text:
|Publication number
|Publication type
|Application number
|Publication date
|May 23, 1978
|Filing date
|Sep 10, 1976
|Priority date
|Sep 10, 1976
|Also published as
|Publication number
|Richard L. Smith, Ralph C. Farrar, Daniel H. Willis
|Original Assignee
|Phillips Petroleum Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (13), Referenced by (10), Classifications (30)
|External Links: USPTO, USPTO Assignment, Espacenet
The invention relates to rubbery, substantially random copolymers of a conjugated diene with a monovinyl aromatic compound. In another aspect, the invention relates to the continuous polymerization of a conjugated diene with a monovinyl aromatic compound.
Continuous polymerization of a conjugated diene with a monovinyl aromatic compound in the production of random copolymers by organolithium initiation in solution polymerization systems offers real production advantages. Polymerization procedures operated as a continuous process rather than as a batch process provide for the more economic production and more uniform compositions. Process variables can be readily adjusted in a continuous operation so as to optimize operations for a given polymerization recipe. Minor adjustments of monomer feed rates, initiator rates, randomizer rates, temperature control, pressure control, solvent usage, all can be readily made in a continuous process, in effect "fine tuning" so as to maintain relatively consistently a product with optimum properties.
The equipment employed comprises at least two reactor means operated as a reactor series or train through which the polymerization reaction mixture flows in its progress of polymerization from initiation to final termination. Unfortunately, such a continuous solution polymerization process has the disadvantage of a tendency toward fouling, especially in the first reactor means in the chain through a buildup of polymeric materials on the surfaces of the reactor means in contact with the reactants, fouling of heat transfer surfaces, stirring or circulation means, and the like, often ending prematurely a continuous polymerization run. It is readily apparent that the longer that equipment can be operated on a continuous basis, the more economical the overall results. Having to stop the entire process, clean the equipment, and then start up all over again, means, again, attendant startup problems and necessity to again fine tune the operation.
Heretofore, silicon polyhalides have been used at the end of polymerization as terminating agents. We have discovered, unexpectedly, an effective means of deterring, substantially, fouling in the first reactor means of a continuous polymerization process by employing a silicon halide as an additive in the first reactor means of a train or series of reactors. Thus, a silicon halide is employed as an active component during the polymerization stage according to our invention. Our process results in solution-polymerized, substantially random, conjugated diene/monovinyl-substituted aromatic compound rubbery copolymers in a continuous polymerization process, yet substantially without fouling in the first of the reactor means. This means longer runs, more economical products, more consistently uniform products.
The rubbers prepared according to our invention are organolithium-initiated, solution-polymerized, substantially random conjugated diene/monovinyl aromatic compound copolymers, produced under continuous polymerization conditions employing a ratio or a series of reactor means operated in series and employing a silicon halide in the first reactor means during and in the polymerization of the monomers in an amount effective to reduce substantially reactor fouling in the first of the reactor means.
The equipment employed comprises at least two reactor means operated as a reactor series or train, presently preferably three reactor means connected in series to provide two for polymerization and a third for coupling. A minimum of two reactor means is employed in accordance with the process. The actual number of reactor means through which the polymerization reaction mixture flows in its process of polymerization to final termination is not actually a limiting factor, though we find that two reactor means for the polymerization stages, and the third or final reactor for the termination step, is a practical and convenient approach. Two reactor means in series gives higher conversion than does a single reactor. Three reactors would be expected to result in still higher conversion, though diminishingly so, and so on as still more reactor means are added. Manipulations, of course, become more complex as more reactor means are added, and our presently preferred 2+1 mode represents a practical and satisfactory balance.
The first reactor means receives the respective monomers including at least one polymerizable conjugated diene and at least one copolymerizable monovinyl-substituted aromatic compound; polymerization diluent; organolithium initiator, preferably and conveniently supplied as a solution in a diluent which conveniently can be the same diluent as is employed as the polymerization diluent; a randomizer compound also preferably and conveniently supplied as a solution in a diluent again preferably and conveniently the same as the polymerization diluent; and the additive in accordance with our invention, a silicon halide, also preferably and conveniently supplied as a solution in a diluent again preferably and conveniently the same as the polymerization diluent.
Each of the reactant materials and diluents being employed, including the silicon halide additive which is the further additive in accordance with our invention, preferably have been previously purified as may be necessary in accordance with techniques known in the art for solution polymerization systems. The several polymerization process components including diluents should be protected against moisture, air (oxygen), and against stray terminating agents such as carbon dioxide, carbon monoxide, and the like. Where necessary, purification can be effected including steps such as distilling, treating with molecular sieves, and the like, as known to the art.
Several materials are fed to the first reactor means in the train or series wherein the reactor contents are maintained under suitable solution polymerization conditions of temperature and pressure for effective polymerization of the monomers, utilizing exterior or internal heating/cooling means, and pressurization methods as necessary such as with an inert gas such as nitrogen, and the like. Polymerization is initiated in the first of the reactor means upon addition of the initiator and upon reaching suitable polymerization temperature, and allowed to proceed. The polymerization reaction admixture moves continuously or substantially continuously through the reactor train wherein the polymerization reaction is conducted in all but the last reactor means. After a suitable average residence time so that polymerization is substantially complete by the time the polymerization admixture reaches the last reactor means of the train, for example the third reactor means, termination procedures then are applied to the reaction admixture. Termination can be simple inactivation of active lithium, or can be coupling with a coupling agent to provide a linear or branched polymer. Thereafter, an antioxidant can be added if desired, and normal recovery procedures employed to recover the polymer for further processing, blending, compounding, and the like.
The polymerization process in accordance with our invention is one of the copolymerization of at least one polymerizable conjugated diene and at least one copolymerizable monovinyl aromatic compound under random polymerization conditions, with the term "polymerizable" referring to solution polymerizable monomers polymerizable with an organolithium initiator.
The polymerizable conjugated dienes generally contain 4 to 12 carbon atoms per molecule for convenience and availability, those containing 4 to 8 carbon atoms being preferred for commercial purposes, and presently most preferred for similar reasons are butadiene and isoprene. Examples include 1,3-butadiene and isoprene, as well as 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, 2-phenyl-1,3,-butadiene, and the like, alone or in admixture. As suitable conjugated diene feedstocks, we can also employ mixtures of 1,3-butadiene, or other suitable conjugated dienes, in admixture with other low molecular weight hydrocarbons. Such admixtures, termed low concentration diene streams, are obtainable from a variety of refinery product streams such as naphtha-cracking operations or can be intentionally blended compositions, available from product streams produced in the modern complex oil refining and petrochemical facilities sometimes termed a petrocomplexity. Low concentration diene streams may contain such as from less than 30 to more than 50 weight percent of 1,3-butadiene, though the concentration can range widely. Examples of typical low molecular weight hydrocarbons which may be admixed with 1,3-butadiene in the polymerization feed include such as propane, propylene, iso- and n-butane, 1-butene, isobutylene, trans-2-butene, cis-2-butene, vinylacetylene, cyclohexane, and the like.
Monovinyl-substituted aromatic compound monomers employed in the context of our invention are those known to polymerize with organolithium initiators in solution polymerization systems. These monovinyl-substituted aromatic compounds typically contain 8 to 20 carbon atoms per molecule, more usually 8 to 14 for commercial purposes, and most preferred is styrene as the most readily commercially available monomer. Exemplary species include the presently preferred styrene, as well as 1-vinylnaphthalene, 2-vinylnaphthalene, and various alkyl, cycloalkyl, aryl, alkaryl and aralkyl derivatives thereof, such as 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4-phenylbutyl)styrene, and the like, alone or in admixture.
The relative amount of conjugated diene or dienes and monovinyl aromatic compound or compounds employed can vary over a wide range. In preparing rubbery polymers, the proportion of the conjugated diene versus the monovinyl-substituted aromatic compound should be sufficient so as to result in a substantially rubbery or elastomeric copolymer product. There is no sharp break point as to the amount of conjugated diene versus monovinyl-substituted aromatic compound that confers rubbery or elastomeric properties on the resulting copolymer, though in general at least 50 parts by weight of conjugated diene are required on an exemplary basis. Thus, for a rubbery copolymer, as is preferred in accordance with our invention, the weight ratio of conjugated diene to monovinyl aromatic compound in the monomer charge would be in the range of about 50:50 to 95:5. Of course, mixtures of conjugated dienes as well as mixtures of monovinyl-substituted aromatic compounds can be utilized.
Organolithium initiators employed in the process of our invention include the monofunctional and multifunctional types known for solution polymerization of the monomers as described hereinabove. The multifunctional organolithium initiators can be either specific organolithium compounds, or can be multifunctional types which are not necessarily specific compounds but rather represent reproducible compositions of regulable functionality.
The choice of initiator can be governed by the degree of branching and the degree of elasticity desired for the polymer, the nature of the feedstock, and the like. With regard to the feedstock employed as the source of conjugated diene, for example, the multifunctional initiator types generally are preferred when a low concentration diene stream is at least a portion of the feedstock, since some components present in the unpurified low concentration diene stream may tend to react with carbon-lithium bonds to deactivate initiator activity, thus necessitating the presence of sufficient lithium functionality in the initiator so as to override such effects.
Among the multifunctional initiators, again which are not necessarily specific compound, are those prepared by reacting an organomonolithium compound with a multivinylphosphine or with a multivinylsilane, such reaction preferably being conducted in an inert diluent such as a hydrocarbon or a mixture of a hydrocarbon and a polar organic compound. The reaction between the multivinylsilane or multivinylphosphine and the organomonolithium compound can result in a precipitate, which can be solubilized if desired, by adding a solubilizing monomer such as a conjugated diene or monovinyl aromatic compound, after reaction of the primary components. Alternatively, the reaction can be conducted in the presence of a minor amount of the solubilizing monomer. Relative amounts of organomonolithium compound and multivinylsilane or multivinylphosphine preferably should be in the range of about 0.33 to 4 mols of organomonolithium compound per mol of vinyl group present in the multivinylsilane or multivinylphosphine employed.
Exemplary organomonolithium compounds include ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n-eicosyllithium, phenyllithium, 2-naphthyllithium, 4-butylphenyllithium, 4-tolyllithium, 4-phenylbutyllithium, cyclohexyllithium, and the like.
Exemplary multivinylsilane compounds include tetravinylsilane, methyltrivinylsilane, diethyldivinylsilane, di-n-dodecyldivinylsilane, cyclohexyltrivinylsilane, phenyltrivinylsilane, benzyltrivinylsilane, (3-ethylcyclohexyl) (3-n-butylphenyl)divinylsilane, and the like.
Exemplary multivinylphosphine compounds include trivinylphosphine, methyldivinylphosphine, dodecyldivinylphosphine, phenyldivinylphosphine, cyclooctyldivinylphosphine, and the like.
Other multifunctional polymerization initiators can be prepared by utilizing an organomonolithium compound, further together with a multivinylaromatic compound and either a conjugated diene or monovinylaromatic compound or both. These ingredients can be charged initially, usually in the presence of a hydrocarbon or a mixture of a hydrocarbon and a polar organic compound as diluent. Alternatively, a multifunctional polymerization initiator can be prepared in a two-step process by reacting the organomonolithium compound with a conjugated diene or monovinyl aromatic compound additive and then adding the multivinyl aromatic compound. Any of the conjugated dienes or monovinyl aromatic compounds described can be employed. The ratio of conjugated diene or monovinyl aromatic compound additive employed preferably should be in the range of about 2 to 15 mols of polymerizable compound per mol of organolithium compound. The amount of multivinylaromatic compound employed preferably should be in the range of about 0.05 to 2 mols per mol of organomonolithium compound.
Exemplary multivinyl aromatic compounds include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4'-trivinylbiphenyl, 1,3-divinyl-4,5,8-tributylnaphthalene, and the like. Divinyl aromatic hydrocarbons containing up to 18 carbon atoms per molecule are preferred, particularly divinylbenzene as either the ortho, meta, or para isomer, and commercial divinylbenzene, which is a mixture of the three isomers, and other compounds such as the ethylstyrenes, also is quite satisfactory.
Other types of multifunctional initiators can be employed, such as those prepared by contacting a sec- or tert-organomonolithium compound with 1,3-butadiene, in a ratio of such as about 2 to 4 mols of organomonolithium compound per mol of 1,3-butadiene, in the absence of added polar material in this instance, with the contacting preferably being conducted in an inert hydrocarbon diluent, though contacting without the diluent can be employed, if desired.
Alternatively, specific organolithium compounds can be employed as initiators, if desired, in the preparation of the polymers in accordance with our invention. These can be represented by R"'(Li)x wherein R"' represents a hydrocarbyl radical of such as 1 to 20 carbon atoms per R"' group, and x is an integer of 1 to 4. Exemplary organolithium compounds are methyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n-decyllithium, phenyllithium, 1-naphthyllithium, 4-butylphenyllithium, p-tolyllithium, 4-phenylbutyllithium, cyclohexyllithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyllithium, dilithiomethane, 1,4-dilithiobutane, 1,10-dilithiodecane, 1,20-dilithioeicosane, 1,4-dilithiocyclohexane, 1,4-dilithio-2-butane, 1,8-dilithio-3-decene, 1,2-dilithio-1,8-diphenyloctane, 1,4-dilithiobenzene, 1,4-dilithionaphthalene, 9,10-dilithioanthracene, 1,2-dilithio-1,2-diphenylethane, 1,3,5-trilithiopentane, 1,5,15-trilithioeicosane, 1,3,5-trilithiocyclohexane, 1,3,5,8-tetralithiodecane, 1,5,10,20-tetralithioeicosane, 1,2,4,6-tetralithiocyclohexane, 4,4'-dilithiobiphenyl, and the like.
The organolithium initiated polymerization process in accordance with our invention employs a mixture of monomers with the polymerization preferably conducted in a hydrocarbon diluent, further with a randomizing agent to substantially avoid formation of substantial block content. The randomizing agent is included in the polymerization reaction mixture. Any suitable polar organic compound known in the art for randomization can be employed for such purposes, including the hydrocarbyl ethers, thioethers, and amines. Such polar compounds, particularly the ethers such as tetrahydrofuran, tend to lead to polymers of substantial vinyl unsaturation content with respect to the portion derived from the conjugated diene monomer.
Where randomization without vinylization or with minimum vinylization is desired, then compounds of other types can be readily employed to produce low vinyl copolymers. Examples of such other types of compounds include the alkylpotassium compounds such as methylpotassium, ethylpotassium, n-propylpotassium, isopropylpotassium, tert-butylpotassium, tert-amylpotassium, n-hexylpotassium, cyclohexylpotassium, and the like.
Other suitable randomizing agents include the potassium salts of mono- and polyhydric alcohols, mono- and polyhydric phenols, including bis-phenols, and sulfur analogs of same. Specific examples of such compounds include the potassium salts of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, tert-butyl alcohol, tert-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, benzyl alcohol, phenol, catechol, resorcinol, hydroquinone, pyrogallol, 1-naphthol, 2-naphtol, 2,6-di-tert-butyl-4-methylphenol, ethanethiol, 1-butanethiol, 2-pentanethiol, 2-isobutanethiol, thiophenol, 1,12-dodecanedithiol, 2-naphthalenethiol, cyclohexanethiol, 1,8-octanedithiol, 1,4-benzenedithiol, and the like. Also the potassium salts of 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-isopropylidene-bis(6-cyclohexyl-p-cresol), and the like.
Potassium salts of mono- and polycarboxy acids and sulfur analogs can be employed such as the potassium salts of isovaleric acid, caprylic acid, lauric acid, stearic acid, oleic acid, linolenic acid, cyclopentane-carboxylic acid, phenylacetic acid, benzoic acid, azelaic acid, phthalic acid, 1,8,16-hexadecanetricarboxylic acid, 2-naphthoic acid, hexanedithioic acid, thiolobenzoic acid, and the like.
Examples of suitable potassium carbonates and sulfur analogs include the potassium salts of tert-butylcarbonic acid, n-hexylcarbonic acid, 3,5-dimethylhexylcarbonic acid, n-dodecylcarbonic acid, and the like.
Examples of potassium salts of secondary amines suitable for use as randomizers include the potassium salts of dimethylamine, di-n-butylamine, methyl-n-hexylamine, di(3,5-diethyloctyl)amine, diphenylamine, dibenzylamine, and the like.
Other effective low vinyl randomizing agents are the hexaalkylphosphoramides employed alone, or employed in conjunction with the above potassium compounds, particularly and preferably with the potassium alkoxides. Examples of compounds of this type include the presently preferred hexamethylphosphoramide, as well as hexaethylphosphoramide, hexa-n-propylphosphoramide, trimethyltrihexylphosphoramide, and the like.
In all references to potassium randomizers above, the equivalent sodium, cesium, or rubidium compound can be employed, though potassium compounds and particularly the potassium alkoxides are preferred for effectiveness and availability. Thus, we refer to alkali metal, other than lithium, randomizers.
Silicon halides employed in the polymerization phase in the continuous polymerization process in accordance with the process of our invention can be represented by Rn SiX4-n. The X is halogen and can be chlorine, bromine, or iodine. R is hydrogen or an alkyl group containing from 1 to 10 carbon atoms. The n is zero or an integer of 1, 2 or 3. When R is alkyl, it can be normal, secondary or tertiary, though normal alkyl groups are preferred. The value of n is preferably 0 or 1. Thus, the suitable silicon halides include silicon di-, tri-, or tetra- chloride, bromide, and iodide, methyltrichlorosilane, dichlorodimethylsilane, chlorotrimethylsilane, n-butyltribromosilane, n-decytriiodosilane, di-sec-butyldichlorosilane, t-amyltribromosilane, trichlorosilane, dibromosilane, iodosilane and the like, alone or in admixture. Any of these can be used alone, or mixtures can be employed, if desired. The presently preferred type for convenience and availability are the silicon tetrahalides, and especially preferred is silicon tetrachloride.
Polymerization preferably is carried out in the presence of a hydrocarbon diluent which can be one or more aromatic, paraffinic, or cycloparaffinic compounds, preferably such as one or more of those containing 4 to 10 carbon atoms per molecule, and which is a liquid under the conditions of the process. Examples include butane, pentane, isooctane, cyclohexane, benzene, toluene, xylene, ethylbenzene, hexane, and the like, alone or in admixture.
Polymerization temperatures can vary over a broad range, for example from about -20� C. to 150� C., although a preferred temperature range is about 30� C. to 125� C. Pressure used is sufficient to maintain substantially liquid phase conditions in the reaction zone.
The quantity of initiator employed can vary broadly, such as from about 0.2 to 5, preferably about 0.2 to 1.5, milliequivalents of active lithium per 100 grams monomer.
Employing the presently preferred potassium randomizer, a broad range can be employed such as about 0.25:1 to 100:1 atom ratio Li:K, more preferred about 1:1 to 50:1, again remembering that the "K" also can be any alkali metal other than lithium. It should be kept in mind that a silicon tetrahalide, or other silicon halide employed for purposes of gel suppression, effectively destroys an alkali metal randomizer in the process of addition, and therefore it is necessary to add an amount of such alkali metal randomizer equal to the number of milliequivalents of the silicon (tetra)halide added for gel suppression, plus the effective amount of randomizer needed to provide effective randomization of the conjugated diene with a monovinyl-substituted aromatic compound desired.
When employing an alternative randomizing additive, such as a hexaalkylphosphoramide, hydrocarbyl ether, thioether, or amine, a ratio of mols of randomizer to gram atoms of lithium in the initiator in the range of about 0.2:1 to 0.01:1, preferably about 0.1:1 to 0.01:1 is considered exemplary and suitable.
The silicon halide additive employed in the first reactor means in accordance with the process of our invention is employed in an amount sufficient and effective to substantially reduce fouling in the first reactor means. For this purpose, we consider a suitable and exemplary amount in the range of about 0.1 to 2 milliequivalents of silicon halide (based on milliequivalents of halogen) per 100 grams of total monomer, more preferred about 0.2 to 1, wherein it is considered that one halide group is considered equivalent to one lithium.
The silicon halide can be applied to the first reactor means as a solution or dispersion in a hydrocarbon diluent, such as cyclohexane, at a convenient concentration. The silicon halide alternatively can be admixed with and fed with one or other of the monomers, or with the diluent streams, or separately, as may be desired or convenient, though, of course, it should not be fed with either the randomizer or the initiator.
As the polymerization reaction mixture passes from the next to the last reactor means in the series, polymerization should be substantially complete. The process is operated in such a manner that the time for polymerization is sufficient to permit substantially complete polymerization by this stage. In the final reactor means of the series, the polymerization admixture is terminated, i.e., the polymerlithium is terminated either by a conventional noncoupling type of termination such as with water, acid, lower alcohol, or the like, or by reaction with a coupling agent. The highly rubbery polymers according to our invention are organolithium initiated conjugated diene/monovinylaromatic random copolymers prepared with the use of an effective amount of a silicon halide in the first reactor means, and with or without coupling in the last reactor for additional branching.
Coupling agents presently are used in our preferred mode because the resulting products exhibit desirable reduction in cold flow as well as other properties.
In our use of the term "coupling" as herein employed, the term is a broad generic term meaning the bringing together and joining by means of central coupling atom of coupling moiety, two or more of the living lithium-terminated polymer chains.
A wide variety of compounds suitable for such purposes can be employed. Among the suitable branching agents are the multivinylaromatic compounds, multiepoxides, multiisocyanates, multiimines, multialdehydes, multiketones, multihalides, multianhydrides, multiesters which are the esters of polyalcohols with monocarboxylic acids, and the diesters which are esters of monohydric alcohols with dicarboxylic acids, and the like.
Examples of suitable multivinylaromatic compounds include divinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, and the like. The divinylaromatic hydrocarbons are preferred, particularly divinylbenzene in either its ortho, meta, or para isomer. Commercial divinylbenzene which is a mixture of the three isomers and other compounds is quite satisfactory.
While any multiepoxide can be used, we prefer those which are liquid since they are more readily handled and form a relatively small nucleus for the radial polymer. Especially preferred among the multiepoxides are the epoxidized hydrocarbon polymers such as epoxidized liquid polybutadiene and the epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil. Other epoxy compounds such as 1,2,5,6,9,10-triepoxydecane, and the like, also can be used.
Examples of suitable multiisocyanates include benzene-1,2,4-triisocyanate, naphthalene-1,2,5,7-tetraisocyanate, and the like. Especially suitable is a commercially available product known as PAPI-1, a polyarylpolyisocyanate having an average of 3 isocyanate groups per molecule and an average molecular weight of about 380. Such a compound can be visualized as a series of isocyanate-substituted benzene rings joined through methylene linkages.
The multiimines, which are also known as multiaziridinyl compounds, preferably are those containing 3 or more aziridine rings per molecule. Examples of such compounds include the triaziridinyl phosphine oxides or sulfides such as tri(1-aziridinyl)phosphine oxide, tri(2-methyl-1-aziridinyl)phosphine oxide, tri(2-ethyl-3-decyl-1-aziridinyl)phosphine sulfide, and the like.
The multialdehydes are represented by compounds such as 1,4,7-naphthalene tricarboxyaldehyde, 1,7,9-anthracene tricarboxyaldehyde, 1,1,5-pentane tricarboxyaldehyde, and similar multialdehyde-containing aliphatic and aromatic compounds.
The multiketones can be represented by compounds such as 1,4,9,10-anthracenetetrone, 2,3-diacetonylcyclohexanone, and the like.
Examples of the multianhydrides include pyromellitic dianhydride, styrene-maleic anhydride copolymers, and the like.
Examples of the multiesters include diethyladipate, triethylcitrate, 1,3,5-tricarbethoxybenzene, and the like.
Among the multihalides, we presently prefer the silicon tetrahalides such as silicon tetrachloride, silicon tetrabromide, and silicon tetraiodide, and the trihalosilanes such as trifluorosilane, trichlorosilane, trichloroethylsilane, tribromobenzylsilane, and the like. Also preferred are the multihalogen-substituted hydrocarbons, such as 1,3,5-tri(bromomethyl)benzene, 2,5,6,9-tetrachloro-3,7-decadiene, and the like, in which the halogen is attached to a carbon atom which is alpha to an activating group such as an ether linkage, a carbonyl group, or a carbon-to-carbon double bond. Substituents inert with respect to lithium atoms in the terminally reactive polymer can also be present in the active halogen-containing compounds. Alternatively, other suitable reactive groups different from the halogen as described above can be present.
Examples of compounds containing more than one type of functional group include 1,3-dichloro-2-propanone, 2,2-dibromo-3-decanone, 3,5,5-trifluoro-4-octanone, 2,4-dibromo-3-pentanone, 1,2,4,5-diepoxy-3-pentanone, 1,2,4,5-diepoxy-3-hexanone, 1,2,11,12-diepoxy-8-pentadecanone, 1,3,18,19-diepoxy-7,14-eicosanedione, and the like.
In addition to the silicon multihalides as described hereinabove, other metal multihalides, particularly those of tin, lead, or germanium, also can be readily employed as coupling and branching agents.
Difunctional counterparts of these agents also can be employed, whereby a linear polymer rather than a branched polymer results.
Broadly, and exemplarily, a range of about 0.01 to 4.5 milliequivalents of coupling agent are employed per 100 grams of monomer, presently preferred about 0.01 to 1.5 to obtain the desired Mooney viscosity. The larger quantities tend to result in production of polymers containing terminally reactive groups or insufficient coupling. One equivalent of treating agent per equivalent of lithium is considered optimum amount for maximum branching, if this result is desired in the production line. The coupling agent can be added in hydrocarbon solution, e.g., in cyclohexane, to the polymerization admixture in the final reactor with suitable mixing for distribution and reaction.
As is commonly practiced in polymerization processes, it is preferable to add an antioxidant to the effluent from the final reactor to retard potentially deleterious effects of contact with oxygen. A typical antioxidant is 2,6-di-t-butyl-4-methylphenol, and an exemplary amount is in the range of about 0.5 to 1 part by weight per hundred parts monomers.
The reaction mixture is treated to destroy residual carbon-lithium bonds which may be present and to recover the polymer. Thus, the polymer can be precipitated and the remaining lithium moieties, if any, inactivated by the addition of such as a lower alcohol, such as isopropyl alcohols, followed by separation of the product polymer from the polymerization diluent and residue by means such as decantation, filtration, centrifugation, or steam stripping, together with removal of volatiles at reduced pressure and moderate temperature such as about 60� C.
The polymers can be compounded with a variety of ingredients including fillers, dyes, pigments, curing or crosslinking agents, softeners, reinforcing agents, and the like, in various compounding operations.
The rubbery polymers produced in accordance with the invention have utility in applications where synthetic and natural rubbers are employed, and can be manufactured or formed into a variety of finished articles, by molding, extruding, or the like. The rubbery random copolymers made in accordance with our invention have particular application as tire tread and sidewall stock.
The examples provided are intended to assist in an understanding of the invention, and are directed to those of skill in the art. Particular species employed, particular conditions, relationships, and the like, are designed to be illustrative, and not limitative of the reasonable scope of the invention and variations thereof.
The equipment employed in these runs consisted of a three-reactor train, i.e., three reactors connected in series. Lines to the first reactor provided, by pumping from respective reservoirs, styrene, butadiene, cyclohexane, a cyclohexane solution of the initiator, and a cyclohexane solution of the randomizer. These reagents have been purified, prior to use, by individually appropriate techniques known to the art. The first two reactors were maintained at 100� C. by heating the feed and by heating the reactors externally. Butadiene and styrene were blended with hot cylohexane just prior to introduction of this hot, 85�-110� C., mixture into the bottom of the first reactor via a common line. The randomizer, potassium t-amyloxide, was delivered to the first reactor through the monomer/solvent line. Silicon tetrachloride was added to the reactors through a separate line.
The first two reactors were stirred, 3-pint, round-bottomed glass flasks each jacketed by a water bath of controlled temperature, said reactors each being equipped with a cooling coil.
The third reactor was a 15 inch � 2 inch (38 cm long by 5 cm diameter) iron pipe. The bottom cap was attached to two smaller concentric pipes with polymer cement entering through the outer and silicon tetrachloride or other coupling agent through the inner pipe. These streams were mixed with a helical stirrer turned to force the cement downward. The pressure was allowed to drop to atmospheric, and the volatiles were vented off as the polymer cement was removed through a side-arm near the top of the pipe. A one-way valve on the effluent line prevented air from entering the third reactor.
Approximately 0.5 to 1 phr (part by weight per one hundred parts by weight rubber) of 2,6-di-t-butyl-4-methylphenol in isopropyl alcohol solution was added to the effluent of the third reactor. The polymer was coagulated in isopropyl alcohol, collected by decantation, and volatiles removed under reduced pressure at approximately 60� C.
The following polymerization recipe and table give the polymerization conditions and results.
______________________________________Polymerization RecipeButadiene 85 phm1Styrene 15 phmButenes and other hydrocarbons2 103 phmCyclohexane 700 phmInitiator (MCI)3 VariablePotassium t-amyloxide (KTA) VariableSilicon tetrachloride in reactor 1 VariableSilicon tetrachloride in reactor 2 VariableSilicon tetrachloride in reactor 3 VariableTemperature (Reactors 1 and 2)4 100� C.PressureReactor 1 110 psigReactor 2 105 psigReactor 3 Ambient4Average residence timeReactor 1 13 minReactor 2 13 minReactor 3 13 min______________________________________1 Parts by weight per one hundred parts by weight ofmonomer.2 Hydrocarbon Wt. %______________________________________C3 & lighter 0.04Isobutane 0.04n-Butane 0.161-Butene 39.4Isobutylene 59.2trans-2-Butene 0.29cis-2-Butene 0.15Isoprene 0.09Cyclohexane 0.46Residue 0.073 A 1,3-butadiene solubilized multilithium initiatorprepared by tumbling a mixture of 420 ml cyclohexane,0.258 mole 1,3-butadiene, 24 mmoles of mixed isomers ofdivinylbenzene and 75 mmoles n-butyllithium at 70� C.for 40 minutes followed by dilution with cyclohexane toa concentration of 0.145 as determined by hydrolysisand titration with standard acid.4 The third reactor was not heated, and the temperaturevaried through the third reactor from an estimated 40�C. to an estimated 80� C. Pressure was allowed to dropto atmospheric.
TABLE__________________________________________________________________________(Asterisk denotes continuation of preceding run with changes in feedstockas noted.)REACTOR 1 REACTOR 2 REACTOR 3 PRODUCT MCI, KTA, SiCl4, Gel1, Conv.2, SiCl4 Conv., SiCl4 Mooney3 Styrene4Run meqhm5 mhm6 meghm mm % meghm % meghm ML-4 %__________________________________________________________________________ 1 1.0 0.33 0.27 0 87 0 97 0 76.5 4.5 2* 0.95 154 --7 3 1.0 0.33 0.33 1 86 0 93 0 85 -- 4* 83 0.1 92 0 118 -- 5* 87 0.2 93 0 154 -- 6 1.2 0.37 0.27 0 89 0.13 95 0 84 9.3 7* 88 0.20 96 0 100 -- 8* 87 0.27 96 0 110 10.3 9* 86 0.33 96 0 127 --10* 87 0.40 96 0 140 10.811 1.0 0.33 0.27 film9 85 0.21 91 0 135 --12* 0.51 slip10 --13 0.67 0.67 0 2 90 100 0 47 --14* 0.93 90 --15* 85 0.19 95 0 69 --16* 0.75 153 --17 0.91 0.13 0 3 88 0 99 0 9 --18* 1.14 12 --19* 92 0.27 99 0 17 --20* 1.16 32 --__________________________________________________________________________ 1 Gel layer on interior wall of reactor. Measured as thickness in millimeters of wet, swollen gel accumulated over an 8 to 12 hour period. 2 Determined from weight percent solids in reactor effluent. 3 ASTM D-1646-63. 4 Determined by ultraviolet analysis. 5 Gram milliequivalents per one hundred grams of monomer. 6 Gram millimoles per one hundred grams of monomer. 7 Dash denotes not determined. 8 Accumulated over 5.5 hour run. 9 Film of gel observed - insufficient to measure. 10 Too high to measure.
The results given in the preceding table illustrate the usefulness of this invention in inhibiting the buildup of gel in the first reactor of a three reactor train. Inventive Runs 1 through 12 contained silicon tetrachloride in the first reactor. The gel buildup in the first reactor of Runs 1 to 12 was significantly less than that observed in comparative Runs 13 to 20.
The inventive runs also illustrate that coupling agent (silicon tetrachloride in these runs), if employed, can be added to either the second reactor or the third reactor or both reactors. However, if coupling of the polymer is desired, the inventive and comparative runs show a greater efficiency of utilization of coupling agent if at least a portion of the coupling agent is added to the second reactor.
It is also noted in runs according to the invention that styrene is incorporated into the polymer in an amount slightly less than that in the monomer charge. Consequently, in order to obtain a polymer of specific composition, it may be desirable to enrich the monomer charge slightly in styrene.
The disclosure, including data, illustrate the value and effectiveness of our invention. The examples, the knowledge and background of the field of the invention, and general principles of chemistry and other applicable sciences have formed the bases from which the broad descriptions of the invention including the ranges of conditions and generic ranges of operant components have been developed, which have formed the bases for our claims here appended.
|Cited Patent
|Filing date
|Publication date
|Nov 14, 1961
|Aug 3, 1965
|Phillips Petroleum Co
|Continuous process for the preparation of block copolymers
|Oct 24, 1960
|Apr 5, 1966
|Phillips Petroleum Co
|Silicon-containing polymers
|Jul 16, 1962
|Oct 18, 1966
|Phillips Petroleum Co
|Reducing cold flow in conjugated diene polymers with a polyvinyl aromatic compound
|Aug 9, 1962
|Oct 25, 1966
|Phillips Petroleum Co
|Branched polymers prepared from monolithium-terminated polymers and compounds having at least three reactive sites
|Nov 14, 1963
|Dec 27, 1966
|Phillips Petroleum Co
|Preparation of conjugated diene polymers
|Dec 21, 1962
|Jan 10, 1967
|Phillips Petroleum Co
|Continuous process for producing block copolymers of dienes and vinyl aromatic compounds
|Apr 9, 1962
|Dec 5, 1967
|Phillips Petroleum Co
|Continuous process for producing block copolymers of dienes and vinyl aromatic hydrocarbons
|Feb 7, 1966
|Feb 11, 1969
|Exxon Research Engineering Co
|Metal-filled plastics comprising a styrene polymer and an elastomer
|Jan 11, 1965
|Apr 15, 1969
|Exxon Research Engineering Co
|Laminating varnish consisting of low viscosity,curable block copolymer
|Jul 29, 1970
|Aug 1, 1972
|Firestone Tire & Rubber Co
|Process for the polymerization of conjugated dienes
|Sep 7, 1971
|Oct 2, 1973
|Phillips Petroleum Co
|Random copolymerization of conjugated dienes with monovinyl aromatic monomers
|Dec 16, 1971
|Jan 22, 1974
|Firestone Tire & Rubber Co
|Continuous process of copolymerizing butadiene and styrene
|Title not available
|Citing Patent
|Filing date
|Publication date
|Nov 18, 1977
|Jul 17, 1979
|Sumitomo Chemical Company, Limited
|Process for production of the maleic anhydride adduct of a liquid polymer
|Aug 26, 1980
|Jan 19, 1982
|Phillips Petroleum Company
|Continuous solution polymerization process
|Oct 28, 1991
|May 18, 1993
|Shell Oil Company
|Method for preparing asymmetric radial polymers
|Feb 28, 1992
|Jun 1, 1993
|Xerox Corporation
|Toner and developer compositions with coupled liquid glass resins
|Mar 26, 1993
|Nov 23, 1993
|Fina Research, S.A.
|Process for the preparation of block copolymers
|Oct 17, 1996
|Nov 21, 2000
|China Petrochemical Corporation
|Multifunctional organic alkali metal initiator and its synthesis, anionic polymerized star polymers and their preparation
|Feb 1, 2002
|Feb 18, 2003
|Bayer Aktiengesellschaft
|Continuous process for producing elastomers
|Oct 17, 1995
|Oct 20, 1999
|Method for synthesizing star-shaped solution polymerized styrene-butadiene rubber
|Oct 17, 1995
|Feb 2, 2000
|Multi-functional group organic alkali metal initiator and synthesizing method thereof
|Jan 25, 2002
|Aug 15, 2002
|Bayer Aktiengesellschaft
|Continuous method for producing elastomers
|U.S. Classification
|526/178, 525/123, 525/385, 525/292, 526/74, 525/359.6, 526/179, 525/342, 526/180, 526/181, 526/65, 525/153, 525/386, 525/122, 525/366, 525/154, 525/289, 526/174
|International Classification
|Cooperative Classification
|European Classification


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Panda Express vs Subway
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- Epitome of good customer service 2
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- Home
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Built to replace the obsolete TBD Devastator, the TBF torpedo bomber was produced by Grumman and were licensed by Grumman and produced by General Motors, to allow Grumman to concentrate on building the F6F Hellcat.
The TBF was used primarily for anti-sub patrols, bombing missions and rocket-firing strike aircraft. Note the dorsal turret which was operated by the radio/gunner.
The first TBF's flew across the Pacific and arrived just in time for the Battle of Midway June 4, 1942. Able to sink a Japanese ship with as little as three hits, the Yamato and Musashi battleships were two of its later victims.
President George Herbert Walker Bush flew TBMs during his tour of duty in WW II.
The Avenger remained in service with the Navy until 1954. After this time the threat from new-generation deep-dive nuclear subs created a need for more specialized aircraft.
Service History
Delivered: November 24, 1942
USS Enterprise, NAS San Diego, CA, Puuene, Barbers
Point, HI and Ford Island, HI, Noema, USS Saratoga,
VF-12 Henderson Field, Guadalcanal.
Strikes on Kolombagra Island, Naura and Rabaul
Stricken: July 31, 1945
|MFG: Grumman
First Produced: 1942
Powerplant: Wright R-2600-8
Horsepower: 1,700 lbs
Prop: Hamilton C/S
Service Ceiling: 22,400 ft
Cruise: 145 mph
Top Speed: 271 mph
Range: 1,215 miles
Empty Weight: 10,080 lbs
Gross Weight: 15,905 lbs
Wing Span: 54'2"
Wing Area: 490 sq. ft
Length: 40'
Height: 16'5"
Armament: (1) .30 cal machine
gun firing through the
prop (1) .50 cal machine gun
in turret, 2,000 lbs of bombs
or 22" torpedo
Number Built: 9,839 total
2,293 Grumman, 7,546 GM
This Avenger was a MGM movie prop before it was acquired by Yanks on August 18, 1980.
During restoration of this TBF, Japanese 27 mm bullets were found in the tail.


text:
NEW: Writing the Resistance with Wendy Willis | Dec 10
Meets: Saturday Dec 10, 9am - 3pm
The election is over. So begins the epoch of us asking ourselves "what can I do?" Since we're writers, I guess the first answer is: "Write." In that spirit, we've decided to offer a pop-up workshop with poet, essayist, and lawyer, Wendy Willis. We will spend the day reading those who have written in times of political turmoil and repression and who have kept the light on for the rest of us. (Think Allende, Milosz, Szymborska.) We'll leave plenty of time to think and write and share and commiserate. Please let us know if expense is a barrier. All genres and writing experience welcome.


text:
Guest reviews
Overall Rating
8.1 Excellent
Based on 47 reviews
Good to know
"Nice building"
"Friendly service"
"Room service is perfect"
"Great reception"
data provided by TrustYou
Located just a five minutes walk from the yatra slip counter, taxi stand and the main bus stand, a budget property, Hotel Kashmir Residency provides car rental service, in house laundry service and spacious parking facility. The hotel has an air conditioned multi cuisine restaurant that serves delectable vegetarian food. It also caters to special requirements like cooking food without onions and garlic. Gujarati thali and packed lunch is also available at the restaurant. It is 55 kilometers away from the airport and railway station in Jammu. The hotel offers comfortable accommodation in 40 well furnished rooms that are appointed with a well-stocked mini bar, television and telephone.


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A 4:30A journey to the office this morning gave me lots of time to reflect, because . . . well, I was the only one on the road. Last week was a sad week for our family while attending Nicole's … Read More
Williamsburg Coffee & Tea
Custom Business Website Design + CMS + eCommerce Shopping Cart Development for Williamsburg Coffee & Tea
The beauty of working with a client like Williamsburg Coffee & Tea is that when you are tasked with designing their website, there is no shortage of fantastic artwork to use. Our client asked us to design a website that … Read More


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Asked by older at 10:23 AM on Jun. 23, 2011 in Crazy for CreditsLevel 69 (2,285,492 Credits)
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69519 Territorial, Lawrence MI, 49064
3 beds , 3 Full baths
3,512 sqft
Status: Active
Last Updated: 12/8/2016 2:17 PM
Description for 69519 Territorial Lawrence, MI 49064
New Price: Contemporary Christie Lake home, with 114' frontage. Home features a spacious kitchen that flows into an impressive great room with soaring ceiling, fieldstone fireplace and fabulous lake views. Open floor plan provides a great space for entertaining on the grand scale. The finished lower level walkout provides extra living space with a family room, game room, wet bar, study, full bath plus exercise room. The expansive deck and patio provide a perfect space for exterior living during those warm summer days. Beautifully landscaped with lush plantings, waterfall with a nice yard that opens up to the sandy beach and waterfront area. Now add 3 bedrooms, 3 baths and over 3500 SF of living space.
Lawrence Twp
Van Buren
3 Full
3,512 (approx)
Listing Information
Lawrence Twp
Softener Own
Electric, Telephone
School Information
Room Information
Living Room
Interior Features
Dishwasher, Freezer, Microwave, Range, Refrigerator
Central Air, Ceiling Fan(s)
Propane, Forced Air
Basement, Full
Insulated, Screened, Skylights
1, Gas logs
Wet Bar
Exterior / Lot Features
Detached Garage, 3 Car Garage
Deck, Patio
Lake, Dock, Waterfall, Public Roads, Acreage
Driving Directions
I-94 exit 56 south on M 51 to Paw Paw rd. Take to end and go right, North on 46th to West on 64th to Territorial. Turn left, on Territorial to sign / mailbox. Property is on a private road off of (Territorial just South of Main.)
Financial Considerations
Listing Price History
Lawrence Real Estate
Lawrence is located in Michigan. Lawrence, Michigan 49064 has a population of 1,115.
The median household income in Lawrence, Michigan 49064 is $34,265. The median household income for the surrounding county is $44,425 compared to the national median of $53,046. The median age of people living in Lawrence 49064 is 30.4 years.
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Thu, Jul. 14, 7:31 AM
- Cree (NASDAQ:CREE) +6.4% premarket after Germany chipmaker Infineon Technologies (OTCQX:IFNNF, OTCQX:IFNNY) agrees to acquire its Wolfspeed Power and RF division for $850M.
- Cree says the deal speeds its transition to a more focused LED lighting company and will use the proceeds, combined with improved free cash flow, to fund acquisitions and support additional stock buybacks.
- Cree also provides an FQ4 update, saying preliminary revenue came in at the upper end of its target range at ~$388M.
- Infineon says Wolfspeed will complement last year's acquisition of International Rectifier, a maker of low-power, energy efficient chips.
Tue, Feb. 2, 9:09 AM
- Infineon Technologies AG ADR (OTCQX:IFNNY): FQ1 EPS of €0.17.
- Revenue of €1.56B (+38.1% Y/Y).
Dec. 14, 2015, 7:49 AM
- Last week's unsolicited $21.70 bid from an unnamed suitor (OTCQX:IFNNY?) does not constitute a superior proposal to the $20 offer from ON Semiconductor (NASDAQ:ON), concludes the Fairchild (NASDAQ:FCS) board.
- The stock closed on Friday at $20.65.
Jun. 2, 2015, 11:15 AM
- Continuing its recent string of patent portfolio acquisitions, WiLAN (NASDAQ:WILN) has bought "the vast majority" of the patents owned by Infineon's (OTCPK:IFNNF) Qimonda memory unit for $33M.
- The portfolio contains over 7K patents and applications (~5K in the U.S.), and is said to cover "technologies related to DRAMs, FLASH memories, semiconductor processes, semiconductor manufacturing, lithography, packaging, semiconductor circuitry and memory interfaces."
- WiLAN CEO Jim Skippen: "This is WiLAN's most important patent acquisition to date ... It is WiLAN's belief that a significant percentage of the microchips currently being manufactured in the world today most likely are covered by claims associated with the patents ... Consequently, our team is excited about the licensing potential of the portfolio, and will begin immediate efforts to launch a major licensing campaign."
- In tandem with the purchase, WiLAN announces DRAM/NAND flash giant Samsung has licensed the Qimonda portfolio through a multi-year deal.
- Thanks to the events, WiLAN now expects Q2 revenue of more than $34M; the company previously forecast Q2 sales of "at least" $18.3M.
Oct. 13, 2014, 9:58 AM
- Pac Crest has downgraded analog/mixed-signal IC vendors Freescale (FSL -2.9%), ON Semi (ONNN -5.5%), and Silicon Labs (SLAB -3.4%) following Microchip's calendar Q3 warning. In-line with Microchip's cautious remarks, the firm cites evidence of a distributor inventory correction and weak Chinese demand.
- All three names sold off on Friday on account of Microchip, with Freescale and ON registering double-digit declines.
- Meanwhile, JPMorgan has downgraded European chipmakers STMicroelectronics (STM -3.4%) and Infineon (OTCPK:IFNNF) to Neutral. The firm is worried about the impact of German and Chinese macro trends.
Oct. 3, 2014, 4:21 AM
- In a note yesterday, BofA/ML listed the following Buy ideas:
- ABB (NYSE:ABB), CRH (NYSE:CRH), Gamesa (OTCPK:GCTAF, OTCPK:GCTAY), Hugo Boss (OTCPK:BOSSY, OTC:HUGPF), Imperial Tobacco (OTCPK:ITYBF, OTCQX:ITYBY)
- Firm also listed the following Underperform ideas:
- Daimler (OTCPK:DDAIF, OTCPK:DDAIY), Infineon (OTCPK:IFNNF, OTCQX:IFNNY)
Sep. 2, 2014, 3:48 PM
- Home Depot (HD -2.4%) confirms it's looking into "unusual activity" as it works with law enforcement officials in relation to a possible loss of customer credit card and debit card information.
- Early reports indicate the breach occurred in late April and could involve over 2K Home Depot stores.
- Shares of Home Depot have recouped a bit from their initial slide after the breach report broke. Some retail analysts called the peeling off of $3.5B in market cap somewhat overdone.
- What to watch: If the breach is as large as some banks are reporting, an increased push by the industry toward the adoption of smart card technology could be on the way.
- Related EMV stocks: PAY, NCR, MA, V, OTCQX:IFNNY, NXPI,
Aug. 27, 2014, 11:52 AM
- Credit Suisse has started STMicroelectronics (STM -1%) at Underperform, and European chip peer Infineon (OTCPK:IFNNF +0.7%) at Outperform.
- Bernstein downgraded STM to Underperform a month ago, predicting 2015 revenue growth will be 300 bps below consensus. Shares go for only 0.9x 2015E sales.
- Infineon has rallied since announcing last week it's buying International Rectifier for $3B.
Aug. 20, 2014, 12:18 PM
- Infineon (OTCPK:IFNNF) is paying $40/share, or $3B, in cash to acquire International Rectifier (NYSE:IRF). The price represents a 51% premium to Tuesday's close, and is well above the ~$2B reported by Bloomberg.
- Infineon is paying ~$2.4B net of cash for the analog chipmaker. The deal will be financed with a mixture of existing cash and credit facilities, and is expected to close in late 2014 or early 2015.
- The companies declare IRF's gallium nitride (GaN) power management discrete components and ICs complement Infineon's own GaN offerings, and (echoing arguments made for recent chip deals) that the combined company will benefit from greater R&D scale and manufacturing/operational synergies.
- IRF is now up 47.4% to $39.16. The company has posted its FQ4 report in tandem with the Infineon announcement.
Aug. 20, 2014, 10:15 AM
- Bloomberg reports Infineon (OTCPK:IFNNF) "nearing an agreement to acquire a U.S.- based semiconductor company for about $2 billion," and that a deal could be announced as soon as today.
- No word on whom Infineon is looking to buy. Bloomberg notes it reported last month analog/mixed-signal chipmakers Fairchild (FCS +5.6%), Power Integrations (POWI +11.3%), and Semtech (SMTC +8%) are considered M&A targets, as the chip industry continues to consolidate.
- Shares of all three companies are up sharply, as are those of peers International Rectifier (IRF +5.8%) and Intersil (ISIL +4.4%). FCS and IRF are currently worth $2B; POWI is worth $1.9B; ISIL is worth $1.8B; and SMTC is worth $1.7B.
- "[Infineon] would like to build a stronger presence in power management," says Liberum Capital's Janardan Menon. He adds the market has "high barriers to entry and strong growth prospects," a fact that also hasn't been lost on Texas Instruments and other industry players.
Jun. 14, 2013, 1:57 PM
Jun. 26, 2012, 11:52 AM
Infineon (IFNNY.PK) provides the latest evidence the chip industry's recovery from its inventory correction is losing momentum (I, II, III): the company warns it expects June quarter revenue to be down slightly Q/Q, compared with prior guidance of flat sales. The warning led Infineon shares to fall 13.4% on the Frankfurt exchange, and could also be pressuring shares of rival Euro chipmaker STMicroelectronics (STM -4.9%).| Jun. 26, 2012, 11:52 AM
Jan. 28, 2011, 3:58 PM
Chipmaker PMC-Sierra (PMCS) tumbles -12.9% after failing to meet Q4 profit expectations and offering a disappointing Q1 revenue forecast. PMC's woes may be having a ripple effect on other chipmakers, such as LSI Corp. (LSI -1.4%), Broadcom (BRCM -4%), and Qualcomm (QCOM -2%).| Jan. 28, 2011, 3:58 PM | 1 Comment
Jan. 18, 2011, 2:56 PM
Semiconductor capital equipment supplier ASM Intl. (ASMI +2.6%) hits a new 52-week high, exceeding its prior $39.47/share peak. Given ASMI's surge, Goldman Sachs downgrades it to Sell, noting 2011 will be a peak year for spending on semiconductor manufacturing and assembly gear.| Jan. 18, 2011, 2:56 PM
Jan. 18, 2011, 2:32 PMARM Holdings (ARMH) isn't the only European semiconductor firm looking strong. The market is boosting lithography equipment maker ASML Holding (ASML -2.1%), too. Other companies on the upswing include Dialog Semiconductor (DLGNF.PK), Infineon Technologies (IFNNY.PK), and STMicroelectronics (STM +3.3%). | Jan. 18, 2011, 2:32 PM | 1 Comment
Nov. 16, 2010, 10:11 AMInfineon (IFNNY.PK) bucks today's downward trend in tech, rising 6.6% after declaring its first dividend in a decade and posting strong Q4 earnings. | Nov. 16, 2010, 10:11 AM


text:
Magnifico, screwed Komentarze (0)
27. grudnia 2009 20:07:00
27. grudnia 2009 20:07:00
Ebling Mis was there, head bent down over the eyepieces of the projector, motionless, a frozen, questing body. Near him sat Magnifico, screwed up into a chair, eyes sharp and watching—a bundle of slatty limbs with a nose emphasizing his scrawny face. Bayta said softly, "Magnifico—" Magnifico scrambled to his feet. His voice was an eager whisper.
erayasmin : :


text:
Home » Business Services » Everything Else » Fishing Lodges Zambia » Ad ID: 4687
Fishing Lodges Zambia
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Dec 09, 2016
Province: Gauteng
Find fantastic and affordable fishing lodges in Zambia along with all features. Sekoma provide you river side luxury lodge for your great accommodation. They have lots of activity to enjoy your vacation and family trip such as Fishing, Bird Watching and Game Viewing etc.
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Source: Enn Loit
Heimtali is a few kilometres from Viljandi; here, a culture enthusiast finds a local history museum, Heimtali manor and distillery, and an old circular stable that has been converted into a unique sports hall.
When travelling towards Loodi, make sure to visit the site of an ancient stronghold and spring in Sinialliku, as well as use a hiking trail that begins behind Loodi manor and takes you to Loodi Põrgu aka Loodi Hell – a large red sandstone outcrop. At the beginning of the trail, you find a small artificial lake and a recreation area.
In the vicinity, you find Kaasiku farm's flower garden with a lace and museum room, open only upon advance notice.
When you continue towards Paistu, you can enjoy various activities at Viljandimaa sports and leisure centre.
Ruins of the Viljandi Order Castle
Tasuja puiestee 6, Viljandi 71011
Starting point
Heimtali Museum of Domestic Life
Museums & Galleries
Heimtali küla, Viljandi vald, Viljandi maakond 71102
Heimtali Distillery
Castles & Manors
Heimtali küla, Viljandi vald, Viljandi maakond
Spring Siniallikas
Nature Sites
Loodi bussipeatus Õisu metskond 124, Sinialliku küla, Viljandi vald, Viljandi maakond 71105
Loodi nature park and sand denudation
Nature Sites
Loodi bussipeatus Piimapunkt, Loodi küla, Viljandi vald, Viljandi maakond 69603
Kaasiku farm gardens, nature trail & museum
Parks & Gardens
Loodi küla, Viljandi vald, Viljandi maakond 69603
Sultsi küla
|Further information


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What does À®š.À®®.À®‰ stand for?
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We have found 4 4 bedroom properties for sale in Shadwell, E1.
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4 bedroom house for sale
Built in 1824 and fantastically located moments from the River Thames, this unique four bedroom house includes two generously sized bathrooms, a conservatory, a large reception room and wonderful gardens. Freehold. Read more.
4 bedroom apartment for sale
Ideally located within a secure gated development, this spacious four bedroom duplex flat boasts large reception room, a modern kitchen, two balconies and four generously sized bedrooms. Leasehold. Read more.
4 bedroom flat for sale
Situated on the residential Cable Street, this charming renovated pub benefits from bright and spacious interiors with high ceilings and high-quality wood flooring. Leasehold. Read more.
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Spotlight Article:
Selling Thermostats that Save Customers Energy and Money
When you think of industries offering the latest technology, computer software, social media, and cell phone companies may come to mind first. But when I reflect back on my 27 years in the residential HVACR industry, ...
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Researchers Approach Builders on Duct Location
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It is common practice in California to put ducts outside the conditioned space, in attics and crawlspaces. These duct systems are typically 50%-70% efficient due mostly to air leakage and heat transfer losses, while sealed conditioned-space duct installations have efficiencies over 90%. O [continue reading]
Air Sealing in Occupied Homes
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There are few areas of residential construction that are so commonly misunderstood as air movement within and through houses. [continue reading]
Oh, How I Wish You Could Have Seen ISH!
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If you've ever pulled into a gas station in Europe, you know these folks are serious about energy conservation. [continue reading]
Air Conditioner Shading Shows Minimal Savings
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A study by the Florida Solar Energy Center (FSEC) on the effects of shading outdoor air conditioner condensers indicates that energy savings benefits are modest at best--less than 5%. [continue reading]
Carbon Monoxide from Ovens: A Serious IAQ Problem
archive CONTENT
Traditionally, few people have considered gas ovens to be a major source of carbon monoxide (CO), even though all their exhaust products are often vented directly into the indoor air of a residence. Yet unvented space heaters with a similar output of combustion gases have been banned in many states because of indoor air quality (IAQ) dangers inherent in their use. [continue reading]
The Best Boiler and Water Heating Retrofits
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When the Minneapolis Energy Office (now the Center for Energy and Environment) first addressed the issue of improving energy efficiency in multifamily buildings in 1981, the task was a little daunting. [continue reading]
Jim Gunshinan
Healthy Homes and a Healthy Bottom Line
There has been a lot of interest of late in the weatherization and broader home performance community in putting a ...
Rob Nicely
Side Benefits of a Passive House
There's no doubt that building to Passive House standards results in energy consumption that's about 70 to 80 ...


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(Builders Direct Online .com)
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Get Cash Back on Your New Home in Shiloh Commons, Lancaster SC If you plan on buying a new home in Shiloh Commons or anywhere else in Lancaster SC, WHY NOT get an additional 1% Cash Rebate on your Purchase? ... I'll show you how! View Lancaster Homes for Sale Print Your Cash Back Coupon and SAVE ...
Lancaster, SC Real Estate Professionals


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This busy 6 surgery, mixed practice in Luton are looking to recruit a dental associate to start as soon as possible
Hours: 8am to 2pm (week 1) and 2pm to 8pm (week 2) rotating shift pattern
Working Saturday and Sunday
• Digital Radiography
• Fully computerised
• Premium materials and rotary endo
• Full managerial/administrative support
• Close to M1 and commutable from London
This practice is open 8am-8pm.
1500 plus UDA's
This practice is brand new, fully equipped and computerised using Software of Excellence.
Candidates must have an active performer number and 2 years post VT experience.
For more information contact Nahila and quote reference DEN-37060
Call us on 01332 609318
Email us at [email protected]
View more information at http://www.medicruit.co.uk/positiondetails.aspx?id=37060
Dental Associate – Bedfordshire
Posted by Medicruit on 21 June 2016
Reference: 37060Apply Back


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ERIC Number: ED195140
Record Type: RIE
Publication Date: 1979
Pages: 18
Abstractor: N/A
Reference Count: 0
Getting Around. Unit 1: Reading Maps and Asking Directions. Student Lesson #5. English for Living.
New York State Education Dept., Albany. Bureau of Bilingual Education.
To assist the youthful learner of English as a second language in dealing with finding his way around, a series of dialogs, comprehension questions, readings, and points of discussion are presented. The text is illustrated with maps. (JB)
Publication Type: Guides - Classroom - Learner
Education Level: N/A
Audience: N/A
Language: English
Sponsor: Office of Bilingual Education and Minority Languages Affairs (ED), Washington, DC.
Authoring Institution: New York State Education Dept., Albany. Bureau of Bilingual Education.
Identifiers: Directions; Survival Competencies
Note: For related documents, see FL 011 955-975.


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Based on the original Mediterranean diet, The French Women's Diet will show you how to eat healthily and divinely and lose weight—with American grocery stores in mind. It's a step-by-step guide to show you how you don't have to give up bread, wine or chocolate to stay slim!
French Women's Diet
New Updated 2015 Edition
Susan Kiernan-Lewis
Copyright 2011 by San Marco Press. All rights reserved.
Published by San Marco Press at Smashwords
Smashwords Edition, License Notes
This ebook is licensed for your personal enjoyment only. This ebook may not be re-sold or given away to other people. If you would like to share this book with another person, please purchase an additional copy for each recipient. If you're reading this book and did not purchase it, or it was not purchased for your use only, then please return to Smashwords.com and purchase your own copy. Thank you for respecting the hard work of this author.


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Because Knetbooks knows college students. Our rental program is designed to save you time and money. Whether you need a textbook for a semester, quarter or even a summer session, we have an option for you. Simply select a rental period, enter your information and your book will be on its way!
The story behind the stunning, extreme weapons we see in the animal world--teeth and horns and claws--and what they can tell us about the way humans develop and use arms and other weapons
In Animal Weapons, Doug Emlen takes us outside the lab and deep into the forests and jungles where he's been studying animal weapons in nature for years, to explain the processes behind the most intriguing and curious examples of extreme animal weaponsfish with mouths larger than their bodies and bugs whose heads are so packed with muscle they don't have room for eyes. As singular and strange as some of the weapons we encounter on these pages are, we learn that similar factors set their evolution in motion. Emlen uses these patterns to draw parallels to the way we humans develop and employ our own weapons, and have since battle began. He looks at everything from our armor and camouflage to the evolution of the rifle and the structures human populations have built across different regions and eras to protect their homes and communities. With stunning black and white drawings and gorgeous color illustrations of these concepts at work, Animal Weapons brings us the complete story of how weapons reach their most outsized, dramatic potential, and what the results we witness in the animal world can tell us about our own relationship with weapons of all kinds.


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Upgrade your ride with the ultimate car stereos, amps, speakers, subwoofers and GPS.
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Pioneer provides high quality computer accessories. Products from SATA and USB Blu-ray and DVD burners, to on-ear or earbud headphones and USB powered computer speakers.
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Pioneer Home USA offers the latest technology in AV Receivers, Blu-ray Disc Players, High-Resolution Audio Players, and Speakers.
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Pioneer DJ Products are the standard for Professional DJs including Digital Turntables, DVD Turntables, CD Players, Mixers, and Headphones.
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Suggested Price: $100.00
Big sound, small package: only 6-1/8" wide, the compact GM-3000T offers 1-, 2-, and 3-channel operation (including a bridged 100W x 1 into 4 ohms), plus a Hi-Volt Input Level Control (400mV ~ 6.5V) and a Selectable Low-Pass Filter for added control and flexibility. It features a pulse width modulation (PWM) circuit that efficiently outputs only the lower frequencies — perfect for powering a sub. Oversized screw-type power/ground terminals and RCA inputs are provided, and the 2-channel speaker level input offers added control.


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Michelle Jenneke
Millionaire businessman Ehsan Abdulaziz, 46, was charged with raping an 18-year old woman at his London flat.
The Saudi property developer said he had already had sex with the young woman's 24-year-old friend and it was possible his penis may have been poking out of his underwear when he tripped and fell on her. .
The jury acquitted Abdulaziz after just 30 minutes of deliberations. [story]
Labels: I am not making this up
Tail Pipes
Posted by Rodger the Real King of France | 12/17/2015 07:05:00 AM | PERMALINK
Abdulaziz? Why am I not surprised at the name? His defense to any rape charge is that he was merely emulating his prophet, Mohammed, the perfect man (piss be upon him), who was not only a rapist but a pedophile, murderer and thief.
Ah the classic Seinfeld defense; "I'm tellin ya Doc, it was a one in a million chance". Jackie Chiles could get this guy off, no problem. -Anymouse
You know, having looked at the basic tenets of Islam (which I choose to pronounce EYE-SLAM), the Church of Scientology is looking more mainstream by comparison...
At least he was not cutting heads off, as did muhammad to a 1,000 people in Medina(look up the Banu Qureiza massacre)Mud slimes are duty bound to emulate their bestial prophet and worship their satanic idol, Allah...
Way back in time I took a history course about the development of cities. The professor who taught the course had visited Egypt and said that the current farmers were nothing like the ancient Egyptians. He said the story was some were hired for a dig and they were too dumb to figure out how to use a wheel barrel. Three of them loaded it up then three of them picked the barrel up and moved it. While the Pharaohs were inbred there were enough overthrows to compensate. Also they drank a lot of beer and avoided a lot of the diseases of the era. Now you have diseased cousin marrying Arabs using up the oxygen.
All of the Pharaohs after Alexander the Great (Ptolemy) were Greeks. I laugh when I hear people try to make Cleopatra into a black chick. Her grandpappy was Macedonian. I once sat on a plane beside a ship captain that ran a boat out of Egypt in the oil industry. He was telling me of the incredible stupidity of those folks. He said, "If they build those pyramids all by themselves, they are upside down". -Anymouse
A field engineer friend of mine was assigned a project in a factory in Egypt about 35 years ago. The factory toilets were the kind with a hole in the floor with footpads, a bucket of water and a broom.
Out of respect for him, the factory owners brought in a sit-down American style flush toilet. Friend told me that before it could be connected, the local factory workers stood on the seat and crapped in the tank until it overflowed.
They threw it out.
People who've never traveled other than on touristy guided trips have no idea how different, backward and unadaptable to new ideas some cultures can be. We need a universal draft just to mature and discipline our kids, and broaden their horizons.
Lt. Col. Gen. Tailgunner dick
toadold: Have you ever watched "'Til Death" with Brad Garrett and Joely Fisher? In one episode, Eddie and Joy argue because Joy says "wheel barrel" instead of "wheelbarrow".
We meant to type Londonstan.
Michael Savage said that soccer hooligans might be the only thing that could save the UK. We'd sure like to see a bunch of 'em go Buford Pusser on these "no-go" areas...
Ann Hedonia & Sam Paku
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