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VIEWS: 33 PAGES: 11 CATEGORY: Synthetic Resins Or Natural Rubbers POSTED ON: 8/24/2010
FIELD OF THEINVENTIONThis invention relates to 1,3-propanediol-based polyesters such as polytrimethylene terephthalate. In one aspect, the invention relates to polytrimethylene terephthalate which exhibits an excellent combination of ease of dyeability of PTTfabrics and fibers and stability under oxidative conditions which can reduce the need for adding stabilizers. More particularly, the invention relates to a new polytrimethylene terephthalate composition which can be made by a new all-melt process whichis a unique composition which has an optimum level of dipropylene glycol units.BACKGROUND OF THE INVENTIONPolytrimethylene terephthalate (PTT) is primarily a linear aromatic polyester which can be prepared from the condensation polymerization of 1,3-propanediol (PDO) and terephthalic acid (TPA). It is useful for carpet and textile fiberapplications. For such commercial applications, it is desired to produce a product which has an intrinsic viscosity greater than about 0.70 dl/g, preferably greater than 0.8 dl/g, and good color stability. It is also desired to produce polytrimethyleneterephthalate from PDO and TPA which has low tendency to generate acrolein when the polymer is heated in air, as it commonly is during downstream processing such as spinning into fibers. It is known that this instability can be controlled with additivessuch as hindered phenols such as described in copending, commonly assigned U.S. patent application Modified Polytrimethylene Terephthalate, Ser. No. 09/756,595, filed Dec. 7, 1998). It would be desirable, however, to produce polytrimethyleneterephthalate (PTT) having an inherent stability against acrolein generation, i.e., having a lower dipropylene glycol (DPG) content, and which also is easy to dye when used to make fibers and fabrics. The tendency to produce acrolein is related to theamount of dipropylene glycol produced in the polymer during polymerization. DPG affects the dyeing of PTT and generally for that reason, the D
United States Patent: 6509438 ( 1 of 1 ) United States Patent 6,509,438 Kelsey , et al. January 21, 2003 Optimum dipropylene glycol content polytrimethylene terephthalate compositions Abstract According to the invention, a polytrimethylene terephthalate is provided having 0.6 to less than 2 mole percent dipropylene glycol. Such compositions have a reduced tendency to generate acrolein when heated in air. These PTT polymer compositions exhibit improved and enhanced dyeability as compared to conventional PTT made by the DMT process and the TPA polycondensation/solid state polymerization processes. Inventors: Kelsey; Donald Ross (Fulshear, TX), Scardino; Betty Marrou (Katy, TX), Dangayach; Kailash (Houston, TX), Brown; Houston Slade (Houston, TX), Reitz; Hans (Rosbach, DE), Seidel; Eckhard (Frankfurt am Main, DE), Wilhelm; Fritz (Karben, DE) Assignee: Shell Oil Company (Houston, TX) Appl. No.: 09/840,411 Filed: April 23, 2001 Current U.S. Class: 528/279 ; 528/285; 528/286; 528/302; 528/308.6 Current International Class: C08G 63/00 (20060101); C08G 63/672 (20060101); C08G 63/183 (20060101); C08G 63/20 (20060101); D01F 6/84 (20060101); C08G 063/78 (); C08G 063/82 (); C08G 063/87 () Field of Search: 528/279,280,285,286,302,308.6,180,181,194,195,206,212,272 References Cited [Referenced By] U.S. Patent Documents 4434276 February 1984 Horlbeck et al. 5340909 August 1994 Doerr et al. 5798433 August 1998 Schmidt et al. 6093786 July 2000 Kelsey 6242558 June 2001 Kelsey 6281325 August 2001 Kurian et al. 6316101 November 2001 Kato et al. 6335421 January 2002 Kurian et al. Foreign Patent Documents 1016741 Mar., 1999 EP 1046662 Oct., 2000 EP 2001032136 Jul., 1999 JP WO 9911709 Mar., 1999 WO WO 9911845 Mar., 1999 WO WO 01/14450 Mar., 2001 WO WO 01/58980 Aug., 2001 WO WO 01/58981 Aug., 2001 WO WO 01/58982 Aug., 2001 WO Other References International Search Report of 30/10/01. . "Identification and Characterization of Reaction Byproducts in the Polymerization of Polyethylene Terephthalate," by J. M. Besnoin and K. Y. Choi, JMS-REV. Macromol. Chem. Phys., C29(1), 55-81 (1989) pp. 63-65. . "Synthesis and Properties of Fiber-Grade Poly(Trimethylene Terephthalate)," by H. L. Traub, P. Hirt, H. Herlinger, W. Oppermann, Die Angewandte Makromolekulare Chemie 230 (1995) pp. 179-187.. Primary Examiner: Seidleck; James J. Assistant Examiner: Ribar; Travis B Attorney, Agent or Firm: Haas; Donald F. Parent Case Text This application claims the benefit of U.S. Provisional Application No. 60/199,035 filed Apr. 21, 2000, the entire disclosure of which is hereby incorporated by reference. Claims We claim: 1. Polytrimethylene terephthalate polymer characterized by a dipropylene glycol unit content of 1.0 to 1.8 mole percent, based on total diol units. 2. The polymer of claim 1 wherein the intrinsic viscosity, as measured in a solution of 0.4 g polymer in 100 ml of a 60:40 solution of phenol:tetrachloroethane at 30.degree. C. is 0.6 dl/g or greater. 3. The polymer of claim 1 wherein some of the polymer chains have at least one terminal stabilizer group. 4. Polytrimethylene terephthalate polymer characterized by a dipropylene glycol unit content of 1.0 to 1.8 mole percent, based on total diol units, wherein some of the polymer chains have at least one terminal stabilizer group which has the formula ##STR3## in which R is a C.sub.1-12 alkyl group; x is an integer from 1 to 4; at least one R group is ortho to the phenolic hydroxyl group; R' is --(CH.sub.2)-- or alkyl-substituted methylene; and y is an integer from 1 to about 20. 5. The polymer of claim 4 wherein the C.sub.1-12 alkyl group is selected from the group consisting of methyl, ethyl, isopropyl, t-butyl, t-amyl, and 2-phenyl-2-propyl. Description FIELD OF THE INVENTION This invention relates to 1,3-propanediol-based polyesters such as polytrimethylene terephthalate. In one aspect, the invention relates to polytrimethylene terephthalate which exhibits an excellent combination of ease of dyeability of PTT fabrics and fibers and stability under oxidative conditions which can reduce the need for adding stabilizers. More particularly, the invention relates to a new polytrimethylene terephthalate composition which can be made by a new all-melt process which is a unique composition which has an optimum level of dipropylene glycol units. BACKGROUND OF THE INVENTION Polytrimethylene terephthalate (PTT) is primarily a linear aromatic polyester which can be prepared from the condensation polymerization of 1,3-propanediol (PDO) and terephthalic acid (TPA). It is useful for carpet and textile fiber applications. For such commercial applications, it is desired to produce a product which has an intrinsic viscosity greater than about 0.70 dl/g, preferably greater than 0.8 dl/g, and good color stability. It is also desired to produce polytrimethylene terephthalate from PDO and TPA which has low tendency to generate acrolein when the polymer is heated in air, as it commonly is during downstream processing such as spinning into fibers. It is known that this instability can be controlled with additives such as hindered phenols such as described in copending, commonly assigned U.S. patent application Modified Polytrimethylene Terephthalate, Ser. No. 09/756,595, filed Dec. 7, 1998). It would be desirable, however, to produce polytrimethylene terephthalate (PTT) having an inherent stability against acrolein generation, i.e., having a lower dipropylene glycol (DPG) content, and which also is easy to dye when used to make fibers and fabrics. The tendency to produce acrolein is related to the amount of dipropylene glycol produced in the polymer during polymerization. DPG affects the dyeing of PTT and generally for that reason, the DPG level in the polymer has to be controlled within a narrow range (e.g. +/-0.1%) so that the polymer will dye consistently from lot to lot. DPG is used here to mean the residual unit [--OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 O--] in the polymer chain. The following formula shows how the DPG units are copolymerized into the polymer to form a random copolyester (and how some end groups, such as allyl, carboxyl, methyl ester, may be incorporated): ##STR1## comprising units A and B connected randomly to each other by ester bonds and wherein E is an endgroup attached to the diol end and consisting of either H or the residuum of a hindered phenol (defined herein), E' is an endgroup attached to the carboxyl end and consisting of a PDO [--OCH.sub.2 CH.sub.2 CH.sub.2 OH], a DPG [--OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 OH], an allyl [--OCH.sub.2 CH.dbd.CH.sub.2 ] group, a hydroxy [--OH] or, in the case when terephthalate diesters are used, alkoxy [--OR] group, such as methoxy [--OCH.sub.3 ], and where the average (or overall) molar proportion of DPG units to the total diol units, including endgroups, is the ratio of the sum of y+E' (where E' is the DPG endgroups only) to the sum of x+y+E' (where E' is the diol endgroups, including allyl, but excluding the hydroxy and alkoxy endgroups) and is in the range of from 0.006 to 0.02. The average degree of polymerization is x+y and is greater than about 50 and preferably greater than 80, typically greater than 100. The average number of endgroups E+E' is 2 or less relative to x+y. PTT made by prior art processes with dimethyl terephthalate (DMT), such as described in Japanese published patent application 51-142097 or U.S. Pat. No. 5,340,909, is inherently oxidatively stable (as shown in the comparative examples below) and does not form very much acrolein because the milder, less acidic DMT process reaction conditions form very little DPG (as shown in the examples below, 0.55 mole percent or less) but the polymer made this way is difficult to process. These DMT polymers are not as dyeable as the polymers of the present invention. Current commercial processes for making PTT using TPA by polycondensation and solid state polymerization produce PTT, hereinafter referred to a "TPA PTT," with higher levels of DPG (thus exhibiting an increased capacity to produce acrolein in downstream processing), i.e., generally in the range of 2 to 4 mole percent. These polymers are not as dyeable as the polymers of the present invention. BRIEF SUMMARY OF THE INVENTION According to the invention, a polytrimethylene terephthalate is provided having less than about 2 mole percent based on diol units, preferably 0.6 to 1.9 mole percent, more preferably 1.0 to 1.8 mole percent, dipropylene glycol monomer units copolymerized into the polymer. Total diol units also includes endgroups such as allyl, PDO, and DPG. Such compositions have a reduced tendency to generate acrolein when heated in air. These PTT polymer compositions exhibit improved and enhanced dyeability as compared to PTT made by the DMT processes and the TPA polycondensation/solid state polymerization processes. DETAILED DESCRIPTION OF THE INVENTION The invention compositions are prepared by the reaction of a molar excess of 1,3-propanediol (PDO) and terephthalic acid (TPA) by esterification followed by polycondensation, with the important proviso that the reaction conditions include maintenance of relatively low concentration of PDO and TPA in the melt reaction mixture. The condensation polymerization of polytrimethylene terephthalate can generate as much as about 2 to 4 mole percent of dipropylene glycol which, in effect, becomes a comonomer and is incorporated into the polyester chain. The all-melt process by which the PTT of this invention can be made dramatically decreases the amount of DPG generated (and hence also decreases the tendency for generation of acrolein during polymer processing) while maintaining a desired (for dyeability) minimum amount of DPG of 0.6 to less than 2.0, preferably 0.6 to 1.9, most preferably 1.0 to 1.8, mole percent based on total diol units. This PTT is referred to as "all-melt PTT." One could adjust the DPG level by adding DPG monomer to the polymerization mixture or by treating the PDO with acid before polymerization (as shown in the examples). As used herein, "1,3-propanediol-based aromatic polyester" refers to a polyester prepared by the condensation polymerization reaction of one or more diols with one or more aromatic diacids or alkyl esters thereof (herein referred to collectively as "diacid") in which at least 80 mole percent of the diol(s) is 1,3-propanediol. "Polytrimethylene terephthalate" refers to such a polyester in which at least about 80 mole percent of the diacid(s) is terephthalic acid. Other diols which may be copolymerized in such a polyester include, for example, ethylene glycol, diethylene glycol, 1,4-cyclohexane dimethanol, and 1,4-butanediol; and other aromatic and aliphatic acids which may be copolymerized include, for example, isophthalic acid and 2,6-naphthalane dicarboxylic acid. The preparation of the invention composition can be conveniently described by reference to an esterification step, a prepolymerization step, and a polycondensation step. The process can be carried out in batch or continuous mode. Each step can be carried out in multiple stages in a series of reaction vessels if desired for optimum efficiency in the continuous mode or for product quality. Each step is preferably carried out in the absence of oxygen. The following will describe the process in terms of the preferred continuous mode. In the process, which will be described below in terms of the reaction of terephthalic acid and 1,3-propanediol to prepare polytrimethylene terephthalate, careful regulation of conditions in the esterification step is critical to the production of a high intrinsic viscosity (IV) PTT without the necessity of a solid state polymerization step. The important conditions are believed to be the instantaneous concentration of 1,3-propanediol monomer (and TPA monomer) in the reaction mass, which is affected by the reaction pressure, reaction temperature, and monomer addition rate. These conditions are controlled so as to minimize the production of dipropylene glycol and maximize the IV. In the esterification step, the instantaneous concentration of unreacted 1,3-propanediol in the reaction mass is maintained relatively low. This is accomplished by regulation of pressure and monomer feed. 1,3-propanediol and terephthalic acid are fed to a reaction vessel in a total feed molar ratio within the range of 1.15:1 to 2.5:1. Selection of the diol:diacid ratio within this preferred relatively narrow range is a factor in achieving the desired product quality. In batch reactions, this is difficult to calculate. It is controlled by the paste feed molar ratio which is generally lower, i.e., about 1.15:1 to 1.4:1. It is also preferred to add the 1,3-propanediol and terephthalic acid gradually so as to allow time to allow the conversion to ester to take place and keep the PDO and TPA concentrations low. Also, to maintain the desired instantaneous concentration of 1,3-propanediol a relatively low reaction pressure should be maintained in the esterification step. Conventional polytrimethylene terephthalate processes employ pressures greater than atmospheric to promote reaction between the monomers and to eliminate the need for an esterification catalyst. To make the invention composition, the esterification reaction pressure is maintained below about 3 bar absolute, generally within the range of about 0.7 to about 1.5 bar. Because 1,3-propanediol boils at about 214.degree. C. at atmospheric pressure and the esterification reaction is conducted at 240.degree. C. and above, the esterification conditions permit efficient removal of excess or unreacted 1,3-propanediol from the reaction medium, which in turn is believed to reduce dimerization of 1,3-propanediol to dipropylene glycol and/or reaction of 1,3-propanediol with propanediol endgroups of the oligomer to form dipropylene glycol. Unfortunately, high temperatures also favor formation of dipropylene glycol. The temperature of the esterification step will therefore be maintained as low as reasonably possible, generally within the range of 240 to 270.degree. C. The time of the esterification step will typically range from about 1 to about 4 hours. Water is produced as a by-product of esterification and is removed by suitable means such as overhead distillation. The presence of strong acid also promotes formation of dipropylene glycol. Therefore, conditions which suppress the instantaneous concentration of strong acid, such as dissolved terephthalic acid, are desirable. Such conditions include gradual addition of terephthalic acid and PDO feed, and the use of an esterification catalyst. An esterification catalyst is optional but preferred in an amount of about 5 ppm to about 100 ppm (metal), preferably about 5 ppm to about 50 ppm, based on the weight of final polymer. Because of the desirable lower temperatures under which the esterification is carried out, the esterification catalyst will be of relatively high activity and resistant to deactivation by the water byproduct of this step. The currently preferred catalysts for the esterification step are titanium and zirconium compounds, including titanium alkoxides and derivatives thereof, such as tetra(2-ethylhexyl)titanate, tetrastearyl titanate, diisopropoxy-bis(acetylacetonato) titanium, di-n-butoxy-bis(triethanolaminoato)titanium, tributyl monoacetyltitanate triisopropyl monoacetyltitanate and tetrabenzoic acid titanate; titanium complex salts such as alkali titanium oxalates and malonates, potassium hexafluorotitanate and titanium complexes with hydroxycarboxylic acids such as tataric acid, citric acid or lactic acid, catalysts such as titanium dioxide/silicon dioxide coprecipitate and hydrated alkaline-containing titanium dioxide; and the corresponding zirconium compounds. Catalysts of other metals, such as antimony, tin, zinc, and the like can also be used. The currently preferred catalyst for esterification, prepolymerization, and polycondensation is titanium tetrabutoxide. The catalyst is preferably formulated and added to the monomer feed, prior to or during the esterification, as a dilute liquid solution in 1,3-propanediol. This catalyst feed will preferably contain 5 wt % or less titanium. The presence of an organic acid, such as a C.sub.1-8 alkyl carboxylic acid such as acetic acid or a C.sub.4-12 dicarboxylic acid such as isophthalic or terephthalic acid, in the catalyst solution helps prevent agglomeration, catalyst flashoff, and side reactions which can produce undesired insoluble particles. The esterification step can be carried out in stages in a single or multiple vessels, with catalyst addition in or between any stage as desired to provide a total added metal catalyst within the range of 20 to 250 ppm, preferably 25 to 100 ppm, based on final polymer. For example, a two-stage esterification step would include a first stage carried out at about atmospheric pressure or a little above followed by a second stage at or below atmospheric pressure. The temperature is 240 to 270.degree. C. In such a two-stage esterification process, a liquid catalyst feed could be introduced in each stage. In the first stages, a catalyst feed of 5 to 50 ppm titanium can be introduced as a paste with the monomer feed. The first-stage reaction is continued until about 90 to 95% of the terephthalic acid is consumed. For the second stage, an additional 20 to 150 ppm titanium may be injected, the pressure is maintained in the range of about 0.5 to about 1.2 bar, preferably near atmospheric, and the reaction is continued until consumption of about 97 to 99% of the terephthalic acid. In a continuous process, the stages would be carried out in separate reaction vessels. A 1,3-propanediol slurry of TiO.sub.2 will typically be added to the esterification step as desired for making delustered product. The conditions of the esterification step are selected so as to produce a low molecular weight oligomeric product having an intrinsic viscosity (i.v., as measured in 60:40 phenol:tetrachloroethane at 30.degree. C.) of less than about 0.2, usually within the range of about 0.05 to about 0.15 (corresponding to a degree of polymerization of about 3 to about 10). In the prepolymerization step, the pressure on the esterification product mixture is reduced to less than 200 mbar, preferably to 2 to 200 mbars, and the temperature is maintained within the range of 250 to 270.degree. C. 1,3-propanediol and byproduct water are removed overhead. The time required for this step will generally be less than about 2 hours. The product will have an intrinsic viscosity within the range of 0.15 to 0.40 dl/g (corresponding to a degree of polymerization of about 10 to about 30). The prepolymerization step, particularly in the continuous mode, is preferably carried out in two vacuum stages, with the initial stage between 50 and 200 mbar and the second stage between 2 and 20 mbar. For the polycondensation step of this process for making the polymers of this invention, the reaction mixture is maintained under vacuum, preferably within the range of 0.2 to 2.5 mbars, and at a temperature within the range of 250 to 270.degree. C. In general, the polycondensation step will require about 1 to about 6 hours to reach the desired molecular weight, with shorter reaction times preferred to minimize the formation of color bodies. The polycondensation step is most suitably carried out in a high surface area generation reactor capable of large vapor mass transfer, such as a cage-type, basket, perforated disk, disk ring or twin screw reactor. Optimum results are achievable in the process from the use of a cage type reactor or disk ring reactor, which promote the continuous formation of large film surfaces in the reaction product and facilitate evaporation of excess 1,3-propanediol and polymerization byproducts. In keeping with the desire to maintain control of the temperature to which the oligomer or polymer is exposed during each stage of the process including polycondensation, the average temperature of the walls of the reaction vessels contacting the melt reaction product are maintained below 300.degree. C., preferably below 290.degree. C., because contact of the polymer with excessively hot vessel walls is a cause of polymer degradation and also promotes formation of dipropylene glycol. The polycondensation process is carried out in the presence of a polycondensation catalyst, preferably a titanium or zirconium compound as discussed above because of the high activity of these metals. The currently preferred polycondensation catalyst is titanium butoxide, preferably present in an amount within the range of 25 to 100 ppm titanium. The polymerization process may optionally include addition of stabilizers, coloring agents, and other additives for polymer property modification. Specific additives include delustering agents such as titanium dioxide; coloring agents such as cobalt acetate or organic dyes; stabilizers such as phosphorus compounds and hindered phenols; branching agents such as polyfunctional carboxylic acids, polyfunctional acid anhydrides, polyfunctional alcohols, and carboxyphosphonic acids or esters thereof. The polymer of the present invention achieves relatively low acrolein levels without the addition of stabilizers. The use of stabilizers may be desirable to achieve even lower acrolein levels. This can be achieved at lower levels of stabilizer than those described in copending commonly assigned U.S. patent application Modified Polytrimethylene Terephthalate, Ser. No. 09/756,595, filed Dec. 7, 1998, which is herein incorporated by reference, which describes stabilized high DPG content PTT wherein some of the polymer chains have at least one terminal group of the formula ##STR2## in which R is a C.sub.1-12 alkyl group including methyl, ethyl, isopropyl, t-butyl, t-amyl, 2-phenyl-2-propyl and the like; x is an integer from 1 to 4; at least one R group is ortho to the phenolic hydroxyl group; R' is --(CH.sub.2)-- or alkyl-substituted methylene; and y is an integer from 1 to about 20. It is advantageous if lower concentrations of stabilizer additives are required to prevent acrolein formation for the invention compositions than for conventional polytrimethylene terephthalate because hindered phenols can cause formation of color when the polymer is exposed to air. Thus, using less hindered phenol can result in improved color. Such hindered phenol stabilizers will generally be added to the polymerization in an amount within the range of 0.0005 to 1 mmol per mole of diacid(s), preferably 0.001 to 0.1 mmole/mole of diacid(s). Following polycondensation in the melt, the product can be fed directly to melt spinning or alternately can be solidified, granulated, and crystallized. The granulate can be further processed as desired. Thermal treatment of the solid polymer may be used, for example, for devolatilization of low molecular weight byproducts and water. The invention 1,3-propanediol-based aromatic polyester prepared by the invention process has an intrinsic viscosity (IV) of at least 0.6, preferably 0.7 or greater, most preferably 0.8 or greater, and for some applications, preferably within the range of about 0.9 to about 1.3, as measured in a solution of 0.4 g polymer in 100 ml of a 60:40 solution of phenol:tetrachloroethane at 30.degree. C. (or as a dilute solution in another solvent such as hexafluoroisopropanol, and converted by known correlation to the corresponding IV in 60:40 phenol:tetrachloroethane). The polymer has a dipropylene glycol unit content less than about 2.0 mole %, preferably 0.6 to 1.9, most preferably 1.0 to 1.8, mole %, based on total moles of diol units in the polymer, including allyl and diol endgroups. DPG content in the polymer was measured by proton NMR (nuclear magnetic resonance) on polymer dissolved in a 50/50 by volume mixture of deuterated trifluoroacetic acid and chloroform; the methylene next to the ether oxygen of the DPG units has a characteristic triplet resonance of 3.9 ppm. The absolute mole percent of DPG units in the polymer was determined using the integrated value of the 3.9 ppm resonance compared to the integrated NMR signals for the PDO and allyl units. The estimated precision was +/-0.04 mole % (absolute). By virtue of this low dipropylene glycol content, the invention polytri-methylene terephthalate has a significantly improved stability when heated in air. It also exhibits enhanced dyeability as demonstrated in the following examples. EXAMPLES The following experiments were undertaken to prepare PTT using DMT according to literature conditions having very low DPG content. We then compared the dyeability of these DMT PTT polymers to the all-melt PTT and to the conventionally produced TPA PTT. We also compared the acrolein formation in aging experiments. The results show that the all-melt PTT composition with about 0.6 up to about 2 mole % DPG units is an optimum composition range with better dyeing than the DMT-based products and, surprisingly, equal to or better than the TPA PTT product having higher DPG. The results also show that acrolein formation from the all-melt composition is less than from the TPA PTT composition with higher DPG content, but the DMT-based products with very low DPG content show even less acrolein Therefore, the structure of the all-melt PTT is an overall or global optimum composition, having less acrolein formation than the higher DPG compositions but still retaining very good dyeability, which is compromised by the very low DPG compositions made from DMT. Examples 1-3 were prepared essentially as follows: in the course of several batch polymerizations, a paste consisting of about 99 kg PDO, 180 kg TPA (molar paste feed ratio about 1.3), toner (in Example 2 - 15.2 gm cobalt acetate; 20 ppm Co based on TPA; as 2% solution in PDO), 0.09 gm antifoam agent (0.5 ppm based on polymer), and 19.8 gm titanium butoxide catalyst (15 ppm Ti based on TPA; added as 2% solution in PDO/TPA or 7.3% solution in PDO/acetic acid) was added gradually over a period of about 2 hours to about 76 kg of stirred PTT oligomer ("heel") that had been prepared essentially in the same manner as described herein. The temperature of the oligomer heel was about 265.degree. C. at the beginning of the paste addition and about 253.degree. C. at the end of the paste feed. The reaction pressure was about 2 bar (absolute) and about 50 minutes after the end of the paste feeding, the pressure was reduced step-wise to about 1.8 bar over about 5 minutes, then to about 1.4 bar over about 5 minutes, and then to about atmospheric pressure (1.0 bar) over about 5 minutes. After an additional esterification time of about 1.3 to 1.5 hours after the end of the paste feeding, after which the temperature was about 258 to 260.degree. C., 85.7 gm titanium butoxide catalyst (65 ppm Ti; as solution in PDO/TPA or PDO/acetic acid) was added. After this esterification step, a prepolymerization step was conducted in which the pressure of the reactor was lowered from about atmospheric to about 50 to 65 mbar and the reaction temperature was about 255 to 257.degree. C. over about 30 minutes. After the prepolymerization step, the oligomer was transferred to a disk-ring, high surface area reactor for polycondensation. The pressure in this reactor was ramped down from about 300 mbar to a final pressure of less than 1 mbar over about 45 to 60 minutes. The reaction temperature was about 251 to 263.degree. C. After about 3 hours, the polymer had reached the desired molecular weight and was discharged and pelletized to yield about 210 to 230 kg product. For Examples 1 and 3, the Co toner was replaced by blue (1 ppm based on polymer) and red (0.3 ppm) toners (Estafil), respectively. For Examples 2 and 3, 14.4 gm of hindered phenol stabilizer, methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (as 10% suspension in PDO; about 64 ppm based on final polymer or about 0.22 mmol/Kg), was added to the paste feed. In Example 4, PTT was prepared similar to Examples 1-3 using a paste feed of about 99 kg PDO, 180 kg TPA, 144 gm of 10% suspension of the hindered phenol stabilizer used in Example 2 (14.4 gm; about 64 ppm based on final polymer), 64.6 gm titanium butoxide catalyst (50 ppm based on TPA), and 20 ppm Co (based on TPA) as cobalt acetate toner added over about 2 hours to the stirred PTT oligomer heel. The temperature of the heel was about 281.degree. C. at the beginning of the paste addition, 266.degree. C. after 30 minutes, and 245.degree. C. at the end of the paste feed. The reaction pressure was essentially atmospheric pressure. After an additional esterification time of about 30 minutes, after which the temperature was 254.degree. C., 133.9 gm phosphoric acid (25 ppm based on TPA) was added to react with the cobalt toner and then 32.3 gm titanium butoxide catalyst (25 ppm Ti based on TPA) was added. In the prepolymerization step, the pressure was lowered from about atmospheric to about 40 mbar and the reaction temperature was about 256.degree. C. over about 30 minutes. The polycondensation was conducted at about 255 to 266.degree. C. to produce the desired molecular weight and the product was discharged and pelletized to yield about 225 kg. Endgroup analyses showed about 10 to 11 mequiv/Kg carboxyl (COOH) endgroups for Examples 1-3 and typically about 9 to 17 mequiv/Kg in similar polymerizations. Allyl endgroups were about 0.3 mole. Endgroup analyses showed carboxyl (COOH) endgroups were in the range of about 8 to 16 mequiv/Kg for Comparative Examples T and H. Allyl endgroups were in the range of about 0.2 to 0.4 mole %. Since these are very similar, endgroup content can be dismissed as a reason for differences in dyeability and spinnability between the PTT of this invention and the prior art DMT PTT. The following table summarizes the Examples and Comparative Examples in this study: TABLE 1 Stabi- IV DPG, mol % Example Lot # lizer (R-100) (NMR) 1 P1242-5 no 0.89 1.6 2 P1214-14 yes 0.90 1.70 3 P1214- yes 0.92 1.30 See 39/40 discussion A 10ZPB002 yes 0.92 2.4 SSP product B 4-3B1-44-1 no 0.92 3.0 SSP product T-1 P1240-10 no 0.92 0.51 T-2 P1240-11 yes 0.91 0.48 T-3 P1240-14 no 1.08 0.55 High IV H-1 P1240-15 no 0.91 0.50 H-2 P1240-16 yes 0.91 0.21 H-3 P1240-12 no 0.91 0.22 50 ppm Ti H-4 P1240-13A yes 0.91 0.35 50 ppm Ti H-5 P1240-13 yes 0.92 0.11 50 ppm Ti; lower temp Examples 1 and 2 are the compositions of the Invention. Example 1 was prepared using a small amount of blue (1 ppm) and red (0.3 ppm) toners to reduce the 20 initial color (b*) of the polymer and also was made without hindered phenol stabilizer. Example 2 was prepared with 20 ppm Co acetate toner instead of blue/red toner and contained 80 ppm (based on TPA) of hindered phenol stabilizer (methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), which is about 64 ppm stabilizer based on final polymer (about 0.22 mmol/Kg). Example 3 contained blue/red toners as in Example 1 and hindered phenol stabilizer as in Example 2. Example 3 is included in the data here for completeness but considerable evidence suggests that this was an abnormal sample, particularly with regard to spinning and dyeing. This sample had been in storage for over a year. Tenacity data for this polymer suggests that it spun abnormally. Unlike the other examples, spinning of this material was difficult and only about 3 minute (or less) bobbins could be made because of breaks in the fibers. An extrusion film test of this material showed over 15,000 defects compared to generally <7,000 defects for normal polymer samples, indicating contamination by a small amount of nylon, as determined by infrared analysis. We believe that the dyeing data for Example 3 is suspect. Comparative Example A is the composition containing higher DPG content prepared in a small commercial-scale plant under conditions similar to Example C. It contained 0.025% Irganox 1076 (octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) which is equivalent to about 138 ppm of the stabilizer used in Example 2 (or about 0.47 millimole/Kg). Note the higher level of stabilizer compared to the other Examples. Allyl groups were about 0.3 mole %. Comparative Example B is a solid stated sample made in a benchscale reactor without any hindered phenol stabilizer. This sample was used in the aging studies only and was not spun or dyed. Comparative Example C is a typical preparation of high DPG PTT. An oil-heated stainless steel reactor was charged with about 11.5 lbs. (5.2 Kg) of 1,3-propanediol and about 19.3 lbs. (8.8 Kg) of terephthalic acid and heated to about 250 to 260.degree. C. at an oil jacket temperature set point of about 265.degree. C. under 10 to 60 psig nitrogen. The aqueous distillate was removed as the reaction continued over about 4 hours. To the resulting oligomeric product was added about 9.6 lbs (4.4 Kg). PDO and about 16.1 lbs (7.3 Kg). TPA, and the reaction was continued under similar conditions for less than about 3 hours to form an oligomer with an average degree of polymerization of about 4 to 8. Approximately half of the oligomer was transferred to a second reactor. For subsequent batches, PDO (9.6 lbs.; 4.4 Kg) and terephthalic acid (16.1 lbs.; 7.3 Kg) were added rapidly to the oligomer remaining in the first reactor and the oligomerization under pressure was repeated. Titanium butoxide [Ti(OBu).sub.4 ] was added as a solution in PDO/HOAc to the second reactor, the reaction mixture was heated at about 231 to 235.degree. C. at an oil jacket temperature set point of about 250.degree. C., the pressure was reduced to less than 2 mm Hg, and the excess PDO was distilled off over about 1 to 2 hours at full vacuum and about 240 to 250.degree. C. (oil about 260.degree. C.) until the desired molecular weight was achieved (i.v.=0.65 to 0.70). The molten polymer (about 20 lbs. product) was discharged from the reactor as strands, cooled, and pelletized. The polymers were advanced to higher molecular weight (i.v.=0.90 to 0.94) by solid state polymerization by heating at about 210 to 220.degree. C. under vacuum for about 4 to 5 hours or more. The final polymer in this example contained about 3.7 moles DPG (by proton NMR). Examples T-1, T-2 and T-3 were made in the same reactor as Examples 1 and 2 using dimethyl terephthalate (DMT) using conditions as close as practical to those described in Japanese patent application 51-142097, filed Dec. 7, 1976, using about 2.2 molar feed ratio of PDO/DMT, and 100 ppm Ti catalyst (720 ppm titanium tetrabutoxide added as solution in PDO/acetic acid). The blue/red toners were also used, as in Example 1. Thus, for Examples T-1 and T-2, the first reactor was charged with about 164 liters of 1,3-propanediol and the catalyst and heated to about 160.degree. C. Melted dimethyl terephthalate (DMT; about 200 Kg) was added to the stirred mixture over about 90 minutes while heating the mixture to about 177.degree. C. The esterification reaction was continued for about 2 more hours while the temperature was increased to about 217 to 222.degree. C. and methanol was distilled overhead. Vacuum was applied to reduce the pressure to about 60 to 70 mbar over about 1 hour and the reaction temperature at the end of this period was about 242 to 249.degree. C. The reactor contents were transferred to the high surface area reactor and heated at about 244 to 255.degree. C. melt temperature (oil set point 245.degree. C.) under vacuum (<1 mbar at the end of the polycondensation) for about 4 to 4.5 hours to provide polymer with the desired IV of about 0.92 for spinning. The polycondensation time for T-3 was about 5.5 hours and because the IV was so high, this sample was not spun. The hindered phenol stabilizer (17 gm; about 80 ppm based on final polymer) was added to T-2 and T-3 as in Example 2. Examples H-1 and H-2 were made in the same reactor using PDQ/DMT feed ratio of about 1.4 under conditions as close as practical to those described in U.S. Pat. No. 5,340,909 using 14 ppm Ti catalyst (100 ppm titanium tetrabutoxide added as a solution in PDQ/acetic acid) for the esterification step, and 450 ppm butylstannoic acid (Fascat 4100) for the polycondensation step. The catalyst amounts are based on DMT. Blue/red toners were used for all the "H" examples. Example H-2 used hindered phenol stabilizer as in Example T-2. Thus, the first reactor was charged with about 105 liters of 1,3-propanediol and the Ti catalyst and heated to about 180 to 184.degree. C. Molten DMT (about 200 Kg) was added to the stirred reactor over about 90 minutes and the esterification reaction was continued for an additional time of about 2.5 to 3 hours while increasing the temperature to about 225.degree. C. and distilling methanol overhead. The pressure was reduced to about 50 to 60 mbar over about 1 hour at a reaction temperature starting about 228 to 237.degree. C. and raised to about 250 to 253.degree. C. The tin catalyst was added to the oligomeric product and the reactor contents transferred to the high surface area reactor. Polycondensation was conducted at about 241 to 253.degree. C. (final pressure of <1 mbar) for a total of about 3 hours to reach the desired IV of about 0.92 for spinning. The polycondensation times were determined by the time needed to achieve 0.92 IV product rather than the times given in the patent. Examples H-3 and H-4 were run under modified conditions similar to H-1 and H-2 but using 50 ppm Ti catalyst instead of 14 ppm in the esterification step. The reaction temperatures and times were about 182 to 236.degree. C. over 3.3 to 4.5 hours (including DMT feed) for the esterification, about 237 to 244.degree. C. and about 30 minutes for the vacuum pulldown, and about 236 to 250.degree. C. (oil set point 245.degree. C.) and about 2.7 to 3 hours for polycondensation to reach about 0. 92 IV. Example H-5 was conducted similar to H-3 and H-4 but using a lower temperature in the esterification step (181 to 187.degree. C. for about 2.3 hours. The temperature was then raised to about 220.degree. C. during the vacuum pulldown and polycondensation was conducted at about 245 to 250.degree. C. for about 2.3 hours. Spinning The dried polymer chips were extruded and spun to make 80 and 150 denier partially oriented yarns (POY) using a 50-hole, 0.25/0.50 mm spinnerette and 245 to 255.degree. C. extruder zone temperatures, 1500 to 1700 psi outlet pressure, 2.4 cc/rev melt pump at about 12 rpm and 23 rpm (for 80 and 150 denier, respectively), top and bottom godets at 4570 to 4580 m/min, type SW4 winder at 4500 m/min, interlacer at 4 bar and 60 psi, quench temperature 15.degree. C., and Lurol PT 7087 spin finish. Generally, 10 and 30 minute bobbins were prepared at each denier. Samples of the POYs were drawn using 9 wraps at 280 m/min on the first godet heated at 50.degree. C., 14 wraps at 400 m/min on the second godet heated at 100.degree. C., and a 400 m/min winder. Dyeing Procedure The dyes were C.I. Disperse Blue 56 and 79. Disperse Blue 56 is a low energy dye with a small anthraquinone structure and a molecular weight of 305 g/mole. Disperse Blue 79 is a high energy monoazo dye with larger molecular size than Disperse Blue 56 and a molecular weight of 639 g/mole. The POY samples were dyed in one set of experiments and the drawn yarns were dyed separately in another set of experiments. Yarns from each example were single knit to form fabrics using a Lawson-Hemphill Model FAK sample knitting machine. All fabrics (POY or drawn) from different examples with the same denier were dyed together. The competitive dyeing was performed with 0.5% owf (on weight of fabric) of either Disperse Blue 56 or Blue 79 at 20:1 liquor ratio using an AATCC Standard Atlas Launder-Ometer. Dyebath temperature was raised at 2.degree. C./min from ambient to 100.degree. C. and held for 45 minutes. The dyed fabrics were water rinsed and air dried. After dyeing, the dye uptake was evaluated and compared by their K/S values at the wavelength with maximum absorbance, which is broadly used as a description of shade depth and is directly proportional to dye concentration on the fiber if the shade depth is not too high. Color differences between the yarns were measured by their CIELab values. To describe the differences of K/S and CIELab values among the yarns, %K/S and Delta E values were calculated using the yarn with the highest shade depth, i.e., Example 1 for both deniers, as the standard. Color measurement used a BYK Gardner Model TCS spectrophotometer. Generally, a Delta E larger than 0.5 or a %K/S difference larger than 5S indicated a visual color difference. Comparing the K/S values between yarns with different denier, 150 denier was dyed darker than 80 denier, probably due to the larger diameter of the fiber and yarn of the 150 denier materials. Delta E (.DELTA.E) is the overall color difference (see T. L Vigo, "Textile Processing and Properties," Elsevier, 1994, p. 330-331) between Example 1 and the compared sample and is calculated as [(L*s-L*r).sup.2 +(a*s-a*r).sup.2 +(b*s-b*r).sup.2 ].sup.1/2, where L*, a* and b* are the measured Cielab color values and s and r are the sample and the reference (Example 1), respectively. The larger the value of .DELTA.E, the larger the difference in color compared to the reference sample, viz. higher .DELTA.E values indicate less dye uptake than Example 1. K/S or "shade depth" is a measure of the opacity and reflectance (see Vigo) and is defined as (1-R).sup.2 /2R, where R is the reflectance and S is the scattering coefficient. For Blue 56, the reflectance measurement was made at 630 nm and for Blue 79 the measurement was made at 610 nm. %K/S is the relative magnitude compared to the reference sample (Example 1). TABLE 2 80 Denier With Blue 56 Example Denier L* a* b* Delta E K/S 630 nm % K/S Process % DPG 1 82 48.34 -6.95 -32.65 0.00 5.815 100% TPA melt 1.64 2 77 47.88 -6.76 -32.69 0.50 5.961 103% TPA melt 1.7 A 78 48 -6.85 -33.7 1.11 6.157 106% TPA SSP 2.4 T-1 78 49.43 -9.45 -28.64 4.85 5.264 91% DMT 0.51 T-2 82 48.93 -9.72 -28.63 4.92 5.511 95% DMT 0.48 H-1 82 50.61 -5.87 -34.61 3.19 5.013 86% DMT 0.5 H-2 80 50.8 -5.59 -34.87 3.58 4.934 85% DMT 0.21 H-3 82 48.9 -6.11 -34.31 1.94 5.71 98% DMT 0.22 H-4 82 52.05 -7.04 -32.7 3.71 4.457 77% DMT 0.35 H-5 82 51.92 -7.14 -32.51 3.59 4.487 77% DMT 0.11 Table 2 shows the dyeing results for 80 denier drawn yarns with Blue 56 dye. Example 1 and 2 were the darkest (.DELTA.E 0.0 and 0.5, respectively). Based on .DELTA.E, all the other fibers, including Example A, did not dye as well. Based on %K/S, Examples 1,2 and A were similar and all the DMT-based polymers were lighter, although H-3 was almost as high as Ex. 1. Table 3 shows similar results for Blue 79 dye. Again, Example 1 is darkest overall (.DELTA.E=0.0) compared to the others, including Example 2 and A. In terms of %K/S, Example 1 and 2 are the best, Example A is next best, and all the other samples are not as good. TABLE 3 80 Denier With Blue 79 Example Denier L* a* b* Delta E K/S 610 nm % K/S Process % DPG 1 82 42.16 -5.56 -23.71 0.00 5.997 100 TPA melt 1.64 2 77 44.83 -6.42 -23.69 2.81 5.132 85.6 TPA melt 1.7 A 78 46.13 -6.56 -24.13 4.12 4.741 79.1 TPA SSP 2.4 T-1 78 45.19 -6.42 -23.3 3.18 4.944 82.4 DMT 0.51 T-2 82 47.26 -6.58 -23.1 5.24 4.261 71.1 DMT 0.48 H-1 82 46.63 -6.38 -23.05 4.59 4.417 73.7 DMT 0.5 H-2 80 47.1 -6.41 -22.89 5.08 4.256 71 DMT 0.21 H-3 82 47.04 -6.32 -23.12 4.97 4.28 71.4 DMT 0.22 H-4 82 47.78 -6.53 -23.17 5.73 4.112 68.6 DMT 0.35 H-5 82 47.87 -6.5 -23.05 5.82 4.07 67.9 DMT 0.11 The results at 150 denier appear to be generally similar although somewhat less definitive results in that occasionally a DMT-based sample gives %K/S similar to or higher than Example 1. However, Example 1 is still the darkest based on .DELTA.E. See Tables 4 and 5. TABLE 4 150 Denier With Blue 56 Example Denier L* a* b* Delta E K/S 630 nm % K/S Process % DPG 1 152 42.6 -5.49 -33.54 0.00 8.889 100% TPA melt 1.64 2 140 42.58 -5.61 -33.61 0.14 8.96 100.8% TPA melt 1.7 3 150 42.96 -6.05 -32.79 1.00 8.614 96.9% TPA melt 1.3 A 152 43.58 -5.4 -34.52 1.39 8.491 95.5% TPA SSP 2.4 T-1 152 41.72 -8.01 -29.75 4.64 9.31 104.7% DMT 0.51 T-2 152 42.73 -8.07 -29.7 4.63 8.58 96.5% DMT 0.48 H-1 151 43.84 -3.74 -35.88 3.17 8.117 91.3% DMT 0.5 H-2 152 44.53 -3.67 -35.89 3.54 7.656 86.1% DMT 0.21 H-3 153 43.48 -4.41 -34.82 1.89 8.268 93.0% DMT 0.22 H-4 152 44.33 -4.67 -35.01 2.41 7.865 88.5% DMT 0.35 H-5 152 44.3 -4.69 -34.6 2.16 7.764 87.3% DMT 0.11 TABLE 5 150 Denier With Blue 79 Example Denier L* a* /b* Delta E K/S 610 nm % K/S DPG 1 152 40.97 -5.54 -24.54 0.00 6.751 100 TPA melt 1.64 2 140 41.2 -5.52 -24.84 0.38 6.686 99 TPA melt 1.7 3 150 42.89 -5.8 -24.7 1.94 5.93 87.8 TPA melt 1.3 A 152 43.38 -5.74 -25.43 2.58 5.812 86.1 TPA SSP 2.4 T-1 152 40.17 -5.37 -24.93 0.91 7.214 106.9 DMT 0.51 T-2 152 40.97 -5.52 -24.75 0.21 6.785 100.5 DMT 0.48 H-1 151 43.26 -5.76 -24.34 2.31 5.697 84.4 DMT 0.5 H-2 152 43.46 -5.76 -24.22 2.52 5.59 82.8 DMT 0.21 H-3 153 42.35 -5.63 -23.92 1.52 5.996 88.8 DMT 0.22 H-4 152 43.31 -5.75 -24.25 2.37 5.648 83.7 DMT 0.35 H-5 152 43.89 -5.76 -24.15 2.95 5.406 80.1 DMT 0.11 Generally, the data shows that not only does the composition of the Invention (Examples 1 and 2) dye better than the DMT-based polymers with low DPG content, but also the Invention composition dyes better than the TPA-based polymer with higher DPG content. Thus, the Invention compositions with about 0.6 to about 1.9 mole % DPG, represent optimum compositions in terms of dyeability. Results on POY Yarns Tables 6 to 9 show the data for POY (partially oriented yarn) samples. Overall, the results are similar to the drawn samples. In every case, Example 1 has the lowest .DELTA.E and generally the highest O K/S compared to the DMT-based polymers and compared to the current SSP product. Note that data for Example 3 is included, although we believe this is not representative of the properties of the polymer of the invention for reasons previously stated. TABLE 6 80 Denier POY With Blue 56 Example L* a* b* Delta E K/S 630 nm % K/S Process % DPG 1 42.04 -5.03 -34.33 0.00 9.486 100 TPA melt 1.64 3 44.04 -3.44 -37.13 3.79 8.373 88.3 TPA melt 1.3 A 43.55 -5.83 -33.79 1.79 8.511 89.7 TPA SSP 2.4 T-1 44.04 -3.4 -37.01 3.72 8.339 87.9 DMT 0.51 T-2 44.46 -8.13 -30.61 5.41 7.75 81.7 DMT 0.48 H-1 45.3 -4.69 -35.75 3.57 7.56 79.7 DMT 0.5 H-2 44.55 -4.49 -36.09 3.11 8.078 85.2 DMT 0.21 H-3 42.99 -5.46 -35.17 1.34 9.293 98 DMT 0.22 H-4 44.83 -4.71 -35.48 3.03 7.764 81.8 DMT 0.35 H-5 44.34 -8.25 -30.51 5.50 7.861 82.9 DMT 0.11 TABLE 7 80 Denier POY With Blue 79 Example L* a* b* Delta E K/S 610 nm % K/S Process % DPG 1 41.24 -6.17 -24.11 0.00 6.759 100 TPA melt 1.64 3 42.78 -5.73 -23.95 1.61 5.876 87 TPA melt 1.3 A 43.16 -6.39 -24.79 2.05 6.015 89 TPA SSP 2.4 T-1 43.92 -5.71 -23.09 2.90 5.286 78.2 DMT 0.51 T-2 42.31 -6.41 -24.6 1.20 6.377 94.3 DMT 0.48 H-1 44.02 -5.57 -23.36 2.94 5.259 77.8 DMT 0.5 H-2 43.39 -5.6 -23.62 2.28 5.545 82 DMT 0.21 H-3 42.84 -6.42 -25.14 1.92 6.242 92.4 DMT 0.22 H-4 44 -5.84 -23.67 2.81 5.349 79.1 DMT 0.35 H-5 42.57 -6.41 -24.5 1.41 6.233 92.2 DMT 0.11 TABLE 8 150 Denier POY With Blue 79 Example L* a* b* Delta E K/S 630 nm % K/S Process % DPG 1 38.75 -3.64 -35.11 0.00 12.085 100% TPA melt 1.64 3 40.88 -4.88 -34.22 2.62 10.224 84.6% TPA melt 1.3 A 40.86 -3.76 -36.62 2.60 10.798 89.4% TPA SSP 2.4 T-1 41.33 -7.29 -31.25 5.91 9.822 81.3% DMT 0.51 T-2 39.2 -6.66 -31.33 4.86 11.377 94.1% DMT 0.48 H-1 40.15 -1.38 -38.56 4.36 11.237 93.0% DMT 0.5 H-2 43.04 -2.59 -38.11 5.34 9.122 75.5% DMT 0.21 H-3 41.31 -3.08 -36.73 3.08 10.152 84.0% DMT 0.22 H-4 41.91 -3.09 -37.13 3.79 9.784 81.0% DMT 0.35 H-5 43.11 -3.39 -37.27 4.87 9.043 74.8% DMT 0.11 TABLE 9 150 Denier POY With Blue 79 Example L* a* b* Delta E K/S 610 nm % K/S Process % DPG 1 38.9 -5.49 -24.82 0.00 8.039 100.0% TPA melt 1.64 3 39.98 -5.67 -25.11 1.13 7.486 93.1% TPA melt 1.3 A 42.93 -5.95 -26.44 4.37 6.289 78.2% TPA SSP 2.4 T-1 41.21 -5.78 -24.66 2.33 6.76 84.1% DMT 0.51 T-2 41.94 -5.88 -24.9 3.07 6.459 80.3% DMT 0.48 H-1 41.61 -5.36 -24.59 2.72 6.436 80.1% DMT 0.5 H-2 42.85 -5.59 -24.34 3.98 5.873 73.1% DMT 0.21 H-3 42.4 -5.5 -24.24 3.55 6.037 75.1% DMT 0.22 H-4 39.72 -5.14 -24.13 1.13 7.31 90.9% DMT 0.35 H-5 42.93 -5.47 -24 4.11 5.775 71.8% DMT 0.11 Acrolein Generation--Aging Study Aging experiments were conducted to determine the stability of the polymer. Four-gram polymer pellets were placed in a forced-air drying oven and the temperature was set at 170.degree. C. (independently checked by pyrometer). The tests were done at 170.degree. C. to accelerate the test. At normal temperatures, the acrolein formation would be much slower. Periodically, a sample was removed after the aging time specified in Table 13 and analyzed. The acrolein was measured by headspace gas chromatography on pellets after heating the sample under air at 200.degree. C. for 40 minutes. Results are reported as ppm based on polymer weight. Intrinsic viscosity was measured in hexafluoroisopropanol and converted by known correlation to the corresponding values for 60/40 phenol/tetrachloroethane solvent at 30.degree. C. The DPG content was measured by proton NMR (nuclear magnetic resonance) on polymer dissolved in a 50/50 volume mixture of deuterated trifluoroacetic acid and chloroform. The methylene next to the ether oxygen shows a characteristic resonance at 3.9 ppm and is reported as moleo of total PDO plus DPG units and wt % of polymer. Table 10 shows the results for the samples made without hindered phenol stabilizer. It is clear that the polymers with low DPG content produce less acrolein. The polymer with the highest DPG (Example B) shows the highest acrolein generation early in the aging. The DMT-based polymers with very low DPG show very low acrolein generation even after 27 days, again showing that the acrolein generation is related to DPG level. The polymers of the Invention (Example 1) with moderate DPG level show somewhat higher acrolein formation than the DMT-based polymers. The compositions of this Invention should thus require less stabilizer to suppress acrolein formation compared to compositions with higher initial DPG content. TABLE 10 Acrolein Formation (ppm) After Aging at 170.degree. C. (no stabilizer) Days 1 B T-1 H-1 H-3 1 170 188 17 7 6 3 192 205 16 27 16 8 159 150 24 28 19 12 157 148 25 30 21 17 113 92 20 28 15 21 94 65 22 27 16 27 89 58 20 25 12 Initial DPG (%) 1.6 3 0.51 0.5 0.22 Table 11 shows the change in DPG content as the polymers were aged at 170.degree. C. The decrease in DPG, which is due to oxidation of DPG to acrolein, is highest for the polymers with the highest initial DPG content. Thus, the decrease in DPG for Example B is almost 1% (from 3 to 2%) compared to about 0.66% loss for Example 1. TABLE 11 Change in DPG (mole %) 1 3 8 12 17 21 27 Overall Example stabilizer unaged day days days days days days days change 1 no 1.64 1.61 1.56 1.27 1.06 0.97 0.94 0.98 -0.66 B no 3 3.2 2.92 2.52 2.14 2.48 2.28 2.03 -0.97 T-1 no 0.51 0.46 0.54 0.52 0.44 0.44 0.43 0.48 -0.03 H-1 no 0.5 0.42 0.52 0.5 0.43 0.41 0.42 0.39 -0.11 H-3 no 0.22 0.22 0.24 0.25 0.19 0.25 0.19 0.19 -0.03 Table 12 shows the change in IV during the aging study. Note that the DMT-based examples show less IV change, even without stabilizer. In some cases, the change is near the potential error of the IV measurements, so the effect of stabilizer at these low DPG levels is very small, at best. Overall, the results are completely consistent with generation of acrolein by oxidation of DPG units, which results in chain cleavage and lower IV. TABLE 12 IV Data on Aged Samples Example Stabilizer Initial IV IV @ 27 days Change* 1 No 0.89 0.63 0.26 3 Yes 0.92 0.81 0.11 A Yes 0.92 0.81 0.11 B No 0.92 0.74 0.18 T-1 No 0.92 0.87 0.05 T-2 Yes 0.91 0.89 0.02 H-1 No 0.91 0.84 0.07 H-2 Yes 0.91 0.83 0.08 H-3 No 0.91 0.87 0.04 H-4 Yes 0.91 0.86 0.05 H-5 yes 0.92 0.86 0.06 *Total error can be +/- 0.04 because error for each IV measurement is +/- 0.01. TABLE 13 Acrolein Generation (ppm) after Aging at 170.degree. C. (with hindered phenol stabilizer) Days Example 2 Example 4 1 13 9 3 13 8 8 72 13 12 242 22 17 171 28 21 126 38 27 102 12-30 Initial DPG (%) 1.7 0.6 Comparative Example D makes high DPG PTT with added stabilizer. The polymerization of Example C was repeated except that 0.0137 wt % (based on final polymer weight) of hindered phenol stabilizer used in Example 2 was included in the reactor charge. The dipropylene glycol level of this polymer was 4.0 mole %. Comparative Example E also makes high DPG PTT with added stabilizer. A polymer was prepared as described in Example C except that 0.025 wt % Irganox 1076 hindered phenol stabilizer was used. The initial DPG level of this polymer was 3.3 mole %. Comparative Example F shows the preparation of PTT with very high DPG. A high DPG-content 1,3-propanediol was prepared by adding 0.1 g of p-toluenesulfonic acid to 500 g of PDO, degassing with nitrogen, and heating in a 200.degree. C. oil bath for about 2 hours. Gas chromatography of the product showed about 78% PDO, 19% DPG and 3% higher ether diols. A 1 liter stainless steel pressure reactor fitted with a distillation column, condenser and collection vessel was charged with 222g of the high DPG 1,3-propanediol and 346 g terephthalic acid (about 1.25 mole), 0.21 g Irgafos 168 (an organophosphite, 0.05 wt %) and 0.107 g of Irganox 1076. The reactor was pressurized to 50 to 80 psi with nitrogen and released pressure three times to degas, then repressurized to 20 psi, and heated to 250.degree. C. For the first hour, the pressure was maintained near 50 psi and then lowered in about 5 psi increments every 15 minutes thereafter. After a total of about 3 hours, any pressure was released and the molten oligomer was poured into a pan and cooled. The oligomer (140 g) and 0.074 g titanium butoxide (85 ppm based on Ti) were charged to a 500 mL 3-neck flask. The flask was degassed with nitrogen, evacuated to about 200 mbar with a small nitrogen sweep, heated in an oil bath to 260.degree. C., stirred at about 20 rpm, and the pressure was reduced to about 2 mbar. After 3 hours, the reaction mixture was cooled and the polymer was isolated. Intrinsic viscosity (i.v.) measured in hexafluoroisopropanol was 1.15. NMR showed about 14.2 wt % (29 mole %) DPG-type units in the final polymer. A similar polymer, Example G, was made with the high DPG PDO, except that no phosphite or hindered phenol was added. The i.v. was 1.08 and the polymer contained about 14.6 wto DPG-type units. Table 14 shows the headspace GC results for Examples F and G. TABLE 14 Under Nitrogen Under Air Acrolein Allyl alcohol Acrolein Allyl alcohol Ex. Stabilizer (ppm) (ppm) (ppm) (ppm) F Yes 214 4.2 702 5.1 G No 139 3.5 684 4.6 * * * * *


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The 10 Best Independent Men's Stores in America
Never before have there been so many one-of-a-kind, smartly curated shops in America, and never before have they been so influential in driving trends and styles. Here are the ten best independent men's stores in America—plus the labels, collaborations, insiders, and must-have items you need to know now
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Best Answer
the person behind the mask is the sage of the six paths. there are many clues that lead to this. the clues start to show when naruto kills pain all the way till now in the manga number 560. if you notice that when the masked man or how people been calling him " madara " goes to retrive nagatos rennigan he says " they were originally my eyes to begin with" and also. the only one who could beat and capture the 10 tailed beast ( all the tailed beasts combined ) was the one and only known "god" the sage. and no one else could ever do that. so the mask man is going to do it because hes the only one with that power. thats why hes capturing them. and also. if we go way back to the beginning of all this..the sage was the creator of all uchiha because he is one of them him self. and the rennigan is the last stage of the sharigan. only a god can reach that stage. and madara was the son of the sage so when the sage passed on to capture the 10 tailed beast. his son ( madara" could take over as god. but he did not like the sages way to control the world. so he released the beast in to 1-9 tailed. from there a war broke out because the sage created other nations but madara wanted to concer all the world and takeplace as god in his rules. but he was badly hurt. so he takes his brothers eyes which was the other half of the sages power but into his other son. so with his new eyes hes one step closer to becoming a god. so he fights his father. and on the last few seconds of the fight. madara posses the rennigan and kills his father ( thats what he thought ) then madara died. so the beasts went on there own and the natons captured them sepratly. but right befor madara died or the sage died. he grabed one of madaras eyes ( thats why the man in the mask is like a ghost because he has only half his spirtual power. and that brings to to when kabuto shows the man in the mask ( the sage ) of the impure world ressurection and shows madaras body..the sage got scared and joined him cos hes scared of madara..and as u see in the manga madara uses the rennigan. but not the full power of the real one. cos the real pne was nagatos cos the sage had madara, Izuna, and nagato as his son. and trusted nagato the most. but in the manga the masked man only posses one rennigan because he still wants to maintain the spirtual form of madaras eye so the sage can have an upper hand in war. there is alot more to tell but i dont want to ruin the exciment for u all. this was only a little information about this believe it or not.
i signed up for many official naruto projects web sites and know what they are planing because of my membership and i do alot of research and know people that work for the naruto manga and Tokyo channel 7 that have the future of the manga planed out already. so call this a legal leak of there plans cos of my membership. if you want more information contact my email, if you want the sites i signed up for email me and ill send you them
Other Answers (10)
it could be izuna because he was forced to give up his eyes to madara from his clan and survived it then he takes eyes from madara after he was defeated by first hokage
but there was a picture of him in the coffin thing
it could be the sage of the six paths evil son...dont think it ever shows him dead it just says that he was defeated so now he is weakened and since he is evil...he wants to become complete again and destroy the world :P
but my best guess would be kagami uchiha because he was in 2nd hokages squad with 3rd hogake and the 3 elders...the elders r the ones that locked the uchiha in that little corner of the village then plotted them kill them all...it never shows him apart from that 1 scene...he looks about that age when he shows his eye to sasuke
alot of ppl seem to think its obitos body with madaras spirit for some reason and that is so wrong
masked dude fought with 4th hokage when the fox was attacking and back then kakashi and obito were students of the 4th so they were young
and how can it b madaras spirit inside him....madara was dead (most likely dead) for like a 100 yrs im sure there would have been plenty of other non crushed bodies for madaras spirit to go in before then
its also not shisui :P itachi killed him to awaken his mangekyou sharingan and took 1 eye then gave to naruto and danzo took the other eye
so i believe its either izuna or evil sages son or kagami uchiha or 2nd hokage like john hanna said
and dont think it could be obito or shisui
also it would b lame if its really madara behind the mask
he goes around saying he is madara then we wonder who is behind the mask after madaras body comes up...then find its really madara behind the mask ...not very interesting :PSource(s):
i think its KAGAMI UCHIHA...in squad with 2nd and 3rd hokage and the 3 elders -
i think the same... it's his brother, Izuna, probably... i think, he can cause this much chaos... what if, he proclaimed to all that he was madara, but was not... he is the most powerful uchiha clan member, other than madara... think of it... they awakened their mangekyo sharingan at the same time... they fought each other as training for themselves, which would mean that Izuna is equal to madara, in terms of power and regardless of age... what if he got the Rinnegan (which was awakened by madara, some time before his death), and gave it to nagato... what if he was able to awaken the rinnegan himself? keep this in mind... the rinnegan toys, will possess the rinnegan eyes, which shows that they are under the rinnegan of the controller... it can't be obito, because tobi fought the 4th hokage, and obito was still a child at that time... if, tobi is obito, then who fought the 4th hokage...?
I maybe coming from left field with this one, but I think it's the 2nd hokage. Think about it if u actually do your research it says you have to have senju blood to actually awaken the rinnegan which fits for him. Secondly, during the 3rd great shinobi war he used his self as decoy against 20 water village shinobi but no one actually seen him die and let's be serious 20 regular shinobi could not have killed the 2nd hokage. And don't forget that tobi was controlling the water villiage's kage for a while. And lastly ( this is my weakest point) the man behide the mask calls himself tobi, could it be short for tobirama the 2nd's actually name. And I kno some people are going to say he was resurrected by orochimaru but he is the inventor of the resurrection justu, so I think he could of man a fake version of hisself to futher fool people. but thats just my opinion.
Myself -
No, i don't think so, in a super strange way he might still be madara. Remember itachi said he is a shell of his former body. I think that's why he can be revived.
But let's better wait for next week to figure it out. -
the masked man has both of his eyes with sharingan but during battle with konan his left eye lost its power by using izanagi so he cant be madara's brother
manga reader -
From what i heard is that you can obtain the rinnegan by fully mastering your sharingan,but if you can get the rinnegan by mastering sharingan then why would tobi need to take nagatos rinnegan?why give it to someone just to take it back?unless he really needs a sharingan and a rinnegan at the same time,but i believe it could possibly be izuna.
I also think that it's Madara's brother, but I also think that it could be another 'Madara.' I mean, since he can use the Rinnegan, it's possible, right?
mangareader.net -
just wait for the new issue
its obito
I don't think so.
3 answers hidden
The masked man in Naruto is Madara's brother who disagrees?
The resurrected Madara has his left eye he took his brother Izuna's left eye for himself but the masked man still has his right eye. That masked man has been lying all the way through
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roasted peaches with gluten free crisp and creme fraiche
When I plan a meal, I have several check points I go through. I want to be sure that the meal is comprised of ingredients from the current season, and that on a whole, the meal feels cohesive from start to finish. If we are having friends join us, I also try to plan a dessert of some sort. This is usually my favorite part of the meal and the item I spend the most time thinking about. I'm a self diagnosed sugar fiend, so naturally this area excites me the most.
Most often, I like to dream up desserts that have several elements and can take hours, but when we are planning a meal for the middle of the week that doesn't always work out very well. Unless we just decide to forgo dinner altogether and serve dessert alone, I better think of something a little more speedy.
During the summer, I tend toward the natural bounty of fruit that needs little done to it, if anything at all. Fresh peaches, while amazing in cobblers and crisps, can be divine all by themselves and as far as I'm concerned, make an excellent dessert. However, roasting them for a bit and then topping them a sprinkle of crisp and a dollop of creme fraiche won't make anyone I know turn up their nose.
There is a lesson to be learned in this recipe: dessert does not have to take hours to be awesome. I'm going to repeat that to myself: dessert does not have to take hours to be awesome. This is a great mantra for me to remember. Too often I jump right to something unnecessarily complicated. Maybe after repeating this to myself a few hundred times I'll think more simply the next time I want to make a dessert that takes three days.
This dish is just as versatile as it is quick. You can use whatever fruit is available at your farmers market, in fact I think apricots would be delicious here, so would plums or nectarines. The crisp topping can be frozen and used to stir into yogurt or crumbled onto pies, I also think it could be a great base for a granola too. (more…)
chocolate sour cream bundt cake
Tartine is an incredible french bakery in the Mission District of San Francisco. They specialize in all things amazing, including, but not limited to, this mouth watering, coma inducing chocolate tea cake.
My sister moved here a few months back, and as part of a "get to know your city" tour, I fulfilled my sisterly duty by taking her around to all the places that would help her get through the stress and loneliness of moving to a new, strange place and since this place is on my essential "go here after a bad day" list, I decided it was a must. click here for the full post!
peach galette
Summer is coming to an end, and while I am beyond excited for the most wonderful time of the year (I have already listened to my Frank Sinatra Holiday station on Pandora more than once. I know. I'm that girl), I always seem to feel like I didn't get enough out of summer. There were so many strawberries I didn't eat, and pickles that I never made. Those jars I bought, and promisedto use for fresh tomato sauce, are now holding beans and the occasional arrangement of flowers. The fresh bounty from those summer months just slips on by each year, and I always vow to be better next season. Well, this year, I tried a tiny bit harder to capitalize on the delicious, mouth watering produce that I have neglected during all those long lost summers.
chocolate cupcakes
This week, I have often found myself wishing I always had cupcakes at the ready to give to someone when the urge arises. In the last few days, there have been so many instances where I have wanted to show someone just how much I appreciate them for going way beyond what is expected, and what better way to do that than with a soft, sweet cupcake? The particular cupcake we're talking about today would make the most appropriate thank you cupcake ever, because it is absolutely perfect. And although I'm not sure that there actually is a way to be perpetually prepared with fresh chocolate goodness in those times of gratitude, for now, a sincere thank you will have to do.
These chocolate cupcakes are the best I've ever had . They are seductively moist and they are deeply chocolatey. I would recommend you make them as soon as you possibly can, and maybe carry one in your car, just in case you find someone who deserves a chocolate thank you. click here for the recipe
rosemary shortbread
As my palate evolves, I find that I am more interested in the delicate combination of savory and sweet. When things sound like they shouldn't go well together, I want to eat them. Like the apple pie with cheddar cheese crust or these rosemary shortbread cookies. Maybe the excitement lies in the unchartered territory of these seemingly odd flavor combinations. Almost as if they have never existed together before. My immense desire to try new things is satiated by this new world.
panforte ice cream
I remember my mother making homemade ice cream when I was a kid. We had an old wooden hand crank machine that used ice and rock salt packed around a metal canister. These cooling agents worked on the cream and sugar inside to create a deliciously dreamy frozen dessert. She usually made good old-fashioned vanilla from a recipe my great-grandfather used in his restaurant in Santa Barbara. He eventually sold that recipe to a large commercial ice cream manufacturer. The recipe consisted of a lot of cream, sugar, and more cream. It was sinful and could be dangerous for those of us without the metabolism of our youth.
oreos and four legged cuteness
My husband and I had the distinct privilege of taking care of some ridiculously adorable dogs this past week. One of which, I have fallen head over heels for. His name is Odin, and I'd like to keep him. His parents won't let me of course. I understand. There is only so much cuteness to go around. My hope is that they will let us dog sit more often. Because who could withstand a long absence from a face like this?
Now, I don't know about you, but I love to reflect on the nostalgic things of childhood, especially when times are tough. (That face!) You know them well. Sweets like rockcandy on a stick, 50/50 bars, fun dip, and the ultimate milk companion, oreos. Speaking of nostalgia, I made these about two months ago, but have not been able to get them out of the front of my brain (or hippocampus as it were). I'd like to find an occasion to make these near perfect clones again. I'm sure you'll think of something won't you?
Homemade Oreos www.smittenkitchen.com makes a whole bunch
For the chocolate wafers:
1 1/4 cups all-purpose flour
1/2 cup unsweetened Dutch process cocoa
1 teaspoon baking soda
1/4 teaspoon baking powder
1/4 teaspoon salt
1 to 1 1/2 cups sugar [see recipe note]
1/2 cup plus 2 tablespoons (1 1/4 sticks) room-temperature, unsalted butter
1 large egg
For the filling:
1/4 cup (1/2 stick) room-temperature, unsalted butter
1/4 cup vegetable shortening
2 cups sifted confectioners' sugar
2 teaspoons vanilla extract
- Set two racks in the middle of the oven. Preheat to 375°F.
- In a food processor, or bowl of an electric mixer, thoroughly mix the flour, cocoa, baking soda and powder, salt, and sugar. While pulsing, or on low speed, add the butter, and then the egg. Continue processing or mixing until dough comes together in a mass.
- Take rounded teaspoons of batter and place on a parchment paper-lined baking sheet approximately two inches apart. With moistened hands, slightly flatten the dough. Bake for 9 minutes, rotating once for even baking. Set baking sheets on a rack to cool.
- To make the cream, place butter and shortening in a mixing bowl, and at low speed, gradually beat in the sugar and vanilla. Turn the mixer on high and beat for 2 to 3 minutes until filling is light and fluffy.
- To assemble the cookies, in a pastry bag with a 1/2 inch, round tip, pipe teaspoon-size blobs of cream into the center of one cookie. Place another cookie, equal in size to the first, on top of the cream. Lightly press, to work the filling evenly to the outsides of the cookie. Continue this process until all the cookies have been sandwiched with cream. Enjoy with cold milk.
strawberry tarts and small injuries
I love to cook. (Does this surprise you?) There are other things that I'd like to care just as much about, like recycling, exercising or saving the baby seal. However, this is my affliction. I think about food morning, noon, and night. My husband often lovingly reminds me that I am obsessed. You know, he is totally correct and that is perfectly fine with me. Don't get me wrong. There are plenty of other things that I love doing, like taking beautiful photos, and spending time with the most incredible man on the planet.
side note: I am, by far, the luckiest woman in the world. You know what my husband did for me last night? He took me on a date. You know where? The nail salon. My handsome man took me to get a pedicure for a date. I don't know if it gets any better than that. If that doesn't make you drool, I don't know what will. Man am I glad that I snatched this one up before someone else figured out how amazing he is!
But food. I mean, it really gets me somehow. And when I say 'gets me', I mean a couple of things. See food captures every strand of attention I possess, and lately has literally stolen parts of me. In the last few weeks, I have successfully sliced my finger with a mandolin, gashed another with the blade of the food processor, and most recently, boiled my left thumb with very hot jam. Now, I wouldn't say any of this was worth it (except the tart dough, and maybe the jam, oh and the pork tenderloin with baby carrots, coming soon!), but I would say that I should have learned a lesson by now.
After the previously mentioned incident with the food processor, in which I was excitedly mixing together a flaky tart dough out of my new Tartine Cookbook, I took a little break and let the dough chill. At this point the bleeding had stopped and it was nearly 8pm. So, I did not entirely follow the directions because I was in pain and wanted a tart to make me feel better (you understand don't you?). So, I skimped on the chill time. According to the master tart maker, Elisabeth Prueitt from Tartine, the chill time is what makes the dough so flaky. I'm sure that if I had not shaved a whole hour off of the chill time, the dough would have been even more flaky, but it was super delicious just the way it was. The pastry cream recipe however, was horrible. It was a total flop. I'm not even going to give you the recipe. When I find something that measures up, I'll let you know. Disclaimer: The pastry cream recipe was something I found online. I'm sure the one in the Tartine Cookbook is awesome. I'll have to give it a try.
This tart dough is not sweet. It would be good with something savory as well, but we chose strawberries since we had some left over from the 14 pounds (!) we had picked the day before and they were luscious and wanted so badly to be eaten. I made a "pastry cream" because I thought the strawberries would be perfect on top of something sweet and creamy. They would have been better on just about anything, but whip cream sounded wildly appealing after being subjected to such a horrible pastry cream glob. Usually whip cream is not a good idea for tarts if you want to save them because it makes the bottom of the tart shell soggy, although these babies didn't stand a chance of being wrapped up for storage.
Please let me know what your plans are for this versatile and incredibly easy dough! You can make a large tart with this dough, or you could make adorable tartlets.
Flaky Tart Dough Elisabeth Prueitt Tartine Cookbook
Makes enough for two 9- or 10-inch tart shells.
1 tsp. (5 ml) salt
2/3 cup (150 ml) very cold water
3 cups plus 2 tablespoons (455 g) all-purpose flour, plus more for work surface
1 cup (2 sticks) plus 5 tablespoons (300 g) very cold unsalted butter, cut into 1-inch pieces
In a small bowl, mix together salt and water. Keep very cold until ready to use.
Place flour and butter in the bowl of a food processor. Pulse briefly until mixture forms large crumbs. Add the salt water mixture and continue pulsing until a dough has just formed but is not smooth.
On a lightly floured work surface, evenly divide dough. Form each piece of dough into a disk about 1 inch thick. Wrap each disk with plastic wrap and chill at least 2 hours and up to overnight.
To line the tart pan or pie dish, place a disk of dough on a lightly floured surface and roll out 1/8 inch thick, rolling from the center. Lift and rotate dough a quarter turn every few strokes to discourage sticking. Lightly dust the dough with more flour as needed.
If lining a pie pan, cut out a circle 2 inches larger than the dish. If lining a tart pan with a removable bottom, cut out a circle 1 1/2 inches larger. Carefully transfer the round to the dish/pan, easing it into the bottom and sides, pressing gently into place. With a sharp knife, trim the dough even with the rim of the dish/pan.
Line the pastry shells with parchment paper and fill with pie weights (you can also use dried beans.) For a fully baked shell, bake at 375 degrees F for about 25 minutes, or until the surface looks light brown. Remove from the oven and remove the parchment paper and weights. Return to the oven and continue baking until golden brown, about 5 minutes longer.
Cool completely on wire racks before filling.
tomato and corn salad followed by ridiculously good strawberry shortcake.
Fathers Day is synonymous with grilling. I tried for days to come up with a menu that didn't include the grill, but really that would just go against all things man, or Dad as it were. I don't mind grilling, in fact it's a wonderful way to cut calories, and get incredible taste out of so many things. I just love to do new things, but when you're cooking to honor someone else, it's good to make something you know they'll like. So, I decided on hamburgers (always a hit) with a tomato and corn salad, some smashed potatoes, and to top it all off, fresh strawberry shortcake. It all turned out to be fantastic, especially the dessert, which is of course, the most important part.
The burgers were pretty normal as far as burgers go. Some sirloin, some chuck, a little garlic along with a few splashes of Worcestershire. I can't actually tell you if they were good, because I made myself a little turkey burger (I don't really eat red meat if I can help it), but everyone seemed to like 'em. The shining stars of the evening were undoubtedly the so-good-you-have-to-take-a-doggy-bag strawberry shortcake and the succulent tomato and corn salad.
This tomato and corn salad is extremely easy and can be tweaked in so many ways. I think I'll add some feta next time, because as you'll learn, it's basically my favorite thing on earth.
P.S. This being kind of a special day, I really didn't take inventory of the calories for any given dish. I did lighten my meal by using a whole wheat bun, and having turkey instead of beef. The tomato and corn salad is something that is definitely on the lower side of caloric consideration. The strawberry shortcakes however, can be as bad as they want because something that good can just be that way, and we'll let it.
Tomato and Corn Saladserves 6
3 ears corn
3 pints cherry tomatoes
1 bunch chives, finely chopped
2 medium cloves garlic, minced
1 1/2 tbsp extra virgin olive oil, plus a little extra for brushing
juice of half a lemon
salt and pepper to taste
1. Pre-heat the grill to high heat.
2. Shuck the corn and remove all of the hair like things (real name anyone?).
3. Brush the corn with a bit of olive oil.
4. Place corn on the grill, turning occasionally to avoid burning, roughly about 8-10 minutes.
5. While the corn is cooking to perfection, cut all of the tomatoes in half, crosswise. Place into medium size bowl.
6. Add the rest of the ingredients except for the corn. Mix to incorporate.
7. Once the corn is done, let it cool a bit. Then with a knife, remove the kernels by slicing down the cob. Try not to slice too deep or you'll get the tough stuff underneath.
8. Mix well.
This salad can be made up to an hour or two ahead of time. Letting it rest a bit helps all of the juices to blend well.
Strawberry ShortcakesParade, May 2008
via epicurious.com
serves 6
- 4 pints strawberries, lightly rinsed, hulled and halved*
- 1 tablespoon fresh lemon juice
- 1 tablespoon sugar**
- 2 cups heavy (whipping) cream
- 1 tablespoon sugar
- 6 shortcakes (see recipe below), for serving
- 6 whole strawberries, for garnish
- 2 cups self-rising flour***
- 2 1/2 tablespoon sugar
- 1/8 teaspoon salt
- 1/2 cup (1 stick) cold, unsalted butter, cut into small pieces
- 3/4 cup milk
- 2 tablespoon heavy (whipping) cream
For the shortcakes:
1. Preheat the oven to 400°F. Grease a baking sheet.2. Combine the flour, sugar and salt in a bowl.
3. Add the butter. Using a pastry blender or your fingers, rub it into the dry ingredients until mixture resembles a coarse meal. Stir in the milk until a very soft dough is formed. Do not overwork.
4. Drop the dough in 6 equal portions onto the prepared baking sheet. Lightly pat the dough into rounds—3 to 3 1/2 inches in diameter—and lightly brush the tops with the cream.
5. Bake the shortcakes in the center of the oven for 15 to 20 minutes or until golden brown. Cool on a wire rack.
For the Strawberries:
1. Place strawberries in a bowl. Sprinkle with lemon juice and sugar, then gently toss with a rubber spatula. Let rest for 1 1/2 to 2 hours for juices to develop.2. Just before serving, whip cream with 1 Tbsp sugar until it holds soft peaks.
3. To serve, slice off the top third of each shortcake. Place the bottoms on 6 dessert plates and top with 1/3 cup of the prepared berries and juice, plus a spoonful of whipped cream. Cover with the top. Spoon over more berries and juice, then dollop with whipped cream. Garnish each with a whole berry and drizzle with any remaining juice.
*This seems like a lot of strawberries, but I promise you'll want at least this much. You may even want to make extra so that you can have some on your cereal, or on oatmeal, or on ice cream. Oh the possibilities are endless.
**I definitely like my whip cream a little sweeter than this. I used about 2 1/2 tablespoons of sugar and also added a splash of vanilla. To me, without those things, it just tastes like fluffy milk, which is less sweet than what I was going for.
***I could not find self-rising flour, so my husband, being the extremely resourceful one that he is, figured out that all that means is they have already added baking powder and salt for you. So, we just added our own to the mix. For this recipe I used 3 teaspoons of baking powder and 1 teaspoon of salt in addition to the salt that the recipe already called for.


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17 Throwback Mugs All '90s Kids Will Appreciate
Chillin' out, maxin', relaxin' all cool with your coffee.
Chillin' out, maxin', relaxin' all cool with your coffee.
Are you classically sweet or boringly bland?
You can probably still smell a Koosh ball in your head.
Does the Aggro Crag still haunt your dreams at night? Not sure? Well FIGURE IT OUT.
Vous voulez vous sentir vieux ? C'est parti.
It was the time of neon EVERYTHING.
Never let go.
"I've just got the Facebook!" From Brent Weinbach.
Get onboard the nostalgia train!
Sext me a pic of your Oreo O's.
French Toast Crunch or Oreo O's?!?!
♫ My heart will go on. ♫ And so will this movie, FOREVER.
She literally personified the 1990s.
Did Justin know what he was going to put in that box?
A BuzzFeed Elusive Report.
OK, so they may not all be classics, but they are the films that help get us into the holiday spirit.
The quiz of the decade.
Can you imagine TLC singing "…Baby One More Time"?!
They have class and you don't.
In 1994, Andre was a mild hit, but the fate of the animal at its center remained decidedly unclear. This is the story of how the sea lion lead of a film "based on a true story" became a movie star, a Katrina hurricane refugee, and a Bahamian expatriate.
Nostalgia is good for the soul.
We should all take a moment and ask ourselves, how you doin'?
All your favorite drinks have been missing an essential, neon-green ingredient: SURGE.
Hey, anything can happen — they brought back Surge and Boy Meets World!
From Sarah Michelle Gellar's spectacularly '90s outfit to President Bill Clinton sending his first email, it's all in this #ThrowbackThursday roundup.
How many of these trends did you sport on your first day of high school?
Victoria and David Beckham at the 2003 MTV Movie Awards kicks off this week's #ThrowbackThursday roundup.
Oops! You smiled again.
Are You Afraid of the Dark SECRETS OF YOUR CHILDHOOD?
Hugh Jackman (before he was buff!) kicks off #ThrowbackThursday.


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39 year old man | Quincy, MA, USA | Seeking women 27-35 within 25 miles of Boston, MA
Well I guess I will start with a little about...
Well I guess I will start with a little about me, and then what I'm looking for. I am an old school kind of guy. I still believe that a lady needs to be treated as such. I know what I want in life and someday I will have it. I work hard, and I take care of myself and my home. I have a promising career and most importantly I love what I do. I live every day to the fullest and I look forward to what life has in store next. I am an honest, loyal, trustworthy, intelligent, and funny (from what my friends say). I like to stay in shape and be active. I love doing things outside, whether it be camping, going to the beach, or going out on the water. But a night in watching movies or going to a lounge or club can be cool too. Family is very important to me and hope to find a woman that feels the same way. I have a 7 year old daughter that I am very proud of. Children are god's greatest gift. She lives mostly with her mom but I spend a lot of time with my princess. My daughter's mom and I are very close. We have a parental and friend relationship. I'm very thankful for everything I have. I would like to someday (no rush) start a family with someone new. As lucky as I feel I am, and the great situation I have with my daughter and her mom I don't ever want to start a family with another woman unless it's going to work permanently. Here's some other random quirky things about me which I hope one day someone might find endearing: 1. I take butter in my coffee. Don't frown. It tastes great! Really, it does. 2. Fave foods are fried chicken, sushi, steak tartare, slow cooked pork, pho and Asian soups in no particular order. Love them all. 3. Everything in my home is black and white with clean lines. I may need some interior designer tips? How do you add color without making it look feminine? About you: I would like to find someone who has a high level of self-respect, integrity and education. Someone with goals in life and can complement mine and push me to be better. I like a kind of girl that loves to do some of the things I enjoy like being outside and active. Keeping themselves healthy and in shape. A girl with a sense of humor is a must; you have to enjoy smiling at least once a day with me! I am not looking for a picture perfect princess, but someone who like to be treated like one, but like in any relationship it's has to mutual, a two way street.
Camping , Coffee and conversation , Business networking , Cooking , Dining out , Gardening/Landscaping , Movies/Videos , Museums and art , Music and concerts , Exploring new areas , Nightclubs/Dancing , Performing arts , Playing cards , Playing sports , Political interests , Religion/Spiritual , Shopping/Antiques , Travel/Sightseeing , Volunteering , Watching sports , Wine tasting
Baseball, Basketball, Billiards / Pool, Bowling, Football, Other types of exercise, Running, Skiing, Swimming, Tennis / Racquet sports, Walking / Hiking, Weights / Machines
I exercise 5 or more times per week.
I have Dogs
I like Cats, Exotic Pets, Fish, Horses
I have a cute teacup Yorkie. I know what you're thinking but there's a story behind that. You'll just have to ask :)
Middle of the Road
Sushi restaurants, coffee shops, crossfit, CV, Toro, Empire, Seaport area
Fat guy food, music, good conversation, having a great day, coming home after the cleaners have been in my condo, buying expensive things for 50% off like on 'living social", if you don't know what living social is google it, it's great.
Haven't finished them yet but right now I have a marketing book and a Joel Olsteen book on my desk.
Him | What he is looking for | |
Appearance | ||
Height: | 5'9" (175cms) | 5'0" (152cms) to 5'8" (172cms) |
Body type: | Athletic and toned | No preference |
Eyes: | Blue | No preference |
Hair: | Dark brown | No preference |
Lifestyle | ||
Smoke: | No Way | No Way, Occasionally, Yes, but trying to quit |
Drink: | Social Drinker | Never, Social Drinker, Moderately |
Occupation: | Self-Employed / Entrepreneur | No preference |
Income: | I'll tell you later | No preference |
Relationship: | Never Married | No preference |
Have kids: | Yes, and they sometimes live at home (1) | No preference |
Wants kids: | Definitely | Definitely, Someday, Not sure |
Background | ||
Ethnicity: | White / Caucasian | No preference |
Irish/Italian, you don't see too many in Boston I know... |
Faith: | Christian / Other | No preference |
Church is good for balance. |
Languages: | English | English |
Education: | Bachelors degree | No preference |
I have a deep appreciation for education. I feel like I a PHD in business. |


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problem was the fire. They survived the impact with no issues. The steel was sprayed with fireproofing put no one would ever consider filling a floor with jet fuel
here is the crazy part, if air fares do go down that will just increase demand. I just do not see how the airlines lose here.
Lotta fun making big money every day.
not sure why the sell off here
what was the purpose of the following that have resulted in nothing new Birther Solyndra Fast and Furious NSA IRS Bengahzi 1 - 8 Ebola there are two sides in the political games
so you think the Saudis will cut back to make sure north Dakota drillers stay in business, OK sure. I heard the exxon CEO, they pretty much want oil to go down so they can buy out the little guys cheap. We will be down for a long time
I am not greedy
a 33% decrease in oil will save them 4 billion a year. Oh snap
95.50 - 61.75 = 33.75. Sounds like that would be a no


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Light Color | Red |
Length | - |
LED Number | - |
Socket Type | For USA/Canada |
Weight | 14.12 oz |
Customer Reviews
- They work perfectly. Review by Kevin W
Value Price Quality They work perfectly. Plugged in,the long string of lights are rapid blinking. I'm glad I bought them. (Posted on October 3, 2012)


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Vladimiro Ristorante Marcello
- r
- RichardNYC Sep 4, 2012 12:55 PM
- 0
- Follow
Any recent experiences with Vladimiro Ristorante Marcello in Rome? We've enjoyed it a lot whenever we ate there, most recently about three years ago, but a number of recent reviews on other sites are rather negative. I'm hoping it hasn't changed for the worse and that the negative reviews are not representative.


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WoW Pro Lore Episode 12 The Seven Kingdoms
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The Kingdom of Strom struggles to keep humanity under 1 banner, and so Stormwind, Kul Tiras, Stromgarde, Lordaeron, Dalaran, Gilneas and Arathi are founded!
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The Seven Kingdoms
The Seven Kingdoms In-Game Book Do not add to, edit, or remove any of the story, unless the...
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current | 12:42, April 18, 2013 | 02:40 | 480 × 269 (21 KB) | Tankingmage (Talk | contribs) | created video |