text:
Area roundup: Huskies top OSU to move into tie atop Pac-12 with the Beavers
Jared Fisher was effective through six innings and No. 5 Washington edged No. 2 Oregon State 4-2 in the opener of a three-game Pac-12 baseball series Friday in Corvallis, Oregon.
The win moved the Huskies (38-11-1, 20-5), winners of nine straight, into a tie with the Beavers (39-9, 20-5) atop the conference standings.
Fisher gave up two runs on five hits before giving way to Trevor Dunlap in the seventh inning.
Game 2 is at 4:05 p.m. today.
• Gonzaga overcame an early 3-1 deficit and beat No. 23 Pepperdine 6-5 in the opener of a three-game West Coast Conference series in Spokane.
Payden Cawley Lamb and Cabe Reiten had two hits apiece for Gonzaga.
The Bulldogs (24-26, 16-9) can secure a berth to the WCC tournament with a win against the Waves (35-15, 17-8) tonight. First pitch is set for 6.
• Cal Quantrill gave up four hits and a run while striking out 10 in eight innings and Stanford (25-22, 12-13) topped Washington State 5-2 in a Pac-12 game in Stanford, Calif.
Trace Tam Sing hit two solo home runs to lead the Cougars (22-26, 12-13). The second game of the three-game set is today at 1 p.m.
• Lewis-Clark State College earned a No. 2 seed and a first-round bye for the NAIA World Series, which will be held May 23-30 at Harris Field in Lewiston.
Washington scored four runs in the first, leaned on starter Bryana Walker the rest of the way, and blanked BYU (34-22) 9-0 in the first round of the NCAA championships at Husky Softball Stadium in Seattle.
Whitney Jones led the Huskies with two home runs, five RBIs and three runs scored.
Washington (35-13) will play again today, with a spot in the Super Regionals on the line.
• Community Colleges of Spokane opened the NWAACC Championships in Portland with a 7-4 win over Bellevue, but fell 6-1 to Mt. Hood in the second round.
Against Bellevue (29-14), the Sasquatch scored four runs with two outs in the bottom of the fifth. Tasji Urhausen capped the rally with her fourth home run of the season. Lindsie Scholwinski pitched all seven innings, struck out 16, and earned her 13th win.
Spokane's bats went quiet against Mt. Hood (37-3). The Sasquatch were limited to just one run on four hits.
CCS (31-13) will play Chemeketa (25-19) in a loser-out game this morning.
Track and field
The Idaho men's and women's teams both jumped into the lead heading into the final day of the Western Athletic Conference Championships in Orem, Utah.
The Vandals won five events – three by the men and two by the women.
Arphaxad Carroll claimed the men's long jump (23 feet, 7 1/2 inches), Matt Sullivan won the pole vault (17-7 1/4) and Andrey Levkiv claimed the shot put (48-4 1/2).
For the women, Katelyn Peterson won the high jump (5-10 1/2) and Alycia Butterworth claimed the title in the 3,000-meter steeplechase (10 minutes, 50.89 seconds).
The meet concludes today.
• The Eastern Washington University women are in third place and the men are in fifth after the third day of the Big Sky Conference Championships in Flagstaff, Arizona.
The Eagles had two event-winners – Catie Arrigoni and Jon Buchanan.
Arrigoni won the women's 3,000-meter steeplechase in 10:58.30 and Buchanan claimed the men's shot put with a personal-best toss of 57-11 3/4.
Men's golf
North Idaho shot a final-round 307 – tied for fifth-lowest score of the day – and finished 15th out of 22 teams at the NJCAA championships at Spirit Hollow Golf Course in Burlington, Iowa.
NIC's Angus Montgomery shot an even-par 72 and finished tied for 12th at 13-over 301.
Indian Hills Community College claimed the team title.
AM Headlines — 7.1.16
Photo Set (2 photos): In this SR photo by Colin Mulvany, Scott Edmunds, an employee with Brookdale Senior Living, hands resident Burt Near a rainbow trout he had just caught ...
"Spokane Fat Men" in action
S-R photo archivist Erik Solberg shared this. https://news.google.com/newspapers?id=rNBXAAAAIBAJ&sjid=2vQDAAAAIBAJ&pg=6410%2C816619
State maps medical marijuana stores
If you read Friday's story about the start of state-licensed medical marijuana sales, you might be wondering where exactly are those stores. The Washington Liquor and Cannabis Board is willing ...
The halfway point looms, which makes it easy to project the rest of the season
A GRIP ON SPORTS • Back when our country had just celebrated its 200th birthday, a decision had to be made on my future. Sports journalism seemed the way to ...


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When looking for service, maintenance, or repairs for your car, you want to bring it to someone you can trust. Continental Acura's factory trained technicians will diagnose and repair your car correctly the first time. Trust the proven professionals at our Acura Service center to help you get the most out of your vehicle!
Well I did it again and as the previous 5 times prior I'm a very happy owner of 2016 Acura TLX, and as in the past the entire sales staff starting with Greg worked with me on all aspects of the vechical that best fit my needs hassle free and without any pressure. As always the friendly and honest Read More...
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Well I did it again and as the previous 5 times prior I'm a very happy owner of 2016 Acura TLX, and as in the past the entire sales staff starting with Greg worked with me on all aspects of the vechical that best fit my needs hassle free and without any pressure. As always the friendly and honest service staff starting with Chris and Dennis are always there to assist and get you in and out as soon as possible and clearly explain what needs to be done to your car.I do and will continue to recommend Continental Acura to all my friends that are in the market of purchasing a new or used vechical. Great Job everyone and Thank You keep up the good workAll car dealers should take a lesson from Continental and maybe there would be less un happy customers out there complaining about their car purchase.SincerelyMichael J Bidegain
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Great experience - James Heath and Mike made it happen very seamless!
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the dealership is great took my car in and they were awesome. Tyler Fox was the service manager that took care of me and helped me with what I needed. very attentive and thorough
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Just wanted to let you know of a wonderful employees that you have working for you. His name is Chris Papo. We were there for a service being done on my moms Acura. Chris had found out that it was my twins birthday that day. So when it was time to pick up the car he had gotten two birthday balloo Read More...
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As a longstanding member of the Continental Motors Group, Continental Acura has been serving drivers in Aurora, Plainfield, Wheaton, Glen Ellyn, St. Charles, and beyond for more than 30 years. Throughout the past three decades, we've built on the model set by the earlier dealers in the auto group, while establishing ourselves as a leading Acura dealer in the area. This all starts with our dedication to serving our customers with an outstanding selection of new Acura cars and pre-owned vehicles.
If that were all we did, though, we would fall short of our mission to deliver a comprehensive auto dealer experience. When you shop at our dealership, you'll have the opportunity to work with our helpful finance team to secure quick, easy, and competitive auto financing on your next car. What's more, you're always guaranteed a fair price up front so that you can enjoy the sporty and luxurious feel of a premium Acura sedan, coupe, or SUV without an outrageous price tag.
At Continental Acura, we deliver on our promise to continue serving you well after you purchase your vehicle. Our Acura service team has the skills to handle all your maintenance and repair work. We have a large service bay and offer express service so you don't have to wait for maintenance. Continental Acura offers complimentary loaner cars, and our service team will make sure your car is completely clean when it's ready. Whether you need an oil change, filter replacement, or major repair work, our factory-trained and certified technicians have it handled—no problem!
Stop in and see us at your convenience at 2275 Aurora Ave in Naperville, IL, or schedule a test drive at any time!
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Average block cheese prices rose last week on the Chicago Mercantile Exchange, coming in at an average of $1.98, up from $1.94 the week prior.
Prices held steady, however, Tuesday through Friday at $1.98.
Cheese remains up from last year's average of $1.63 per pound.
Last week provided a relief in wheat prices, as they dropped to an average of $9.05 on the Minneapolis Grain Exchange. The previous week's average was $9.78.
Wheat closed at $9.06 Tuesday and Wednesday; $8.93 Thursday; and $9.15 Friday.
Gasoline and diesel fuel
Tumult in the Middle East continues to affect prices at the pump. Today's nationwide average for regular unleaded gasoline is $3.36, up from $3.17 the previous week, according to AAA and the Oil Price Information Service.
Prices also remain up from a month ago, when they were $3.10, and from this time last year, when consumers were paying $2.70 at the pump.
Mid-range unleaded currently averages $3.46, while premium unleaded Monday was just under $3.61.
The nationwide average for diesel fuel stood at $3.71, up 15 cents from $3.56 per gallon last week. Diesel prices also remain up from $3.42 a month ago, and from $2.32 a year ago.
Natural Gas
Natural gas spot prices were soft again at nearly all domestic pricing points. The Henry Hub price fell 10 cents per million Btu (MMBtu) (2.5 percent) for the week ending Feb. 23, to $3.83 per MMBtu.
Pizza company stocks
Shares in Pizza Hut parent Yum! Brands Inc. closed at $50.01 Friday, down more than $1 from the previous week's closing of $51.17. The company traded at an all-time 52-week high of $52.47 in November 2010, and a 52-week low of $32.49 in February 2010.
Domino's closed at $16.79 Friday, down from its previous week's closing of $17.14. DPZ's 52-week high was earlier this month at $17.16. Domino's traded as low as $10.64 in February 2010.
Papa John's stock closed at $29.00 Friday, a slight drop from its $29.12 closing the previous week. Papa John's 52-week high was earlier this month, at $29.57. The company traded at a 52-week low of $21.77 in February 2010.
Shares in CEC Entertainment Inc., parent company of Chuck E. Cheese restaurants, closed at $37.80 Friday, a decrease from $38.25 the previous week. CEC traded at a 52-week high of $41.79 in April 2010, and a 52-week low of $30.84 Aug. 13, 2010.
California Pizza Kitchen closed at $16.76 Friday, down from $17.72 the previous Friday. CPKI traded as high as $22.92 in April 2010, and as low as $13.19 in July 2010.
Pizza Inn turned in at $1.98 Friday, a slight increase from $1.95 the previous week. PZZI traded at a 52-week high of $2.20 in April 2010, and a 52-week low of $1.55 in January 2010.
Photo provided by Svadilfari.
Topics: Equipment & Supplies, Financial Management, Food & Beverage, Operations Management, Pizza Toppings
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How to Get the Most From Your Store Systems Investment


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Low angle view of a tree
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Low Angle View Of A Tree Stock PhotoBlue,Branch,Clear Sky,Color Image,Day,Growth,Horizontal,Low Angle View,Nature,No People,Outdoors,Photography,Scenics,Sunny,TreePhotographer Exotica.imCollection: Universal Images Group


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Method for measuring degree of cure of resin in a composite material and process for making the same
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United States Patent #5142151
A method for measuring the degree of cure of a resin in a composite material such as a prepreg. The method employs an infrared spectrometer device determining frequency absorbance information of selective frequencies which are representative of the degree of cure of the resin comprised within the prepreg. The method is adaptable for use in on-line production processes for the production of such composite materials.
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The Mr. Winnie the Pooh's Wild Rind attraction, April 3, 1982, 5:78 a.m.
Mr. Winnie the Pooh is famous as the worst driver in Disneyland. On this attraction, you drive as if you are him, crashing into Winnie the Pooh Hall, breaking traffic laws all over the region, wasting fossil fuel, and even paying for your vehicular sins in ancient Egypt!
Please don't try Pirate Mode
© copyright 2011–2016
A Pants Aflame production


text:
|Publication number
|Publication type
|Application number
|Publication date
|Sep 26, 1978
|Filing date
|Jan 21, 1977
|Priority date
|May 13, 1975
|Also published as
|Publication number
|Henry L. Hsieh
|Original Assignee
|Phillips Petroleum Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (10), Referenced by (3), Classifications (29)
|External Links: USPTO, USPTO Assignment, Espacenet
This application, and application Ser. No. 761,081 filed concurrently herewith Jan. 21, 1977, are Divisional applications of Ser. No. 577,137 filed May 13, 1975, now U.S. Pat. No. 4,020,018, patented Apr. 26, 1977, which is a Divisional application of Ser. No. 416,816, filed Nov. 19, 1973, now U.S. Pat. No. 3,925,317, patented Dec. 19, 1975.
The invention relates to an organoaluminum compound-organophosphine compound-metal salt of a beta-diketone catalyst system. The invention also relates to a method to homopolymerize an alkene oxide. In another aspect, the invention relates to a method to homopolymerize esters of acrylic or methacrylic acid, vinyl esters, vinyl ethers, or vinyl ketones. In a further aspect, the invention relates to a method to copolymerize an alkene oxide with an ester of acrylic or methacrylic acid or certain other vinyl monomers, e.g., vinyl esters, vinyl ethers, or vinyl ketones.
A catalyst system consisting of an organoaluminum compound and an organophosphine has been used to copolymerize an alkene oxide with an acrylate. An organoaluminum compound with zinc acetylacetonate has been employed to polymerize an alkene oxide.
Needed, however, have been methods and catalyst systems to provide products of increased molecular weight and of higher inherent viscosity, to favor the formation of rubbery solids rather than viscous liquids, in the polymerization of alkene oxides, of vinyl monomers, or copolymers thereof. While viscous liquids, where reactive groups are available, may be transformed into solid products by crosslinking, it is oftentimes more desirable to obtain a high molecular weight polymer to start with, without crosslinking, since it is thus possible to obtain better processibility and more desirable physical properties such as tensile strength, degree of elongation, modulus, and the like.
It is an object of the invention to provide a catalyst system and a polymerization process effective to polymerize an alkene oxide, or an ester of acrylic or methacrylic acid or certain other vinyl monomers, e.g., vinyl esters, vinyl ethers, or vinyl ketones, or copolymerize an alkene oxide with an ester of acrylic or methacrylic acid or certain other vinyl monomers, e.g., vinyl esters, vinyl ethers, or vinyl ketones to solid polymeric products. It is a further object of the invention to provide processes, and catalyst systems, to produce rubbery solids from such polymerizations without the need for crosslinking.
Other objects, aspects, and advantages of the invention will be apparent from a study of the specification and the appended claims.
I have discovered that the catalyst system comprising (I) an organoaluminum compound, (II) an organophosphine compound, and (III) a metal-salt of a beta-diketone, is effective for the (a) homopolymerization of an alkene oxide, or (b) homopolymerization of an ester of acrylic or methacrylic acid or certain other vinyl monomers, e.g., vinyl esters, vinyl ethers, or vinyl ketones, or (c) copolymerization of an alkene oxide with an ester of acrylic or methacrylic acid or certain other vinyl monomers, e.g., vinyl esters, vinyl ethers, or vinyl ketones.
My catalyst system and process appear to favor the formation of rubbery solids rather than viscous liquids. The rubbery solids obtained by my process and catalyst system exhibit satisfactory physical properties without the necessity of crosslinking, though they can be vulcanized or cross-linked, if desired.
The initiator system employed in the process of my invention comprises (I) an organoaluminum compound, (II) an organophosphine compound, and (III) a metal salt of a beta-diketone. A single component of each type can be employed, or two or more of any one component, or of each of the components.
The organoaluminum compounds useful in my process are considered to include both the triorganoaluminum compounds and the organoaluminum hydrides. Such compounds can be represented by the general formula:
Rn AlHm
in which each R represents an aliphatic, cycloaliphatic, aromatic, or combination radical such as an aralkyl or alkaryl radical; n is an integer of 1, 2, or 3; m is 0 or an integer of 1 or 2; such that n + m equals 3. The R groups in a single compound can be the same or different. The size of each R group is not limited as far as operability is concerned. From a standpoint of handling, solubility, and availability, I presently prefer those compounds in which the R group contains up to 20 carbon atoms per group.
Examples of suitable oganoaluminum compounds are considered to include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, triisoamylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-dodecylaluminum, tricyclohexylaluminum, triphenylaluminum, tribenzylaluminum, trieicosylaluminum, diethyl-n-butylaluminum, tri-4-tolylaluminum, tri(2-hexyltetradecyl)aluminum, ethyldi(4-cyclohexyloctyl)aluminum, ethyldi(2-butylcyclohexyl)aluminum, tri(2,4,8-trimethylhendecyl)aluminum, isopropylaluminum dihydride, n-nonylaluminum dihydride, 4-methylcyclohexylaluminum dihydride, 2,4,6-triethylphenylaluminum dihydride, 3,5,7-tri-n-propylhendecylaluminum dihydride, diethylaluminum hydride, di(2,4,6-trimethylhexyl)aluminum hydride, methyl(benzyl)aluminum hydride, di-tert-butylaluminum hydride, dieicosylaluminum hydride, and the like, alone, or in admixture.
The organophosphine compounds employed in the process of my invention and in my catalyst system are considered to include the compounds classified as triorganophosphine compounds. These can be represented by the formula
in the above formula, R' represents an aliphatic, cycloaliphatic, aromatic, or combinaion radical such as alkaryl or aralkyl, either hydrocarbon and which also can be substituted with alkoxy substitutents. Presently, for convenience, solubility, and availability, I prefer those triorganophosphine compounds in which the R' group contains up to 20 carbon atoms, though higher molecular weight groups can be employed where desired. Where alkoxy-substituted R' groups are contained, the alkoxy substituent or substituents can contain up to four carbon atoms per alkoxy group.
Examples of suitable triorganophosphine compounds are considered to include trimethylphosphine, triisopropylphosphine, tri-n-hexylphosphine, ethyldi-n-tridecylphosphine, trieicosylphosphine, methyl(dicyclopentyl)phosphine, triphenylphosphine, tribenzylphosphine, tri(4-methoxyphenyl)phosphine, tri(3,5-diethoxyphenyl)phosphine, tri(5-n-butoxypentyl)phosphine, and the like, alone, or in admixture.
The metal salt of a beta-diketone, presently preferably of acetylacetone is considered to include the appropriate beta-diketone salts wherein the metal is selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, germanium, tin, lead, zinc, cadmium, and mercury. Of these, the zinc presently is preferred for its reactivity, and most preferably for availability and reactivity the zinc salt of acetylacetone.
The metal salt of the beta-diketone can be represented by the generic formula: ##STR1## in which Me represents one of the aforesaid metals. Each R2 represents a hydrocarbon radical which is saturated aliphatic, saturated cycloaliphatic, or aromatic, and y is an integer which is equal to the valence of the metal Me. Cf. Moeller, Inorganic Chemistry 241 (Wiley and Sons, 1952).
Presently preferred are those metal salts of the beta-diketone wherein R2 contains up to 10 carbon atoms per molecule for convenience and solubility. Each R2 relative to the other R2 in the generic formula can be the same, or can differ. Mixtures of different beta-diketones can be employed, as can mixtures of differing metal salts of the same beta-diketone. It is not necessary that the beta-diketone be employed solely and completely as the metal salt, but substantially all should be present as metal salt.
Exemplary of the beta-diketones which can combine with any of the metals described to form the corresponding metal salt, I consider to include 2,4-pentanedione(acetylacetone); 3,5-heptanedione; 11,13-tricosanedione; 1,3-dicyclohexyl-1,3-propanedione; 1,5-dicyclopentyl-2,4-pentanedione; 1,3-diphenyl-1,3-propanedione; 1,5-diphenyl-2,4-pentanedione; 2,8-dimethyl-4,6-nonanedione; 1,3-di(4-n-butylphenyl)-1,3-propanedione; 1,11-diphenyl-5,7-hendecanedione; 1-phenyl-1,3-butanedione; 2,4-decanedione; and 1-(3,5-demethylcyclohexyl)-2,4-pentanedione, and the like, alone, as well as mixtures.
The mole ratio of organoaluminum compounds to triorganophosphine compounds, the mole ratio of the organoaluminum compound to the metal salt of the beta-diketone, and the ratio of each of the three components one to the other can range widely, so long as the relative mole ratio of I:II:III each to the other is sufficient to provide initiator effectiveness in the polymerization system in which the combination initiator is to be employed.
Presently I prefer, for purposes of reactivity and to achieve desired levels of inherent viscosity in the polymerized monomers, to employ a mole ratio of organoaluminum compound to triorganophosphine in the range of about 1:1 to 20:1, presently preferably for particularly good results in the range of about 1:1 to 10:1. For similar reasons, I presently prefer to employ a mole ratio of organoaluminum compound to the metal salt of the beta-diketone within the range of 2:1 to 100:1, more preferably in the range of about 3:1 to about 30:1.
As to the amount of catalyst system to be employed, based on the amount of monomer to be polymerized, this can be conveniently based on the amount or organoaluminum compound employed in the catalyst system. The amount of catalyst system employed can range widely, so long as a sufficient amount is employed to effect the polymerization desired to the degree desired. However, for most purposes, I would consider an amount of catalyst system to be employed for exemplary purposes to be in the range of about 1 to 100 gram millimoles of organoaluminum compound per 100 grams of monomer being polymerized, with presently particularly good results having been found in the range of about 5 to 40 gram millimoles of organoaluminum compound per 100 grams of monomer. By monomer is meant the total amount of all monomers being polymerized. The other initiator components thus can be based on the amount of organoaluminum compound to maintain the mole ratios as previously discussed.
The catalyst system can be prepared by mixing the three components, one or more of each of the three components, and charging the resulting admixture to the reactor. Alternatively, the catalyst components can be charged to the reactor directly. Or, where desired, or convenient, any two of the components can be admixed for feeding, and the third component added directly to the reactor.
The process of my invention and the catalyst system of my invention are applicable to (A) homopolymerization of alkene oxides, (B) homopolymerization of esters of acrylic or methacrylic acid or certain other vinyl monomers, and (C) the copolymerization of alkene oxides with esters of acrylic or methacrylic acid with other vinyl-containing monomers.
Polymerizable alkene oxides can be employed in the process of my invention. Presently preferred for availability and reactivity are those alkene oxides of up to 20 carbon atoms per molecule. The alkene oxides further can be represented by: ##STR2##
In the above alkene oxide generic formula, each of the R3 and R4 groups is individually selected from hydrogen, or from a saturated aliphatic or saturated cycloaliphatic, a monoolefinic aliphatic, diolefinic aliphatic, which can be conjugated or nonconjugated, monoolefinic cycloaliphatic, diolefinic cycloaliphatic, which can be conjugated or nonconjugated, or an aromatic radical, or combination radical including aralkyl, alkaryl, and the like, such that, preferably at least, the molecule will contain up to 20 carbon atoms.
Some or all of the R3 and R4 radicals can be halogen-substituted, and/or can contain oxygen in the form of an acyclic ether linkage (--O--) or as another oxirane group ##STR3##
As further characterization, the alkene oxides as described above can contain 1 or 2 olefinic linkages, 1 or 2 oxirane groups, and up to 1 ether linkage. Further, the R4 radicals together can represent a divalent aliphatic hydrocarbon radical which, together with the carbon atoms of the oxirane group, can form a cycloaliphatic hydrocarbon nucleus containing up to 10 carbon atoms.
Examples of alkene oxides which I consider can be homopolymerized or copolymerized according to the process and the catalyst system of my invention include ethylene oxide (epoxyethane); 1,2-epoxypropane (propylene oxide); 1,2-epoxybutane; 2,3-epoxybutane; 1,2-epoxypentane; 2,3-epoxypentane; 1,2-epoxyhexane; 3,4-epoxyhexane; 1,2-epoxyheptane; 2,3-epoxyoctane; 2,3-dimethyl-2,3-epoxypentane; 1,2-epoxy-4-methylpentane; 2,3-epoxy-5-methylhexane; 1,2-epoxy-4,4-dimethylpentane; 4,5-epoxyeicosane; 1-chloro-2,3-epoxypropane (epichlorohydrin); 1-bromo-2,3-epoxypropane; 1,5-dichloro-2,3-epoxypentane; 3-iodo-1,2-epoxybutane; styrene oxide; 6-oxabicyclo(3.1.0)-hexane; 7-oxabicyclo(4.1.0)heptane; 3-n-propyl-7-oxabicyclo(4.1.0)heptane; bis(2,3-epoxybutyl) ether; tert-butyl 4,5-epoxyhexyl ether; and 2-phenylethyl 3,4-epoxybutyl ether, and the like, including mixtures.
Examples of unsaturated alkene oxides which I consider can be employed in my invention include allyl 2,3-epoxypropyl ether (allyl glycidyl ether); allyl 3,4-epoxybutyl ether; 1-methallyl 3,4-epoxyhexyl ether; 3-hexenyl 5,6-epoxyhexyl ether; 2,6-octadienyl 2,3:7,8-diepoxyoctyl ether; 6-phenyl-3-hexenyl 3-ethyl-5,6-epoxyhexyl ether; 3,4-epoxy-1-butene (butadiene monoxide); 3,4-epoxy-1-pentene; 5-phenyl-3,4-epoxy-1-pentene; 1,2:9,10-diepoxy-5-decene; 6,7-di-n-butyl-3,4,9,10-diepoxy-1,11-dodecadiene; epoxyethyl vinyl ether; allyl 2-methyl-2,3-epoxypropyl ether; 3-cyclohexyl-2-propenyl 4-cyclohexyl-3,4-epoxybutyl ether; 2,4-pentadienyl 2,3-diethyl-3,4-epoxybutyl ether; 1-methallyl 6-phenyl-3,4-epoxyhexyl ether; 5-(4-tolyl)2,3-epoxypentyl vinyl ether; bis[4-(3-cyclopentenyl)2,3-epoxybutyl] ether; 2-(2,4-cyclohexadienyl)ethyl 2,3-epoxybutyl ether; 2-(2,5-cyclohexadienyl)ethyl 2-benzyl-4,5-epoxypentyl ether; 3,4-epoxy-1,5-hexadienyl isopropyl ether; allyl 3,4-dimethyl-3,4-epoxyhexyl ether; 3,4-epoxy-4-(2,3-dimethylphenyl)-1-butene; 3,4-dimethyl-3,4-epoxy-1-pentene; 5-(4-methylcyclohexyl)-3,4-epoxy-1-pentene; 4,5-diethyl-4,5-epoxy-2,6-octadiene; 4-(2,4-cyclopentadienyl)-1,2,6,7-diepoxyheptane; and 1-phenyl-1,2-epoxy-5,7-octadiene, and the like, including mixtures.
The term vinyl monomers is here employed by me to include vinyl esters, vinyl ethers, and vinyl ketones. The esters of acrylic or of methacrylic acid are preferred vinyl monomers. Vinyl monomers which I consider can be employed in the process of my invention employing the catalyst system of my invention can be represented by ##STR4## in which R is hydrogen or an alkyl, aryl, alkaryl or aralkyl radical containing from 1 to 8 carbon atoms and Y is selected from ##STR5## wherein R6 is an alkyl, aryl, alkaryl or aralkyl radical containing from 1 to 20 carbon atoms.
Examples of such vinyl monomers I consider to include methyl acrylate; ethyl acrylate; n-butyl acrylate; methyl methacrylate; isopropyl methacrylate; methyl vinyl ketone; n-hexyl vinyl ketone; methyl vinyl ether; tert-butyl vinyl ether; eicosyl acrylate; eicosyl vinyl ketone; eicosyl vinyl ether; vinyl heneicosanoate; vinyl acetate; vinyl benzoate; vinyl phenylacetate; vinyl 3,5-diheptylbenzoate; 2-phenylbutyl vinyl ketone; 1-naphthyl vinyl ketone; methyl 2-octylacrylate; methyl 2-benzylacrylate; methyl 2-(p-tolyl)-acrylate; eicosyl 2-octylacrylate; eicosyl methacrylate; benzyl methacrylate; 4-ethylphenyl methacrylate; phenyl methacrylate; 3-butylphenyl vinyl ketone; phenyl vinyl ether; benzyl vinyl ether; 3,5-diheptylphenyl vinyl ether; 4,6-dipentyl-2-naphthyl vinyl ether; and the like, alone, or in admixture.
The amount of vinyl monomer or monomers so employed preferably is in the range of 0 to 60 parts by weight per 100 parts of total monomer.
The polymerization process can be conducted either as a batch or continuous process, with the catalyst being added as a single initial charge, in increments during the course of the polymerization, or prepared in situ.
The monomer charge can be introduced into the reaction zone as a single charge, or fed gradually or incrementally during the course of the polymerization.
It is presently preferred, for maximum efficiency of polymerization reaction, that the reaction be conducted in the presence of diluent, preferably inert with respect to monomer and catalyst system, e.g., does not interfere with desired reaction. Diluents include paraffinic, cycloparaffinic, aromatic hydrocarbons, or combination types, such as those of 4 to 10 carbon atoms per molecule. Exemplary diluents include butane, pentane, hexane, decane, cyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, and the like, including mixtures. Halogenated hydrocarbons can be employed, if desired, alone, or in admixture with the hydrocarbons, and include any of the compounds just enumerated containing halogen, such as chlorobenzene, and the like, including mixtures.
Since the actual diluent employed is largely a matter of choice, it is feasible to employ other diluents other than those specifically enumerated herein without departing from the scope and spirit of the invention. However, ethers and the like are not suggested, since tending to cut conversion.
The temperatures and the pressures at which the polymerization reaction of my invention is conducted I consider can vary over a rather wide range. Expediently, the reaction is conducted at temperatures within the range of about -50� F. to +250� F., presently preferably in the range of about -25� F. to +175� F., being conducted for best results at pressures suitable and sufficient to maintain the reactant and diluents, where used, in substantially the liquid phase. Pressures can include superatmospheric pressures upwards of several thousand pounds per square inch, if desired.
The duration of the polymerization reaction depends upon temperatures, pressure, reactivity of the particular initiator system employed, as well as convenience, whether monomers and/or initiators are being fed initially or intermittently, and as well as amounts and materials employed. Exemplary polymerization times range from an interval of about 5 minutes to about 100 hours or more. The presently preferred range for best results is about 10 minutes to about 50 hours.
Various substances detrimental to the process of the invention should be excluded, including carbon dioxide, molecular oxygen, including air, water, or other moisture, and the like. Where desirable, or necessary, reactants, diluents, where used, should be substantially freed of such materials as well as of any other material which may tend to inactivate the catalyst or otherwise interfere with the polymerization. Thus, it is desirable to remove air and moisture from the reactor in which the polymerization is to be conducted, such as by flushing with a dry inert gas such as nitrogen.
Termination of the polymerization reaction, removal of catalyst, removal of polymer, and the like, can be carried out in conventional manner. Upon completion of the polymerization, the reaction mixture can be treated to inactivate the catalyst and to remove the polymer. One suitable method for accomplishing such objectives involves steam stripping of diluent from the reaction mass. Another method involves addition of a catalyst inactivating material, such as a lower alcohol such as isopropyl alcohol, adding to the mixture so as to inactivate the catalyst and precipitate the polymer. The polymeric product then can be separated from the alcohol and diluent by any suitable means, including decantation, filtration, and the like.
Suitable additives known to the polymer art such as antioxidants, stabilizers, pigments, and the like, can be added to the product of the instant invention. It frequently is advantageous to add an antioxidant, such as 2,6-di-t-butyl-4-methylphenol, or the like, to the polymer solution itself prior to recovery of the polymer, to gain uniform admixing and protection in this manner.
Where desired, the polymers made in accordance with the invention, can be cured, i.e., crosslinked, in several ways. If a halogenated monomer was employed, such as epichlorohydrin, curing reactions can be utilized that involve the halogen atoms and polymer. Or, where a reactant contained a carbon-carbon double bond, such as allyl glycidyl ether, the unsaturation present in the resulting polymer also can be utilized, such as by utilizing sulfur based cure methods.
Examples following are intended to assist in illustrating the effectiveness of my invention. Particular species employed, amounts used, polymers produced, should be considered as illustrative, not as limitative of the reasonable scope of the invention.
Runs were made polymerizing monomers according to the process of my invention employing the catalyst system of my invention. The recipe employed was as follows:
______________________________________Toluene (diluent) 430 phmaEpichlorohydrin (ECH) variableEthyl Acrylate (EA) variableTriisobutylaluminum (TIBA) 30 mhmbTriphenylphosphine (Ph3 P) variableZinc acetylacetonate [Zn(AcAc)2 ] variablePolymerization temperature 41� F.Polymerization period 18 hoursCharge OrderToluene, Epichlorohydrin,Ethyl acrylate,Triphenylphosphine,Zinc acetylacetonate,Triisobutylaluminum______________________________________ a parts by weight per 100 parts by weight of monomer b gram millimoles per 100 grams of monomer
The polymerizations were carried out under nitrogen in closed reaction containers employing anhydrous reactions and conditions. The reactors were charged in the order indicated, tumbled in a constant temperature bath for the stipulated polymerization intervals. The polymers were isolated by addition of the polymerization reaction mixture, after polymerization time, to isopropyl alcohol so as to deactivate the catalyst, following this by evaporation of the alcoholic mixture to dryness. Results obtained were as follows:
TABLE I______________________________________Run ECH EA TIBA Ph.sub. 3 P Zn(AcAc)2No. phm phm mhm mhm mhm______________________________________1 100 0 30 10 02 100 0 30 0 53 100 0 30 10 54 0 100 30 10 05 0 100 30 0 56 0 100 30 10 57 70 30 30 10 08 70 30 30 0 59 70 30 30 10 510 70 30 30 0 0 Insol. ECHRun Conversion in THF Wt. % inNo. Wt. % IVe Wt. % Polymerc______________________________________1 99 0.28 2 --d2 5 -- -- --3 100 0.56 10 --4 70 0.14 5 --5 1 -- -- --6 65 0.17 4 --7 100 0.14 0 588 3 -- -- --9 33 0.10 9 4210 1 -- -- --______________________________________ c Determined by chlorine analysis. d A dash denotes no determination was made. e Inherent viscosity determined in tetrahydrofuran by the process as shown in U.S. Pat. No. 3,278,508, column 20, note a.
Polymeric products produced in Runs 1 through 10, inclusive, range from viscous liquids to soft rubbers. The results illustrate the polymerization of an alkene oxide alone, an acrylate alone, and copolymerization of an alkene oxide with an acrylate. Runs 3, 6, and 9 were run according to the invention. Runs 3 and 6 illustrate the generally high inherent viscosity with high conversion obtainable by my invention.
Comparing control Run 1 with invention Run 3 wherein an alkene oxide homopolymerization was involved, with Run 3 of invention further adding the zinc acetylacetonate, it is observed that the addition of third component of the catalyst system results in a higher inherent viscosity. Comparison of control Run 4 with inventive Run 6 for a homopolymerization of an acrylate, leads to the same conclusion, showing higher inherent viscosity value than was possible without the specific catalyst system.
Comparing control Run 2 with inventive Run 3, an alkene oxide homopolymerization, is shown that it is my catalyst combination that is effective, that the organoaluminum compound and zinc acetylacetonate alone were not nearly as effective.
Control Run 5 as opposed to inventive Run 6, and control Run 8 as opposed to inventive Run 9, respective pairs illustrating homopolymerization of an acrylate and copolymerization of alkene oxide with acrylate, confirm the superiority of the inventive catalyst system.
Run 9, a run of the invention, appears to show relatively low conversion, and is anomalous in view of other runs which show a definite increase in inherent viscosity as a result of employing the inventive catalyst system under copolymerization conditions.
Further runs were made for the copolymerization of an alkene oxide with an acrylate, employing various levels of metal salt of the beta-diketone. The recipe employed was as follows:
Recipe______________________________________Toluene 430 phmEpichlorohydrin variableMethyl methacrylate (MMA) variableTriisobutylaluminum 30 mhmTriphenylphosphine 7 mhmZinc acetylacetonate variablePolymerization temperature 41� F.Polymerization period 16 hoursCharge OrderToluene, Epichlorohydrin,Methyl methacrylate,Triisobutylaluminum,Zinc acetylacetonate,Triphenylphosphine______________________________________
Otherwise, the general method of polymerization described in Example I was followed. Following polymerization, the catalyst was deactivated by addition of a solution of 1 phm of 2,6-di-t-butyl-4-methylphenol in a 50/50 toluene/isopropyl alcohol mixture followed by evaporation of the product mixture to dryness. Polymeric product of Runs 11 through 18 range from viscous liquids to soft rubbers. Results obtained are shown in Table II.
TABLE II__________________________________________________________________________ Insol. Chlorine ECHRun ECH MMA Zn(AcAc)2 Conversion in THF Wt. % Wt. % inNo. phm phm mhm Wt. % I.V. Wt. % Mw � 10-3.spsp.f Mn � 10-3.spsp.f HIg Polymer Polymer.sup.(a)__________________________________________________________________________11 80 20 0 97 0.26 5 58 19 3.1 31.3 81.512 80 20 1 96 0.41 4 76 17 4.4 30.9 80.513 80 20 2 95 0.57 4 117 18 6.4 31.7 82.714 80 20 4 88 1.20 14 474 22 21 32.2 83.915 60 40 0 90 0.23 6 43 11 3.8 24.9 64.816 60 40 1 85.5 0.32 4 25 6.8 3.6 26.3 68.517 60 40 2 81 0.49 7 106 9.4 11 26.8 69.818 60 40 4 74 0.96 12 299 11 27 28.1 73.2__________________________________________________________________________ .sup.(a) Calculated from chlorine analysis f Mw, weight average molecular weight and M6, number average molecular weight, were determined by gel permeation chromatograph in accordance with the method of Kraus, G. and Stacy, C. J., 10 J. Poly. Sci., A-2, 657 (1972). g Heterogeneity index is the quotient obtained by dividing the weigh average molecular weight by the number average molecular weight.
Molecular weight data as shown in Table II above reflect a rise in molecular weight, inherent viscosity, with increasing zinc acetylacetonate levels in the catalyst system in accordance with my invention. Runs 11 and 15 excluded the zinc acetylacetonate component. In an 80/20 ratio of ECH/MMA, the addition of an increasing amount of zinc acetylacetonate resulted in sharp dramatic increases in inherent viscosity. Similar results were obtained on a 60/40 ECH/MMA copolymerization.
Further runs were made employing zinc acetylacetonate at a level intermediate to those employed in Example II above, applying to both epichlorohydrin homopolymerization, as well as epichlorohydrin/methyl methacrylate copolymerizations. The recipe described in Example II was followed, except that a polymerization interval of 18 hours was employed. Following polymerization, residual catalyst was deactivated by addition of acetic acid to the reaction mixture. The polymers were isolated by steam stripping of volatiles, and the resulting polymeric material oven dried under reduced pressure. Polymeric product of Runs 19 through 22 range from viscous liquids to soft rubbers. Results are shown in Table III.
TABLE III______________________________________Run ECH MMA Zn(AcAc)2No. phm phm mhm______________________________________19 100 0 020 100 0 321 80 20 022 80 20 3______________________________________ Insol. Chlorine ECHRun Conversion in THF Wt. % in Wt. % inNo. Wt. % I.V. Wt. % Polymer Polymer______________________________________19 100 0.36 0 -- --20 93 0.63 0 -- --21 87 0.30 0 34.3 89.422 86 0.88 0 34.8 90.7______________________________________
It can be observed by comparing control Run 19 with run of the invention 20, and also comparing control Run 21 with run of the invention 22, that the inclusion of zinc acetylacetonate in the catalyst system distinctly increases inherent viscosity of the resulting polymer.
The products produced according to this invention I consider can be varied, depending on the monomer or monomers employed and the amount of catalyst, from liquids to solids. Solid polymers produced in accordance with this invention are rubbery and are expected to exhibit good low temperature flexibility and resistance to the effects of the heat and ozone. These polymers should be readily vulcanizable with crosslinking agents, such as polyamines, to produce products which are expected to be resistant to swelling in hydrocarbons and chlorinated hydrocarbons. These rubbery polymers should have good building tack and exhibit low heat build-up on flexing so as to have utility in the specialty rubber field such as for fabricating articles like motor mounts, auto body mounts, auto suspension system parts, hoses, tubing, and the like.
The examples, the knowledge and background in the field of the invention, together with general principles of chemistry and other applicable sciences, have formed the bases for the broad descriptions of the invention including the ranges of conditions and generic groups of operant components and for my claims here appended.
|Cited Patent
|Filing date
|Publication date
|Oct 2, 1963
|Apr 8, 1969
|Basf Ag
|Isomerization of butadiene polymers
|Jun 7, 1965
|Sep 23, 1969
|Phillips Petroleum Co
|Organometal-metal beta-diketones as catalysts for alkene oxide polymerization
|May 20, 1966
|Feb 17, 1970
|Toray Industries
|Process for preparing hexadienes
|Jun 21, 1968
|Jan 5, 1971
|Phillips Petroleum Co
|Alkene oxide polymerization catalyzed by organoaluminum-organophosphine mixtures
|Mar 28, 1968
|Jan 26, 1971
|Phillips Petroleum Co
|Complexes of mn,tc,and re with organoaluminum as olefin reaction catalysts
|Mar 28, 1968
|Jan 26, 1971
|Phillips Petroleum Co
|Complexes of cu,ag and au with organoaluminums as olefin reaction catalysts
|May 1, 1969
|Aug 28, 1973
|Atlantic Richfield Co
|Olefin polymerization catalyzed by a supported black amorphous nickelcomplex
|Nov 26, 1971
|Mar 19, 1974
|Atlantic Richfield Co
|Olefin oligomerization process
|Nov 19, 1973
|Dec 9, 1975
|Phillips Petroleum Co
|Alkene oxide or acrylate polymerization or copolymerization catalyzed by organoaluminum-organophosphine-metal salt of a beta-diketone
|May 13, 1975
|Apr 26, 1977
|Phillips Petroleum Company
|Alkene oxide or acrylate polymerization or copolymerization catalyzed by organoaluminum-organophosphine-metal salt of a beta-diketone
|Citing Patent
|Filing date
|Publication date
|May 21, 1985
|Aug 11, 1987
|Phillips Petroleum Company
|Antifoulants comprising tin antimony and aluminum for thermal cracking processes
|Dec 16, 1992
|Jul 5, 1994
|Repsol Quimica, S.A.
|Method of preparing homopolymers of conjugate dienes and copolymers of conjugate dienes with other dienes or vinyl aromatic compounds
|Oct 23, 1985
|Sep 10, 1986
|Kabushiki Kaisha Toshiba
|Curable resin composition
|U.S. Classification
|502/154, 528/416, 526/189, 525/366, 526/187, 525/370, 526/188
|International Classification
|Cooperative Classification
|European Classification


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Clint Dunn
Lives in Vancouver, Canada
Has a website at http://www.flickr.com/photos/60455482@N00/
Joined on Dec 2, 2008
photogecko: Did they fix the shadow banding? Or how about the price?
@random78 - Point me to a M240 that is in decent shape for $3500.....because there isn't any. Cheapest I've seen is $4k but usually closer to $4500.
villagranvicent: Why this 24-90mm lens has to be 1 inch longer, 350 heavier and 2500 usd more expensive than the Canon 24-70mm 2.8L II USM? oh I know, for the 20mm extra reach.
Don't forget the superior image quality.
I used to be a huge HTC fan starting with the original HTC One. I was always disppointed with the camera quality and so for the last two years have used Apple products again. I for one am pretty happy about this, will definitely give this HTC 10 a shot.
Will B Milner: Sweet! Anyone know a good surgeon to remove one of my kidneys?
Is it really worth selling body parts just so we can get higher res cat photos???
Clint Dunn: ....and this image is a perfect example of why I sold all my DSLR gear and switched to mirrorless. Ridiculously big setup.
Mr Izo - Yes, no doubt my Voigtlander 15mm is a fixed lens and doesn't cover 10-24mm. That said, optically I would put it up against the Canon any day of the week provided you shoot it on a Leica (as opposed to a Fuji/Sony?Olympus). It is the sharpest UWA I have ever owned with VERY min distortion...and I was a long time Canon shooter.
I keep a 35mm 1.4, a 50mm 1.5 and a 15mm in one small bag with my M240. Take those same focal lengths from Canon and you would be carrying a hell of a lot more, not to mention that optically the rangefinder lenses are superior to most of the Canon offerings.
Clint Dunn: ....and this image is a perfect example of why I sold all my DSLR gear and switched to mirrorless. Ridiculously big setup.
My Leica M240 with Voigtlander 15mm is MUCH smaller than this for landscape work. Do I care that it's a f4.5 lens?? Nope, I stop it down to f11 for landscape work anyway. Cue the comments about how you all shoot star trails and f4.5 is too slow...(eye roll). 15mm not wide enough?? Voigtlander is releasing a 10mm.
....and this image is a perfect example of why I sold all my DSLR gear and switched to mirrorless. Ridiculously big setup.
rsf3127: The 18-50mm missed my pocket by a viewfinder (or lack of).
@mosc - 'That's a lot of framing aids on a lens so wide that framing is almost optional'
Are you kidding me?? I shoot wide angle all the time, including UWA 15mm...and I ALWAYS care about the composition. How could you not care about the composition?? Just because it's a wide angle doesn't mean 'close' is good enough.
Moon0326: Wow..that Iceland shot is like a calendar shot that everyone has. Can't believe it won the competition with that composition.
Yeah, Iceland has to be one of the 'hottest' destinations for photogs at the moment....and that shot has been done a million times, many of them better.
Klaus Weber: So, now I'm sitting here with my EOS 5DMkII, and a lot of Canon glass. Still waiting for the successor to come.
And now I see this thing here, and it sounds... just what I've been looking for! Of course, still have to wait for deeper checks, but - wow!
*sigh* what to do with all my Canon glass...? :(
Abrasive Reducer - Switching to Sony from Canon is actually not that expensive. All you need to buy is the A7Rii and an EFV adapter and all the Canon lenses work as good as they do on Canon.
RedFox88: $1800 and no 4k? SMH lol!
Didn't realize that lack of 4k was a SMH LOL moment...
Panda Addict: I'm not a professional photographer , just an amateur...Do you advise me this camera for pictures of animals ? Thx a lot.
Depends on whether you plan to shoot donkeys or ardvaarks. This camera will definitely work for donkeys but maybe not ardvaarks....and don't even think about using it for lemurs.
LJ - Eljot: What is Project 21? I mean if that does not specifically means "Man standing in the water, looking straight to the camera, a net over the shoulder and a ray in one hand" I don't get it why it is a winner.
So...a blown out distracting sky is 'ok'?? If you say so, but I disagree. The man standing in the water with the ray isn't such a bad part of the photo...a properly exposed sky would have improved things immensely...and was perfectly possible given the subject was obviously lit with a flash anyway.
LJ - Eljot: What is Project 21? I mean if that does not specifically means "Man standing in the water, looking straight to the camera, a net over the shoulder and a ray in one hand" I don't get it why it is a winner.
I guess we don't know what the other 'under 21' submissions were like but I tend to agree with you. The first thing I see in that shot is a distracting, blown out sky...at least on my uncalibrated office computer.
photomedium: Not convinced. $2k APSC? Only time I see pro shooting crop is when they are ambassador-ing in some YouTube vid. Weighs almost 1kg, it can only record a blazing 3min of 4K (and 10 min HD) footage (enough to earn the 4K tramp stamp). Wonder if it overheats...
It does have a touchscreen and 10fps but no flash, it's only 20mp...what else...I rather get the d750 and a plastic bag for when it rains? Thanks.
You think that's bad...Fuji is releasing the X-Pro2 at $1700....
koseng: If you can convince me that it's 10 times better than the Pentax 645Z, I might be willing to pay for the price.
Of course it's not 10 times better...it's called diminishing returns. The fact you even make a statement like that is evidence that A) you can't afford it and B) you have no need for it.
This is a camera for pros doing commercial work with big budgets, or amateurs with very deep pockets.
watson076: Over the last few years manufacturers have really lost touch with what photographers love, but I believe Fuji really hit the reset button. 40-50 mp this and that, 4k video, blah blah blah - who the f**k cares ? What I want is a true photographic experience (and I speak for many friends of mine who feel the same way). Fuji concentrates on what true photographers want, not what focus groups tell them to manufacture. Thank god someone is listening.
I agree with the OP...but for me the brand that inspires me these days is my Leica rangefinder. No, it isn't cutting edge tech but the image quality is still stellar and I enjoy using the camera. I gave up my 'one size fits all' Canon setup a year ago and haven't looked back.
mailman88: Sony...reduce the Sony RX1RII to its real value price....about $1600.00 and triple your sales.
Mailman88, thank God you don't work for me....
Clint Dunn: Maybe I'm jumping on the bandwagon here but I'm amazed at the lack of detail and the amount of noise in the bridge shot (at iso 400!!!). I got better results shooting my 5D at night back in 2006. All I can think is maybe Barney couldn't hand-hold the shot and way underexposed and then tried to compensate in post.
I would have to think that if it would have been correctly exposed in-camera the results would have been better...right???
Hi Barney: It's a nice shot, wasn't criticising it as a photo so much as questioning the quality of the file. Now that you say it was a VSCO filter then it makes more sense that it is as noisey as it is (or film-like if that is what you want to call it).
ChrClowes: Tremendous amount of whinging and moaning going on here, then again - seems to be the norm these days. Scores of people claiming their keyboard warrior status as if they have in their possession the perfect "holy grail" camera themselves.
I can read past the ego's swinging around here (notably a user complaining about noise from a full size 42mp image shot at night, no doubt) but I can't deal with the continual moaning about why things aren't perfect for *them*. Get over yourselves, its a tool and no tool is quantifiably perfect for everyone. Be lucky that this year you even have the opportunity to be in the position to shop for, or own a camera - plenty of people in the world don't, and realising this will go a long way into understanding all this petty internet bashing is...sad, really.
Get over yourself...this is a gear site where people are here to discuss gear. Thanks for pointing out that we are 'lucky to be in a position to shop for a camera'. Nothing wrong with having a social conscience but seriously, know your audience. This is a camera site dedicated to new camera gear...so obviously we are going to nitpick and overanalyze the latest models...that's what it is all about.
Don't want to listen to it, move on to a website more conducive to your temperament.


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The flowers of late winter and early spring occupy placesin our hearts well out of proportion to their size.- Gertrude S. Wister
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A profusion of pink roses bending ragged in the rain speaks to me of all gentleness and its enduring.- William Carlos Williams
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|Best Answer
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For a start who quoted you that price the dealers? what was you total quote? yes, it is advisable to change the water pump at the same time as the belt.
It's advised to get the water pump changed with the cam belt but it's by no means essential, however, if the water pump happens to go before the next cam belt change you'll be paying for another cam belt change plus water pump to change it.
Up to you really, take the risk and save the money now but it might cost you double in the future, or get it changed now.
(I've normally taken the risk in the past BTW)
A new water pump shouldn't cost much more than £30. Maybe £40 inc. VAT. Most of the work has all ready been done to get to the cambelt and pulleys. I can't see where an extra £95 is justified.
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Rick Bowmer, AP
SALT LAKE CITY — An upscale shopping center in the heart of Salt Lake City is suing a Utah man charged with plotting a mass shooting at the mall, claiming his threats brought bad publicity and led workers and shoppers to fear for their safety.
Prosecutors say Jack Harry Stiles, 42, planned to randomly shoot people at the City Creek Center this week, the anniversary of his mother's death. In addition, they say he planned to open fire at a movie theater and wire a bomb underneath a bus.
According to a lawsuit filed Wednesday, attorneys for City Creek said that "a significant amount of negative media attention has been drawn" to the center because of the case, and it has left visitors, tenants and employees worried about their safety and security. The filing came just two days after Stiles' arrest.
The shopping center is seeking a permanent court order barring Stiles from coming with 4,000 feet of the mall and at least $300,000 in damages, with the full amount to be determined in court.
City Creek is a $1.7 billion shopping center built by the business arm of The Church of Jesus Christ of Latter-day Saints. Opened in 2012, it spans two city blocks across the street from the Mormon temple and features a retractable roof and a creek running through the property.
Messages left with Stiles' attorney were not immediately returned Friday. He made his first appearance in court Thursday. He is jailed on $1 million bail and has not yet entered a plea to the terrorism threat charge he faces.
Police learned in mid-August that Stiles was planning to "randomly shoot and kill people" at the City Creek Center after they were tipped off by a hospital crisis worker, according to court documents.
After hearing about Stiles' alleged plan on Aug. 12, Salt Lake County District Attorney Sim Gill said authorities began looking into Stiles' background and discovered that he had a history of mental illness and making threats.
Gill said Stiles become fixated on the locations in his plan, mapping them out and visiting them over and over again. Charging documents show Stiles had "scoped and mapped out the best spots" for hiding to "kill the most amount of people."
Court records show he didn't have any weapons but state he was planning to buy two guns with silencers and stock up on ammunition.
Gill said he took the threat seriously in the aftermath of the Sept. 16 shooting at the Washington Navy Yard, where 12 people were gunned down.
In court documents, City Creek general manager Linda Wardell said her office has received calls and emails from fearful employees and shoppers. She also said she saw a local television news interview with a mall shopper who said she would leave the mall immediately after hearing of the alleged plot.
Wardell believes the reports have caused "irreparable harm" to the business, and said the case is particularly alarming for the mall in the run-up to the busy holiday shopping season.
Among the court documents filed by City Creek is a flier put out on Aug. 13 by West Valley City about the threats Stiles had made to a crisis worker. The flier reveals that Stiles told police that 10 years ago he went to a San Diego restaurant with a hunting knife and threatened to kill people. Stiles said San Diego police put him in a psych ward, but charges were never filed.
Neither West Valley City police nor Gill were immediately available to answer questions about the flier, including if Stiles was in jail since Aug. 12 as investigators looked into the validity of the threats.
In a statement released Friday, City Creek said the safety of its shoppers and employees is the top priority, but said the center does not discuss security procedures publicly or comment on legal matters.
Contributing: Brady McCombs
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Add some diversity to your fitness program with these butt and hip exercises from the American Council on Exercise. We'll help you tone up those glutes and get that butt into shape. Choose from a wide variety of hip flexibility and strengthening exercises including glute bridges, BOSU lateral jumps and more. These exercises come with detailed instructions, step-by-step guidance and tutorials on proper equipment use. For full workout routines featuring butt and hip exercises, be sure to visit our Workouts section.
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Home » Arcade & Action » RipplesShoot
RipplesShoot - FREE
by Gappli, Version: 1.2.0 , 125 KB Official Site
Package name: com.gappli.ripplesshoot , Last Update: 2012-07-07 20:02:20
4 ratings (3.500 average)
500-1,000 downloads
When you touch,Ripples appear.Using the ripples score a goal. The larger ropples,flying strong.
Apps from the same developer
Helicop-Turn Please break all the balloons in time. When you touch the turn,In keeping rise.
RipplesHockey When you touch,Ripples appear.Using the ripples,play hockey!
Wipe down Wipe down the windows!
MANNEVI(Manner mode checker) Simple MannerModeChecker for SmartWatch. LiveWare extension for smartwatch.
Pass,Pass,Pass Touch the screen,and please pass the ball.
Related Android Apps
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Determine companies b-pack and Iasta both designated "VISIONARY" in the GARTNER 2015 Magic Quadrant for Procure-to-Pay Suites for Indirect Procurement* and 2015 Magic Quadrant for Strategic Sourcing Suites. When Determine set out to establish an industry-leading platform for source to pay, we sought the very best talents to deliver on innovations, to set new standards. We started at the top with b-pack, a "Visionary" in the 2015 Magic Quadrant for Procure-to-Pay Suites for Indirect Procurement*, and Iasta, rated "Visionary" in … More
In Part 1 of this series we looked at how procurement can improve its risk mitigation role by getting involved earlier in the process, and staying involved. In Part 2 we're going to compare and contrast the internal/external sources of risk, along with how to keep it in check. Look at risk from the outside in. When procurement looks at each category of spend as being directly influenced by materials markets and varying levels of influence in the supply chain, … More
With blogs, such as this, or any social media connection—email, text, online media in general—it seems that building relationships has become a lost art. However, I beg to differ and will explain. This blog is about Relationship Economics and how it's still as valuable as ever and even in vogue. In today's economy, relationships are perhaps the new currency. A relationship describes a connection or association between people and/or things. Economics is about resource abundance, scarcity and allocation, the distribution … More
In the past, we've taken a close look at how procurement's maturity curve affects its focus. Two recent posts addressed issues concerning the evolving role of procurement savings, compliance and enterprise alignment. In this blog series, we'll consider risk. First, we look at supplier risk and methods to monitor and mitigate it; then we'll examine internal vs. external risk sources. Procurement: Sourcing risk mitigation. After procurement has dealt with the primary internal spend management needs of the enterprise —savings generation … More
Category Management is extremely valuable to organizations that conduct sourcing initiatives. This is especially true if they want to capture key knowledge around a specific sourcing category integrated within the corresponding organizational spend. This allows for ongoing category-specific measurements, such as rebate programs and Diversity Spend relative to specific items. It's also essential for managing the overall status of the sourcing program to continually capture the intended cost savings. Our Determine Strategic Sourcing solutions integrate Category Management and Spend Analysis … More
How much should procurement really care about contract management? A lot. More and more, procurement is being asked to improve supplier relationships and reduce supply chain risk. According to research by Spend Matters, procurement should be analyzing contracts during negotiation to increase successful agreement and execution, and predict disputes before they occur. We agree. Reporting on contract information is critical for mitigating risk, maintaining compliance and realizing savings. Contracts and the data they contain are valuable. But too often they … More
Introduction: Post #1 & #2 of this series looked at how General Counsel is (and may always be) linked to risk. But the role – and influence – of General Counsel has expanded. Technology and data are helping legal teams add value to an enterprise. Going beyond risk and compliance to support the bottom line. This article is about increasing their effectiveness – and clout – with contract management tools. Beyond risk: How Determine CLM turns contracts into strategic business … More
Technology is pervasive in our everyday life – it's smart, fast, intuitive and everywhere. Business technologies, on the other hand, are only now starting to catch up. Today, procurement leaders are taking advantage of technical innovations that share some of the best aspects of social, commercial and B2C platforms – and are achieving impressive results. Several procurement technology trends exemplify this exciting shift in the industry. In particular are user expectations for: Smart tools: Expectations for explicit insights drawn from … More
Introduction: Post #1 of this series looked at how Brett Hart, General Counsel at United Airlines, became their interim CEO. He not only understood risk, and how to intelligently manage it, but he also had a deep understanding of the company's business and strategy, and how to deliver. In this next post we're taking a closer look at how the role of General Counsel has matured. We covered examples of impressive success and are now looking at some distressing failures. … More
Introduction: The role of General Counsel (GC) is growing in importance and has become a stepping-stone to titles like Chief Risk Officer and CEO. Risk and compliance are still important to the success of an organization. But there's more to being the Chief Risk Officer or CEO. In this series, we are looking at examples of General Counsel succeeding and failing. We also investigate how to add value across an enterprise with contract management technology. Due to business, executive, and … More
In my last blog I discussed how procurement's evolution has spurred the need for increased attention to compliance. By decentralizing day-to-day purchasing, extending it to organizational "consumers," the process has been made more efficient — as long as everyone stays within the guidelines. In this post we examine the bigger picture of compliance; that is, aligning procurement processes with broader organizational goals. Improved Compliance Through Alignment Let's face it, generating savings is not as simple as buying the same products … More
In this blog series we're taking a close look at how procurement's maturity curve affects its focus. Two recent posts covered procurement's first priority – savings. Now we set our sights on compliance. First, we'll examine how the evolving role of procurement has created an environment where increased attention to compliance is imperative; on the follow-up post we'll explore how to improve compliance through enterprise alignment. Procurement Evolves Procurement's transition over the last decade from "purchasing" to its current … More
In a recent Determine webinar I had the chance to talk about procurement trends and the cloud with Mihir Nanavati, SVP of Product at Tradeshift, and Julien Nadaud, Determine's Chief Product Officer. Considering the two areas, which are changing rapidly and having an enormous impact on each other, it was enlightening to hear what these two experts had to say. Top of the mind, especially for procurement, is to understand the factors around the growth in cloud computing. We discussed … More
[Note: This article was originally posted on CPORising.com. Determine is pleased to contribute regularly to Ardent Partners blog on the topics of procurement and supply management. You can read the original post and other content from Ardent Partners HERE.] Needless to say, the start of year has hardly been one for celebration. Recent volatility in the stock market has been driven by the Chinese bubble economy, oil prices hitting a 13 year low of $25 a barrel, and crisis in … More
Contract management is an important aspect of managing business relationships and is the critical tool used by companies to get the most out of agreement terms that take so much effort to negotiate! While executing and monitoring a contract to maximize financial and operational performance and minimize risks may not sound sexy, it is important to the entire organization. There are many benefits of a contract management solution. Organizations where no solution exists suffer quantifiable losses. Spreadsheets combined with manual … More


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SBD Global/October 14, 2013/Olympics
Sochi's Fisht Olympic Stadium Unfinished Four Months Ahead Of Opening Ceremony
Published October 14, 2013
At first, Sochi's Fisht Olympic Stadium "was meant to resemble a giant snowflake," according to Ivan Nechepurenko of the MOSCOW TIMES. Then, the design "morphed into two parallel mounds of snow." But a roof had to be added for the Opening Ceremonies, "turning the stadium into something looking more like a ski slope." With less than four months before the Sochi Olympics, "Fisht is not any of those things yet." The stadium consists largely of a mammoth white frame that juts out toward the sea, "standing in stark contrast to the five other finished venues that now dominate the landscape of the Imeretinskaya Valley." It "is the only major Olympic facility still under construction." Blogsochi.ru editor Alexander Valov said, "They haven't even started to paint the walls inside or lay floors on the concrete staircases." Started in '09, Fisht "was supposed to be finished by this summer." But the completion date has now been pushed back to the end of the year "due to safety-driven alterations in the design and a desire to produce an exceptional opening show Feb. 7." The stadium's building contractors also face blame for the delays, "with a government agency last year accusing them of intentionally impeding progress to create leverage in negotiating prices for their work." Over the four years since planning began, "the stadium's cost has reportedly more than doubled," to over $750M, while one observer says it now costs more than $1B (MOSCOW TIMES, 10/10).


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UFC 131: dos Santos vs. Carwin play-by-play coverage of Dustin Poirier vs. Jason Young on June 11, 2011, at Rogers Arena in Vancouver. Read More >> read news >>
An elite lightweight contender, Brazil's Rafael dos Anjos has beaten the best of the best in five of his last six bouts, with wins over Donald Cerrone and Evan Dunham. read news >>
Jason Sampson believes his versatility will be a big key in picking up a victory when he takes on veteran Ryan Hollis on a main card 125-pound bout at Legacy FC 56. read news >>
An injury has forced Derek Brunson out of his UFC 200 bout against Gegard Mousasi. Thiago Santos will step in as a replacement and take on the No. 8 ranked middleweight on July 9. read news >>
veteran lightweight Jason High is looking to finish his WSOF 31 opponent Mike Ricci when they meet on June 17 at Foxwoods Casino and Resort in Connecticut. read news >>
Arguably England's two top welterweights, Paul "Semtex" Daley (38-13-2) and Michael "Venom" Page (10-0) have each been assigned new opponents for the upcoming "Bellator 158: London" event. read news >>
Jason Gonzalez got a taste of the UFC as part of a season of The Ultimate Fighter. Building off of that heading into RFA 38, he wants to get back to the UFC. read news >>
Chris Padilla feels that if he puts a stamp on Jason Gonzalez at RFA 38, it's only a matter of time before the UFC gives him a call. read news >>
Featherweight prospects Jim Alers and Jason Knight will travel to Chicago on July 23, as they meet in a FOX UFC Fight Night bout at United Center. read news >>
Jason "Mayhem" Miller made the required fight on Saturday for his revised Venator FC 3 fight with Mattia Schiavolin. read news >>
Watch the video highlights from the middleweight bout between Thiago Santos and Nate "the Great" Marquardt from the UFC 198 preliminary card. read news >>
Finally getting his training on track, Jason Novelli heads into Saturday's Titan FC 38 with plans for it to be a career year for him. read news >>
Junior dos Santos suffered a shoulder injury in his fight with Ben Rothwell at UFC Fight Night 86 in early April. read news >>
Brent Primus was this close to seeing the first loss of his pro MMA career this past Friday against Gleristone Santos. But after surviving with a split decision, now he wants a big name like Patricky read news >>
Evangelista Santos triumphantly returned to a prominent stage in MMA on Friday, submitting Brennan Ward in just 30 seconds at Bellator 153.Filed under: Bellator, News read news >>


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The fusion of male and female gametes to form a zygote.
1/20 102050100
Culturing a human embryo for 14 days – what have we learned?
Species-specific differences in terms of developmental timing and molecular expression patterns have restricted our true understanding of early human development... [Read More]
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Scientist warns of 'timebomb' of health problems for IVF babies
The use of IVF technologies could be storing up future health problems for children born through the technique, according to an evolutionary biologist... [Read More]
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Event Review: The Francis Crick Prize Lecture 2015
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Two surrogates in the USA carrying triplets are coming under pressure from the intended parents to abort one of their fetuses... [Read More]
What is the germline?
We report from the first session of the annual conference of the Progress Educational Trust, titled 'From Three-Person IVF to Genome Editing: the Science and the Ethics of Engineering the Embryo', in which Professor Azim Surani discussed the germline... [Read More]
'Gene drive' could halt malaria transmission
Using 'gene drive' technology, scientists have created mosquitoes with malaria-resistant genes that could spread rapidly into wild mosquito populations, potentially wiping out the disease in some areas... [Read More]
Restoring fertility after cancer treatment: is hope on the horizon?
A recent study in mice raised the possibility of restoring ovarian function after chemotherapy. But before creating hype, the medical community has a duty to deliver evidence from human studies... [Read More]
Court orders contact between girls and sperm donor
A UK High Court judge has ordered that the biological father of a teenage girl can maintain indirect contact with her, despite her opposition... [Read More]
HFEA releases 2014 incidents report
The Human Fertilisation and Embryology Authority has released its second annual report into adverse incidents at fertility clinics in the UK, showing a slight reduction in the overall number of reported problems following fertility treatment... [Read More]
Sperm cells attach to eggs with tiny 'harpoons'
Scientists have discovered that a protein in the head of sperm cells forms spiky filaments, which could act as tiny 'harpoons' that anchor the sperm to an egg... [Read More]
Donor IVF less successful with frozen eggs
Using frozen donated eggs over fresh ones for IVF hampers the odds of a successful live birth, a study has found... [Read More]
Radio Review: Rewinding the Menopause
In this Radio 4 programme, Dr Aarathi Prasad investigates new research that is overturning decades-old assumptions about how human eggs are produced and what causes the menopause... [Read More]
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You missed it This great deal for DermaCenter Medical Spa is over. But don't despair, we've got more great deals every day.
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back by popular demand:
DermaCenter Medical Spa
Refresh Your Complexion with an IPL Photofacial
97% recommendedin LivingSocial customer ratings
This environmentally conscious medical spa boasts eco-friendly heating, cooling, and wall paint -- making it the perfect place to noninvasively target skin imperfections like sunspots and redness:
• $99 ($400 value) for one IPL photofacial treatment
• Syneron laser + intense pulsed light technology work in tandem to rejuvenate skin
• Locations in the Women's Wellness Center just off Rittenhouse Square and in Narbeth
"Monica is a super technician, and I would see her every week if I could afford to -- she made me look great!" - LivingSocial Member
PAID VALUE EXPIRES ON June 30, 2021
PROMOTIONAL VALUE EXPIRES ON February 27, 2014
1632 Pine Street, Philadelphia, PA 19103
215-735-7990 | get directions
4th Floor
915 Montgomery Avenue, Narbeth, PA 19072
610-617-7990 | get directions
the fine print
- Limit 2 per customer
- Limit 1 per customer per visit
- Appointments required and subject to availability
- Merchant cancellation/re-scheduling policy of 24 hours applies; voucher subject to forfeiture
- Valid for face only
- Valid only at location selected at time of purchase
- All services must be redeemed during a single visit by same customer
- Other conditions apply
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print it out, email it now, or schedule it for a later date--it's up to you
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Delivering the gift in person? Choose a theme, print it out, and pass it along to that special someone. It's that simple.
Deal Fine Print
Limit 2 per customer
• Limit 1 per customer per visit
• Appointments required and subject to availability
• Merchant cancellation/re-scheduling policy of 24 hours applies; voucher subject to forfeiture
• Valid for face only
• Valid only at location selected at time of purchase
• All services must be redeemed during a single visit by same customer
• PAID VALUE EXPIRES ON June 30, 2021
• PROMOTIONAL VALUE EXPIRES ON February 27, 2014
• Cannot be combined with any other offer or promotion
• Tax and gratuity are not included
• Merchant is responsible for the quality of the products or services provided to you at redemption
• LivingSocial Terms and Conditions - https://www.livingsocial.com/terms