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Publication number | US4375357 A |
Publication type | Grant |
Application number | US 06/271,913 |
Publication date | Mar 1, 1983 |
Filing date | Jun 9, 1981 |
Priority date | Jun 9, 1981 |
Fee status | Lapsed |
Publication number | 06271913, 271913, US 4375357 A, US 4375357A, US-A-4375357, US4375357 A, US4375357A |
Inventors | Robert E. Wingard, Jr., Steve Y. W. Ng, Sally A. Swanson |
Original Assignee | Dynapol |
Export Citation | BiBTeX, EndNote, RefMan |
Patent Citations (7), Referenced by (23), Classifications (10), Legal Events (5) | |
External Links: USPTO, USPTO Assignment, Espacenet | |
1. Field of the Invention
This invention relates to polymeric colorants, particularly water-soluble polymeric black colorants useful as water-based printing ink components.
2. The Prior Art
An ideal black dye exhibits a strong absorbance throughout the visible color range. There are two basic ways to achieve this. The first is to intentionally or inadvertently combine a number of colors which separately absorb various portions of the color range. Nigrosine, a widely accepted black dye, is such a mixture. This method has an advantage that color shading is simply accomplished by varying the mixture's composition and the disadvantage of separating into its components under certain conditions.
The second type of black dye employs a single chromophore having a very broad absorbance. This is easily done with insoluble "carbon black" type materials but far more difficult to attain with soluble systems. The present invention relates to such a "single dye" soluble system.
The colorant of this invention is a polymeric colorant. Polymeric colors are known to offer advantages in use of noncorrosivity (U.S. Pat. No. 3,976,797, issued Aug. 24, 1976) and nonmigration in substrates (U.S. Pat. No. 3,937,851, issued Feb. 10, 1976). In addition, they can be made water-soluble--an advantage today with increasing opposition to widespread use of organic solvented dye systems which release organic solvents into the workplace.
We and our coworkers have prepared and reported a number of polymeric colors heretofore. For example, U.S. Pat. No. 3,920,855, issued Nov. 18, 1975 discloses a family of nonabsorbable polymeric food colors. These materials employ known chromophores. U.S. Pat. No. 4,018,826, issued Apr. 19, 1977 discloses poly(vinylamine) as a colorant backbone and shows a range of polymeric colorants. U.S. Pat. Nos. 4,051,138, issued Sept. 27, 1977; 4,096,134, issued June 20, 1978; 4,182,885, issued Jan. 8, 1980; and 4,233,328, issued Nov. 11, 1980 are representative of other patents dealing with polymeric colorants. These references have either achieved polymeric forms of colors having hues that match those of their known monomeric equivalents or have employed newly discovered chromophore units. In contrast, the present colors employ a known chromophore unit (Acid Blue 92), but modify and couple it in a way that changes its color from a monomeric blue to a polymeric black.
We have now discovered a polymeric black colorant that is a deep rich black, is water-soluble and, like many soluble polymers is noncrystalline. Our colorant has a structure ##STR2## is an aromatic ring present in an organic polymeric backbone, M is a cation and n is an integer greater than one.
In another aspect, this invention relates to the preparation of such a colorant by the coupling of Acid Blue 92 to diazotized aromatic amine-containing polymer.
In further aspects, this invention relates to inks and dyes containing these colorants in solution and the use of these colorants as inks fast to paper.
In the present description and claims, reference will be made to several terms which are expressly defined as follows:
The term "Chrom" as used in the Formulae shall be a short hand notation for the chemical group having the structure ##STR3##
The term "water soluble" shall mean the property of being soluble in water to an extent of at least 1000 ppm by weight.
The terms "organic polymeric backbone" and the like shall mean a synthetic compound comprising repeating units linked together by carbon-carbon or carbon-oxygen covalent bonds.
The term "average molecular weight" shall designate a mean molecular weight as determined by gel permeation chromatography comparison with known standard molecular weight polymers.
The term "recurring" is used to describe repeating units in a polymer chain. As so used, the term is intended to encompass not only the situation wherein a single unit repeats in a "homopolymer" structure, but also the situation wherein a unit appears in a polymer chain interspersed with other different units in a "copolymer" structure.
Structure of the Polymeric Colorants
The colorants of this invention are polymeric in nature and comprise 8-(4-anilino-5-sulfo-1-naphthylazo)-1-naphthol-3,6-disulfonic acid groups (or salts thereof) bonded through their "2-carbon" position via azo links to aromatic carbons present in aromatic organic polymer backbones. Pictorially, such materials may be represented as shown in General Structural Formula I, ##STR4## wherein M is hydrogen or a cation selected from among the monovalent metal cations such as the metal cations found in period 3, group I, and period 4, group I, of the Periodic Table of the Elements. Preferably, M is hydrogen, or cations of Na or K so that the group is present as a acid group or as a sodium or potassium salt. Most preferably, M is sodium such that the group is a tri-sodium salt.
In pictorial representation I., ##STR5## represents a portion of an aromatic-group-containing organic backbone from an aromatic carbon-atom of which extends an azo link and therefrom the chromophoric group. "n" is an integer that is greater than 1.
The Polymeric Backbones
The aromatic-group-containing polymer backbone may take either of two structures. In one, the aromatic groups are present as groups pendant from an organic chain which links them together into the desired polymer backbone. Such a structure has n recurring ##STR6## wherein C is a portion of a covalent organic polymer chain linking the units together, n is an integer greater than 1 and R is a carbon to carbon single linking group. Examples of such linking groups include amine links, sulfonamide links, ether links, ester links, amide links, carbamate links, alkyl links, and the like. Preferred as R are carbon-carbon single bonds and sulfonamide links.
The polymer backbones employed themselves are stable under the conditions of use and do not break down under these conditions.
The second backbone aromatic group configuration which can be employed in the present polymeric compounds has the aromatic groups as an integral part of the backbone; such a structure has recurring arylene units, i.e., ##STR7## The azo links are attached to carbons of these arylene units. The backbones in either of these two configurations can be linear, or branched so long as they present the requisite aromatic carbon groups required to affix the azo bonds in the final product. Preferably, they are substantially linear. A number of examples of suitable polymeric backbones and an outline of the method of their use are given in a series of preferred embodiments. These are merely representative and are not to be construed as limiting the scope of the backbones useful in the practice of this invention. It is considered that the present invention involves polymeric forms of this chromophore, generally and is not limited to a particular backbone. Accordingly, other art-known backbones which would provide the desired aromatic backbone carbons could be employed as well as the materials herein specifically embodied.
Backbone: Polystyrene
Preparation: ##STR8##
In this and all the other embodiments, only one polymer repeat unit is shown. This is done for simplicity. It will be appreciated that the several reactions may not be completely quantitative in yield. Accordingly, while the final product will have the unit shown as a recurring unit, it may also have minor amounts of other unreacted precursor units. In this embodiment, for example, the product might be expected to have four different units in an overall structure. ##STR9##
It will be further appreciated that, since the Chrom-containing units are the only colored units, it is generally desired to maximize the proportion of this unit and minimize the residual precursor units. Preferably, the Chrom-containing units make up at least 25% (more preferably from 50 to 100%) of the maximum number theoretically possible. (In other words, preferably at least 1 out of 4 backbone aromatic units carry an azo-linked chrom group.)
In practice, it may be of importance to assay for the presence of Chrom units as well as for the presence of other units present in the polymer. Conventional analytical techniques known to the art will serve for these determinations. Representative analytical methods include the following:
Azo Bond Content is determined by reductive titration with chromous ion.
Aromatic Amine (on precursor polymer) is determined by redox titration with NaNO2.
Aromatic Amide is determined by proton NMR using the methyl group proton signal for quantitation.
Aliphatic Amine is determined by a modified van Slyke method in which primary aliphatic amine is converted to N2 gas. Measured volume of evolved N2 is used to quantitate original amount of polymeric primary aliphatic amine.
Backbone: Poly(vinylamine)*-Based Polysulfanilamide.
Preparation: ##STR10## EMBODIMENTS 3, 4 AND 5. Backbone:
The same as in Embodiment 2 except that the following units are copolymerized with the vinylamine units: acrylic acid, vinyl sulfate, ethylene.
Embodiment 3
Acrylic acid (1-50 mole% basis number of total vinyl units). Such backbone materials and their preparation are shown in U.S. Pat. No. 3,920,855.
Embodiment 4
Vinyl sulfonate (1-50 mole% basis number of total vinyl units). Such copolymers and their preparation are shown in U.S. Pat. No. 4,096,134.
Embodiment 5
Ethylene (1-50 mole% basis number of total vinyl units). Such copolymers and their preparation are shown in U.S. Pat. application Ser. No. 110,071 filed Jan. 7, 1980.
Poly(ethyleneimine)-Based Polysulfanilamide.
Preparation: ##STR11## EMBODIMENTS 7, 8, 9, 10 AND 11. Backbone:
Polyvinylamine, its copolymers, shown in Embodiments 3, 4 and 5, and poly(ethyleneimine) following reaction with ##STR12## Representative Preparation: ##STR13## EMBODIMENTS 12, 13, 14, 15 AND 16. Backbone:
Poly(vinylamine), its copolymers shown in Embodiments 3, 4 and 5, and poly(ethyleneimine) following reaction with ##STR14## Representative preparation: ##STR15## EMBODIMENTS 17, 18, 19, 20 AND 21. Backbone:
Polyvinylamine, its copolymers shown in Embodiments 3, 4 and 5, and Poly(ethyleneimine) following reaction with ##STR16## Representative Preparation: ##STR17## EMBODIMENT 22. Backbone:
Poly(N-methylvinylamine) following reaction with ##STR18## Preparation: ##STR19## EMBODIMENT 23. Backbone:
Copolymer of N-methylvinylamine, with from 1-50 mole % (basis total vinyl units) of ethylene, vinylsulfonate or acrylic acid.
Poly(vinyl alcohol) following reaction with ##STR20## Preparation: ##STR21##
This same embodiment can also employ a copolymer of vinyl alcohol.
Poly(vinyl alcohol) (or copolymers of vinyl alcohol) following reaction with ##STR22## Preparation: ##STR23## EMBODIMENT 26. Backbone:
Poly(vinyl alcohol) or copolymers of vinyl alcohol following reaction with ##STR24## Preparation: ##STR25## EMBODIMENT 27. Backbone:
Poly(vinyl alcohol) or copolymers thereof following reaction with ##STR26## Preparation: ##STR27## EMBODIMENT 28. Backbone:
Poly(acryloyl chloride) following reaction with ##STR28## Preparation: ##STR29## EMBODIMENT 29. Backbone:
Poly(acryloyl chloride) following reaction with ##STR30## Preparation: ##STR31## EMBODIMENT 30. Backbone:
Poly(vinylisocyanate) following reaction with ##STR32## Preparation: ##STR33## EMBODIMENT 31. Backbone:
Poly(vinylisocyanate) following reaction with ##STR34## Preparation:
This would be the same as the preparation shown in Embodiment 29 substituting poly(vinylisocyanate) as a starting material. The intermediate product would be ##STR35## EMBODIMENT 32. Backbone:
Poly(epichlorohydrin) following reaction with p-nitrophenol.
Preparation: ##STR36## EMBODIMENT 33. Backbone:
Poly(epichlorohydrin) following reaction with ##STR37## Preparation: ##STR38## Preferred Backbones
Some classes of backbones are preferred because of their ease of use in synthesis. For example, water-soluble backbones are generally easier to use, diazotize and couple than are water-insoluble backbones. Backbones based on alkylamine-group-containing polymers, especially those shown in Embodiment 2 through 6 are preferred. These materials are available and artknown, or based on available art-known precursors.
Generally, the backbone should have an average molecular weight of at least 1000 daltons with an average weight of from about 2000 to about 2,000,000 daltons being preferred and average molecular weights of from about 3,000 to about 1,000,000 daltons being more preferred and average molecular weights of from 5,000 to 500,000 being most preferred.
These desired molecular weights also give rise to preferred value for n, the integer defining the number of units of Chrom on the polymer. As previously noted, n is at least 1. Preferably, n is from 5 to 20,000, with values of from 10 to 10,000 being more preferred.
The degree of substitution, that is the fraction of backbone aromatic rings that are substituted with azo-linked chromophore groups can vary. No advantage is seen in very low substitution as it means that exaggerated amounts of backbone need be consumed. Substitutions of from about 25 to 100% are generally preferred with a more preferred range of substitution being about 50 to about 100%.
Preparative Methods
In the illustrative embodiments, a variety of preparative methods are briefly set forth. The examples describe several methods in detail. In this section a general expansion of the methods of the illustrative embodiment is provided.
A. In Embodiment 1 and in many later embodiments, an azo group is introduced by (1) nitrating an aromatic ring, (2) reducing the resulting aromatic nitro group to an amine. In all embodiments diazotizing and coupling are shown. The nitration of aromatic rings may typically be carried out by standard methods such as those found in C. A. Buehler and D. E. Pearson, Survey of Organic Syntheses, Vol. I, Wiley-Interscience, New York, New York, 1970, pp 980-991. Preferred methods include the use of (1) KNO3 in 96% H2 SO4, (2) mixed acid (HNO3 --H2 SO4), and (3) red fuming nitric acid.
The reduction of these nitro groups to amines may be conducted using standard procedures such as those found in C. A. Buehler and D. C. Pearson, Survey of Organic Syntheses, Vol. I, Wiley-Interscience, New York, New York, 1970, pp 413-417. Preferred methods include (1) treatment with Na2 S, (2) treatment with sodium dithionite (Na2 S2 O4), (3) treatment with metal (e.g., Fe, Sn, or Zn) and acid, (4) catalytic reduction (e.g., 5% Pd on C and H2), and (5) treatment with phenylhydrazine, with sodium dithionite reduction being generally preferred.
The diazotization of the aromatic amine groups is carried out on an acidic solution or suspension of the polymers. The solution or suspension is contacted with a slight excess of a nitrite, such as sodium nitrite, potassium nitrite or the like at low temperatures (0� C. to about 35� C.). The diazotization is generally very quick, requiring only a minute or two so that reaction times of from 0.1 minute to about 2 hours may be used. If a relatively water-insoluble polymer is to be diazotized, this may be carried out in nonaqueous media. In such a reaction nitrosyl chloride, nitrosyl bromide, alkyl nitrite esters or nitrosyl sulfonic acid or the like may be used in standard organic solvents such as lower alcohols or chlorinated hydrocarbons. This would be carried out at low temperatures.
The coupling of the Chrom group is effected promptly after the amines are diazotized. The solution or suspension of diazotized polymer is mixed with a solution of Acid Blue 92 at low temperature (0� C. to about 45� C., preferably 10� C. to 35� C.). An excess of Acid Blue 92 is generally employed. The pH is maintained basic, such as above about pH 10, preferably pH 12.0-13.5 by addition of base, such as KOH or NaOH. The mixing may be done stepwise. The time required for coupling is from about 0.25 hour to about 5 hours with times of 0.5 to 1.0 hours generally giving good results.
B. It has been pointed out that the group may be present as a free acid or as a salt. If the acid is desired, the coupling product is acidified with a strong acid such as hydrochloric acid or the like. If a salt is desired as is preferred, acidification need not be carried out.
C. In preferred embodiments 2-6, an alkylamine is converted into a sulfonamide group as the required pendant aromatic ring is introduced. This step is well effected by a "Schotten-Baumann" type reaction wherein the alkyl amine is contacted with an aromatic compound containing an amine precursor functionality and a sulfonyl chloride functionality ##STR39## at relatively low temperatures (40� C. or less) and a pH of about 9-10. A typical reaction employs an aqueous reaction solvent, preferably also containing some water-miscible polar organic solvent such as tetrahydrofuran, dioxane, dimethoxyethane, diglyme, isopropanol, t-butanol or 2-methoxyethanol and vigorous agitation.
Suitable aromatic compounds for use herein are N-acetylsulfanilyl chloride, ##STR40## and the like.
The concentration of polyamine in the solution should be maintained at from about 1% to about 20%. As a rule, the aromatic compound should be added gradually over a period of at least about 0.25 hours. During this addition, the pH should be monitored and maintained between about pH 9 and 10. After the addition is completed, the pH may suitably be raised somewhat, such as to 10-11, and the mixture stirred for an additional 0.5 to 4 hours. The reaction which occurs is as follows in the case where N-acetylsulfanilyl chloride is employed: ##STR41##
The product of this reaction may be isolated by stripping off the organic solvent and filtering. It is then contacted with acid (generally a substantial excess of aqueous mineral acid solution such as from 3-10 equivalents of acid per equivalent of acetyl groups) to deacetylate it. The deacetylation proceeds at a moderate rate, requiring 2-6 hours at temperatures of 80�-100� C. Higher or lower temperatures (200� C. or 50� C.) could be used if desired with accompanying changes in reaction time. This deacetylation produces the polymer ##STR42## wherein X- is the anion corresponding to the mineral acid employed.
D. In Embodiments 7-11, the condensation of a polymeric amine with ##STR43## is shown. This reaction may be carried out by contacting the polyamine with an excess of the acid chloride in aqueous media of alkaline pH at moderate temperatures (roughly 0�-35� C.) for 0.5-3 hours.
E. In Embodiments 12-21 and 25 and 26, coupling reactions with ##STR44## are shown. The polyamine couplings may be conducted with an excess of the isocyanate or the isothiocyanate in aqueous media at moderate temperatures (about 0�-35� C.) for 0.5-3.0 hours. The coupling reactions with polyvinyl alcohol are best conducted neat or in an inert solvent (e.g., dimethyl sulfoxide or hexamethylphosphoramide). These reactions also require higher temperatures and longer contact times.
Use of the Polymers
The polymers of this invention have the property of having a deep black color. As such they find use as color components of dyes and inks.
In this use in dyes and inks, the polymers of this invention are formulated with a suitable solvent to yield a dye solution or ink. Solvents for this use are aqueous solvent systems, that is a solvent containing at least 50% by weight water. They may, as well, contain a variety of art-known other materials to aid the ink's pentration or adhesion to paper or other cellulosic webs in use. Such other materials include water-soluble organics having some oleophillic character such as C4 -C8 alkanols and glycol ethers and the like; for example n-butanol, n-pentanol, n-hexanol, the ethyl, propyl and butyl monoethers of ethylene glycol, the ethyl, propyl and butyl ethers of diethyleneglycol and the like. It is preferable to minimize the amount of organics added to the solution as the essential absence of volatile organics is an advantage of the present dye systems. Preferably, the dye system is a water base containing 1000 ppm to 20% (by weight) of polymeric dye and up to 40% (by weight) of water-soluble organics. More preferably it contains from 2000 ppm to 15% dye and 2% to 20% water-soluble organics.
Two or more species of the present polymeric black colorants can be used in combination if desired as can combinations of these polymeric colorants with other monomeric, or preferably, polymeric colorants. Thus an ink or dye may contain the present polymeric black colorants in solution with art-taught monomeric colors or with polymeric colors as are disclosed in U.S. Pat. Nos. 3,920,855; 4,051,138; 4,096,134; 4,182,885, or 4,233,328 or the like. These patents are incorporated herein by reference. Addition of other polymeric colorants to tint or shade the color offers the advantage that the resulting mixture can have, to a large extent, uniform polymeric colorant physical and/or chemical properties. The amounts of these "other" dyes can vary as required to obtain the shade or tint desired.
Such dyes are formulated by simple admixing techniques known in the art. They may be applied to cellulosic stock, particularly paper, by letter press, lithographic, electrophotographic, screen or spray processes or off-set techniques all as known to the art.
Purification of the Colorant
Following their synthesis, it may be desired to purify the colors such as to remove unreacted feeds, side products or other nonpolymeric contaminants. This may be easily effected by filtration, centrifugation, dialysis and like processes but preferably is carried out by means of ultrafiltration, a process offering advantages of speed and efficiency. Ultrafiltration of polymeric dyes is fully described in U.S. Pat. Nos. 4,189,380 and 4,225,432 both of which are incorporated herein by reference.
The invention will be further described by the following examples. They are intended solely to exemplify the invention and are not to be construed as limiting its scope.
Precursor polymer 1 was prepared using the procedure of Gless et al., U.S. Pat. No. 4,018,826 and JACS 98:19 Page 5996 (Sept. 15, 1976). In a typical preparation a 2-l., three-neck flask, equipped with an overhead stirrer, thermometer, and dryice condenser, was charged with 532 g (9.0 mol) of technical acetamide. With stirring, 12.4 ml of 6 M H2 SO4 and 134 g (3.0 mol) of acetaldehyde were added sequentially and the reaction vessel was heated with a 100� C. oil bath. After the reaction had stirred for 10 minutes, the internal temperature (Ti) was 75� C. and the mixture was homogeneous. The condenser was removed as an exotherm began, which raised Ti to 100� C. within 2 minutes. Ethylidene bisacetamide crystallized rapidly from the mixture, causing a further increase in Ti to 108� C. After 7 minutes at or above 100� C., the heating bath was turned off and 60 g (0.60 mol) of CaCO3 (precipitated chalk) was carefully added, followed by 30 g of Celite 503.
The reaction vessel was fitted with a wide-bore, vaccum-distillation apparatus equipped with a Vigreux column and the pressure was slowly decreased to 30-40 mm of Hg. The bath was heated to 200� C. and the mixture was distilled to dryness (˜4 h).
The crude distillate was melted, diluted with 250 ml of isopropyl alcohol, and cooled to 5� C. for 18 hours. Filtration afforded 125 g of acetamide and a filtrate which was 38.7 wt. % N-vinylacetamide by bromine titration. This solution was subjected to polymerization without further purification.
A 5-l., four-neck flask, equipped with an overhead stirrer, thermometer, reflux condenser, Ar inlet, and heating mantle, was charged with 1165 g of an N-vinylacetamide solution (451 g, 5.30 mole) prepared as described in the preceding step. After isopropyl alcohol addition (1.3 l.), the reaction mixture was thoroughly deoxygenated and heated to a vigorous reflux under Ar. A solution of 22.3 g (0.14 mol) of AIBN in 83 ml of acetone was added in one portion and the reaction was refluxed for three hours.
After cooling, most of the solvent was removed in vacuo and the resulting thick orange oil was precipitated by slow addition to 10 l. of rapidly stirred acetone. The solid was filtered, washed with acetone (3�2 l.), and dried in vacuo at 50� C. to afford 431 g (96%) of poly(N-vinylacetamide) as a white powder.
A 5-l., four-neck flask equipped with overhead stirrer, thermometer, distillation head, and heating mantle, was charged with 1 l. of H2 O and stirring was begun. The H2 O was boiled, as 1412 g of an acetone-wet filter cake of polymer (424 g, 4.98 mol as determined by drying a sample, Mp ps �104) was added along with 200 ml of H2 O. After the acetone had been removed by distillation, the mixture was cooled and treated with 522 ml of 12 N HCl (6.26 mol). Reflux was resumed under Ar. At 40 h, the cloudy solution was treated with 100 ml of H2 O and precipitated, while still warm, into 14 l. of rapidly stirred isopropyl alcohol. The product, polyvinylamine hydrochloride, was filtered, washed with isopropyl alcohol (6 l.), and dried in vacuo to afford 415 g of an off-white powdery solid.
A 1-l. flask was fitted with an overhead stirrer, a 100-ml dropping funnel containing 8 N NaOH, a pH probe, and a gas inlet tube. The vessel was charged with 14.0 g (176 mmol) of the poly(vinylamine hydrochloride), 140 ml of H2 O, 15 ml of 8 N NaOH, and 70 ml of THF. With vigorous stirring, 15.1 g (64.6 mmol) of powdered p-acetamidobenzenesulfonyl chloride was added and the pH was maintained at 9-10 by base addition as necessary for 5 min. A second portion of the sulfonyl chloride (15.1 g) was then added followed by 70 ml of THF. After an additional 15 minutes at pH 9-10, a third equal portion of the sulfonyl chloride was added followed by 70 ml of THF and the pH was maintained at 10-11 until no further reaction was observed (stable pH, 60 min).
The flask was equipped for vacuum distillation and the THF was removed (35� C. (20 mm)). Schotten-Baumann product 1 precipitated as an easily filterable, light-tan, brittle solid. The yield was 41.7 g (99%) after thorough water washing and drying.
By varying polymerization reaction conditions such as temperature and cosolvent, the molecular weight of the polymer can be varied.
A. Hydrolysis.
A 100-ml, 3-neck flask, equipped with overhead stirrer and oil bath, was charged with 7.20 g (30.0 mmol) of polymer 1 (prepared as shown in the above Precursor Preparation on poly(N-vinylacetamide) of average molecular weight, as determined by GPC comparison with polystyrene standards, Mp ps 1.2�105), 60 ml of H2 O and 15.8 ml (190 mmol) of 12 N HCl. The mixture was stirred vigorously at reflux for 6 hours to effect hydrolysis.
B. Diazotization and Coupling.
A 500-ml, one-neck, round-bottom flask, equipped with magnetic stir bar and ice bath, was charged with 300 ml of H2 O and the above crude hydrolysis solution. The solution was vigorously stirred at room temperature and treated in one portion with 7.20 ml (36.0 mmol) of 5 N NaNO2. The clear polydiazonium salt solution was immediately cooled in an ice-bath, stirred for 5 minutes, and employed for coupling.
A 4-liter beaker was fitted with overhead stirrer, pH probe, thermometer, 250-ml dropping funnel filled with 2.5 N NaOH. The beaker was charged with 2500 ml of H2 O and 104 g (150 mmol) of Acid Blue 92 (Eastman), and stirring (but not polymer introduction) was begun. The dark violet solution (apparently homogeneous, pH 8.9) was treated with 20 ml (160 mmol) of 8 N NaOH (pH to 13.4, solution brown), and the introduction of diazonium salt was begun.
The addition was conducted over 30 minutes with the pH maintained at 13.0-13.5 by the addition of 60 ml (150 mmol) of 2.5 N NaOH. No cooling was employed during the coupling and the final pH was 13.0 and the final volume was 3500 ml.
C. Recovery.
The brownish black solution was stirred one hour at ambient temperature, passed through a coarse-frit glass filter, and ultrafiltered with a model H1P100 cartridge (molecular weight 100,000 cutoff, Amicon Corporation, Lexington, Mass.), until the product was free of low molecular-weight contaminants. The solution was concentrated to a volume of 250 ml and freeze dried to provide 15.2 g (56.0% of theory) of 5. A small sample was submitted for elemental analysis. The N/S ratio (mequiv/g basis) was 1.48 (1.50 in theory).
D. Use.
This material as its neutral aqueous solution is applied to paper. It has a deep black color. It adheres well to bond paper, being essentially fast.
A polymeric black colorant based on Poly(N-methylvinylamine) is prepared as follows: ##STR46## A. Preparation of 2.
N-Methylaminoethanol (250 g, 3.33 mol) is added dropwise over 60 minutes to acetic anhydride (691 g, 6.77 mol) maintained at 115�-120� C. The product is isolated by vacuum distillation (bp 95�-98� C./0.1 mm) in 93% yield as a colorless oil.
B. N-Methyl-N-vinylacetamide (3).
The product of step A is pyrolyzed by passing 642 g (4.04 mol) at a rate of 1.17 g/min through a Pyrex helices-packed quartz tube (3.5 cm diameter, 40 cm length) maintained at 480� C. A 400 ml/minute argon flow is employed. The crude pyrolyzate (629 g of dark orange oil) is distilled to afford 119 g (1.20 mol, 29.8% yield) of 3 (bp 72� C./20 mm).
C. Poly(N-methyl-N-vinylacetamide) (4).
A 2-liter, 3-neck flask, equipped with overhead stirrer, reflux condenser topped with an Argon inlet, and internal thermometer, is charged with 99.0 g (1.00 mol) of distilled N-methyl-N-vinylacetamide, 3.28 g (0.02 mol) of AIBN, and 900 ml of thoroughly degassed H2 O. The flask is thoroughly purged with argon and held in a bath maintained at 65� C. for 24 hours. A TLC (SiO2, ethyl acetate) shows no monomer (Rf 0.47) remaining.
A 4.0-ml sample is removed for analysis, while the bulk is directly employed in part D. The sample is determined by gel permeation chromatography techniques to possess a molecular weight of 1.6�105. Anal. Calcd for (C5 H9 NO)n : C, 60.54; H, 9.15; N, 14.12. Found: C, 59.96; H, 9.49; N, 13.95.
D. Poly(N-methylvinylamine hydrochloride) (5).
The reaction mixture from part C is treated with 208 ml (2.50 mol) of 12 N HCl, placed in a teflon-lined, stirred autoclave, and heated at 125� C. for 72 hours. The crude product is cooled, evaporated to a volume of approximately 300 ml, and precipitated into 15 liters of well-stirred iso-propyl alcohol. The product is filtered, washed with 2 liters of iso-propyl alcohol, and dried (50� C./0.1 mm/48 hours). The yield is 86.2 g of granular solid possessing a nitrogen content of 10.43 mequiv/g by elemental analysis. Titration provides an amine value of 10.5 mequiv/g, indicating that hydrolysis is complete. The yield for polymerization/hydrolysis, based on nitrogen recovery, is 90.0%.
E. Schotten-Baumann Reaction.
A 1000-ml, 3-neck flask, equipped with overhead stirrer, pH probe, and 125-ml dropping funnel filled with 8 N NaOH, is charged with 21.1 g (220 mequiv of amine) of 5 and 300 ml of H2 O. The flask is flushed with argon and stirred until solution is complete. The solution is then treated with 22.5 ml (180 mmol) of 8 N NaOH (pH 10.0) and 150 ml of 2-methoxyethanol.
The N-acetylsulfanilyl chloride (64.5 g, 276 mmol) is then added in three equal portions of 21.5 g. The second and third additions are accompanied by 150 ml of 2-methoxyethanol.
The second addition takes place 5 minutes after the first, with the third addition taking place 15 minutes after the second. During the reaction period the pH is maintained at 9-10 by the addition of 8 N NaOH as necessary. After the final sulfonyl chloride addition, the pH is maintained at 9-10 for 30 minutes, and then raised to 10.5-11.0 and held for 1.5 hours. At the end of the reaction the pH is stable. The amount of 8 N NaOH employed during the Schotten-Baumann reaction is 47.0 ml (376 mmol).
The reaction mixture is added dropwise to 18 liters of well-stirred H2 O and 6 is isolated by filtration, washed thoroughly with H2 O, and dried (50�/0.1 mm/48 hours). The yield is 50.5 g (94.4% of theory). Elemental analysis provides a sulfur content of 3.78 mequiv/g and an N/S ratio (mequiv/g basis) of 2.06 (2.00 in theory).
F. Preparation of Polysulfanilamide 7.
A 2-liter, 3-neck flask, equipped with oil bath, overhead stirrer, and reflux condenser, is charged with 50.5 g of 6 (191 mequiv of sulfur), 846 ml of H2 O, and 95.5 ml (114 g, 1.15 mol) of 12 N HCl. The initial polymer concentration in this mixture is 5.0 wt%.
With overhead stirring, the bath temperature is raised to 125� C. (gentle reflux) and held for 18 hours. The solution of 7 is allowed to cool to room temperature, passed through a coarse-frit funnel, and directly employed in step G.
G. Diazotization and Coupling.
The solution from step F (964 g total weight) is placed in a 3-liter, 3-neck flask equipped with an overhead stirrer. The polymer solution is diluted with 1500 ml of H2 O to provide an overall polymer concentration of approximately 2 wt %.
19.5 g (229 mmol) of KNO2 is dissolved in 8.0 ml of H2 O by briefly stirring. The solution of 7 is stirred at a moderate rate as the KNO2 is added in one portion at room temperature. The perfectly clear polymeric diazonium salt solution that is produced is immediately immersed in an ice bath and stirred. A positive KI-starch test is obtained.
A plastic bucket (capacity ˜10 liters), fitted with overhead stirrer, thermometer, pH probe, and 250 ml dropping funnel filled with 8 N KOH, is charged with 418 g (600 mmol) of Acid Blue 92, 3000 ml of H2 O, and 80 ml (640 mmol) of 8 N KOH. The mixture is stirred until solution is complete (<5 minutes).
The Acid Blue 92 solution (pH 13.3) is cooled to 15� C. by the addition of a small amount of ice and the diazonium salt solution (held in the ice bath) is added at a steady rate via peristaltic pump over 20 minutes. During the coupling the pH is maintained at 13.1-13.3 by the dropwise addition of 8 N KOH (170 ml, 1360 mmol). The final volume of the coupling solution is 7.0 liters, and the temperature rises to 17� C.
The dark solution is diluted to 18 liters with H2 O, passed through a coarse-frit filter, concentrated by ultrafiltration with a model H1P10 cartridge (molecular weight 10,000 cutoff, Amicon Corp., Lexington, Mass.), and then ultrafiltered for 6�4-liter diavolumes with the same cartridge.
The solution is concentrated to 1500 ml and freeze dried to provide 136.9 g (78.1% of theory) of black polymer 8. A small sample is dried (50� C./0.1 mm/8 hours) and submitted for elemental analysis. The N/S ratio (mequiv/g basis) is 1.46 (1.50 in theory).
A black polymeric dye based on polystyrene is prepared as follows: ##STR47## A. Preparation of 100% Nitric Acid.
Pure HNO3 is prepared following the procedure of P. Liang, "Organic Syntheses," Col. Vol. III, E. C. Horning, Ed., John Wiley and Sons, New York, N.Y., 1955, pp. 803-5. A 500-ml, one-neck flask is charged with 150 ml of 96% H2 SO4 and 150 ml of 90% HNO3 (J. T. Baker cat. no. 9624), and rigged for distillation under argon. There is obtained 131.5 g (2.09 mol) of HNO3 (bp 79�-81� C.) as a light yellow liquid. The acid is stored in the freezer prior to step B.
B. Nitration of Styrene.
A 250-ml, 3-neck flask, equipped with overhead stirrer, low-temperature thermometer, argon inlet, and cooling bath, is charged with 131.5 g (2.09 mol) of HNO3 and cooled to an internal temperature of -30� C. Finely powdered polystyrene (21.0 g, 0.202 mol, molecular weight determined to be 1.3�105 by gel permeation chromatography techniques) from Cellomer Associates (Webster, NY) is added portionwise over 2 hours while maintaining the temperature at -30� C. After stirring for an additional hour at this temperature, the viscous mass is allowed to slowly warm to ambient temperature and stir for 24 hours.
Crude 2 is isolated by direct precipitation of the reaction mixture into 3 liters of ice water. The product is filtered, washed with H2 O, and thoroughly ground in a commercial blender with H2 O. The product is again filtered, washed with H2 O and then acetone, and dried (50�/0.1 mm/24 hours). The yield of off-white solid is 33.1 g (110% of theory): Anal. Calcd. for (C8 H7 NO2)n : C, 64.43; H, 4.70; N, 9.39. Found: C, 63.72; H, 4.49; N, 9.83.
C. Preparation of p-Aminopolystyrene (3).
A 100-ml, 2-neck flask, equipped with overhead stirrer and argon inlet, and rigged for distillation, is charged with 2.00 g (13.4 mmol) of 2 and 50 ml of 97% phenylhydrazine (Aldrich Chemical Co., Milwaukee, Wis.). With vigorous stirring, the mixture is heated to 200� C. (bath) and there maintained for 3 hours. During this period the polymer dissolves, and approximately 5 ml of low boiling liquid is removed by distillation.
The reaction mixture is cooled to room temperature and directly precipitated into 2 liters of diethyl ether. The p-aminopolystyrene obtained is filtered and immediately dissolved in 500 ml of 0.5 N HCl. This solution is evaporated and the product dried (25� C./0.1 mm/18 hours) to give 2.00 g (12.9 mmol, 96.2% yield) of p-aminopolystyrene hydrochloride (3). Anal. Calcd for (C8 H10 NCl)n : C, 61.74, H, 6.43; N, 9.00; Cl, 22.83. Found: C, 62.00; H, 6.61; N, 8.81; Cl, 22.56.
D. Diazotization and Coupling.
A 5-liter, 3-neck flask, equipped with overhead stirrer and cooling bath, is charged with 75.0 g (0.482 mol) of 3, 101 ml (120 g, 1.21 mol) of 12 N HCl, and 3555 ml of H2 O. The mixture is stirred until solution is complete, cooled to 10� C. (internal), and treated (rapidly in one portion) with 116 ml (0.580 mol) of 5 N NaNO2. The perfectly clear polymeric diazonium salt solution that is produced is immediately cooled to 0� C. with continued stirring. A positive KI-starch test is obtained.
A 25-liter battery jar, equipped with overhead stirrer, thermometer, pH probe, and 500-ml dropping funnel filled with 8 N NaOH is charged with 0.723 mol of Acid Blue 92, 5000 ml of H2 O, and 100 ml (0.80 mol) of 8 N NaOH. The mixture is stirred until solution is complete (pH 13.40), and cooled to 8� C. by the addition of ice.
The polymeric diazonium salt solution (maintained at 0� C.) is added to the Acid Blue 92 solution by peristaltic pump over 30 minutes. During this period, the pH is maintained at 13.0-13.5 by the addition of 8 N NaOH (123 ml, 0.982 mol) and the temperature is controlled at 15�-20� C. by the addition of ice.
The solution (approximately 15 liters in volume) is passed through a coarse-frit filter, concentrated by ultrafiltration with an H1P10 cartridge, and ultrafiltered for 6�10-liter diavolumes with the same cartridge.
The solution is concentrated to 5000 ml and freeze dried to provide 308.3 g (77.5% by theory) of 4 as a black solid. A small sample is dried (50� C./0.1 mm/18 hours) and submitted for elemental analysis. This provides a nitrogen content of 6.05 mequiv/g, a sulfur content of 3.63 mequiv/g, and a C/N ratio of 6.80 (6.80 in theory). Anal. Calcd. for (C34 H22 N5 O10 S3 N9.sbsb.3)n : C, 49.46; H, 2.69; N, 8.48; S, 11.65. Found: C, 48.86; H, 3.01; N, 8.32; S, 11.49.
A polymer in black colorant based on poly(ethyleneimine) (PEI) is prepared as follows: ##STR48##
The poly(ethyleneimine) used in this example is obtained from Polysciences, Inc., Warrington, Pennsylvania (lot #2632). The sample is labeled as a 33 wt % aqueous solution of molecular weight 4.0-6.0�104 polymer. Elemental analysis of the solution provides a value of 8.07 mequiv N/g, and titration of the solution shows 5.29 mequiv titratable amine/g.
A. Schotten-Baumann Reaction.
A 1000-ml, 3-neck flask, equipped with overhead stirrer, pH probe, and 125-ml dropping funnel filled with 8 N NaOH, is charged with 23.4 g of poly(ethyleneimine) solution, 300 ml of H2 O, and 150 ml of THF. Stirring is begun under argon. The solution is clear and possesses a pH of 10.
The solution is treated with 18.4 g (78.7 mmol) of N-acetylsulfanilyl chloride (2), stirred for 5 minutes, and the pH maintained at 9-10 by the addition of 8 N NaOH (12 ml, 96 mmol). The solution is then treated with a second equal portion of sulfonyl chloride 2 and 150 ml of THF while maintaining the pH at 9-10 by the addition of 8 N NaOH (12 ml, 96 mmol) over 15 minutes.
The mixture, now an emulsion, is treated with a third equal portion of 2 and 150 ml of THF. The pH is maintained at 10-11 by the addition of 8 N NaOH (15 ml, 120 mmol) over 60 minutes.
The emulsion is transferred to a 2-liter, one-neck flask and subjected to rotary evaporation. After all the THF is evaporated, polymer 3 is obtained as a granular off-white solid. The product is broken up, filtered, washed well with H2 O, and dried (50� C./0.1 mm/5 hours). The yield is 37.0 g, and elemental analysis (C, 50,85; H, 5.72; N, 12.04; S, 12.09) provides a sulfur content of 3.77 mequiv/g.
B. Hydrolysis.
A 500-ml, 3-neck flask, equipped with overhead stirrer, oil bath, and reflux condenser, is charged with 5.00 g of 3 as prepared above (18.9 mequiv of sulfur), 9.43 ml (113 mmol) of 12 N HCl, and 234 ml of H2 O. With stirring, the mixture is refluxed for 10 hours, cooled, filtered (coarse-frit funnel), and directly employed in step C.
C. Diazotization and Coupling.
The solution of 4 is placed in a 500-ml, 3-neck flask equipped with an overhead stirrer. The solution is stirred at a moderate rate as 4.70 ml (23.5 mmol) of 5 N NaNO2 is added in one portion at room temperature. The clear solution is cooled in an ice bath as stirring is continued. A positive KI-starch test is obtained.
A 2-liter beaker, fitted with overhead stirrer, thermometer, pH probe, and 50-ml dropping funnel filled with 8 N NaOH, is charged with 42 g (60 mmol) of Acid Blue 92, 400 ml of H2 O, and 8 ml (64 mmol) of 8 N NaOH. The mixture is stirred until solution is complete (<5 minutes).
The Acid Blue 92 solution (pH 13.6) is cooled to 15� C. by the addition of ice, and the diazonium salt solution is added dropwise over 25 minutes via a dropping funnel. The pH is maintained at 13.0-13.5 throughout the coupling by the addition of 8 N NaOH.
The dark solution is diluted to 2 liters with H2 O, passed through a coarse-frit filter, concentrated by ultrafiltration with a model H1P100 cartridge (molecular weight 10,000 cut-off, Amicon Corp., Lexington, Mass.), and then ultrafiltered for six�400 ml diavolumes with the same cartridge.
The solution is concentration to 150 ml and freeze dried to provide black polymer 5.
Cited Patent | Filing date | Publication date | Applicant | Title |
US3484390 * | Feb 25, 1966 | Dec 16, 1969 | California Inst Res Found | Chelating resin coupling product of diazotized cellulose and dithizone or oxine |
US4000118 * | Feb 11, 1975 | Dec 28, 1976 | Dawson Daniel J | Colorings |
US4018826 * | Nov 4, 1974 | Apr 19, 1977 | Dynapol Corporation | Process for preparing polyvinylamine and salts thereof |
US4051138 * | Dec 8, 1975 | Sep 27, 1977 | Dynapol | Water-soluble amine-linked polymeric colorants |
US4096134 * | Dec 8, 1975 | Jun 20, 1978 | Dynapol | Ethylsulfonate-alkylamine copolymers as colorant backbones |
US4144252 * | Feb 7, 1977 | Mar 13, 1979 | Dynapol | Water-soluble amine-linked polymeric colorants |
US4190716 * | Dec 20, 1978 | Feb 26, 1980 | Dynapol | Polymeric agent for releasing 5-aminosalicylic acid or its salts into the gastrointestinal tract |
Citing Patent | Filing date | Publication date | Applicant | Title |
US4645727 * | Apr 17, 1986 | Feb 24, 1987 | Xerox Corporation | Colored toner compositions comprising dye chromophores |
US4664708 * | Nov 12, 1985 | May 12, 1987 | Xerox Corporation | Waterfast ink jet compositions |
US4962190 * | Nov 21, 1988 | Oct 9, 1990 | Basf Aktiengesellschaft | Azo dyes containing polyethyleneimine with an aniline diazo component and a hydroxynaphthalene, aminopyridine or acetoacetic coupling component |
US5104942 * | Mar 28, 1989 | Apr 14, 1992 | Towle Ian H | Preparation of side-chain polymers |
US5120799 * | Aug 30, 1989 | Jun 9, 1992 | E. I. Du Pont De Nemours And Company (Inc.) | Polymeric compounds having pendant sulphonato groups and method of producing the polymeric compounds |
US5200290 * | Oct 1, 1990 | Apr 6, 1993 | Xerox Corporation | Liquid developers containing colored polymers with a color chromophore covalently bound thereto |
US5278022 * | Mar 18, 1992 | Jan 11, 1994 | E. I. Du Pont De Nemours And Company | Polymeric compounds having pendant sulphonate groups for use in a radiation sensitive composition |
US5534052 * | Nov 29, 1994 | Jul 9, 1996 | Bayer Aktiengesellschaft | Polymeric dyestuffs and their use in inks for ink jet printing processes |
US6025412 * | Sep 29, 1995 | Feb 15, 2000 | Xerox Corporation | Colored particulates for ink jet inks |
US6083310 * | May 28, 1998 | Jul 4, 2000 | Marconi Data Systems, Inc. | Colored inks comprising polymeric colorants for binary array printing and method of using |
US6384108 | Sep 29, 1995 | May 7, 2002 | Xerox Corporation | Waterfast ink jet inks containing an emulsifiable polymer resin |
US6727296 | Dec 13, 1999 | Apr 27, 2004 | Avecia Limited | Ink-jet ink compositions |
US7576146 * | Dec 5, 2003 | Aug 18, 2009 | Sun Chemical Corporation | Polymeric colored dispersants and colorant dispersions containing same |
US7732509 | Aug 24, 2006 | Jun 8, 2010 | Eastman Kodak Company | Polymeric colorant-based ink compositions |
US9017921 * | Mar 29, 2013 | Apr 28, 2015 | Samsung Display Co., Ltd. | Photoresist composition and method of forming a black matrix using the same |
US20050124727 * | Dec 5, 2003 | Jun 9, 2005 | Huber Gregory T. | Polymeric colored dispersants and colorant dispersions containing same |
US20080122915 * | Aug 24, 2006 | May 29, 2008 | Eastman Kodak Company | Polymeric colorant-based ink compositions |
US20140065542 * | Mar 29, 2013 | Mar 6, 2014 | Samsung Display Co., Ltd. | Photoresist composition and method of forming a black matrix using the same |
EP0217535A2 * | Aug 26, 1986 | Apr 8, 1987 | Raychem Limited | Preparation of side-chain polymers |
EP0217535A3 * | Aug 26, 1986 | Dec 13, 1989 | Raychem Limited | Preparation of side-chain polymers |
EP0540248A2 * | Oct 22, 1992 | May 5, 1993 | Hewlett-Packard Company | Water-soluble dyes and inks formulated by insolubilizing reactions initiated by loss of water |
EP0540248A3 * | Oct 22, 1992 | Mar 16, 1994 | Hewlett Packard Co | Title not available |
WO2000037575A1 * | Dec 13, 1999 | Jun 29, 2000 | Avecia Limited | Ink-jet ink compositions |
U.S. Classification | 8/647, 525/353, 525/333.4, 525/351, 8/919, 525/333.6 |
International Classification | C09B69/10 |
Cooperative Classification | Y10S8/919, C09B69/106 |
European Classification | C09B69/10K |
Date | Code | Event | Description |
Sep 25, 1981 | AS | Assignment | Owner name: DYNAPOL, 1454 PAGE MILL RD., PALO ALTO, CA. 94304 Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:WINGARD, ROBERT E. JR.;NG, STEVE Y. W.;SWANSON, SALLY A.;REEL/FRAME:003944/0012;SIGNING DATES FROM 19810224 TO 19810302 |
Mar 15, 1985 | AS | Assignment | Owner name: DYNAPOL SHAREHOLDERS LIQUIDATING TRUST THE 265 A Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. EFFECTIVE AUGUST 4, 1982;ASSIGNOR:DYNAPOL A CA CORP;REEL/FRAME:004375/0514 Effective date: 19850219 |
Sep 30, 1986 | REMI | Maintenance fee reminder mailed | |
Mar 1, 1987 | LAPS | Lapse for failure to pay maintenance fees | |
May 19, 1987 | FP | Expired due to failure to pay maintenance fee | Effective date: 19870301 |


text:
Libratone Q Adapt On-Ear Stormy Black
Libratone Q Adapt On-Ear Stormy Black wireless headphone - on-ear design, bluetooth 4.1 aptX, 40 mm neodymium drivers, touch control on headphone, adjustable, active noise cancelling with City Mix, up to 20 h running time, weight 200g, includes USB charging cable, audio cable with 3,5 mm plug and bag, colour: stormy black
Smart Navigator
- Libratone HiFi Headphones at a glance
- display HiFi Headphones in price range 200 € - 300 €
- go to product group HiFi Headphones
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- show manufacturer details for Libratone
- Libratone Accessories at a glance
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Further Libratone items
Offers include 24% Greek VAT and are valid as long as stocks last. Shipping costs to Greece are 20 EUR, free shipping on orders above 298 EUR. Please click here for international Shipping rates. We do not accept liability for typographical errors or inaccurate information of any kind. *RRP = manufacturer's / distributor's recommended retail price in Germany

subset: commoncrawl


text:
Arlington Ruby Message Board › Looking for great developers
Joshua S. |
Hey Fellow Rubyists!
I'm Josh, CTO at Optoro, a startup in the DC area (Lanham, MD) focusing on the reverse logistics industry. We're revolutionizing how people deal with customer returns, liquidation, overstock, end-of-life, and other alternative goods. We're looking to hire two more full-time developers to join our small team, one senior and one junior. Ideally, we're looking for people who know ruby, rails, and related technologies, but we've brought people in from non-ruby backgrounds, so if you have web development experience, please contact me. We offer competitive salary, 401k, health benefits, and equity in our rapidly growing business. We have lots of interesting problems around big data (automatic pricing, product research), marketplace management, inventory management, usability, operational efficiency, and ecommerce. Our systems are used constantly internally and externally, so we deploy often and get rapid feedback. There's a lot of hidden depth to our industry, so if you're looking for interesting problems, we have them! Some awesome technologies that we're currently using include rails 3.1, ruby 1.9, mysql, mongodb, redis, memcached, rspec, jquery, haml, sass, ember.js, active merchant, active shipping, httparty, plucky, nginx, and unicorn. We're a fun team that is active in the local ruby community. We have other perks like bagels every morning, company outings, company lunches, continuous learning activities, and flexible schedules. Feel free to challenge us to a game of darts; our dart board gets a lot of use! For more information, check out our websites (www.optoro.com and www.blinq.com) and our full job listing: http://optoro.com/emp... (yes, that site is in PHP... it needs to be reworked asap, maybe a good first project?). Contact me any time—I'm firstname.lastname@example.com or at 301-880-1218 Thanks! -Josh Szmajda CTO Optoro, Inc. 301-880-1218 email@example.com |
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text:
Certificate of Compliance for Landlords & Managing Agents - Communal & Commercial Signal Distribution Systems
A Scheme for Landlords & Managing Agents
The Need for a Compliance Certificate
As far back as the 1960 with the advent of colour TV, many social and commercial landlords installed communal satellite dishes and aerials and unknowingly overlooked legislation governing TV and radio aerial system installation. With the rapid growth of satellite TV in the 1990's, despite broadcaster operator best efforts, our trade witnessed a common ignorance of required planning law. This continues to be the case in many instances and has resulted in many multiple occupancy buildings having a proliferation of receiving equipment, many of which are no longer in use. (Sky's, Sky Homes estimates that 44% of satellite dishes of all description are redundant and no longer used on a daily basis).
In reality there are millions of homes served by shared antenna distribution systems that have been installed outside of current standards and indeed with little regard or knowledge of the regulation that exists.
The Confederation of Aerial Industries Ltd has therefore evolved a scheme that seeks to redress this by presenting a case to the housing industry for regular assessment or audit of its signal distribution systems. The scheme will provide a route map for all types of property owners to engage with a CAI installing company that offers a systematic and comprehensive assessment for ensuring all their signal distribution systems comply with current legislation.
The UK has just completed the largest changeover in broadcasting history with the switch to digital only TV reception. All residents within a multi-dwelling establishment have a basic expectancy of public service TV and radio channels and over 30% require access to satellite broadcasting. The antenna skyline of Britain's apartment block is gradually transforming with an antenna mast being shared with at least one TV aerial, an FM radio aerial, a digital radio aerial and a satellite dish.
What is the Certificate of Compliance
The complexity of signal distribution in UK homes now needs a careful, responsible and reputable certification of compliance. At the moment there is no guidance at all on periodic assessment of signal networks. This document is therefore intended to provide commercial and communal property owners, landlords and managing agents with enough information to ensure that their signal and data distribution systems;
- Operate within recognised parameters.
- Are maintained to the required standards of safety, both mechanical and electrical.
In fact, regulation 4 of the Electricity at Work Act 1989 states
- All systems shall be at all times be of such construction as to prevent, so far as is reasonably practicable, danger.
- As may be necessary to prevent danger, all systems shall be maintained so as to prevent, so far as is reasonably practicable, such danger.
Properties Covered
Buildings that could be covered by these proposals include;
- Communal housing.
- Mixed occupancy housing (often broadly termed multi-dwelling units, with leaseholders and tenants in the same building).
- Pubs, restaurants and leisure facilities.
- Hospitals, schools and colleges.
- Retail premises.
- Anywhere where terrestrial and satellite receiving equipment distributes TV, sound, data services and a commercial buildings insurance is in place.
Benefits to Landlords & Managing Agents
- Knowledge the system is working properly.
- Knowledge the system is electrically and mechanically safe.
- Savings on service charges as checked annually & problems notified and correct at this time.
- Advised of any work that may need doing to keep the system working.
- Advised of unauthorised dishes etc that have been installed.
- Advised of new technologies that may better suit your needs.
- Possible savings on insurance premiums.
- Helps to avoid unexpected and expensive emergency call-outs.
How to get a Certificate of Compliance for my Communal/Commercial System
- Download a copy of 'Certificate of Compliance - A Scheme for Landlords & Managing Agents'. It is your responsibility to make sure the building you are responsible for is safe for anybody entering that building so we highly advise you download the document and find out more.
- Employ a reputable company who are CAI system installing members to check the installation on a regular basis. Find a CAI installing Member through the CAI user friendly search facility.


text:
Listen to free music played by BlipStarr
Blip.fm is internet radio made social. It's easy to search for, play, and discover free music recommended by real people. Join today to create your own free station and start listening to @BlipStarr.
ducks2007 gave props on Feb 21 at 9:32 pm
What other DJs are saying about Moby - Dream About Me
Awww ...sniff..sniff. Sad video :`( @77ozzie: "OH DREAM...BABE...TELL ME NO TRUTHS - IF IT IS BAD...THERE IS ENOUGH IN MY LIFE - TO MAKE ME SO SAD..."
Dream About Me


text:
3 guest cabins (2 double and one twin with ensuite head) + independent crew cabin with head, full equipped: 48.000 btu air conditioning- generator 17 kw- desalinator 130 lt/hr- stern electric winches - whirpool oven, ceramic hobs and dishwasher- Smeg fridge and freezer- Isotherm fridge in the kitchen- fridge in crew cabin- satellite antenna- electric rollaway bimini in the cockpit- bimini top at the bow- all set covers.
This unit is the only one in light wood instead of mohogany with parque floors.
Most beautiful apreamare 60, only one owner.
tel. + 39 3315769054 office +39 06 65029702
Mob. +39 331 5769054 Tel. +39 06 65029702
via della Mandriola 10


text:
EUdict :: English-Japanese(Kanji) dictionary
Results for: shingling,Translations: 1 – 2 / 2 | |
English | Japanese(Kanji) |
shingling, shingled roof | 柿葺き [こけらぶき] |
shingling, shingled roof | こけら葺き [こけらぶき] |
Search time: 0.001 seconds. |
About Eudict
EUdict (European dictionary) is a collection of online dictionaries for the languages spoken mostly in Europe. These dictionaries are the result of the work of many authors who worked very hard and finally offered their product free of charge on the internet thus making it easier to all of us to communicate with each other. Some of the dictionaries have only a few thousand words, others have more than 250,000. Some of the words may be incorrectly translated or mistyped. More information
Please help us improve this site by translating its interface into your language!
Total number of language pairs: 414
Total number of translations (in millions): 11.6
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Total number of language pairs: 414
Total number of translations (in millions): 11.6
Mobile version


text:
truck toolbox
Moderator: opnwhl23
truck toolbox
I have an old truck toolbox for sale its for a small truck like a dakota,ranger,s-10 it is white with a few dings and a rust spot about the size of a half dollar. Not pretty but would work great for a work truck with that said you pick it up and its your for $20. I live in springfield.
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text:
AXI Stator Coating - What IS that stuff?
My Axi was sounding a little raspy when spinning the prop after one of my "nosedig" incidents, and the shaft had been drive back a fraction of a millimeter such that groove which seats the tiny retainer clip was no longer visible (the retainer clip was still on the shaft, though). I suspected I may have gotten some dirt into the can, so I disassemble it to take a look. Here's a pic of what I found.
What is that resinous coating on the outer surface of the stator plates? Obviuosly I "sanded" some of it off by getting dirt into the can, but the motor has been used a number of times since, and performance seems normal. So, I don't think any serious damage has been done, but this stuff was put there for a reason. If anyone knows what it's for, what it is made of, or whether it needs to be replaced, I'd like to hear from you. My best guess is it was put there for abrasion resistance for the ends of the stator plates in case you get dirt inside the can Finally, I need to loosen the set screw holding the shaft to the can so I can move the shaft forward a few thousandths to expose the clip ring groove again. I don't have an allen wrench small enough... does anyone know what size it is? |
Last edited by Tom Frank; Sep 23, 2004 at 11:02 PM.
I know it as winding varnish and it is common practice with motor winders and transformer manufactures to seal their products against moisture and loose winding movement, what the formulation is today i dont know ,but i use epoxy. as for the hex key probably a metric size.
I can easily smear on a little epoxy over the abrasions if I keep it thin so the magnets don't make contact. Thanks. Tom |
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text:
Dr. Tom C. Rakow
Christian Deer Hunters Association ®
Phone: 320-327-2266
Additional bio information at this website.
From left to right:
South Dakota mule deer
Minnesota turkey
Wisconsin public land whitetail
Minnesota public land longbow
As a full-time pastor Dr. Rakow (also known as
the bear tooth pastor) is available for a limited number of
speaking engagements.
Cost: Travel expenses, lodging (if necessary), and an honorarium from
the church or sponsoring group(s). Arrangements can be made for sponsoring
group(s) to sell books at a reduced rate for fundraising purposes.
January 8, 2006 Greenville, IL - First Christian Church
January 12, 2006 Fargo, ND - Bethel Evangelical Free
January 28, 2006 Grantsburg, WI (Community Event)
February 4, 2006 Lodi, OH - Victory Baptist Church
April 8, 2006 Dassel, MN - Evangelical Covenant Church
June 16-20, 2006 Nester Falls, Ontario - God's Great Outdoors
September 15-16, 2006 MI - Wesleyan Church Father/Son Retreat
September 22-23, 2006 IA - Hunt for Handicapped Youth
November 2, 2006 Gaylord, MI - Gaylord Evangelical
Free Church
November 16, 2006 Wisconsin Rapids, WI - First English Lutheran
November 25, 2006 Ithaca, WI - Willow Valley UMC Father
& Child Event
January 5-6, 2007 NC - Southeastern Baptist Theological Seminary
February 2&3, 2007 Pottstown, PA - Berean
Bible Church
March 1, 2007 Cedar Falls, IA - Prairie Lakes Church
March 23, 2007 Dodge Center, MN - Praise Fellowship Church
April 28-29, 2007 IA - Special Youth Challenge Turkey Hunt
June 20-22, 2007 Ontario, Canada - Rushing Wind Retreat
September 7, 2007 Macungie, PA - Salem Bible Church
September 29, 2007 Mason City, IA - Trail to Adventure
October 6, 2007 Bemidji, MN - Oak Hills Bible College
October 26, 2007 Mount Horeb, WI - New Hope Evangelical
November 15, 2007 Wisconsin Rapids, WI - First English Lutheran
December 1, 2007 Winthrop, MN - Winthrop Evangelical Covenant
January 4-5, 2008 NC Southeastern Baptist Theological Seminary
February 9, 2008 Roanoke, VA - East Gate Nazarene Church
February 23 & 24, 2008 Chambersburg, PA - Air Hill
Brethren in Christ
March 1, 2008 Ogama, WI - Highway 13 Sportsmen's Wild Game
Event (First Baptist of Phillips, Ogama Baptist, &
Woodland Community)
March 8, 2008 Big Lake, MN - Multiple Church Event -
(Riverside Church, Bridgeview Church, & Oakwood Church)
August 22-23, 2008 Fort Worth, TX - SW Baptist Theological Seminary
September 5, 2008 Oley, PA - New Life Bible Fellowship Church
September 19-21, 2008 Little Pine Island Camp, MI
(Western Michigan
& Northern Indiana Division Men's Camp)
February 21, 2009 Sioux Falls, SD -
March 20, 2009 (Friday), Silver Lake, MN -
Trail to Adventure Conf. April 18, 2009 Norwalk, IA -
Fellowship Community
May 15-17, 2009 Finlayson, MN -
Salvation Army Camp
August 14, 2009 Baxter, MN -
Heritage Assembly of God
October 3, 2009 Roseau, MN -
First Baptist Church
October 9, 2009 Ashby, MN -
Christian Network
January, 29 2010 Bismarck, ND -
Evangel Assembly of
February 5, 2010 New Richmond, WI -
Cornerstone Assembly of God
February 6, 2010 Wausau,
WI - St. John Lutheran
February 20, 2010 Watertown, MN -
Watertown Evangelical Free
February 27, 2010 Milaca, MN - Milaca Evangelical Free Church
March 6, 2010 Hixton, WI - Contact
Craig @
March 13, 2010 Apple Valley, MN -
Mount Olivet Assembly
of God
March 27, 2010 Fairmont, MN -
Bethel Evangelical Free
September 10-11 Calvary Evangelical Free Church Rochester, MN
September 25 Menomonie Alliance Church Sportsman's Group
November 19 Resurrection Life Church - Eden Prairie, MN www.rezlife.org Tickets required.
January 22, 2011 Jesus Assembly of God - St. Peter, MN Winter Wild Game Feed
March 5, 2011 East Lake Community Church - Moneta, VA Outdoor Ministries Wild Game Dinner
March 26, 2011 Hillside Community Church and Living Hope Evangelical Free Church - Neillsville, WI Father and Son Wild Game Feed
March 31, 2011 First Reformed Church - Sheldon, IA Sportsmen's Banquet
September 24, 2011 Praise Fellowship of Church - Dodge Center, MN The Sportsman Outdoor Adventure
November 5, 2011 Dallas Area Christian Mens Group - First Annual Hunters Rendezvous Event
February 25-26, 2012 Air Hill Brethren In Christ - Chambersburg, PA
February 4, 2012 Wild Game Feed - First Baptist Church of Cambridge, MN (4-9pm)
February 21, 2012 Marksman Metals - (Private Business Presentation for Employees – with the dogs) St. Michael, MN
March 10, 2012 Wild Game Feed - Glendorado Evangelical Country Church - Foley, MN
March 23. 2012 Game Feed - Wadena, MN Wadena Evangelical Church
March 31, 2012 Outdoor Expo at the Maranatha E. Free Church in Rice Lake, WI. Proceeds to benefit Catch-A-Dream. Pointers 101 Seminar 1:00 pm
June 9, 2012 "You're The Pick of The Litter" presentation Lac Qui Parle, MN
September 15, 2012 Deer Hunting Tips Seminar/Pointers 101 Seminar at Trout Lake Camp at Pine River, MN
September 22, 2012 Sportsmen's Dinner at Grindstone Lake Bible Camp in Sandstone, MN
November 17, 2012 TBA
December 7, 2012 Men's Game Feed at Fillmore Free Methodist Church in Wykoff, MN
February 23, 2013 Men's Game Feed - Eagan, MN -
Eagan Hills Church
March 23, 2013 Wild Game Feed - Ebenezer Mennonite Church - Bluffton, OH
April 6, 2013 Wild Game Feed - Blackduck Evangelical Free Church - Blackduck, MN
April 13, 2013 Trail To Adventure! Conference - Hope Community Church -
West Salem, Wisconsin
April 9, 2013 12 Noon - "Outdoor Ministry" Kiwanis Club at the
Hutchinson, MN VFW Building
April 27, 2013 12 Noon - Father/Son Banquet (Lost Arrow will also be present)
September 14, 2013 Seminars at Trout Lake Camp at Pine River, MN
October 26, 2013 Major Men's Fall Outdoor Event Moose Lake, MN
October 27, 2013 Blaze Orange Sunday - Tibbetts Brook Chapel - Milaca, MN
November 30, 2013 Parent/Child Banquet (Lost Arrow will be present)
Willow Valley Church
January 3,4, and 5,2014 10th Annual Pastor's Quail Hunt - Alva Wesleyan Church, Cedar Grove Wesleyan, and Hopeton Wesleyan Church
Saturday, February 22,2014 10:30 am - Men's Game Brunch - Cushing Baptist Church
Theme - Antique Weapons
March 8, 2014 Deer Fry - New Castle Bible Church - Mackinaw, IL
March 28, 2014 The Sportsman's Big Event - Praise Fellowship Church - Dodge Center, MN
April 4, 2014 Outdoorsman's Main Event Crossroads Church - Albert Lea, MN
April 5, 2014 Game Feed Chippewa Valley Bible Church - Chippewa Falls, WI
April 26, 2014 Trail to Adventure Conference Lenards Restaurant - International Falls, MN
January 30, 31, February 1, 2015 10th Annual Pastor's Quail Hunt - Alva Wesleyan Church, Cedar Grove Wesleyan, and Hopeton Wesleyan Church
February 22, 2015 Glencoe, MN Business Expo — Booth with Lost Arrow and/or Blessing the English pointer
March 5, 2015 Gibson City Bible Church Wild Game Feed
March 7, 2015 Grace Fellowship Church of Pella, Iowa
March 21, 2015 Big Little Hunting & Fishing Expo McLeod County Fairgrounds, Hutchinson, MN
March 28, 2015 Glendorado Evangelical Country Church (Foley, MN)
April 24-25, 2015 Arrowhead Bible Camp Sportsman's Archery Weekend
June 27, 2015 Fun N Faith in the Outdoors
August 16, 2015 Beulah Wesleyan Church 90th Anniversary
September 25-26, 2015 Special Youth Challenge Ministries
- Iowa
January 20, 2016 First Baptist Church of Cokato - English pointer presentation - Cokato, MN
February 27, 2016 The Total Outdoorsmen - Pella, Iowa - presentation plus pointers
March 19, 2016 The Big Little Hunting & Fishing Expo - visit Lost Arrow at this event! McLeod County Fairgrounds - Hutchinson, MN
April 2-3, 2016 Sportsman's Dinner & Service - Milford Bible Church - Milford, PA
April 8, 2016 Men's Wild Game Feed - Hillside Church - Mankato, MN
April 16, 2016 Black Duck Evangelical Free Church Wild Game Feed - Black Duck, MN
April 29-30, 2016 Trail To Adventure Conference/Linder's Angling Edge Studio Tour - Pequot Lake, MN
February 1, 2017 First Baptist Church of Cokato - English pointer presentation (Lost Arrow, Blessing, and debut of Treasure) - AWANA (free event)
February 18, 2017 Men and Boys Breakfast - English pointer presentation (Lost Arrow and Blessing) - Grace Baptist Church, Chippewa Falls, WI
February 24, 2017 Men and Boys Wild Game Feed - English pointer presentation (Lost Arrow and Blessing) - Pequot Lakes Baptist Church, Pequot Lakes, MN
April 21-22, 2017 Sportsman's Archery Weekend - English pointer presentation (Blessing) - New Auburn, WI
Facebook for Lost Arrow (Tom's English pointer)
More than four decades ago (at the ripe-old-age of eleven) Tom C.
Rakow poached his first deer with a twenty-two caliber rifle. Unfortunately,
this was just the beginning of some very bad hunting habits.
Then in 1977, Tom came to know Jesus Christ as his personal Lord and Savior
while watching a Billy Graham Crusade on television (Testimony appeared
in "Decision Magazine" in June 1995) . Not surprisingly, one of the first
things that happened was that Tom's hunting attitudes and activities
began to be transformed. Although Rakow would be the first to admit
that God still has a whole lot of work left to do in his life, he's convinced
that a return to biblical principles (which predate aluminum arrows, game
wardens, black powder, and the Second Amendment) will serve as a helpful
bridge between divergent views held by hunters and non-hunters alike.
Dr. Rakow has written for major publications and also authored
Me!" Bible Quizzes,
Hunting & the Bible: A Scripture Safari,
Hunting Basics And Beyond,
Raccoon Hunting Questions (audio),
Devotions for Dog
Lovers, Hunting Arguments: Biblical Responses to a Loaded
Issue, Devotions for Hunters & Anglers,
and is a contributor and editor of
Devotions for Bird
He is a featured speaker on The Trail To Adventure DVD
teaching series, and is included in True Stories of Pro Outdoorsmen both
produced by God's Great Outdoors (www.ggoutdoors.org). In addition,
Tom is in demand as a speaker for wild game banquets and also hosts a
weekly radio broadcast called "First Light." In 1994, he founded
the Christian Deer Hunters Association (
), a national, non-profit, interdenominational, volunteer ministry
to deer hunters. More recently he founded the Christian Anglers Association
). He is Co-owner of Rock Dove Publications (www.rockdove.com).
His conversion experience aired in January, 2006 on the Unshackled Radio
Program (The longest-running radio drama in history) and can be listened
to online at (www.unshackled.org Program #A2875).
Dr. Rakow has studied the Bible in its original languages of Hebrew,
Aramaic, and Greek and regularly researches hunting-related issues as
they pertain to a biblical world view approach. He holds degrees
from the University of Wisconsin, Moody Bible Institute (IL), Asbury Theological
Seminary (KY), and Bethel Theological Seminary (MN). Rakow has been
listed in the Dictionary of International Biography - 23rd Edition, and
Who's Who in Religion . Tom and his wife, Beth, and their four daughters
(along with their four English pointers)
reside in Minnesota where he has served as full-time pastor of Grace Bible
Church ( http://silverlakechurch.org
) since 1989.
A SAMPLE OF SOME OF DR. RAKOW'S MEDIA EXPERIENCE (Radio)
God's Great Outdoors
(National Radio Broadcast) - A guest numerous times.
Minnesota Public Radio
Light Radio Broadcast
Present host for the past 15 years.
Currently airs
on KARP 106.9 FM
The Zone with Chip Howard.
Salt Block Radio Program - Co-hosted for approximately two years.
Worship With Polka Music
Radio Program
(Once a month program)
June 2005) on KDUZ 1260 AM
SRN News
(Salem Radio Network)
...and many more!
A SAMPLE OF SOME OF DR. RAKOW'S MEDIA EXPERIENCE (Papers)
Although Dr. Rakow has been interviewed by a variety of papers over the years, here are a couple articles available online.


text:
Milf Jennifer gets spied on by a young boy while masturbating on the sofa. Now she can't deny she was getting nasty on her own, as Felix wants to see her pleasing herself. Well, that isn't exactly all this youngster wants her to do, as his cock needs some attention too. So he makes the mature chick gag on his sturdy pecker, and then pounds her snatch in doggystyle making her scream from his raw attack.
Download Clip1
Download Clip2
Older missises under brutal assault of nasty younger boys!
Action-packed, uncut photos and movies!
Download Clip3
All models appearing on this website are 18 years old or older.
18 U.S.C. 2257 Statement : http://maturesunderboys.com/2257.html
All rights Reserved © www.MaturesUnderBoys.com


text:
Hard work and dedication to the sport of basketball has paid off for several players who were named to the all-region team.
Williamstown Lady Demons Jaclyn Stith and Tori Wilhoit were named to the girls' team, while Grant County Braves Caleb Kinmon and Kody Thompson were named to the boys' team. Grant County coach Ron Kinmon was named all-region coach.
Stith was named to the team for the second year in a row.
If you currently subscribe or have subscribed in the past to the Grant County News, then simply find your account number on your mailing label and enter it below.
Click the question mark below to see where your account ID appears on your mailing label.
ZIP Code: | |


text:
High Performance Distributed Network Operation (HiPerDNO)
High Performance Distributed Network Operation (HiPerDNO)
Existing electricity distribution management systems (DMS) have been designed using operational and algorithmic procedures that are highly centralised. As more of the distribution network becomes active, moving rapidly from the current minority to the future majority1, accurately estimating the state of the system becomes essential and therefore algorithms and procedures must be highly scalable to achieve the required near to real-time state estimation.
Presently there are severely limited data processing, storage and communications resources within existing DMS. Data communications bandwidth is one example of potentially severe bottlenecks in state-of-the-art DMS. Furthermore, existing electricity distribution networks lack significant monitoring or metering points and hence do not support the massively distributed connection of active network assets (sensors and instrumentation, responsive load) or active electricity customers (smart meters, small-scale embedded generation).
Many European countries are planning or beginning major asset replacement and renewal programmes with regard to electricity distribution networks. EDF Energy in the UK is committed to major asset replacement and renewal over the next five years. Such a major asset replacement initiative represents an ideal opportunity for the massively distributed deployment of state of the art network metering, monitoring and instrumentation. However, major research and development of high performance ICT infrastructure will also be required to fully exploit the investment return on such new assets and to defer further asset deployment. Future potential financial benefits and cost savings to large-scale distribution network owners and operators can be measured in hundreds of millions of Euros.
Due to the size of the collaboration only members of the project from University of Oxford are listed below. Please go to http://www.hiperdno.eu for full collaborator details.
Local Principal Investigator
- Dr Stef Salvini, Oxford e-Research Centre
- Mr Piotr Lopatka,
- Mr Sebastiaan van Schaik, Oxford e-Research Centre
D. Wallom, S. Salvini, P. Lopatka, A computational platform for advanced energy Distribution Network Operations, Digital Research 2012.
D.C.H. Wallom, S. Salvini and P. Lopatka, High Performance Computing Platform for Advanced Distributed Network Operations. Innovative Smart Grid Technologies (ISGT Europe), 2012 3rd IEEE PES International Conference and Exhibition on , 14 - 17 Oct 2012.


text:
This morning Olivia helped Grandma water the plants in the garden. She has an amazing stubborn streak - once she gets something in her head she is not easily dissuaded. She was just determined to water everything by stepping on it first, making sure to break off any new growth, THEN water it. Grandma didn't particularly like that plan so my girl was most annoyed. And she has started the "I can do it myself" stage of toddlerhood. But the thing is, she CAN'T really do it herself. So she gets frustrated. Poor kid. Learning our limitations can really suck sometimes.
In any case she loves playing in water, with water, beside water, if it gets her wet she's happy.
Her swimming lessons went well tonight. I still hate parading around in my bathing suit. I doubt that is going to change anytime soon. Especially since I have been a little on the stressed out side lately and I have a bit of a problem with stress-eating. Like food is going to help me feel better or something. Not.
We are going to our denominations General Assembly the first week of July. It is in our fair country's capital city, Ottawa. Which also happens to be where my husband is from. The plan, for several months now, has been to wean Olivia by the time we go so that she can be easily babysat by my dear mother-in-law and sister-in-law (and their husbands of course).
As I have mentioned before the weaning process has not gone well. Because of me. I am having a dreadful time saying no to her. I am feeling very traumatized about letting go of her babyhood. And I feel mean! Why is that? It's not like I'm starving her or abandoning her. And yet I feel terrible.
I know part of the reason is because I am feeling so stressed out about other areas in my life that I don't feel like messing up an area that is going along so smoothly. But really, it isn't. Instead of being LESS interested in nursing, my sweet little girl is only increasing her interest in it. Really. She wants to nurse A LOT these days. Probably because she is teething horribly but in any case she really is too old to be nursing 8 or more times per day and several times per night if she had her way.
The crazy part about the night is that I don't even remember fully waking up to nurse her anymore. I can be in a whole other room and I will half-dazed sleep walk to her room and nurse her. It is very hard to be firm about putting her to sleep using alternative methods when I don't even remember her waking up. Sleep deprivation is just grand ain't it?
So tonight she is in her crib. With her door closed. And I will be in our room. With the door closed. Wearing my most difficult-to-nurse-in nightgown. That ought to do it.
Now if only I would stop feeling so awful about it.
But honestly she wouldn't enjoy General Assembly. It's all meetings and voting on rather boring stuff and seminars... no toys, no play mates, no fun, no place for a toddler. I KNOW she will have a much better time with my sons and her grandparents and aunt and uncle. Until she wants to go to sleep. Then she will be miserable. And I will feel guilty.
And it's not like I even have to fully wean her. She just has to be able to go for 8 hours without nursing and fall asleep with an alternative method for her nap. This is NOT an unreasonable expectation for a nineteen month old child is it?
Emotions suck.
ANYWAY my boys spent last night sleeping in our tent trailer with daddy. They had SO much fun.
Owen ended up coming in half way through the night but Aiden stayed out the whole night! And now he would like to live in the trailer indefinitely.
He even brought all of his precious lego out and spent a good portion of the day today in their playing with it. He really really loves it. I think it's like his own personal play house to him.
He fully intends on spending the entire summer out there. I told him he can't spend EVERY night out there since he still has school. He very reluctantly agreed to sleep inside tonight as long as I PROMISED to let him sleep outside tomorrow night. I told him he could if he had a good day at school. Lucky daddy!
Speaking of good days at school Aiden did AWESOME on his last day of school - he got 10 out of 10 good behaviour happy faces. I'm so proud of how much he has improved this year. I really hope it doesn't take 8 months to get him adjusted to grade one next year. I have a meeting at the school on Thursday to meet with his next years teacher and teacher's assistant along with his teacher and assistant this year to discuss the transition. I must say our school is being really great about all this now.
And I would like to thank all of you who have told me you are praying for me these days. I really do appreciate it. And obviously I need it so don't stop!
How to Thrive Despite Chronic Illness
16 hours ago


text:
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View Poll Results: I measured the test tone at: | |||
2 volts or less | 209 | 37.93% | |
Between 2-5 volts | 180 | 32.67% | |
Between 5-10 volts | 73 | 13.25% | |
Between 10-20 volts | 38 | 6.90% | |
Over 20 volts. | 51 | 9.26% | |
Voters: 551. You may not vote on this poll |
Thread Tools | Search this Thread |
8th February 2012, 12:04 AM | #481 |
diyAudio Moderator
Thanks Revb. Not disgruntled, just a bit frustrated. You are right about people reading their own biases into it, but I had not expected it.
Yes, I'm glad that Tom is here, he has a lot of good advice. Some of the things that have come up deserve their own threads. |
8th February 2012, 01:13 AM | #482 |
diyAudio Member
Join Date: Oct 2002
Location: England
Ah I've been assuming that as the original sine wave was recorded at -12dB as an average level that the output on the amplifier, when measured in an rms voltage was also representative of the rms figure. Hence if you multiplied it by 4 you'd end up with the equivalent requirement for an rms wattage. I may have added to some slight confusion in some of my posts.
Going through the maths though its obvious as the peaks of the -12dB tone actually hit -9dB and if multiplied by 4 we end up with +3 which is impossible. The -12dB tone might be recorded as an rms value and the DMM might read an rms voltage, and indeed to figure out how much peak voltage you need to reproduce the -9dB peaks you need to multiply it by 1.41. Now you're up at a peak level = -9dB, so to raise that up to a 0dB peak you actually need to multiply 1.41 up by 2.82 = 4 volts. That is 4 volts to reproduce the peaks of a sine wave with peaks hitting 0dB. Naturally if one starts out with an rms figure of 1 volt for the -12dB, you multiply it up by 4 to arrive at 4 volts, which as explained above = the peak value of a maximum amplitude sine wave. I had assumed that this was the rms value and hence you can convert it directly into an 8 ohm watt figure. You cannot, to do that you have to divide it by 1.41 first. In other words, if I've just figured this out correctly () the people who are in category 1 and measuring less then 2 volts are actually using no more then 4 watts, and those in category 2 are using between 4 and 25 watts rms, as measured into a resistive 8 ohm load. If that's correct then it appears that I inadvertently added to some of the confusion.
What the hell are you screamin' for? Every five minutes there's a bomb or somethin'! I'm leavin! bzzzz! Now with website! www.5een.co.uk under construction. |
8th February 2012, 01:13 AM | #483 |
diyAudio Member
Join Date: Jan 2011
Location: Willamette Valley
deserve their own threads
X2 on that. So meaty.
8th February 2012, 01:47 AM | #484 |
diyAudio Member
Join Date: Apr 2005
Location: Sitting behind the 'puter screen, in Illinois, USA, planet earth
Hi mr push pull
The reason for the null test is it would show you if your amplifier has run out of voltage swing, is large enough for what your listening to. Usually clip indicators and normally level indicators only show the level as averaged over a longer period of time compared to what is happening cycle by cycle like I am talking about. Thus, as one might find with an oscilloscope, an amplifier may be instantaneously clipping while showing no signs of that on a level meter or clip indicator or be audible as a familiar flaw (an example of it I cited earlier). I suggested this test because well before clipping makes a sound that you recognize, it is compressing the dynamics of the signal. If preserving the dynamics is important or desirable, having "enough" is also desirable. With that null test, if the amp input and output are the same, there is nothing left to hear and no problem. AS soon as an amplifier misbehaves and cannot follow the input signal (like instantaneous clipping) a large difference signal is produced. The presence of that signal (your amp running out of swing or distorting etc) tells you that for what you were trying to do, your amp is not big enough. The null test would work with any recording at any level. 5th, sorry you were having trouble with it, the program has been out for a good while. In the way old days, one could do this with a pair of mic or signal transformers, the input drives one, an attenuator made of a 10k resistor and 2k pot could be used to make it adjustable connected to the output, the out puts are put in serried but out of phase to cancel. You put in a sine wave or other signal at a low level and adjusted the pot to get the minimum level, the null. Then you could amplify the difference and do the same thing, instantly hear when it isnt following the input signal. This old way works real time but I dont imagine many folks have a pair of mic or signal transformers lying around and I figured software might be easier. The cool part about the old way is it doesnt care about ground convention and allows you to see or rather hear real time when you have run out of gas well before you would be able to hear it from your speakers and it works with any signal at any level with any program material.. So, if one considers the instant an amplifier is no longer able to do what its told is an indicator its not powerful enough or otherwise unable then this seems like a good bet and doesn't require an oscilloscope. Best, Tom
Bring back mst3k and futurama |
8th February 2012, 03:02 AM | #485 |
diyAudio Member
Hi Tom,
if only determining if clipping occurs is what you're after, simply using the sound board as a scope may be even simpler. one can even record and do post-analysis. not to mention real-time analysis. an advantage of recording real music through the sound card instead of using sines is that one can capture behavior with a real, reactive load with the added bonus of not risking to burn a driver with high power sines. I guess I'm among the very few that sent some 100W of pure sine into a $1000 woofer (it is alive and well, thank you).
we all love a good ol' stereotype until it's against us |
8th February 2012, 10:30 AM | #486 | |
diyAudio Moderator
8th February 2012, 03:44 PM | #487 |
diyAudio Member
Join Date: Jun 2011
My measured value.
Thanks Pano for an educational and informative thread.
My measured value is. 1.9 V -12dB at 120Hz. Loudspeaker sensitivity of 92dB (2.83V/1m). Room 4x5m. If I understand correctly. this means?? My max value is 4x1.9 = 7.6 V My RMS W value of 8ohm is 1.9 Vx2, 83 = 5.38 V -- SQR 5.38 / 8 = 3.6 W. If my speakers has its lowest impedance 3.5 ohms at 120Hz. My maximum power peak is aprox. 16.5 W (SQR 7,6/3,5).????? Thanks Pelle |
8th February 2012, 04:34 PM | #488 |
diyAudio Member
Join Date: Apr 2005
Location: Sitting behind the 'puter screen, in Illinois, USA, planet earth
Hi Push pull
A problem with a sound card based oscilloscope and the file comparator software that uses a sound card that I had suggested earlier is like I also said, that what youre looking for can contain or predominantly be information above what the sound card can capture. For audio work, one wants an oscilloscope with at least a decade greater BW than what youre looking at. For example, a sound card can capture a 20KHz sine wave, but if your amp was clipped to a full square wave at 20KHz, all the 16/44 sound card would see / capture is a sine 20KHz wave. Now, most of the audio is well below that and so a sound card based method would be of value (and is why I suggested it). I mention the old way too because 5th had problems with the software but the idea is you compare the input to output, the amp gain is only scaling, it does not change the wave shape and THAT is what youre looking for (the output NOT matching the input, such as at instantaneous clipping). I mention the transformer based approach because that is real time and an ancient way to get the difference between an input and output but mention it last because if people dont have test equipment lying around, they probably dont have a pair of signal transformers lying around. Unfortunately, to examine features in signals that happen very quickly and are over just as fast, takes more than ones ears or a simple meter. Best, Tom
Bring back mst3k and futurama |
8th February 2012, 05:34 PM | #489 | |
diyAudio Member
Join Date: Jan 2008
8th February 2012, 06:11 PM | #490 |
diyAudio Member
e friend (he's not a member here) just did the measurement: he actually listens at about 200W maximum with 90dB speakers. wow!
we all love a good ol' stereotype until it's against us |
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text:
I have had the ipod touch since they first came out, when I heard about the iPad, I had to have one. I was one of those people who logged on to the Apple site first thing March 12! Glad I found this firum because I bet there will be lots to talk about in the future!:ipad-front:
Welcome to the site! What model did u go with? March 12th (pre-order day) was a record day for new Members on the site but I have a feeling we'll break that tomorrow!


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Don't forget to check out what Wandering Through the Shelves picked, the blog that started Thursday Movie Picks.
Wednesday, 8 July 2015
Thursday Movie Picks: Road Trip Movies
Don't forget to check out what Wandering Through the Shelves picked, the blog that started Thursday Movie Picks.
12 comments:
- joelnox9 July 2015 at 14:57
I haven't seen Wristcutter's yet, it looks intriguingly bizarre, but LOVE your other two choices. Susan Sarandon and Geena Davis are perfect in their parts and of course the side dish of Brad Pitt ain't bad either. It Happened One Night is such a charmer, Gable just exudes movie star magnetism and Colbert is an excellent match for him. Terrific picks!
ReplyDelete - Andrew Ellington9 July 2015 at 21:37
Love that you went with It Happened One Night. Gable's best performance, in my book, and such a delightful little film. I adore Thelma and Louise, but I haven't seen Wristcutters yet...I'll have to check that one out!
ReplyDelete - joelnox12 July 2015 at 18:21
I meant to ask if you'd ever seen the musical remake of It Happened One Night called You Can't Run Away From It with Jack Lemmon and June Allyson? I finally caught up with it last month on TCM, it's not a patch on the original but a harmless enough time passer. While Lemmon is no Gable this was early in his career and he's a genial presence, June however was almost 40 when she made it, a bit far on to be convincing as a madcap runaway heiress. The biggest problem though is that while Gable & Colbert had tremendous onscreen chemistry Jack & June share little.


text:
With state-of-the-art equipment at their disposal, it seems that nothing stands in the way of today's tunnel engineers. This video segment adapted from Building Big, details the technical challenges involved in completing the Channel Tunnel, an underwater tunnel that links England and France for the first time ever, and shows how building teams from the two countries met those challenges.
This resource was adapted from Building Big: Tunnels.
© 2017 PBS & WGBH Educational Foundation. All rights reserved.


text:
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Chicken Liver Stroganoff with Spicy Chicken Flavored Rice
garlic, mushroom, rice, +yellow onions, +butter, +chicken liver, +cream of mushroom soup, +onion soup mix, +soy sauce, +dijon mustard, +sour cream, +water, +green chilies
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Easy Chicken Pilaf Casserole
This wonderful chicken/rice casserole is a favorite in our house, and it is often requested for supper (Tip: any left over cooked chicken (or cooked turkey,...
rice, mushroom, garlic, +black pepper, +butter, +chicken broth, +chicken, +flour, +parsley, +green pepper, +half and half, +parmesan cheese, +red pepper, +salt
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Chicken Wild Rice Soup Recipe
I make this with the left over roasted chicken I have, if you don't have any cooked chicken, the recipe uses chicken breast. It's a good, thick, warm...
mushroom, rice, garlic, +green onion, +chicken, +onions, +vegetable oil, +cornstarch, +black pepper, +thyme, +tarragon
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Chicken Supreme Dijon
Simple and delicious. I like to double the sauce so that there is plenty to pour on the rice too. My grandkids love this with chicken quarters too. From...
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Beer Chicken Not Beer Butt Chicken Recipe
Unique flavor combo, a beer lovin' bonanza. Prep:30m
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Chicken and Mushroom Chowder
"This is a wonderful all-in-one chicken dish perfect when you need to whip up dinner quickly - even quicker if you already have leftover cooked chicken."
garlic, rice, mushroom, +carrot, +chicken broth, +oregano, +flour, +milk, +olive oil, +onions, +black pepper, +chicken, +water
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Sunday Chicken And Rice Recipe
This is my take on chicken Rice casserole, So easy to assemble, put in oven and forget it till it is nearly done. Easy way to get those veggies in the...
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Chicken With Tomatoes & Mushrooms
I made this up, trying to imitate a dish from a restaurant. It didn't come out like I was aiming for, but it did come out VERY good, so I thought I'd post...
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Chicken Marinade For Chicken Breasts Or Chicken Kabobs Recipe
garlic, +olive oil, +lemon juice, +worcestershire sauce, +soy sauce, +white wine vinegar, +onions, +oregano
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Salsa Chicken Skillet
"Diced chicken and veggies are stirred with spicy salsa to create this satisfying skillet dish from field editor LaDonna Reed of Ponca City, Oklahoma."
rice, garlic, mushroom, +vegetable oil, +celery, +chicken, +corn, +green pepper, +onions, +cheddar cheese, +salsa, +sour cream
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text:
Default ORACLE account DIP available
Severity | CVSS | Published | Added | Modified |
8 | (AV:N/AC:L/Au:N/C:P/I:P/A:P) | December 31, 1991 | August 29, 2006 | October 04, 2015 |
ORACLE creates a default account with the user ID "DIP" and password "DIP". It is best practice to remove default accounts, if possible. For accounts required by the system, the default password should be changed. This account grants user level access to the system.
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