text:
|Publication number
|Publication type
|Application number
|Publication date
|Nov 21, 1989
|Filing date
|Oct 23, 1987
|Priority date
|Oct 23, 1987
|Fee status
|Also published as
|Publication number
|Thomas F. Buckley, III
|Original Assignee
|Chevron Research Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (22), Referenced by (62), Classifications (25), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention
Numerous deposit-forming substances are inherent in hydrocarbon fuels. These substances when used in internal combustion engines tend to form deposits on and around constricted areas of the engine contacted by the fuel. Typical areas commonly and sometimes seriously burdened by the formation of deposits include carburetor ports, the throttle body and venturies, engine intake valves, etc.
Deposits adversely affect the operation of the vehicle. For example, deposits on the carburetor throttle body and venturies increase the fuel to air ratio of the gas mixture to the combustion chamber thereby increasing the amount of unburned hydrocarbon and carbon monoxide discharged from the chamber. The high fuel-air ratio also reduces the gas mileage obtainable from the vehicle.
Deposits on the engine intake valves when they get sufficiently heavy, on the other hand, restrict the gas mixture flow into the combustion chamber. This restriction, starves the engine of air and fuel and results in a loss of power. Deposits on the valves also increase the probability of valve failure due to burning and improper valve seating. In addition, these deposits may break off and enter the combustion chamber possibly resulting in mechanical damage to the piston, piston rings, engine head, etc.
The formation of these deposits can be inhibited as well as removed by incorporating an active detergent into the fuel. These detergents function to cleanse these deposit-prone areas of the harmful deposits, thereby enhancing engine performance and longevity. There are numerous detergent-type gasoline additives currently available which, to varying degrees, perform these functions.
Two factors complicate the use of such detergent-type gasoline additives. First, with regard to automobile engines that require the use of nonleaded gasolines (to prevent disablement of catalytic converters used to reduce emissions), it has been found difficult to provide gasoline of high enough octane to prevent knocking and the concomitant damage which it causes. The chief problem lies in the area of the degree of octane requirement increase, herein called "ORI", which is caused by deposits formed by the commercial gasoline.
The basis of the ORI problem is as follows: each engine, when new, requires a certain minimum octane fuel in order to operate satisfactorily without pinging and/or knocking. As the engine is operated on any gasoline, this minimum octane increases and, in most cases, if the engine is operated on the same fuel for a prolonged period, will reach an equilibrium. This is apparently caused by an amount of deposits in the combustion chamber. Equilibrium is typically reached after 5,000 to 15,000 miles of automobile operation.
The octane requirement increase in particular engines used with commercial gasolines will vary at equilibrium from 5 to 6 octane units to as high as 12 or 15 units, depending upon the gasoline compositions, engine design and type of operation. The seriousness of the problem is thus apparent. A typical automobile with a research octane requirement of 85, when new, may after a few months of operation require 97 research octane gasoline for proper operation, and little unleaded gasoline of that octane is available. The ORI problem also exists in some degree with engines operated on leaded fuels. U.S. Pat. Nos. 3,144,311; 3,146,203; and 4,247,301 disclose lead-containing fuel compositions having reduced ORI properties.
The ORI problem is compounded by the fact that the most common method for increasing the octane rating of unleaded gasoline is to increase its aromatic content. This, however, eventually causes an even greater increase in the octane requirement. Moreover, some of presently used nitrogen-containing compounds used as deposit-control additives and their mineral oil or polymer carriers may also significantly contribute to ORI in engines using unleaded fuels.
It is, therefore, particularly desirable to provide deposit control additives which effectively control the deposits in intake systems of engines, without themselves eventually contributing to the problem.
In this regard, hydrocarbyl poly(oxyalkylene) aminocarbamates are commercially successful fuel additives which control combustion chamber deposits thus minimizing ORI.
The second complicating factor relates to the lubricating oil compatibility of the fuel additive. Fuel additives, due to their higher boiling point over gasoline itself, tend to accumulate on surfaces in the combustion chamber of the engine. This accumulation of the additive eventually finds its way into the lubricating oil in the crankcase of the engine via a "blow-by" process and/or via cylinder wall/piston ring "wipe down". In some cases, as much as 25%-30% of the nonvolatile fuel components, i.e., including fuel additives, will eventually accumulate in the lubricating oil. Insofar as the recommended drain interval for some engines may be as much as 7,500 miles or more, such fuel additives can accumulate during this interval to substantial quantities in the lubricating oil. In the case where the fuel additive is not sufficiently lubricating oil compatible, the accumulation of such an oil-incompatible fuel additive may actually contribute to crankcase deposits, i.e., varnish and sludge, as measured by a Sequence V-D test.
The incompatibility of certain fuel additives in lubricating oils, i.e., oils which contain other additives, arises in spite of the fact that some fuel additives are also known to be lubricating oil dispersants.
Several theories exist as to the cause of the lubricating oil incompatibility of certain fuel additives. Without being limited to any theory, it is possible that some of these fuel additives when found in the lubricating oil interfere with other additives contained in the lubricating oil and either counterbalance the effectiveness of these additives or actually cause dissolution of one or more of these additives including possibly the fuel additive itself. In either case, the incompatibility of the fuel additive with other additives in the lubricating oil demonstrates itself in less than desirable crankcase deposits as measured by Sequence V-D engine tests.
In another theory, it is possible that the accumulation of the fuel additive into the lubricating oil during the drain interval period surpasses its maximum solubility in the lubricating oil. In this theory, this excess amount of fuel additive is insoluble in the lubricating oil and is what causes increased crankcase deposits.
In still another theory, it is possible that the fuel additive will decompose in the lubricating oil during engine operation and the decomposition products are what cause increased crankcase deposits.
In any case, lubricating oil incompatible fuel additives are less than desirable insofar as their use during engine operation will result in increased deposits in the crankcase. This problem can be severe. Accordingly, it would be particularly advantageous to develop a good deposit control fuel additive which does not contribute to ORI and which additionally possesses lubricating oil compatibility.
The instant invention is directed to fuel compositions containing a novel class of alkylphenyl poly(oxyalkylene) aminocarbamates which as a fuel additive controls combustion chamber deposits thus minimizing ORI and in lubricating oil have improved compatibility in the lubricating oil composition. The novel additives of this invention are very long chain alkylphenyl poly(oxyalkylene) aminocarbamates having a molecular weight of about 800 to 6,000 wherein the alkyl group of said alkylphenyl group contains at least 40 carbon atoms.
2. Prior Art
Numerous references disclose C1 to C30 hydrocarbyl poly(oxyalkylene) aminocarbamates as fuel additives. These include the following U.S. Pat. Nos.: 4,160,648; 4,191,537; 4,197,409; 4,236,020; 4,270,930; 4,274,837; 4,288,612; 4,521,610; and 4,568,358.
Of particular relevance is U.S. Pat. No. 4,274,837 which discloses that hydrocarbyl poly(oxyalkylene) aminocarbamates containing certain poly(oxyalkylene) chains, i.e., oxypropylene, when used in fuels employed in combination with certain lubricating oils, produce crankcase varnish. This reference further discloses that lubricating oil compatible hydrocarbyl poly(oxypropylene) aminocarbamates are improved by employing the poly(oxypropylene) as a copolymer having of 1 to 5 C9 to C30 oxyalkylene units.
U.S. Pat. No. 4,160,648 discloses an intake system deposit control additive for fuels which is a hydrocarbyl poly(oxyalkylene) aminocarbamate wherein the hydrocarbyl group is from 1 to 30 carbon atoms including alkyl or alkylphenyl groups. Specifically disclosed hydrocarbyl groups include tetrapropenylphenyl, olelyl and a mixture of C16, C18 and C20 alkyl groups. Likewise, U.S. Pat. No. 4,288,612 discloses deposit control additives for gasoline engines which are hydrocarbyl poly(oxyalkylene) aminocarbamates wherein the hydrocarbyl group contains from 1 to about 30 carbon atoms including alkylphenyl groups wherein the alkyl group is straight or branched chain of from 1 to about 24 carbon atoms. U.S. Pat. No. 4,568,358 discloses diesel fuel compositions containing an additive such as a hydrocarbyl poly(oxyalkylene) aminocarbamate. This reference discloses hydrocarbyl groups such as alkyl groups of 1 to 30 carbon atoms; aryl groups of 6 to 30 carbon atoms, alkaryl groups of 7 to 30 carbon atoms, etc.
U.S. Pat. No. 4,332,595 discloses hydrocarbyl poly(oxyalkylene) polyamines wherein the hydrocarbyl group is a hydrocarbyl radical of 8 to 18 carbon atoms derived from linear primary alcohols.
U.S. Pat. Nos. 4,233,168 and 4,329,240 among others disclose lubricating oil compositions containing a dispersant amount of a hydrocarbyl poly(oxyalkylene) aminocarbamate.
While these prior art references disclose fuel compositions containing C1 to C30 hydrocarbyl poly(oxyalkylene) aminocarbamates, none of these references disclose the unique alkylphenyl group of this invention nor do any of these references suggest that use of this unique alkylphenyl group would provide improved compatibility in lubricating oil compositions.
The instant invention is directed toward a fuel composition containing a novel class of alkylphenyl poly(oxyalkylene) aminocarbamates which as a fuel additive controls combustion chamber deposits thus minimizing ORI and in lubricating oil provide improved compatibility with the lubricating oil composition. In particular, the instant invention is directed toward a fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from about 30 to about 5,000 parts per million of a fuel soluble alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen and an average molecular weight of about 800 to 6,000 and wherein the alkyl group of said alkylphenyl poly(oxyalkylene) aminocarbamate contains at least 40 carbon atoms and the poly(oxyalkylene) polymer is derived from C2 to C5 oxyalkylene units with the proviso that if the poly(oxyalkylene) polymer is a homopolymer of oxyethylene then the poly(oxyethylene) polymer does not contain more than 25 oxyethylene units. The instant invention is based on the discovery that use of the unique alkylphenyl group, i.e., an alkylphenyl group wherein the alkyl group contains at least 40 carbon atoms, imparts to the alkylphenyl poly(oxyalkylene) aminocarbamate improved lubricating oil compatibility without contributing to ORI.
The alkylphenyl poly(oxyalkylene) aminocarbamates of the present invention consist of an amino moiety and an alkylphenyl poly(oxyalkylene) polymer bonded through a carbamate linkage, i.e., --OC(O)N<. The specific alkylphenyl group employed in the instant invention in the alkylphenyl poly(oxyalkylene) polymer is critical to achieving improved lubricating oil compatibility for the alkylphenyl poly(oxyalkylene) aminocarbamates. In particular, it has been found that employing the alkylphenyl group of this invention wherein the alkyl group contains at least 40 carbon atoms results in an alkylphenyl poly(oxyalkylene) aminocarbamate which has improved lubricating oil compatibility.
The preferred alkylphenyl group of the alkylphenyl poly(oxyalkylene) aminocarbamate employed in this invention is derived from the corresponding alkylphenol of Formula I below: ##STR1## wherein R is an alkyl group of at least 40 carbon atoms and m is an integer from 1 to 2.
Preferably, m is one.
Preferably R is an alkyl group of from 50 to 200 carbon atoms. More preferably, R is an alkyl group of from 60 to 100 carbon atoms.
When m is one, the alkylphenyl is a monoalkylphenyl; whereas when m is two, the alkylphenyl is a dialkylphenyl.
The alkylphenols of Formula I above are prepared by reacting the appropriate olefin or olefin mixture with phenol in the presence of an alkylating catalyst at a temperature of from about 60� C. to 200� C., and preferably 125� C. to 180� C. either neat or in an essentially inert solvent at atmospheric pressure. Preferred alkylating catalysts are a sulfonic acid catalyst such as Amberlyst 15� available from Rohm and Haas, Philadelphia, Pa., or boron trifluoride (or an etherate of boron trifluoride). Molar ratios of reactants can be employed. When molar ratios are employed, the reaction yields a mixture of dialkylphenol, monoalkylphenol and unreacted phenol. As noted above, dialkylphenol and monoalkylphenol can be used to prepare the additives used in the compositions of this invention whereas the unreacted phenol is preferably removed from the post reaction mixture via conventional techniques. Alternatively, molar excess of phenol can be employed, i.e., 2 to 2.5 equivalents of phenol for each equivalent of olefin with unreacted phenol recycled. The latter process maximizes monoalkylphenol. Examples of inert solvents include benzene, toluene, chlorobenzene and 250 thinner which is a mixture of aromatics, paraffins and naphthenes.
Particularly preferred alkylphenols employed in this invention are monoalkylphenols represented by Formula II below: ##STR2## wherein R is as defined above.
A particularly preferred class of olefins for use in preparing alkylphenols useful in this invention are polyolefin polymers. Polyolefin polymers are polymers comprising a major amount of C2 to C5 mono-olefin, e.g., ethylene, propylene, butylene, isobutylene and pentene. The polymers can be homopolymers such as polyisobutylene as well as copolymers of two or more such olefins such as copolymers of: ethylene and propylene, butylene, and isobutylene, etc. Other copolymers include those in which a minor amount of the copolymer monomers, e.g., 1 to 20 mole percent is a C4 to C8 nonconjugated diolefin, e.g., a copolymer of isobutylene and butadiene or a copolymer of ethylene, propylene and 1,4-hexadiene, etc.
The polyolefin polymer usually contains at least 40 carbon atoms, although preferably 50 to 200 carbon atoms and more preferably 60 to 100 carbon atoms.
A particularly preferred class of olefin polymers comprises the polybutenes, which are prepared by polymerization of one or more of 1-butene, 2-butene and isobutene Especially desirable are polybutenes containing a substantial proportion of units derived from isobutene. The polybutene may contain minor amounts of butadiene which may or may not be incorporated in the polymer. Most often the isobutene units constitute 80%, preferably at least 90%, of the units in the polymer. These polybutenes are readily available commercial materials well known to those skilled in the art. Disclosures thereof will be found, for example, in U.S. Pat. Nos. 3,215,707; 3,231,587; 3,515,669; and 3,579,450, as well as U.S. Pat. No. 3,912,764. The above are incorporated by reference for their disclosures of suitable polybutenes.
In addition to the reaction of a polyolefin with phenol, many other alkylating hydrocarbons may likewise be used with phenol to produce alkylphenol. Other suitable alkylating hydrocarbons include cyclic, linear, branched and internal or alpha olefins having molecular weights of at least about 560. For example, alpha olefins obtained from the ethylene growth process gives even number carbon olefins. Another source of olefins is by the dimerization of alpha olefins over an appropriate catalyst such as the well-known Ziegler catalyst. Internal olefins are easily obtained by the isomerization of alpha olefins over a suitable catalyst such as silica.
The alkylphenyl poly(oxyalkylene) polymers which are utilized in preparing the carbamates of the present invention are monohydroxy compounds, i.e., alcohols, often termed alkylphenyl "capped" poly(oxyalkylene) glycols and are to be distinguished from the poly(oxyalkylene) glycols (diols), which are not alkylphenyl terminated, i.e., not capped. The alkylphenyl poly(oxyalkylene) alcohols are produced by the addition of lower alkylene oxides, such as ethylene oxide, propylene oxide, the butylene oxides, or the pentylene oxides to the alkylphenol of Formula I, i.e., ##STR3## under polymerization conditions, wherein R and m are as defined above. Preferred poly(oxyalkylene) polymers are those derived from C3 to C4 oxyalkylene units; more preferably C3 oxypropylene units. Methods of production and properties of these polymers are disclosed in U.S. Pat. Nos. 2,841,479 and 2,782,240 and Kirk-Othmer's "Encyclopedia of Chemical Technology", Volume 19, p. 507. In the polymerization reaction, a single type of alkylene oxide may be employed, e.g., propylene oxide, in which case the product is a homopolymer, e.g., a poly(oxypropylene) propanol. However, copolymers are equally satisfactory and random copolymers are readily prepared by contacting the hydroxyl-containing compound with a mixture of alkylene oxides, such as a mixture of propylene and butylene oxides. Block copolymers of oxyalkylene units also provide satisfactory poly(oxyalkylene) polymers for the practice of the present invention.
Homopolymers of poly(oxyethylene) polymers are much more hydrophilic than homopolymers of C3 -C5 poly(oxyalkylene) polymers. Accordingly, when homopolymers of poly(oxyethylene) polymers are employed, the amount of poly(oxyethylene) must be limited so as to ensure fuel solubility and lubricating oil compatibility of the final carbamate. In general, this is accomplished by limiting the poly(oxyethylene) polymer to about 25 oxyethylene units or less; although preferably about 10 oxyethylene units or less; and most preferably about 5 oxyethylene units or less.
Likewise, copolymers containing a mixture of oxyethylene units and C3 -C5 oxyalkylene units are formulated to ensure that the copolymer possesses fuel solubility and lubricating oil compatibility.
In general, the poly(oxyalkylene) polymers are mixtures of compounds that differ in polymer chain length. However, their properties closely approximate those of the polymer represented by the average composition and molecular weight.
In general, the very long chain alkylphenyl terminating group on the alkylphenyl poly(oxyalkylene) aminocarbamates of this invention allow for use of less oxyalkylene e units oxyalkylene) polymer to ensure fuel dispersency/detergency and lubricating oil compatibility than are necessary in prior art carbamate fuel additives. Accordingly, while longer poly(oxyalkylene) polymers are functional in this invention, such longer polymers are not necessary. Therefore, each poly(oxyalkylene) polymer utilized in this invention contains at least 1 oxyalkylene unit, preferably from 1 to about 100 oxyalkylene units, more preferably from about 1 to about 25 oxyalkylene units, even more preferably from about 1 to about 10 oxyalkylene units, and most preferably about 5 oxyalkylene units or less. It is understood that if the poly(oxyalkylene) polymer is a homopolymer of poly(oxyethylene), the polymer length is governed by the constraints discussed above.
An alternative method for preparing alkylphenyl poly(oxyalkylene) polymers having 1, 2 or 3 oxyalkylene units involves employing a compound of Formula III below: ##STR4## wherein q is an integer from 1 to 3 and R1 is hydrogen or a C1 to C3 alkyl group. When employing the compound of Formula III, the phenoxide of the alkylphenol, I, is first prepared and then reacted with the compound of Formula III to yield the desired alkylphenol poly(oxyalkylene) polymer having from 1 to 3 oxyalkylene units. Compounds of Formula III are either commercially available or can be prepared by art recognized methods.
The amine moiety of the alkylphenyl poly(oxyalkylene) aminocarbamate employed in this invention is preferably derived from a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms. The polyamine is preferably reacted with an alkylphenyl poly(oxyalkylene) chloroformate to produce the alkylphenyl poly(oxyalkylene) aminocarbamate additives finding use within the scope of the present invention. The chloroformate is itself derived from alkylphenyl poly(oxyalkylene) alcohol by reaction with phosgene. The polyamine, encompassing diamines, provides the product alkylphenyl poly(oxyalkylene) aminocarbamate with, on average, at least about one basic nitrogen atom per carbamate molecule, i.e., a nitrogen atom titratable by a strong acid. The polyamine preferably has a carbon-to-nitrogen ratio of from about 1:1 to about 10:1.
The polyamine may be substituted with substituents selected from (A) hydrogen, (B) hydrocarbyl groups of from 1 to about 10 carbon atoms, (C) acyl groups of from 2 to about 10 carbon atoms, and (D) monoketo, monohydroxy, mononitro, monocyano, lower alkyl and lower alkoxy derivatives f (B) and (C). "Lower", as used in terms like lower alkyl or lower alkoxy, means a group containing from 1 to about 6 carbon atoms. At least one of the substituents on one of the basic nitrogen atoms of the polyamine is hydrogen, e.g., at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen atom.
Hydrocarbyl, as used in describing all the components of this invention, denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl. Preferably, the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylene and acetylenic, particularly acetylenic unsaturation. The substituted polyamines of the present invention are generally, but not necessarily, N-substituted polyamines. Exemplary hydrocarbyl groups and substituted hydrocarbyl groups include alkyls such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 2-(2-ethoxyethoxy)ethyl, 2-(2-ethoxyethoxy)ethoxy)ethyl, 3,6,9,12-tetraoxatetradecyl, 2-(2-ethoxyethoxy)hexyl, etc. The acyl groups of the aforementioned (C) substituents are such as propionyl, acetyl, etc. The more preferred substituents are hydrogen, C1 -C4 alkyls and C1 -C4 hydroxyalkyls.
In a substituted polyamine the substituents are found at any atom capable of receiving them. The substituted atoms, e.g., substituted nitrogen atoms, are generally geometrically inequivalent, and consequently the substituted amines finding use in the present invention can be mixtures of mono- and poly-substituted polyamines with substituent groups situated at equivalent and/or inequivalent atoms.
The more preferred polyamine finding use within the scope of the present invention is a polyalkylene polyamine, including alkylene diamine, and including substituted polyamines, e.g., alkyl and hydroxyalkylsubstituted polyalkylene polyamine. Preferably, the alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to 3 carbon atoms between the nitrogen atoms. Such groups are exemplified by ethylene, 1,2-propylene, 2,2-dimethyl-propylene trimethylene, 1,3,2-hydroxypropylene, etc. Examples of such polyamines include ethylene diamine, diethylene triamine, di(trimethylene)triamine, dipropylene triamine, triethylene tetramine, tripropylene tetramine, tetraethylene pentamine, and pentaethylene hexamine. Such amines encompass isomers such as branched-chain polyamines and the previously mentioned substituted polyamines, including hydroxy- and hydrocarbyl-substituted polyamines. Among the polyalkylene polyamines, those containing 2-12 amine nitrogen atoms and 2-24 carbon atoms are especially preferred ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, hexylene diamine, diethylene triamine, dipropylene triamine, and the C2 -C3 alkylene polyamines are most preferred, in particular, the lower polyalkylene polyamines, e.g., ethylene diamine, diethylene triamine, propylene diamine, dipropylene triamine, etc.
The amine component of the alkylphenyl poly(oxyalkylene) aminocarbamate also may be derived from heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocycle comprises one or more 5-6 membered rings containing oxygen and/or nitrogen. Such heterocycles may be saturated or unsaturated and substituted with groups selected from the aforementioned (A), (B), (C) and (D). The heterocycles are exemplified by piperazines, such as 2-methylpiperazine, N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-piperazinyl)ethane, and N,N'-bis(N-piperazinyl)piperazine, 2-methylimidazoline, 3-aminopiperidine, 2-aminopyridine, 2-(3-aminoethyl)-3-pyrroline, 3-aminopyrrolidine, N-(3-aminopropyl)-morpholine, etc. Among the heterocyclic compounds, the piperazines are preferred.
Another class of suitable polyamines are diaminoethers represented by Formula IV
H2 N--X1 --OX2 --r NH2 IV
wherein X1 and X2 are independently alkylene from 2 to about 5 carbon atoms and r is an integer from 1 to about 10. Diamines of Formula IV are disclosed in U.S. Pat. No. 4,521,610, which is incorporated herein by reference for its teaching of such diamines.
Typical polyamines that can be used to form the compounds of this invention by reaction with a poly(oxyalkylene)chloroformate include the following: ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine, tetraethylene pentamine, dimethylaminopropylene diamine, N-(beta-aminoethyl)piperazine, N-(beta-aminoethyl)piperidine, 3-amino-N-ethylpiperidine, N-(beta-aminoethyl)morpholine, N,N'-di(beta-aminoethyl)piperazine, N,N'-di(beta-aminoethylimidazolidone-2; N-(beta-cyanoethyl)ethane-1,2-diamine, 1-amino-3,6,9-triazaoctadecane, 1-amino-3,6-diaza-9-oxadecane, N-(betaaminoethyl)diethanolamine, N'-acetyl-N'-methyl-N-(beta-aminoethyl)ethane-1,2-diamine, N-acetonyl-1,2-propanediamine, N-(beta-nitroethyl)-1,3-propane diamine, 1,3-dimethyl-5-(beta-aminoethyl)hexahydrotriazine, N-(beta-aminoethyl)hexahydrotriazine, 5-(beta-aminoethyl)-1,3,5-dioxazine, 2-(2-aminoethylamino)-ethanol, 2[2-2-aminoethylamino)ethylamino]-ethanol.
The amine component of the alkylphenyl poly(oxyalkylene) aminocarbamate may also be derived from an amine-containing compound which is capable of reacting with an alkylphenyl poly(oxyalkylene) alcohol to produce an alkylphenyl poly(oxyalkylene) aminocarbamate having at least one basic nitrogen atom. For example, a substituted aminoisocyanate, such as (R3)2 NCH2 CH2 NCO, wherein R3 is, for example, a hydrocarbyl group, reacts with the alcohol to produce the aminocarbamate additive finding use within the scope of the present invention. Typical aminoisocyanates that may be used to form the fuel additive compounds of this invention by reaction with a hydrocarbylpoly(oxyalkylene) alcohol include the following: N,N-(dimethyl)aminoisocyanatoethane, generally, N,N-(dihydrocarbyl)aminoisocyanatoalkane, more generally, N-(perhydrocarbyl)isocyanatopolyalkylene polyamine, N,N-(dimethyl)aminoisocyanatobenzene, etc.
In many instances the amine used as a reactant in the production of the carbamate of the present invention is not a single compound but a mixture in which one or several compounds, predominate with the average composition indicated. For example, tetraethylene pentamine prepared by the polymerization of aziridine or the reaction of dichloroethylene and ammonia will have both lower and higher amine members, e.g., triethylene tetramine, substituted piperazines and pentaethylene hexamine, but the composition will be mainly tetraethylene pentamine and the empirical formula of the total amine composition will closely approximate that of tetraethylene pentamine. Finally, in preparing the compounds of this invention, where the various nitrogen atoms of the polyamine are not geometrically equivalent, several substitutional isomers are possible and are encompassed within the final product. Methods of preparation of amines, isocyanates and their reactions are detailed in Sidgewick's "The Organic Chemistry of Nitrogen", Clarendon Press, Oxford, 1966; Noller's "Chemistry of Organic Compounds", Saunders, Philadelphia, 2nd Ed. 1957; and Kirk-Othmer's "Encyclopedia of Chemical Technology", 2nd Ed., especially Volume 2, pp. 99-116.
Having described the preferred alkylphenyl poly(oxyalkylene) component and the preferred polyamine component, the preferred alkylphenyl poly(oxyalkylene) aminocarbamate additive of the present invention is obtained by linking these components together through a carbamate linkage i.e., ##STR5## wherein the ether oxygen may be regarded as the terminal hydroxyl oxygen of the alkylphenyl poly(oxyalkylene) alcohol component, and the carbonyl group --C(O)-- is preferably provided by the coupling agent, e.g., phosgene.
The alkylphenyl poly(oxyalkylene) aminocarbamate employed in the present invention has at least one basic nitrogen atom per molecule. A "basic nitrogen atom" is one that is titratable by a strong acid, e.g., a primary, secondary, or tertiary amino nitrogen, as distinguished from, for example, an amido nitrogen, i.e., ##STR6## which is not so titratable. Preferably, the basic nitrogen is in a primary or secondary amino group.
The preferred alkylphenyl poly(oxyalkylene) aminocarbamate has an average molecular weight of from about 800 to 6,000; preferably an average molecular weight of from 800 to 3,000; and most preferably an average molecular weight of from 1,000 to 2,500.
A preferred class of alkylphenyl poly(oxyalkylene) aminocarbamate can be described by the following Formula V ##STR7## wherein R is an alkyl group containing at least 40 carbon atoms; R1 is hydrogen or alkyl of 1 to 3 carbon atoms; R2 is alkylene of from 2 to about 6 carbon atoms; m is an integer from 1 to 2; n is an integer such that the molecular weight of the compound is from about 800 to 6,000; and p is an integer from 1 to about 6 and with the proviso that if R1 is hydrogen then n is an integer from 1 to 25.
The additives employed in this invention can be most conveniently prepared by first reacting the appropriate alkylphenyl poly(oxyalkylene) alcohol with phosgene to produce an alkylphenyl poly(oxyalkylene) chloroformate. The chloroformate is then reacted with the polyamine to produce the desired alkylphenyl poly(oxyalkylene) aminocarbamate.
Preparation of aminocarbamates are disclosed in U.S. Pat. Nos. 4,160,648; 4,191,537; 4,197,409; 4,236,020; 4,243,798; 4,270,930; 4,274,837; 4,288,612; 4,512,610; and 4,568,358, which are incorporated wherein by reference. In general, the reaction of the poly(oxyalkylene) compound and phosgene is usually carried out on an essentially equimolar basis, although excess phosgene can be used to improve the degree of reaction. The reaction may be carried out a temperatures from -10� to 100� C., preferably in the range of 0� to 50� C. The reaction will usually be complete within 1/4 to 5 hours. Times of reaction will usually be in the of from 2 to 4 hours.
A solvent may be used in the chloroformylation reaction. Suitable solvents include benzene, toluene, etc.
The reaction of the resultant chloroformate with the amine may be carried out neat or preferably in solution. Temperatures of from -10� to 200� C. may be utilized, the desired product may be obtained by water wash and stripping usually be the aid of vacuum, of any residual solvent.
The mol ratio of polyamine to polyether chloroformate will generally be in the range from about 2 to 20 mols of polyamine per mol of chloroformate, and more usually 5 to 15 mols of polyamine per mole of chloroformate. Since suppression of polysubstitution of the polyamino is usually desired, large molar excesses of the polyamine will be used. Additionally, the preferred adduct is the monocarbamate compound, as opposed to the bis(carbamate) or disubstituted aminoether.
The reaction or reactions may be conducted with or without the presence of a reaction solvent. A reaction solvent is generally employed whenever necessary to reduce the viscosity of the reaction product. These solvents should be stable and inert to the reactants and reaction product. Depending on the temperature of the reaction, the particular chloroformate used, the mol ratios, as well as the reactant concentrations, the reaction time may vary from less than 1 minute to 3 hours.
After the reaction has been carried out for a sufficient length of time, the reaction mixture may be subjected to extraction with a hydrocarbon-water or hydro-carbon-alcohol-water medium to free the product from any low-molecular-weight amine salts which have formed and any unreacted diamine. The product may then be isolated by evaporation of the solvent. Further purification may be effected by column chromatography on silica gel.
Depending on the particular application of the composition of this invention, the reaction may be carried out in the medium in which it will ultimately find use, e.g., polyether carriers or an oleophilic organic solvent or mixtures thereof and be formed at concentrations which provide a concentrate of a detergent composition. Thus, the final mixture may be in a form to be used directly for blending in fuels.
An alternative process for preparing the alkylphenyl poly(oxyalkylene) aminocarbamates employed in this invention involves the use of an arylcarbonate intermediate. That is to say, the alkylphenyl poly(oxyalkylene) alcohol is reacted with an aryl chloroformate to form an arylcarbonate which is then reacted with the polyamine to form the aminocarbamate employed in this invention. Particularly useful aryl chloroformates include phenyl chloroformate, p-nitrophenyl chloroformate, 2,4-dinitrophenyl chloroformate, p-chlorophenyl chloroformate, 2,4-dichlorophenyl chloroformate, and p-trifluoromethylphenyl chloroformate. Use of the aryl carbonate intermediate allows for conversion to aminocarbamates containing close to the theoretical basic nitrogen while employing less excess of polyamine, i.e., molar ratios of generally from 1:1 to about 5:1 of polyamine to the arylcarbonate, and additionally avoids the generation of hydrogen chloride in the reaction forming the aminocarbamate. Preparation of hydrocarbyl capped poly(oxyalkylene) aminocarbamates via an arylcarbonate intermediate are disclosed in U.S. Ser. Nos. 586,533 and 689,616, which are incorporated herein by reference.
The alkylphenyl poly(oxyalkylene) aminocarbamates of this invention will generally be employed in a hydrocarbon distillate fuel. The proper concentration of this additive necessary in order to achieve the desired detergency and dispersancy varies depending upon the type of fuel employed, the presence of other detergents, dispersants and other additives, etc. Generally, however, from 30 to 5,000 weight parts per million (ppm), and preferably 100 to 500 ppm and more preferably 200 to 300 ppm of alkylphenyl poly(oxyalkylene) aminocarbamate per part of base fuel is needed to achieve the best results. When other detergents are present, a less amount of alkylphenyl poly(oxypropylene) aminocarbamate may be used. For performance as a carburetor detergent only, lower concentrations, for example 30 to 100 ppm may be preferred. Higher concentrations, i.e., 2,000 to 5,000 ppm may result in a clean-up effect on combustion chamber deposits as well as the entire intake system.
The deposit control additive may also be formulated as a concentrate, using an inert stable oleophilic organic solvent boiling in the range of about 150� to 400� F. Preferably, an aliphatic or an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher-boiling aromatics or aromatic thinners. Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents are also suitable for use with the detergent-dispersant additive. In the concentrate, the amount of the additive will be ordinarily at least 5 percent by weight and generally not exceed 50 percent by weight, preferably from 10 to 30 weight percent.
When employing certain of the alkylphenyl poly(oxyalkylene) aminocarbamates of this invention, particularly those having more than 1 basic nitrogen, it can be desirable to additionally add a demulsifier to the gasoline or diesel fuel composition. These demulsifiers are generally added at from 1 to 15 ppm in the fuel composition. Suitable demulsifiers include for instance L-1562�, a high molecular weight glycol capped phenol available from Petrolite Corp., Tretolite Division, St. Louis, Mo., and OLOA 2503Z�, available from Chevron Chemical Company, San Francisco, Calif.
In gasoline fuels, other fuel additives may also be included such as antiknock agents, e.g., methylcyclopentadienyl manganese tricarbonyl, tetramethyl or tetraethyl lead, tert-butyl methyl peroxide or other dispersants or detergents such as various substituted succinimides, amines, etc. Also included may be lead scavengers such as aryl halides, e.g., dichlorobenzene or alkyl halides, e.g., ethylene dibromide. Additionally, antioxidants, metal deactivators and demulsifiers may be present.
In diesel fuels, other well-known additives can be employed such as pour point depressants, flow improvers, cetane improvers, etc.
The following examples are offered to specifically illustrate this invention. These examples and illustrations are not to be construed in any way as limiting the scope of this invention.
Preparation of C65 to C70 Akylphenyl Poly(oxypropylene) Alcohol
To a dried 5-liter, 3-neck flask under a nitrogen atmosphere was added 1.5 liters of dry toluene and 1125 grams H-100� (an alkylphenol, prepared from polybutene-24, having a hydroxyl number of approximately 34, and a number average of approximately 65-70 carbon atoms in the alkyl portion of the alkylphenol. H-10� also contains approximately one-third (1/3) inactive compounds. H-100� is available from Amoco Petroleum Additives Company, Clayton, Mo.). The system was warmed to approximately 60� C. and 5.5 grams (0.14 moles) of metallic potassium cut into small pieces was slowly added with vigorous stirring. The temperature of the reaction system was allowed to increase during this addition and reached approximately 105� C. After 21/2 hours, all of the metallic potassium was dissolved.The reaction system was then allowed to cool to 40� C. Afterwards, 131.5 grams (about 5 equivalents per equivalent of alkylphenol) of propylene oxide was added to the system by an addition funnel at an addition rate slow enough to avoid flooding of the vapor condensing system. The system was then gently refluxed for 13 hours at which point the temperature increased to 113� C. and was held there for an addition 3.5 hours. The system was then cooled to 60� C. and the reaction quenched by the addition of 0.075 liter of 2N HCl solution. The system was then dried by azeotropic distillation to yield a toluene solution of the crude product. The system was then diluted with 1 liter of toluene.
The toluene solution containing the product of Example 1 above in a 5-liter, 3-neck flask under a nitrogen atmosphere was cooled to about 5� C. with stirring. While stirring, 301 grams of a 20% solution of phosgene in toluene was added all at once to the reaction system. The reaction system was allowed to warm to room temperature and stirred gently for 24 hours. In order to remove excess phosgene as well as HCl formed during the reaction, the system was vigorously sparged with nitrogen. After completion of the reaction, an infrared analysis of an aliquot revealed a strong chloroformate absorption at 1785 cm-1 and no detectable alcohol absorption at 3450 cm-1.
The entire chloroformate/toluene solution of Example 2 was diluted with 4 liters of dry toluene. In a separate flask, 487 grams of ethylene diamine (8.1 moles) approximately 20 equivalents per equivalent if chloroformate was also diluted with 4 liters of dry toluene. At room temperature, these two solutions were rapidly mixed using two variable speed Teflon gear pumps and a 10-inch Kenics static mixer. After fifteen minutes, the crude reaction mixture was stripped, diluted with 10 liters of hexane, and washed successively once with water and three times with a slightly basic (pH≃9) brine solution. Phase separation of the aqueous brine solution and the hexane solution was improved by adding isopropanol as needed. The hexane solution was separated, dried over anhydrous sodium sulfate, filtered and stripped to afford the title product as a thick orange liquid having an alkalinity value of 17.7 and 0.44 weight percent basis nitrogen.
In the manner described in Example 3 above, a C65 to C70 alkylphenyl poly(oxypropylene) chloroformate (prepared from 1168 grams of H-100� alkylphenol, 0.73 moles) prepared similarly to t methods described in Examples 1 and 2 above a treated with 814 grams (7.89 moles) approximately 20 equivalents per equivalent of chloroformate, of diethylene triamine to afford the title compound having an alkalinity value of 25.7 and 0.64 weight percent basic nitrogen.
To a 2-liter flask, equipped with stirrer, Dean Stark trap, condensor, and nitrogen inlet and outlet was added 567 grams of tetrapropylene, 540 grams of phenol, 72 grams of a sulfonic acid cation exchange resin (polystyrene cross-linked with divinylbenzene) catalyst (Amberlyst 15� available from Rohm and Haas, Philadelphia, Pa.). The reaction mixture was heated to about 110� C. for about 3 hours with stirring under a nitrogen atmosphere. The reaction mixture was stripped by heating under vacuum and the resulting product filtered hot over diatomaceous earth to afford 626 grams of tetrapropenylphenol and with a hydroxyl number of 205 and with 96% para-alkylphenol content.
Reference alkylphenyl poly(oxyalkylene) aminocarbamates were prepared from the tetrapropenyl alkylphenol of Reference Example A in a manner similar to Examples 1-4 above. Reference Examples B through D found in Table I below summarizes the different tetrapropenylphenyl poly(oxyalkylene) aminocarbamates so prepared.
TABLE I______________________________________COMPOUNDS OF THE FORMULA ##STR8##Exam-ple R3 R1 R2 n p______________________________________B tetrapropenylphenyl C2 H5 CH2 CH2 17 1C tetrapropenylphenyl CH3 CH2 CH2 20 1D tetrapropenylphenyl CH3 CH2 CH2 5 13 C65 to C70 alkylphenyl CH3 CH2 CH2 5 14 C65 to C70 alkylphenyl CH3 CH2 CH2 5 2______________________________________
This procedure was designed to determine the oil solubility/compatibility of different additives in a fully formulated lubricating oil. Insofar as up to 25-30% of a gasoline additive can enter into the crankcase via "blow-by" and/or cylinder wall/piston ring "wipe down", this is an important performance criteria.
The lubricating oil composition was formulated to contain: 6 percent by weight of a mono-polyisobutenyl succinimide; 20 millimoles per kilogram of a highly overbased sulfurized calcium phenate; 30 millimoles per kilogram of a highly overbased sulfurized calcium hydrocarbyl sulfonate; 22.5 millimoles per kilogram of a zinc dithiophosphate; 13 weight percent of a commercial nondispersant C2 -C3 copolymer viscosity index improver; 5 parts per million of a foam inhibitor in 150N Exxon base oil to give a 10 W 40 formulated oil.
The oil solubility of the additive was determined as follows:
To a heated solution (50grams) of the above-described fully formulated lubricating 50 grams of the neat additive. The mixture was then heated with constant stirring to 170� F. and maintained at that temperature for 15 minutes Dilutions were then prepared according to the desired solubility test range using fresh hot reference oil as the diluent. In each case, the diluted samples were stirred to 170� F. for 10 minutes to insure complete mixing. The solutions were then sealed and left to cool undisturbed for from 1-5 days typically at room temperature. Each sample was then rated visually for oil continuity.
Additives that were marginally soluble in this blend separated as a denser secondary phase, and were clearly visible as such without the need for centrifugation. Additives which gave rise to oil incompatibility problems were inherently oil soluble, however, they tended to displace what appears to be the VI improver. This phenomenon resulted in the separation of the VI improver which is less dense than the bulk oil forming a clear thick upper layer. The solubility/compatibility of a gasoline additive was thereby defined as the highest concentration (on a weight basis) which did not result in the formation of either an insoluble lower additive phase or an insoluble upper VI improver phase.
Table II below contains compatibility data for the hydrocarbyl poly(oxyalkylene) aminocarbamate. Oil compatibility is reported as weight percent of additive in the lubricating oil composition.
TABLE II______________________________________Example Oil Compatibility (Wt %)______________________________________3 504 50B 15C 7D 11______________________________________
The above data demonstrates that the additives of the instant invention possess improved oil compatibility over prior art compounds.
|Cited Patent
|Filing date
|Publication date
|May 11, 1960
|Jul 4, 1961
|Standard Oil Co
|Motor fuel composition
|May 27, 1977
|Jul 10, 1979
|Chevron Research Company
|Fuel compositions containing deposit control additives
|Jun 19, 1978
|Mar 4, 1980
|Chevron Research Company
|Fuel compositions of poly(oxyalkylene) aminocarbamate
|Aug 8, 1978
|Apr 8, 1980
|Chevron Research Company
|Poly(oxyalkylene)aminocarbomates of alkylene polyamine
|Jul 3, 1978
|Apr 15, 1980
|Chevron Research Company
|Deposit control and dispersant additives
|Jun 19, 1978
|Nov 11, 1980
|Chevron Research Company
|Lubricant compositions containing dispersant additives
|Jun 18, 1979
|Nov 25, 1980
|Chevron Research Company
|Carbamate deposit control additives
|Aug 9, 1979
|Jan 6, 1981
|Chevron Research Company
|Process for the production of a polymeric carbamate
|Dec 21, 1979
|Jun 2, 1981
|Chevron Research Company
|Clean combustion chamber fuel composition
|Jul 2, 1979
|Jun 23, 1981
|Chevron Research Company
|Deposit control additives and fuel compositions containing them
|Dec 4, 1978
|Jun 23, 1981
|Chevron Research Company
|Process of preparing dispersant lubricating oil additives
|Apr 28, 1980
|Sep 8, 1981
|Chevron Research Company
|Deposit control additives
|Jul 25, 1979
|Sep 15, 1981
|Chevron Research Company
|Deposit control additives and fuel and lube oil compositions containing them
|Jul 25, 1979
|Oct 13, 1981
|Chevron Research Company
|Carboxylic acid salt containing deposit control additives and fuel and lube oil compositions containing them
|Jan 5, 1981
|May 11, 1982
|Chevron Research Company
|Lubricating oil compositions containing dispersant additives
|Mar 13, 1981
|Oct 18, 1983
|Chevron Research Company
|Amine substituted hydrocarbon polymer dispersant lubricating oil additives
|Jul 30, 1982
|Mar 20, 1984
|Chevron Research Company
|Lubricating oil compositions containing polyether polyamine ethanes
|Sep 30, 1982
|Jun 4, 1985
|Chevron Research Company
|Poly(oxyalkylene) aminoether carbamates as deposit control additives
|May 31, 1983
|Aug 27, 1985
|Chevron Research Company
|Lubricating oil compositions containing methylol polyether amino ethanes
|Jul 30, 1984
|Feb 4, 1986
|Chevron Research Company
|Diesel fuel and method for deposit control in compression ignition engines
|Dec 16, 1985
|Aug 5, 1986
|Chevron Research Company
|Deposit control additives--polyether polyamine ethanes
|Feb 15, 1985
|Sep 22, 1987
|Chevron Research Company
|Poly(oxyalkylene) aminoether carbamates as deposit control additives
|Citing Patent
|Filing date
|Publication date
|Mar 20, 1992
|Mar 9, 1993
|Chevron Research And Technology Company
|Fuel additive compositions containing poly(oxyalkylene) amines and polyalkyl hydroxyaromatics
|Sep 26, 1991
|Jun 8, 1993
|Mobil Oil Corporation
|Diisocyanate derivatives as lubricant and fuel additives and compositions containing same
|Apr 1, 1993
|Apr 26, 1994
|Chevron Research And Technology Company
|Poly(alkylene ether) aminocarbamates and fuel compositions containing the same
|Mar 30, 1993
|Oct 4, 1994
|Shell Oil Company
|Fuel compositions
|Dec 18, 1992
|Nov 22, 1994
|Chevron Research And Technology Company
|Fuel additive compositions containing poly(oxyalkylene) hydroxyaromatic ethers and poly(oxyalkylene) amines
|Dec 18, 1992
|Nov 22, 1994
|Chevron Research And Technology Company
|Fuel additive compositions containing poly(oxyalkylene) hydroxyaromatic esters and poly(oxyalkylene) amines
|Sep 1, 1992
|Feb 28, 1995
|Texaco Inc.
|Motor fuel detergent additives-hydrocarbyloxypolyether allophonate esters of 2-hydroxy ethane
|May 2, 1994
|May 9, 1995
|Chevron Chemical Company
|Mannich condensation products of poly(oxyalkylene) hydroxyaromatic carbamates and fuel compositions containing the same
|Sep 19, 1994
|Oct 17, 1995
|Shell Oil Company
|Fuel compositions
|Sep 19, 1994
|Oct 17, 1995
|Shell Oil Company
|Fuel compositions
|May 2, 1994
|Jan 16, 1996
|Chevron Chemical Company
|Poly(oxyalkylene) hydroxy and amino aromatic carbamates and fuel compositions containing the same
|Sep 19, 1994
|Feb 6, 1996
|Shell Oil Company
|Fuel compositions comprising hydantoin-containing polyether alcohol additives
|Sep 19, 1994
|Apr 16, 1996
|Shell Oil Company
|Fuel compositions
|Jan 11, 1995
|Apr 23, 1996
|Texaco Inc.
|Motor fuel detergent additives-hydrocarbyloxypolyether allophonate esters of 2-hydroxy ethane
|Mar 14, 1995
|May 14, 1996
|Huntsman Corporation
|Hydrocarbon compositions containing a polyetheramide additive
|Sep 25, 1995
|Jan 28, 1997
|Ethyl Corporation
|Amine ester-containing additives and methods of making and using same
|Dec 21, 1995
|May 13, 1997
|Ethyl Corporation
|Polyether esteramide containing additives and methods of making and using same
|Dec 29, 1995
|Jun 10, 1997
|Chevron Chemical Company
|Substituted aromatic polyalkyl ethers and fuel compositions containing the same
|Jun 20, 1996
|Jun 10, 1997
|Chevron Chemical Company
|Polyoxyalkylene polylactone aminocarbamates and fuel compositions containing the same
|Jun 20, 1996
|Jul 29, 1997
|Chevron Chemical Company
|Polyactone aminocarbamates and fuel compositions containing the same
|May 14, 1996
|Sep 23, 1997
|Chevron Chemical Company
|Polyalkylphenoxyaminoalkanes and fuel compositions containing the same
|Aug 6, 1996
|Dec 2, 1997
|Shell Oil Company
|Fuel compositions comprising hydantoin-containing polyether alcohol additives
|Dec 30, 1996
|Jan 20, 1998
|Chevron Chemical Company
|Poly(oxyalkylene) esters of substituted polyphenylethers and fuel compositions containing the same
|Dec 29, 1995
|May 19, 1998
|Chevron Chemical Company
|Very long chain alkylphenyl polyoxyalkylene amines and fuel compositions containing the same
|Sep 30, 1997
|Oct 27, 1998
|Chevron Chemical Company Llc
|Substituted biphenyl ethers and fuel compositions containing the same
|Aug 6, 1996
|Nov 17, 1998
|Shell Oil Company
|Fuel compositions
|Sep 30, 1997
|Dec 15, 1998
|Chevron Chemical Company Llc
|Substituted biphenyl poly (oxyalkylene) ethers and fuel compositions containing the same
|Apr 30, 1997
|Dec 22, 1998
|Chevron Chemical Company
|Fuel additive compositions containing polyalkylphenoxy-aminoalkanes and poly (oxyalkylene) amines
|Sep 19, 1997
|Jan 5, 1999
|Shell Oil Company
|Fuel compositions
|Dec 30, 1996
|Sep 14, 1999
|Chevron Chemical Company
|Method to remedy engine intake valve sticking
|Feb 18, 1999
|Apr 17, 2001
|Chevron Chemical Company Llc
|Fuel compositions containing hydrocarbyl-substituted polyoxyalkylene amines
|Sep 27, 1996
|Apr 24, 2001
|Chevron Chemical Company
|Aminocarbamates of polyalkylphenoxyalkanols and fuel compositions containing the same
|May 28, 1998
|Jul 17, 2001
|Shell Oil Company
|Additive concentrates for rapidly reducing octane requirement
|Oct 9, 1997
|Nov 6, 2001
|Shell Oil Company
|Fuel compositions
|Nov 6, 2002
|Sep 9, 2003
|Chevron Oronite Company Llc
|Method for removing engine deposits in a reciprocating internal combustion engine
|Jan 22, 2003
|Nov 25, 2003
|Chevron Oronite Company Llc
|Delivery device for removing interior engine deposits in a reciprocating internal combustion engine
|Jan 23, 2002
|Nov 25, 2003
|Chevron Oronite Company Llc
|Method for removing engine deposits in a gasoline internal combustion engine
|May 23, 2002
|Dec 9, 2003
|Chevron U.S.A. Inc.
|Method for controlling deposits in the fuel reformer of a fuel cell system
|Feb 1, 2010
|Jun 18, 2013
|Butamax Advanced Biofuels Llc
|Gasoline deposit control additive composition
|Jul 24, 2009
|Oct 8, 2013
|Chevron Oronite S.A.
|System and method for screening liquid compositions
|Nov 15, 2011
|Jan 21, 2014
|Chevron Oronite Company Llc
|Method for cleaning deposits from an engine fuel delivery system
|May 16, 2008
|Jan 6, 2015
|Chevron Japan Ltd.
|Method for cleaning internal parts of gasoline engines
|Dec 21, 2001
|Aug 14, 2003
|Cherpeck Richard E.
|Polyalkylphenoxyaminoalkanes and fuel compositions containing the same
|Jun 4, 2004
|Dec 8, 2005
|Chevron Oronite Company Llc
|Fuel additive composition suitable for control and removal of tenacious engine deposits
|May 16, 2008
|Nov 20, 2008
|Chevron Japan Ltd.
|Method for cleaning internal parts of gasoline engines
|May 16, 2008
|Nov 20, 2008
|Chevron Japan Ltd.
|Method for cleaning internal parts of gasoline engines
|Jul 24, 2009
|Jan 27, 2011
|Chevron Oronite S.A.
|System and method for screening liquid compositions
|Oct 25, 1988
|Nov 14, 1990
|Chevron Res
|Fuel compositions and lubricating oil compositions containing very long chain alkylphenyl poly(oxyalkylene) aminocarbamates.
|Oct 25, 1988
|Nov 28, 1990
|Chevron Research Company
|Fuel compositions and lubricating oil compositions containing very long chain alkylphenyl poly(oxyalkylene) aminocarbamates
|Dec 30, 1988
|Apr 3, 1991
|CHEVRON U.S.A. Inc.
|Lubricating oil compositions and fuel compositions containing substantially straight chain pinwheel alkylphenyl poly(oxypropylene) aminocarbamates
|Dec 30, 1988
|Nov 23, 1994
|Chevron Res
|Lubricating oil compositions and fuel compositions containing substantially straight chain pinwheel alkylphenyl poly(oxypropylene) aminocarbamates
|Aug 11, 1993
|Mar 9, 1994
|Texaco Development Corporation
|Hydrocarbyloxypolyether allophonate esters of 2-hydroxyethane as detergent additives for gasoline
|Dec 24, 1996
|Jul 2, 1997
|Chevron Chemical Company
|Substituted aromatic polyalkyl ethers and fuel compositions containing the same
|Dec 19, 1996
|Jul 2, 1997
|Chevron Chemical Company
|Very long chain alkylphenyl polyoxyalkylene amines and fuel compositions containing the same
|Sep 23, 1997
|Apr 1, 1998
|Chevron Chemical Company
|Aminocarbamates of polyalkylphenoxyalkanols and fuel compositions containing the same
|Jul 23, 2010
|Jan 26, 2011
|Chevron Oronite S.A.
|System and Method for Screening Liquid Compositions
|Mar 9, 1993
|Sep 30, 1993
|Chevron Research And Technology Company
|Fuel additive compositions containing poly(oxyalkylene) amines and polyalkyl hydroxyaromatics
|Dec 17, 1993
|Jul 7, 1994
|Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc.
|Fuel additive compositions containing poly(oxyalkylene) hydroxyaromatic ethers and poly(oxyalkylene) amines
|Mar 25, 1994
|Oct 13, 1994
|Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc.
|Poly(vinyl ether) aminocarbamates and fuel compositions containing the same
|Apr 1, 1997
|Oct 9, 1997
|Sk Corporation
|Polyether amino acid ester compounds, preparation method and use thereof
|Feb 3, 2010
|Aug 12, 2010
|Butamax™ Advanced Biofuels LLC
|Gasoline deposit control additive compositions
|Dec 28, 2012
|Jul 4, 2013
|Butamax (Tm) Advanced Biofuels Llc
|Corrosion inhibitor compositions for oxygenated gasolines
|U.S. Classification
|44/387, 560/159, 560/158, 544/398, 544/402
|International Classification
|Cooperative Classification
|European Classification
|Oct 23, 1987
Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CALIFORNI
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BUCKLEY, THOMAS F. III;REEL/FRAME:004800/0999
Effective date: 19871023
Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CALIFORNI
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BUCKLEY, THOMAS F. III;REEL/FRAME:004800/0999
Effective date: 19871023
|Apr 27, 1993
|Fee payment
Year of fee payment: 4
|Apr 23, 1997
|Fee payment
Year of fee payment: 8
|Apr 26, 2001
|Fee payment
Year of fee payment: 12


text:
Business TypeDistributor/Wholesaler
Main MarketsWestern Europe
Product/ServiceElectronics, Flags, Photo-Equipment, Advertising-Products and Give-Aways and much more.
Business OwnerMathias De
EmployeesLess than 5 People
CategoryBusiness Services - Advertising
Company TagsAdvertising - Best Connections - Business Job - Connections - Flags
Company Introduction
Established in switzerland since 1993. As Limited Company (GmbH) since 1997. We like our business, job and we want to be the leader in the swiss-market with our products. You can trust in us and our work. Best connections and trust-profiles at swiss-banks and swiss-marketplaces in every direction.
If you want to send us a fax, please ask us for the number.
If you want to send us a fax, please ask us for the number.
Contact Information
Contact PersonMr. De Rivo Mathias
Telephone41-62-396 36 36
Fax Number41-00-n/a
Post Code4702
AddressPostfach 322, Oensingen, Switzerland
Online MapDe Rivo GmbH Map & Directions

subset: commoncrawl


text:
July 1 is the 182nd day of the year (183rd in leap years). There are 183 days remaining until the end of the year.
Behind the scenesEdit
- 1979 — "A Letter to Diana", the 25th episode of Anne of Green Gables, was broadcast.
- 2016 — "Dull Life Update", the 46th weekly vlog of Anne Shirley and a Project Green Gables episode, premiered on YouTube.
- 2017 — L.M. Montgomery's Anne of Green Gables: Fire & Dew will premiere on YTV.


text:
Featured news
All Star Cast Announced for Ordeal by Innocence
5th July 2017
Discover the full ensemble cast for the new TV adaptation of Agatha Christie's novel, Ordeal by Innocence.
Book of the Month: The Mystery of the Blue Train
Decide if you agree or disagree with Agatha Christie's critique of her 1928 novel The Mystery of the Blue Train.
Agatha Christie HoloLens experience at Port Eliot Festival
Agatha Christie's Elephants Can Remember brought to life in a mixed reality experience.
All Star Cast Announced for Ordeal by Innocence
Discover the full ensemble cast for the new TV adaptation of Agatha Christie's novel, Ordeal by Innocence.
Agatha Christie Festival Programme Revealed
Take a look at this year's festival programme for the International Agatha Christie Festival.
Witness for the Prosecution to open at London County Hall
A brand new production of Agatha Christie's thrilling courtroom drama is opening in a unique London.
Agatha Christie: A Life in Photographs
Find out what to expect from the Agatha Christie exhibition opening at the National Museum Cardiff.
Watch the Murder on the Orient Express trailer now!
Get the first look of Kenneth Branagh, Judi Dench, Daisy Ridley and more taking on this Agatha Christie classic.
Book of the Month: Unfinished Portrait
June's Book of the Month is Unfinished Portrait - the second novel under Christie's pseudonym, Mary Westmacott.
A Note from an Agatha Christie Purist
Agatha Christie expert, Chris Chan, on Poirot being portrayed by different actors and Kenneth Branagh's Poirot moustache.


text:
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Bachelor's degree in Allied Health Field, Physician Assistant, Respiratory Therapy, or other related clinical field OR Diploma, Associate's Degree, or Bachelor…
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Team player, reliable, able to create specials and work late hours. Upscale Lounge looking for late hours, Thursday, Friday and Saturday, 5pm-1am….
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Current Group Fitness certification. If class is empty work to pull members in to class. Provides adequate warm-up, class content, stretching, and cool down….
Amneal Pharmaceuticals – Brookhaven, NY
Bachelor's or Master's Degree in a scientific field. These documents include master batch records for development, exhibit and scale-up batches and various…
American Advisors Group, Inc. – Garden City, NY
Assists with telemarketing calls. Receives and distributes high volume of faxes, mail and messages in a timely manner….


text: This is a list of heroes from the Tomspyk Crew faction. Pages in category "Tomspyk Crew Heroes" The following 5 pages are in this category, out of 5 total. A AdamJ JamesJamieR RhysRoss Retrieved from "http://gota.wikia.com/wiki/Category:Tomspyk_Crew_Heroes?oldid=4343" Ad blocker interference detected! Wikia is a free-to-use site that makes money from advertising. We have a modified experience for viewers using ad blockers Wikia is not accessible if you've made further modifications. Remove the custom ad blocker rule(s) and the page will load as expected. Categories: Heroes by faction Add category Cancel Save


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Over 150 Handmade Doodles pack
Free Over 150 Handmade Doodles pack designed and shared by Latin Vibes. It is a premium product, but is now free, you hurry to download it and enjoy. A totally handmade pack of cute and playful clip arts perfect for anything you want! Over 150 graphics! Perfect to create logos, patterns, cards, decorate a blog, branding, presentations, etc.
Thanks to Latin Vibes. Over 150 Handmade Doodles free for personal use only, See more products other great art of the author.


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Thank soooooooo much again!
Hi Marilyn,
Did I not buy the cigs from you?, my sincere apologies and also thank you for all your help which has been fabulous and therefore also above and beyond, you didn't have to go so far, I must say I will recommend you to my friends, and yes I have it working!
Thank soooooooo much again.
Cheers Jo
Comments are closed.


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(OLNEY) As scattered showers and thunderstorms with some damaging winds rolled thru our listening area last night, the regional rainfall amounts averaged between a half inch up to over an inch and a half in some spots – and it's much the same today thru the upcoming weekend – more unsettled weather with scattered rain and storms possible – a cold front will move thru late Saturday night – listen for updates.
(NEWTON) In state news today – Illinois officials say the fairgrounds in Springfield and Du Quoin will be ready for their respective summer-time events, however the major improvements at each site still await private fundraising and a state spending plan – the State Department of Agriculture says extra funds are available to use in the case of an emergency, such as last year's flash flooding in Springfield.
(OLNEY) The Illinois Department of Natural Resources (IDNR) is looking for a new operator for the Rend Lake Resort & Conference Center, located on the Wayne Fitzgerrell State Recreation Area in Whittington, down in Franklin County – opening back in 1990 with 104 rooms, suites, and cabins adjoining popular Rend Lake, the DNR cited health and safety hazards, including mold, when it terminated its previous lease agreement last December – the Request for Proposals documents, which provides specific details on the resort facilities & requirements for operations, can be found on the DNR website, at www.dnr.illinois.gov.
(NEWTON) The Lincoln Log Cabin State Historic Site, south of Charleston, just west off of State Route 130, is offering two fun ways to celebrate Father's Day this weekend : a Civil War Encampment and Free Fishing : re-enactors portraying members of the 5th Illinois Cavalry will camp at the site this Saturday and Sunday, from 10:00 to 4:00 each day, demonstrating daily camp life and the struggles the Cavalry faced during the Civil War – visitors will also be able to take advantage of the site's fully stocked pond during Illinois' Free Fishing Days celebration, which runs tomorrow thru next Monday, at which time statewide anglers can fish without purchasing a fishing license during the four day period – for more information on the historic site activities, logon at www.lincolnlogcabin.org or look for the cabin on Facebook.
(OLNEY) The Richland County School Board will have its regular monthly meeting for June tonight, starting at 7:00, in the Unit Office Board Room in Olney – the full agenda includes several policies up for their second reading and possible adoption, plus the various administrative reports and a Public Hearing concerning the District's Amended Fiscal Year 2017 Budget – an executive session will include discussion on negotiations, student discipline, litigation, and personnel – the meeting is open to the public.
(NEWTON) The Jasper County School Board will have its regular monthly meeting for June tonight in Newton, in the District's Administrative Office, beginning at 6:30 – the full agenda includes several new business items to consider, plus several policies for final reading and possible adoption – an executive session will be held to discuss litigation, student discipline, & personnel – the meeting is open to the public.
(NEWTON) The 2017 Jasper County Fair is set to kick off this weekend in Newton – it all gets underway with the 4-H General Project Shows at 4:00 tomorrow (Friday) afternoon, followed by the 4-H Public Speaking Contest at 6:30 tomorrow night, all on the Fairgrounds in Newton – plus the Floral Hall Exhibits will be accepted from 5:00 to 7:00 tomorrow evening and from 8:00 to 11:00 Saturday morning, followed by judging – the 4-H Poultry Show is Sunday at 2:00 and the 4-H Rabbit Show is Sunday at 5:00 – the 4-H Sheep & Goat Show is Monday afternoon at 4:00, the 4-H Swine Show is next Tuesday morning at 8:00, and the 4-H Beef Show is Tuesday afternoon at 5:00 – then 4-H Dairy Show is next Thursday morning at 9:30 with everything animal-wise, to wrap up next Thursday evening with the 4-H Youth Auction at 5:00 – as far as entertainment goes over the next week at the Jasper County Fair – the Queen & Little Miss Pageant is next Monday night at 7:30 – Tuesday night is Family Night with armbands available for the rides, plus the Karaoke Contest, the Pedal Tractor Pull, Talent Contest, and Flat Drags – the Rodeo is Wednesday night at 7:00, followed by the IPA Sanctioned Tractor / Truck Pull Thursday night at 7:00 – the Fair's popluar Antique Farm Machinery Show is Friday from 10:00 to 2:00 with Harness Racing next Friday at 12 noon and the Non-Sanctioned Tractor / Truck Pull Friday night at 7:00 – it's the final Harness Racing next Saturday at 12 noon and the Demolition Derby to wrap things up that Saturday night at 7:00 – the Carnival Rides will run each day & night next Tuesday thru Saturday – all at the Jasper County Fair in Newton.
(OLNEY) Construction to replace the Bonpas Township Bridge on Oak Tree Road at Simmons Creek is scheduled to begin next Monday, June 19th – the project is expected to take around six weeks to be completed – the section of Oak Tree Road will be closed during the time of the construction – if any questions, call the Richland County Engineer at the County Highway Office, at 618-392-3141 : also, road construction work continues on Whittle Avenue and Kitchell Avenue in Olney as – alternate routes are needed in these areas until the road work is completed – the patience of all drivers is much appreciated.
(OLNEY) The Lawrence County Longspurs Chapter of the National Wild Turkey Federation will host the 19th annual JAKES Field Day event on Saturday, June 24th, at Red Hills State Park, near Sumner – it's for all area youngsters up to the age of 17 with the various hands-on activities to include archery, air rifle and shotgun shooting, hunting safety, and more – each youth must have a release form signed by a parent and/or guardian to take part and registration begins at 9:30, followed by activities from 10:00 to 3:00 – lunch will be provided, plus a prize for every kid – parents and grandparents are invited to hang around the watch – to get a form in advance or if any questions, call Tyler at 618-553-1828 – all youth are invited to take part.
The St. Mary's Catholic Church in Ste. Marie and the American Red Cross will host a blood drive this Sunday morning from 7:30 to 11:30 in the Parish Hall – all donors can enter their name for a drawing for two Holiday World tickets for this 2017 season – all blood types and platelets are very much needed
Whittle Rock is this coming Saturday afternoon thru night, from 3:00 until midnight – live music from various local bands and individuals, plus food & craft vendors – it's $5 for advanced tickets, $10 at the gate
The Noble Freedom Baptist Church will be hosting a Freedom VBS Sign-Up Party at the Noble Village Park this Saturday night from 5:00 to 8:00 – free hotdogs and drinks and inflatable games for the kids
The American Legion Post #30 will be holding a Pork Burger Sale at the Olney IGA this Saturday from 11:00 until 2:00, or until sold out – all proceeds will help out with local and area events
A "pork burger / bake sale" fundraiser is this Saturday at the Sunrise Seed Company, along Main Street, in downtown Clay City, with serving from 10:30 until sold out, all by open donation and for pickup only – bake sale donations will be accepted until 9:30 – large orders can be called in advance at 618-508-1623
The Olney Fire Department will host a Blood Drive tomorrow from 2:00 until 6:00 at the meeting room on North Walnut Street – visit redcrossblood.org and enter OlneyFD to schedule an appointment
The Annual Salad Luncheon at the Grace United Methodist Church is tomorrow from 11:00 to 1:00 in Newton – the menu includes a variety of salads, ham balls, hot rolls and a drink for a $7 donation
The Richland County Farm Bureau Ag in the Classroom has two programs coming up this summer at the Olney Public Library, the first of which is tomorrow morning at 10:30 with activities to follow
The Latona Church of Christ has a Bake Sale tomorrow morning at the Circle K in Newton starting at 8:00 and continuing until sold out – all the proceeds to help with Youth Group Mission Trip to New Orleans


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Added by Scottish Natural HeritageStarting salary £24,587 per annum pro rata, Fort William
You will contribute to the delivery of Scottish Natural Heritage's objectives within the South Highland Unit. This post will principally deliver work in Lochaber but will also be expected to work flexibly throughout the area. … Read more


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About Cheryl
a truly unique experience
Cheryl's gracious presence at the Fairchild Wellness Retreat is quiet and comforting. She is capable of giving individuals the time and space they need, but is equally available to converse generously and listen reflectively to her guests. Cheryl's years of coaching and professional knowledge make her the quintessential caretaker of this lovely environment and proprietor of such beauty and calmness. Her compassion and energy radiate throughout the gardens and patios of this historic home and wellness retreat.
Cheryl regularly plans group special events and seasonal workshops, and can help you custom design your very own special retreat. Visit the workshops and special events page or learn about wellness retreat options here.
Have questions? Let's chat. Send a message below, and I'll get right back to you.


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Dallas, TX
GED/SPECIAL NEEDS/READING & WRITING50/hour
...areas. Two years into my teaching career, I starting teaching math and writing skills to adults seeking their GED. Tutoring comes as a nature gift due to the one on one needs of most of my students in the... read moreSee Tutors Like This


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When the production of Demon Brides comes to Kembleford and the director of the film is murdered, Father Brown investigates.
This is Father Brown and you are watching TVZion
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The Validation Documentation Matrix, gives a very concise overall picture of your validation program. This four part matrix allows you to list all the equipment and systems that must be qualified. Each entry is allocated a row in the matrix. The row consists of eleven headings as shown below, these may be edited as required. In this matrix there is room to enter the document number, prefixed by, A to D. The document number gives you the instant cross reference to the current document and the A to D prefix, indicates the progress stage.
The basic philosophy underlying the use of a matrix for data verification and validation is to establish clear expectations and requirements that have been ground-tested for practicality and reasonableness this enables the organizations to succeed rather than fail for lack of direction.
An allied concern is that data verification will be viewed as an integral part of validation.
The incremental approach affords time for exercising leadership, changing organizational culture, refining processes, and establishing clear accountability. It avoids imposing a large front-end reporting burden that could meet with resistance and might end up significantly impacting other priorities.
All production process equipment must be listed in an multi-column matrix. Column 1, of this matrix designates the priority that the equipment is to receive in this validation task. Number one will be the first equipment qualified, and then the validation of the listed equipment will follow in chronologically order. Column 2, 3 and 4 are used to identify the item and its location. Columns 5 indicates whether the system generates data that is the subject of a predicate rules requirement. Column 6 will be generated from the execution of the risk assessment against the equipment. Column 7, 8, 9, 10 and 11 are used to assess progress.
This correct execution of this procedure will define whether the equipment under assessment must be validated, what the scope of the validation should be and whether the "equipment produces data" that is classified as predicate data. It therefore enables column 5 and 6 of the matrix to be completed, thus defining the scope and depth of validation that this piece of equipment demands.
During a regulatory visit the inspectors do expect to see a complete
suite of validation documents in place for each validation task. The
use and scope of the individual documents has been documented, discussed
and explained in detail. It is therefore obviously best policy to have
in place exactly what the regulator is looking for. The use of a
document packages ensures a multitude of regulatory requirements are
catered for and possibly a similar multitude of pitfalls, blunders and
omissions are anticipated and negated
Select Preferred Language
When assistance is required; please contact us on TOLL-FREE 877-462-4048
If out of office hours; please leave a voice message.
Validation Documentation Matrix (Issue 6.) -- $29.00
This Matrix must sit along-side your VMP or PVP and together with these documents give a very concise overall picture of your validation program. This four part matrix allows you to list all the equipment and systems that must be qualified. Each entry is allocated a row in the matrix. The row consists of eleven headings, these may be edited as required (but come with all the standard documentation titles inserted). In this matrix there is room to enter the document number, prefixed by, A to D. The document number gives you the instant cross reference to all the associated documents; the A to D prefix shows the progress stage.


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The Steve Bannon National Security Council Appointment is quite a coup for the former head of Breitbart News. As reported by ABC News, not only will the controversial far-right White House chief strategist now sit in on National Security Council meetings, the Director of National Intelligence and the Chairman of the Joint Chiefs of Staff have been ousted from permanent positions on the Council.
WH advisors Bannon and Miller overruled the Dept of Homeland Security's judgment the travel ban should not apply to Green Card holders https://t.co/rK8zAgeCug
— Jim Sciutto (@jimsciutto) January 29, 2017
The Controversies Around Steve Bannon
National Security Council meetings are generally supposed to be free of political considerations and bias. However, as reported by the Associated Press, during his tenure as head of Breitbart News, Steve Bannon has expressed opinions that many consider to be racist, sexist and anti-semitic. So, his placement on the council was certain to generate controversy.
This latest Donald Trump decision is causing an uproar on the Internet, with many on Twitter describing Steve Bannon as "President Bannon." It is also virtually unprecedented for a purely political advisor – which Bannon is supposed to be – to sit in on meetings regarding national security and military matters.
Hi @POTUS President Bannon, what are your thoughts on your subordinate @realDonaldTrump right now? #StopPresidentBannon
— AltHomelandSecurity (@AltHomelandSec) January 29, 2017
Allowing Bannon to have an official standing in the National Security Council meetings – while removing the Director of National Intelligence and the Chairman of the Joint Chiefs of Staff as a permanent presence at such meetings – could easily give the public and foreign leaders the impression that political considerations are influencing Donald Trump's military and intelligence policies.
Pondering President Bannon National Security
Council appointments notwithstanding, there seems to be little evidence that Steve Bannon has either the qualifications or the temperament required for making the kinds of calls that the National Security Council has to make on a regular basis regarding the nation's security and future international and military policies.
BTW:In political circles it's well known Steve Bannon gave Trump the birther idea????????#StopPresidentBannon #trumpleaks #resist #theresistance
— Scott Dworkin (@funder) January 29, 2017
Even though – while he was at Breitbart News – Bannon offered up endless opinions on any number of subjects, ranging from climate change to our posture in the Middle East, these positions were almost always at odds with those of professional international and security experts. Bannon's limited experience as a naval officer hardly qualifies him as an expert in these areas.
Given this, the advice and opinions that Steve Bannon is likely to offer Donald Trump through the National Security Council will spring from a profound lack of experience and paucity of knowledge when it comes to such matters. Despite this, it seems clear that Trump will rely heavily on Bannon for security and foreign policy opinions – otherwise, he would never have put him on the Council to begin with.
In fact, in several of the official White House photos of Donald Trump making phone calls – in which Trump is speaking to foreign leaders – Bannon can be seen standing in the background, as though he is orchestrating things. Foreign policy and security experts find Bannon's involvement in such matters extremely disquieting. And as reported by CNN, Senator John McCain today expressed his concerns about Trump's decision regarding the Bannon National Security Council appointment.
Downgrading of the Joint Chiefs and the DNI
As mentioned above, this apparent Bannon National Security Council coup involves more than just Donald Trump issuing an order placing Bannon on the Council. Along with Bannon's appointment, the Director of National Intelligence and the Chairman of the Joint Chiefs of Staff were removed from permanent positions on the Council.
Note that Bannon has a higher status on the new NSC than the Director of National Intelligence and the Joint Chiefs Chairman. https://t.co/AZsCe8Qk4d
— Matthew Miller (@matthewamiller) January 29, 2017
Instead of regularly attending the meetings of the National Security Council, these highly trained experts – who have years of experience in national security and military matters – will now only be called in when it's deemed necessary. And the person doing the "deeming" is likely to be Steve Bannon.
It seems clear now that Bannon – along with Vice President Mike Pence and Donald Trump himself – will be calling the shots when it comes to national security matters. Thus, the Bannon National Security Council appointment suggests the Trump administration if isolating itself from any voices that might object to its future decisions.
[Featured Image by Win McNamee/Getty Images]


text: Connect with Service Experts Heating & Air Conditioning through Social Media We're connecting with our customers, partner businesses and friends on Facebook. We're tweeting and keeping track of all those hashtags on Twitter. We're connecting with our experts and our local networks – like Provo – across the U.S. and Canada on LinkedIn. We're blogging about topics that can help you easily (and inexpensively!) keep your HVAC equipment running smoothly all year long. And we're posting webinars, HVAC tips and behind the scenes videos on YouTube. Put simply: we're sharing our knowledge on the outlets our customers have asked for. It's just one way we can share our knowledge with you quickly and effortlessly because we want to help you understand how to have HVAC equipment that work for you – not the other way around. Additionally, you can get to know us a little better, too. So like us, follow us and connect with us now to start learning from the experts. We invite you to learn more about Service Experts Heating & Air Conditioning on Facebook, Twitter, YouTube and LinkedIn. Take a look through our page on your favorite social media channel. Check us out. It will give you added insight to who we are and the many ways we can help with your home comfort needs.


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Estate planning attorneys in sioux falls sd
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Engineered mesh provides ventilation for your forefoot while supporting your midfoot. The partial mesh inner sleeve enhances breathability while offering and a sock-like fit. KD 8 Nike Easter Collection 2016 Release Date New KD 8 Kobe Nike KD 8 GS World Kickz Nike KD VIII 8 Lebron XIII Kids Nike Kd V Crimson InVivo Therapeutics. Plush foam and mesh tongue for breathable comfort and Midsole flex grooves provide greater forefoot flexibility KD 8 Waffle outsole for durability and great multi-surface traction.
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3307 Thornbridge Dr, Powder Springs, Georgia
$144,7003 Beds2+ BathsContract Pending
$144,7003 Beds2+ BathsContract Pending
3307 Thornbridge Dr, Powder Springs, Georgia 30127 - Welcome Home! Maintenance free living at its finest! Lovely townhome in quiet, family friendly community. Convenient to shopping, dining and parks. Walking distance to Silver Comet Trails. Highly sought after school district. Incredible open floor plan, hardwood floors, neutral paint and carpet. Spacious master with vaulted ceilings and spa like master bath. Private patio perfect for enjoying quiet mornings. This is it! Wont last, call today!
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Filter Results:
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- Sheng-fa Liu, Wen-feng Peng, +5 authors Jun Xiao
- Systematic parasitology
- 2010
In the literature, 630 species of Digenea (Trematoda) have been reported from Chinese marine fishes. These belong to 209 genera and 35 families. The names of these species, along with their hosts, geographical distribution and records, are listed in this paper.
- Wen-feng Peng, Sheng-fa Liu, Bing-li Wang, Mei-mei Wei
- Systematic parasitology
- 2011
A checklist of the parasitic nematodes of Chinese marine fishes is presented. This fauna comprises 90 species, representing 31 genera, 13 families, nine superfamilies, three orders and two subclasses. Additional details for each species include the hosts, localities and references which represent the source of these data.
- Sheng-fa Liu
- The Journal of parasitology
- 2002
Two new species of lepocreadiid trematodes are reported from marine fishes from the Taiwan Straits, China: Diploproctodaeum spinosus n. sp. from the intestine of Takifugu oblongus (= Fugu oblongus) and Preptetos parapristipomae n. sp. from Parapristipoma trilineatum. Diploproctodaeum spinosus differs from the known species of Diploproctodaeum, with 1 spine… (More)
- Sheng-fa Liu, Ting-bao Yang
- The Journal of parasitology
- 2002
The species Phanurus oligoovus gen. et sp. nov. is described from the intestine of Liza carinatus (Cuvier et Valencienne) from the South China Sea. From the general internal anatomy, it belongs to the Waretrematidae and is distinguished from the other known species of the Waretrematidae by the tail appendage. A new subfamily, Phanurunae, is proposed for the… (More)
- Sheng-Fa Liu, Yan-Hai Wang, Wen-Feng Peng, Shui-Zhou Yu, Wen-Chuan Yang
- The Journal of parasitology
- 2004
Saccocoelium megasacculum n. sp. (Digenea: Haploporidae) was collected from the intestine of the mugilid fish. Liza carinatus (Cuvier and Valenciennes), in the Taiwan Strait. It is the first record of Saccocoelium in China. The parasite most closely resembles Saccocoelium obesum Looss, 1902 and Saccocoelium tensum Looss, 1902 in general morphology and body… (More)
- Sheng-fa Liu, Ting-bao Yang
- The Journal of parasitology
- 2002
Two new species of Pseudohapladena Yamaguti, 1952 (Digenea: Waretrematidae) are described. Pseudohapladena megoorchis n. sp. was obtained from the intestine of Mugil engeli (Bleeker) (Mugilidae), and Pseudohapladena lizae n. sp. from the intestine of Liza carinatus (Cuvier and Valenciennes) (Mugilidae). Pseudohapladena megaorchis is the most closely related… (More)
- Sheng-fa Liu, Ting-bao Yang
- Folia parasitologica
- 2002
Haploporus mugilis sp. n. (Digenea: Haploporidae) was obtained from the intestine of kandas, Valamugil engeli (Bleeker) (Mugilidae, Perciformes) in the Taiwan Straits, China. It most closely resembles Haploporus spinosus Machida, 1996 from the intestine of Crenimugil crenilabis in Japanese and adjacent waters in the intestinal bifurcation posterior to the… (More)
- Sheng-fa Liu, Lin Zhou, Shui-zhou Yu, Jun Liu
- The Journal of parasitology
- 2006
Megasolena dongzhaiensis n. sp. was collected from the intestine of Scatophagus argus (Linnaeus) (Perciformes: Scatophagidae) from the Dongzhai Bay (110 degrees 32'-37'E, 19 degrees 51'-20 degrees 1'N), Hainan Province, China. It resembles Megasolena acanthuri Machida and Uchida, 1991 in having larger body size, but it differs from the latter species in… (More)
- Sheng-fa Liu
- Folia parasitologica
- 2002
Lasiotocus lizae sp. n. (Digenea: Monorchiidae) was collected from the intestine of Liza carinata (Valenciennes) (Mugilidae, Perciformes) in the Taiwan Straits, China. L. lizae is most similar to Lasiotocus glebulentus Overstreet, 1971 from the intestine of Mugil cephalus from the Northern Gulf of Mexico in having tightly compacted vitellaria, a genital… (More)
- Tzu-Chieh Lin, Sheng-Fa Liu, Chih-Yu Chao
- Displays
- 2011
In this article, we propose a mechanical rubbing method to eliminate the optical bounce and decrease the response time of homeotropic liquid crystal (LC) cells with sputtered silicon dioxide alignment films. After gently rubbing the inorganic alignment film (sputtered silicon oxide, SiO 2), the decreasing polar anchoring energy results in slightly smaller… (More)


text: I would recommend using FireBrand and creating a theme containing the new icon. Then you can upload it to our themes section on the website for others to add to their own copy of Fire. The themes section is at: http://fire.sourceforge.net/addons/list.php?type=theme Firebrand is available at: http://prdownloads.sourceforge.net/fire/Firebrand0.7.dmg?download Good Luck! Alan -- Fire Development Team On Mar 14, 2005, at 1:53 PM, Dur wrote: > I've made a new icon for Fire that I think fits the OS X a bit better. > To whom should I submit it? Can I just attach my suggestion here? > > -- > Using Opera's revolutionary e-mail client: http://www.opera.com/mail/ > > > ------------------------------------------------------- > SF email is sponsored by - The IT Product Guide > Read honest & candid reviews on hundreds of IT Products from real > users. > Discover which products truly live up to the hype. Start reading now. > http://ads.osdn.com/?ad_id=6595&alloc_id=14396&op=click > _______________________________________________ > fire-development mailing list > fire-development@... > https://lists.sourceforge.net/lists/listinfo/fire-development


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Cecilie Jørgensen
Flere idéer fra Cecilie
17 Tatuajes que vas a querer tener en tu columna vertebral More
Pineapple Art Print
black daisy tattoo - Google Search ( I personally like the Roman numerals in the upper arm better)
45 Inspirational Sunflower Tattoos | Cuded
Sun Tattoo Designs (10)
sunflowers live tall, bright and strong, conveying warmth and happiness.They always turn to face the sun to drink in as much sunlight as possible.
constellation tattoo
I like gismos and gadgets...wouldnt get this tattoo though
I just like the moon. The entire piece is definitely not my thing, but the moon is gorgeous
pug love tattoo via Tattoologist