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By Rick Warren
— May 21, 2014
"Let's see how inventive we can be in encouraging love and helping out." (Hebrews 10:24 MSG)
Long before he was a superstar, I was blessed to spend an hour or two with Bob the Tomato.
Well, actually, it was Phil Vischer, the voice of Bob the Tomato and creator of the very charming VeggieTales. During our conversation, Vischer said, "There is no happier place than the intersection of God's will and your giftedness."
Pastor Rick teaches that the way God S.H.A.P.E.s you reveals a significant portion of his will for you, and that brings you to the intersection of his will and your giftedness.
S.H.A.P.E. is an acronym Pastor Rick explains in "The Purpose Driven Life":
Ask other Christians who know you to help you determine the things you do best and how you may use your giftedness in ministry.
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Jon Walker's new book, "Breakfast with Bonhoeffer," is a message of hope for anyone longing for another chance at life as God created it to be. It is a story of God's faithfulness, even through job loss, home loss, economic uncertainty, divorce and an incurable disease. Structured like a novel, it reveals how God works through our often messy and inconsistent faith.
This devotional © Copyright 2012 Jon Walker. All rights reserved. Used by permission.
Based on Jesus' very own words in the Beatitudes, this DVD and workbook guides you through eight critical choices that every wounded believer must make in order to experience wholeness, happiness, and healing. These essential decisions will build your trust in God even when you don't understand his plans and your circumstances look hopeless.
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|Publication number
|Publication type
|Application number
|Publication date
|May 15, 2001
|Filing date
|Oct 23, 1998
|Priority date
|Feb 7, 1997
|Fee status
|Also published as
|Publication number
|Howard William Turner, Vincent John Murphy
|Original Assignee
|Exxon Mobil Chemical Patents Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (31), Non-Patent Citations (25), Referenced by (1), Classifications (15), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a divisional of U.S. patent application Ser. No. 08/798,412, filed Feb. 7, 1997, now issued as U.S. Pat. No. 5,851,945.
This invention relates to organometallic compounds comprising a Group 15 polyanionic ancillary ligand covalently bound to a Group 5 metal center, particularly those suitable for catalysis of olefin polymerization.
Coordination polymerization of olefinically unsaturated monomers is well known and has led to the great proliferation of thermoplastic compositions of matter from olefins, such as polyethylene, polypropylene, and ethylene propylene rubber. Early pioneers utilized the early transition metal compounds, particularly those of the Group 4 metals, with such activators as aluminum alkyl compounds. Later developments extended this work to bulky ancillary ligand-containing (e.g., η5-cyclopentadienyl) transition metal compounds ("metallocenes") with activators such as alkyl alumoxanes. Representative work addressing polymer molecular weight effects of substituted mono and bis metallocene compounds is described in EP-A 0 129 368 and its counterpart U.S. Pat. No. 5,324,800. Hetero-atom containing monocyclopentadienyl metallocene compounds are described in U.S. Pat. No. 5,057,475 and silicon bridged biscyclopentadienyl metallocene catalysts are described in U.S. Pat. No. 5,017,714. Recent developments have shown the effectiveness of ionic catalysts comprised of activated metallocene cations stabilized by compatible noncoordinating anions, see for example U.S. Pat. Nos. 5,278,119 and 5,384,299 and WO 92/00333. Each of which is incorporated by reference for purposes of U.S. patent practice.
Transition metal polymerization catalyst systems from Group 5-10 metals wherein the active transition metal center is in a high oxidation state and stabilized by low coordination number polyanionic ancillary ligand systems are described in U.S. Pat. No. 5,502,124 and its divisional U.S. Pat. No. 5,504,049. Suitable low coordination number polyanionic ancillary ligands include both bulky imides and carbolides. Such are said to be suitable alone or in combination with conventional monoanionic ancillary ligands, such as cyclopentadienyl derivatives. Examples 2 and 8 illustrate Group 5 metal catalyst compounds comprising, respectively, (cyclopentadienyl)vanadium(p-tolylimido)dichloride and (cyclopentadienyl)niobium(2,6-diisopropyl-phenylimido)di-methyl. Olefin polymerization catalysts from Group 5 or 6 metal imido complexes are also described in EP 0 641 804. The Group 5 metal complexes include one imido ligand and a monoanionic organic group containing a cyclopentadienyl nucleus. Example 1 illustrates the preparation of (cyclopentadienyl)vanadium(p-tolylimido)dichloride and the Tables on pages 7-9 illustrate polymerization using it. These documents are incorporated by reference for purposes of U.S. patent practice.
Effective olefin polymerization catalysts based upon vanadium alkyl complexes in which the metal center is stabilized in its highest oxidation state are elusive since there are no well established procedures for the synthesis of such compounds. Difficulties associated with the synthesis of vanadium alkyls in which the metal center is stabilized in its highest oxidation state are well documented. See for example, Buijink, J. J. Organomet. Chem 1995, 497, 161-170, Devore, D. D. J. Am. Chem. Soc., 1987, 109, 7408-7416 and other references well known to those skilled in the art.
It would therefore be desirable to provide vanadium alkyl complexes in which the vanadium metal center is stabilized in its highest oxidation state by (a) a low coordination number polyanionic ligand and (b) and suitable additional ancillary ligands.
This invention is directed to Group 5 metal compounds, preferably vanadium, suitable for activation as polymerization catalysts and characterized by comprising one polyanionic ancillary ligand and three single or multidentate uninegative ligands, excluding cyclopentadienyl ligands. The polyanionic ancillary ligand will comprise a Group 15 element covalently bound to the Group 5 metal and the uninegative ligands will comprise Group 14-16 elements as single or multidentate ligands bound to the Group 5 metal. The invention includes a polymerization process characterized by comprising contacting one or more monomers polymerizable by coordination or carbocationic polymerization under suitable polymerization conditions with these catalyst compositions.
The invention Group 5 metal compounds described above can be generically represented by the following symbols:
where M is a Group 5 metal; J is a Group 15 heteroatom ligand covalently bound to M; R is a substituted or unsubstituted aryl, hydrocarbyl or organometalloid group covalently bound to J, preferably substituted or unsubstituted aryl or alicyclic hydrocarbyl; each R′ is, independently, a uninegative ligand, e.g., substituted or unsubstituted aryl, substituted or unsubstituted linear or cyclic hydrocarbyl, silyl, hydride or substituted or unsubstituted organometalloid group, additionally any two R′ maybe joined to form a metallocycle; X is a univalent single or multidentate ancillary ligand comprising at least one Group 14-16 element covalently bound to M; and, Y is an optional covalent bridging group linking R and X, comprising at least one Group 14-16 element, n=1 when X is covalently linked to R and n=0 when X is not covalently linked to R. The term "substituted" means that one or more hydrogen atoms on the hydrocarbyl, aryl or organometalloid group is replaced by a C1-C20 hydrocarbyl radical or any of an aryl radical, a halide radical, a phosphido radical, an alkoxide or aryloxide radical (preferably having from one twenty carbon atoms), or any other radical containing a Lewis acidic or basic functionality.
The Group 5 metal compounds of the invention having one polyanionic ancillary ligand and three univalent single or multidentate ligands can be represented by the figures below:
wherein each of the labeled substituents are as defined above. Suitable single dentate ligands X include those in the group consisting of aryloxides or alkoxides [—OR1], siloxides [—OSiR1 3], thiols [—SR1], amides [—NR1 2], and phosphides [—PR1 2], where R1 can be any member within the group defined above for R′. Suitable multidentate ligands are represented by the bidentate carboxylates [—O2CR1], carboxythiolates [—S2CR1], triflates [—O3SR1], acetylacetates [η2—R1COCR1COR1], amidates [η2—R1NCR1NR1], Group 15 or 16 ortho-substituted pyridines (illustration (a)), Group 15 or 16 substituted hydrocarbyls (illustration (b)), Group 15 or 16 substituted aryls (illustration (c)),
where x=0-6, each x is selected independently, and E is independently a Group 15 element (in which case z may be 1 or 2) or a Group 16 element (in which case z may be 0 or 1).
In addition, multidentate ligands such as shown in illustration (d) may be used
Representative (1) and (2) compounds include the following.
Representative (2) compounds include the following.
wherein E is either a Group 15 element (in which case z=1) or a Group 16 element (in which case z=0); x, R′ is defined as above.
The catalyst compounds of the invention may be prepared in high yields using the following techniques. For vanadium, for example, the synthesis can begin with a reaction between vanadium oxytrichloride and a suitable organic molecule such as an isocyanate, an amine, or an alkali metal salt of an amine (See Scheme 1).
Further chemical modifications can be made through ligand exchange reactions such as metathesis. (See Scheme 2).
For instance, treatment of an arylimido-group (V) trialkyl complex with one equivalent of a protic reagent such as an amine or an alcohol, leads to elimination of one equivalent of alkane along with ligation of an amido group to form compounds of the invention. Alternatively the compounds of the invention may be prepared by initial substitution of a single chloride ligand from an arylimido-group (V) metal trichloride by reaction with, for example, an alkali metal salt of a alcohol, leading to the formation of an arylimido-group (V) metal (alkoxy)dichloride. Alkylation of the arylimido-group (V) (alkoxy)dichloride leads to formation of the compounds of the invention. A previous attempt to prepare compounds of these types has involved direct addition of alkylating agents to (tolylimido)vanadium (V) trichloride. This reaction led to the formation of (tolylimido)vanadium (V) (bis-methyltrimethylsilyl)chloride, see for example: Devore, D. D., J. Am. Chem. Soc., 1987, 109, 7408-7416. The methods described above for the preparation of the compounds of the invention offer greater versatility and control for steric and electronic variations around the metal center.
In addition, the use of (a) a low coordination number polyanionic ligand and (b) and an additional ancillary ligand which can donate lone pair π-electrons to the vanadium metal center (see representative examples of formula (2)) leads to enhanced stability thereby enabling the formation of vanadium alkyl complexes in which the vanadium metal center is stabilized in its highest oxidation state. This unexpected finding is corroborated by (1) the paucity of vanadium alkyl complexes in which the vanadium metal center is stabilized in its highest oxidation state and (2) reports confirming the instability of vanadium (V) alkyl complexes which do not possess the ancillary ligand arrangements of the compounds of the invention. For example, tert-butylimido-cyclopentadienyl vanadium dimethyl is reported to be thermally unstable, decomposing within minutes at room temperature. See Preuss, F. Z. Naturforsch 1990, 45b, 191-198.
Further details may be found in Progress in Inorganic Chemistry, Volume 42, 1994, 239-482, and other references readily available to those skilled in the art.
The Group 5 metal compounds according to the invention may be activated for polymerization catalysis in any manner sufficient to allow coordination or cationic polymerization. This can be achieved for coordination polymerization when one ligand can be abstracted and another will either allow insertion of the unsaturated monomers or will be similarly abstractable for replacement with a group that allows insertion of the unsaturated monomer, e.g., alkyl, silyl, or hydride. The traditional activators of coordination polymerization art are suitable, those typically include Lewis acids such as Ziegler organometallic cocatalysts and alumoxane compounds, and ionizing, anion precursor compounds that abstract one so as to ionize the Group 5 metal center into a cation and provide a counter-balancing noncoordinating anion.
The Ziegler cocatalyst will typically be a organometallic compound of a metal of Groups 1, 2, 12 or 13 of the Periodic table of elements. Preferred are organoaluminum compounds selected from the group consisting of aluminum alkyl, aluminum alkyl halide and aluminum halide. These can be represented by the formulae:
wherein R2 is independently a hydride or C1 to C10 hydrocarbyl radicals including aliphatic, alicyclic or aromatic hydrocarbon radicals, X is a halogen and s is an integer from 0 to 3; and,
Al2R2 3X3, which are hydrocarbylaluminum sesquihalides.
Examples include triethylaluminum, triisobutyl-aluminum, diethyl aluminumchloride, Al2Et3Cl3 and Al2(i-Bu)3Cl3.
Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly for the invention metal compounds comprising halide ligands. The alumoxane component useful as catalyst activator typically is an oligomeric aluminum compound represented by the general formula (R—Al—O)n, which is a cyclic compound, or R(R—Al—O)nAlR2, which is a linear compound. In the general alumoxane formula R is independently a C1 to C10 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and "n" is an integer from 1 to about 50. Most preferably, R is methyl and "n" is at least 4. Alumoxanes can be prepared by various procedures known in the art. For example, an aluminum alkyl may be treated with water dissolved in an inert organic solvent, or it may be contacted with a hydrated salt, such as hydrated copper sulfate suspended in an inert organic solvent, to yield an alumoxane. Generally, however prepared, the reaction of an aluminum alkyl with a limited amount of water yields a mixture of the linear and cyclic species of the alumoxane. Methylalumoxane and modified methylalumoxanes are preferred. For further descriptions see, U.S. Pat. Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 A1, EP 0 279 586 B1, EP 0 516 476 A, EP 0 594 218 A1 and WO 94/10180, each being incorporated by reference for purposes of U.S. patent practice.
When the activator is an alumoxane, the preferred transition metal compound to activator molar ratio is from 1:2000 to 10:1, more preferably from about 1:500 to 10:1, even more preferably from about 1:250 to 1:1 and most preferably from about 1:100 to 1:1.
The term "noncoordinating anion" is recognized to mean an anion which either does not coordinate to the metal cation or which is only weakly coordinated to it thereby remaining sufficiently labile to be displaced by a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer.
Descriptions of ionic catalysts, those comprising a transition metal cation and a noncoordinating anion, suitable for coordination polymerization appear in the early work in U.S. Pat. Nos. 5,064,802, 5,132,380, 5,198,401, 5,278,119, 5,321,106, 5,347,024, 5,408,017, 5,599,671, and international publications WO 92/00333 and WO 93/14132. These teach a preferred method of preparation wherein metallocenes are protonated by noncoordinating anion precursors such that an alkyl/hydride group is abstracted by protonation from a transition metal to make it both cationic and charge-balanced by the noncoordinating anion. Since the abstraction and insertion ligands of such metallocenes also may be ligands of the Group 5 metal compounds of the invention, similar methods of preparation as active polymerization catalyst components may be followed.
The use of ionizing ionic compounds not containing an active proton but capable of producing both the active Group 5 metal cation and an noncoordinating anion is also useful. See, EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No. 5,387,568 for instructive ionic compounds. Reactive cations of the ionizing ionic compounds, other than the Bronsted acids, include ferrocenium, silver, tropylium, triphenylcarbenium and triethylsilylium, or alkali metal or alkaline earth metal cations such as sodium, magnesium or lithium cations. A further class of noncoordinating anion precursors suitable in accordance with this invention are hydrated salts comprising the alkali metal or alkaline earth metal cations and a non-coordinating anion as described above. The hydrated salts can be prepared by reaction of the metal cation-noncoordinating anion salt with water, for example, by hydrolysis of the commercially available or readily synthesized LiB(pfp)4 which yields [Li.xH2O] [B(pfp)4], where (pfp) is pentafluorophenyl or perfluorophenyl.
Any metal or metalloid capable of forming a coordination complex which is resistant to degradation by water (or other Bronsted or Lewis Acids) may be used or contained in the noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold, platinum and the like. Suitable metalloids include, but are not limited to, boron, phosphorus, silicon and the like. The description of noncoordinating anions and precursors thereto of the documents of the foregoing paragraphs are incorporated by reference for purposes of U.S. patent practice.
An additional method of making the active polymerization catalysts of this invention uses ionizing anion pre-cursors which are initially neutral Lewis acids but form a Group 5 metal cation and the noncoordinating anion upon ionizing reaction with the invention compounds, for example tris(pentafluorophenyl)boron acts to abstract a hydrocarbyl, hydride or silyl ligand to yield a Group 5 metal cation and stabilizing noncoordinating anion, see EP-A-0 427 697 and EP-A-0 520 732 for illustration utilizing Group 4 metallocene compounds. See also the methods and compounds of EP-A-0 495 375. The description of noncoordinating anions and precursors thereto of these documents are similarly incorporated by reference for purposes of U.S. patent practice.
When the cation portion of an ionic noncoordinating anion precursor is a Bronsted acid such as protons or protonated Lewis bases (excluding water), or a reducible Lewis acid such as ferrocenium or silver cations, or alkaline metal or alkaline earth metal cations such as those of sodium, magnesium or lithium cations, the transition metal to activator molar ratio may be any ratio, but preferably from about 10:1 to 1:10, more preferably from about 5:1 to 1:5, even more preferably from about 2:1 to 1:2 and most preferably from about 1.2:1 to 1:1.2 with the ratio of about 1:1 being the most preferred.
Thus suitable active catalyst complexes for coordination polymerization can be prepared by activation with the traditional metallocene activators, typically the alkylaluminum halides, alkylalumoxanes and ionizing boron or aluminum compounds known in the art. The active catalysts thus are catalytically active components comprising complexes derived from the Group 5 metal compounds containing the ancillary ligands according to the invention, and aluminum alkyls, alumoxanes or noncoordinating anions. The carbocationic catalyst complexes according to the invention will be those prepared with the ionizing noncoordinating anion precursor compounds.
The catalyst complexes of the invention are useful in polymerization of unsaturated monomers conventionally known to be polymerizable under either coordination polymerization conditions or cationic polymerization conditions using metallocenes. Such conditions are well known and include solution polymerization, slurry polymerization, and low, medium and high pressure gas-phase polymerization. The catalyst of the invention may be supported and as such will be particularly useful in the known operating modes employing fixed-bed, moving-bed, fluid-bed, or slurry processes conducted in single, series or parallel reactors.
When using the catalysts of the invention, particularly when immobilized on a support, the total catalyst system will generally additionally comprise one or more scavenging compounds. The term "scavenging compounds" as used in this application and its claims is meant to include those compounds effective for removing polar impurities from the reaction environment. Impurities can be inadvertently introduced with any of the polymerization reaction components, particularly with solvent, monomer and catalyst feed, and adversely affect catalyst activity and stability. It can result in decreasing or even elimination of catalytic activity, particularly when ionizing anion pre-cursors activate the catalyst system. The polar impurities, or catalyst poisons include water, oxygen, metal impurities, etc. Preferably steps are taken before provision of such into the reaction vessel, for example by chemical treatment or careful separation techniques after or during the synthesis or preparation of the various components, but some minor amounts of scavenging compound will still normally be used in the polymerization process itself.
Typically the scavenging compound will be an organometallic compound such as the Group-13 organometallic compounds of U.S. Pat. Nos. 5,153,157, 5,241,025 and WO-A-35 91/09882, WO-A-94/03506, WO-A-93/14132, and that of WO 95/07941. Exemplary compounds include triethyl aluminum, triethyl borane, triisobutyl aluminum, methylalumoxane, isobutyl aluminumoxane, and n-octyl aluminum. Those scavenging compounds having bulky or C6-C20 linear hydrocarbyl substituents covalently bound to the metal or metalloid center being preferred to minimize adverse interaction with the active catalyst. Examples include triethylaluminum, but more preferably, bulky compounds such as triisobutylaluminum, trisoprenylaluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n-octylaluminum, or tri-n-dodecylaluminum. When alumoxane is used as activator, any excess over the amount needed to activate the catalysts present will act as scavenger compounds and additional scavenging compounds may not be necessary. Alumoxanes also may be used in scavenging amounts with other means of activation, e.g., methylalumoxane and trisobutylaluminoxane. The amount of scavenging agent to be used with Group 5 catalyst compounds of the inventions is minimized during polymerization reactions to that amount effective to enhance activity and avoided altogether if the feeds can be sufficiently free of adventitious impurities.
The catalyst according to the invention may be supported for use in gas phase, bulk, slurry polymerization processes, or otherwise as needed. Numerous methods of support are known in the art for copolymerization processes for olefins, particularly for catalysts activated by alumoxanes, any is suitable for the invention process in its broadest scope. See, for example, U.S. Pat. Nos. 5,057,475 and 5,227,440. An example of supported ionic catalysts appears in WO 94/03056. A particularly effective method is that described in co-pending application U.S. Ser. No. 08/474,948 filed Jun. 7, 1995, now U.S. Pat. No. 5,643,847, and WO 96/04319. A bulk, or slurry, process utilizing supported, invention Group 5 metal compounds activated with alumoxane co-catalysts can be utilized as described for ethylene-propylene rubber in U.S. Pat. Nos. 5,001,205 and 5,229,478, these processes will additionally be suitable with the catalyst systems of this application. Both inorganic oxide and polymeric supports may be utilized in accordance with the knowledge in the field. See U.S. Pat. Nos. 5,422,325, 5,427,991, 5,498,582, 5,466,649, copending U.S. patent applications 08/265,532 and 08/265,533, both filed Jun. 24, 1994, both abandoned, and international publications WO 93/11172 and WO 94/07928. Each of the foregoing documents is incorporated by reference for purposes of U.S. patent practice.
In preferred embodiments of the process for this invention, the catalyst system is employed in liquid phase (solution, slurry, suspension, bulk phase or combinations thereof), in high pressure liquid or supercritical fluid phase, or in gas phase. Each of these processes may be employed in singular, parallel or series reactors. The liquid processes comprise contacting olefin monomers with the above described catalyst system in a suitable diluent or solvent and allowing said monomers to react for a sufficient time to produce the invention copolymers. Hydrocarbyl solvents are suitable, both aliphatic and aromatic, hexane and toluene are preferred. Halocarbon solvents, e.g., methylene chloride will additionally be suitable. Bulk and slurry processes are typically done by contacting the catalysts-with a slurry of liquid monomer, the catalyst system being supported. Gas phase processes typically use a supported catalyst and are conducted in any manner known to be suitable for ethylene homopolymers or copolymers prepared by coordination polymerization. Illustrative examples may be found in U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,382,638, 5,352,749, 5,436,304, 5,453,471, and 5,463,999, and WO 95/07942. Each is incorporated by reference for purposes of U.S. patent practice.
The use of alkyl halide promoters, such as hexachlorocyclopentadiene, ethyltrichloroacetate or benzoyl chloride with Ziegler vanadium catalysts to enhance performance (i.e., increase yields of polyethylene) is well known and may be used with the catalysts of this invention. See, for example, U.S. Pat. Nos. 4,232,140, 4,508,842, and EP-0 44 119 and EP-0 196 830, the descriptions of which are incorporated by reference for purposes of U.S. patent practice.
Generally speaking the polymerization reaction temperature can vary from about −50� C. to about 250� C. Preferably the reaction temperature conditions will be from −20� C. to 220�, more preferably below 200� C. The pressure can vary from about 1 mm Hg to 2500 bar, preferably from 0.1 bar to 1600 bar, most preferably from 1.0 to 500 bar. Where lower molecular weight copolymers, e.g., Mn<10,000, are sought it will be suitable to conduct the reaction processes at temperatures above about 0� C. and pressures under 500 bar. The multiboron activators of U.S. Pat. No. 5,278,119 can additionally be employed to facilitate the preparation of the low molecular weight copolymers of the invention.
Linear polyethylene, including high and ultra-high molecular weight polyethylenes, including both homo- and copolymers with other alpha-olefin monomers, alpha-olefinic and/or non-conjugated diolefins, for example, C3-C20 olefins, diolefins or cyclic olefins, are produced by adding ethylene, and optionally one or more of the other monomers, to a reaction vessel under low pressure (typically <50 bar), at a typical temperature of 20-250� C. with the invention catalyst that has been slurried with a solvent, such as heptane or toluene. Heat of polymerization is typically removed by cooling. Gas phase polymerization can be conducted, for example, in a continuous fluid bed gas-phase reactor operated at 2000-3000 kPa and 60-160� C., using hydrogen as a reaction modifier (100-200 ppm), C4-C8 comonomer feedstream (0.5-1.2 mol %), and C2 feedstream (25-35 mol %). See, U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670 and 5,405,922 and 5,462,999, which are incorporated by reference for purposes of U.S. patent practice.
Ethylene-α-olefin (including ethylene-cyclic olefin and ethylene-α-olefin-diolefin) elastomers of high molecular weight and low crystallinity can be prepared utilizing the catalysts of the invention under traditional solution polymerization processes or by introducing ethylene gas into a slurry utilizing the α-olefin or cyclic olefin or mixture thereof with other monomers, polymerizable and not, as a polymerization diluent in which the invention catalyst is suspended. Typical ethylene pressures will be between 10 and 1000 psig (69-6895 kPa) and the polymerization diluent temperature will typically be between −10-160� C. The process can be carried out in a stirred tank reactor, or more than one operated in series or parallel. See the general disclosure of U.S. Pat. No. 5,001,205 for general process conditions. See also, co-pending U.S. patent applications Ser. No. 08/426,363, filed Apr. 21, 1995, now U.S. Pat. No. 5,696,213, and Ser. No. 08/545,973 filed Oct. 20, 1995, now abandoned. All documents are incorporated by reference for description of polymerization processes, ionic activators and useful scavenging compounds.
Pre-polymerization of the supported catalyst of the invention may also be used for further control of polymer particle morphology in typical slurry or gas phase reaction processes in accordance with conventional teachings. For example such can be accomplished by pre-polymerizing a C2-C6 alpha-olefin for a limited time, for example, ethylene is contacted with the supported catalyst at a temperature of −15 to 30� C. and ethylene pressure of up to about 250 psig (1724 kPa) for 75 min. to obtain a polymeric coating on the support of polyethylene of 30,000-150,000 molecular weight. The pre-polymerized catalyst is then available for use in the polymerization processes referred to above. The use of polymeric resins as a support coating may additionally be utilized, typically by suspending a solid support in dissolved resin of such material as polystyrene with subsequent separation and drying. All documents are incorporated by reference for description of metallocene compounds, ionic activators and useful scavenging compounds.
Other olefinically unsaturated monomers besides those specifically described above may be polymerized using the catalysts according to the invention either by coordination or carbocationic polymerization, for example, styrene, alkyl-substituted styrene, ethylidene norbornene, norbornadiene, dicyclopentadiene, and other olefinically-unsaturated monomers, including other cyclic olefins, such as cyclopentene, norbornene, alkyl-substituted norbornenes, and including isobutylene, isoprene, butadiene, vinyl ethers, vinyl carbazoles, etc. Additionally, alpha-olefinic macromonomers of up to 100 mer units, or more, may also be incorporated by copolymerization.
Lubricating oil additive compositions can be prepared advantageously when low molecular weight alpha-olefin copolymers having vinyl or vinylidene terminal unsaturation are prepared with the catalysts of the invention. See the disclosures of U.S. Pat. No. 5,498,809 and international patent applications WO 93/24359, WO 94/19436 and WO 94/13715 and documents listed therein for further information as to low molecular weight alpha-olefin polymers. Each is incorporated by reference for purposes of U.S. patent practice.
In a similar manner, but utilizing higher molecular weight, (10,000<Mn<300,000) alpha-olefin/diolefin copolymer having a crystallinity low enough to permit of oil solubility (e.g., <40% crystallinity), as in copending U.S. application Ser. No. 08/426,363, filed Apr. 21, 1995, now U.S. Pat. No. 5,696,213, and Ser. No. 08/545,973, filed Oct. 20, 1995, now abandoned, multifunctional viscosity modifying lubricating oil additives can be produced. See the descriptions of lubricating oil modifiers and lubricating oil compositions in U.S. Pat. Nos. 4,749,505, 4,772,406 and WO-A-93/12148, all incorporated by reference for purposes of U.S. patent practice.
Carbocationic polymerization can be effected by use of the catalysts of the invention when converted to active cationic species by activating ionization. Such polymerization techniques are well known in the art, see Kennedy, J. P., Carbocationic Polymerization of Olefins: A Critical Inventory (John Wiley & Sons, 1975). See also, Baird, Michael C., et al, η5-C5Me5TiMe3B(C6F5)3: A Carbocationic Olefin Polymerization Initiator Masquerading as a Ziegler-Natta Catalyst, J. Am. Chem. Soc. 1994, 116, 6435-6436, for conditions under which the first row metal Ti in stable metallocene cationic form was used for carbocationic polymerization. Each is incorporated by reference for purposes of U.S. patent practice.
The catalyst compositions of the invention can be used as described above individually for coordination or carbocationic polymerization or can be mixed to prepare polymer blends with other known olefin polymerization catalyst compounds. By selection of monomers, blends of coordination catalyst compounds or blends of carbocationic catalyst compounds, or any together, polymer blends can be prepared under polymerization conditions analogous to those using individual catalyst compositions. Polymers having increased MWD for improved processing and other traditional benefits available from polymers made with mixed catalyst systems can thus be achieved.
The following examples are presented to illustrate the foregoing discussion. All parts, proportions and percentages are by weight unless otherwise indicated. Ambient temperatures were used for the polymerization examples unless otherwise noted. Although the examples may be directed to certain embodiments of the present invention, they are not to be viewed as limiting the invention in any specific respect. In these examples certain abbreviations are used to facilitate the description. These include standard chemical abbreviations for the elements and certain commonly accepted abbreviations, such as: Me=methyl, Et=ethyl, Pri=isopropyl, Bu=butyl, Ph=phenyl, and THF=tetrahydrofuran.
(a) Preparation of (2,6-Pri 2C6H3N)VCl3.THF
A solution of 25 g of VOCl3(0.14 mol) and 25 g 2,6-diisopropylphenylisocyanate (0.12 mol) in 100 ml. octane were refluxed together for 24 hours. Subsequent solvent removal under reduced pressure yielded a dark green oily solid. This solid was extracted with 50 mL of pentane, filtered and treated with approximately 20 mL of THF to produce a sandy colored precipitate. Collection by filtration yielded 33.6 g of (2,6-Pri 2C6H3N)VCl3.THF. A further 6.0 g was obtained by a second extraction of the remaining green oily solid, subsequent treatment with THF and isolation by filtration. Total yield 39.6 g (0.10 Mol), 69% based on vanadium.
(b) Preparation of (2,6-Pri 2C6H3N)V(CH2C6H5)3
A solution of (2,6-Pri 2C6H3N)VCl3.THF (20 g, 0.049 mol) in 50 mL hexane was cooled to −30� C. A solution of C6H5CH2MgCl (148 mL, 1M solution in diethylether, 0.148 mol) was added dropwise over a period of 15 minutes leading to a change in the color of the solution from green to red. The resultant red solution was allowed to warm up to room temperature whereupon it was filtered and the solvent removed under a stream of nitrogen. Recrystallization of the resultant crude oily solid from hexane yielded (2,6-Pri 2C6H3N)V(CH2C6H5)3 as a dark red crystalline solid (16 g, 0.032 mol, 65%).
(c) Preparation of (2,6-Pri 2C6H3N)V(OC(CF3)3)(CH2C6H5)2
A solution of (2,6-Pri 2C6H3N)V(CH2C6H5)3 (0.53 g, 1.0 mmol) in 20 mL hexane was treated with (CF3)3COH (138 μL, 1.0 mmol) and stirred overnight. Solvent removal under a stream of nitrogen left an oily brown solid. Recrystallization from a hexane solution at −30� C. produced large dark brown crystals of (2,6-Pri 2C6H3N)V(OC(CF3)3)(CH2C6H5)2 in 60% yield (0.40 g, 0.6 mmol).
(d) Preparation of (2,6-Pri 2C6H3N)V(NPhMe)(CH2C6H5)2
A solution of (2,6-Pri 2C6H3N)V(CH2C6H5)3 (0.3 g, 0.6 mmol) in 20 mL hexane was treated with N-methylaniline (65 μL, 0.6 mmol) and stirred for 48 hours. Solvent removal under a stream of nitrogen left an oily brown solid. Recrystallization from a hexane solution at −30� C. produced red crystals of (2,6-Pri 2C6H3N)V(NPhMe)(CH2C6H5)2 in 55% yield (0.17 g, 0.33 mmol).
(e) Preparation of (2,6-Pri 2C6H3N)V(OC6H3-2,6-Pri 2)(CH2C6H5)2
A solution of (2,6-Pri 2C6H3N)V(CH2C6H5)3 (1.2 g, 2.4 mmol) in 20 mL dichloromethane was treated with 2,6-Pri 2C6H3OH (450 μL, 2.4 mmol) and stirred for 48 hours. Solvent removal under a stream of nitrogen left an oily red-brown solid. Recrystallization from a hexane solution at −30� C. produced dark red crystals of (2,6-Pri 2C6H3N)V(OC6H3-2,6-Pri 2)(CH2C6H5)2 in 75% yield (1.05 g, 1.8 mmol).
(f) Preparation of (2,6-Me2-C6H3N)V(CH2C6H5)3
A solution of (2,6-Me2-C6H3N)VCl3.THF (0.50 g, 1.4 mmol) in 20 mL of hexane was cooled to −30� C. A solution of C6H5CH2MgCl (4.3 mL, 1M solution in diethylether, 4.3 mmol) was added dropwise over a period of 15 mins leading to a change in the color of the solution from green to red. The resultant red solution was allowed to warm up to room temperature whereupon it was filtered and the solvent removed under a stream of nitrogen. Recrystallization of the resultant crude oily solid from hexane yielded (2,6-Me2-C6H3N)V(CH2C6H5)3 as a dark red crystalline solid (0.25 g, 0.6 mmol, 40%).
(a) A catalyst solution containing 10 mg (2,6-Pri 2-C6H3N)V(CH2C6H5)3 and 10 mg B(C6F5)3 was prepared in 3 mL of toluene. The catalyst solution, along with 400 mL of hexane, and 45 mL 1-hexene was added to a 1 liter stainless-steel autoclave which had been previously purged with nitrogen. The autoclave was pressurized with ethylene at 150 psi and the mixture was stirred at 30� C. for 1 hour whereupon the autoclave was vented. 4.6 g of polymer was produced using this procedure.
(b) A catalyst solution containing 50 mg (2,6-Pri 2-C6H3N)V(NphMe)(CH2C6H5)2 and 80 mg [PhNHMe2][B(C6F5)4] was prepared in 5 mL of toluene in a serum capped bottle. Ethylene was bubbled through the solution for 10 minutes causing the precipitation of polymer. The bottle was opened and the contents diluted with water. The solid polymer was washed with acetone and dried. The yield of polyethylene was 1 g.
(c) A catalyst solution containing 10 mg (2,6-Pri 2-C6H3N)V(OC(CF3)3)(CH2C6H5)2 in 5 mL of toluene was treated with 5 mL of a solution containing 10 wt % methylalumoxane. The catalyst solution, along with 400 mL of hexane and 45 mL 1-hexene was added to a 1 liter stainless-steel autoclave which had been previously purged with nitrogen. The autoclave was pressurized with ethylene at 100 psi and the mixture was stirred at 25� C. for 1 hour whereupon the autoclave was vented. 7.5 g of polymer was produced from this procedure.
(d) A catalyst solution containing 50 mg (2,6-Pri 2-C6H3N)V(OC6H3-2,6-Pri 2)(CH2C6H5)2 and 78 mg [Ph3C][B(C6F5)4] was prepared in 5 mL of toluene. The catalyst solution, along with 400 mL of hexane and 45 mL 1-hexene was added to a 1 liter stainless-steel autoclave which had been previously purged with nitrogen. The autoclave was pressurized with ethylene at 150 psi and the mixture was stirred at 30� C. for 1 hour whereupon the autoclave was vented. 1 g of polymer was produced from this procedure.
(e) In this example a mixture of 20 mg (2,6-Me2-C6H3N)V(CH2C6H5)3 and 25 mg [PhNHMe2][B(C6F5)4] was prepared in 5 mL of toluene. 10 mL 1-hexene was then added to the resultant mixture. After 1 hour the solvent was removed under a stream of nitrogen and the solid polymer was washed with acetone and dried. The yield of polyhexene was 1 g.
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|Citing Patent
|Filing date
|Publication date
|Aug 9, 2002
|Jul 10, 2003
|Michael Arndt-Rosenau
|Vanadium-imidoaryl complexes for the polymerization of olefins
|U.S. Classification
|526/161, 526/172, 526/169.2
|International Classification
|Cooperative Classification
|European Classification
|Mar 26, 2001
Owner name: EXXONMOBILE CHEMICAL PATENTS INC., TEXAS
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Effective date: 20010125
|Sep 29, 2004
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Year of fee payment: 4
|Sep 18, 2008
|Fee payment
Year of fee payment: 8
|Dec 24, 2012
|Maintenance fee reminder mailed
|May 15, 2013
|Lapse for failure to pay maintenance fees
|Jul 2, 2013
|Expired due to failure to pay maintenance fee
Effective date: 20130515

subset: commoncrawl


text:
|By Marketwired .
Article Rating:
|March 6, 2014 12:30 PM EST
IRVINE, CA -- (Marketwired) -- 03/06/14 -- Universal Bioenergy Inc., (OTCQB: UBRG), a publicly traded independent diversified energy company, announced today that it has filed its Quarterly Report on Form 10-Q for its fiscal second quarter ended December 31, 2013 with the Securities and Exchange Commission. The Report contains the Company's financial statements, management's discussion and analysis (MD&A), its plans and future outlook and other disclosures. The Results of Operations was excerpted from the Form 10-Q Report.
The Company projects that it will continue to experience significant growth in revenues in the next 12 months through higher sales of natural gas, propane, petroleum products, coal and electric power.
Results of Operations
Our revenues for the three months period ended December 31, 2013, increased compared to the three months period ended December 30, 2012. Our primary revenues from this period are from the sale of natural gas and propane. Our revenues for the three and six months ended December 31, 2013 were $18,705,137 and $32,577,523 respectively, as compared to $13,322,660 and $28,885,520 respectively for the same periods in 2012. This resulted in an increase of $3,692,003 in revenues or 12.78% over the previous year.
Our Cost of Sales for the three and six months ended December 31, 2013 were $18,685,525 and $32,545,212 respectively, as compared to $13,303,088 and $28,841,943 for the same periods in 2012.
We incurred losses of $461,400 for the six months ended December 31, 2013; and $874,770 for the same period in 2012. Our accumulated deficit since our inception through December 31, 2013 amounts to $22,539,221. We did not issue any common shares for services for this period which had an aggregate fair value of approximately $0.00 that was included in the $360,281 in general and administrative expenses for the six month period ended December 31, 2013.
We also incurred interest expenses of $295,204 for the six month period ended December 31, 2013. Excluding the value of the common stock that was issued for services and interest expenses, which together totaled $295,204, would correspondingly reduce our net loss of $461,400 to an adjusted net loss of $166,196 for the three month period ending December 31, 2013. Based on an adjusted net loss of $166,196, this loss equals only 0.51% of our total revenues of $32,577,739 for the six month period ended December 31, 2013, as compared to 6.69% for the same period ended 2012.*
Operating Costs and Expenses
Our Cost of Sales for the three months ended December 31, 2013 were $18,685,525 as compared to $13,303,088 for the same period in 2012, and our Cost of Sales for the six months ended December 31, 2013 were $32,545,312 as compared to $28,841,943 for the same period in 2012. This was an increase of $3,703,369 or 12.84% in our Cost of Sales. Our primary operation is the marketing of natural gas, propane and coal to our customers. Our total operating expenses for the three months ended December 31, 2013 were $205,050, as compared to $407,702 for the same period in 2012 and for the six months ended December 31, 2013 were $361,589 as compared to $769,261 for the same period in 2012. We pay our employees and consultants largely in common shares as our cash availability is currently limited.
We decreased our total operating expenses from $769,261 for the six month period ending December 31, 2012, by a total of $407,672, or by 53.00%, to $361,589 for the period ending December 31, 2013.
Our "total assets" have decreased by $3,142,823, or 25.41%, to $9,226,706 for the period ending December 31, 2013, compared to $12,369,529 for the year ended June 30, 2013. This was due to a decrease in the amount of our Accounts Receivables from the sales of natural gas.
Working Capital
Our working capital requirements increased, and we incurred significant fluctuations in our working capital for this period. This resulted in a working capital deficit of ($1,547,430) for the period ending December 31, 2013, as compared to a working capital deficit of ($1,021,031) for the period ending December 31, 2012. This increased our working capital deficit by $526,399 or by 51.56%. The working capital deficit was primarily due to the costs of pursuing acquisitions, funding of NDR Energy's operating expenses, the amount of funds borrowed from our creditors, purchase of natural gas inventories, our capital spending exceeding our cash flows from operations, and from the increase in accrued expenses.
Cash Flows
The prices and margins in the energy industry are normally volatile, and are driven to a great extent by market forces over which we have no control. Taking into consideration other extenuating factors, as these prices and margins fluctuate, this would result in a corresponding change in our revenues and operating cash flows. Our cash flows for the six months ended December 31, 2013 and 2012 were as follows:
Cash Flows from Operating Activities
Our cash, used in operating activities, for the six months ended December 31, 2013, was $218,245, as compared to cash used in operating activities of $1,429,832 for the six months ended December 31, 2012. The decrease was primarily attributable to amortization of beneficial conversion feature, the accruing certain management salaries, and a reduction of prepaid expenses.
Cash Flows from Investing Activities
Cash used in investing activities for the six months ended December 31, 2013 was $40,050 as compared to cash provided by investing activities of $0.00 for the six months ended December 31, 2012.
Cash Flows from Financing Activities
Our cash provided by financing activities for the six months ended December 31, 2013 was $259,550, as compared to $569,067 for the six months ended December 31, 2012. The net cash used in financing activities is primarily attributed to our Notes Payables.
Liabilities / Indebtedness
Current liabilities decreased to $7,586,534 for the six months ended December 31, 2013, compared to $10,197,223 for the same period in 2012. This 25.60% decrease was primarily due to a $3,078,704 decrease in accounts payable from the purchasing costs and supplies of natural gas. Our long term liabilities are $341,653 for the period ending December 31, 2013, compared to $976,248 for the six months ending December 31, 2012. In the past twelve months the Company has significantly reduced its borrowings from its creditors to further reduce its short and long-term debt.
Universal's President Vince M. Guest states, "We are very excited about the financial and operating results for the second quarter of our fiscal year. Our sales increase of 12.78% is very significant, and puts us back in the mode of a double-digit high growth company. Everyone at Universal and NDR Energy Group worked very hard to improve our financial position by reducing our operating expenses by 53.00%, and decreasing our liabilities by 25.60%. We have some very exciting plans for the rest of the fiscal year, and anticipate that these plans could produce higher sales and begin to generate positive earnings in the next six months. We are working on a number of significant energy transactions that we anticipate closing soon, that should have a very positive effect on our stock price and our shareholders."
The full Form 10-Q Quarterly Report is available for viewing on the SEC's website and it is also available at our website at www.universalbioenergy.com Investor Relations, SEC Filings section. *This disclosure of information as presented is a non-GAAP accounting measure, and is not based on GAAP accounting principles or guidelines.
About Universal Bioenergy Inc.
Founded in 2004, Universal Bioenergy Inc., is a publicly traded independent diversified energy company that produces and markets natural gas, petroleum, coal and propane. We market energy resources to the largest public utilities, electric power producers and local gas distribution companies in the U.S., that serve millions of commercial, industrial and residential customers. We are also engaged in the acquisition and development of existing or recently discovered oil and gas fields, leases and surface coal mines. For more information visit www.universalbioenergy.com
Safe Harbor Statement - There are matters discussed in this media information that are forward looking statements within the meaning of Rule 175 under the Securities Act of 1933 and Rule 3b-6 under the Securities Exchange Act of 1934, and are subject to the safe harbor created by those rules. Such statements are only forecasts and actual events or results may differ materially from those discussed. For a discussion of important factors which could cause actual results to differ from the forward looking statements, refer to Universal Bioenergy Inc.'s most recent annual report and accounts and other SEC filings. The company undertakes no obligation to update publicly, or revise, forward looking statements, whether as a result of new information, future events or otherwise, except to the extent legally required.
For inquiries contact:
Media Relations:
Solomon Ali
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19th Cloud Expo, taking place November 1-3, 2016, at the Santa Clara Convention Center in Santa Clara, CA, will feature technical sessions from a rock star conference faculty and the leading industry players in the world. Cloud computing is now being embraced by a majority of enterprises of all sizes. Yesterday's debate about public vs. private has transformed into the reality of hybrid cloud: a recent survey shows that 74% of enterprises have a hybrid cloud strategy. Meanwhile, 94% of enterpri...
Aug. 23, 2016 05:00 PM EDT Reads: 2,880
Using new techniques of information modeling, indexing, and processing, new cloud-based systems can support cloud-based workloads previously not possible for high-throughput insurance, banking, and case-based applications. In his session at 18th Cloud Expo, John Newton, CTO, Founder and Chairman of Alfresco, described how to scale cloud-based content management repositories to store, manage, and retrieve billions of documents and related information with fast and linear scalability. He addres...
Aug. 23, 2016 04:45 PM EDT Reads: 1,766


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This artist creates a Cuisinart of abstract mirror designs borrowing bits from Victorian, Edwardian, paisley, and art nouveau. She also draws orphan cars, and adapts a few very old ads. Most of her work is hand drawn with twists, vines & Celtic knots.
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To see more of this artist's work use the keyword 2084 alone or in combination with a subject word such as 2084+vines.
Pink, chocolate brown, and navy blue (with black and white) combine in not quite Celtic twists and tangles to give this abstract composition a Moorish/Islamic feeling.
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This is what happens when you actually understand your audience. It's not about bombarding your customers with ads, no matter where they go, based on old behavior. It's about understanding their interests, and offering them new products or services that you think will be useful to them.
Jun 27, 2008
Elsevier, publisher of scientific, technical and medical (STM) information, announced an agreement with Portico, a not-for-profit digital preservation service, to aid ScienceDirect, Elsevier's online STM platform, in addressing the challenges of eBook preservation. This agreement will ensure that the collection of eBooks on ScienceDirect is protected for the future. The agreement will allow ScienceDirect to implement a safeguard plan that ensures technological preservation for its entire collection of eBooks on ScienceDirect, and is designed to meet the research demands of ScienceDirect's customers.
(www.info.sciencedirect.com, www.mdconsult.com, www.elsevier.com, www.reedelsevier.com)


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Modern Rustic White Carrara Marble Large Wood Kitchen Sideboard
Every kitchen needs its storage space and counter space, and this sideboard offers both in a natural modern design. Unique, slotted sliding doors conceal two pa ... more
- 32 inches high x 71 inches wide x 22 inches deep
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- Constructed from solid tropical hardwood and Italian white Carrara marble top
- Finished in natural wax finish on wood. Marble is not sealed. A sealant is recommended prior to first use
- Features large sliding wood doors with 2 shelves on each side
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humming noise
5 Answers
id say its ur wheel baring
Wheel Bearing
1 out of 1 people think this is helpful.
id say probably because its american. jk, check your wheel bearing.
Are the ABS, TRAC OFF and SVS lights on? Def Wheel bearing then, VSS can detect worn roller bearings
4 out of 4 people think this is helpful.
its the wheel bearing
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Simple Minds New Gold Dream (81-82-83-84)
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Out of Print: Future availability is unknown
Format: CD
sku: YA7W
Brand New
CD Details
- Released: January 6, 2003
- Originally Released: 2003
- Label: Virgin Records Us
Entertainment Reviews:
Q - 2/04, p.1174 stars out of 5 - "[T]he title track thrillingly evoking Bowie's 'Station To Station' and 'Someone Somewhere' rivaling U2 for elegant rock dynamics."
Uncut - 1/03, p.97Included in Uncut's "100 Best Albums of the Year"
Uncut - 11/02, p.1395 stars out of 5 - "...Their masterpiece...its teetering, auric grace is undiminished..."
CMJ - 1/5/04, p.12Ranked #8 in CMJ's "Top 20 Most-Played Albums of 1983".
- 1.Someone Somewhere In Summertime
- 2.Colours Fly And Catherine Wheel
- 3.Promised You A Miracle
- 4.Big Sleep
- 5.Somebody Up There Likes You
- 6.New Gold Dream (81-82-83-84)
- 7.Glittering Prize
- 8.Hunter And The Hunted
- 9.King Is White And In The Crowd
Product Description:
Simple Minds: Kerr (vocals); Burchill (guitar, saxophone); MacNeil (keyboards); Forbes (fretless bass); McGee (drums, percussion).
Additional personnel: Herbie Hancock (keyboards).
Simple Minds began their career indebted to Roxy Music, David Bowie and Magazine, but over successive releases emerged as a distinctive act. On New Gold Dream the group's ambitions came to full fruition, the awkward dissonance of early recordings replaced by a warm, textured sound. The content ranged from brash stadium rock to melodic ballad, but a singleness of purpose ensured such contrasts enhanced the set's overall cohesion. The quintet had never sounded so confident or assured and the resultant lush textures launched them into the international arena, fulfilling their undoubted promise. On "Promised You A Miracle," did Kerr really sing "guinea pigs are guinea pigs?"
Simple MindsThe Best of Simple Minds (2-CD)
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- Shipping Weight: 0.25/lbs (approx)
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Whenever I go to L.A. to shoot my porn and sex-ed movies, my partner and I stay at his mother's house in Pasadena. And this time, his sister was getting married there in only two weeks. So the house had been transformed into wedding central. Rooms were filled with boxes of color-coordinated napkin rings and tablecloths and party favors. Everywhere you turned, there was a gift from Macy's or a set of silverware or decorations. In addition, about a dozen boxes had arrived for us, filled mostly with items for the movies like brightly colored buttplugs made from the same material as bowling balls, butter-soft leather-dildo harnesses from Aslan Leather, and assorted bondage toys from JT's Stockroom. I kept having nightmares of someone in the family innocently cracking open a box, expecting to find the Waterford-crystal champagne flutes and instead stumbling upon Sportsheets' Under the Bed Restraint System. Yikes! Luckily, I managed to keep the vibrating dildos separated from the personalized M&Ms.
Over seven days, we shot four movies, which is the most we've ever done in one trip. Not surprisingly, there were the typical casting snafus: Tuesday's performer just got her most recent test back, and she has an STD; we need someone else! Her replacement can't get her nails cut short in time for the shoot, which involves fingering buttholes, so we need to replace her! (I'm a stickler about short nails when it comes to anal penetration.) Tomorrow's girl sprained her ankle on the set of a zombie porn movie today, and she can't put any weight on it! There were also some less-than-ideal conditions—like the house in Studio City built on stilts with an amazing view and an air-conditioning system that barely worked. Under bright lights, with seven people breathing in one small room, I could swear it got to be 85 degrees.
On the final day, we were doing a scene with Aiden Starr, a feisty ex–professional dominatrix from New York, and Devin, a newish male performer who has appeared mostly on Internet sites like meninpain.com (where I first saw him). The plan was for Aiden to dominate him and rough him up a bit. While she was in makeup, we all chatted about the scene and they negotiated their limits, especially his, since he would be bottoming. When the scene began, she started taunting and teasing him with her sharp tongue. I think she asked him to bark like a dog a couple of times. Things had just started to get rolling (i.e., the fucking had commenced) when I looked behind me and saw two men I didn't recognize.
"Who are you?" I asked quietly, knowing that the performers couldn't see them from their vantage point and not wanting to disturb the fantastic handjob in progress.
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"L.A. Vice," the one in front responded, and he flashed his badge. It looked pretty real to me. I didn't want to stop rolling, so I led them away from the bedroom into the dining room.
"Do you have a permit?" the vice cop asked.
"Yes, I do," I said. "I'm not sure where my production manager is—he must be getting lunch. Um, let me look for it." I started looking through the production binders somewhat frantically as the officers rolled their eyes at me.
"You're going to have to stop filming until we see a permit," the first cop said firmly.
"It's here somewhere, I swear." They continued to look skeptical. At this point, they clearly did not believe me.
Just like "regular" moviemaking, in Los Angeles as elsewhere, filming porn requires you to apply for and receive a permit from the city (or county). If you're in a residential neighborhood, the neighbors are notified in advance, and sometimes you also have to reach out to the community or homeowners' association in advance. There are rules about when you can film, where you can park, etc.—and for porn, you always have a clause that says nudity and sex cannot be visible or audible to people outside the house. In addition, officials from the permit office can drop in, the fire marshal can do a spot-check, and apparently, the vice squad can stop by, too. Houses become known as "hot" when they are busted too often for shooting without a permit, or the neighbors repeatedly complain, or there are too many companies applying for permits at one location. Apparently, I was filming in the hottest house in Northridge. Just my luck.
"We've busted this house pretty much every time we've come here," one of the cops told me. "No one ever has a permit. And last time we came, people were doing drugs and other bad stuff."
I picked up my phone and called the production manager. He came walking around the corner from another part of the house with a quizzical look, like "Why are you calling me when I'm in the house?" I told him I needed the permit. He produced it in an instant and handed it to the cops. They looked it over and clearly seemed surprised. Everything was legit, and they said we could resume filming. They asked us to call the owner so they could have a chat, and they stuck around for a while waiting for him.
I went back into the bedroom, reassured the performers and crew members that everything was OK, and said that we could get the film rolling again. But let me say that it's not exactly easy to restart yourself, mentally or physically, after a long, unexpected break. Aiden, however, was a real pro, and she had Devin barking again in no time.
Please visit my websites, puckerup.com and openingup.net
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Comment I Use Linux 3.6 (Score 5, Funny) 143
While the new features like quota groups, snapshot diffs and tcp "fast open" are great, what's really bothering this version is its tendency to
Most cars already have some of this. Hit the brakes too hard and the seatbelts tighten.
That's not some magical AI, it's mechanical function.
I took a fish head to the movies and I didn't have to pay. -- Fish Heads, Saturday Night Live, 1977.


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Contract Engineer jobs | Oil and gas Jobs | Jobs 1 - 7 of 7
Process Engineers
SPIE Oil & Gas Services, filiale du Groupe SPIE, propose une gamme complète de services aux entreprises pétrolières et gazières dans 25 pays notamment en Europe, Moyen-Orient, Asie et Afrique. Pour continuer à se développer,
Senior Contracts Engineer
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Senior Contracts Engineer
A Public Sector Oil Company in Kuwait is looking for Senior Contracts Engineer. Potential candidates shall meet the below requirements. Bachelor Of Engineering 20 Plus of overall experience in Oil & Gas industry Candidates shall have expert level exposure to the below
Natural Resources are seeking to recruit on behalf of their client a SENIOR ENGINEERS for their Redevelopment Department on a long term definite contract based in Qatar Snr Process Engineer Snr Telecom Engineer Snr HVAC Engineer Snr Electrical Engineer
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MAIN RESPONSIBILITIES •Management of the commercial aspects of executing the programme management consultant's role on a major programme of infrastructure development works •Interface with other teams to meet overall program deliverables •Assists in the development
Natural Resources are seeking the following personnel for a Field Re-Development Project which is based in Qatar. Candidates who are suitable must be available to attend an interview in Doha, Qatar between 9th – 13th October 2016. Applications will be closed 31st August 2016
Natural Resources are seeking to recruit on behalf of their client a SENIOR CONTRACTS ENGINEER for their Field Redevelopment Project on a long term definite contract based in Qatar Qualification/Experience BSc in Engineering Discipline or Quantity


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Support PDF,DOC,DOCX,TXT,XLS,WPD,HTM,HTML fils up to 5MB
Squire Sanders Latest US Firm to Shed Staff
In a statement first published in law blog abovethelaw.com, Squire Sanders & Dempsey announced a total of 30 support staff and associate layoffs after completing its annual employee reviews. The firm emphasized that current projected business conditions influenced the timing of these decisions, and that they were working closely with all professionals affected to provide assistance and support.
Winston Strawn Gains 19 Thelen Lawyers
Nineteen Thelen lawyers have joined Chicago-based firm Winston & Strawn, becoming the latest group of attorneys from the recently-dissolved Thelen to get picked up by another firm. The 10-associate, nine-partner hiring is the third largest to emerge from Thelen after a 40 lawyer capture by Howrey and a 60-lawyer capture by Nixon Peabody earlier in the month. Seven former Thelen partners joining the Los Angeles and New York offices cover litigation, private equity, international transactions, real estate, energy and intellectual property law.
Mayer Brown Evaluating Practice Areas
The National Law Journal reports that Mayer Brown is evaluating its staffing needs due to slowdown in some practice areas. US law firms generally have seen a decline in real estate development, securitization work, and mergers and acquisitions in light of access to credit and increasingly demanding lending terms. Law blog Above the Law reported rumors that Mayer Brown was laying off lawyers this week, although the firm has declined to confirm these reports.
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RADCLIFF — A robbery in the parking lot of the Radcliff Wal-Mart on Sunday afternoon ended with a victim's gun being wrestled from him.
The incident has police thinking the victim and offender may be on opposite sides of a domestic dispute.
According to Radcliff police, the male victim stopped at the store for lunch around 1:30 p.m. when he was cornered at his vehicle by two black men.
Thinking he was in danger, the man reached for a handgun to defend himself, Radcliff spokesman Bryce Shumate said.
The men wrestled the gun away from the victim and sped off in a blue older-model Chevy Malibu with 22-inch wheels and a large Chevy logo decal, Shumate said.
The vehicle was last spotted headed south on Wilson Road. Police throughout the county were unable to locate it Sunday.
Shumate said the incident may stem from the victim's ties to a former girlfriend and said it doesn't appear the robbery suspects present an immediate threat to the community.
Anyone with information can contact Radcliff police at -351-4470. Anonymous tips can be given to Hardin County Crime Stoppers at (800) 597-8123.
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The Selby
I've been obsessively checking this site ever since I very briefly met Todd in New York last year.
A great idea to take photographs not just of interesting creative types, but also their humble abodes. What's more insightful about a person than seeing all their stuff and where they live?
Also I'm always fascinated by his interview sheets at the bottom of each page. Hand scrawled and spontaneous makes for much more interesting reading than a typed email asking a few tired questions…
The Selby makes the stigma attached to being nosey a thing of the past.
- Envisions, an exhibition breaking down the boundaries of design
- Zsofia Schweger's paintings depict her Hungarian home frozen in time
- Illustrator Nuno Maria's fresh aesthetic and smooth shapes rework ordinary objects
- A cookbook inspired by Brad Pitt's on-screen eating habits
- Uganda's boisterous nightlife as captured by photographer Michele Sibiloni
- Vanguards magazine explores Scotland's undiscovered creative treasure
- Sagmeister & Walsh rebrands fashion label Milly to reflect its "edgy" new personality
- Dominic Wilcox designs art exhibition for dogs (plus exclusive artist sketches)
- Jaemin Lee's gloriously retro exhibition identities and poster designs
- James Jean's phantasmagorical world of technicolour fever dreams
- The Refugee Nation Olympic flag was inspired by a lifejacket
- Things: the inspiring post that got us through the long hot summer nights of August


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By Barry Ritholtz |
November 26, 2014
Industry predictions of holiday sales range from wild guesses to complete fabrications, Barry Ritholtz writes.
By Joyce Hanson |
April 4, 2012
LPL Financial chief market strategist Jeff Kleintop and his team have identified 10 indicators to watch this spring that may warn of an impending slide in the stock market.
By Bob Keane |
December 1, 2007
Ask any group of advisors what first attracted them to the profession or where they find the greatest job satisfaction and the most common answer...
Part I of a series of articles on working with ultra-high-net-worth clients from IMCA's Investments & Wealth Monitor take a look at generational differences in...
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Re: Purchasing my first DSLR
In reply to Sachin Sangi • Aug 18, 2012
Canon 1100D with kit lens will fit your budget. If I remember correct, you can get it little under 23k from ebay.
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Second Annual Mizner Park Downtown Drive Car Show
For car aficionados, bring Pops to the car show at Mizner Park. A showcase of antique, custom-built, classic, and exotic sports cars will be on display from 10 a.m. to 4 p.m. on Sunday.
Sun., June 17, 10 a.m.-4 p.m., 2012
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text: Dear perl-win32-gui-users, hm.. again .. i'm really happy with the win32 development.. i got some simple questions (or more like a wishlist :) ) * is there a spreadsheet (grid) look-a-like solution or component ? * is there a inline webbrowser somewhere ? or a HTML or XML parser ? * is there support for JPG or common image formats like .PNG or .GIF? since i only found how to open a BITMAP image (i assume this is a .BMP file) what about licensing ? if i develop a product in perl with usage of the win32::gui module, and I spread (well lets asume for FREE) to the public.. is it still under GNU license or do we have to pay the win32::gui team something ? GREAT.. the win32::gui Best regards, Danny Zak mailto:dannyz@... co-ceo Euro-Pictures/belGOnet.com Princesse Elisabeth Square 9/11 1030 Brussels Belgium Tel : +32-(0)2-215.67.65 Fax : +32-(0)2-215.66.65


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Posted in the Domestic Violence Forum
1 - 2 of 2 Comments Last updated Apr 18, 2013
#1 Jan 12, 2013
VAWA is a cancer on the Bill of Rights. It is full of pork, with grants to fund DV (domestic violence) advocates --shrewish man-hating women -- in every courthouse. It is full of cutting edge jargon no one but radical feminists understands........ and limitless hatred. It is designed to wage war against the best of men's and fathers' traditional roles in society and transform men into second class citizens.
Just read some of the literature if you'd like to enlighten yourself. Even before the man is convicted the literature calls him the "batterer" and the plaintiff the "victim." Another treatise on this malevolent crusade against American men calls the plaintiff the "victim" and the defendant the "perpetrator."
Read some of the complaints filed, almost invariably without a filing fee which is required in all other lawsuits. A man need only be accused of calling the "victim" a bitch, or slamming a door, or smirking at her, and she suddenly exclaims, "I do not feel safe in my home." It's a nice way of converting men into disposable commodities.
The typical VAWA lawsuit literally begs for, screams out for, perjury. And VAWA-spawned monsters have now crept into the courthouses of all fifty states. VAWA has bled over from married and cohabiting couples to people living in the neighborhoods, where if a woman is angry with a man, or another woman, all she needs to do to punish him, or her, is go to the courthouse without notice to "the batterer" and have the sheriff serve the shocked defendant with a horrid pile of documents officially finding him to be a lawbreaker based solely on her say-so in a tete-a-tete with a judge groomed for the gig.
And she doesn't have to say much. "He yelled at me" is a sufficient lie. The vaguer the better the allegations because as the DV advocate understands, she doesn't want to be cross-examined on details. But she needs to say he did it more than once. So she is advised by the shadowy DV advocate who helps her fill out the pre-printed forms already dripping with unconstitutional venom. Then the obligatory lie: "I don't feel safe in my home."
You've heard the expression, "Hell hath no fury like a woman scorned?" Well, folks, VAWA and all the little bastards it has spawned are her quick and easy revenge.
#2 Apr 18, 2013
This is why i oppose VAWA. Seriously, slamming a door isn't abusive, unless he purposely slammed it on her head. WAVA is BS
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Elijah Wood Hits Back at Wranglers Claiming 'Hobbit' Producers Mistreated Animals
After "The Hobbit: An Unexpected Journey" producers were hit with accusation of mistreating animals during the filming in New Zealand, Elijah Wood has spoken up in defense of the movie bosses. The actor, who will reprise his role as Frodo in the adventure movie, thinks the wrangles who made such claim are trying to make quick money.
Calling the deaths of 27 animals "heartbreaking," the "Wilfred" star said he never saw poor condition during the filming. He tells TMZ when met at LAX, "I never saw any of those conditions when I was down there."
He further insists, "All of the technicians who worked on the film take the utmost care of the animals." Considering the timing of complaints, which is less than a month before the movie is released, Wood is suspicious that the wranglers are trying to sabotage the film.
A group of wranglers in New Zealand recently claimed that the producers were responsible for the deaths of those animals due to the condition of the animals living quarters, which was said to be filled with bluffs, sinkholes and other "death traps." The filmmakers have since rejected the accusation.
"Extraordinary measures were taken to make sure that animals were not used during action sequences or any other sequence that might create undue stress for the animals involved," the producers stated. "Over 55% of all shots using animals in The Hobbit are in fact computer generated; this includes horses, ponies, rabbits, hedgehogs, birds, deer, elk, mice, wild boars, and wolves."
The first "Hobbit" movie will hit theaters across the U.S. on December 14. Its second installment "The Hobbit: The Desolation of Smaug" will open next year on December 13, while the final chapter "The Hobbit: There and Back Again" is set to arrive in cinemas on July 18, 2014.
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