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|NBA Basketball
|Player News
Dale, Michael and Jerry dig into the details of this draft for the Patriots with ESPN's Mike Reiss.
Giardi and Price discuss the Tom Brady appeal getting overturned and Roger Goodell's victory tour. The guys can't believe the victory lap and some of his behavior. The more you listen to him, the more frustrating his behavior becomes.
Giardi and Price break down how the teams in the AFC East altered their futures after the NFL Draft weekend.
Sam Packard is joined by Celtics 2nd Round draft pick Abdel Nader to discuss his path to the the NBA and how he plans to improve his game. Sam then talks to Player Development Coach Nick Friedman from Elite Skills Training, the pre-Draft camp Nader attended. Friedman also gives his opinion on the Celtics performance at summer league and the development of Jaylen Brown.
Isaiah Thomas talks to Glenn and Lou about why he loves Boston, the NBA Money Bump, oh, and some Durant guy
Danny Ainge joins Glenn and Christian to explain the Celtics draft process; and he also discusses the trade rumors that permeated the night.
Tim Neverett talks with Red Sox manager John Farrell before game 3 of their series with the Tigers. John talks about the struggles Steven Wright has had in inclement weather or days with high heat and humidity and how that might factor in to giving Wright the start on a particular day.
Drew Pomeranz looked stronger in his second Red Sox start but the offense wasn't there to back him up tonight. Mut recaps the 4-2 loss to the Tigers. Thoughts on the manager, the bullpen, and your Sox calls as well.
Joe Castiglione & Tim Neverett talked to the new Sox reliever, who got his first save for the team today against the Twins.
Joey Mac joins Ken Laird on his Saturday show to discuss the David Backes addition and Loui Eriksson departure in NHL free agency
DJ and Pete continue to assess the season that was for the Bruins and look toward the future for the franchise and how they can improve.
DJ and Pete are together for the final Sunday Skate of the season. They get into their overall thoughts on the season, the Bruins keeping Claude Julien on as head coach and the end-of-season press conferences last week. They discuss the rebuild process, what the Bruins need and how they can obtain it. Plenty of callers have their own theories and opinions on all of these topics as well.
Dino, Gerry and Mike Mutnansky discuss the Red Sox getting swept at home by Detroit and the state of the team heading out on an 11-game road trip.
Mut dishes on a few strained -- or perceived strained -- relationships he has at WEEI these days.
A compilation of the morning's Patriots talk with John, Gerry and Mut as the first Patriots practice is set to open in Foxboro.
The guys talk about the Red Sox sweep at Fenway by the Tigers and their recent struggles at home. They then preview the tough road trip ahead for the Sox
The OMFers discuss what it will be like with Jimmy Garoppolo under center. The guys get into Mut's complaint from earlier in the morning that Fauria ignored him in the gym
New Patriot's receiver Chris Hogan joins OMF to talk about being the new guy, and his experience with Rex Ryan in Buffalo
Dale and Holley w/Thornton talk about some of the lingering issues about the Pats heading into training camp.
With the news that Tom Jackson is leaving ESPN we take a look back at some of Jackson's greatest hits.
Dale and Holley close out the show with the best sound of the day!
Mut fills in for Kirk Minihane on this episode of Enough About Me and sits down with Bob Neumeier. Mut and Bob talk about his time at WBZ feuding with 5 & 7. Bob talks about his job at WEEI, why he didn't talk to the other hosts and his exit from the station. Bob talks in depth about his stroke and recovery.
Kirk Minihane is joined by Boston comedy legend Lenny Clarke. If you are a fan of stand up comedy this is the podcast for you. Kirk and Lenny talk about Carlin, Pryor, Williams, Murphy and many more.
Kirk Minihane is joined by former ESPN ombudsman and New York Times writer Robert Lipsyte. Kirk and Robert discuss the current state of ESPN and how Robert feels he did in his role as ombudsman. They both criticize ESPN for the lack of journalism at ESPN and look at some of the curious decisions the world wide leader has made in the past few years.
Mut fills in for Kirk Minihane on this episode of Enough About Me and sits down with Bob Neumeier. Mut and Bob talk about his time at WBZ feuding with 5 & 7. Bob talks about his job at WEEI, why he didn't talk to the other hosts and his exit from the station. Bob talks in depth about his stroke and recovery.
This week we preview the last major of the year, The PGA Championship.
John Dennis and Gerry Callahan bring Gary Tanguay in the podcenter to discuss Tango's bargaining position for Dino's job when it opens next year. The guys also discuss Kirk Minihane's latest podcast with Lenny Clarke.
John Dennis and Gerry Callahan bring Gary Tanguay in the podcenter to discuss Tango's bargaining position for Dino's job when it opens next year. The guys also discuss Kirk Minihane's latest podcast with Lenny Clarke.More from this show
John, Gerry and Bradfo discuss a rare political stance by Michael Jordan, and the ensuing criticism he received from ESPN talking head Kevin Blackistone. A Black Lives Matter discussion ensues.More from this show
Dino, Gerry and Tanguay discuss night two of the Democratic Convention, "highlighted" by Bill Clinton's attempt to humanize Hillary Clinton with tales of their courtship.More from this show
The 8am hour with Dino, Gerry and Tanguay is a bit of a hodge-podge of discussion, starting with the Democratic Convention and moving on to marathon swimming and archery at the Olympics and ending with Tanguay's defense of Hillary during the Benghazi attacks.More from this show
Dino, Gerry and Rob Bradford give their thoughts on the opening night of the Democratic Convention in Philly. Paul Simon, Al Franken, Sarah Silverman, Michelle Obama and Bernie are among those discussed.More from this show


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The clerk working inside the St. Clair One Stop Phillips 66 gasoline service station said quick action by her father-in-law prevented the teenager who allegedly robbed the store from getting away with all of the money that he had demanded and had been given moments earlier.
Susan Wright, who was the lone employee working at the business at 1125 Sycamore Lane, said she was robbed and threatened at knifepoint at about 1:45 p.m. on Monday by a male who entered the store wearing a handkerchief over his face.
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Commission: Flamon by kojikaWatch
©2011-2016 kojika
Commission I got at YoumaCon. Got it okayed to color, so I did (obviously). I dnno, I had a lot of fun with this guy XD he might be my fave Digimon (well, at least out of the like 7 I know, haha)
Flamon (c) Digimon
Art et al (c) meh
Flamon (c) Digimon
Art et al (c) meh


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I love halloween and halloween shirts! This one is a great addition to my collection. It fits nicely and is comfortable.
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|Publication number
|Publication type
|Application number
|Publication date
|Jul 6, 1982
|Filing date
|Jan 12, 1981
|Priority date
|Aug 29, 1979
|Fee status
|Publication number
|Gerald Sugerman, Salvatore J. Monte
|Original Assignee
|Kenrich Petrochemicals, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (3), Referenced by (17), Classifications (31), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
Xc Ti[OP(O)(OR1)OP(O)(OR2)OR3)]4-c
(NR4 R5 R6)d[P(OR7)(OR8)(OR9)]e,
Xc Ti[OP(O)(OR1)OP(O)(OR2)(OR3)]4-c (NR4 R5 R6)d [P(OR7)(OR8)(OR9)]e
This is a division, of application Ser. No. 070,907, filed Aug. 29, 1979, Pat. No. 4,277,415.
The present invention relates to adducts of tetrasubstituted pyrophosphato titanates with phosphites and/or amines. The pyrophosphato titanate adducts of the present invention are useful in controlling the viscosity, flow and the conductivity of many filled resins. They improve the physical and chemical properties of many filled resins thereby permitting more valuable and more stringent usage with maintained ease of processing. They also serve as acid catalysts in various applications and inhibit water/salt caused corrosion in treated substrates.
The titanates of the present invention differ from the pyrophosphato titanates disclosed in U.S. Pat. Nos. 4,122,062 and 4,087,402 primarily by the controlled reactivity of the titanates presently mentioned which permits long term storage of said titanates and of the treated filler/pigment resin at ambient to moderately elevated temperatures, and a very specific initiation of functional rates of activity to occur at controlled temperatures depending upon the specific adduct ligand employed. Other advantages conferred upon pyrophosphato titanates by adduction as taught in the present invention include a substantially reduced tendency for such adducts to crystallize as compared to their non-adducted analogs thereby permitting greater ease of dispersion in more vehicles and decreased acidity. In addition, many of the nitrogeneous adducts are water soluble, thereby permitting use of aqueous vehicles in conjunction with fillers and pigments which were heretofore incompatible in water as well as the incorporation of water as a diluent in organic systems which were previously incapable of accepting significant water dilution.
The pyrophosphato titanate adducts of the present invention may be represented by the following formula:
Xc Ti[OP(O)(OR1)OP(O)(OR2)(OR3)]4-c -
(NR4 R5 R6)d [P(OR7)(OR8)(OR9)]e I
In Formula I, c is 1 or 2; d is 0, 1 or 2; and e is 0, 1 or 2, with the proviso that d plus e must be 1 or 2. When c is 2, X is either RO-- or a group which taken together with the Ti to which it is attached forms a ring having the following Formula VI: ##STR1## when c is 1, however, X must be RO--. In Formula VI, each of f, g, h and i is 0 or 1, with the proviso that at least one of g, h and i is 1 and that the sum of f, g, h and i is 2 or 3. Each R is independently chosen from among 1 to 10 carbon alkyl groups, 3 to 10 carbon alkenyl groups, 7 to 10 carbon aralkyl groups, 2 to 10 carbon oxyalkylene groups and 3 to 10 carbon dioxyalkylene groups. R1, R2, R4, R7, each R10 and R11 are independently chosen from among hydrogen, 6 to 10 carbon aryl groups, 7 to 20 carbon aralkyl groups, 1 to 20 carbon alkyl groups, 3 to 20 carbon alkenyl groups, 2 to 20 carbon oxyalkylene groups and 3 to 20 carbon oligooxyalkylene groups, except that one and only one of R1 and R2 must be hydrogen. R5, R6, R8 and R9 are independently chosen from the same groups as R1, R2, R4, R7, R10 and R11 except that R5, R6, R8 and R9 may not be hydrogen. R5 and R6 may also be independently chosen from among 1 to 10 carbon alkyl, 3 to 10 carbon alkenyl, 6 to 10 carbon aryl and 7 to 10 carbon aralkyl groups. These last four groups optionally have from 1 to 3 carboxylate groups or from 1 to 3 carboxamide groups as substituent. Each such substituent may be saturated or unsaturated and have from 1 to 5 carbon atoms. R5 and R6 may also be independently chosen from among 1 to 10 carbon alkanols, 2 to 6 carbon alkadiols or 7 to 10 carbon aralkanols. When aromatic carbons are present in R, R2, R4, R7, R10 and R11 groups, each of said carbons is optionally substituted by 1 or 2 independently selected halogen atoms (for example, fluorine, chlorine, bromine or iodine).
The present invention also relates to the use of such adducts for treating particulate fillers, including pigments, the compositions of fillers and the aforesaid adducts with thermoplastics, thermosets and coating or casting resins, and the use of such adducts in conjunction with coating and casting resin compositions in the absence of particulates.
The aforementioned alkyl and alkenyl groups, and alkyl and alkylene portions of the other aforementioned groups may be straight chain, branched chain or cyclic. Examples of alkyl groups are methyl, hexyl and decyl. Examples of cyclic alkyl groups are cyclohexyl and cyclooctyl. Allyl and crotyl are examples of alkenyl groups. Oxyalkylene groups are exemplified by methoxymethyl and methoxyethyl. Aralkyl groups are exemplified by benzyl and beta naphthyl methyl. Examples of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 are likewise numerous. In addition to the above mentioned groups cited as examples of R, these groups are also exemplified by higher carbon analogs of the above such as octadecatrienyl and 2,4,6-trimethyl-1-cyclohexyl as well as by naphthyl and biphenyl aralkyl groups such as 2-phenethyl, 2-chloro,4-bromophenyl or naphthyl. In addition to the above, R5 and R6 are exemplified by such groups as 3-methacrylpropyl, and 2-acrylamidoethylhydroxy methyl and dihydroxy octyl.
The inorganic materials that may be treated with the titanate adducts of the present invention may be particulate or fibrous and of any shape or particle size, the surfaces of which are reactive with the hydrolyzable group of the organo-titanium compound by means of hydroxyl groups, or absorbed water, or both. Examples of such reactive inorganic materials are the metal oxides of zinc, magnesium, lead, and calcium and aluminum, iron filings and turnings, and sulfur. Examples of inorganic materials that are reinforcing materials are metals, clay, carbon black, calcium carbonate, barium sulfate, silica, mica, glass and asbestos. Examples of such inorganic materials that are pigments are titanium dioxide, iron oxides, zinc chromate and ultramarine blue. As a practical matter, it is preferable that the particle size of the inorganic material should not be greater than 1 mm, preferably from 1 micron to 500 microns.
It is imperative that the titanate adduct be properly admixed with the inorganic material so as to permit the surface of the latter to react sufficiently. The optimum amount of the titanate to be used is dependent on the effect to be achieved, the available surface area of and the bonded water in the inorganic material.
Reaction is facilitated by admixing under the proper conditions. Optimum results depend on the properties of the titanate, namely, whether it is a liquid or solid, and its decomposition and flash point. The particle size, the geometry of the particles, the specific gravity and the chemical composition, among other things, must be considered. Additionally, the treated inorganic material must be thoroughly admixed with the polymeric medium. The appropriate mixing conditions depend on the type of polymer, for example, whether it is thermoplastic or thermosetting, and its chemical structure, as will be readily understood by those skilled in the art.
Where the inorganic material is pretreated with the titanate adduct, it may be admixed in any convenient type of intensive mixer, such as a Henschel (trademark of Prodex) or Hobart (trademark of Hobart Corporation) mixer or a Waring (trademark of Dynamics Corporation of America) blender. Even hand mixing may be employed. The optimum time and temperature is determined so as to obtain substantial reaction between the inorganic material and the organic titanate. Mixing is performed under conditions at which the organic titanate is in the liquid phase, at temperatures below the decomposition temperature. While it is desirable that the bulk of the hydrolyzable groups be reacted in this step, this is not essential where the materials are later admixed with a polymer, since substantial completion of the reaction may take place in this latter mixing step.
Polymer processing, e.g., high shear mixing, is generally performed at a temperature well above the second order transition temperature of the polymer, preferably at a temperature where the polymer will have a low melt viscosity. For example, low density polyethylene is best processed at a temperature range of 177� to 232� C.; high density polyethylene from 204� to 246� C.; and polystyrene from 232� to 260� C. Temperatures for mixing other polymers are known to those skilled in the art and may be determined by reference to existing literature. A variety of mixing equipment may be used, e.g., two-roll mills, Banbury (trademark of Farrel Corporation) mixers, double concentric screws, counter or corotating twin screws and ZSK type of Werner and Pfleiderer (trademark of Werner & Pfleiderer) and Bussex (trademark of Bussex Corp.) mixers.
When the titanate adduct and the inorganic materials are dryblended, thorough mixing and/or reaction is not readily achieved and the reaction may be substantially completed when the treated filler is admixed with the polymer. In this latter step, the titanate adduct may also react with the polymeric material if one or more of the groups on the titanate adduct is reactive with the polymer.
The ratio of pyrophosphato titanate to adducting agents is preferably 1:1 or 1:2, with the latter ratio most preferred. Each adducting ligand may be the same or different. In those formulations in which either the phosphorus based or the nitrogen based adducting agents are different, the product obtained is usually a mix of possible adducts including mixed as well as identical ligands. In those adducts wherein combinations of nitrogen and phosphorus are employed, it is often possible by control of stoichiometry and mode of addition to maintain an almost complete dispersity of product, if so desired.
When used in conjunction with particulates, the adducts of the present invention are employed at levels of at least 0.01 parts by weight, preferably from 0.1 to 5 parts by weight, and most preferably from 0.2 to 2 parts by weight, per 100 parts by weight of inorganic solid. The portion of adduct actually chosen by one skilled in the art is a function of the inorganic solid, its surface area and the particular titanium adduct selected. Upon reaction between the titanate and the surface of the inorganic solid, the titanate becomes chemically bonded to at least a portion of the inorganic solid, thereby modifying the surface considerably. The modified inorganic solid is generally far more easily dispersed in organic media than is the untreated solid. For treatment purposes, the titanate may be added to a suitable vehicle, such as water or a resin to be filled depending upon the investigator's desire and/or the nature of the titanate being employed. This addition is followed by appropriate shear to create an adequate level of dispersion. The treated particulate, in addition to being more effectively coated, will almost certainly have substantially valuable additional properties, such as the ability to act as a catalyst, improved adhesion to substrate, and/or the ability to activate a cross-linking agent in appropriate vehicle systems, primarily due to the availability or organo-functionality added by attached titanate molecules.
The amount of treated filler added to a resin generally ranges from about 1% to about 15% for a pigment and from about 1% to about 500% for an extender (all percentages are % by weight based on the weight of the resin). A wide variety of resins may be filled with fillers that are treated with the titanate adducts of the present invention. Examples of such resins are coating resins, casting resins, thermoplastic resins and thermosetting resins. Examples of all of the foregoing may be found in the reference Modern Plastics Encyclopedia.
In many instances, it is advantageous to dilute the titanate with an appropriately compatible fluid before the titanate is introduced into resin vehicles or before it is mixed with an inorganic particulate. Examples of appropriate inert fluids are aromatic hydrocarbons, ethers and glycol ethers. In many applications involving the use of nitrogeneous adducts of pyrophosphato titanates, water may also be utilized as a solubilizing inert vehicle, particularly in applications involving subsequent use in aqueous systems, such as latex products.
The compounds of the present invention may be prepared by numerous routes. Among the synthetic routes which have proven successful are the addition of appropriate phosphites (Formula II) and/or amines (Formula III) to the corresponding pyrophosphato titanates (Formula IV) described in U.S. Pat. No. 4,122,062 and U.S. Pat. No. 4,087,402. The reaction of tetraalkyl titanate phosphite adducts (Formula V), preparation of which is described in U.S. Pat. No. 4,080,353 with addition of an appropriate pyrophosphate, an amine and/or a phosphite and/or a chelating agent may also be utilized, as may processes employing titanium tetrachloride in place of tetraalkyl titanates. The aforementioned formulae are shown below: ##STR2## In Formulae II, III, IV and V, the various notations and functional groups have the definitions given above for Formula I.
Another synthetic route found useful for the preparation of the phosphite adducts of the present invention wherein the adduct ligands are homogeneous is the reaction of tetraalkyl titanate with an admixture of disubstituted pyrophosphoric acid and the phosphite ligand(s). This last technique is the preferred one for the preparation of mono and di- phosphite adducts of such pyrophosphato titanates. Variations of the aforementioned synthetic routes will be apparent to those skilled in the art.
The preparation of phosphite adducts of corresponding pyrophosphato titanates may be accomplished under adiabatic conditions (since minimal heat evolution occurs) at any convenient temperature between approximately -20� C. and approximately 150� C. The addition of the phosphite to the pyrophosphato titanate in either direct or reverse order of addition will, in general produce minimal visual or thermal indication of reaction. However, typically a bathochromic shift of the absorption maximum toward, and, occasionally even into the visual absorption range, will generally be observed. Additionally, the melting point will be depressed below that of the corresponding unadducted precursor. Solubility of the resulting titanate in hydrocarbon media will generally be increased at the expense of the dispersibility in water. By contrast, those adducts produced by the addition of appropriately substituted amines to pyrophosphato titanates or their phosphite adducts will generally provide substantial exotherms of formation together with displacement of stoichiometric proportions of phosphite, if present, and will produce products of considerably enhanced water solubility as compared to the parent pyrophosphato titanate. Techniques employing the addition of dibasic pyrophosphates to tetrasubstituted titanate adducts of phosphite and/or amines will also generate substantial exotherms of formation and in both of these latter two synthetic approaches, temperatures should be kept within the range of approximately 0� C. to approximately 150� C. by external cooling in order to minimize product degradation and/or by-product formation. Examples 1 through 4 below, are illustrative of the above mentioned techniques in the order indicated above for the preparation of pyrophosphato organo titanate adducts of the present invention. Subsequent examples 5 through 18 are illustrative of the utility of the materials of the present invention for a variety of applications, such as corrosion control, pigment/filler dispersion, catalyst activity control and impact improvement. Preferred methods of incorporation of the titanate adducts of the present invention into filled resin systems and their uses both in the presence and in the absence of fillers, for purposes other that those listed above are also illustrated.
This example illustrates the sequential addition mode of phosphite adduct formation.
206 g of dimethyl acid pyrophosphate (1 mole) and 296 g of dibutyl acid pyrophosphate (1 mole) were charged into a 2 liter stainless steel and glass assembly comprising a mechanically stirred 2 liter glass vessel equipped with a thermometer, addition funnel, and a water cooled jacket. 285 g of tetraisopropyl titanate (1 mole) was added via the addition funnel over a period of 1 hour. Cooling sufficient to prevent the reaction mass temperature from exceeding 150� C. was maintained throughout the addition period. After 20 minutes of further mixing, 62 g of ethylene glycol (1 mole) were added over a period of about 20 minutes, at an addition rate and at a cooling rate such that the temperature of the reaction mass was kept between 42� and 46� C. 612 g dioctyl phosphite (2 moles) were then added, all at once. The resulting mass was transferred to a 2 liter flask equipped for vacuum distillation and was distilled from a water bath to give a pot residue having a boiling point of 80� C. 231 g of isopropyl alcohol (3.85 moles, GLC assay greater than 98%) were recovered as a distillate via liquid nitrogen cooling of volatiles. Product recovery was 1246 g (100% yield). The product was a pale yellow low viscosity liquid which crystallized slowly from a 40% solution in n-hexane at -20� C. to give light amber platelike crystals having a melting point of 48��3� C. Recovery was 1014 g (81%). The omission of byproduct isopropanol removal lowered product recovery on crystallization to 63%, but otherwise gave unchanged results.
This example illustrates the preparation of the example adduct in situ.
The procedures, reaction conditions and materials exemplified in Example 1 were employed except that the dioctylphosphite was introduced with the pyrophosphates prior to titanate addition. The nature of the crude product produced and its yield (1248 g, 100%) were essentially unchanged, but this order of addition was found to provide several operating advantages. Among the advantages were lower and more uniform exotherms of tetraisopropyl titanate addition (possibly due to the larger mass in the pot "heat sink," and/or to the more efficient cooling made possible by the reaction mass' considerably lower viscosity) and virtual freedom from the formation of crystalline intermediates of undetermined nature which formed copiously during the procedure given in Example 1, unless the dispersion of tetraisopropyl titanate added was extremely efficient.
It should be noted that other tetraalkyl titanates, e.g., methyl, n-butyl, t-butyl, or sec-octyl may be substituted for the tetraisopropyl titanate used in the illustration. However, the use of n-alkyl titanates frequently results in ligand exchange with the pyrophosphate moiety and may therefore result in complex product mixtures, especially via the procedure outlined in Example 1. Furthermore, the removal of higher boiling by-product alkanols, if desired, usually proved more difficult than the removal of the more volatile lower alkanols. The removal of by-product alcohol is optional and is not required for the preparation of the products of the present invention. Said removal merely facilitates product purification and/or may eliminate side reactions in alcohol sensitive substrates such as polyesters and urethanes and/or may provide decreased product flammability.
Tetraisopropyl titanate di(dioctylphosphite), 901 g (1 mole), was charged to a 2 liter stainless steel vessel equipped with an efficient agitator and external cooling. Temperature was maintained at or below 45� C. during the sequential addition of 206 g (1 mole) of dimethyl acid pyrophosphate followed by 296 g (1 mole) of dibutyl acid pryophosphate over a period of approximately one hour each. Ethylene glycol 62 g (1 mole) was then added. The reaction mixture was then transferred to a Pyrex (trademark of Corning Glass for heat resistant borosilicate glass) glass system equipped for simple vacuum distillation and was distilled to give 1238 g (99% yield) of pale yellow oil having a boiling point of greater than 90� C. which slowly crystallized to produce a white waxy crystalline mass having a melting point of 49�4� C.
This procedure was not as satisfactory as that of Example 1, because it suffered from the formation of localized gels during pyrophosphate addition. These gels made mixing difficult.
Numerous examples of chelated pyrophosphato titanate adducts prepared via the procedure given in Examples 1 to 3 are given in Table 1. Each titanate adduct is identified by a symbol in the extreme left hand column that similarly identifies the adduct in the Examples that follow.
TABLE 1__________________________________________________________________________ Method of Melting CalculatedPyrophosphato Titanate Adduct Preparation Point �C. % P/Found % P__________________________________________________________________________(A) ethylene di(butyl, octyl)pyro- 1,2,3 <0 16.4/16.1 phosphato titanate di(tris- ethylphosphite)(B) 1-oxo-1,3-propylene di(bis- 2,3 42 � 5 15.0/14.8 phenyl)pyrophosphato titanate dilaurylphosphite(C) 1-oxo-2-phenylethylene, di(2- 1,2,3 54 � 3 11.3/11.2 chloro-p-cresyl, methyl)pyro- phosphato titanate, triphenyl phosphite(D) neopentenyl, di(bisoctadecyl) 1,3 27 � 6 9.74/9.5 pyrophsphato titanate di(butyl, propyl phosphite)(E) 1,3 propylene, di(bisoctadecyl) 1 <0 9.26/9.3 pyrophosphato titanate di(di- benzyl phosphite)(F) oxoethylene di(butyl, methoxy- 1,2 <0 9.46/9.3 ethoxyethyl) pyrophosphato titanate dimethoxethylphosphite(G) ethylene di(methyl, 11, 14-hexa- 1,2,3 34 � 6 16.2/16.1 decadienyl) pyrophosphato titanate di(bismethyl phosphite)(H) 1,2-propenyl, di bis(2-bromo-3- 1,3 64 � 2 12.5/12.6 chloro-4-t-butylphenyl) pyro- phosphato titanate di(bishexa- decyl phosphite)(I) ethylene di(butyl, methyl) pyro- 1,2,3 73 � 4 16.9/16.8 phosphato titanate di(tris- ethylamine)(J) oxoethylene di(butyl, octyl) 1 42 � 5 13.3/12.9 pyrophosphato titanate 2-di- methylaminoisobutanol(K) ethylene di(bisoctyl)pyrophos- 1,3 82 � 4 9.65/9.9 phato titanate di(3-dimethyl- aminopropylmethacrylamide(L) benzylethylene di(phenyl, lauryl) 1 76 � 4 9.57/9.7 pyrophosphato titanate di(ethyl- aminoethyl acrylate(M) ethylene, di(butyl, methyl) pyro- 1 not isolated* phosphato titanate di(bisoctyl) phosphite(N) oxoethylene di(butyl, octyl)pyro- 1 not isolated* phosphato titanate diphenyl phos- phite(O) 2-methyl-2,4-butenyl di(di-p- 1 not isolated* chlorobenzyl)pyrophosphato titanate di(butoxyethyl, methyl phosphite(P) oxoethylene, di(benzyl, 2- 1,2 not isolated* pentenyl)pyrophosphato titanate di(2-dimethylamino) isobutanol(Q) 2,3-butenyl di(bis-4-methoxy- 1 not isolated* phenyl)pyrophosphato titanate diethylamine(R) 2,3-dimethyl-2,3-butenyl di(bis- 1 not isolated* methyl)pyrophosphato titanate triethylamine, dibutyl phosphite(S) oxoethylene di(p-bromobenzyl) 1 not isolated* pyrophosphato titanate methyl- aminoethanol(T) 1-oxoprop-1,3-enyl di(butoxy- 1 not isolated* methoxyethyl, isobutyl)pyro- phosphato titanate di(bistridecyl) phosphite(U) methoxyethylene di(bispropyl) 1 not isolated* pyrophosphato titanate di propylamino ethyl methacrylate(V) isopropyl, tri(butyl, methyl) 1,2,3 <0 17.0/16.8 pyrophosphato titanate di(bis- octyl phosphite)(W) isopropyl, tri(bisoctyl)pyro- 1,2, 16 � 5 12.9/12.8 phosphato titanate triethanol- amine(X) isooctyl, tri(bismethyl)pyro- 1,2,3 not isolated* phosphato titanate tripropyl phosphite(Y) ethoxytriglycolyl, tri(4-bromo- 1 14 � 6 15.3/15.1 phenyl, methyl)pyrophosphato titanate di(methoxyethyl) phosphite(Z) 4-ethoxybenzyl tri(di-alphanaph- 1 64 � 5 10.4/10.1 thyl) pyrophosphato titanate di (di-ethylaminoethyl(methacrylate)(AA) t-butyl, tri(bisbutyl) pyro- 1 12 � 4 17.2/17.0 phosphato titanate tri-methyl phosphite, dimethylaminoethanol(AB) methyl, tri(bis-4-chlorophenyl) 1 48 � 3 15.8/15.5 pyrophosphato titanate dioctyl phosphite, dimethylaminoethyl formamide(AC) allyl, tri(allyl, methyl)pyro- 1,3 23 � 3 20.2/19.9 phosphato titanate trimethyl phosphite, dioctyl phosphite(AD) (2,2-diallyloxymethyl)ethyl 1,2 38 � 4 11.9/11.7 tri(bisbutyl)pyrophosphato titanate di(trisphenyl phosphite)(AE) 1-(2-butenyl)tri(methyl, octyl) 1 31 � 3 13.1/12.9 pyrophosphato titanate, tri- ethylamine, dioctyl phosphite__________________________________________________________________________ *by-product alcohol not removed, reaction mixture used as such.
This example illustrates the utility of various titanate adducts of the present invention as corrosion retardants.
Xylene degreased 20 mil panels of cold rolled steel were dip coated with a 1 weight percent solution of additive in toluene followed by a toluene wash and were then oven dried at 150� C. in a nitrogen atmosphere. The dried panels were cooled, weighed, subjected to 100 hours of 100% humidity at 40� C. exposure in an environmental cabinet, re-dried, cooled, and re-weighed. The corrosion rate in mils per year was calculated from the following equation: ##EQU1## The results of a study of selected examples of the titanates of the present invention are given in Table 2.
TABLE 2______________________________________ Indicated CorrosionAdduct Rate (mils/yr) % of Control______________________________________None (control) 172 100A 38 22B 26 15C 69 40D 81 47E 24 14F 13 8G 32 19H 19 11I 20 12J 31 18K 38 22L 35 20X 17 10Y 20 12AB 26 15AC 18 10AD 41 24AE 38 22______________________________________
In each instance, the materials of the present invention improved humidity resistance of cold rolled steel by at least two-fold and in the case of the F material, the improvement was twelve-fold.
Titanate adducts M through U, identified above, were compounded into an alkyl-melamine baking enamel having a brown color as indicated below. The resultant formulations were each oven baked at 100� C. for a period adequate to provide a film pencil hardness (Society of Coatings Technology Test) of F-H at 1.3�0.2 mils dry film thickness. The results of this study are given in Table 3.
The following materials were premixed, on a high shear disperser, at ambient temperature for fifteen minutes:
______________________________________Material Kilograms Liters______________________________________soya alkyd short oil, 172 174Cook #S-157-A-2 (trademark ofCook Paint and Varnish Co.)pyrophosphato titanate adduct 0.397 0.33titanium dioxide, DuPont #R-960 21 5.08(trademark of E.I. DuPontde Nemours, Co.)magnesium silicate 32 12.0lamp black 0.9 0.512red iron oxide 3.2 0.648yellow iron oxide 15 3.72bentonite clay 1.1 0.633fumed silica 1.1 0.523soya lecithin 1.4 1.42______________________________________
Tetraoctyltitanate di(dioctyl)phosphite (0.188 kilograms, 0.20 liters) was added to the above mixture and the mixture was further mixed on a sand mill until the particle size was Hegman 6.5 grind guage. The resulting blend was added to the following Material Letdown Solution and was mixed at ambient temperature.
______________________________________Material Letdown Solution Kilograms Liters______________________________________xylene 41.8 48.5Butyl Cellosolve (trademark of Union 10.2 11Carbide Corporation)triethylamine 2.0 2.73n-butanol 0.90 1.1250% melamine formaldehyde resin, 74.5 76Cargil #2218 (trademark ofCargill Inc.)6% Cobalt naphthenate 0.90 0.95______________________________________
The resulting paint composition had the following properties:
______________________________________weight per liter 1.05viscosity (#2 Zahn � 6 sec.) 28.0volume solids (%) 32.0weight solids (%) 49.0thickness dry film 1.0-1.75pencil hardness F-Hgloss (�5�) 55.0letdown solution to grind ratio 5:1______________________________________
The bake time at 93� C. required to achieve specification hardness was determined for several titanate adducts of the present invention. The results are shown in Table 3.
TABLE 3______________________________________ Bake Time at 93� C. Time required toPyrophosphato Titanate achieve specificationAdduct Employed hardness (+2 minutes)______________________________________None (control) 117M 43N 41O 57P 84F 21Q 39R 48S 83T 42U 38______________________________________
The reduction in bake time required in order to achieve specification properties is clearly shown to be substantial for all members of the class tested. A considerable reduction in cost results from the savings in both time and energy expended during baking.
This example illustrates the utility of certain pyrophosphato titanate adducts in the simultaneous control of viscosity and pot life of polyester casting resins.
Polyester resin composites were prepared by thoroughly admixing in the following order, 100 g of polyester resin (#30001, trademark of Reichhold Chemical Co.), 0.5 g of pyrophosphato titanate adduct, 100 g of talc (#42, trademark of Englehard Mineral & Chemical Co.), and 1 g of 6% cobalt naphthenate. The resultant dispersions were deaerated by mixing in vacuo to eliminate variable air entrainment. The viscosities of the dispersions were then measured employing a Brookfield RVF viscosimeter (trademark of Brookfield Corp., Stoughton, Mass.). Thereafter, 0.5 g of methyl ethyl ketone peroxide was added to 100 g aliquots of deaerated dispersion and pot life was measured (time to achieve 2 million cps viscosity) at 21� C. The results are given in Table 4.
TABLE 4______________________________________ Viscosity of CompositeAdduct Employed (thousands of poise) Minutes______________________________________None 2.7 33N 1.6 109O 1.3 127F 0.8 18T 1.4 142U 0.6 14V 3.7 37W 5.2 35______________________________________
The data show that the phosphite adducts N, O and T retard the increase of viscosity due to premature gellation, thereby providing substantially increased useful working pot life, whereas the unsaturated nitrogen based adducts F and U act as accelerators, useful where rapid cure is desired. Furthermore, all of the adducts tested, other than V and W, provided the bonus of lower composite viscosities useful in many low energy application situations. Adducts V and W acted as thixotropes without material effect on pot life, a characteristic not shared by conventional thixotropes such as fumed silica and asbestos which, normally, markedly slow peroxide cures.
This example illustrates the use of various pyrophosphato titanate adducts to improve the scrubbability of a latex coating.
Test batches of latex paint were prepared by mixing 25 g of titanium dioxide (DuPont #R931, trademark of E. I. DuPont de Nemours) in 20 g of ethylene glycol monobutyl ether containing 0.25 g of pyrophosphato titanate adduct on a high shear disperser (at constant torque) to a Hegman grind gauge of minus 6. This was followed by letdown (dilution) with 100 g of acrylic latex (Ucar 4550, trademark of Union Carbide Corp.). Test panels were then prepared as 3 mil wet (about 2 mil dry) drawdowns on toluene degreased mild steel and the resultant films were dried at 25� C. for 48 hours prior to scrub testing. The scrub tester employed was a 1/8" wide, 10 micron silica impregnated phenolic grinding wheel rotated at 10 RPM. Grinding was continued in each case until magnetic dust was detected. Results are given in Table 5.
TABLE 5______________________________________ Grind Time (minutes)Adduct Required for -6(Hegman) Scrub Cycles______________________________________Control 22 38B 14 57C 12 83D 13 71E 9 46Q 14 143G 15 71H 12 62I 14 49J 13 53K 15 168______________________________________
These data show that the use of the adducts of the present invention markedly improved both the grinding efficacy and the scrub resistance in those formulations in which they were employed and that in several cases (C, F and K) the improvements in scrub resistance were twofold or higher.
This example illustrates the utility of pyrophosphato titanium adducts of the present invention for the improvement of epoxy polyamide coatings.
The coating components A and B were prepared separately by mixing the ingredients listed in Tables 6A and 6B, respectively, in the order indicated at 33� C. to 45� C., using a Cowles dissolver (trademark of Moorhouse Cowles Co.). Components A and B were admixed at ambient temperature using the same equipment. Q-panels (trademark of Q-Panel Corp.) of cold rolled steel were coated with portions of the test coating to provide a film one mil dry thickness. The coatings were aged for one week at ambient temperature before testing. Test results are given in Table 6C.
TABLE 6A______________________________________Component A BLSC Control Silica SystemIngredient Parts by weight Parts by weight______________________________________epoxy resin (Araldite 210 210571CX80, trademarkof Ciba-Geigy Corp.)basic lead silicochromate 480 None(BLSC)titanium dioxide 30 30red iron oxide 15 15fumed silica 6.4 6.4talc 235 235amorphous silica None 400xylene 193 193diacetone alcohol 96 96urea formaldehyde resin 10.5 10.5(Beetle 216-8, trademarkof America Cyanamid Corp.)chelated pyrophosphato None 3.3titanate adductparts by weight 1276 1199______________________________________
TABLE 6B______________________________________Component B BLSC Control Silica SystemIngredient Parts by weight Parts by weight______________________________________polyamide curative 105 105(Araldite 820, trademarkof Ciba-Geigy Corp.)xylene 24 24butanol 12 12parts by weight 141 141______________________________________
The cost per gallon of the Component A BLSC Control was $1.35; the cost per gallon of the Component A titanate adduct formulation was about $0.66.
TABLE 6C______________________________________ Rusting Stripped after 1000 panel rust- hour salt ing after Initial Four Month fog expo- 500 hours, viscosity viscosity sure at 100% humid-Adduct KU* KU 27� C. ity at 27� C.______________________________________BLSC(Control) 192 216 M (moderate) S (severe)B 112 126 Sl (slight) SlC 103 104 Sl MD 106 118 Sl SlE 102 104 Sl SlQ 116 109 Sl MG 109 111 M MH 113 115 Sl SlI 96 100 M SlJ 101 107 Sl Sl______________________________________ *Krebs units
Note that as compared with the BLSC Control, each of the pyrophosphato titanate adducts of the present invention provided improved protection against corrosion at a cost considerably lower than that of the BLSC Control without the employment of environmentally damaging heavy metals as required by the best previously available technology. Also demonstrated are the massive viscosity reduction achieved via the use of the products of the present invention as a major contributing capability to the functional utility of the silica system since control viscosity would otherwise prevent effective application coverage.
This example illustrates the utility of pyrophosphato titanium adducts of the present invention as adhesion promoters for polymer laminates.
The titanate adducts listed in Table 7 below were compounded into virgin low density polyethylene (LDPE). Thirty mil sheets of the LDPE were extrusion laminated onto preformed 50 mil Surlin (trademark of DuPont de Nemours for metalated polyolefin) ionomer sheets at 107� C., employing a 24:1 vented National Plastics Machinery (trademark) extruder. The peel strength of each laminate was measured with a constant speed motor and a strain gauge at 27� C. after 24 hours at ambient temperature and pressure. The results PG,23 are given below in Table 7. The formulations contained 0.2 weight percent of the indicated chelated pyrophosphato titanium adduct on LDPE.
TABLE 7______________________________________Adduct Peel Strength, kg/cm2______________________________________Control 4.8A 9.0B 19C 20D 17E 20G 17H 16I 24Z 13______________________________________
Note that in each instance, the use of the adducts improved peel strength (bonding) between the dissimilar polymer layers.
This example illustrates the utility of pyrophosphato titanium adducts of the present invention in enhancing the tensile and elongation properties of cellulosics (cross-linked low density polyethylene filled with cotton linters).
One hundred parts by weight of low density cross-linkable polyethylene, 20 parts cotton linters (chopped to 20-45 micron length, 0.5 parts dicumyl peroxide and 0.2 parts of pyrophosphato titanate adduct were compounded on a two roll mill at 93��6� C. (all parts given are parts by weight). Samples were then press cured at 149� C. for 20 minutes. The samples were equilibrated at 21� C. for 24 hours prior to testing on an Instron (trademark of Instron Corporation) tensile tester at an extention rate of 0.2 inches/min. The results are given below in Table 8.
TABLE 8______________________________________Adduct Tensile Strength, kg/cm2 Elongation at Break, %______________________________________Control 6.11 � 103 80A 6.53 � 103 90D 7.95 � 103 170Q 10.9 � 103 230K 8.80 � 103 210______________________________________
This example illustrates the use of pyrophosphato titanate adducts as viscosity control agents and/or dispersants in dissimilar media (for example, water and mineral oil).
In each instance, the indicated titanate was precoated at 0.5 weight percent on HiSil 223 (trademark of PPG Industries) in a household type blender prior to dispersion in the liquid vehicle (water or mineral oil) at 70 weight percent HiSil using a Hochmeyer disperser (trademark of Hochmeyer Corp.). The resulting dispersions were evaluated at 27� C. using a Brookfield RVF viscometer (trademark). The results are given in Table 9.
TABLE 9______________________________________ Aqueous dispersion visco- Mineral Oil dispersionAdditive sity MCPS (103 centipoise) viscosity MCPS______________________________________Control 152 23A 130 28B 37 56C 52 72D 168 22E 182 18Q 154 21G 172 19H 41 62I 227 separates rapidlyJ 47 62K 164 18Z 194 17Y 184 18AD 171______________________________________
This example demonstrates the wide range of viscosity control available in vehicles as diverse as water and mineral oil via the employment of small proportions of pyrophosphato titanium adducts in conjunction with a single (silica) particulate.
This example illustrates the utility of pyrophosphato titanium adducts as promoters of conductivity in metal filled polymer composites. In each instance, the metal indicated was precoated with the specified adduct by admixture in a household type blender prior to incorporation into the polymer base on a laboratory two roll mill. The formulations were press cured and formed as 6 inch�6 inch�100 mil sheets for 20 minutes at 170� C. and stress relieved at 27� C. for 24 hours, prior to evaluation. Resistivities were measured using a field effect transistor type ohmeter equipped with a decade runup box of 101 to 109 ohms range on a through the sample basis. The results are given in Table 10 (Tables 10a, 10b and 10c).
______________________________________ Resistance ResistanceAdduct ohm/cm Nickel ohm/cm Tin______________________________________Control 1.3 � 106 3.9 � 106B 16 6.2 � 102C 28 4.8 � 102Q 45 87E 63 1.1 � 102K 1.1 � 102 96______________________________________
______________________________________Adducts Resistance ohm/cm______________________________________Control 1.6 � 108B 2.0 � 104C 1.4 � 104E 4.7 � 102Q 6 � 102K 1.7 � 102Y 5.7 � 105Z 6.2 � 103AA 4.1 � 103AB 8.1 � 101AD 6.2 � 102AE 3.8 � 102______________________________________
TABLE 10c______________________________________Formulation (in parts by weight): Viton E430 (trademark of E.I.duPont de Nemours for fluoroelastomer), 24; calcium hydroxidepowder, regent grade (manufactured by J.T. Baker ChemicalCompany), 1.28; nickel (1 micron nominal powder), 75; pyrophos-phato titanium adduct, 0.25.Adduct Resistance ohm/cm______________________________________Control 9 � 108B 5 � 105C 7 � 104E 1.8 � 102Q 38K 61F 6.1 � 106M 5 � 103P 8 � 103AB 3.4 � 102______________________________________
In each and every instance the use of pyrophosphato titanate adduct provided for substantial conductivity enhancement versus the control, despite the gross variation in polymer binders employed; (i.e. the silicone and Viton (trademark) are grossly differing thermosets, and the PVC is a thermoplastic).
This example illustrates the use of selected pyrophosphato titanium adducts as insulation value enhancers in hard clay filled flexible polyvinyl chloride.
SP-33 Clay (trademark of Burgess Pigment Co.), 20 parts by weight; dioctyl phthalate, 50; and pyrophosphato titanium adduct, 0.01; were admixed in a household type blender. The resulting mixture was added to polyvinyl chloride resin (Geon 103EP, trademark of B. F. Goodrich Co.), 100; epoxidized soybean oil, 3; powdered lead diphthalate, 3; and stearic acid, 0.3, all quantities are in parts by weight. The mix was compounded on a laboratory two-roll mill at 135� C. and press-formed for 10 minutes at 160� C. prior to evaluation of resistance of a sheet having a cross-section of about 100 mils by employing a mehohm Bridge coupled to a 104 -105 ohm decade box assembly. The results are shown in Table 11.
TABLE 11______________________________________Adduct Resistance ohms/cm______________________________________Control 5 � 1012B 2 � 1013C 3 � 1013D 8 � 1012Q 7 � 1012J 1 � 1013______________________________________
These data show that significant resistivity increases result from the employment of pyrophosphato titanate adducts in vinyl based insulation.
This example illustrates the advantages in terms of shelf stability resulting from the adduction of pyrophosphato titanates with certain types of amines and/or phosphites.
Test formulations containing 40 weight percent Bakelite CK-1634 phenolic resin (trademark of Union Carbide Corp.) and 10 weight percent of powdered coal (Carbofil #1--Shamokin Filler Co.), together with 0.2 weight percent of pyrophosphato titanate (as shown) in xylene were coated on aluminum Q-pannels (trademark of Q-Pannel Corp.) to a wet film thickness of 5 mils and placed in a 150� C. forced draft oven until the resultant film showed a pencil hardness of 3H. A second sample of each formulation was shef aged in a closed container, at 25��3� C. to determine package stability. The test results are shown in Table 12.
TABLE 12______________________________________Pryophosphato Titanate Shelf Life (days).sup.(1) Cure Time Min.______________________________________Control (none) 60 � 3 25 � 3A 55 � 5 16 � 2non-adducted A.sup.(2) 22 � 2 15 � 2B >120 14 � 2non-adducted B 20 � 3 15 � 2J >120 17 � 2non-adducted J 20 � 3 16 � 2(same as A)K >120 20 � 2non-adducted K 28 � 3 19 � 2Q >120 16 � 2non-adducted Q 22 � 3 15 � 2(same as A)AA 74 � 5 11 � 2non-adducted AA 18 � 3 10 � 2AE 82 � 5 12 � 2non-adducted AE 16 � 4 12 � 2______________________________________ .sup.(1) Time to 100% Brookfield (trademark) viscosity increase .sup.(2) Prepared as disclosed in U.S. Pat. No. 4,122,062 or 4,087,402
This example shows that while both adducted and non-adducted pyrophosphato titanates decrease cure time with consequent reduction in energy requirements when employed in conjunction with phenolic resins, the non-adducted analogs negatively effect formulation shelf life whereas their adducted analogs either effect shelf life positively or negligibly compared to the control. This example also shows that the choice of adducting agent also has a substantial effect on the properties of the resulting adduct.
This example shows the advantages of appropriate adduction of pyrophosphato titanates for purposes of melting point depression and ease of dispersion. One gram of the specified adducts of the present invention and, separately, their non-adducted analogs were added to separate 200 mil portions of water. 100 grams of Optiwhite Calcined Clay (trademark of Burgess Corp.) was then dispersed at 30��5� C. using a Hochmeyer disperser and the viscosity of each dispersion measured immediately and after boiling for two hours at 30��1� C. using a Brookfield RVF viscometer (trademark of Brookfield Corp.). The results are shown in Table 13.
TABLE 13______________________________________Pyrophosphato Initial 30� C. Boiled dispersionTitanate Employed viscosity (cps) 30� C. viscosity (cps)______________________________________Control 4.3 � 105 >107I 6.7 � 103 >107non-adducted I 4.1 � 105 >107J 3.9 � 103 5.2 � 104non-adducted J 4.5 � 105 >107K 6.3 � 104 4.7 � 104non-adducted K 5.0 � 105 >107L 3.9 � 103 8.4 � 103non-adducted L 4.0 � 105 >107W 6.1 � 103 >107non-adducted W 4.2 � 105 >107Z 4.8 � 105 5.2 � 105non-adducted Z 4.5 � 105 >107AB 2.9 � 102 >107non-adducted AB 4.5 � 105 >107AE 8.2 � 104 9.5 � 105non-adducted AE 4.1 � 105 >107______________________________________
This example shows that pyrophosphato titanate adducts of the present invention may be utilized to achieve controlled viscosity reduction of aqueous clay dispersions at ambient temperature with or without controlled viscosity lowering after boiling whereas their non-adducted analogs give essentially negligible response in comparable formulations.
This example shows the utility of adduction of pyrophosphato titanates with amines of Formula III and/or phosphites of Formula II with respect to melting point reduction and with respect to solubility enhancement in selected media.
The indicated phosphato titanates, prepared according to the procedures described in U.S. Pat. Nos. 4,122,062 or 4,087,402, were converted to the indicated adducts via the procedure outlined in Example 1 and solubility (as weight percent) at 25��3� C. was measured in n-hexane (Hexane sol.). Melting points of the phosphato titanate were determined before and after adduction. The results are given in Table 14.
TABLE 14______________________________________Pyrosphos- Pyrophos-phato non- Hexane phato Hexaneadducted Melting sol. Titanate Melting sol.Titanate Point �C. wt. % adduct Point �C. wt. %______________________________________I dec 182 <0.5 I 73 � 4 7V 171-174 <0.5 V <0 >25AA 158-161 1 AA 12 � 4 >25AC 179-184 <0.5 AC 23 � 3 >25AE 129-134 3 AE 31 � 3 12______________________________________
This example shows the improvement in hexane solubility and melting point lowering effected upon prior art phosphato titanates via the practice of adduction as described in the present invention.
This example shows the utility of pyrophosphato titanate adducts as thermally activated catalysts in the controlled interconversion of esters, i.e., the transesterification of ethyl propionate with methyl butyrate in solutions containing ethyl acetate.
In a 2 liter pyrex flask equipped with facilities for mechanical agitation, pot and head thermometers, innert gas inlet, fractionating column (30 theoretical plates), automatic reflux-takeoff assembly, vacuum receivers, external heat and vacuum sources was placed 3 M each of ethyl acetate, ethyl propionate and methyl butyrate, together with 1.0 g of the indicated catalyst. Vacuum and reflux ratios were adjusted to 25 mm and 25:1, respectively, and the pot contents distilled to recover 97�1% of the feed overhead. Analysis of the distillate(s) was performed by gas liquid chromatography results are given in Table 15.
TABLE 15______________________________________ % Yield % % Re- % Re- By- % Re- Yield covery covery product covery Methyl Ethyl MethylCatalyst Methyl Ethyl Pro- Pro- Buty-Employed Acetate Acetate pionate pionate rate______________________________________SulfuricAcid 97 2 <1 95 <1AluminumChloride 94 5 4 97 <1B 13 85 84 13 3Non adducted B 89 9 8 90 3H 7 91 90 8 1Non adducted H 91 8 5 92 2I <1 99+ 94 5 3Non adducted I 87 11 10 88 2J 2 96 93 5 2Non adducted J 94 4 5 95 1______________________________________ a All numerical data in mole %.
Note that both conventional acid catalysts and non-adducted pyrophosphato titanates, when employed in the above system, produce substantial proportions of by-product methyl acetate due to preferential volatilization of same once formed, whereas the adducts of the instant invention, having little catalytic activity until temperatures in excess of 50� C., permitted recovery by vacuum distillation of the bulk of the ethyl acetate prior to onset of catalytic transesterification.
|Cited Patent
|Filing date
|Publication date
|Apr 19, 1976
|May 2, 1978
|Kenrich Petrochemicals, Inc.
|Organo-titanate chelates and their uses
|Sep 30, 1975
|Oct 24, 1978
|Kenrich Petrochemicals, Inc.
|Alkoxy titanate salts useful as coupling agents
|Oct 31, 1977
|May 1, 1979
|Kenrich Petrochemicals, Inc.
|Titanate phosphite adducts and their use
|Citing Patent
|Filing date
|Publication date
|Mar 26, 1982
|Nov 22, 1983
|Kenrich Petrochemicals, Inc.
|Pyrophosphato titanate adducts
|Sep 20, 1989
|Dec 31, 1991
|Imperial Chemical Industries Plc
|Novel composition comprising isocyanate-reactive hydrogen-containing compounds
|Jan 24, 2005
|Jun 24, 2008
|Biotech Products, Llc
|Compostable vinyl halide polymer compositions and composite sheets
|Mar 8, 2011
|Biotech Products, Llc
|Compostable vinyl halide polymer compositions, composites and landfill biodegradation
|May 10, 2011
|Biotech Products, Llc
|Compostable vinyl acetate polymer compositions, composites and landfill biodegradation
|Jul 10, 2009
|Jun 7, 2011
|Biotech Products, Llc
|Anaerobically compostable polymeric compositions, articles and landfill biodegradation
|Feb 21, 2011
|Jul 16, 2013
|Biotech Products, Llc
|Heavy metal-free and anaerobically compostable vinyl halide compositions, articles and landfill biodegradation
|Jan 24, 2005
|Jul 27, 2006
|Ultraflex Systems, Inc.
|Compostable vinyl halide polymer compositions and composite sheets
|May 11, 2007
|Sep 6, 2007
|Grossman Richard F
|Compostable vinyl halide polymer compositions, composites and landfill biodegradation
|Mar 17, 2008
|Jul 10, 2008
|Biotech Products, Llc
|Compostable Vinyl Acetate Polymer Compositions, Composites and Landfill Biodegradation
|Apr 7, 2008
|Oct 8, 2009
|Biotech Products, Llc
|Compostable Olefin Polymer Compositions, Composites and Landfill Biodegradation
|Jul 10, 2009
|Nov 5, 2009
|Biotech Products, Llc
|Anaerobically Compostable Polymeric Compositions, Articles and Landfill Biodegradation
|Jun 30, 2011
|Biotech Products, Llc
|Heavy metal-free and anaerobically compostable vinyl halide compositions, articles and landfill biodegradation
|Sep 19, 1989
|Apr 4, 1990
|Imperial Chemical Industries Plc
|Novel composition comprising isocyanate-reactive hydrogen containing compounds
|Oct 19, 2007
|Nov 20, 2008
|Biotech Products, Llc
|Compostable vinyl halide polymer compositions, composites and landfill biodegradation
|Jun 17, 2010
|Jan 13, 2011
|Biotech Products, Llc
|Anaerobically compostable polymeric compositions, articles and landfill biodegradation
|Sep 23, 2011
|Aug 30, 2012
|Biotech Products, Llc
|Heavy metal-free and anaerobically compostable vinyl halide compositions, articles and landfill biodegradation
|U.S. Classification
|502/162, 987/301, 987/226, 560/234, 502/167
|International Classification
|Cooperative Classification
|European Classification
|Feb 8, 1983
|Certificate of correction
|Jan 2, 1986
|Fee payment
Year of fee payment: 4
|Feb 6, 1990
|Maintenance fee reminder mailed
|Feb 26, 1990
|Surcharge for late payment
|Feb 26, 1990
|Fee payment
Year of fee payment: 8
|Dec 20, 1993
|Fee payment
Year of fee payment: 12


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I recently just posted on my obgyn telling me to stop nursing while pregnant. I have decided to continue nursing but wean her slowly off within the next two - three months. However, my baby girl refuses to drink from a bottle or sippy cup. i need advice on how to get her to. She is my first so i do not have any experience with this. She SOMETIMES drinks an ounce or two from a bottle of diluted juice, but that is maybe every other day. HELP
You might try having somebody besides you offer the bottle. Sometimes they'll take it better if they think you're not available, so try leaving the house entirely for an hour or two, and then let whoever's caring for baby offer the bottle. You might also try different styles of nipple, or different styles of cup. For us, what finally did it was that he got old enough to take notice of what his twin was doing, and started imitating her-- and she took the bottle or cup readily.
Some babies will prefer if you hold them in a nursing position, while they drink from cup or bottle. Others need a totally different position-- like lying propped on a pillow facing you, so you can make eye contact.
Good luck! It can be tough to overcome that resistance.
BTDT. My DS was 6 months old when I got pregnant with DS2. My milk dried up when he was 10 months. He would not take a bottle. His percentile dropped from 50th to 10th in a matter of 2 months. He was eating a ton of solids with lots of butter, oil and cream mixed in to up the calories. I think the hardest part for him was that he could not figure out how to latch onto the bottle. He would chew on the nipple and get a few teaspoons of goats milk (that's what our naturopath recommended) but that's it. After about 2 months he finally figured out how to latch. I almost cried I was so relieved. Here's my recommendation, try several bottles to find the one that works for your LO. Breastfed babies seem to do best with ones that have a wide base on the bottom part of the bottle. Try different positions including letting her hold it on her own. Have your DH or a friend try to bottle feed her (often mommy=nursing not bottle). Offer her a bottle regularly even if she doesn't seem to want it of know how to use it. She will figure it out eventually. Even though my DS used a bottle for milk he nursed through my entire pregnancy for comfort and closeness. You should have seen his face when my milk finally came in after DS2! Good luck mama. Just keep trying, she will eventually figure it out.
As a side note, once my son figured out how to use the bottle his percentile jumped back up to the 50th. He also nursed until just after his 3rd birthday.
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for family fun, homeschooling, books, simple living, and 6 fabulous children, including twin toddlers
You probably talk about this in your other thread that you mentioned, but what is the reason why your OB says you need to wean? I know a lot of moms who go through pregnancy and keep nursing the whole time, and tandem nurse once the newb is out.
bedsharing, knitting, toddler-nursing, nerdy, babywearing mama!
Ladies, thanks for your advice. I also, forgot to mention she co-sleeps with my husband and I and is a night nurser. This last week has been tough she is nursing 4-6 times a night. I am not getting the sleep i need. I just hope and pray something gives here.
Kim and baby Allyson
Hi, it was my first prenatal visit and she just said all of the nutrients need to go to the new baby and if I continue nursing the nutrients will not go where they need to. I am a first time mom and I was so confused to hear this I called my bf who was a breastfed for 6 years and she informed me about this website. I am grateful for her since I had never visited mothering.com. My next visit to the ob is in one month, and I know my baby will not be weaned seeing she won't even drink from a bottle or cup. She did drink from a bottle for about 4 months and recently she has switched backed to nursing only. I will then have to have a talk with my ob and let her know that for now I will continue to nurse. If she does not agree with me I will look for another ob....
I honestly don't think that is true, or at least it's not true for everyone, since I know so many people who have continued to nurse all through their subsequent pregnancies. Now, some women can't-- their supplies dry up, or it becomes excruciatingly painful-- but if you can, I say stick with it. That's just my opinion though!
bedsharing, knitting, toddler-nursing, nerdy, babywearing mama!
wow... idk if you have special circumstances that put you at risk for weaning, but if you don't, you shouldn't have to wean. i listened to my body and had to cut back on the length of nursing sessions, but nursed 8-10x/day when i got pregnant and didn't fully wean til 8 months (and by then DS was 2.5).
if you do need to wean for history of miscarraige or ptl, i might try a straw cup?
A PhD = + +
You can continue nursing through your pregnancy. Scary how doctors can be so misinformed!
I nursed my daughter during pregnancy, and she is still nursing along with my 8 month old baby. When my milk dried up she still wanted to nurse some, it was important to her. Nursing them together now is so sweet, they hold hands and my older daughter says it's her favorite time of day when they nurse together before bed.
The book Adventures in Tandem Nursing has so much great info, you should get a copy! It answered every single one of my questions about nursing during pregnancy. It also was very reassuring, especially when it talked about feelings you have towards older siblings once your new baby comes. Love this book so much.
Momma to Sweet Rosie 7/06, Lost Baby J 1/09 at 12 weeks pregnant, Spitfire Ada born 4/21/10, and Baby Boy due July/August 2013!
Aspiring urban homesteader, photographer, homeschooling momma! Blog link in my profile.
Just adding my experience - I've nursed through 2+ pregnancies (am well into my 3rd!). Each time my milk dried up around 13 weeks but my nurslings don't care - they still want the comfort and each one has nursed all the way to the renewal of the milk after the babe was born. If you're intent on following your OB's advice, it might be worth it to ask her where she got her info. AFAIK, OBs have very little training in breastfeeding. Try www.kellymom.com also for more info.
"So let us be loving, hopeful and optimistic. And we'll change the world." - Jack Layton
Just adding my experience - I've nursed through 2+ pregnancies (am well into my 3rd!). Each time my milk dried up around 13 weeks but my nurslings don't care - they still want the comfort and each one has nursed all the way to the renewal of the milk after the babe was born. If you're intent on following your OB's advice, it might be worth it to ask her where she got her info. AFAIK, OBs have very little training in breastfeeding. Try www.kellymom.com also for more info.
To add to this, if your milk dries up but your baby wants to keep nursing anyway, you can try using an SNS. That is what I use-- I have a low supply and my girl gets donated milk in the SNS. You run the small tube alongside your nipple so that when she latches on, she gets both your nipple and the tube. That way your baby could still nurse and actually get milk.
bedsharing, knitting, toddler-nursing, nerdy, babywearing mama!
Ladies, thanks for your advice. I also, forgot to mention she co-sleeps with my husband and I and is a night nurser. This last week has been tough she is nursing 4-6 times a night. I am not getting the sleep i need. I just hope and pray something gives here.
Kim and baby Allyson
I nightweaned in pregnancy for this reason! It was really rough at night, since..lets just say needing to pee a couple times a night is always my first symptom. So, she'd wake to nurse and *would not let go* and I was just like, uuugghhh I need to go SO BAD! So I'd finally get her to sleep, get up, pee, then she'd wake again when I got back into bed, then nurse for a little more, and by the time she's done I'm so awake I can't fall back asleep easier.. and before I even manage to fall back asleep.. she's up AGAIN! Repeat that process at least twice and that was a typical night :/ We put a mattress on the floor, dh was in charge of night time comforting, and after 3 rough nights, she accepted that the all you can drink milk bar.. has established some business hours.
dd (9) ds (7), ds (4) & ds (1)
Like others have said - nursing while pregnant is entirely up to you - your unborn baby will be fine either way. My son nursed through pregnancy, though it was somewhat uncomfortable in the middle when the milk dried up and colostrum hadn't come in yet. If he had been relying on that for significant nutrition at that point, he would have needed supplementing. So continuing to work to get her to take a bottle or cup is probably a good idea, whatever you decide. And I just delivered a nearly 10lb baby, who apparently suffered not at all in the nutrition department from her older brother's nursing.
You don't need to wean her entirely, especially at night. just make sure YOU are eating really well and drinking a lot of fluids.
Also, my 9 month old wouldn't take a bottle or sippy cup either (and I am a midwife and have to be away for long stretches sometimes, so it was a real problem). We tried about every bottle/cup on the market until we found one she would take: Think Baby sippy cup. It's a sippy cup with a soft nipple, like a bottle. For some reason, she will take this.
Your baby may not take this one, but there will be SOMETHING she will take if you keep on trying.
I agree with all the PP about not needing to wean. I just wanted to chime in and add that my 9.5 mo doesnt take a cup or a bottle. My DH is home pretty much all the time now that its too cold for him to work, and he has been watching her more often. She is drinking water from an open cup. We dont use formula, but sometimes he will give her a little rice milk (its what I drink, so its in the fridge) or keifer with water and mashed fruit (we call them "baby smoothies") if he feels like she might be needing a little more. We are starting to have a little luck with the sippy, but you have to coat the outside of the part she drinks out of with the stuff inside to get her to drink from it. Unless she is really hungry, she gets bored pretty quickly. Hopefully you wont have to give up nursing! Congrats on your pregnancy!
Holly and David
Adaline (3/20/10), and Charlie (1/26/12- 4/10/12) and our identical twins Callie and Wendy (01/04/13)
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My co-workers called me today to look at our website, and they reported that they cannot add new pictures to the blog... Apparently, when you click on the "Select Files" button, nothing happens, nothing at all. I've verified this, and found also that even the new WP3 drag and drop uploader is nowhere to be found! Now, I know this site worked fine just a few weeks ago, what could have happened? I see no evidence of hacking... anyone got any ideas???
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The Best of Me
|PG-13 (for sexuality, violence, some drug content and brief strong language)
|Drama, Romance
|Release Date:
|October 17, 2014
|Running time:
|118 minutes
|Michelle Monaghan, James Marsden, Liana Liberato, Luke Bracey, Sebastian Arcelus
|Michael Hoffman
|Nicholas Sparks, Denise Di Novi, Ryan Kavanaugh
|Nicholas Sparks, Will Fetters, J. Mills Goodloe, Michael Hoffman
|Relativity Media
Web Site: http://www.facebook.com/BestOfMeMovie
Description: The story of Dawson and Amanda, two former high school sweethearts who find themselves reunited after 20 years apart, when they return to their small town for the funeral of the beloved friend. Their bittersweet reunion reignites the love they've never forgotten, but soon they discover the forces that drove them apart twenty years ago live on, posing even more serious threats today. Spanning decades, this epic love story captures the enduring power of our first true love, and the wrenching choices we face when confronted with elusive second chances.
Movie summaries and listings powered by Cinema-Source


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twentyten theme :
I don't use titles for my posts I just want the date to act as the title.
Each post currently has this ex. "Posted on September 28, 2010 by pauldiehl"
I would like to change it to just have ex. " September 28, 2010"
I can't find in the PHP where to change this. From reading other posts it looks as if it would bee in loop.php but I can't seem to find it.
Any help is much appreciated.
my site for reference http://dport7.com/


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*image shown is 5 x 8 or larger rug
*smaller sizes will not show complete pattern, will be scaled down to fit.
Additional 10% discount will be applied in cart once discount code is entered.
Name: Bombay 496
Manufacturer: Surya
Collection: Bombay
Material: Wool
Construction: Hand Tufted
Thickness: approx. 0.625 in
Colors: Blacks/Greys , Tans/Browns/Rusts
Made in: India
Description: Encompassing the flavors of transitional, traditional and contemporary, this collection features a series of versatile designs to complement any decor. Hand-tufted in India, each rug is produced from the finest hand-spun and twisted New Zealand yarn to provide a truly unique texture. (Bombay 496 - Hand Tufted Wool Rugs from Surya)
Other Related Patterns You Will
Related products are usually selected because they employ the same materials and colours of the product featured above but in different patterns and therefore are often perfect for use in the same or adjacent rooms.


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2014 NFF Hampshire Honor Society Membership Announced
Eight USD Football players selected in the Society's eighth year
Toreros host Western New Mexico Mustangs Saturday at 6:00 pm
USD puts 12-game home winning streak on the line
33 Toreros Named to PFL Academic Honor Roll
33 USD football players maintained a 3.0 GPA during the 2012 fall semester
Six Toreros named to PFL All-Academic Teams
Beathard, Olario and Peleti earn 1st team honors for second straight year
League-best 12 Toreros honored on All-PFL Teams
Six Toreros named to All-PFL First Teams
USD: Fourth-year Torero will compete with defensive secondary at safety... In 2012 started all 11 contests... Ranked 5th on team with 44 tackles (24 solo) to go with 1 interception (Davidson)... Season best 8 tackles at Davidson... 7 stops at Cal Poly... 6 tackles in three other contests... Appeared in all 11 contests in 2011 for the Toreros... Tied for sixth on the team with 40 tackles (29 solo)... Career-high 10 tackles in 48-44 victory at Morehead State... Interception at University of Dayton in 31-28 win... Named 2011 Most Improved Defensive Player and to 2011 PFL All-Academic First Team... Appeared in 10 contests in 2010... Season-high 9 tackles against Valparaiso... Chipped in eight tackles against UC Davis... Finished 10th on the team in total tackles with 25 (nine solo)... Named to PFL Honor Roll... Was a redshirt in 2009.
HIGH SCHOOL: Attended La Jolla HS...honored as the Brent Woodall Award winner, which is given to the most well-rounded student-athlete at La Jolla High...led the Vikings in rushing yards and touchdowns during his senior year...1st-team All-Western League performer during his senior year, as well as being named Team Iron Man award winner...in his junior year, earned his second Defensive Coach's Award and was named to the 2nd-team All-Western League...recorded the 3rd-most career tackles for defensive backs at La Jolla High...also a three-time letterman in baseball.
PERSONAL: Born on November 9, 1990 in San Diego, CA...Parents are Mark and Rhonda Beathard of San Diego, CA...Chose USD for its competitive football team, great education, and perfect location...Also recruited by Columbia, University of Redlands, Pomona-Pitzer, and Occidental College...Named to USD's Dean's List... Would like to go to medical school and become an orthopedic surgeon.
MAJOR: Accounting
Meet the Toreros: Jose Martinez
6'10" freshman forward from Cayey, Puerto Rico.
Meet the Toreros: Frank Ryder
6'10" freshman forward from Boulder, Colo.
2015-16 Highlight Video
All the top plays from 2015-16
Jordan Angus - Male Torero of the Year
Angus reflects on his time at USD
Malina Hood - Female Torero of the Year
Malina Hood looks back at her USD career
NCAA Tournament Preview
San Diego faces Vanderbilt in first round
2016 Celebration of Excellence
Behind the Scenes at the COE
Toreros Participate in Linda Vista Parade
Toreros Participate in Linda Vista Parade
Men's Tennis senior Day
The Toreros host LMU and Pepperdine Saturday and Sunday
Softball WCC Preview
The Toreros host Saint Mary's Saturday and Sunday
2016 San Diego Crew Classic
The Toreros show speed against the nation's top crews
The Torero Baseball Experience
Kris Bryant & Brian Matusz reflect on their time at USD
MBB Senior Night
Jito Kok and Duda Sanadze prepare for the final home game
USD Baseball Season Preview
Season starts at No. 3 Vanderbilt February 19
USD Softball Season Preview
Season starts February 12
UCLA Preview
USD travels to No. 9 UCLA Friday
Toreros Host Kentucky Saturday
USD looks to defend home court against No. 22 Kentucky
Toreros Host Pepperdine & LMU
USD returns home after four-game road trip
Toreros Team Up with PYBL
Men's Basketball hosts annual clinic for Challenged Division
Men's Tennis 2016
USD opens at home vs UC Irvine and UCSD Saturday
BYU Preview
Preview of USD women's basketball WCC opener vs. BYU.
City Championship Highlights
Relive the Toreros' Upset over SDSU at Petco Park
Toreros to Host Hope International
The 9-1 Toreros will host Hope International in their final game before WCC play
Toreros Stun Aztecs at Petco
Postgame reaction and press conferences
Toreros Return Home
USD will host Bethesda before Sunday's City Championship at Petco Park
Men's Basketball Season Tickets
Starting as Low as $99
Butler Preview
Pono Keni and Coach Lindsey talk about Saturday's Senior Day game against Butler
CSUN Preview
Coach Fisher and forward Maya Hood talk about Tuesday's home-opener against CSUN
USC Preview
Coach Smith and Brett Bailey preview the season opener at USC
Davidson Preview
Jonah Hodges and Dale Lindsey talk about Jonah's return and preview Davidson game
San Diego Fall Classic Preview
Coach Dagman previews the San Diego Fall Classic
Nevada Preview
USD's Women's Basketball team will start their season at Nevada this weekend
USD Men's Basketball - The Origins (1955-1973)
A Glance at the Beginnings of Torero Hoops
Campbell Preview
Coach Lindsey and Jeff Starr preview Campbell
Stetson Preview
Coach Lindsey and Jereke Armstrong talk about the season so far
WCC Media Day
Behind the scenes with Men's and Women's Basketball at WCC media day
Warner Recap
Dale Lindsey and Anthony Lawrence on USD's 45-14 win
Warner Preview
Anthony Lawrence and Coach Lindsey preview game vs. Warner
Torero Community Service
USD Athletics helps out at Father Joe's Village in downtown San Diego
Men's Basketball Camp Update
Kok and Carter talk about the upcoming season
Drake Preview
Toreros host Bulldogs for Homecoming game
Dayton Preview
Toreros look for 4th straight win
LMU Preview
Pack the Stadium Night
ITA All-American's Preview
Petronijevic, Angus, & Vittek Prepare
Marist Preview
USD Looks to Extend Home Win Streak
Valparaiso Preview
Toreros First True Road Game of 2015
CSUN and UCSB Preview
Toreros Look to Extend Win Streak
Aztec Invite Recap
Both Squads Finish Second
SDSU Preview
Toreros Take on Cross-town Rival
WNMU Recap
Highlights from 45-21 win
2015 Home Opener
Previewing Western New Mexico
Volleyball Tournament Preview
A preview of the USD Tournament
Men's Soccer Season Opener
Previewing No. 16 Cal
Training Camp Update
Coach Lindsey Recaps the First Two Weeks
2015 WSOC Preview
A brief preview of the 2015 Toreros.


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About Falindraun
"Putting in place regulations to limit those services seems to be backfiring"
or as the existing cab companies would say 'working as intended' (the elimination of uber / lyft)
except that it doesn't and is not acceptable by all parties that count, namely small business owners and other small entrepreneurs that don't have the big lobbying dollars that the big mega-corps and other wealthy entrepreneurs have. have you ever heard the term the squeaky wheel gets the grease? well in this case that grease is money and the squeaky wheel are those are and have been negotiating this TPP in secret.
in which case Australia would just ban the import of all tobacco products
at least the court recognized that PM was treaty shopping and properly smacked them down for it.
the whole "kids" and "underage" and "below the age of legal age of consent" parts put a gigantic kibosh on the whole "consensual activities" part. you might want to go read up on child pornography laws.
since the fcc has a good enough of what is and is not robocalling or a robocall why dont they just define it and ban the practice of robocalling and all associated hardware.
its reasons such as this why i will never be owning a new car with any iot in it
i wonder when bcbs will be suing the red cross over the shape of its logo?
in all honesty i would have told the Public Utilities Commission to puc off and sued them over their perceived right to require this kind of information to begin with.
i could have ran over about a dozen people on my way home from work on friday, but did I? No I didn't.
If we as Americans were arrested on what we could have done or might have done, then everybody would be in jail. I hope this kid gets a good lawyer and sues the sh*t out of the school district and the sheriff for this misuse and abuse of justice and the law.
Technically speaking since the mobile carrier requested to the mobile phone maker that tethering be disabled by default on all phones for their network, then yes they are blocking a lawful, non-harmful service.
more like 'Holy cash cow batman!'
when it comes to cell phones, the government cant hack what i dont own or possess.
hey hey hey, isnt that called torture in some countries to be forced to listen to U2, let alone have to look at Bono naked?
i havnt seen an ad in years and years. i use adblock. there is also another ad-on that helps you hide the ads that make it past that.
i can neither confirm nor deny the existence or non-existence of a funny and or witty comment.
3 months is more than enough time to destroy any and all relevant evidence. anyone who thinks this is not possible or has already happened has their heads screwed on backwards. its way to easy to find out which hard drive the data in question is on and use a press to punch out the spindle of the hard drive and replace it.
the problem is that is exactly what verizon wants, so that verizon's customers use verizon's video streaming service instead.
or the 'extra' spaces could have been removed automatically.
"And Level 3 already showed at least with Comcast that there was some evidence that this was going on."
you are exactly right. this is the kind of thing that net neutrality was supposed to fix. as verizon would love for all of netflix's customers to just use verizon's video streaming service instead and part of how verizon tries to do this is by intentionally slowing down their customers traffic to netflix then blaming the entire thing on netflix.


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Rotorua Things to Do Tips by jag17
Rotorua Things to Do: 276 reviews and 543 photos
Most RecentBest Rated
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Theater Entrance
As part of the Maori hangi and concert, we were given the opportunity to purchase tickets to the Realm of Tane. At the time, I wasn't really sure what I was signing up for. It turned out to be a seperate performance that we attended earlier in the day. An interactive story in which a grandmother is passing down the culture/stories of her childhood to her grandaughter. Part guided tour, character theater, and story telling. My friend and I were the only one in attendance which seemed a little odd at first, but the cast did a great job of performing, and it was very touching. We really felt like we had attended something special as we lef the theater.
Address: 1220 Hinemaru St
Village Entrance
If you get the chance, you should check out the Tamaki Maori Village. The fun begins the minute the painted bus comes to pick you up from your hotel. Horn honking, singing, and laughter while you travel to the village (you should know/practice your national anthem/country song because you will be expected to sing)! You will be delivered to the grounds where they will explain the rules of entering the sacred village, and someone (a male guest) will be selected to perform in the entrance ceremony. After the chief allows you to enter, you will have plenty of time to wander around the many demonstrations displaying the Maori culture before heading off to the concert, and tradional Maori Hangi. Enjoy dinner, and a stroll around the craft stores before the bus delivers you safe and sound back to your hotel. More honking, singing, etc! Even though you will enjoy many laughs, this is a cultural event and very interesting.
Address: Hinemaru St, Rotorua.
Directions: Catch the tour in the city.
Phone: 07 - 346 2823
Website: http://www.maoriculture.co.nz
Steaming Pools
You have a few choices if you want to check out one of the many thermal reserves in Rotorua. We selected Whatarewarewa, and were not disappointed. You are free to wander on your own, or enjoy the guided tour. The guide was very interesting and informative. A small Maori population still lives at the reserve; bathing and cooking with the thermal waters. You even have the chance to purchase corn on the cob cooked right in the waters. The hightlight is the Pohutu Geyser which erupts several times a day; some eruptions over 60' into the air (great photo ops). Be sure and check out the Maori culture show which is also included in your admission price.
Address: Tyron St, Rotorua.
Directions: Off Fenton St,into Sala St, then Tryon St.
Phone: 07 - 349 3463
Website: http://www.whakarewarewa.com
If you have come to Rotorua, you must spend some time at the spa! Yes, even you male readers that have never had a spa experience! Trust me, you will love it! It is very well done, organized and the staff will walk you through the entire thing. All you have to do it show up, relax, and melt into relaxation! Plan in advance for the treatment(s) you want to schedule. They do book up quickly, so don't delay. They will instruct you to arrive at least 1 hour prior to your appointment, so that you have time to enjoy the hot springs. Four pools at different temperatures will set the tone for your spa treatment.
I enjoyed a 60 minute mud wrap, with a 30 minute foot therapy treatment. It was messy, but heavenly. I walked out like mush. After completing treatments, we slipped into our robes and wandered down to the lounge area to relax further with a glass of wine. No need to hurry!
Address: Hinemoa Street, Rotorua.
Directions: Right in the centre of town.
Phone: 07 - 348 1328
Website: http://www.polynesianspa.co.nz
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text:
Bryan Sweeley
Broker Associate
(650) 793-0355
CalBRE LIcense
It is my pleasure to present...
6971 Chantel Court, San Jose
Bryan Sweeley,
Broker Associate
Serving the greater Silicon Valley area
Kitchen recently updated with granite slab countertops, cabinet refacing, tile backsplace, tile flooring, new stainless steel range, microwave and dual sink. Pop-out garden window over sink looks out over tree tops towards mountains.
Pop-out window over kitchen sink is ideal for an indoor herb garden.
The indoor laundry is located next to the kitchen.
A half-bathroom/powder room is also next to the kitchen.
Large Living-Dining room opens out to patio deck with lots of natural light and fresh air. Recently updated with wood laminate flooring.
A 2-bedroom Condo with Cupertino schools. Two full bathrooms and a half-bath with 1,044 sqft of living space plus a nice patio deck off the living room. Updated kitchen with granite slab countertops, newer range and microwave. Detached one-car garage nearby. Condo is located in the quiet interior of the complex, just around the corner from the community swimming pool. The development is located off of De Anza Blvd just south of Hwy 85 interchange. Cupertino schools: Blue Hills Elementary (949 API), Miller Middle (984 API) and Lynbrook High (942 API).
Located in the quiet interior of the complex, just around the corner from the community swimming pool and spa.
It is a two-story Condo on the second floor with no one above you.
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The Community Pool and Spa is just around the corner making it easy for a quick dip or to relax with a good book.
This Condo is located near the De Anaza/Saratoga-Sunnyvale and Hwy 85 interchange. Close to Westgate and Vallco shopping centers.
Susan Sweeley
Broker Associate
(650) 793-0828
CalBRE LIcense
Bryan Sweeley
Broker Associate
(650) 793-0355
CalBRE LIcense
Master Suite is full of light and air from large window that looks out onto trees and mountains. Laminated wood flooring just installed. Two large closets provide lots of storage space. The Master Bathroom was recently updated with new cabinet facing and tile flooring.
The second Bedroom is light and airy and looks out over the front entry. Laminate wood flooring just installed. The upstairs hall bathroom was recently updated with new cabinet facing and tile flooring.
The Patio deck off of the Living Room provides a nice balance of sun and shade to relax in or grow vegetables and flowers.
The Condo is located in the interior of the community to the left of the swimming pool. The HOA consists of 100 units with 80% owner-occupied. There is a rental restriction that says no more than 30 units may be leased or rented at any time.
2 Bedrooms
2 Full Bathrooms
1 Partial Bathroom
1,044 sqft of living space
Detached one-car garage
Indoor Laundry
Patio deck
Community Pool and Spa
Cupertino Schools
Blue Hills ES (949 API)
Miller MS (984 API)
Lynbrook HS (942 API)
Offered at $749,000