text:
|Publication number
|Publication type
|Application number
|Publication date
|Jan 25, 2000
|Filing date
|Jul 18, 1997
|Priority date
|Jul 23, 1996
|Fee status
|Also published as
|Publication number
|Robert K. Rosen, James C. Stevens
|Original Assignee
|The Dow Chemical Company
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|Patent Citations (30), Referenced by (24), Classifications (35), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This application claims the benefit of U.S. Provisional Application No. 60/022,061 filed Jul. 23, 1996.
This invention relates to compositions of matter which are useful as addition polymerization catalysts, to a method for preparing these catalyst compositions and to a method of using these catalyst compositions. More particularly, this invention relates to improved olefin polymerization catalyst compositions comprising a Group 4 metal complex and a Group 13 amide or silylamide and to an improved method for polymerizing addition polymerizable monomers using the same.
Constrained geometry metal complexes, their preparation, methods of activation, active catalysts formed therefrom including cationic catalysts and methods of use are disclosed in EP-A-416,815; EP-A-514,828; EP-A-520,732; U.S. Pat. No. 5,064,802; U.S. Pat. No. 5,374,696; U.S. Pat. No. 5,470,993; U.S. Pat. No. 5,055,438, U.S. Pat. No. 5,057,475, U.S. Pat. No. 5,096,867, U.S Pat. No. 5,064,802, U.S. Pat. No. 5,132,380, and U.S. Pat. No. 5,453,410. For the teachings contained therein, the aforementioned United States patents and published European Patent Applications are herein incorporated in their entirety by reference thereto.
Although previously known active catalysts, especially the cationic catalysts disclosed in the foregoing applications and publications, have excellent activity, they are extremely sensitive to catalyst poisons, such as polar impurities, that may be contained in a polymerization mixture. Because of this fact, catalyst efficiencies and lifetimes have been limited and molecular weights of the resulting polymers have been reduced.
It is previously known in the art to utilize adjuvants such as trialkylboron and trialkylaluminum compounds to remove catalyst poisons from biscyclopentadienyl containing olefin polymerization catalysts. Disadvantageously however, such adjuvants have proven to be less effective in combating the inhibition of catalytically activated constrained geometry catalysts, and when used in the polymerization of olefin monomers, actually may interfere with the desired catalytic process. The previously disclosed U.S. Pat. No. 5,453,410 disclosed the combination of an alumoxane adjuvant with a cationic constrained geometry catalyst composition. However, alumoxanes are rather less soluble than is desired in aliphatic hydrocarbon solvents used in common polymerization systems. Additionally, alumoxanes are pyrophoric and are relatively expensive. Thus, it would be desirable to reduce the quantity of alumoxane used in a polymerization process or more desirably still, to eliminate use of alumoxanes entirely. Instead it would be desirable to utilize an adjuvant which is not pyrophoric and is more soluble in aliphatic hydrocarbons.
Finally, components in polymerization processes or their reaction products ultimately become incorporated into the polymer produced by the polymerization process unless a technique for their removal is available. Alumoxanes are relatively high molecular weight polymeric aluminum oxide compounds. Their presence in residual quantities in the polymerization product is generally not considered to be beneficial to polymer properties, and may actually degrade some polymer properties, particularly polymer clarity.
The present investigations have led to certain improved catalyst compositions that are highly active as addition polymerization catalysts, desirably having improved resistance to catalyst poisons, and improved efficiency.
According to the present invention there is now provided a catalyst composition comprising in combination:
a) a metal complex corresponding to the formula: CpI MXp Lq,
that has been or subsequently is rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique,
wherein: M is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of +2, +3 or +4, bound in an η5 bonding mode to one or more Cp groups;
Cp independently each occurrence is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octahydrofluorenyl-group optionally substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, aminohydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, dihydrocarbylphosphino, silyl, aminosilyl, hydrocarbyloxysilyl, and halosilyl groups containing up to 20 non-hydrogen atoms, or further optionally two such Cp groups may be joined together by a divalent substituent selected from hydrocarbadiyl, halohydrocarbadiyl, hydrocarbyleneoxy, hydrocarbyleneamino, siladiyl, halosiladiyl, and divalent aminosilane, groups containing up to 20 non-hydrogen atoms;
X independently each occurrence is a monovalent anionic σ-bonded ligand group, a divalent anionic σ-bonded ligand group having both valences bonded to M, or a divalent anionic σ-bonded ligand group having one valency bonded to M and one valency bonded to a Cp group, said X containing up to 60 nonhydrogen atoms;
L independently each occurrence is a neutral Lewis base ligating compound, having up to 20 atoms;
I is one or two;
p is 0, 1 or 2, and is I less than the formal oxidation state of M when X is an monovalent anionic σ-bonded ligand group or a divalent anionic σ-bonded ligand group having one valency bonded to M and one valency bonded to a Cp group, or p is I+1 less than the formal oxidation state of M when X is a divalent anionic σ-bonded ligand group having both valencies bonded to M; and
q is 0, 1 or 2; and
b) a Group 13 compound according to the formula
wherein R1 and R2 independently each occurrence is a hydrocarbyl, silyl, halocarbyl, halohydrocarbyl, hydrocarbyl-substituted silyl, halocarbyl-substituted silyl, or halohydrocarbyl-substituted silyl group, said R1 and R2 having from 1 to 30 carbon, silicon, or mixtures of carbon and silicon atoms, and
M" is a Group 13 metal,
the molar ratio of a):b) being from 1:0.1 to 1:100;
or the resulting derivative, reaction product or equilibrium mixture resulting from such combination.
Further according to the present invention there is provided a process for polymerization of addition polymerizable monomers or mixtures thereof comprising contacting said monomer or mixture of monomers with a catalyst system comprising the above catalyst composition under addition polymerization conditions. Preferred addition polymerizable monomers include C2-20,000 σ-olefins. Polymers prepared by the foregoing invented process are usefully employed for molding, film, sheet, extrusion foaming and other applications.
All references to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
The compositions of the present invention are believed to exist in the form of a mixture of one or more cationic, zwitterionic or other catalytically active species derived from the foregoing metal complex a) in combination with the Group 13 compound, b), or alternatively, a mixture of the metal complex or a cationic, zwitterionic or other catalytically active derivative thereof with a derivative formed by interaction of the Group 13 compound with the cocatalyst. Fully cationic or partially charge separated metal complexes, that is, zwitterionic metal complexes, have been previously disclosed in U.S. Pat. Nos. 5,470,993 and 5,486,632, the teachings of which are herein incorporated in their entirety by reference thereto. Derivatives of the Group 13 compound and cocatalyst may arise, for example, by ligand exchange. In particular, where the cocatalyst is a strong Lewis acid, such as tris(fluorophenyl)borane, some quantity of fluorophenyl substituents may exchange with the ligand groups of the Group 13 compound to form fluorophenyl substituted derivatives thereof.
The cationic complexes are believed to correspond to the formula: CpI M+ Xp-1 A- wherein:
M is a Group 4 in the +4 or +3 formal oxidation state;
Cp, X, I and p are as previously defined; and
A- is a noncoordinating, compatible anion derived from the activating cocatalyst.
The zwitterionic complexes in particular result from activation of a Group 4 metal diene complex that is in the form of a metallocyclopentene, wherein the metal is in the +4 formal oxidation state, (that is X is 2-butene-1,4-diyl, or a hydrocarbyl substituted derivative thereof, having both valencies bonded to M) by the use of a Lewis acid activating cocatalyst, especially tris(perfluoroaryl)boranes. These zwitterionic complexes are believed to correspond to the formula: CpI M+ Xp-1 L**-A- wherein:
M is a Group 4 metal in the +4 formal oxidation state;
Cp, X, I and p are as previously defined;
L** is the divalent remnant of the conjugated diene, X', formed by ring opening at one of the carbon to metal bonds of a metallocyclopentene; and
A- is a noncoordinating, compatible anion derived from the activating cocatalyst.
As used herein, the recitation "noncoordinating" means an anion which either does not coordinate to component a) or which is only weakly coordinated therewith remaining sufficiently labile to be displaced by a neutral Lewis base, including an α-olefin. A non-coordinating anion specifically refers to an anion which when functioning as a charge balancing anion in the catalyst system of this invention, does not transfer a fragment thereof to said cation thereby forming a neutral four coordinate metal complex and a neutral byproduct. "Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerizations.
Preferred L groups are phosphines, especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR)3, wherein R is as previously defined; ethers, especially tetrahydrofuran; amines, especially pyridine, bipyridine, tetramethylethylenediamine (TMEDA), and triethylamine; olefins; and conjugated dienes having from 4 to 40 carbon atoms. Complexes including conjugated diene L groups include those wherein the metal is in the +2 formal oxidation state.
Examples of coordination complexes a) used according to the present invention include the foregoing species: ##STR1## wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 or +4 formal oxidation state;
R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (i.e., a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system,
X" independently each occurrence is an anionic ligand group of up to 40 non-hydrogen atoms, or two X" groups together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together are a conjugated diene having from 4 to 30 non-hydrogen atoms forming a π-complex with M, whereupon M is in the +2 formal oxidation state,
R* independently each occurrence is C1-4 alkyl or phenyl,
E independently each occurrence is carbon or silicon, and
x is an integer from 1 to 8.
Additional examples of metal complexes a) include those corresponding to the formula: Cp MXp Lq (III) wherein Cp, M, X, L, p and q are as previously defined. A preferred metal complex belongs to the foregoing class (III) and corresponds to the formula: ##STR2## wherein: M is titanium, zirconium or hafnium in the +2, +3 or +4 formal oxidation state;
R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (i.e., a hydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fused ring system,
each X" is a halo, hydrocarbyl, hydrocarbyloxy, hydrocarbylamino, or silyl group, said group having up to 20 non-hydrogen atoms, or two X" groups together form a neutral C5-30 conjugated diene or a divalent derivative thereof;
E* is --O--, --S--, --NR*--, --PR*--;
Z is SiR*2, CR*2, SiR*2 SiR*2, CR*2 CR*2, CR*═CR*, CR*2 SiR*2, or GeR*2, wherein R* is as previously defined, and
n is an integer from 1 to 3.
Most preferred coordination complexes a) used according to the present invention are complexes corresponding to the formula: ##STR3## wherein: R3 independently each occurrence is a group selected from hydrogen, hydrocarbyl, halohydrocarbyl, silyl, germyl and mixtures thereof, said group containing up to 20 nonhydrogen atoms;
M is titanium, zirconium or hafnium;
Z, E*, X and L are as previously defined;
p is 0, 1 or 2; and
q is zero or one;
with the proviso that:
when p is 2, q is zero, M is in the +4 formal oxidation state, and X is an anionic ligand selected from the group consisting of halide, hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido, di(hydrocarbyl)phosphido, hydrocarbylsulfido, and silyl groups, as well as halo-, di(hydrocarbyl)amino-, hydrocarbyloxy- and di(hydrocarbyl)-phosphino-substituted derivatives thereof, said X group having up to 20 nonhydrogen atoms,
when p is 1, q is zero, M is in the +3 formal oxidation state, and X is a stabilizing anionic ligand group selected from the group consisting of allyl, 2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethyl)-aminobenzyl, or M is in the +4 formal oxidation state, and X is a divalent derivative of a conjugated diene, M and X together forming a metallocyclopentene group, and
when p is 0, q is 1, M is in the +2 formal oxidation state, and L is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, said L having up to 40 carbon atoms and forming a π-complex with M.
More preferred coordination complexes a) used according to the present invention are complexes corresponding to the formula: ##STR4## wherein: R3 independently each occurrence is hydrogen or C1-6 alkyl;
M is titanium;
E*X is --O--, --S--, --NR*--, --PR*--;
Z* is SiR*2, CR*2, SiR*2 SiR*2, CR*2 CR*2, CR*═CR*, CR*2 SiR*2, or GeR*2 ;
R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 non-hydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from E* form a ring system;
p is 0, 1 or 2;
q is zero or one;
with the proviso that:
when p is 2, q is zero, M is in the +4 formal oxidation state, and X is independently each occurrence methyl or benzyl,
when p is 1, q is zero, M is in the +3 formal oxidation state, and X is 2-(N,N-dimethyl)aminobenzyl; or M is in the +4 formal oxidation state and X is 2-butene-1,4-diyl, and
when p is 0, q is 1, M is in the +2 formal oxidation state, and L is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene. The latter diene is illustrative of unsymetrical diene groups that result in production of metal complexes that are actually mixtures of the respective geometrical isomers.
The complexes can be prepared by use of well known synthetic techniques. A preferred process for preparing the metal complexes is disclosed in U.S. Ser. No. 8/427,378, filed Apr. 24, 1995, the teachings of which are hereby incorporated by reference. The reactions are conducted in a suitable noninterfering solvent at a temperature from -100 to 300� C., preferably from -78 to 100� C., most preferably from 0 to 50� C. A reducing agent may be used to cause the metal M, to be reduced from a higher to a lower oxidation state. Examples of suitable reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercury amalgam and sodium/potassium alloy, sodium naphthalenide, potassium graphite, lithium alkyls, lithium or potassium alkadienyls, and Grignard reagents.
Suitable reaction media for the formation of the complexes include aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, and xylene, C1-4 dialkyl ethers, C1-4 dialkyl ether derivatives of (poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoing are also suitable.
Suitable activating cocatalysts useful in combination with component a) are those compounds capable of abstraction of an X substituent therefrom to form an inert, noninterfering counter ion, or that form a zwitterionic or other catalytically active derivative of a). Suitable activating cocatalysts for use herein include perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordinating anions, and ferrocenium salts of compatible, noncoordinating anions. Suitable activating techniques include the use of bulk electrolysis (explained in more detail hereinafter). A combination of the foregoing activating cocatalysts and techniques may be employed as well. The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, U.S. Pat. No. 5,321,106, EP-A-520,732; and U.S. Pat. No. 5,350,723, the teachings of which are hereby incorporated by reference.
More particularly, suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A- . As used herein, the term "noncoordinating" means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base. "Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.
Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitrites. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
Preferably such cocatalysts may be represented by the following general formula:
(L*-H)+ d (A)d-
L* is a neutral Lewis base;
(L*-H)+ is a Bronsted acid;
Ad- is a noncoordinating, compatible anion having a charge of d-, and
d is an integer from 1 to 3.
More preferably Ad- corresponds to the formula: [MI Q4 ]- ; wherein:
MI is boron or aluminum in the +3 formal oxidation state; and
Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, hydroxy-substituted hydrocarbyl, halosubstituted hydrocarbyloxy, and halo-substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy-and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No. 5,296,433, the teachings of which are herein incorporated by reference.
In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A-. Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula: (L*-H)+ (BQ4)- ; wherein:
L* is as previously defined;
B is boron in a formal oxidation state of 3; and
Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
Most preferably, Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group.
Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as:
trimethylammonium tetrakis(pentafluorophenyl) borate,
triethylammonium tetrakis(pentafluorophenyl) borate,
tripropylammonium tetrakis(pentafluorophenyl) borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,
tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,
N,N-dimethyl-N-dodecylammonium tetrakis(pentafluorophenyl) borate,
N,N-dimethyl-N-octadecylammonium tetrakis(pentafluorophenyl) borate,
N-methyl-N,N-didodecylammonium tetrakis(pentafluorophenyl) borate,
N-methyl-N,N-dioctadecylammonium tetrakis(pentafluorophenyl) borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,
N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,
N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,
N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate,
N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate,
N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate,
N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,
N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate,
trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate, and
N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate;
disubstituted ammonium salts such as:
di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and
dicyclohexylammonium tetrakis(pentafluorophenyl) borate;
trisubstituted phosphonium salts such as:
ntriphenylphosphonium tetrakis(pentafluorophenyl) borate,
tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and
tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate;
disubstituted oxonium salts such as:
diphenyloxonium tetrakis(pentafluorophenyl) borate,
di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and
di(2,6-dimethylphenyl)oxonium tetrakis(pentafluorophenyl) borate;
disubstituted sulfonium salts such as:
diphenylsulfonium tetrakis(pentafluorophenyl) borate,
di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and
bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl) borate.
Preferred (L*-H)+ cations are N,N-dimethylanilinium, tributylammonium, N-methyl-N,N-di(dodecyl)ammonium, N-methyl-N,N-di(tetradecyl)ammonium, N-methyl-N,N-di(hexadecyl)ammonium, N-methyl-N,N-di(octadecyl)ammonium, and mixtures thereof. The latter three cations are the primary ammonium cations derived from a commercially available mixture of C14-18 tallow amines, and are collectively referred to as bis-hydrogenated tallowalkyl methylammonium cation. The resulting ammonium salt of the tetrakis(pentafluorophenyl)borate anion accordingly is know as bis-hydrogenated tallowalkyl methylammonium tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula:
(Oxe+)d (Ad-)e.
Oxe+ is a cationic oxidizing agent having a charge of e+;
e is an integer from 1 to 3; and
Ad- and d are as previously defined.
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag+ or Pb+2. Preferred embodiments of Ad- are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula: �+ A- wherein:
�+ is a C1-20 carbenium ion; and
A31 is as previously defined. A preferred carbenium ion is the trityl cation, i.e. triphenylmethylium.
A further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula:
R'3 Si+ A-
R'is C1-10 hydrocarbyl, and A- are as previously defined.
Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof. Silylium salts have been previously generically disclosed in J. Chem Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in U.S. Ser. No. 08/304,314, filed Sep. 12, 1994.
Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such cocatalysts are disclosed in U.S. Pat. No. 5,296,433, the teachings of which are herein incorporated by reference.
The technique of bulk electrolysis involves the electrochemical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising a noncoordinating, inert anion. In the technique, solvents, supporting electrolytes and electrolytic potentials for the electrolysis are used such that electrolysis byproducts that would render the metal complex catalytically inactive are not substantially formed during the reaction. More particularly, suitable solvents are materials that are: liquids under the conditions of the electrolysis (generally temperatures from 0 to 100� C.), capable of dissolving the supporting electrolyte, and inert. "Inert solvents" are those that are not reduced or oxidized under the reaction conditions employed for the electrolysis. It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte that are unaffected by the electrical potential used for the desired electrolysis. Preferred solvents include difluorobenzene (all isomers), dimethoxyethane (DME), and mixtures thereof.
The electrolysis may be conducted in a standard electrolytic cell containing an anode and cathode (also referred to as the working electrode and counter electrode respectively). Suitable materials of construction for the cell are glass, plastic, ceramic and glass coated metal. The electrodes are prepared from inert conductive materials, by which are meant conductive materials that are unaffected by the reaction mixture or reaction conditions. Platinum or palladium are preferred inert conductive materials. Normally an ion permeable membrane such as a fine glass frit separates the cell into separate compartments, the working electrode compartment and counter electrode compartment. The working electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, supporting electrolyte, and any other materials desired for moderating the electrolysis or stabilizing the resulting complex. The counter electrode is immersed in a mixture of the solvent and supporting electrolyte. The desired voltage may be determined by theoretical calculations or experimentally by sweeping the cell using a reference electrode such as a silver electrode immersed in the cell electrolyte. The background cell current, the current draw in the absence of the desired electrolysis, is also determined. The electrolysis is completed when the current drops from the desired level to the background level. In this manner, complete conversion of the initial metal complex can be easily detected.
Suitable supporting electrolytes are salts comprising a cation and a compatible, noncoordinating anion, A-. Preferred supporting electrolytes are salts corresponding to the formula G+ A- ; wherein:
G+ is a cation which is nonreactive towards the starting and resulting complex, and
A- is as previously defined.
Examples of cations, G+, include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 nonhydrogen atoms. Preferred cations are the tetra(n-butylammonium)-and tetraethylammonium-cations.
During activation of the complexes of the present invention by bulk electrolysis the cation of the supporting electrolyte passes to the counter electrode and A- migrates to the working electrode to become the anion of the resulting oxidized product. Either the solvent or the cation of the supporting electrolyte is reduced at the counter electrode in equal molar quantity with the amount of oxidized metal complex formed at the working electrode. Preferred supporting electrolytes are tetrahydrocarbylammonium salts of tetrakis(perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group, especially tetra(n-butylammonium)tetrakis(pentafluorophenyl) borate.
A further recently discovered electrochemical technique for generation of activating cocatalysts is the electrolysis of a disilane compound in the presence of a source of a noncoordinating compatible anion. All of the foregoing techniques are more fully disclosed and claimed in U.S. Pat. No. 5,372,682. In as much as the activation technique ultimately produces a cationic metal complex, the amount of such resulting complex formed during the process can be readily determined by measuring the quantity of energy used to form the activated complex in the process.
The most preferred activating cocatalysts are trispentafluorophenylborane and a mixture of long chain ammonium salts of tetrakis(pentafluorophenyl)borate, especially N,N-dioctadecyl-N-methylammonium tetrakpentafluorophenylborate and N,N-ditetradecyl-N-methylammonium tetrakpentafluorophenylborate. The latter mixture of borate salts is derived from hydrogenated tallow amine, and is referred to as bis-hydrogenated tallowalkyl methylammonium tetrakis(pentafluorophenyl)borate.
The molar ratio of metal complex: activating cocatalyst employed preferably ranges from 1:10 to 2:1, more preferably from 1:5 to 1.5:1, most preferably from 1:5 to 1:1.
The Group 13 component, component b) of the catalyst composition of the invention, preferably corresponds to the formula R1 2 AI(NR2 2) wherein R1 and R2, independently each occurrence are hydrocarbyl, halocarbyl, halohydrocarbyl, silyl, or hydrocarbyl-substituted silyl radicals of from 1 to 20 carbon, silicon or mixtures of carbon and silicon atoms, most preferably, methyl, ethyl, isopropyl, t-butyl, benzyl, 2,6-di(t-butyl)-4-methylphenyl, and pentafluorophenyl. Most highly preferred Group 13 compounds include: dimethylaluminum-N,N-dimethylamide, dimethylaluminum-N,N-diethylamide, dimethylaluminum-N,N-diisopropylylamide, dimethylaluminum-N,N-diisobutylamide, diethylaluminum-N,N-dimethylamide, diethylaluminum-N,N-diethylamide, diethylaluminum-N,N-diisopropylylamide, diethylaluminum-N,N-diisobutylamide, diisopropylaluminum-N,N-dimethylamide, diisopropylaluminum-N,N-diethylamide, diisopropylaluminum-N,N-diisopropylylamide, diisopropylaluminum-N,N-diisobutylamide, diisobytylaluminum-N,N-dimethylamide, diisobutylaluminum-N,N-diethylamide, diisobutylaluminum-N,N-diisopropylylamide, diisobutylaluminum-N,N-diisobutylamide, dimethylaluminum-N,N-bis(trimethylsilyl)amide, diethylaluminum-N,N-bis(trimethylsilyl)amide, diisobutylaluminum-N,N-bis(trimethylsilyl)amide, diisobutylaluminum-N,N-bis(trimethylsilyl)amide, and derivatives thereof formed by ligand exchange with fluorophenyl substituted borane compounds, especially pentafluorophenylborane.
The molar ratio of metal complex to component b) employed in the present invention preferably ranges from 1:1 to 1:100, more preferably from 1:1 to 1:20, most preferably from 1:1 to 1:10.
The process may be used to polymerize ethylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination. Preferred monomers include monovinylidene aromatic monomers, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene and C2-10 aliphatic α-olefins (especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 1-octene), C4-40 dienes, and mixtures thereof. Of the dienes typically used to prepare EPDMs, the particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD). The especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD). Most preferred monomers are ethylene, mixtures of ethylene, propylene and ethylidenenorbornene, or mixtures of ethylene and a C4-8 α-olefin, especially 1-octene.
In general, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250� C., preferably 30 to 200� C. and pressures from atmospheric to 30,000 atmospheres or higher. Suspension, solution, slurry, gas phase, solid state powder polymerization or other process condition may be employed if desired. A support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1:100,000 to 1:10, more preferably from 1:50,000 to 1:20, and most preferably from 1:10,000 to 1:30.
In most polymerization reactions the molar ratio of catalyst:polymerizable compounds employed is from 10-12 :1 to 10-1 :1, more preferably from 10-9 :1 to 10-5 :1.
Suitable solvents for polymerization are inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C4-10 alkanes, and the like and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 1-hexane, 4-vinylcyclohexene, vinylcyclohexane, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), and the like. Mixtures of the foregoing are also suitable.
The catalysts may be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties.
Utilizing the catalyst compositions of the present invention copolymers having high comonomer incorporation and correspondingly low density, yet having a low melt index may be readily prepared. That is, high molecular weight polymers are readily attained by use of the present catalysts even at elevated reactor temperatures. This result is highly desirable because the molecular weight of α-olefin copolymers can be readily reduced by the use of hydrogen or similar chain transfer agent, however increasing the molecular weight of α-olefin copolymers is usually only attainable by reducing the polymerization temperature of the reactor. Disadvantageously, operation of a polymerization reactor at reduced temperatures significantly increases the cost of operation since heat must be removed from the reactor to maintain the reduced reaction temperature, while at the same time heat must be added to the reactor effluent to vaporize the solvent. In addition, productivity is increased due to improved polymer solubility, decreased solution viscosity, and a higher polymer concentration. Utilizing the present catalyst compositions, α-olefin homopolymers and copolymers having densities from 0.85 g/cm3 to 0.96 g/cm3, and melt flow rates from 0.001 to 10.0 dg/min are readily attained in a high temperature process.
The catalyst compositions of the present invention are particularly advantageous for the production of ethylene homopolymers and ethylene/α-olefin copolymers having high levels of long chain branching. The use of the catalyst compositions of the present invention in continuous polymerization processes, especially continuous solution polymerization processes, allows for elevated reactor temperatures which favor the formation of vinyl terminated polymer chains that may be incorporated into a growing polymer, thereby giving a long chain branch. The use of the present catalyst compositions advantageously allows for the economical production of ethylene/α-olefin copolymers having processability similar to high pressure, free radical produced low density polyethylene.
The present catalysts system may be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or ethylene/α-olefin mixtures with low levels of a "H" branch inducing diene, such as norbornadiene, 1,7-octadiene, or 1,9-decadiene. The unique combination of elevated reactor temperatures, high molecular weight (or low melt indices) at high reactor temperatures and high comonomer reactivity advantageously allows for the economical production of polymers having excellent physical properties and processability. Preferably such polymers comprise ethylene, a C3-20 α-olefin and a "H"-branching comonomer. Preferably, such polymers are produced in a solution process, most preferably a continuous solution process.
As previously mentioned, the present catalyst composition is particularly useful in the preparation of EP and EPDM copolymers in high yield and productivity. The process employed may be either a solution or slurry process both of which are previously known in the art. Kaminsky, J. Poly. Sci., Vol. 23, pp. 2151-64 (1985) reported the use of a soluble bis(cyclopentadienyl) zirconium dimethyl-alumoxane catalyst system for solution polymerization of EP and EPDM elastomers. U.S. Pat. No. 5,229,478 disclosed a slurry polymerization process utilizing similar bis(cyclopentadienyl) zirconium based catalyst systems.
The catalyst composition may be prepared as a homogeneous catalyst by addition of the requisite components to a solvent in which polymerization will be carried out by solution polymerization procedures. The catalyst system may also be prepared and employed as a heterogeneous catalyst by adsorbing the requisite components on a catalyst support material such as silica gel, alumina or other suitable inorganic support material. When prepared in heterogeneous or supported form, it is preferred to use silica as the support material. The heterogeneous form of the catalyst system is employed in a slurry polymerization. As a practical limitation, slurry polymerization takes place in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent. Likewise the α-olefin monomer or a mixture of different α-olefin monomers may be used in whole or part as the diluent. Most preferably the diluent comprises in at least major part the α-olefin monomer or monomers to be polymerized.
In contrast, solution polymerization conditions utilize a solvent for the respective components of the reaction, particularly the EP or EPDM polymer. Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures. Illustrative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and Isopar E™, available from Exxon Chemicals Inc.; cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene.
At all times, the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture. Therefore, the catalyst components and catalysts must be prepared and recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of an dry, inert gas such as, for example, nitrogen.
Generally the polymerization process is carried out with a differential pressure of ethylene of from about 10 to about 1000 psi (70 to 7000 kPa), most preferably from about 40 to about 400 psi (30 to 300 kPa). The polymerization is generally conducted at a temperature of from 25 to 200� C., preferably from 75 to 170� C., and most preferably from greater than 95 to 160� C.
The polymerization may be carried out as a batchwise or a continuous polymerization process A continuous process is preferred, in which event catalyst, ethylene, α-olefin, and optionally solvent and diene are continuously supplied to the reaction zone and polymer product continuously removed therefrom.
The skilled artisan will appreciate that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed. The following examples are provided as further illustration of the invention and are not to be construed as limiting. Unless stated to the contrary all parts and percentages are expressed on a weight basis.
A stirred 3.8 liter reactor was charged with about 1440 g of lsopar-E™ mixed alkanes solvent (available from Exxon Chemicals Inc.) and about 130 g of 1 -octene comonomer. Hydrogen (10 mMol) was added as a molecular weight control agent using a mass flow meter. The reactor was heated to the polymerization temperature of 130� C. and saturated with ethylene at 450 psig (3.1 MPa). Catalyst ((t-butylamido)dimethyl(η5 -tetramethylcyclopenta-dienyl)silanetitanium (II) η4 -1,3-pentadiene (TI), or bis(n-butylcyclopentadienyl)-zirconium dimethyl (ZR)) and cocatalyst (trispentafluorophenylborane (FAB), bis-hydrogenated tallowalkyl methylammonium tetrakis(pentafluorophenyl)borate (BFA), or bis-hydrogenated tallowalkyl methylammonium hydroxyphenyltris(pentafluoro-phenyl)borate (BHI)) were dissolved in Isopar E™ and premixed in a drybox with diethylaluminum-N,N-diisopropylamide (DEA) or diisobutylaluminum-N,N-bis(trimethylsilyl)amide (DIB), and transferred to a catalyst addtion system and injected into the reactor over approximately 4 minutes using a flow of high pressure Isopar E™ solvent. The polymerization conditions were maintained for 10 minutes with ethylene supplied on demand to maintain 450 psig reactor pressure. The ethylene consumed during the reaction was monitored using a mass flow meter and this consumption was used to calculate the catalyst efficiency. Results are contained in Table 1.
TABLE 1__________________________________________________________________________ Catalyst Ratio1 Solvent 1-octene Efficiency2Run (μmol) Cocatalyst Scavenger M:B:Al (g) (g) Kg/g__________________________________________________________________________1 TI (1.5) FAB DEA 1:3:10 1437 123 1.22 " BFA " 1:1.5:10 1417 139 1.73 " " DIB 1:1:5 1451 131 2.44 TI (1.0) " " 1:1:10 1453 132 3.55 TI (0.75) " " 1:1:15 1434 128 4.36 " " " 1:1:30 1448 127 4.37 TI (1.5) BHI " 1:1:10 1455 122 1.08 ZR (1.5) BFA DEA 1:1.5:10 1409 126 2.1__________________________________________________________________________ 1. molar ratio of metal complex:cocatalyst:scavenger 2. Kg of polymer per gram titanium or zirconium
|Cited Patent
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|Jun 7, 1966
|Exxon Research Engineering Co
|Aluminum hydroaminate activators in olefin polymerization
|Aug 1, 1963
|Mar 28, 1967
|Snam Spa
|Process for polymerizing isoprene with a catalyst consisting of titanium tetrachloride and an aluminum hydride
|May 22, 1964
|Jun 4, 1968
|Snam Spa
|Terpolymers of a polycyclic diolefin and two mono-olefins
|Oct 14, 1965
|Sep 16, 1969
|Snam Progetti
|Catalytic compositions for polymerization and copolymerization of alpha-mono-olefins,and processes using such compositions
|Nov 8, 1968
|Sep 23, 1969
|Snam Progetti
|Catalytic compositions for butadiene polymerization and processes using said compositions
|Oct 12, 1965
|Sep 30, 1969
|Snam Progetti
|Polymeric iminic-aluminium compounds as catalysts for alpha-olefin polymerization
|Nov 8, 1968
|Nov 4, 1969
|Snam Progetti
|Polymerization of isoprene with catalyst of transition metal and polyiminoalane
|Apr 23, 1965
|Jan 13, 1970
|Showa Denko Kk
|Polymerization of olefins
|Aug 9, 1961
|Nov 30, 1971
|Olin Mathieson
|Reaction products of alkali metal amides and trialkyl aluminum compounds
|May 15, 1970
|Mar 27, 1973
|Du Pont
|Coordination catalyst
|Mar 10, 1971
|Dec 25, 1973
|Snam Progetti
|Novel diamidodialanes and process for the preparation thereof
|Feb 15, 1973
|May 20, 1975
|Snam Progetti
|Production of synthetic lubricants from alpha-olefins through a ternary catalytic system
|Nov 19, 1970
|Sep 9, 1975
|Inst Francais Du Petrole
|Process for the dehydrogenation of secondary alcohols
|Sep 10, 1973
|Sep 16, 1975
|Snam Progetti
|Catalyst system for the homo- and co-polymerization of olefins, conjugated or unconjugated dienes
|Feb 11, 1977
|Jun 13, 1978
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|Ziegler type catalyst system
|Mar 7, 1979
|Sep 23, 1980
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|Novel hindered alkyl aluminum amide cocatalysts
|Jun 4, 1990
|Oct 8, 1991
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|Oct 15, 1991
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|Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization
|Jul 3, 1990
|Nov 12, 1991
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|Sep 13, 1990
|Mar 17, 1992
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|Monocyclopentadienyl transition metal olefin polymerization catalysts
|Sep 12, 1991
|Jul 21, 1992
|The Dow Chemical Company
|Metal complex compounds
|Apr 14, 1992
|Mar 22, 1994
|Minnesota Mining And Manufacturing Company
|Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom
|Jan 21, 1993
|Dec 20, 1994
|The Dow Chemical Company
|Addition polymerization process using stabilized reduced metal catalysts
|Dec 1, 1992
|Sep 26, 1995
|The Dow Chemical Company
|Catalyst composition
|May 12, 1994
|Nov 28, 1995
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|Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom
|Jun 28, 1994
|Jan 23, 1996
|The Dow Chemical Company
|Group 4 metal diene complexes and addition polymerization catalysts therefrom
|Feb 18, 1993
|Mar 31, 1998
|Solvay (Societe Anonyme)
|Catalytic solid usable for the stereospecific polymerisation of alpha-olefins, process for preparing it and process for polymerising alpha-olefins in its presence
|Aug 30, 1990
|Mar 13, 1991
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|Constrained geometry addition polymerization catalysts, processes for their preparation, precursors therefor, methods of use, and novel polymers formed therewith
|May 19, 1992
|Nov 25, 1992
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|Preparation of addition polymerization catalysts
|Jun 22, 1992
|Dec 30, 1992
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|Homogeneous olefin polymerization catalyst by ligand abstraction with lewis acids
|Citing Patent
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|Exxonmobil Chemical Patents Inc.
|Catalyst system of enhanced productivity and its use in polymerization process
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|Exxonmobil Chemical Patents Inc
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|Ziegler-Natta catalyst with amine for polymerization
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|Asahi Kasei Kabushiki Kaisha
|Olefin polymerizaion catalyst and method for polymerizing an olefin using the catalyst
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|Olefin polymerization catalyst composition comprising group 13 amide derivatives
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|Apr 15, 2004
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|Blend functionalized polyolefin adhesive
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|Romer Duane R
|Olefin polymerization catalyst composition comprising group 13 amide derivatives
|Aug 2, 2007
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|Peijun Jiang
|Multiple catalyst system for olefin polymerization and polymers produced therefrom
|Aug 2, 2007
|Mar 12, 2009
|Peijun Jiang
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|May 13, 2009
|Nov 19, 2009
|Lg Chem, Ltd.
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|Apr 7, 2011
|Jul 28, 2011
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|Polymerization modifiers
|Apr 7, 2011
|Aug 11, 2011
|Dow Global Technologise LLC
|Polymerization modifiers
|May 13, 2005
|Jul 20, 2011
|Dow Global Technologies LLC
|Technique for selecting polymerization modifiers
|May 13, 2005
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|Dow Global Technologies LLC
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|U.S. Classification
|502/124, 502/132, 526/127, 526/163, 502/128, 526/348.2, 526/943, 502/103, 526/160, 502/117, 502/129
|International Classification
|Cooperative Classification
|European Classification
|Jul 2, 1999
Owner name: DOW CHEMICAL COMPANY, THE, MICHIGAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ROSEN, ROBERT K.;STEVENS, JAMES C.;REEL/FRAME:010067/0328
Effective date: 19970904
|Mar 20, 2001
|Certificate of correction
|Jun 16, 2003
|Fee payment
Year of fee payment: 4
|Jun 29, 2007
|Fee payment
Year of fee payment: 8
|Jun 22, 2011
|Fee payment
Year of fee payment: 12


text:
When your Chevrolet C1500 Suburban was born, it was destined for a driver who prioritizes long-lasting quality in their automobile. Anyone who operates a Chevrolet knows that when it comes to maintaining their vehicle only the highest quality replacement parts will do. It's not all the time that you realize that you have to buy a replacement Window Regulator to fix your automobile. Car aficionados appreciate the a trusted name built into each Chevrolet, and know that only top quality replacement C1500 Suburban parts will suffice when your car or truck needs fixing.
In order to get full functionality out of your car, you have to be able to raise and lower your windows. Your Chevrolet C1500 Suburban window regulator moves the window glass; keeping the environment outside your car separate from the passengers inside your car. It's easy to take the window regulator on your vehicle for granted when it's working, but easy to see how vital it is when yours doesn't work anymore. It's not fun to be forced to drive your Chevrolet C1500 Suburban with the windows down in the dead of summer while air conditioning escapes from your car because your window regulator doesn't work.
Don't let a broken Window Regulator bring about the demise of your car, truck, or SUV, and don't risk lowering its resale value by using anything but the best replacement parts. At Car Parts Discount, we have live customer service members available with enough expertise to help you buy the appropriate Chevrolet C1500 Suburban part for your needs. Given all the hassles associated with fixing broken parts on your car or truck, let www.carpartsdiscount.com be the number one store you go to make purchasing it easy. If your car or truck was built in 1999, 1998, 1997, 1996, 1995, 1994, 1993, 1992, then you will find the correct Chevrolet C1500 Suburban Window Regulator parts right here.

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not installed yet, but love them! perhaps framed will show better???
Painting looks well done and nice!
Nice paintings well made and attractive
I am not sure if they look as good as the pictures
but they are fine.
These two paintings are absolutely lovely I am very satisfied!
Ordered these pictures for a large wall which needed 'something special'. They arrived within a week in great packaging, we were even supplied some white gloves to protect the pictures while being mounted.
All I can say is, they are beautiful, can't stop looking at them. Colours are vibrant, detail is perfect, we absolutely love them. Thank you
Received in good condition. Thanks
Leuke schilderijen!
Jammer van de hoge douanekosten
These two paintings arrived well packed and in perfect conditition. I am very pleased with the colours and quality.


text:
Soft summer palette
Explore related topics
Find out how to pick your best and worst colors. Crucial information for a capsule wardrobe. Do you have neutral undertones? Do you have gray in your eyes? Find out how all your features work together to create your unique complexion.
Soft summer wardrobe that could easily be converted to the other seasons.
"Soft Summer Palette" by nyrvelli on Polyvore
The Soft Summer Color Pallet~ please do take in to consideration that the colors may vary slightly from the original due to the translation from the canvas to your computer screen.
Soft Summer Color Palette (linked from http://expressingyourtruth.blogspot.co.uk/2013/02/invent-your-image.html)
"Soft Summer" by ashleyrhardt on Polyvore - need to buy these colors instead of others
Best colors for Soft Summer seasonal color women
"Soft Summer deeps" created by sabira-amira on Polyvore
"Soft Summer Red" by colorazione on Polyvore More
палитра цветотипа мягкое лето


text:
Kids Eat Right Month is celebrated each year in August and is sponsored by the Academy of Nutrition and Dietetics and its Foundation. Kids Eat Right Month highlights the importance of a lifestyle of exercise and nutritious eating for children and their families.
Kids Eat Right Month
Making Your Own Baby Food
Academy of Nutrition and Dietetics.
Cooking With Preschoolers
Nemours Kids Health.
Exploring Food Together Curriculum
Cooking Matters
Kid Friendly Veggies and Fruits
USDA. Center for Nutrition Policy and Promotion.
Start a Garden Container With Your Family
Academy of Nutrition and Dietetics.
We Can! Family Recipe Cards
DHHS. NIH. National Heart Lung and Blood Institute.
We Can! Healthy Snack Tips for Parents
DHHS. NIH. National Heart Lung and Blood Institute.
SuperKids Nutrition Pre-K Activity Sheets
SuperKids Nutrition Inc.
Nutrition and Your Child
USDA. ARS. Children's Nutrition Research Center.
Go, Slow, and Woah! Food Chart
DHHS.NIH. National Heart Blood and Lung Institute.
Coping With Picky Eating Phases
Academy of Nutrition and Dietetics.
Dos and Don'ts for Baby's First Foods
Academy of Nutrition and Dietetics.
MyPlate Resources
USDA. WIC Works Resource System.


text:
This is Red, I have taken over Zoomi's thing for a moment to put up a random fic that is my version of her fic, which is incomplete at the moment. Psycho, I know, but it's fun.
AN: I was crazy, eatin' me some honey while I wrote this (tho I haven't even opened the honey jar). This exotic moment was brought to u by KY jelly, lube it up!
Disclaimer: The flaming monkeys r not mine! Neither are the HP chars! JK's, they are her creations, her children, her -- (sorry Zoomi, I'll stop)
It was a beautiful day in the dark dank halls of Hogwarts. The sun was shining outside, and within the castle the torture of young students continued as it had for centuries upon centuries.
Two students were not where they were supposed to be though. (they were probably ditching class, I mean, who doesn't?)
They were supposed to be in Potions, where Snape's evil plan was meant to commence, but hey, we all have our off days. Snape would just have to wait for another day to curse the two -- coughs I mean to make fruit punch.
Anyway, the two students were walking (or skipping in some cases) down the halls which were sunny, yet not. (so maybe like kinda cloudy? Or something…)
Suddenly Draco spied the effeminate looking Harry and gasped. Is that Potter? Or do my eyes deceive me?
The girly boy turned and Draco smirked, it was Potter. The Gryffindor stopped and turned in question, only one person referred to him by his surname.
"Malfoy," Harry hissed.
Draco walked by and knocked Harry's folder out of his hand, scattering papers and books onto the ground. (AN: just like Mr. McKinley does) (inside joke) (u know who I'm talking about Zoomi)
"What was that for you bloody prick?" Harry scowled as he bent over to pick up his scattered books, clearly showing his bum. (AN: shut up (again, if u look down) Zoomi)
"Why, Potter, I knew you were a bottom boy, but you're practically throwing yourself at me now. Put your arse away before your precious redhead sees and blows his load."
"Shut it."
"Ouch, your scathing tongue wounds me."
"Ha ha," Harry rolled his eyes.
Draco smirked, "Don't be jealous of my mad skills, Potter."
"What mad skills would those be?"
A high pitched giggle was his reply, "Oh, I'll show you my mad skills, just you wait. You'll be blown away by their… um, madness."
"Right, try not to trip over your inflated ego, Malfoy. Any bigger and I'll run into it," Harry began walking away.
"Don't walk away from me you- you- girl!"
Harry froze and slowly turned back toward the Slytherin, eyes cold and narrowed.
"What did you call me?" he asked lowly.
Draco laughed, "I called you a sissy little girl! Ehehehe! That's what you are, Potter! I bet you take it up the arse too!"
(AN: Shut up Zoomi )
"You do, that's why you have no excuse! Wait until I tell everyone your dirty little secret."
Harry scowled, "The only secret I have is that I wear women's underwear… I mean, I have no secrets!"
"You wear women's panties?" Draco repeated, "Isn't that a bit kinky for a Gryffindor?"
"The Hat always told me I would do better in Slytherin," Harry said.
"Now you're having sex with hats, Potter?" Draco teased.
"I never said that!"
Draco grinned evilly, "That's not what my recording device says." He reached into his pocket and pulled out a… dildo.
"What the fuck is that!" Harry cried.
Draco looked down, eyes widening, "Shit, this isn't mine! I must've taken the wrong robe this morning!"
Harry narrowed his eyes, "I bet, who's the kinky one now, Malfoy?"
"It's not mine, I swear!" Draco argued.
"Look at me, I'm Draco Malfoy," Harry taunted, shaking his bum. "I like to shove huge, hard things up my arse!"
"Shut up, Potter!"
Draco turned away and ran down the hall crying like the girl he was (totally forgetting the dildo he had dropped) (though I didn't mention it before, he did drop it). On his way around the corner he tripped and fell, he sent Harry a dirty look as he lifted himself and began running again.
"That's right, Malfoy, you better run!"
Harry smirked to himself, I showed him. He shifted his book bag (which was once a folder) and turned in the opposite direction Malfoy had taken. Now it's time for some pie!
His eyes became blurry with a sudden dizziness and he fell forward. His last thought was, I want me some pie!
(this moment was brought to you by pie, a delicious snack that you can eat in your spare time)
(also brought to u by, Zoomi, she does a body good.)
AN: This was a random moment in Zoomi's fic (which at the moment does not exist) (so technically, doesn't it make it my fic since I posted first?) She gave me permission to post it though, so there!


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Southsidedaily.com is your source for free local news and information in Virginia Beach
Dennis J. Walsh, 58, of Norfolk, Va., went to be with the Lord on Aug. 4, 2016.
He is survived by his wife, Theresa Walsh; two daughters, Michelle and Victoria Case; two grandchildren, Mireya and Rios Case; sister, Donna Jetter (Bruce); brother, David Walsh (Laurie); and many nieces and nephews.
The family will receive friends from 6 to 8 p.m. Monday, Aug. 8. 2016, at Hollomon-Brown Funeral Home, 8464 Tidewater Drive, Norfolk, Va.
A graveside service will be at 11 a.m. Tuesday, Aug. 9, at Forest Lawn Cemetery, 8100 Grandby St., Norfolk, Va., followed by a memorial service, led by Pastor Brian Barnes, at 12:30 p.m. at Azalea Baptist Church, 3314 E. Little Creek Road, Norfolk, Va.
Condolences may be offered to the family at www.hollomon-brown.com.


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When I Finally Found my Blogging Voice From the day you start blogging people are constantly telling you to "find your niche." It's EVERYWHERE. Find your niche. Develop your niche. Know your niche. It used to kill me. I didn't have a niche and I was happy with that. I write a lifestyle blog and I was convinced that meant that I didn't have a niche. I wrote about life, life is all-encompassing, therefore my blog was all-encompassing and thus, I didn't have a niche. I was content. Now, I'm backpedaling a little bit. A little bit. See, I still don't think I have a niche, but I did find my blogging voice and honestly, I think that should be our focus.
I found my blogging voice when I sat down one night and told my husband, "I am thinking of starting another blog." He looked at me like I'd suddenly sprouted three new heads. "Another blog? What's wrong with the one you have?" I went off on this long diatribe but basically the short version is this, "I don't feel like I can write about what I really want to write about on there. I want to write about what I know and what I'm good at which really is corporate life and balancing the crazy long to-do list I have. The problem though is that people don't want to read that stuff so I need another blog." He just said, "Just write that stuff on your current blog." When I moaned about how I'd lose followers he shook his head and just said to me, "and you'll gain new followers. If you don't like what you're writing, write something new. If you don't like what your blog has become, change it. Don't start over, just evolve." It was that conversation that led to my a-ha moment. Blogging isn't about finding your niche, it's about finding your voice. It's about looking deep down inside and finding who you are, then sharing that with the world. I'm so much more than A Silver Twig used to let me be. I had written myself in a corner by trying to conform to a niche or trying to appeal to a specific audience. Somewhere in there I'd lost my voice and I stopped caring about my blog. My life consists of working a corporate career, running my own business strategy company, spending time with my husband, being a fur-momma, struggling with infertility, etc. Somehow over half of me was lost when it came to my blog. My husband helped me find my blogging voice. I still may not feel like I've found a 'niche' but I've found a voice that personally, I think that's far more important. What about you? Do you have a niche or a voice? Does your blog reflect who you really are?


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|Om <bigosma...@gmail.com>
|[MENTOR] InstallApacheFlex AIR app related questions
|Mon, 16 Jul 2012 23:19:50 GMT
(Carol/Alex, please free to jump in as well) This page http://people.apache.org/~bigosmallm/installapacheflex/ lets you download a binary file. For this discussion, the InstallApacheFlex AIR app = 'Installer' 1. Should the installer be signed in the same way as the Apache Flex SDK binary is signed? The process for signing AIR apps is described here [1<http://livedocs.adobe.com/flex/3/html/help.html?content=distributing_apps_4.html>] How do we do this in the Apache way? 2. The installer downloads the binary distribution of the Apache Flex sdk. Should the installer programatically verify the downloaded binary file's signature before uncompressing it? 3. I see that mirrors are preferred over downloading directly from Apache servers. Is there a standard list of mirror locations that I can access from somewhere? I think I will need to modify the installer to dynamically select a mirror for downloading from, right? [1] http://livedocs.adobe.com/flex/3/html/help.html?content=distributing_apps_4.html Thanks, Om
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GP Week : Issue 161
Cal Crutchlow GETTING STARTED ONCE YOU'VE STOPPED TEST RIDERS AND REAL RIDERS: THE DIFFERENCE COUNTS Casey Stoner was livid. Not because he'd crashed (well, perhaps that too). It was because he hadn't been able to restart again. The leaders' gap to the rest meant that with his bike basically undamaged, had he got going again, he might conceivably have managed to save a top-10 finish, maybe better. But the marshals wouldn't let him. "I'm frustrated I wasn't allowed to try and score some points," he said. "The bike was perfect, but the marshals pushed me away." Actually, it's a moot point whether he would have been able to go, but he's right to be cross and the marshals were wrong to stand in his way. MotoGP policy is that as long as there is no obvious danger then riders should be allowed and even helped to get going again. The difficulty was that his engine had stopped, and his bike was a long way into the gravel. It was quite a push back to the track, and then a difficult task to push-start a 1000cc MotoGP bike with a slipper clutch. Especially uphill. Honda modified their clutch to make it easier after a similar incident at Jerez last year. Stoner was knocked off by Rossi. Both fell. Rossi's Ducati was push-started and he continued. Marshals (eventually) came to help Casey as well, but they couldn't get the engine going. Why had the engine stopped? An HRC official described that the cut-out switch reads many parameters. Other manufacturers have simpler systems. In practice they stop the motor as soon as the bike goes down ... but in a race a delay is programmed in to give the rider a chance to jump back on. Not in this case. On the other hand, it could have been worse. Lorenzo's engine kept running when he was knocked down at Assen, which would have been okay for a short time if it was only idling. Instead it was jammed at full throttle, and it was rapidly destroyed because of no oil pressure. Stoner may have lost some points, but at least he didn't lose one of his six precious engines. Ducati's test rider Franco Battaini made a return to grand prix racing at the Sachsenring, taking the place of injured satellite Ducati rider Karel Abraham. On a bike he helped develop and should know intimately, he did his reputation no favours. He qualified last, and finished third from last, behind all but two of the humble production-engined CRT bikes. It might seem more than a little unfair to criticise a race-rusty rider who retired from active service several years ago – his last grand prix was at this same circuit in the 250 class in 2006. Nonetheless, his lack of pace was a serious worry to the Ducati riders of this season. And it highlights a problem that is far from exclusively Ducati's ... that test riders in general simply don't go fast enough to be of much use for anything except clocking up the miles to check the endurance of components. Bikes start to behave differently when you push them to their very limits. The same syndrome explains why Stoner and Pedrosa suffer tyre chatter problems while the other Honda riders don't. They're riding that much harder. It may only be a few tenths in lap time, but it's a world of difference to the guy in the saddle. It's certainly also an explanation of Ducati's current difficulties with understeer and excessive tyre wear. Nobody except current racers go fast enough to bring the problems out ... and although it's a bit freer this year than last, their opportunities to test remain limited. They're left to iron out imperfections at race weekends. But who can you find who is fast enough to take the testing process further? If Nicky Hayden is pushed out of Ducati next year, as seems possible, he would surely be the guy for them. Or for Suzuki, working on developing their own entry for 2014. Trouble is, if riders are still fast enough to race, that's what they prefer to do. 40 GPWEEK.com // PARTNERS: MOTOGP >>> SACHSENRING
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Chasing Sophea (Paperback)
Special Order
Poignant and gripping . . . a heartfelt portrayal of a family's shameful secrets and the power of unconditional love.
Tracy Price-Thompson, author of A Woman's Worth
People don t usually name tornadoes, but that year, Daddy insisted. Any twister that beautiful and that dangerous can only be female. Reminds me of a woman I used to know named Sophea. He laughed. Sophea, Sophea.
Dahlia's life should be perfect. She's a successful businesswoman with a wonderful husband and a beautiful daughter. But Dahlia senses that something isn t quite right. More and more often, she has the feeling of being lost in her own body, completely mystified by the simplest things, like traffic lights and car horns. These spells strike at anytime, anywhere. And though aware that she's off balance, Dahlia has no idea what could be the cause.
As Dahlia's grasp on reality loosens, the signs lead to a traumatic event from her childhood that has made its way into her adult life. There is someone else lurking in the back of Dahlia's mind and she wants out. Now she must revisit the painful past, and the memories of a mother who had her own mental demons. The only problem is: Dahlia might have to lose herself entirely if she wants to discover the secrets of that long-ago day when Sophea came to town.
About the Author
Gabrielle Pina received her MA from the University of Southern California Master of Professional Writing Program. She is a lecturer at the University of Southern California and a member of the adjunct faculty at Pasadena City College. She lives in Southern California with her husband, Ron, and her children, Julian, Maia, and Langston.


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That is not as far-fetched as it sounds. Having beaten Telford Tigers in last weekend's play-offs to reach this weekend's qualifying rounds proper, they promptly disposed of Ayr Raiders 12-4 and drew 7-7 with Murrayfield Racers.
Admittedly, Ayr have suffered pre-season off-ice rumblings about their continued existence and their start to the season is beacuse of help from Gardner- Brown, who has committed himself to their survival.
The Racers, who had lost Scott Neil to the Steelers, found the newcomers troublesome. Fittingly, Neil opened the scoring and not even three goals from the Racers' Chris Palmer in the first period could deter the English. Late in the final period, the Racers' favourite son, Tony Hand, restored their lead but with 90 seconds left Mark McKie grabbed a point for Sheffield.
The highest scoring game of the weekend saw Cardiff Devils beat Bracknell Bees 16-10, while the 2-2 draw between Humberside Seahawks and Nottingham Panthers was the lowest scoreline since the Premier League began in 1983.
Seahawks took a two-goal lead after six minutes but Jim Graves, the Panthers' new goalminder, and his opposite number, Frank Killen, then dominated proceedings until the Panthers drew level through Dan Dorion and Ashley Tait.
BENSON AND HEDGES CUP Qualifying rounds: Saturday: Basingstoke 14 Slough 2; Fife 13 Murrayfield 10; Medway 3 Humberside 10; Romford 4 Billingham 6; Sheffield 12 Ayr 4. Sunday: Cardiff 16 Bracknell 10; Humberside 2 Nottingham 2; Murrayfield 7 Sheffield 7; Peterborough 9 Medway 7; Whitley 10 Wasps 7.
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The Compensation Committee (the Committee) of The First Bancorp, Inc. is appointed by the Company's Board of Directors (the Board) to discharge the responsibilities of the Board relating to the compensation of the company's President/CEO and other executive officers. The Committee has overall responsibility for evaluating and approving all compensation plans, policies and programs that affect the President/CEO and other executive officers and for significant company-wide compensation matters and policies in general.
The Committee shall consist solely of independent directors, and at minimum, must have two members appointed by the Board.
The Committee shall meet at least annually and hold such other meetings from time to time as may be called by the chairperson or any two members of the Committee. A majority of the members of the Committee shall constitute a quorum, and shall decide any question brought before any meeting of the Committee. Minutes shall be taken of each meeting, approved by the Committee at its next meeting and retained by the Secretary of the Company as permanent records.
The Compensation Committee has the authority to retain or obtain the advice of any compensation consultants, outside legal counsel or other advisors (external advisors) as the Committee deems appropriate. The Committee shall be directly responsible for the appointment, compensation and oversight of the work of such external advisors that it retains, and the Company shall provide appropriate funding and other resources for such advisors. The Committee will approve the external advisors fees and other retention terms, and will have the authority to termination any external advisor. The Committee shall also have the authority to obtain advice and assistance from Management as needed.
The Committee may, at its discretion, delegate all or a portion of its duties and responsibilities to a subcommittee of the Committee consisting of one or more members. In particular, the Committee may delegate the approval of certain transactions to a subcommittee consisting solely of members of the Committee who are "non employee Directors" for the purposes of Rule 16b-3 under the Securities Exchange Act of 1934, and in effect from time to time, and "outside directors" for the purpose of Section 162(m) of the Internal Revenue Code as in effect from time to time.
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The actress who's playing a tomboy in the upcoming edition of Golmaal has a pet dog called Facebook, reports Mumbai Mirror. Interestingly the dog was seen earlier in All The Best.
Apparently director Rohit Shetty has named the dog Facebook.
A source reveals, Golmaal 3 is funnier than Golmaal Returns, in which Kareena's role was a spoof on Ekta Kapoor. In Golmaal 3, she plays a tomboy and has a pet dog called Facebook. Kareena will sport a lot of t-shirts with funny one-liners written on them like, 'Crime master gogo', 'Mogambo khush hua' to name a few."The source adds, "When Rohit mentioned the idea of naming the dog so, the entire cast was in splits but they all loved the idea. In fact, the director has decided to name his first pet Facebook, if he ever keeps one that is."
Well, we hope Kareena becomes more active on Facebook after the movie.


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In 1863, Desmond Fitz-gerald, the editor of The Electrician, a popular electrical magazine, responded to his readers' frequent requests for more information about the medical uses of electricity with an editorial on the subject. He claimed that electrotherapy was by then a well-attested form of medical treatment and singled out Dr Golding Bird as one of… (More)
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60, Seattle, WAGreetings! I realize how important it is for me to share my life with someone who lives from a faith perspective, enjoys a healthy lifestyle, and shares a sense of adventure. As a high school teacher my outlook is enthusiastic and I love learning. Looking forward to a deep and lasting relationship, based on trust, honesty, and a zest for life. That's it!
66, Richland, WAWelcome to my profile! (Profile pic. Is proverbial selfie taken Feb. 2017) I am a practicing Catholic, passionate about an active life. Searching a match, who is athletic and enjoys hiking, cycling, snow skiing, kayaking, ballroom, and/or travel, and who also brings his own activities to the table. Granted, all of these can make you tired, but it's a good kind of tired. Relaxation is good, too, but no chronic couch potatoes please! I'm too young for that. :)
38, Oak Harbor, WA
39, Maple Valley, WAI enjoy Mass on a frequent basis and enjoy participating in volunteer activities. I have lots of hobbies and enjoy a good adventure. I've traveled throughout the Caribbean, Mexico and Europe. I've taken motorcycle trips with my Dad and Brother across this great country and met some really great people. I listen to a variety of music, and just found the station Air1. I have a quirky sense of humor and appreciate the eccentric. I absolutely LOVE to cook. My faith life is very important to me, and looking for someone who believes/lives the same. My Myers-Briggs is INFJ
53, Vancouver, WAIm a lifelong practicing Catholic. Grew up in a large Irish Catholic family in which our faith was a large part of our upbringing. I am a mother of two great kids. They are grown and living independently. I am a full figured women. I love to laugh so a sense of humor is a must. My family is very important to me,and a big part of my life. I like to go camping, hiking, reading and road trips. Its fun going to the movies,trying fun restaurants, listening to live music. I enjoy going to plays as well as hanging out at home cuddling while watching a movie.
24, Seattle, WAIntroverted cat-lover who will never turn down an opportunity for a pun. PNW born and raised. Combination of Pam Beasley and Leslie Knope. 5'2 and hips that couldn't lie if they tried. I enjoy curling up with a cup of tea and a good book or crossword puzzle. I am a convert from Evangelical Protestantism. I fell in love with the liturgy and rhythms of the Church and I can't go back, because once you've tasted such pure beauty nothing else comes close. However, no matter how many Masses I attend or how many times I pray the rosary, the happy-clappy Jesus music and spontaneous prayers of my childhood will always be my mother tongue. I'm learning, and am fully committed to the Church, but I think I'll always be struggling to reconcile the faith of my growing-up years with my newfound Catholic faith.
21, Seattle, WAMy name is Mary. I'm a Seattle native, but I'm studying abroad in Rome at the moment. Finishing up my BA in Psychology/Theology next spring. Looking to grad school next. You can catch me on my porch playing ukulele. I am very family oriented, and I accredit much of my love for the faith to their witness. Anything else, just ask :)
50, Mukilteo, WAHow do I start? I am fairly new to this, so not really sure how. :) Well, I moved to the Northwest more than 2 yrs ago, so far, it's good. I am passionate about my faith, family and friends. I love to read on my spare time, listen to music, eat out and travel, am looking forward to visiting more places/countries in the future. I am a nice, caring woman with a good heart.
48, Port Orchard, WAsimple, family, friends, foodie, smiles, dog, long drives, walks, hikes, ocean, mountains, sun, stars, tea, lazy afternoons, laughter and faith-living
69, Bainbridge Island, WAI love to travel and I speak some Italian and go to Italy often. My faith is important to me, as are my friends and family. I have two children and five grandchildren. I am a private person but will share when I feel trust.
23, Spokane, WAI'm a current graduate student studying speech-language pathology. I enjoy working with children and helping them succeed. I also enjoy traveling, spending time talking over coffee, playing the piano and teaching piano, and singing choral music in our church choir.
30, Seattle, WAHi! A friend introduced me to this site and here I am. We went to Catholic high school together and I didn't stay active in he church like she did. I believe in the teachings of Catholicism and most importantly would like to find the man that can help me find my place and grow in the Church. I haven't lost my faith in any way, just my attendance in the brick and mortar church. I am passionate about people and put significant value in helping others feel worthy. I devote time to friends and family and am committed to to whatever work I'm doing. I've worked with real estate values and taxation over the last five years and intend to stay in the industry. I also work on some side jobs depending on the season. I'm also really big onto DIY projects and prefer to remodel or improve things myself first. I've recently learned the value in hiring some things out though. Beyond work and my house, I love playing indoor soccer year round, softball in the spring/summer, and whatever else might come up. I keep my schedule pretty full, by choice, and I'm looking for a man great enough for me to reprioritize. I hope to find him here.
Catholic Dating By Major City:
- Seattle,
- Spokane,
- Tacoma,
- Vancouver,
- Perth,
- Olympia,
- Everett,
- Bellevue,
- Renton,
- Federal Way,
- Puyallup,
- Yakima,
- Kent,
- Bothell,
- Kirkland,
- Bellingham,
- Kennewick,
- Auburn,
- Redmond,
- Lynnwood


text:
So the family is coming for the holidays. You know what you're doing for Christmas/Chanukah dinner, but what about all of those other meals?
When you get Shapiro's to help, your crowd will be pleased and you'll be the hero!
Shapiro's Delicatessen can help your meal planning with carry out corned beef, brisket and cheeses by the pound, hot dinners for any number of people, our famously delicious meat and cheese trays or a hot buffet for a holiday meal for a dozen or more people!
New Year's Day always brings a morning of lazy thoughts. Why not plan ahead and buy what you need for those hangover hunger pains with supplies for Reubens from Shapiro's? You know you want corned beef (even if you don't care about the cabbage) to start the new year off right. Plus, January 1st brings a home Colt's game to downtown Indy and you don't want to have to fight that crowd. Buy a couple of pounds of corned beef, our German Swiss cheese, Shapiro's famous rye bread and, except for some kraut, you're set for Reuben's in your pj's on New Year's Day!
Let the team at Shapiro's Delicatessen help you make feeding your family the easiest part of the holidays!


text:
Talk to any car enthusiast and they'll tell you buying an Audi, VW or Skoda is a great first step. But,
Once upon a time the place to buy diesel was a truck stop. Occasionally, you'd find a diesel pump stuck a
"We like to use only the highest quality components for your Skoda, Volkswagen and Audi vehicle and recommend the use of ATE brakes"


text:
Fulham manager Martin Jol goes into tonight's Premier League clash at Manchester United full of praise for Michael Carrick, fuelling speculation that he will seek to be reunited with the England midfielder when the summer transfer window opens.
It was Jol who gave Carrick his first start for Tottenham following a £2.75million move from West Ham in the summer of 2004.
And this product of the Wallsend Boys Club on North Tyneside where Alan Shearer and Peter Beardsley also honed their talents went on to become a mainstay of Jol sides at White Hart Lane.
Carrick was transferred to Manchester United for £18.6m in 2006. But while he has gone on to make over 250 appearances for Sir Alex Ferguson in all competitions, the 30-year-old has been the target of criticism for what some observers regard as his lack of impact and goals.
Jol will have none of that. "I feel Carrick is better than people give him credit for," said the former Tottenham manager. "He is an all-round player with specific qualities as well.
"He has vision, he plays it forward all the time, he can make interceptions, he never loses the ball and he can pass it with his right foot and his left foot.
"He has given Manchester United a lot of value for their money over the years."
Carrick is under contract until 2014 but Jol could seek to tempt him back to the capital as a replacement for his current midfield general, 35-year-old Danny Murphy. The former Liverpool player is expected to be on the Fulham bench tonight after making way for ex-Real Madrid star Mahamadou Diarra for the defeat at home against Swansea 10 days ago.
Jol said after that game: "There was not one player on the day who performed in the way I would like to see. So we need to give a response, hopefully against Manchester United."
Orlando Sa, Steve Sidwell and Zdenek Grygera remain sidlined by injury.
- More about:
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By KENNETH N. GILPIN
Published: October 18, 1983
The Chase Manhattan Corporation, the nation's third-largest bank holding company, reported yesterday that third-quarter net income declined 11.5 percent from the same period a year ago. The company said that the decline in earnings from levels a year earlier was primarily attributable to a lower level of nonfee-based income and higher operating expenses.
Two other of the nation's 10 largest bank holding companies - the First Chicago Corporation and the Security Pacific Corporation - reported higher earnings for the third quarter, citing improved interest and noninterest income. Chase Manhattan
Chase Manhattan reported third- quarter net income of $108 million, or $2.76 a share, down from $122 million, or $3.20 a share, in the comparable quarter a year ago.
Net income for 1983's first nine months was up 54.1 percent from the same period a year ago, to $319 million, or $8.18 a share. The company said that results for 1982's first nine months reflected a special after-tax loss of $117 million related to Chase's liquidation of Government securities positions assumed from Drysdale Securities. After Drysdale collapsed a year ago, Chase, which acted as the middleman for Drysdale's trades, paid off the company's obligations.
Chase reported that provision for possible loan losses in the third quarter fell to $70 million from $75 million in the third quarter of 1982. Net charge-offs during the period just ended totaled $64 million, down from $68 million a year earlier.
For the first nine months of 1983, provision for possible loan losses amounted to $210 million, the bank said, up from $185 million for the same period a year ago. Actual charge-offs totaled $193 million, up from $177 million.
The size of Chase's nonperforming loan category at the end of the third quarter was little changed from the end of the second quarter, but was up 58 percent from a year earlier.
As of Sept. 30, Chase had $1.9 billion of nonperforming loans, up from $1.8 billion at the end of the second quarter but sharply higher than the $1.2 billion in nonperforming loans at the end of last year's third quarter. The bank estimated the negative impact on third-quarter net from nonperforming loans at $13 million.
Slightly more than a quarter of Chase's nonperforming loans at the end of the third quarter were held by Latin American borrowers, with $224 million of loans to Mexico classified as nonperforming, $135 million in Argentina, $42 million in Brazil and $107 million in Venezuela. First Chicago
At First Chicago, the nation's eighth-largest bank, third-quarter earnings jumped 50.2 percent from the same period a year ago, to $49.1 million, or $1.05 a share, from $32.7 million, or 81 cents a share.
Barry F. Sullivan, chairman, attributed the increase to improved net interest income and substantial growth in noninterest income.
In the third quarter, net interest income rose to $193.2 million from $183 million a year ago, while noninterest income increased to $101.1 million from $70.7 million.
A major factor contributing to the increase in noninterest income was a $13.8 million gain on sales of equities, Mr. Sullivan said. Nonperforming assets totaled $1.01 billion at the end of the third quarter, up 14 percent from the end of the second quarter. A year ago, First Chicago had $850 million of nonperforming loans. Security Pacific
Third-quarter earnings at Security Pacific in Los Angeles, the nation's ninth-largest bank, rose 5.8 percent from the same period a year ago, to $67.4 million, or $1.83 a share, from $63.7 million, or $1.76 a share.
Richard J. Flamson 3d, chairman and chief executive, cited strong profit growth in Security's consumer banking business and higher earnings in the bank's specialized financial services group.


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text:
Now that David Haye has apparently become the retiring sort – though should the Klitschkos make him an offer he would be wiser to refuse, you can bet he will swiftly unretire – there is a charisma chasm at the top of boxing's heavyweight division. But not for long.
Step forward Anthony Joshua, 21, 6ft 7in, strikingly handsome and with a pleasantly engaging personality that is a promoter's dream.
Moreover, he can fight. The silvermedal with which he returned last week from the World Amateur Championships in Baku, Azerbaijan,is testimony to that.
Sometimes silver is an unwelcome consolation prize. The look on Sebastian Coe's face as he glanced down at his after Steve Ovett had pipped him in the 1980 Olympic800 metres final was one of disgust rather than delight. You sensed he might disdainfully have tossed it into the Moscow River.
It is a feeling that should not be shared by Joshua and his fellow world silver medallists Luke Campbell (bantamweight) and Andrew Selby (flyweight). In an outstandingchampionships for British boxers theirs were no bits of bling. Indeed, they could well be worth their weight in Olympic gold in London next year.
Especially Joshua's. For the young super-heavyweight is already on his way to becoming a superstar after first dethroning the reigning Olympic and double world champion Roberto Cammarelle, an Italian policeman, and then losing an arguably home-town decision by a single point to the Azerbaijani competitor in the final.
There is one problem. Will he be able to resist the rustle of banknotes from ear-bending promoters urging him to turn pro before the Games? Just over a year ago, after boxing for only two years, he won the ABA title in his 18th bout and received an offer of £50,000 to go pro there and then. He could get 10 times that amount now. But gold in London would be worth a couple of million.
Therein lies Big Josh's dilemma. Olympic gold would set him up for life, but there is always a risk. He could get injured or beaten and that world championship silver would lose its market value. It was a risk the then 17-year-old Amir Khan was not prepared to take after Athens, cashing in his silver in return for a seven-figure cheque from Frank Warren.
However, I am assured Joshua is committed to staying on for London. "I didn't take up the sport to earn money," he insists. "I did it to win medals. The thought of boxing in the Olympics gives me a beautifulfeeling." So, beauty KO's booty?
Had Joshua's bout against Magomedrasul Medzhidov been the 2012 Olympic final, there is no doubt he would have got the decision. In Baku the odds were stacked against him, with the Azerbaijani president sitting alongside the AIBA chief, Dr C K Wu, and thousands of screaming fans desperate to see the tournament conclude with a gold medal for the hosts. No surprise, then, that Medzhidov got the nod as Mr President warmly shook the hand of Dr Wu.
The British-born son of Nigerian parents, Joshua was brought up in Finchley, north-west London, where he is coached at the local amateur club by the former British featherweight champion Sean Murphy. As a child he was a talented footballer and ran 11 seconds for the 100 metres aged 15. It is this fleet-footedness which helps make him a less robotic version of Frank Bruno.
In his 29 bouts he has shown commodities that make a potentially great heavyweight: balls, a good chin and a decent punch. Yet earlier this year there was a good chance he would not make the Olympics, or any further international appearances, after being suspended by the Amateur Boxing Association of England when charged with possession of an illegal recreational substance with intent to supply. He was in danger of being kicked off the GB squad for good.
Joshua always protested his innocence, claiming he was set up, and the case appears to have been quietly dropped, much to everyone's relief.
While he may not have the chat and chutzpah of Haye, here is a genuine heavyweight with a smile that could make him one of the poster faces of 2012. Tomorrow he will receive his first accolade, having been voted the Amateur Boxer of the Year by the Boxing Writers' Club.
He may still be learning the ropes inside them and out, but Joshua now has the world at his fists. The questionis: can Josh resist the dosh?Reuse content


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And Conference Chuck Zimmerman August 9, 2014 at 7:46 am LOL.
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