mixed with the amide in the presence of acetic acid and sulphuric acid. In the most preferred method of the invention, however, trifluoroacetic acid is used as the acid catalyst. In that case, the trifluoroacetic acid may also act as, or as a component of, the solvent and may, if desired, be recovered from the reaction mixture and recycled, so that the method is economical in terms of materials.
It is a further advantage of the method of the invention that the reaction may, if desired, be carried out in the presence of water whereas, in contrast, the catalysts used in certain previously known polymer functionalisation methods are sensitive to water. Whilst water-sensitive catalysts may, with appropriate choice of conditions, be used in the method of the invention, they are less preferred than catalysts that may be used in an aqueous environment.
The amidoalkylation product manufactured in accordance with the method of the invention may be hydrolysed, for example, by refluxing in aqueous-ethanol alkaline solutions, in aqueous acid solutions, or in alcoholic KOH in methyl isobutylketone. If the product is obtainable from an α,β-unsaturated amido or imido compound, for example from an N-substituted acrylamide or maleimide, it may advantageously be reacted with an amine, an amino alcohol or a thiol.
Amine compounds useful for reacting with the product include mono- and (preferably) polyamines, most preferably polyalkylene polyamines, having about 2 to 60, preferably 2 to 40 (e.g., 3 to 20), total carbon atoms and about 1 to 12, preferably 3 to 12, and most preferably 3 to 9 nitrogen atoms in, the molecule. These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy groups, amide groups, nitrile groups, or imidazoline groups. Hydroxyl amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups, are particularly useful. Preferred amines are aliphatic-saturated amines, including those of the general formulas: ##STR7## wherein R, R', R" and R"' are independently selected from the group consisting of hydrogen; C1 to C25 straight or branched chain alkyl radicals; C1 to C12 alkoxy C2 to C6 alkylene radicals; C2 to C12 hydroxy amino alkylene radicals; and C1 to C12 alkylamino C2 to C6 alkylene radicals; and wherein R'" can additionally comprise a moiety of the formula: ##STR8## wherein R' is as defined above, and wherein s and s' can be the same or a different number of from 2 to 6, preferably 2 to 4; and t and t' can be the same or different and are numbers of from 0 to 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t' is not greater than 15. To facilitate reaction, it is preferred that R, R', R", R'", s, s', t and t' be selected in a manner sufficient to provide the compounds of formulas IV and V with typically at least one primary or secondary amine group, preferably at least two primary or secondary amine groups. This can be achieved by selecting at least one of said R, R', R" or R'" groups to be hydrogen or by letting t in formula V be at least one when R'" is H or when the moiety of formula VI possesses a secondary amino group. The most preferred amine of the above formulas are represented by formula V and contain at least two primary amine groups and at least one, and preferably at least three, secondary amine groups.
Non-limiting examples of suitable amine compounds include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; poly ethylene amines for example diethylene triamine, triethylene tetramine, and tetraethylene pentamine; poly propylene amines, for example, 1,2- propylene diamine, di-(1,2-propylene)-triamine, and di(1,3- propylene) triamine; N,N-dimethyl-1,3-diaminopropane; N,N- di-(2-aminoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; trishydroxymethylaminomethane (THAM); diisopropanol amine; diethanol amine; triethanol amine; mono-, di-, and tri-tallow amines; amino morpholines, for example N-(3-aminopropyl) morpholine; and mixtures thereof.
Other useful amine compounds include: alicyclic diamines, for example 1,4-di(aminomethyl)cyclohexane, and heterocyclic nitrogen compounds, for example imidazolines, and N-aminoalkylpiperazines of the general formula ##STR9## wherein p1 and p2 are the same or different and are each integers of from 1 to 4, and n1, n2 and n3 are the same or different and are each integers of from 1 to 3. Non-limiting examples of such amines include 2-pentadecyl-imidazoline and N-(2-aminoethyl)piperazine. Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines involves the reaction of an alkylene dihalide (for example, ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylene tetramine, tetraethylene pentamine and isomeric piperazines. Low cost poly(ethyleneamine) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially, for example under the trade names "Polyamine H", "Polyamine 400", and "Dow Polyamine E-300".
Useful amines also include polyoxyalkylene polyamines, for example those of the formulas: ##STR10## where m has a value of about 3 to 70 and preferably 10 to 35; and ##STR11## where n has a value of about 1 to 40 with the provision that the sum of all the n's is from about 3 to about 70 and preferably from about 6 to about 35, and R is a polyvalent saturated hydrocarbon radical of up to ten carbon atoms wherein the number of substituents on the R group is represented by the value of a, which is a number of from 3 to 6. The alkylene groups in either formula VIII or IX may be straight or branched chains containing about 2 to 7, and preferably about 2 to 4 carbon atoms.
The polyoxyalkylene polyamines of formulas VIII or IX above, preferably polyoxyalkylene diamines and polyoxyalkylene triamines, may have average molecular weights ranging from about 200 to about 4,000, and preferably from about 400 to about 2,000. The preferred polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2,000. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.
Still other classes of amines capable of yielding functionalised polymers having dispersant activity comprise the amino alcohols including, for example, aminoalkylene-, and aminoarylene-substituted alcohols having one or more aminoalkylene or aminoarylene radicals.
Hydroxy amines which can be reacted with the product obtained according to the method of the invention to form dispersants include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(beta-hydroxy-propyl)-N'-(beta-aminoethyl)piperazine, amino-1-butanol, ethanolamine, and beta-(beta-hydroxyethoxy)ethylamine. Mixtures of these or similar amines can also be employed. The above description of nucleophilic reactants suitable for reaction with the amidoalkylation product includes amines and compounds of mixed amine and hydroxy containing reactive functional groups, i.e., amino-alcohols.
Suitable thiols include those having one or more thiol group that is suitable for attaching the thiol molecule at the carbon--carbon double bond of the amidoalkylation product, for example, by Michael addition. The thiols preferably also contain hydroxyl and/or amino groups, which by virtue of the resulting polarity impart dispersant activity to the product. For example, tris(hydroxymethyl)methanethiol may be used.
The amidoalkylation product obtained in accordance with the method of the invention, for example, the hydroxyacrylamido polymer, is readily reacted with the amine, aminoalcohol or thiol by heating a solution of said compound and the amidoalkylation product in a suitable solvent, for example, oil.
The functionalised polymers (that is, the amidoalkylation products and their derivatives) manufactured in accordance with the invention for use as lubricating oil additives are oil-soluble or (in common with certain of the other additives/referred to below) are dissolvable in oil with the aid of a suitable solvent, or are stably dispersible materials. Oil-soluble, dissolvable, or stably dispersible as that terminology is used herein does not necessarily indicate that the additives are soluble, dissolvable, miscible, or capable of being suspended in oil in all proportions. It does mean, however, that the additives are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
The functionalised polymers manufactured in accordance with the present invention can be incorporated into the oil in any convenient way. Thus, they can be added directly to the oil by dispersing or by dissolving them in the oil at the desired level of concentration, typically with the aid of a suitable solvent such, for example, as toluene, cyclohexane, or tetrahydrofuran. Such blending can occur at room temperature or an elevated temperature.
Base oils with which the functionalised polymers may be used include those suitable for use as crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, and these may be synthetic or natural base oils.
The lubricating oil base stock conveniently has a viscosity of from 2.5 to 12 cSt (2.5�10-6 to 12�10-6 m2 /s) and preferably 2.5 to 9 cSt. (2.5�10-6 to 9�10-6 m2 /s) at 100� C.
The functionalised polymers manufactured in accordance with the present invention may be employed in a lubricating oil composition which comprises lubricating oil, typically in a major proportion, and the functionalised polymers, typically in a minor proportion. In the preferred composition the functionalised polymers are present in a dispersing amount. For example, the composition may contain from 0.1 to 25 parts by weight of functionalised polymer manufactured in accordance with the invention, per 100 parts by weight base oil, and preferably from 0.5 to 8 parts by weight functionalised polymer per 100 parts base oil. Additional additives may be incorporated in the composition to enable it to meet particular requirements. Examples of additives which may be included in lubricating oil compositions are viscosity index improvers, corrosion inhibitors, oxidation inhibitors, friction modifiers, detergents, metal rust inhibitors, anti-wear agents, pour point depressants, and anti-foaming agents.
Some of the above-mentioned additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor.
When lubricating compositions contain one or more of the above-mentioned additives, each additive is typically blended into the base oil in an amount which enables the additive to provide its desired function. Representative effective amounts of such additives, when used in crankcase lubricants, are as follows:
______________________________________ Mass % a.i.* Mass % a.i.*Additive (Broad) (Preferred)______________________________________Viscosity Modifier 0.01-6 0.01-4Corrosion Inhibitor 0.01-5 0.01-1.5Oxidation Inhibitor 0.01-5 0.01-1.5Friction Modifier 0.01-5 0.01-1.5Detergents/rust inhibitors+ 0.01-6 0.01-3Anti-wear Agent 0.01-6 0.01-4Pour Point Depressant 0.01-5 0.01-1.5Anti-Foaming Agent 0.001-3 0.001-0.15Mineral or Synthetic Oil Base Balance Balance______________________________________ *Mass % active ingredient based on the final oil. + Relatively larger proportions, for example, at least 10 mass % are normally used for marine applications.
When a plurality of additives are employed it may be desirable, although not essential, to prepare one or more additive concentrates comprising the additives (a concentrate sometimes being referred to herein as an additive package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The concentrate(s) or additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the additive package is/are combined with a predetermined amount of base lubricant. Thus, one or more of the functionalised polymers manufactured in accordance with the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from about 2.5 to about 90 mass %, and preferably from about 5 to about 75 mass %, and most preferably from about 8 to about 50 mass % by weight, additives in the appropriate proportions with the remainder being base oil.
The final formulations may employ typically about 10 mass % of the additive-package with the remainder being base oil.
The functionalised polymers of the invention having a Mn of from 350 to 2,000 for use as dispersants in fuel oils maybe used especially, for example, in petroleum-based diesel fuels. The functionalised polymers obtainable in accordance with the invention are also applicable to vegetable based fuels, for example, fuels based on derivatives of rapeseed oil, alone or in combination with petroleum-based fuels. Additional additives for improving low temperature and/or other properties, for example, pour point depressants and wax-anti-settling additives may be present. Such additives are in use in the art or known from the literature.
The present invention further provides a method of preparation of a dihydrooxazine comprising reacting, in the presence of trifluoroacetic acid,
(i) a C2 to C25 -olefin; and
(ii) an α,β-unsaturated acid amide or acid imide of which the amido or imido nitrogen atom, respectively, is substituted by a group --CH X R2 in which X is a group that, under the reaction conditions, acts as a leaving group and R2 is hydrogen or a hydrocarbyl radical having from 1 to 12 carbon atoms.
The use of trifluoroacetic acid as a catalyst in the amidoalkylation of olefinic compounds has been found, surprisingly, to give better yields as compared with the use of other acid catalyst systems, for example, sulphuric acid/acetic acid, to catalyse amidoalkylation of the same compounds.
The N-substituted amide or imide may be an amido compound of general formula R1 CONHCHXR2, in which R1 is a hydrogen atom or a hydrocarbyl radical having from 1 to 12 carbon atoms.
Preferably, R2 is a hydrogen atom. The N-substituted compounds. Suitable are, in particular, those N-substituted amides and imides mentioned above in relation to functionalisation of polymers. Preferred N-substituted compounds are acrylamides, methacrylamides, benzamides and crotonamides. The leaving group may be selected from hydroxy, alkoxy, hydrocarbyloxy (especially aryloxy, aralkyloxy and alkaryloxy) and amido groups, and is advantageously a hydroxy, aryloxy or amido group, especially a hydroxy or amido group.
The olefinic compound preferably has a terminal double bond. It is advantageously a compound of general formula R12 (R13)C═C(R14)H in which R12, R13 and R14 may be the same or different and each represents a hydrogen atom or a hydrocarbyl radical having from 1 to 12 carbon atoms, the total number of carbon atoms not exceeding 25 carbon atoms.
Trifluoroacetic acid may be used in molar excess, and may advantageously be, or be a component of, the solvent in which the reaction is carried out. The dihydrooxazines are useful as chemical intermediates. For example, they may be reacted with amines, including primary or secondary amines, for example C1 to C12 amines, or hydrolysed to give amido alcohols.
The following Examples illustrate the invention:
In the Examples, N-(Hydroxymethyl)acrylamide was used as a 48% aqueous solution ("Aldrich" product). N-(Hydroxymethyl)formamide was prepared according to the procedure reported in German Patent No. 1,088,985. Commercially available benzamide, paraformaldehyde and trifluoroacetic acid were used without additional purification. The polymers used have a carbon--carbon double bond in the terminal position or in the vicinity thereof.
Polymer samples--poly-n-butene ("PNB") or ethene-propene copolymer ("EPC")--were reacted with an amidoalkylation agent using one of the Methods A to D described below. In the Examples, the term amidoalkylation agents is to be understood to include reactants that, under the reaction conditions, are converted to amidoalkylation agents. For example, PhCONHCH2 OH may be obtained in situ by using a mixture of benzamide and paraformaldehyde as the amidoalkylation agent.
Method A
A mixture of polymer, amidoalkylation agent and 15 ml trifluoroacetic acid ("TFA") was heated at 70�-75� C. for 1.5 with vigorous stirring. TFA was distilled off under vacuum, and the residue poured into ice-cold 15% aqueous NaOH solution (20 ml) and extracted with chloroform (100 ml�4). The chloroform layer was dried over MgSO4, and the solvent was removed under vacuo. The residue was treated with ether (150 ml), and crystalline unreacted amidoalkylation agent filtered off. The ether solution was dried over MgSO4, the solvent was removed under vacuum, and the viscous residue (-1.2-1.3 g) was isolated.
Method B
A mixture of polymer (0.001 mol) and TFA was stirred at room temperature, and the amidoalkylation agent was added dropwise. The mixture was stirred vigorously at 85� C. for 1 hour and worked up as described in Method A.
Method C
The polymer was dissolved in 20 ml hexanes. To the vigorously stirred solution, a mixture of amidoalkylation agent and TFA was added, and the mixture was heated at 70�-75� C. for 1.5 hours, with vigorous stirring. TFA and hexanes were distilled off under vacuum, and 20 ml ice-cold 15% aqueous NaOH solution was added under vigorous stirring to the residue. A viscous product was extracted with hexanes (100 ml�4). The hexane layer was washed with water and dried over MgSO4 and the solvent was removed under vacuum. The residue was treated with hexanes (150 ml) and left overnight. A crystalline precipitate was filtered off, and the solvent from the filtrate was removed under vacuum at first at 60� C., and then at 110� C. The viscous residue was isolated and dried from hexanes by heating in a vacuum oven at 130� C. for 5 hours.
Method D
The polymer (0.001 mol) was dissolved in 20 ml hexanes and 20 ml TFA. The amidoalkylation agent (0.01 mol) was added dropwise to the stirred solution at room temperature. The mixture was stirred vigorously at 85� C. or 1 hour and worked up as described in Method C.
Table I gives the results of Examples 1 to 11.
TABLE I______________________________________ ActiveEx- 13CNMR, δ, Ingredientample Polymer R1 Method C═O %______________________________________1 PNB(Mn 730) Ph A 168.50 872 PNB(Mn 730) CH2 ═CH A 166.46 603 PNB(Mn 730) H B b 504 PNB(Mn 1710) Ph A 168.46 815 PNB(Mn 1710) CH2 ═CH A 166.53 636 EPC Ph A 168.48 937 EPC CH2 ═CH A 166.45 258 EPC H B b 589 PNB(Mn 2600) Ph C 6610 PNB(Mn 2600) CH2 ═CH C 4411 PNB(Mn 2600) H D 11______________________________________ b: The signal is too weak to be noticed.
In the Table, R1 corresponds to hydrocarbyl group R1 of the amide of general formula I. In Examples 1, 4, 6 and 9, the amidoalkylation agent was PhCONHCH2 OH, which was generated in situ from benzamide and paraformaldehyde. In Examples 2, 5, 7 and 10, the amidoalkylation agent was N-(hydroxymethyl)acrylamide. In Examples 3, 8 and 11, the amidoalkylation agent was N-(hydroxymethyl)formamide.
The amounts of active ingredient represent the amount of active polymer remaining after removal of impurities from the products obtained according to the Examples. IR spectra exhibited absorptions for the carbonyl group at 1652-1655 cm-1 for the products of Examples 1, 4 and 6, at 1670-1672 cm-1 for the products of Examples 2, 5 and 7, and at 1676-1684 cm-1 for the products of Examples 3 and 8, together, in each case, with a weak hydroxyl absorption at 3200-3300 cm-1.
In the case of the products of Examples 1, 4 and 6, the phenyl group was observable in the 1 H NMR spectra as two multiplets in 2:3 ratio at δ-7.5 and 7.90 and in the 13 C NMR spectra at δ-126.0, 127.8, 130 and 134.0. The carbonyl group was also visible in the 13 C NMR spectra (see Table I). The measured data already mentioned, together with the absence of C═C signals in the 13 C NMR spectra of the products of Examples 1, 4 and 6, indicate the presence in the product of an aminoalcohol.
As may be seen from Table I, Examples 3 and 8 gave low yields of active ingredient. Although the IR spectra included a carbonyl stretching band, no C═O group was observable in the 13 C NMR spectra, suggesting that only small amounts of carbonyl-containing material were present.
The products of Examples 2, 5 and 7 displayed signals for the carbonyl group and signals for the double bond of the acrylamido fragment (1 H NMR δ: 5.70-5.90 (dd,1H), 6.10-6.20 (dd, 2H); 13 C NMR, δ: 127.3 and 130.4), suggesting the presence of the acrylamidoalkyI substituted polymer.
The Mn values in Table I were determined by gel permeation chromatography comparisons with polyisobutene or with other appropriate standards. The active ingredient determinations were made using column chromatography over a column of silica gel with heptane as eluent and using IR to detect the onset of elution of a polar material.
Reaction of amidoalkylated poly-n-butene with butylamine
A mixture of 1.2 g of the amidoalkylation product of Example 2 (amidoalkylated PNB derived from PNB of Mn 730), 0.02 mol butylamine and 40 ml ethanol was refluxed for 24 hours. Ethanol and excess butylamine were removed under vacuum at 95� C., yielding a residue of 1.2 g (containing 80% active ingredient).
Reaction of amidoalkylated poly-n-butene with butylamine
Example 12 was repeated except that, instead of the product of Example 2, 1.2 g of the amidoalkylation product of Example 5 (amidoalkylated PNB obtained from PNB of Mn 1710) was used. The reaction product contained 78% active ingredient.
Reaction of amidoalkylated ethene-propene copolymer with butylamine
Example 12 was repeated except that, instead of the product of Example 2, 1.2 g of the amidoalkylation product of Example 7 (amidoalkylated EPC) was used. The reaction product contained 34% active ingredient.
A mixture of 1.2 g of the amidoalkylation product of Example 10, 1 g butylamine and 40 ml ethanol was refluxed for 24 hours. Ethanol and excess butylamine were removed under vacuum at 100� C., and a viscous light yellow residue (-1.0 g, 56% active ingredient) was isolated.
The 1 H and 13 C NMR spectra of the products of Examples 12 to 15 indicated that amine addition had occurred at the double bond of the acrylamido fragment. The 1 HNMR spectra exhibited three triplets for the CH2 groups in the --CH2 NHCOCH2 NHCH2 -- fragment arising from amine addition at δ-2.4, 2.6 and 2.9. The 13 C NMR spectra included a signal corresponding to the carbonyl group (δ173.0 to 173.3) and showed the absence of the C═C double bond, which in the starting polymers was observable in the 13 CNMR spectrum at δ-109.2 and 150.4 for the PNB of Mn 730, at δ-109.3 and 150.3 for the PNB of Mn 1710 and at δ-106.4 and 109.6 for the EPC. Carbonyl absorptions were also observed at 1653-1654 cm-1 in the IR spectra of the products of Examples 12 to 15.
1 H and 13 C NMR spectra of the products of Examples 1 to 15 were recorded on a Varian VXR 300, spectrometer (at 300 and 75 MHz, respectively), using CDCl3 as solvent and tetramethylsilane as internal reference. IR spectra were recorded on a Perkin Elmer 1600 FT-IR Spectrometer in CHCl3 solutions, using a CaF2 cell.
The products of Examples 1 to 15 can be dissolved in a base oil, to give concentrates suitable for imparting dispersant properties to oleaginous compositions.
In Example 16 and Comparative Examples A to C, the effectiveness of TFA as catalyst was compared with sulphuric acid/acetic acid in amidoalkylation of a number of olefins.
A mixture of olefin (0.01 mol), an amidoalkylating agent (0.01 mol) and 10 ml TFA was heated 70� C. for 1 hour with vigorous stirring. TFA was distilled off under vacuum and the residue poured onto ice-cold 15% aqueous NaOH solution (20 ml) and extracted with ether (2�30 ml). The ether layer Was dried over MgSO4 and the solvent removed under vacuum.
A mixture of benzamide (0.01 mol), paraformaldehyde (0.01 mol) and the olefin (0.01 mol) was stirred in 10 ml of glacial acetic acid over 10 minutes at room temperature, and a mixture of 12.5 ml of glacial acetic acid and 1.5 ml of 98% sulphuric acid was added dropwise at 10�-15C. for 10 minutes. The mixture was stirred at 65�-70� C. for 1 hour and poured into ice-water (50 ml). It was washed with ether (30 ml�2), neutralised with 25% aqueous sodium carbonate solution to pH7-7.5 while stirring vigorously, and extracted with ether (30 ml�2). The ether layer was dried (MgSO4), and the solvent removed under vacuum.
A mixture of olefin (0.01 mol), N-(hydroxymethyl)-acrylamide (0.01 mol) and glacial acetic acid (10 ml) was stirred at 50� C. for 10 minutes, and a mixture of 12 ml glacial acetic acid and 2.5 ml 98% sulphuric acid was added dropwise over 10 minutes. The mixture was stirred at 70� C. for 1 hour and worked-up as described in Comparative Example A.
A mixture of acrylamide (0.01 mol) and paraformaldehyde (0.01 mol) in 12.5 ml glacial acetic acid and 1.5 ml 98% sulphuric acid was heated at 70� C. for 10 minutes under vigorous stirring and the olefin (0.01 mol) was added dropwise over 10 minutes. The mixture was stirred at 80�-85� C. for 30 minutes and worked-up as described in Comparative Example A.
Table II compares the yields obtained on amidoalkylation of olefins R12 (R13)C═C(R14)H using as amidoalkylation, agent compounds R11 CONCHCH2 OH, in which R11 is Ph or CH═CH2, using TFA (Example 16), and sulphuric acid/acetic acid (Comparative Examples A, B and C).
Yields of other oxazine products obtained in accordance with the method of Example 16 are given in Table III.
TABLE II__________________________________________________________________________ Comparative ExampleR12 R13 R14 R11 Yield % Ex. 16__________________________________________________________________________H H (CH2)5 Me Ph 50 (A) 65H H (CH2)5 Me CH═CH2 62 (B) 74 52 (C)H Me CH2 CMe3 CH═CH2 65 (B) 75 68 (C)--(CH2)4 -- H CH═CH2 62 (B) 72 55 (C) (CH2)3 Me Me H CH═CH2* 58 (C) 63 Me (CH2)3 Me H CH═CH2__________________________________________________________________________ *designates a mixture of the two isomers indicated.
TABLE III______________________________________R12 R13 R14 R11 Yield %______________________________________H H (CH2)5 Me H 50H Me CH2 CMe3 H 53--(CH2)4 -- H H 50______________________________________
|Cited Patent
|Filing date
|Publication date
|Aug 14, 1961
|Jun 22, 1965
|Union Oil Co
|Amidomethylation of olefins
|Jul 13, 1964
|Dec 9, 1969
|Allied Chem
|Carbon-nitrogen backbone chain polymers
|Jul 13, 1964
|Feb 9, 1971
|Allied Chem
|2-substituted - 2 - oxazolines and 2-substituted -5,6 -dihydro-1,3,4-oxazines and their preparation
|Jul 24, 1967
|Aug 1, 1972
|Allied Chem
|Process for the preparation of cyclic iminoethers
|Jul 27, 1976
|Jul 25, 1978
|Exxon Research & Engineering Co.
|Oxazoline additives useful in oleaginous compositions
|Jul 30, 1976
|May 8, 1979
|Exxon Research & Engineering Co.
|Oxazoline additives useful in oleaginous compositions
|Mar 18, 1985
|Aug 26, 1986
|The Dow Chemical Company
|Cyclic iminoether modified copolymers as improved adhesives
|Nov 12, 1987
|Mar 28, 1989
|Basf Aktiengesellschaft
|Terminally functionalized polymers and preparation thereof
|Nov 5, 1987
|Jul 13, 1988
|BASF Aktiengesellschaft
|Terminally functional polymers and process for their manufacture
|Nov 2, 1988
|May 10, 1989
|ELF ATOCHEM ITALIA S.r.l.
|Process for the preparation of imidized acrylic polymers
|Oct 26, 1988
|Aug 30, 1989
|Petrolite Corporation
|End-functionalized low molecular weight polymers of ethylene
|Apr 14, 1989
|Nov 23, 1989
|BP Chemicals Limited
|A process for the preparation of a polybutene having a thioether function
|May 22, 1990
|Dec 5, 1990
|Exxon Chemical Patents Inc.
|Multifunctional viscosity index improver derived from amido amine exhibiting low temperature viscometric properties
|Apr 24, 1991
|Apr 15, 1992
|Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
|Modified polyolefin polymer, production thereof, and resin composition containing the same
|Title not available
|Title not available
|Title not available
|Title not available
|Dec 3, 1990
|Jun 27, 1991
|Exxon Chemical Patents Inc.
|Selective catalytic process for preparing n-halothiosulfonamide modified polyolefins
|C. Giordano et al., Gazzetta Chimia Italiana, "5,6-Dihydro-4H-1,3-Oxazines by Polar 1,4-Cycloaddition of Amidoalkyl Ions to Olefins. Configurational and Conformational Nuclear Magnetic Resonance Analysis of the Products", 104 (11-12), pp. 1181-1193 (1974).
|C. Giordano et al., Gazzetta Chimia Italiana, 5,6 Dihydro 4H 1,3 Oxazines by Polar 1,4 Cycloaddition of Amidoalkyl Ions to Olefins. Configurational and Conformational Nuclear Magnetic Resonance Analysis of the Products , 104 (11 12), pp. 1181 1193 (1974).
|C. Giordano et al., Synthesis "5,6-Dihydro-4H-1,3-oxazines from Olefins", Montecatini-Edison, (2), pp. 92-95, (1971).
|C. Giordano et al., Synthesis 5,6 Dihydro 4H 1,3 oxazines from Olefins , Montecatini Edison, (2), pp. 92 95, (1971).
|Chemical Abstracts No. 66:18690x: W. Seeliger et al., Justus Liebigs Ann. Chem., "Synthesis of 5,6-dihydro-4H-1,3-oxazines", 697, pp. 171-180 (1966).
|Chemical Abstracts No. 66:18690x: W. Seeliger et al., Justus Liebigs Ann. Chem., Synthesis of 5,6 dihydro 4H 1,3 oxazines , 697, pp. 171 180 (1966).
|Chemical Abstracts No. 83:97317h: G. Ribaldone et al., "Dihydro-1,3-oxazines and derivatives". Ital. 886,285 (Mar. 1, 1971).
|Chemical Abstracts No. 83:97317h: G. Ribaldone et al., Dihydro 1,3 oxazines and derivatives . Ital. 886,285 (Mar. 1, 1971).
|Chemical Abstracts No. 86:55459n: C. Giordano, "Dihydro-1,3-oxazines and derivatives", Ital. 927,515 (Sep. 1, 1972).
|Chemical Abstracts No. 86:55459n: C. Giordano, Dihydro 1,3 oxazines and derivatives , Ital. 927,515 (Sep. 1, 1972).
|Chemical Abstracts No. 87:135353j: H. Matsuoka et al., "2-Oxazoline and 5,6-dihydro-4H-1,3-oxazine", Japan, Koka 77-19,660 (Feb. 15, 1977) (see AT below).
|Chemical Abstracts No. 87:135353j: H. Matsuoka et al., 2 Oxazoline and 5,6 dihydro 4H 1,3 oxazine , Japan, Koka 77 19,660 (Feb. 15, 1977) (see AT below).
|D. Ben Ishai et al., Journal Heterocycl. Chemistry, The Amidoalkylation of Aromatic Compounds and Olefins with 5 Alkxoyhydantoins 91,2) , 7(6), pp. 1289 1293 (1970).
|D. Ben Ishai et al., Tetrahedron, A New Synthesis of Amino Acids II. Amidoalkylation of Olefins with Glyoxylic Acid Derivatives ,33(12) pp. 1533 1542, (1977).
|D. Ben-Ishai et al., Journal Heterocycl. Chemistry, "The Amidoalkylation of Aromatic Compounds and Olefins with 5-Alkxoyhydantoins 91,2)", 7(6), pp. 1289-1293 (1970).
|D. Ben-Ishai et al., Tetrahedron, "A New Synthesis of Amino Acids--II. Amidoalkylation of Olefins with Glyoxylic Acid Derivatives",33(12) pp. 1533-1542, (1977).
|Derwent Abstracts No. 22483Y: Mitsui Petrochem. KK, JP52 19,660 (Feb. 15, 1977). (see AR above).
|Derwent Abstracts No. 22483Y: Mitsui Petrochem. KK, JP52-19,660 (Feb. 15, 1977). (see AR above).
|Derwent Abstracts No. 58505R: Sumitomo Chem., JP 7024582 (Aug. 15, 1970).
|E.S. Levchenko et al., Journal Organic Chemistry USSR, "Synthesis Based on N-Aroylsulfinylamines" 12(2), pp. 432-435. (1976).
|E.S. Levchenko et al., Journal Organic Chemistry USSR, Synthesis Based on N Aroylsulfinylamines 12(2), pp. 432 435. (1976).
|L.Simon et al., Acta Chimica Hungarica, "Stereochemical Studies, 80. Cyclic Amino Alcohols and Related Compounds. Preparation of cis-2-(alkylaminomethyl)-and (aralkylaminomethyl)-1-cyclanols from olefins via the 5,6-dihydro-4H-1,3-oxazine derivatives", 118(2), pp. 1319-145 (1985).
|L.Simon et al., Acta Chimica Hungarica, Stereochemical Studies, 80. Cyclic Amino Alcohols and Related Compounds. Preparation of cis 2 (alkylaminomethyl) and (aralkylaminomethyl) 1 cyclanols from olefins via the 5,6 dihydro 4H 1,3 oxazine derivatives , 118(2), pp. 1319 145 (1985).
|Revue de l Institut Francais du Petrole vol. 41, No. 2, Mars Avril 1986 Iminoethers 1,3 Cycliques : pp. 275 295 (Translation for Chimie Et Applications Dans Le Domaine . . . see above).
|Revue de l'Institut Francais du Petrole vol. 41, No. 2, Mars-Avril 1986--"Iminoethers-1,3 Cycliques": pp. 275-295 (Translation for Chimie Et Applications Dans Le Domaine . . . see above).
|Seymour et al., "Polymer Chemistry", Second Edition, (1992), 467, Marcel Dekker (New York).
|Seymour et al., Polymer Chemistry , Second Edition, (1992), 467, Marcel Dekker (New York).
|Synthesis International Journal of Methods in Synthetic Organic Chemistry No. 2 (Feb. 1979).
|W. Seeliger et al., Angew. Chemical International Edition, "Recent Syntheses and Reactions of Cyclic Imidic Esers", 5 (10), pp. 875-888 (1966).
|W. Seeliger et al., Angew. Chemical International Edition, Recent Syntheses and Reactions of Cyclic Imidic Esers , 5 (10), pp. 875 888 (1966).
|Citing Patent
|Filing date
|Publication date
|Mar 12, 2007
|Jan 11, 2011
|J.P.M.E.D. Ltd.
|Homogenous granular solid matrix containing vegetable protein
|Mar 27, 2015
|Aug 2, 2016
|Angus Chemical Company
|Oxazoline compounds as open-time extenders for latex paints
|Feb 8, 2001
|Jan 30, 2003
|Friedman Doron I.
|Homogenous solid matrix cotaining vegetable proteins
|U.S. Classification
|525/374, 525/350, 525/379, 525/381, 525/380, 525/359.3, 525/359.5
|International Classification
|Cooperative Classification
|European Classification
|Sep 8, 1995
Owner name: EXXON CHEMICAL PATENTS INC., DELAWARE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TACK, ROBERT DRYDEN;EMERT, JACOB ISSAC;KATRITZKY, ALAN R.;AND OTHERS;REEL/FRAME:007647/0328;SIGNING DATES FROM 19950609 TO 19950731
|Apr 20, 2001
|Fee payment
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Effective date: 20051104


text:
Galería La Pinacoteca
Museo de Arte de El Salvador
An impressive collection of many sketches and paintings tracking the development of prominent local and foreign artists; some of the...
Museo Nacional de Antropología David J Guzmán
This small museum has an excellent range of Maya and Olmec (pre-Maya) statues and relics from ancient Cuscatlan. The traditional crafts...
Los Rinconcitos
Karaoke is a universal language and Salvadorans love to lip-synch. While not the classiest place you'll drink in, the business model...
Caminito Chocos
The pseudo-Argentine food here is really just heart-stopping BBQ, burgers and fries; you won't see your personal trainer here, unless...
Galería La Pinacoteca information
The best independent gallery in the city, featuring both rising and established Salvadoran painters and sculptors, and the irrepressible curator, Ana Lynn de Lima.

subset: commoncrawl


text:
The Economist ponders future of news as apps
The Economist
The Babbage Blog on Economist.com examines the business of selling news via mobile apps and points out some of the advantages publishers feel they have in this new tablet economy.
The blog post also highlights the potential newfound power of apps (Wired, Time) to allow publishers to charge for content, though it may be too early in the game to judge that attempt a success.
>Growth in mobile applications: Apps and downs (The Economist)


text:
Lol I know it sounds kinda creepy, but I've always loved staying up late n watching scary movies or strange weird stuff on YouTube about UFO'S or any kind of mysteries about the Universe, but that's just me dark, creepy, mysterious, poetic, romantic, artistic, weird, humorous and always misunderstood ......
VIEW 7 of 7 COMMENTS
VIEW 3 of 3 COMMENTS
Let's see how much pain I feel tomorrow after my grueling workout, not much I'm use to it ;)
No didn't feel sore at all, I'm just glad I care enough to take care of My Body, cause if I didn't I would look like such a Gross sLob ;( lol !!!!


text:
|This article is of interest to the following WikiProjects:
- 1 Legality
- 2 Nonsensical
- 3 Obsolete
- 4 Exportation of plant
- 5 Merger of Coca tea
- 6 Coca Sek Controversy Section Cleanup
- 7 Tone of the historical references
- 8 Reorganization proposed
- 9 How about removing the "balance" tag now?
- 10 Is the BBC reliable?
- 11 WikiProject Food and drink Tagging
- 12 Coca vs. Cocaine - not synonyms
- 13 Euphoric and psychoactive effects?...
- 14 Cocaine in Coca Cola
- 15 Binomial spelling
- 16 Nutritional content of Coca leaf
- 17 We should briefly define "de-cocainized"
- 18 mummies
- 19 Citations
- 20 Coca vs. Erythroxylum coca
- 21 Eastern Peru
- 22 Pharmological Aspects
- 23 recent edits 1 Aug 2012
- 24 Transnational Institute
- 25 Incorrect year in NYT citation
- 26 Coca and condoms?
- 27 Depression?
- 28 External links modified
In what countries is it legal to grow coca?
It is legal on certain registered farmers in Bolivia but ONLY for it's consumption in it's unrefined state (ie not for onward processing into cocaine). The sale of a wide range of products made from coca leaves (shampoo, toothpaste, creams etc etc) is legal in Bolivia, although any attempt to import any such items into neighbouring Chile is illegal. —Preceding unsigned comment added by 22.214.171.124 (talk) 14:54, 3 January 2008 (UTC)
There are also legal coca farmers in Peru. —Preceding unsigned comment added by 220.127.116.11 (talk) 04:18, 15 October 2008 (UTC)
Coca tea is legal in most South American countries (not sure about Brazil and Paraguay). You can also buy coca tea (in bags, imported from Peru) in South Africa. I think more research should be done. — Preceding unsigned comment added by 188.8.131.52 (talk) 12:48, 30 October 2012 (UTC)
- Some anesthetics such as Novocaine are derived from the coca plant.
Novocaine (procaine) is NOT derived from coca. It is entirely synthetic.Nomad57 17:30, 18 April 2007 (UTC)
- The LD50 of coca extract is 3450 mg/kg, however, the LD50 of the extract based on its cocaine content is 31.4 mg/kg, indicating that the coca leaf contains constituents other than cocaine that may contribute to a toxic effect of the plant.
A higher LD50 (lethal dose to 50% of population) means the substance is LESS toxic. This is saying "it takes a lot of the plant extract to kill someone. It takes very little of the cocaine part of the extract to kill someone. Therefore, the plant must have something in it that's more toxic"Lesqual 05:49, 4 August 2006 (UTC)
These paragraphs look obsolete:
- In the Kew Bulletin for January 1889 is an account of the history and botany of the plant, which has been so long under cultivation in South America that its original home is doubtful.
- As the result of this cultivation, numerous forms have arisen.
- The writer distinguishes from the typical Peruvian form with pointed leaves a variety novo-granatense, from New Granada, which has smaller leaves with a rounded apex.
- The plant is now cultivated in the West Indies, India, Sri Lanka, Java and elsewhere.
- The preparations of coca leaves are incompatible with certain drugs which might often be prescribed in combination with them, such as salts of mercury, menthol and mineral acids, which latter decompose cocaine into benzoic acid and ecgonine.
If this information can be confirmed from more recent sources, we can reintroduce it.
-- Viajero 21:56, 31 Jul 2003 (UTC)
"The Coca-Cola Company buys 115 tons of coca leaf from Peru and 105 tons from Bolivia per year, which it uses as an ingredient in its Coca-Cola formula (famously a trade secret). The cocaine itself does not end up in the drink nowadays, however, and is generally sold to the pharmaceutical industry where it is used for various surgical procedures." If Coca Cola suposedly buys it to use it in its formula, how come it doesn't end in the drink itself?
- Cocaine is merely a single chemical ingredient in coca leaves. One would gather from this that Coca Cola uses other ingredients from the coca leaves for flavoring rather than cocaine.
- I beleive that the leaves are "de-cocainized." The cocaine is sold for use in anaesthetics and apparently cough syrups (that's what was said in coca-cola's talk page). I would imagine the DEA makes sure it goes somewhere legit... I never knew cough syrups could have cocaine in them. I'm sure if not there, the DEA has the cocaine destroyed. As for the early years, cocaine was probably used for both the taste and the stimulant effect, same thing as caffeine nowadays (of course caffeine is a much weaker drug and doesn't have any euphoric effect, and is thus legal)--AK7 10:07, 23 January 2006 (UTC)
- Actually, caffeine can have euphoric effects in large enough amounts, but it's concentration in beverages (soda, coffee, tea) is actually very low. That's the real reason you don't get a true high from drinking any reasonable amount of coffee, tea, or caffeine-containing soda. I mention this because the effect also actually applies to cocaine, which explains why chewing coca leaves is nowhere near as harmful as snorting purified cocaine. The Mysterious El Willstro (talk) 02:32, 15 December 2010 (UTC)
- I beleive that the leaves are "de-cocainized." The cocaine is sold for use in anaesthetics and apparently cough syrups (that's what was said in coca-cola's talk page). I would imagine the DEA makes sure it goes somewhere legit... I never knew cough syrups could have cocaine in them. I'm sure if not there, the DEA has the cocaine destroyed. As for the early years, cocaine was probably used for both the taste and the stimulant effect, same thing as caffeine nowadays (of course caffeine is a much weaker drug and doesn't have any euphoric effect, and is thus legal)--AK7 10:07, 23 January 2006 (UTC)
The proper translation of "coca no es cocaína" is "coca is not cocaine," so I have changed the author's paraphrase. Kemet 9 Jan 2006.
Exportation of plant[edit]
The article mentions the exporting of cocoa leaves, but I have never heard of coca plants being grown outside of south america (which is remarkable considering how much money a drug ring could make if they grew their coca locally). In the Coca eradication page it is said that coca is a very resilient plant- why hasn't it been grown elsewhere? Or perhaps it has? --AK7 10:14, 23 January 2006 (UTC)
Merger of Coca tea[edit]
Coca tea is a relatively short article, and much of the information on health benefits seems as if it would apply to coca consumed in the traditional manner (chewing) as well. It seems it would be best incorporated into the "Traditional Uses" section here. Please comment on this proposal. (forgot to sign original comment) Choess 23:06, 22 February 2006 (UTC)
- I agree with your assessment. Though of course the proper length of the Coca tea article is a matter of debate itself at the moment. -- Veyklevar 09:26, 24 February 2006 (UTC)
- I believe this article should be merged with the coca section. -- Ukiemob 13:26, 24 February 2006 (UTC)
- I concur. Merge the articles. Helzagood 12:47, 17 March 2006 (UTC)
coca-cola <3
Coca Sek Controversy Section Cleanup[edit]
This section of the article has some serious bias that needs to be corrected. Things like "gaining the respect it deserves" have to be edited. I don't know enough about this controversy to do it myself, but someone who does should see if they can make some changes.
Tone of the historical references[edit]
I'm a little concerned that phrases like "_Even today_, chewing coca leaves is a common sight ..." are non-neutral and/or patronizing, implying that this custom should be expected to have died out. Any objection to editing those?
Also, the article says Coca-Cola "used to buy" coca leaf for flavoring ingredients; I understood (according to the article on Coca-Cola) that they still do.Ckeavney (talk) 19:04, 26 November 2007 (UTC)
Reorganization proposed[edit]
I have been working (off-line) on a significant reorganization of this article. It seems clear that different sources have been pulled together and the same information is repeated in different places. I propose to rearrange the sections, combine some paragraphs, delete some of the statements that are unsourced and dubious, add a few sources and references to other related Wikipedia articles.
Ckeavney (talk) 18:51, 19 February 2008 (UTC)
How about removing the "balance" tag now?[edit]
This is my first significant edit on Wikipedia. I have combined paragraphs that covered the same subject, moved others around, and deleted some dubious or slanted statements (including references to Shakespeare, Queen Victoria, Pope John Paul II, Bill Gates, and Princess Anne, and nutritional claims that seemed doubtful). I hope I have improved the organization and balance of the article. Do people think we can remove the "Unbalanced" tag now? Ckeavney (talk) 03:31, 21 February 2008 (UTC)
Is the BBC reliable?[edit]
Yes it is. The problem is, the BBC news story linked does not actually say that Coca Cola uses an extract of trujillo as flavoring. The article says that the Coca Cola company does not disclose its flavorings as the recipe is propriatary information. In other words, the article cited is not a reliable source for the claim made in this article and it is that unsourced claim which I deleted. Reliable sources is not simply a matter of whether some source won the Nobel Prize or something, it is about using sources appropriately and accurately. Slrubenstein | Talk 17:57, 15 May 2008 (UTC)
Someone put the claim back in, with more irrelevant non-references, and I have removed it again. One reference was a web-page that itself provides no sources for the claim - clearly not a reliable source. Another was an editorial that, after asserting the claim, immediately went on to day that Coca Cola doesn't support the claim. All the other sources include only one fact: Coca Cola does not disclose its recipe. In short, none of the sources provided offer any reliable evidence that Coca Cola uses coca leaves. One source claims that Coca Cola received a license to import coca leaves; I contacted both the DEA and the FDA and both responded that they had no knowledge of any such arrangement ... so who did Coca Cola get the license from? This is just an urban myth and I see no reason for Wikipedia to repeat unsourced and meaningless claims. Note: I have no objection to the claim whatsoever, if we had a reliable source that actually said that Coca Cola used coca leaves today, with appropriate evidence, then I would be all for putting the claim back in the article. Just find a source that actually documents this fact - not one that speculates or rehashes web-gossip. Wikipedia is an encyclopedia. Let's have some standards. Slrubenstein | Talk 09:46, 21 May 2008 (UTC)
- This is ridiculous. Just look at Coca-Cola formula and you will find referenced sources that say that Coca Cola uses de-cocainized coca leaves as a flavouring agent. One of the standards of Wikipedia is to check information – something you are obviously incapable of. - Mafia Expert (talk) 13:26, 21 May 2008 (UTC)
Um, yeah, I am obviously incapable of checking information, right. Well, your idea of checking information is googling the web. Good plan - wikipedia, a web-based encyclopedia, will just reproduce information already on the web, meaning often misinformation. My idea of checking information is to go to reliable sources. I e-mailed the Food and Drug Administration which has regulatory oversight over Coca Cola and coca leaves. Their reply to me:
- The source of any ingredient is proprietary but coca leaves are not permitted under DEA law. Cola nuts can be imported into the US. There is a great deal of misinformation on the internet.
- Jeannine Ertter, A.S.C.P.
- Senior Public Affairs Specialist
- Communication and Coordination Staff
- Office of Food Defense, Communication,
- Educations and Response
- Center for Food Safety and Applied Nutrition
Isn't this an example of checking information? Slrubenstein | Talk 16:06, 21 May 2008 (UTC)
- No, this is a very partial check of information. It says nothing about the importation of coca leaves under special licence and also says nothing about de-cocainizing the leaves. If you think three lines of the FDA solve the problem, you are wrong. There is Article 1f) of the 1961 Single Convention that specifies that "coca leaf" means the leaf of the coca bush except a leaf from which all ecgonine, cocaine and any other ecgonine alkaloids have been removed. See: Single Convention on Narcotic Drugs
- Coca-Cola changed its formula in 1906, using the coca leaf as a flavouring agent without the cocaine alkaloids; this was made legitimate under Article 27 of the Single Convention of 1961 (Additional provisions relating to coca leaves):
- 1. The Parties may permit the use of coca leaves for the preparation of a flavouring agent, which shall not contain any alkaloids, and, to the extent necessary for such use, may permit the production, import, export, trade in and possession of such leaves.
- 2. The Parties shall furnish separately estimates (article 19) and statistical information (article 20) in respect of coca leaves for preparation of the flavouring agent, except to the extent that the same coca leaves are used for the extraction of alkaloids and the flavouring agent, and so explained in the estimates and statistical information.
- Coca leaves from which the alkaloid has been extracted are no longer considered coca leaves and are not covered by the Convention. The residue of the leaves can therefore be commercialised with no control, which particularly favours the Coca-Cola Company. In fact, it was tailormade for Coca Cola with the help of US diplomacy. Moreover, under Article 27§2 Coca Cola does not have to provide estimates (meaning the amount of coca leaves it needs) because it imports the leaves through Stepan Company which provides the flavouring residue to Coca Cola and the alkoloids to another company. This way Coca Cola can hide its imports which may reveal its precious formula. You can find all of this on the Internet if you know how to research an issue. - Mafia Expert (talk) 16:43, 21 May 2008 (UTC)
Yet, these were not in the original sources provided for the claim in this article. If this is what it takes to get you to provide the reliable sources, i am glad I did not waste my efforts. Good job! Slrubenstein | Talk 17:56, 21 May 2008 (UTC)
WikiProject Food and drink Tagging[edit]
This article talk page was automatically added with {{WikiProject Food and drink}} banner as it falls under Category:Food or one of its subcategories. If you find this addition an error, Kindly undo the changes and update the inappropriate categories if needed. The bot was instructed to tagg these articles upon consenus from WikiProject Food and drink. You can find the related request for tagging here . Maximum and careful attention was done to avoid any wrongly tagging any categories , but mistakes may happen... If you have concerns , please inform on the project talk page -- TinucherianBot (talk) 01:31, 4 July 2008 (UTC)
Coca vs. Cocaine - not synonyms[edit]
"The drug was first introduced to Europe in the 16th century" and "Cocawine (of which Vin Mariani was the best-known brand) and other cocaine-containing preparations" are misleading in that coca by itself is not a drug, and though wines that contained coca naturally also contained cocaine, to call them "cocaine-containing preparations" is misleading. "These products became illegal in most countries outside of South America in the early 20th century, after the addictive nature of cocaine was widely recognized." This also seems to make coca and cocaine synonymous. There should probably be some sort of explanation that though the reason they became illegal is because of fear of addiction to cocaine, it should be noted that products that simply used coca as an ingredient should not be frivolously lumped in with products that contained pure cocaine, even though that is what the US government erroneously did.Kunderscoreuy (talk) 23:23, 25 July 2008 (UTC)
Euphoric and psychoactive effects?...[edit]
The article reads: "Absorption of cocaine from the leaf is much less rapid and efficient than from the purified forms of cocaine, and it does not cause the euphoric and psychoactive effects associated with use of the drug."
I've never used refined cocaine, so I wouldn't know how chewing coca would compare with that, but I have chewed coca leaves quite a few times here in the Peruvian Andes, and did often get a euphoric effect, or "high" - albeit a fairly mild one - maybe about the same as after quite a few sips of Argentine mate....
I guess the effect is different for each person, but it might be good to slightly modify the article to reflect this. 220.127.116.11 (talk) 23:43, 23 March 2009 (UTC)
As the contributor of the excerpt above, I have to admit that I also have no personal experience with refined cocaine. But "fairly mild" is not how its effects are usually described. Ckeavney (talk) 03:51, 22 May 2010 (UTC)
Cocaine in Coca Cola[edit]
As has been discussed before, the flavoring and the cocaine are separately extracted from the coca leaves. The flavoring, and hence Coca Cola, will inevitably always contain some trace amounts of cocaine. These trace amounts will be so small as to have no physiological effect however. This should be added to the article as it is fairly significant and clears up a lot of misconceptions. Kernow (talk) 08:29, 15 July 2010 (UTC)
Binomial spelling[edit]
The binomial is correctly spelled Erythroxylon coca, not Erythroxylum as the Article currently shows it. The Mysterious El Willstro (talk) 02:37, 15 December 2010 (UTC)
- ✗ Not done. What is your authoritative source? 126.96.36.199 (talk) 06:40, 15 June 2013 (UTC)
Nutritional content of Coca leaf[edit]
Should the nutritional content be added to this page? Coca leaf is used for chewing and as tea, and therefore some nutrients must be absorbed by the gut. Which are those?
Asuka Rei (talk) 01:00, 28 December 2010 (UTC)
We should briefly define "de-cocainized"[edit]
"A de-cocainized extract of coca leaf is reportedly one of the flavoring ingredients in Coca-Cola." -- so as to reaffirm that the use of "de-cocainized" coca in Coca Cola, Red Bull, and other food products, is not particularly controversial (as far as I know), we should briefly explain what it is. I'm personally at a loss as to the specifics of that -- does anyone know exactly what is involved in the "de-cocainizing" process, and whether or not it actually guarantees that the intoxicating factor is removed (i suppose what's left is just a "flavor component"?)? Is there a "cocaine" byproduct that has to be destroyed according to some protocol? 184.108.40.206 (talk) 09:00, 11 March 2011 (UTC)
I guess it is becoming more common to refer to all mummified corpses as mummies these days, but when I was very young any reference to "mummies" automatically led one to think of Egypt. If anyone else can sympathize with my confusion, maybe the wording in the history section could be changed to "andean [mummies]"? Msybe I'm wrong, and to help get the idea across to us last few people living under a rock, it is useful to intentionally leave it that way so we educate ourselves. :) --— robbie page talk 12:44, 3 July 2011 (UTC)
Why not just put at the top of the article that it lacks proper citations for it's data. Why put 1000 "Citation Needed" throughout the article?? It makes it look stupid and I think the reader gets it. I've seen many other articles that just put the notice on top so people know the article does not use proper citations throughout! — Preceding unsigned comment added by 18.104.22.168 (talk) 08:36, 13 November 2011 (UTC)
- I believe you should count them again. Tagging specific statements particularly identifies where the article makes dubious claims. Some people think it looks stupid when there is an apostrophe in the word its or when a small number is grossly exaggerated. 18.104.22.168 (talk) 06:50, 15 June 2013 (UTC)
Coca vs. Erythroxylum coca[edit]
It seemed appropriate to move the information specifically about Erythroxylum coca to a page on the species and no longer have the Erythroxylum coca redirect to this page. There are 2 coca species, so this page should be for both rather than serve as the primary page for Erythroxylum coca. — Preceding unsigned comment added by Timepastandtimepresent (talk • contribs) 02:35, 16 December 2011 (UTC)
Eastern Peru[edit]
Eastern Peru is jungle and therefore it isnmt credible that coca leaf is an important cash crop there so I have removed the word eastern. I cannot verify the reference but it strikes me we need a much more accurate description of the parts of Peru where coca is a cash crop or leave it just saying Peru, which isnt wrong. Thanks, ♫ SqueakBox talk contribs 17:09, 4 January 2012 (UTC)
Pharmological Aspects[edit]
First of all, this section is so sloppily written with such poor grammar and punctuation and such a lack of discernible sentence structure that even when I tried to edit merely for these aspects I had difficulty (for example, some sentences just cut off halfway through, making it hard to discern what the author was trying to say).
Also, while there may be some truth to what the author is saying, the section remains incredibly biased and utterly non-neutral. Since its issues are more than merely terrible grammar/punctuation/structure, also lying largely in questionable content, I propose that the entire section (or at least the paragraph in question) be killed.
-Ryan Kroner, 2/15/2012 — Preceding unsigned comment added by 18.104.22.168 (talk) 15:11, 15 February 2012 (UTC)
- I have tried to make the paragraphs flow better, and have added more citations. The whole section could probably be divided up and spread throughout the rest (for instance, quite a bit of research has been done on coca tea and chew discretely as they have different absorption rates, etc.) I have left in the TNI reference, though I'd like to find a more direct, reputable, and non-biased source. Onychoprion (talk) 19:45, 4 August 2014 (UTC)
recent edits 1 Aug 2012[edit]
IP editor removed referenced material "because it would help the neutrality of the article"? I do not see how. Please explain. Thanks. Gtwfan52 (talk) 05:59, 2 August 2012 (UTC)
- I agree with the IPs removal, though I also agree that there needs to be prior consensus for it. There are several problems with the text that was removed. First, it does not belong in the lede of the article, but that would be easily fixed by moving it into the article body. Second, it contains synthesis, a form of original research - for instance "However, the coca leaf is not cocaine, just as grapes are not wine." Third, this section relies very heavily on one single source, the Transnational Institute, which is a reputable source but admittedly slightly biased in this question - and more importantly, when we look for corroboration in the source for the specific facts that are referenced to the TNI, those facts are not in the source. I'm sure they may be somewhere on the website, but not in the source provided. Fourth, a lot of it is not sourced at all. Fifth, the (unsourced) last sentence, "Furthermore, current U.S.A. extraction methods use the chemicals methanol and benzoic acid to extract coca out of a coca product at a molecular level for scientific testing." does not seem to be connected to the rest of the article, I don't understand how it belongs in the article at all. Sixth, the section has a POV tone, it reads like a defense against some kind of accusation that hasn't been levelled at it in the article. (And that agrees with what the IP said.)
- The part of the text that, in my opinion, should be saved is the sentence "The coca alkaloid content in coca leaves is negligible: between .25% and .77%", because that is connected to the previous sentence and it makes sense to mention it in the lede. The rest should at the very least be moved further down in the article and rewritten (and the unsourced parts need to be sourced or removed), or, preferrably, removed altogether.
- Btw, Gtwfan52, could you change the heading to read "Aug 1 2012" or something like that? I keep looking at the heading and thinking it's about the 8th of January :-) --bonadea contributions talk 09:49, 2 August 2012 (UTC)
To answer your question as to why the sentence,Furthermore current U.S.A. extraction methods use the chemical reagants benzoic acid and ethanal to extract coca out of a coca specimen,should remain is because any chemist knows that all chemistry is like a recipe.If you do not add those 2 chemicals ,plus the coca,then you will never ever get molecular benzoylecgonine.Thus proving the test method makes the benzoyleconine,not that anyone ever consumes it via a cup of tea or eating coca leaves.Which can further be proven very simply by putting a urine dip stick in a cup of coca tea,but that is for another section.This is why it was important to leave all that knowledge that was 100 percent verifiable,but for some reason no-one in the U.S.A. wanted that information out to the public,184.108.40.206 (talk) 17:54, 11 September 2012 (UTC)PAITA
Transnational Institute[edit]
Hi, it seems to me that the article is overly-reliant on the Transnational Institute's "Coca Myths" Report. I don't think that TNI is a reliable source on the subject. After reading the report, this seems to be reinforced by the fact that its author lacks a PhD. Going through the report, it is evident that the author is extremely POV. I'm not saying that that precludes the report from being used, but that it should be used and cited with care to avoid carrying the report's POV into the article. Finally, the report is readily available via a Google Search, but there the article doesn't contain a link or page numbers in the reference. Without a link or page numbers, WP:V is a lot more difficult, especially when the same article is cited 15 times. --Lacarids (talk) 04:35, 31 October 2012 (UTC)
Incorrect year in NYT citation[edit]
Citation number 3 refers to a NY Times article describing that coca extracts are used in coke. The citation has the date of the article wrong. It is actually July 1, 1988 (http://www.nytimes.com/1988/07/01/business/how-coca-cola-obtains-its-coca.html). I tried to correct it, but wiki's not showing me all the citations. — Preceding unsigned comment added by 2620:0:1005:9:9D0:3A07:6818:5777 (talk) 18:56, 17 May 2013 (UTC)
- Fixed -- Fyrael (talk) 19:00, 17 May 2013 (UTC)
- Thank you. I added the url too so that anyone can click through to the source.
Coca and condoms?[edit]
The article says the following: In recent times (2006), the governments of several South American countries, such as Peru, Bolivia and Venezuela, have defended and championed the traditional use of coca, as well as the modern uses of the leaf and its extracts in household products such as teas, toothpaste and condoms.
How do you use coca or cacain with condoms? I googled it and found nothing. Can someone explain what is meant here? — Preceding unsigned comment added by 184.108.40.206 (talk) 15:56, 1 July 2013 (UTC)
- It was probably just some old vandalism, I've removed it from the article. It was added in 2011 in this edit by an unregistered user, i.e. not by the same author who wrote the rest of the paragraph. jonkerz ♠talk 17:22, 1 July 2013 (UTC)
In the lead in to the article it says: "This means that chewing the leaves or drinking coca tea does not produce the intense high (euphoria, megalomania, depression)..." Depression? Since when do stimulants cause depression? Also megalomania is questionable. Maybe it would make sense to delete the whole parenthetical expression. Senor Cuete (talk) 14:33, 7 May 2015 (UTC)
External links modified[edit]
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Harris County (GA) TaQuon Marshall is a complete athlete as he plays quarterback, defensive back and also returns punts and kickoffs for his high school team. On Saturday at Georgia Tech's Junior Day, this versatile athlete was enjoying his visit to the Flats when a good day ended up even better.
Marshall had an in-depth conversation with Coach Johnson and learned that he could add an option to his list of schools. "He said that he would love for me to come to Georgia Tech and offered me a scholarship. He told me that I am a player that can help at many positions that they would be recruiting me as an athlete."
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Florida Gators vs. Marquette Golden Eagles
The Florida Gators and the Marquette Golden Eagles battle it out on Thursday Night in the NCAA Tournament with a spot in the Elite Eight going to the winner. The Golden Eagles are -1 point favorites over the Gators with an over/under point total set at 146.
The Florida Gators have been a streaky team all season long and when Billy Donovan's team gets the hot hand few are hotter but when they get cold, it's ice cold, and the Gators appear to be grasping at straws. The question for this game is which Florida Gators' team shows up for this game. Florida has stars and with five players averaging double digits the Gators have no shortage of options. Kenny Boynton is the top scoring option, Bradley Beal can score and grab rebounds, Erving Walker can create, score, and pass, and Patric Young is carrying around a world of expectations. Thus far in the tournament Florida has been able to have their way and hit their shots and they are seen as the major beneficiary of Missouri's early exit as they drew Norfolk State in the second round. Where Florida has struggled and disappointed this season is against the better teams. Florida is going to do what they do and that is throw up a ton of threes but when they aren't dropping it looks very ugly as a lot of their shots happen early in the shot clock and often they don't look like they get the best looks at the hoop. As the old saying goes, you have to be in it to win it and Florida is definitely in it at this point.
The Marquette Golden Eagles have been in the top 10 for the bulk of the season and despite that ranking Buzz Williams' team has been somewhat under the radar all season long as well. Marquette has lost five times since January first, all to teams who are in the NCAA Tournament and twice since the first week in February and both of the teams to beat them are still alive in the Sweet 16 when the day began. One concern for the Golden Eagles is that in their earlier game against an SEC team this season they were blasted at home by Vandy by 17 points but that was in December and Marquette is playing far better now. Jae Crowder was the Big East Player of the year, Darius Johnson-Odom averages more points than any player playing in this game at 18.5 and players like Junior Cadougan and Vander Blue stir the pot. Marquette lives off of turnovers and getting their opponents flustered and it isn't uncommon for them to be trailing at the half. Against a team like Florida one of the big concerns early for Marquette will be to keep this one in reach.
Florida is 5-1 against the spread in their last six NCAA Tournament games, 8-3 against the spread against the Big East, and 9-3-1 against the spread in their last 13 games as an underdog. Marquette is 5-2 against the spread following a win, 4-1 against the spread in their last five NCAA Tournament games, and 2-5-1 against the spread in their last eight non-conference games.
The total for this one sets up to be a high scoring game but I see it to be a shade lower than the aggressive total that has been posted and that will be my pick here.
Under 146


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You have to choose the program, you wish to view from the list. Hand Gestures and their Meanings Hand gestures are expressive actions, which we display to communicate our messages. All these types require different writing skills, and the writing tips also differ for each of them. It has been in the forum of development which was grossly influenced by the European, African and native Indian cultures. Your Best Friend Cs. The East African cuisine rarely features meat forms and includes corn, rice, saffron, cloves, cinnamon, tomatoes, pineapple, orange, lemon and bananas. Just like there are variations in their geographical properties, differences also exist in their cultures. Culture is a complex system of behaviour, values, beliefs, traditions and artefacts, which is transmitted through generations. No mention of Topic A should be made here. Our culture gives us an identity, and helps build our character.
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Language barriers need to be overcome. All the important ideas are highlighted so that they are surely covered in the essay. Topic B should not be mentioned in this section at all. What's cookie to one, is biscuit for the other. For example, women from male-dominated societies perceive men to be superior. If it fails, they point and laugh as though they wouldn't have followed suit. Initially, billboards started by hand painting huge boards, and eventually graduated to putting up printed sheets. The knowledge necessary for survival, and adaptation to our natural and social environment, is acquired through culture. Advertisers also like this forum for communicating about their products.


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Propositional Logic Propositional Logic Truth Functions
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Introduction Introduction In 6.1 we symbolized simple statements and applied operators to natural language in order to show the logical form of statements. In this section we will learn how to assess the truth of logical forms by defining the operators that compose them. Last, we will reveal various problems with our symbolic language in capturing the meaning of natural language.
Truth-Functional Definitions of Truth-Functional Definitions of the Logical Operators the Logical Operators Logical operators are functional in that the truth value of a compound proposition is determined by the truth value of its components in relation to the definition of the operator. The definitions of the logical operators are presented in terms of statement variables, such as the lower-case letters p, q, r, and s. These variables stand for any possible statement, say A or ∼ (A • B).
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Statement Forms Statement Forms Statement variables are used to construct
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- Fall '06
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