text:
|Publication number
|Publication type
|Publication date
|Oct 11, 1966
|Filing date
|Jul 25, 1962
|Priority date
|Jul 25, 1962
|Publication number
|Van R Gaertner
|Original Assignee
|Monsanto Co
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (18), Referenced by (12), Classifications (11)
|External Links: USPTO, USPTO Assignment, Espacenet
3,278,560 POLYGLYCIDYLPOLYAMINE COMPOUNDS Van R. Gaertner, Ballwin, Mo., assignor to Monsanto Company, a corporation of Delaware No Drawing. Filed July 25, 1962, Ser. No. 212,438 4 Claims. (Cl. 260-348) This invention relates to a series of polyamine compounds and to compositions thereof. More particularly, this invention provides new and useful derivatives of polyalkyleneamines.
Another object of this invention is to provide polyglycidylpolyamine compounds, and mineral acid salts thereof.
An object of this invention is to provide new hydrophobic alkyl, alkenyl, and alkyl-substituted aryl polyglycidylpolyamines.
Another object of this invention is to provide methods for sizing paper without need of curing at elevated temperatures. 5
Another object of this invention is to provide methods for rendering textile materials water-repellent in an improved manner.
Other aspects, objects, and advantages of this invention will be apparent from a consideration of the accompanying disclosure and the appended claims.
It has been found according to this invention that new and valuable p'olyamine Compounds can be prepared by contacting and reacting an amine of the formula H R H Blasts Rea H wherein R is selected from the group consisting of alkyl radicals having from to carbon atoms, alkenyl radicals having from 10 to 25 carbon atoms, and alkylsubstituted aryl radicals having from 10 to 25 carbon atoms in the alkyl substituent, n plus 112 equals a whole number integer having a total of from 1 to 6, n is at least 1, and m is a whole number integer of from 0 to 5, and each R denotes a bivalent alkylene radical having from 2 to 6 carbon atoms, with an epihalohydrin such as epichlorohydrin, epibromohydrin, and epiiodohydrin. The resulting reaction products are valuable as intermediates for preparing polyglycidylpolyamines.
According to one aspect of this invention, there are provided, as new compounds, polyglycidylpolyamines of the formula wherein R, is selected from a group consisting of alkyl radicals having from 10 to 25 carbon atoms, alkenyl radicals having from 10 to 25 carbon atoms, alkylsubstituted phenyl, and biphenylyl radicals having from 10 to 25 carbon atoms in the alkyl substituents R is a bivalent alkylene radical having from 2 to .6 carbon atoms, n plus m' equals a whole number of from 1 to 6, n is a whole number of at least 1,'m is a whole number of from 0 to 5, and Z is selected from the group consisting of hydrogen, and the radical and at least a substantial number of the Z radicals are the radical The compounds described above may be prepared and recovered as such, or as'the mineral acid salts of said compounds, which are included in the embodiments of this invention.
Patented Oct. 11,1966
Compounds described by the above general formula are prepared first by the reaction of an epihalohydrin such as epibromohydrin, epichlorohydrin, or epiiodohydrin with an amine of the formula wherein R, R, m and n are as defined above. Following this, the reaction product can be contacted and reacted with an aqueous basic material to dehydrohalogenate the resulting intermediate to obtain as a reaction product, a compound with the general formula above. By dehydrohalogenation is meant the reaction of the basic material with the intermediate in such a Way as to remove hydrogen halide therefrom, causing the formation of the glycidyl oxirane linkage, and a by-product which is the salt of the base and hydrogen halide given off in the reaction.
For preparing the intermediates, the polyamine starting material is contacted and reacted with the epihalohydrin in an amount sufficient to form the intermediate reaction product having at least 50 percent of the Z position groups in the product in the form of the halopropanol radical, that is, the radical of the formula wherein X is the halogen derived from the epihalohydrin used. Sufficient epihalohydrin, generally an excess, is used to form as completely as possible an intermediate product wherein all of the Z positions groups are the halopropanol groups. The epihalohydrin reactant generally reacts preferentially with hydrogen atoms bonded to nitrogen atoms having two such hydrogen atoms, that is, with primary amine nitrogen hydrogens, and then more slowly with the hydrogens bonded to secondary nitrogen atoms, that is, with nitrogen atoms having two carbon bonds. The amount of epihalohydrin used for a given molar amount of the amine starting material will depend to some extent on the amount or degree of reaction desired. For most applications, an excess amount of epihalohydrin sufiicient to replace all such hydrogen atoms bonded to nitrogen atoms is used. However, as a practical matter it is generally quite diflicult to obtain complete replacement of all such hydrogen atoms with halopropanol groups. Satisfactory products are obtained for polysaccharide treatment purposes when at least 50 percent of hydrogens in the Z positions in the product are replaced with the halopropanol groups.
The reaction between the amine and the epihalohydrin starting material is conducted in the presence of at least a trace amount of an hydroxyl-containing material, pref erably a lowmolecular weight, volatile alkanol, such as methanol, ethanol, or propanol, which can be used as solvent for the reaction mixture as well the the reaction initiator. The hydroxyl-containing material needed to start the reaction can be supplied in a variety of ways. For example, the small amount of water normally present in some commercially available solvents, such as hexane, heptane, etc. is sufiicient to initiate the reaction. However, water is not generally desired as the solvent for this reaction mixture. The hydroxyl-containing material can also be supplied by some of the intermediate since, as indicated above, this product contains an hydroxyl group. The hydroxyl-cont-aining material can also be any other hydroxyl compound, a few simple examples of which are phenol, alkylene glycols such as ethylene glycol, propylene glycol, etc. The provision of the hydroxylcontaining material to initiate the reaction is critical in the sense that in its absence the reaction between the epihalohydrin and the amine starting material does not take place. For example, attempts to conduct the reaction using dry hexane as solvent resulted in no product being formed. However, for most purposes the small amount of hydroxyl-containing material needed to initiate the reaction can be supplied by any source such as are indicated above with no other requirements as to type, amount, etc. being critical. Solvents which can generally be used for this step of the process include the hydrocarbons which are relatively low-boiling, readily volatilizable solvents having molecular weights no higher than those approximating hexane, heptane, etc. as well as the lower molecular weight alkanols such as, methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanols, hexanol, and mixtures thereof. The reaction is conducted at low temperatures, generally, on the order of from C. to 50 C. at atmospheric pressure with temperatures of 2040 C. being preferred. Time periods ranging from 1 to 100 hours are generally sufficient to afford complete reaction of in excess of 50% of the hydrogen atoms in the Z position on the amine starting material with epihalohydrin. Specific time periods within this range can be optimized by those skilled in the art and will vary depending upon the reactants chosen, the solvent, the molar proportions of the reactants, the temperat-ure used, etc. When the reaction is complete any excess epihalohydrin together with most of any diluent or solvent used is removed at low temperatures not above 50 C., from the reaction product, preferably by distilling or flashing ofi said materials under reduced pressure. It is not essential to remove all of any diluent or solvent, but it is preferred to remove substantially all of the excess epihalohydrin.
These intermediates are used in preparing the polyglycidylpolyamines. When it is desired to recover said poly(halopropanol)polyamine compounds either for use as such, e.g., as sizing agents, or water-proofing agents, or for storing for later reaction, it is preferred to stabilize said intermediates against undesired reaction in any of various ways. The product can be kept cold, that is, at 0 C. or a lower temperature. It is preferred, however, to stabilize said products by making mineral acid watersoluble salts thereof. The making of Water-soluble salts of said products accomplishes several purposes. Besides making the poly(c-hloropropanol)polyamine products water soluble, the mineral acid salts thereof serves to protect them against undesired reaction, and provides a good mechanism for purifying the intermediate from the reaction mixture of any retained solvent or excess epihalohydrin reactant. Examples of acids which may be used to make the water-soluble salts are the mineral acids, preferably hydrochloric, phosphoric and sulfuric. On the contrary, carboxylic acid salts, such as acetates formed with acetic acid, are detrimental to uses as carbohydrate modifiers. The acid salts of said poly- (halopropanol)polyamine products can be made at any convenient time after reaction between the epihalohydrin and the polyamine starting material is complete. Conveniently, the acid material, for example, hydrogen chloride is added to the organic reaction mixture solution before the excess epihalohydrin and solvent or diluent used is removed from the poly(halopropanol)polyamine product. Then, after removing any excess epihalohydrin from the reaction mixture, the resulting acid salt product, e.g., the hydrochloride salt product, may be separated from the reaction mixture by adding a suitable precipitating agent, tag, a dialkyl ether such as ethyl ether which separates the salt as the desired product. By redissolving the salt product and reprecipitating the product with precipitating agent the product can be effectively purified from unwanted diluents. The amount of acid added is generally at least stoichiometrically sutficient to make salts of each nitrogen atom in the product. Generally, a slight excess for such purpose is used.
In preparing compounds of this invention the product resulting from the reaction of epihalohydrin with the amine starting material is contacted with an aqueous basic material to dehydrohalogenate the reaction product, preferably in the presence of a lower dialkyl sulfoxide. The aqueous basic material is generally the oxide, hydroxide, carbonate, or by-carbonate of an alkali metal or alkaline earth metal admixed with water to provide anefficient working basic material. The ex amples of such basic materials include sodium, potassium, lithium, calcium, barium, strontium, and magnesium oxides, hydroxides, carbonates, and bicarbonates. Most preferred examples are the plentiful, inexpensive basic materials such as sodium hydroxide, potassium hydroxide, sodium and potassium bicarbonates, calcium and magnesium oxides, and mixtures thereof. Aqueous solutions and suspensions of such materials in dilute or concentrated form can be used. Generally, concentra-.
tions of the basic material on the order of 0.1 to 15 N can be used with concentrations on the order of those equivalent to 10% to 50% by weight of the basic material, being preferred. To effect the desired dehydrohalogenation of the reaction product of the first step in economically efficient manner, the basic material is preferably used in excess molar proportions, although stoichiometric proportions may be used. The reaction of the second step of the process involves the reaction of the basic materials with the reaction product of the first step of the process and is preferably conducted in the presence of a substantial amount of a dialkyl sulfoxide.
A lower dialkyl sulfoxide is preferably used in the dehydrohalogenation step for preparing any polyglycidylamine product, described above, since its use aids in accomplising complete dehydrohalogenation, thereby enhancing the yield and purity of the product. I consider the use of a dialkyl sulfoxide essential to the process when the amine starting material is hydrophobic, that is, when R is a long chain alkyl or alkenyl group having, say, some 10 to 25 carbon atoms, or an alkyl-substituted aryl group having, say, a total of at least 10 carbon atoms in the alkyl substituent on the aryl nucleus. Quantities of dialkyl sulfoxides which may be used range from about 10% to large excesses by weight, based on the weight of the reaction product of the first step which is to be dehydrohalogenated. Prefererd quantities of dialkyl sulfoxide are those approximating the weights of the products to be dehydrohalogenated, say, about to based on the weight of the material to be dehydrohalogenated. Examples of dialkyl sulfoxides which may be used are dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, diisopropyl sulfoxide, dibutyl sulfoxide, methyl ethyl sulfoxide, ethyl propyl sulfoxide, etc., with dimethyl sulfoxide being preferred. I have found that in the presence of a dialkyl sulfoxide, best results are obtained by employing a slight stoichiometric excess of the basic material, say, from about 1.1 to 1.5 equivalents of the basic material per equivalent of halopropanol moiety in the intermediate at ordinary, moderately decreased, or moderately increased temperatures, for example, at temperatures of from 0 to 60 C. at atmospheric pressure. External heating is normally not employed, although for etficient reaction, for example, when reaction is conducted using dilute aqueous basic material or in the presence of a small excess of a basic material, say, below 25%, it may be desired to operate at slightly elevated temperatures while agitating the reaction mixture for a time of a few minutes to several hours to insure complete reaction.
The reason for the effectiveness of a dialkyl sulfoxide in this step of the process is not established but I believe it to be due to the fact that it promotes rapid complete dehydrohalogenation, avoiding hydroxyl-containing impurities which may initiate polymerization. In any event, with its use I have been able to obtain higher yields, and more readily separable reaction products.
When the dehydrohalogenationreaction is complete the excess basic material and'dialkyl sulfioxides are removed. Most of both materials are removed from the polyglycidylamine product by merely separating the resulting aqueous layer from the organic layer. The excess basic material can also be removed by adding an acidic material such as a mineral acid in sufiicient amounts to neutralize the excess basic material. Additional small quantities of unreacted basic material are also removed by adding to the organic layer a clarifying absorbent or adsorbent material, such as charcoal, which is acid acting. I prefer to use a combination of such means of base removal. Forf example, acids such as hydrochloric, phosphoric, sulfuric, nitric acids and other mineral acids may be added to the reaction mixture to partially neutralize unreacted basic material before the aqueous base is separated from the organic layer. Separation of the aqueous and organic phases also removes ,a large amount of any unreacted base. Then adding a clarifying agent, such as charcoal to the organic layer removes any re? maining basic material from the product. I
In preparing compounds of this invention the intermediate product, resulting from the addition of anepihalohydrin to the amine nitrogen atoms-having hydrogen bonded thereto, is treated with an aqueous basic material as defined above to dehydrohalogenate. the halopropanol groups bonded to nitrogen, forming as a reaction product the respective polyglycidylpolyamine product. For example, when aqueous sodium hydroxide l is added to N,N,N",N" tetra(3 chloro 2 hydroxypropyl) N'- docosyldibutylenetriamine, the resulting reaction product is N,N,N",N" tetra(2,3-epoxypropyl)-N'-docosylbutylenetriamine.
Compounds of the intermediate type, that is, those compounds obtained by reacting an epihalohydrin with the amine nitrogen atoms having hydrogen bonded thereto are referred to herein generally as poly(halopropanol) polyamines. Examples of such compounds and the reactants from which they are obtained are:
N,N',N',-tris(3-chloro-2-hydroxypropyl)-N-(tertdodecylphenyl)hexylenediamine obtained by reacting N-(4-tert-dodecylphenyl)hexylenediamine with epichlorohydrin;
N,N,N",N"-tetra(3-chloro-2-hydroxypropyl (-N'-tetra decyldibutylenetriamine obtained by reacting N'- tetradecyldibutylenetriamine with epichlorohydrin;
N-pentacosyl-N,N'N",N"-tetra(3-iodo-2-hydroxypropyl)- diethylenetriamine obtained by reacting N-pentacosyldiethylenetriamine with epiiodohydrin;
N-n-octadecenyl-N,NN,N"-tetra 3-chloro-2-hydroxypropyl)-dipropylenetriamine obtained by reacting N-n-octadecenyl-dipropylenetriamine with epichlorohydrin;
N (dinonylphenyl)-N,N',N",N"-tetra(3-bromo-2- hydroxypropyl)-dibutylenetriamine obtained by reacting N-(dinonylphenyl)-dibutylenetriamine withepibromohydrin;
N-decyl-N,N',N",N"'-tetra(3-chloro-2-hydroxypropyl)tripentylenetetramine obtained by reacting N-decyltripentylenetetramine with epichlorohydrin;
N'-(4-pentacosylphenyl)-N,N,N",N"',N',-penta(3- chloro-2-hydroxypropyl) tributylenetetramine obtained by reacting N'-(4-pentacosylphenyl)tributylenetetramine with epichlorohydrin;
N"-tridecyl-hexa(3-chloro-2-hydroxypropyl)tetraethylenepentamine obtained by replacing all of the hydrogen atoms bonded to nitrogen in N"-tridecyltetraethylenepentamine with epichlorohydrin;
N"-7-hexadecenyl-penta (3-chloro-2-hydroxypropy1) tetrapropylenepentamine obtained when all but 1 hydrogen atom bonded to nitrogen in N"- (7-hexadecenyl)tetrapropylenepentamine is reacted with epichlorohydrin;
In preparing polyglycidylpolyamines of this invention the respective poly(halopropanol) amines are contacted and reacted with an aqueous basic material preferably in the presence of a dialkyl sulfoxide in the manner described above. As a result of the reaction with the basic material the halogen of the halopropanol groups is removed as the neutral salt in a lay-product, and the oxygen atom from the hydroxy group becomes bonded to each of two carbon atoms of the resulting propyl group forming a terminal epoxide group. t
For example, by treating N-n-dodecyl-N,N',N",N"', N penta(3 bromo-Z-hydroxypropyl)tributylenetetramine with aqueous potassium hydroxide there is obtained N n dodecyl-N,N',N,N",N"-penta(2,3-epoxypropyl) tributylenetetramine.
Additional examples of such polyglycidylpolyamine products obtained by treating with aqueous basic material as defined above the corresponding poly(3-halo-2-hydroxypropyl)polyamines are:
N"-tetrac.osyl-N,N,N,N,N'"-penta(2,3-epoxypropyl) triethylenetetramine, N"-nonadecyl-N;N,N',N'f',N"",N"f'-hexa(2,3-epoxypropyl)-tetraethylenepentamine, N-undecyl-N,N,N'-tris(2,3-epoxypropyl)pentylenediamine, N'-hexadecenyl-N,N,N",N"-tetra(2,3-epoxypropyl)dipropylenetriamine, N"-docosenyl-N,N,N',N',N"'-pcnta(2,3-epoxypropyl) triethylenetetramine, N-(4-tert-dodecylphenyl)-N,N',N'-tris(2,3-epoxypropyl) -propylenediamine, N-(3dodecylbiphenylyl)-N,N',N',N"'-tetra(2,3-
epoxypropyl)diethylenetriamine, N'-(3,5-dinonylphenyl)-N,N,N',N"",N'",-penta(2,3:
epoxypropyl)tripropylenetetramine, and r N-(3methyl-4-dodecyl-N,N',N, N"", N""', N"""- hexa 2,3 -epoxypropyl) pentaethylenehexamine.
Mixtures of alkyland alkenyl-substituted amines i.e., where R is alkyl and alkenyl are likewise useful for preparing compounds of this invention. The alkyl-substituted amines are often derived from the respective alkenylamines by reduction of the unsaturated bond of the alkenyl group. Mixtures of alkyland alkenylamines having carbon chains of varying length may also be used. Examples of products obtained from such mixtures are:
A mixture of N-octadecyland N-octadecenyl-N,N,N- tris(S-chloro-Z-hydroxypropyl)ethylenediamines obtained from the use of a mixture of N-octadecyland N'octadecenylethylendiamines;
A mixture of N-'hexadecyl-, N-hexadecenyl, N-octadecyl-, and N octadecenyl-N,N',N",N'",N""-penta-(3- .chloro-Z-hydroxypropyl)tripropylenertetramines obtained from the use of a mixture of N-hexadecyl-, N-hexadecenyl-, N-octadecyl-, and N-octadecenyltripropylenetetra- N',N penta (3-chloro-2-hydroxypropyl)triethylenertetramine obtained by the use of a mixture of N- alkyl triethylene-tetramines.
Examples of salts of poly(halopropanol) polyamines described above are:
N,N,N',N'-tetra 3-chloro-2-hydroxypropyl propylenediamine disulfate,
N-octadecyl-N,N',N-tris(3-chloro-2-hydroxypropyl) ethylenediamine dihydrochloride;
N-docosyl-N,N,N",N"-tetr.a(3-bromo-2-hydroxypropyl) dibutylenetrimaine trihydrobromide,
N-hexadecenyl-N,N,N',N"',N-penta(3-chlor0-2- hydroxypropyl) triethylenetetramine tetraphosphate, and
N-(tert-dodecylphenyl-N,N,N",N"-tetra(3-chloro-2- hydroxypropyl)tripropylenetetramine tetrahydrochloride.
The products can contain isomers, where the higher polyalkylenepolyamines are used as the starting materials and when less than 100 percent of the amine hydrogens are replaced -by the halopropanol groups in the intermediate products and the respective glycidyl groups in products of this invention. It is not essential to separate the isomeric products or to determine the exact position of the substituent group since such isomers are useful for the same purposes. For example, when tetraethylenepentamine is reacted with sufficient epichlorohydrin to replace all but 1 hydrogen with chloropropanol groups, the product obtained can be a mixture of isomers including tetraethylenepentamine, N,N,N,N",N",N"" hexa(3- chloro-Z-hydroxypropyl)tetraethylenepentamine, and N, N,N",N"',N"",N""-hexa(3 chloro 2-hydroxypropy1) tetraethylenepentamine.
A particular embodiment of this invention is to provide polyglycidylpolyamine compounds having a hydrophobic group bonded to a nitrogen atom. These compounds are provided in accordance with this invention by having R denote an alkyl or alkenyl radical of at least ten carbon atoms, or an alkyl-substituted aryl group having at least carbon atoms in the alkyl-substituents on the aryl nucleus. When R is an alkyl-substituted aryl radical it is preferred that the aryl nucleus contain one or two aromatic rings such as phenyl, naphthyl, biphenylyl, etc. with the monocyclic G-membered aromatic ring being preferred, e.g., phenyl. These compounds having the hydrophobic groups ar particularly valuable in uses as polysacchride modifying agents such as water-proofing agents, sizing agents, etc. for starchand cellulose-based prodducts. A particular advantage of these compounds is that they provide good paper product sizing properties which cure at room temperature, that is, the treated polysaccharide material does not have to be heat cured to effect the sizing action of the compounds, although the use of a mild heating step may be preferred. These compounds are also useful for sizing and water-proofing starch and raw natural and modified cellulosic material such as cotton, and various textile materials including cellulose containing filaments, fibers, yarns, and fabrics. These materials are particularly valuable because they provide good permanent sizing and water-proofing properties that rae not removed from the starch or cellulosic substrate by washing. This enhanced sizing and waterproofing effect is believed to be due to the fact that the polyglycidylamines react with the hydroxyl groups of the starch or cellulosic substrate, for example, when applied as the paper product is being made, and effectively crosslink the cellulosic fibers to provide the desired enhanced property.
The compounds may be applied to the paper products according to techniques known to those skilled in the art. For example, the compounds may be applied to finished paper stock directly, in solution, as an emulsion, or in otherwise dispersed form. However, for best results it is preferred to apply, admix, or react the presently claimed compounds with the cellulosic paper stock in the pulp preparation stage in'media providing a pH of at least 7, preferably a pH of from 9 to 11, before the pulp is formed into paper sheets, boards, etc. In this manner the sizing of the paper stocks with these compounds is most efficient and effective at low concentration. Concentrations of the sizing agent ranging from 0.01% to 5.0% by weight, based on the weight of the finished paper product, are generally sulficient to provide a permanently sized paper product. Concentration on the order of 0.1 to 1% by weight of the sizing agent, that is, the polyglycidylamine based on the weight of the dry paper pulp are preferred A variety of pulps may be treated with the compounds described above and used to make permanently sized paper according to this invention including bleached and unbleached sulfite pulp, bleached and unbleached kraft pulp,
soda pulp, hardwood pulp, and mixtures of ground wood pulp with unbleached kraft pulp and other pulps.
The water-proofing of textile materials is accomplished according to this invention by impregnating the cellulosic textile material comprising cellulose filaments, fibers, fabrics with a solution of the polyglycidylpolyamine compound in an appropriate solvent and then volatilizing off the solvent, for example, by drying and curing, and thereafter subjecting the treated material to elevated temperatures to produce a substantially water insoluble finish on the cellulosic textile. The textile material may be impregnated with from 0.01% to 5% by weight of the polyglycidylpolyamine. The total amount of such polyamine compounds impregnated into the textile material is usually at least 0.075% by weight.
The compositions may be applied to the textile materials in various ways so long as impregnation of the textile materials is obtained. For example, the textile materials may be dipped or immersed in the composition or the composition may be dripped or sprayed on the textile material until the textile material is wetted out with the composition. In order to facilitate the control of deposition of the polyglycidylpolyamine compounds of this invention on the textile material and reduce the drying time, it is desirable to extract the textile material to remove excess solution therefrom. This is suitably accomplished by padding, wring-ing, squeezing, or hydroextracting the textile material. The amount of poly glycidylpolyamine compound applied to the textile material is controlled by the degree of extraction used and/or the concentration of these materials in the solution, and
may be varied widely depending on the amount of water repellency desired in the textile material. -In general, the amount of such ingredients applied is between about 0.01 and 5% by weight, based on the dry textile material, but good practical water repellent effects are obtained on most textiles by applying from about 0.1 to 2% by weight based on the dry textile material.
After the compounds have been applied, in solution, the textile material may then be dried atnormal drying temperatures and finally heated at elevated temperatures of about 250 to 360 F. to obtain a water-repellent finish on the textile material. The temperature may be higher than 360 F. depending on the particular textilev material, the type and amount of catalyst and the duration of heating is limited only by the stability of the textile material. The duration of heating may vary widely depend-ing primarily on the liquid content and the temperature used but is generally between about 1 and 15 minutes with the longer times corresponding to the lower temperatures. The textile material thus obtained may be given the usual finishing operation such as a refinish wash to remove water-soluble materials, steam framing and the like. Such operations may be desirable, but are not essential.
A large variety of textile materials comprising celllulose fibers may be treated in accordance with the processes of this invention, but the textile material should contain at least 40% by weight of cellulose fibers and probably 60% by weight or more of cellulose fibers. The textile materials treated may be woven or 'knitted fabrics, referred to generally as fabrics or yarns, filaments or fibers, but it is preferred to treat fabrics. The cellulose fibers may be natural cellulose fibers such as cotton, linen, flax or ramie fibers or regenerated cellulose staple fibers or filaments produced by the viscose or cuprammoniurn processes. It is preferred, however, to treat cotton fibers or viscose rayon staple fibers or filaments. The preferred textile materials are cotton woven fabrics or 100%, viscose rayon woven fabrics or woven fabrics composed entirely of cotton and viscose rayon.
The compounds described above are incorporated into cellulosic substrates in various manners, usually in the form of organic solutions or aqueous emulsions which are prepared according to techniques 'known in the art. The aqueous emulsions containing one or more of the above described compounds is usually accomplished with one or more of various types of cationic, anionic, or nonionic emulsifying agents which are known in the art. The solutions and aqueous emulsions of the above compounds may also contain'other paper making or textile auxiliaries such as stiffening or bodying agents, softening agents, curing agents, wetting agents, antifoaming agents, and the like, but such agents are not essential.
As examples of stiffening or bodying agents which may be employed may be mentioned aqueous dispersions of water-insoluble thermoplastic vinyl resins such as polyvinyl acetate, polyvinyl chloride, polystyrene, polyalkyl acrylates, polyalkyl meth-acrylates, vinyl chloride, vinyl acetate copolymers and the like and/or water-soluble thermoplastic resins such as polyvinyl alcohol; watersoluble partially hydrolyzed polyvinyl acetates; watersoluble salts of styrene-maleic anhydride copolymers, styrene-alkyl acid maleate copolymers, vinyl acetate-maleic anhydride copolyrners, vinyl aeetate-crotonic acid co polymers, vinyl acetate-alkyl acid maleate copolymers; or the like. Generally such agents are employed in amounts of about 0.05 to by weigh-t of the composition.
As examples of softening agents may he mentioned water solu-ble alkali metal salts of sulfonated mineral oils, sulfonated fatty alcohols such as sulfoniated cetyl and stearyl alcohol, su lfon-a ted castor oil and the like; watersoluble or wa-ter-dtispersible polyethylene oxides of high molecular weight; the water-soluble reaction products of ethylene oxide or propylene oxide with aryl and analkyl alcohols or with esters of a fatty acid and sorbitan and she like; cationic type softeners such as cetyl dimethyl benzyl ammonium chloride, or the like. Genenally such agents are employed in amounts of 0.05 to 5% by weight of the composition.
As examples of wetting agents which may be used may be mentioned sodium salts of alkylated benzene sulfona-tes such :as sodium deeyl benzene sulfonate, sodium dodecyl benzene sullfon'a-te; sodium lauryl sulfate; the sodium salt of methyl steararni-de ethioru'c acid; di-octyl sodium sulfosuccinate; and the like. In general, such agents are employed in amounts of about 0.05 to 3% by weight of the composition.
As examples of anti-foaming agents may be mentioned water-insoluble silicone compounds, water-insoluble oils, water-insoluble alcohols and the like. The amount of such agent used varies with iis effectiveness in minimizing foaming, but, in general, amounts of about 0.1 to 5% by weight of the composition may be employed.
The invention is further illustrated by but not limited to, the following examples:
Example 1 In 150 ml. of hexane -there was dissolved 24.2 g. (0.10 mole) of N-alkyl-l,3 propylenedi-amine, in which the alkyl groups were derived from coconut oil. To the resulting solution there was added 38.1 g. of epichlorohydrin. This reaction mixture was cooled overnight at 2025 C. and periodically analyzed to determine the extent of reaction. Afterl117 hours at 25 C., the reaction mixture was aspirated to remove hexane and excess epichlorohydrin to 25 C./O.2 mm., leaving as residue 49.8 g. of an amber oily product (50.0 g. is theory) mainly of 'the formula alkyl (mainly C12) ClCH1?HCHy-N-OHgCIhCII N-(CIhQH OH Clz), OH H wherein alkyl is an alkyl radical, mainly dodecy-l, derived from coconut oil. The product was stored at about 20 to prevent polymerization.
Example 2 To 18.5 g. of the diamino-tris(chlonopropanol) product obtained in Example 1, in 40 ml. of dimethyl sulfoxide,
, total of 42 hours.
10 there was added 10.00 ml. of 9.32 N sodium hydroxide at once. The temperature rose so 35 C. and 20 ml. of water was added. Another 10.00 ml. of 9.32 N sodium hydroxide was added (total of 186.4 milliequivalents) and the mixture was stirred for 1 hour at 25 -35 C. Hexane was added to aid sti-rning and the excess sodium hydroxide was hack-titrated to a pH of about 7 with 2.61 N hydrochloric acid. A total of 39.62 of hydrochloric acid was required (103.4 milliequivalen-ts), which denoted the use of 83.0 m-illiequiv-alents of sodium hydroxide to dehydroh alogenate the starting material or 78% of theory for triglycidyl-ralky-l-l,3epropy-lenediami-ne. The product was isolated by extraction with ether and hexane and, after washing and removal of solvents, weighed 120 g., I311 amber viscous oil.
Example 3 In 250 ml. of hexane there was dissolved 64.1 g. (0.20 mole) of melted tallow :alkyl (mainly n-C 1,3-propylenediamine (Armo-ur-Duomeen T) and cooled to 15 C. At this temperature 111 g. of epichlorohydrin (approximately 2 molar equivalents of e-pichlorohydrin per amine hydrogen) was added napidly. The mixture was cooled to 7 C. and stirred overnight for 18 hours allowing the bath to warm to room temperature. The mixture became homogenous as the stirring was continued a The reaction mixture was then aspirated below 35 C. to remove hexane, and finally subjected to vacuum of less trhan'l mm. for 2 hours to complete the removal of excess epichlorohydrin, leaving 119.3 g. of a viscous amber oil product (theory 119.7 g.) mainly of the formula yl n) o1cII orIcH2N-orI2orI2CH,Ncmortcmor),
H \OIH Example 4 In about 200 ml. of hexane there was dissolved 49.0 g. (0.15 mole) of pure N-n-octadecyl-l,3-propylenediamine (equivalent weight: 164, found; 163.3, calculated for C H N aided by gentle heating to 60 C. The
solution was cooled to 30 C. at which temperature there was added 52.1 g. (25% excess) of epichlorohydrin. The
total weight of the reaction mixture was 229.0 g. After stirring 48.5 hours at 20-25 217.6 g. (95% of the original reaction mixture) was aspirated to a viscous residue, to 25 C. (and finally to 35 C./ 0.2 mm.) to constant weight (total of minutes) leaving 84.6 g. of a light yellow hyd-noxypropyl -Noctadecyl- 1 ,3-propyllenediamine, which when treated with aqueous base in dimenhyil sulfoxide gave N,N',N tris(2,3 epoxypropylyN- octadecy'l 1,3- propylenediamine, having a glycidyl content which was 82% of the theoretical value.
Example 5 A mixture of 9.50 g. (0.050'm0le) of tetraethylenepentamine, 40.5 g. of epichlorohydrin, and 87.5 g. of methanol solvent was allowed to stand for 43 hours at 20-25 Aspiration of solvent and excess epichlorohydrin to 30/0.1 mm. left 36.9 g. of viscous amber product of which 21.3 g. was dissolve-d in 30 ml. methanol, cooled, and treated with 48.6 ml. of 3.82 N hydrogen chloride in methanol. The resulting hydrochloride was precipitated by slowly adding 250 ml. of ethyl ether to obtain a gummy product. The product was purified by redissolving it in methanol, clarifying with charcoal, filtering 01f the charcoal, and reprecipitating the amine salt product with ether. The product was aspirated to less than 1 mm. at 30 C. to remove retained solvents. The product had a neutralization equivalent of 243 (theory 204), analyzed as containing 36.63% total chlorine, 17.82% ionic chlorine, corresponding to an average of 4.9 chloropropanol residues and 4.7 hydrochlorides per mole of polyamine as compared with the maximum possible 7 epichlorohydrins and hydrochlorides.
Example 6 ether and hexane, the organic product layer was separated, dried over magnesium sulfate, filtered, aspirated to dryness below 25, down to 0.1 mm., leaving a viscous amber fluid, 16.4 g.- or 88% yield, calculated as the triglycidyldiamine.
This isolated product was analyzed by two methods for oxirane oxygen content. The Durbetaki titration (anhydrous hydrobromic acid in glacial acetic acid) indicated 5.30% oxirane oxygen; this figure was obtained after correction for the reagent used by the amine nitrogens. The Ross method gave a direct value of 5.24% oxygen after six hours at 60 in aqueous acetone with continuous neutralization with standard acetic acid. The excellent agreement of the two methods indicated that the product had 54.254.7% of maximum glycidyl content when compared to the theoretical 9.70% oxygen. The data illustrate the experimental difficulties of preparing and isolating these highly reactive products; this result is considered the best attainable on a practical preparative scale. Extensive experience with distillable diglycidylamines has shown that, using these same techniques, this type of purity data can be confirmed completely by isolation of pure materials in yields corresponding to the purity found.
Example 7 An amine mixture was prepared by adding 106.1 g. (2.0 mole) of acrylonitrile to 53.9 g. (0.20 mole) of n-octadecylamine, heating and stirring at reflux (77 C.) for one hour, then adding 1.0 ml. of 35% methanolic Triton B methoxide (benzyltrimethylammonium methoxide) catalyst, refluxing at 72-75 C. for 6 hours, neutralizing the catalyst with 2 milliliters of acetic acid, concentrating the reaction mixture under aspirator vacuum to 105 C. leaving 76.7 g. of crude product.
This material (37.6 g.) was reduced with 10.0 g. of 95% lithium aluminum hydride in 400 ml. of ethyl ether by stirring until hydrogen evolution stopped, cautiously adding about 20 ml. of water, 7 ml. of 20% sodium hydroxide and then 2.8 ml. more of water, filtering off the crystals (21.6 g. of octadecyl-l,3-propylenediamine), concentrating the filtrate to dryness to obtain an amine mixture, 14.9 g., having a neutralization equivalent of 150.3, indicating that the product was a mixture of 30% N'-noctade-cyldipropylenetriamine and 70% N-octadecyl-1,3- propylenediamine. This (14.2 g.) was dissolved in 100 ml. of hexane and treated with 19.6 g. of epichlorohydrin excess) and kept at 2l22 C. until the reaction had proceeded to 89% of theory, when two layers had separated. The excess epichlorohydrin and hexane were aspirated 01f to C./0.1 mm. leaving 26.5 g. of an amber oil, a mixture of the adducts of the starting amines.
Example 8 of which layer, did not change after 6 hours of additional stirring. The reaction mixture was aspirated and finally stirred at 35 C./1.0 mm. to remove hexane and excess epichlorohydrin; leaving 45.1 g. of an amber viscous oil product. The added weight due to epichlorohydrin reaction was 23.5 g. or 0.254 mole which.denotes an addition of 3.17 epichlorohydrin moles per mole of N-dodecyldiethylenetriamine starting material. The product is A small sample of this product was analyzed in acetone by treating it with excess 0.0932 N sodium hydroxide to dehydrohalogenate the chloropropanol groups. Upon back-titration with acid, it was found that the sample required 75% of theory for conversion of thc chloropropanol groups to glycidyl groups, based on 3 chloropropanol residues per mole of. the triamine. Ross analysis of glycidyl content showed 62% of the theoretical 3 per molecule for N-dodecyl N',N",N"-tris-(2,3-epoxypropyl) diethylenetriamine.
Example 9 In ml. of hexane there was dispersed 27.0 g. (0.10 mole) of N-keryldiethylenetriamine (assumed mol. wt. 269.46) prepared from a chlorinated kerosene averaging C The mixture was cooled to 20 C., and treated with 46.3 g. (0.50 mole) of epichlorohydrin, added rapidly. The mixture was stirred for 68 hours then evaporated under aspirator vacuum to low volume. At 15 C. the product formed a heavy layer. The mixture was further concentrated in a rotary evaporator at less than 25 C./ 1 mm. for a total of 4.5 hours leaving 58.7 g. of viscous amber oil as product mainly N-keryl (averaging C N',N",N" tris(3 chloro-2-hydroxypropyl)diethylenetriamine, containing an average of 3.43 chloropropanol moles per mole of the N-keryldiethylenetriamine starting material. The product was stored in a deep-freeze to prevent further reaction.
A portion of the product was later converted to the corresponding glycidylamine product requiring 68.3% of the alkali expected for 3 glycidyl groups per molecule.
Example 10 In 150 g. of methanol there was dissolved 14.6 g. (0.1 mole) of triethylenetetramine. The mixture was cooled to 510 C. and treated with 69.4 g. (0.75 mole) of epichlorohydrin (25% molar excess). The resulting reaction mixture was allowed to warm to room-temperature (2025 C.) in an ice bath. The mixture was allowed to stand for 76 hours, and was periodically sampled to determine the extent of reaction and then all but 15 ml. of the reaction mixture was cooled to 20 C. to stop the reaction. The mixture was later warmed and concentrated below 30 C./0.1 mm. to obtain'68.3 g.
(99% of theory) of a viscous pentakis(3-chloro-2-hydroxypropyl)triethylenetetramine.
A 35.3 g. portion of this product was redissolved in about 50 m1. of methanol by shaking at room temperature, kept below 25 C., and treated with 65.5 ml. of 3.82 N hydrogen chloride (0.25 mole of HCl) in methanol. The mixture was allowed to stand for 2 days and then aspirated to a viscous residue which was washed with 200 ml. of dry ethyl ether to purify the product. The product was aspirate-d to remove ethyl ether finally to less than 30 C./0.5 mm. Thedried product was broken up, redried at 1 mm. leaving 38.7 g. of penta(3- chloro-2-hydroxypropyl)triethylenetetramine tetrahydrochloride, which analyzed as containing 39.13% total chlorine, 17.14% ionic chlorine, 6.74% nitrogen corresponding to 5.0 3-chloro-2-hydroxypropyl groups and 4.4 hydrochloride groups per mole of triethylenetetramine 13 starting material, as compared with the maximum possible 6 3-chloro-2-hydroxypropyl groups and 4 hydrochloride groups per mole of the triethylenetetramine.
Example II tion for 4200 seconds, after washing. Samples of such paper cured at 105 C., for 60 minutes gave 8200 sec., before washing, and 12,000 seconds, after chloroform washing. Cured samples of such paper prepared using 5 triethylenediamine as a catalyst showed greater than 5500 This example illustrates the utility of the compounds 56661145 before g and 19,300 Seconds after chlofo" of this invention as cellulose modifying agents. For this {01111 gexample the compounds were tested as paper-sizing agents Anothel' pl Of the Same. O alkylrmainly according to various sizing methods: m) ,3-P YP PY -P py The following compounds were tested according to one n yd id salt sizing composition as a disperor more of the described sizing m thod sion was added to pulp containing 100 ml. of pH 9 buffer plus enough sodium hydroxide to neutralize all of the g gj ggggi ggggigfig 'ms(3'chloro'z'hydmxypm' hydrochloride present and leave a pulp of pH 9.1 after (2) N (tanw alkyl mainl & Nhmsedchlormb hydrochloride neutralization. Off machine samples of hydroxypropynd legedialnine paper formed from such pulp were tested for ink pene- (3 N (n octadecy l) N gi' 0x r0 tration and gave 4800 seconds, after washing with chloro- 1 p yp py form. Cured samples (105 C./60 minutes) gave 12,000 propy lamme seconds, after washing, and cured samples catalyzed with T tests d were as f ll triethylenediamine gave 18,300 see. after washing with Solvent .dip.-Dissolve 0.5 g. of the test compound in chloroform- 100 ml. of xylene, dip strips of Whatman No. 1 filter Control samples of paper treated with solutions haypaper into this solution. The concentration and pickup of mg 311 of the lngl'edlents except f test compounds 11! the solution is such that the treated paper has 0.35% by each 9 the abv test? were all instantaneously D weight of the test compound thereon, after drying. rated the Penetratlon test- Wet end meth0d.-In 5 ml. of xylene there is dissolved 0.75 g. of the test co'mpound. The resulting solution is Example 12 emulsified with 20 ml. of 0.1% hexadecyltrimethylam- To 10.3 g. (0.1 mole) of diethylenetriamine dissolved monium bromide, and this mixture is added to bleached in 125 g. of methanol, and cooled to 5-10" C., there was refined Gatineau sulfite pulp. The thus treated pulp is added 57.8 g. of epichlorohydrin (0.625 mole). The made basic with alkali to pH 9 and hand sheets of paper mixture was stirred, allowed to warm slowly to 20-25 C., are made from the treated pulp on the Noble-Wood maand sampled periodically to determine the extent of rechine. The dried paper directly from the machine is action. The reaction was allowed to proceed for 3 days termed off machine paper.- Cured samples of the treated during which time reaction proceeded to 104.6% of the paper are prepared by heating oil? machine paper in an theoretical amount for the addition of 5 moles epichlorooven for 60 minutes at 105 C. hydrin per mole of amine. The reaction mixture was The treated papers, prepared by any one of the above stored overnight in deep freeze (-20 C.) and then described methods are then tested according to the standaspirated to 30 C./1 mm. to remove methanol and exard ink penetration test in which the time, in seconds, cess epichlorohydrin, leaving 55.2 (100% theoretical required for ink to penetrate through the paper floating yield) of a very light yellow viscous oily gum. The prodon the surface of the ink bath is noted. not had a glycidyl equivalent of 65.5% of the theoretical Samples of the treated papers are washed in chloro- (NaOH back-titration method) and a glycidyl content of form for at least one hour, dried, and then tested in a. 52% of theory (Ross method). A portion of the prodsimilar manner in the ink penetration test. not was dissolved in methanol and treated with hydro- Some of the treated paper strips which were allowed chloric acid as described in Example 5 to prepare the hyto age or cure at room temperature for 29 to 38 days drochloride salt thereo. The hydrochloride product were also tested. l analyzed as containing 37.56% total chlorine, 14.66% The results were as follows: ionic chlorine, which corresponds to 5.3 moles of chloro- Cure Sizing c1101, Compound Percent Method of Application Unwashed Washed Time Temp. (Min) 0.)
0. as so 105 2, 500 4, 500 1. 0 (so 105 2, 500 4, 500 0.35 n) (0 3.200 1, 500 0. 35 Above paper stood 38 days 1; room i, 800 1, 700
temperature. 0.35 Wet End, paper stood 29 days at 500 7,800
room temperature.
1 08 machine.
The hydrochloride salt of N-(tallow alkyl-mainly C propanol and 2.8 moles hydrogen chloride per mole of N,N',N-tris(3-chloro-2-hydroxypropyl) 1,3 propylenediethylenetriamine, as compared with 5 moles of chlorodiamine was prepared by adding twice the stoichiometric propanol and 3 moles of hydrogen chloride for penta(3- amount of aqueous hydrochloric acid needed to form the chloro 2 hydroxypropyl)diethylenetriamine trihydrodichloride salt. The mixture was stirred overnight to chloride. obtain a dispersion of solid material in water. This dis- 1 claim: persion was added to bleached refined Gatineau sulfite 1. Acompound of the formula pulp containing 100 ml. of a pH butter (NaOH, KCl, 0 R 0 H 80 and additional sodium hydroxide was added to f i f neutralize all hydrogen chloride present. The pH of the C HOH:
pulp before the hydrochloride salt was added was 9.05. After neutralization the pH was 8.3. Chloroform was used to wash the paper for 1 hour.
In the ink penetration test of such salt treated paper wherein R is selected from the group consisting of alkyl radicals having from 10 to 25 carbon atoms, alkenyl having from 10 to 25 carbon atoms, alkyl-substituted phenyl,
sheets, the off machine" samples resisted ink penetraand biphenylyl radicals having from 10 to 25 carbon atoms and at least 50% of the Z radicals are the radical -C HgCHCHg 2. A compound according to claim 1 wherein. R is an alkyl radical having from 10 to 25 carbon atoms.
3. N dodecyl-N,N',N'-tris(2,3-epoxypropyl)-diethy1- enetriarnine.
4. N-n-octadecyl -'N,N',N' tris(2,3-epoxypropyl)-1,3- propylenediamine.
References Cited by the Examiner UNITED STATES PATENTS 8/ 1941 Schirm 260--348 X 5/1942 Bock et al. 117-443 X 9/1946 Borden et a1 117-154 5/1952 Daniel et al. 923
11/ 1954 Reynolds.
16 2,726,164 12/1955 Eichmeier l175.l 2,841,595 7/1958 Pezzaglia 260-3486 2,884,406 4/1959 Wegler et a1 260-348 X 2,891,970 6/1959 Frank et al. 260348.6 5 2,913,496 11/1959 Clutf 260-584 2,694,629 II/ 1954 Reynolds. 2,953,579 9/ 1960 Wil1iams et al. 260-448 2,969,302 1/1961 Green 162-164 3,031,505 4/1962 Pollitzer 260584 10 3,050,437 8/1962 Arlt 162-158 3,084,092 4/ 1963 Arlt 162158 FOREIGN PATENTS 933,219 12/ 1947 France. 15 955,835 1/1957 Germany. 1,132,146 6/ 1962 Germany.
OTHER REFERENCES McKelvey et al.: Jour. Org. Chem., vol. 24, pp. 614-616 (1959). 20 McKelvey et al.: Iour. Org. Chem., vol. 25, pp. 1424- WALTER MODANCE, Primary Examiner.
Assirtam Examiners.
|Cited Patent
|Filing date
|Publication date
|Jun 26, 1937
|Aug 12, 1941
|Heberlein Patent Corp
|Process of rendering textiles water repellent
|Dec 8, 1938
|May 12, 1942
|Rohm & Haas
|Process of waterproofing
|Nov 17, 1944
|Sep 3, 1946
|Riegel Paper Corp
|Antifungus wrapper, etc.
|Aug 3, 1946
|May 6, 1952
|American Cyanamid Co
|Wet strength paper and process for the production thereof
|Apr 18, 1951
|Nov 16, 1954
|American Cyanamid Co
|Production of sized alkaline paper
|Feb 28, 1952
|Dec 6, 1955
|Burgess Cellulose Company
|Stereotype mat
|Jan 31, 1955
|Jul 1, 1958
|Shell Dev
|Process for manufacture of glycidyl ethers of polyhydric phenols
|Sep 11, 1956
|Apr 28, 1959
|Bayer Ag
|Production of cured epoxide resins
|Dec 6, 1955
|Jun 23, 1959
|Farbenfabriken Bayeraktiengesedschaft
|Process for preparing basic
|Jun 7, 1957
|Nov 17, 1959
|Du Pont
|May 7, 1958
|Sep 20, 1960
|Shell Oil Co
|Epoxy aldimines
|Feb 14, 1957
|Jan 24, 1961
|Nalco Chemical Co
|Method of making paper
|Dec 3, 1958
|Apr 24, 1962
|Universal Oil Prod Co
|Amine-epihalohydrin-alkylene polyamine reaction product
|Jun 16, 1959
|Aug 21, 1962
|American Cyanamid Co
|Manufacture of sized paper
|Jun 16, 1959
|Apr 2, 1963
|American Cyanamid Co
|Sized paper manufacture
|Jan 28, 1955
|Jan 10, 1957
|Bayer Ag
|Verfahren zur Herstellung von nassfestem Papier
|Dec 6, 1954
|Jun 28, 1962
|Bayer Ag
|Verfahren zur Herstellung von basischen aliphatischen N-Diepoxyden
|Title not available
|Citing Patent
|Filing date
|Publication date
|May 26, 1969
|Dec 1, 1970
|Cassella Farbwerke Mainkur Ag
|Dyed textile materials having improved wet fastness properties and method of producing same
|Sep 13, 1974
|Sep 2, 1975
|Kao Corp
|Process for preparation of cationic polyurethane emulsions
|Sep 13, 1974
|Sep 2, 1975
|Kao Corp
|Process for preparation of amphoteric polyurethane emulsions
|Sep 13, 1974
|Dec 23, 1975
|Kao Corp
|Process for preparation of anionic polyurethane emulsions
|Jul 31, 2000
|May 20, 2003
|The Procter & Gamble Company
|Microorganism filter and method for removing microorganism from water
|Sep 16, 2008
|May 11, 2010
|Pur Water Purification Products, Inc.
|Water filter materials and water filters containing a mixture of microporous and mesoporous carbon particles
|Jun 22, 2010
|The Procter & Gamble Company
|Methods for treating water
|May 13, 2009
|Jun 22, 2010
|The Procter & Gamble Company
|Methods for treating water
|May 13, 2009
|Jul 6, 2010
|The Procter & Gamble Company
|Methods of treating water
|May 13, 2009
|Dec 14, 2010
|The Procter & Gamble Company
|Water treating methods
|Jul 10, 2009
|Apr 12, 2011
|The Procter & Gamble Company
|Water filter materials and water filters containing a mixture of microporous and mesoporous carbon particles
|Mar 7, 2011
|Feb 21, 2012
|The Procter & Gamble Company
|Water filter materials and water filters containing a mixture of microporous and mesoporous carbon particles
|U.S. Classification
|549/552, 564/506, 8/115.6, 162/158, 564/487, 564/367, 549/514, 8/196
|International Classification
|Cooperative Classification
|European Classification


text:
After what seems like years waiting for the impossible to happen, getting invited to the awesome inspiration bookmarking site, FFFFound, it happened. I have made passionate pleas before seeking invites, but always the same sad ending. However, on the 14th September 2009, someone heard my passionate request and sent me their one and only invite for FFFFound.
Thanks to @Embee
Huge thanks to Embee on Twitter for putting me out of my misery and sending me that one precious invite to FFFFound. I am very much in your debt, and been having lot's of fun with it.
Please don't email me asking for an invite. I don't have any to give.
My Profile on FFFFound
So if you have any interest in hooking up with me on FFFFound or just seeing the type of images that inspire me, then you can check out my profile : http://ffffound.com/home/imjustcreative/found/
Would you like a Sweetie? @ShareSomeCandy & Inspiration
Buying New Fonts for a New Logo Project – Risky Move?
If you're looking to hire a Freelance Logo Designer, or want to work with a multi-disciplinary Graphic Design Studio, then look no further than The Logo Smith.
With over 25 years experience,
I'd be thrilled to hear from you, and find out how I can help you with your logo and brand identity design requirements. Please visit my
Follow @thelogosmith
Home » Logo Design Blog | The Logo Smith: Freelance Logo Designer » Design Inspiration » FFFFound – Finally An Invite – Thanks to @Embee
More Logo & Graphic Design Posts -
Main Blog Index
Logo Artwork Sheet
Mentioned a few weeks back that I'd make a version of my Client Logo Artwork Sheet available as a quick downloadable template.
Here's that template: Logo_Artwork_Sheet_for_Download.zip, and it's pretty simples, and nothing at all
Great little find by John Gruber, of Daring Fireball, the other day: Evolution of the 007 James Bond Movie Logo Design, which was originally posted on The James Bond Lexicon, a Tumblr site.
Don't think I've ever really given
Free Font Katana's Edge, designed by Dimitris Bouskos, is one of many many many new free fonts that as graphic designers, we can all be a little grateful for.
The continued generosity of so many graphic and type designers, is
Happened upon this rather nice Ford Edge Ambigram car logo concept, by reddit user hadukem (don't have a website URL or anything like that, just the reddit link and the imgur link that hadukem posted to.)
Have read some of the
Testimonial: Homes Alive Pets Logo & Brand Identity Design
"Graham is the most legitimate logo designer I have ever met. His discovery process is thorough to ensure that he understands your brand so that he can
The Client Project Budget: Just one of a few tricky, and challenging, aspects of being a self employed freelance logo designer.
Well OK.
It's not tricky if a potential new client appreciates and understands the value of
Rocket Science VFX (tv and movie visual effects company), is a logo & brand identity re design project that I've been working on now for a little while now.
Just like a previous case study post
This free font: Apple-Sans-Adjectives is certainly quite fun, and intriguing, but not so sure on the practical side of things
Apple-Sans-Adjectives was designed [email protected] & @Rich_Cahill, and they have kindly made this font available as a freed
Some of you designers' may already be familiar with a few very challenging problems that I've experienced with VERY unscrupulous clients, and a very rigid and 'you are guilty until proven innocent' approach by Paypal.
Some of my
Came across this post on Virgin's official blog: Virgin Logo The original Virgin Logo Design was used for Virgin Records way back in the 1970's, and the logo was designed by English artist, and illustrator, Roger
Freelance Graphic Designers: How do you Find New Work and Clients?
Thought I'd poll all you freelance graphic designers, logo and web designers out there, and see how you all collectively find yourself new clients, or
VIEW'D - Logo Design Case Study
VIEW'D is a new logo design and iOS app icon design project, which I'm currently working on, and am happy to share the ongoing logo design case study of this
Work-in-Process: Wordpress Theme Developer Logo Design
'codetipi' is a logo design project currently in progress for a popular Wordpress Theme and Website Developer.
In this post are just a few snapshots of the later stages of the
New SETI Institute Logo Designed by Trevor Beattie
Only just received a press release for the SETI Institute Logo and branding redesign, designed by Trevor Beattie, Founder and Chairman of BMB.
This logo design has certainly piqued my interest, and I
Steve Jobs Tribute Typographic Poster Designed by Oliver Gareis
This Steve Jobs Tribute Typographic Poster has to be one of the best graphic design tributes I've seen in a while. Oliver Gareis has done an outstanding job
Custom Logo Designs For Sale
This page shows some of the custom logo designs that I have available, for sale, on here on this page: Custom Logos, Symbols & Icon Designs For Sale.
I have thought long and hard about having
My AC Academy Choir Logo Design Seen at the Royal Albert Hall
A short while back I took on pro bono logo design project for AC Academy, which is a London academy for children to take
NASA Mars Wanted Posters Designed by NASA
Been meaning to post a link to these NASA Mars Recruitment Graphic Design Posters for a while, but always something else getting in the way. Finally here we are,
Download Free Fonts and Specimens of Digital Typefaces by The Pyte Foundry
Where can I download free fonts and typefaces? Well, The Pyte Foundry is an interesting, and useful, typographic resource to add to your collection
What Kolor is this? Colour Matching Game by Jorge Moreno
There's not an awful lot to say about What Kolor is This, by Jorge Moreno, as it's pretty self explanatory as an online gaming concept.
However, don't be
Copyright © 2006-2016 All Rights Reserved Goddammit!
The Logo Smith : Freelance Logo Designer, Brand Identity & Graphic Design Studio
Providing PR Services with The PR Room: Technology PR, Smart Home PR, Internet of Things PR and Lifestyle PR Agency.
25 Years Experience in: Logo & Brand Identity Design, Graphic Design, Advertising, Marketing, and Commercial Print.
Website by Me
Built with Semplice;
Powered by WordPress;
Protected by CloudFlare;
Hosted by York Hosting;
Updated almost Daily.
The Logo Smith
Graham Smith
10 Badgers Copse,
Seaford, England
+44 (0) 7816 527 462
[email protected]
Home | Hire Me | Testimonials | Client FAQ | Portfolio | Monomarks | Case Studies | Contact | Blog | Logos for Sale | Logos in Use | Privacy | Subscribe

subset: commoncrawl


text:
By staff Writer |
November 4, 2003
Jason Weiner, manager since April 2003 S&P Ra
By staff Writer |
April 29, 2003
April 28, 2003 -- Less than a year after taking over Fidelity Fifty (FFTYX), portfolio manager J. Fergus Shiel has left Fidelity Investments. Shiel, who succeeded...
Secure the future of your business with customers from the largest generation in history.
Part II in a series of articles on working with ultra-high-net-worth clients from IMCA's Investments & Wealth Monitor takes a look at the biggest trends...
Maximize client retention and promote firm growth by using this 6 step interactive client review process.
Oct 05, 2016
Some broker-dealers have already decided to exit certain lines of business and are sizing up how the rule will impact their IT and compliance budgets....
Sep 21, 2016
Join Eric Ryles, Managing Director at Judy Diamond Associates, for a 60 minute session of mutual fund analysis within the Defined Contribution market. Using...
Sep 13, 2016
Nationwide is providing a deeper look into the rule's implications and a discussion of decisions firms will need to make in order to comply.
Copyright © 2016 ALM Media, LLC. All Rights reserved.
Advertisement. Closing in 15 seconds.
Register for an Account | Forgot Your Password


text:
The lab examined the items collected pursuant to search warrants for any evidence with potential relevance to the Diane Coates investigation.
The local newspaper reports on the arrest of Diane Coates' alleged killer.
The detectives interviewed the suspect arrested for killing Diane Coates at the Yoknapatawpha County Sheriff's Department.
Guest, you have 0 Case Credits.
Create a free account and earn Case Credits. If you already have an account, log in to see your current Case Credits. Redeem 200 Case Credits for a 30-day paid subscription.
Learn more about the benefits of paid subscriptions.
Crime Scene
3440 N 16th St, Suite #4
Phoenix, AZ 85016
Voice (623) 565-8573
Fax (602)-274-7280


text:
Fresh Air
Fresh Air with Terry Gross is weekday magazine of contemporary arts and issues with intimate conversations and unusual insights.
Recent Episodes
Best Of: 'Living (And Dying) While Black' / "Street Doctor" Treats Boston's Homeless
Author D. Watkins discusses growing up during Baltimore's crack epidemic. Maureen Corrigan reviews Jojo Moyes' novel, 'After You.' "Street doctor" James O'Connell treats Boston's most isolated patients, the homeless.
The Birth Of The Pill
In the '50s, four people collaborated to create a pill that would allow women to enjoy sex. Jonathan Eig details the history in 'The Birth of the Pill.' [Originally broadcast Oct. 2014.] David Edelstein reviews 'The Martian.'
Baltimore Author On 'Living (And Dying) While Black'
Author D. Watkins says that crack destroyed his East Baltimore neighborhood. "Everybody's parents were junkies, and all the kids were selling or using," he says. His new book is 'The Beast Side.' Book critic Maureen Corrigan reviews Jojo Moyes' novel 'After You.'
Tracing The Origins Of The Islamic State
Journalist Joby Warrick, author of 'Black Flags,' traces the Islamic State's development from an al-Qaida-related insurgency in Iraq to a successful jihadist movement that now holds territory in Syria and Iraq.
A "Street Doctor" On Caring For The Homeless
James O'Connell refers to himself as a "street doctor." Since 1985, he has cared for homeless patients in Boston, sometimes making visits on park benches or in alleys. His memoir is 'Stories from the Shadows.' David Bianculli gives his first impression of Trevor Noah's 'Daily Show' debut.
Actress Juliette Binoche / Palliative Care Nurse & Author Theresa Brown
Palliative care nurse Theresa Brown provides in-home, end-of-life care to patients. "It's incredible the love that people evoke" at the end of their lives, she says. Brown's new book is 'The Shift.' Julliette Binoche plays Antigone in a new translation of Sophocles' 2,000-year-old tragedy. The Oscar-winning actress spoke to Fresh Air contributor Anna Sale about acting, aging, and family.


text:
Hey, guys!
Just want you to know that a friend of mine just created a DA account! Care to show her some luv?
Here --> Anima-aminA
|I started drawing since I was 10, but ya know, my drawings were like crap . But know, I guess it's good but it is nowhere near Hiyonori- Yumiko profession but I'm learning and I'm getting better and that's what that counts.
|Can u guys donate some points to me? Please and thank u!


text:
A choice of a reliable broker company is a major task for any trader, as brokers not only act as an intermediary but also ensure transparency of transactions. Undeniably, any enterprise that offers broker services must have a spotless reputation and responsive client support.
In essence, a broker company is a liaison between the trader and the market. The speed and accuracy of order processing have tremendous effect on the end result — the client's profit.
FXFINPRO Capital has a long-standing reputation in the financial market as a reliable partner for traders in various trading venues. We give both beginners and professionals the opportunity to make profit from their talent in trading. We offer PAMM investments, trading binary options, stocks and futures as well as limitless opportunities in Forex.
On our website, you will find tons of useful information for trading such as statistics, analytics, and historical data. Beginners can hone their skill by practicing on a demo account, while professionals can appreciate some additional income working as traders or partners.
Today, Forex is the most accessible place for trading. The FXFINPRO Capital company has been known as a reliable Forex broker for many years. We offer our clients numerous instruments for working in the currency market. Modern platforms, high-performance programs, 24-hour information and analytical support from the professionals. All these services aim at making the work of traders the most comfortable and profitable.
Not all Forex brokers are the same. Why trust unknown and untested brokers with your money? The work of FXFINPRO Capital is regulated by the Cyprus Securities and Exchange Commission which guarantees its integrity and transparency in all transactions.
High service quality and professional approach to each and every client — all this helps us achieve the highest results. We work with you, for you!


text:
Nicholas Dellaventura's Family Sues High School for Football Workout Death
Last summer, 15-year-old Nicholas Dellaventura collapsed and died after a football conditioning sessions at St. Joseph by-the-Sea High School in Staten Island.
A year later, his mother thinks the adults who had been overseeing him should be held liable. Earlier this month, Maria Dellaventura sued the school, five of its employees, and the Archdiocese of New York.
The complaint, first reported by Courthouse News Service, claims that Dellaventura died from heat stroke.
It happened on July 23, 2012. Dellaventura had finished a 90-minute off-season workout with teammates. The 5-foot-8, 210-pound offensive lineman had played JV as a freshman and was preparing to step into a bigger role for his sophomore season. The group took a knee to hear coach Rich Clark speak.
Upcoming Events
New York Yankees vs. Los Angeles Dodgers
TicketsTue., Sep. 27, 7:05pm
New York Yankees vs. Boston Red Sox
TicketsTue., Sep. 27, 7:05pm
New York Rangers vs. New Jersey Devils
TicketsThu., Sep. 29, 7:00pm
New York Yankees vs. Baltimore Orioles
TicketsFri., Sep. 30, 7:05pm
The New York Post reported at the time that, according to New York Archdiocese spokeswoman Fran Davies, "As Clark addressed the team, coaches and teammates realized Dellaventura was struggling to breathe and couldn't stand up on his own."
The called 911 and an ambulance rushed him to Staten Island University Hospital. He died there.
The workout, for which Dellaventura wore shorts and T-shirts, had started in the late afternoon. Dellaventura reached the hospital at 6:09 p.m. And the day hadn't been particularly hot--in the mid-80s, CBS News reported.
A week after the death, news outlets reported that initial autopsy reports had been inconclusive as to the cause of death. There were signs, however, that pointed to heat stroke. The boy's body temperature soared, and he succumbed to cardiac arrest.
On July 31, 2012, Dellaventura's death was briefly mentioned in a New York Times story headlined, "Families of Athletes to Sue Over Heat-Related Deaths."
The story focused on two families, one from Georgia and one from Florida, "whose sons died last summer after strenuous workouts" and who were "suing in hopes of holding school officials accountable."
Over the past 20 years, the Times noted, 40 high school football players had died from heat stroke, according to the National Center for Catastrophic Sport Injury Research at the University of North Carolina.
The article continued:
Most of the deaths have taken place during initial summer workouts, when the heat index is high and players are out of shape, said Lesley Vandermark of the Korey Stringer Institute, which seeks to prevent deaths in sports, particularly heat-related ones. Mr. Stringer, who played for the Minnesota Vikings, died of heat stroke after a practice in 2001.
Most of these deaths are preventable, Ms. Vandermark said, adding that high school coaches need to be better educated about heat stroke and need to move slowly into conditioning sessions.
Whether that was the case with Dellaventura's death and whether that means his school should be held liable will now be for the courts to decide.
Send story tips to the author, Albert Samaha
Follow @villagevoice
Get the This Week's Top Stories Newsletter
Every week we collect the latest news, music and arts stories — along with film and food reviews and the best things to do this week — so that you'll never miss Village Voice's biggest stories.
In Case You Missed It
Upcoming Events
New York Giants vs. Washington Redskins
TicketsSun., Sep. 25, 1:00pm
New Jersey Devils vs. Philadelphia Flyers
TicketsMon., Sep. 26, 7:00pm
New York Islanders vs. Philadelphia Flyers
TicketsMon., Sep. 26, 7:00pm
New York Rangers vs. New York Islanders
TicketsTue., Sep. 27, 7:00pm
Popular Stories
Sponsor Content


text:
did we trade the wrong goalie?
Halak leads, or is tied for the lead, in all goalie categories...
This place is in love with price and, I don't understand why, he has done nothing special; yet, he's treat as if he is some god.
He reminds me of Luongo, and his time in florida, except without such good numbers on a bad team.
Halak reminds me of Kipper, a guy that can win games on his own but will have his share of off nights.
IMO, we traded the wrong guy, and we probably get more for price.
Is this for real? He had a 14 save shutout.
Sometimes I question the sanity of this fanbase.
in on roll bread
Is this real life?
Is this just fantasy?
Wow, the stupid threads are really coming out this weekend aren't they?
Oh boy...:badidea:
Not even sure if this is a troll thread
We should've kept Aebischer.
Hahaha after one game Halak is leading in all categories! We have no issues at Goalie but we def need some help scoring and i cant wait till PK comes back as the PP gave me nightmares last night I woke up in my sleep last night screaming " SET up the box and Pass!!!!!" fer f sakes it was just a bad dream! lol
Halak faced 14 shots yesterday. 2 in the first period. He only made one good save in the only real scoring chance. St. Louis runs a very effective machine that will make every goalies look good. Hell, even Elliot was spectacular in the Hitchcock system. Put Price on that team and you would get similar or better result.
No we didn't, but we didn't get nearly enough for Halak.
I still feel Carey gets adored a little too much around here. I don't think he's anywhere near a top 5 goalie and certainly not worth being the 3rd highest paid goalie in the league, but he's a very good goalie. I was happy either way.
Just a word of advice. You lose a bit of credibility posting this immediately after Halak records a 14 save shutout though.
Nothing good will come from this thread..
It's gotta be a joke thread? right.... Righttttt RIGHT?
|All times are GMT -5. The time now is 05:25 AM.
vBulletin Copyright ©2000 - 2016, Jelsoft Enterprises Ltd.
HFBoards.com, A property of CraveOnline, a division of AtomicOnline LLC ©2009 CraveOnline Media, LLC. All Rights Reserved.


text:
rating plugin
This project is now closed with a project budget of $8 - $15 USD / hour.Get free quotes for a project like this
Skills Required
Project Budget$8 - $15 USD / hour
Project Description
I'm looking for a rating plugin made or modified for a forum.
Here's what I'm looking for:
1) rating feature shows up ONLY in 1 section of forum.
2) rates ONLY the responses—NOT the question.
3) ONLY admin posts questions. In other words, it can't be a "post a
new topic" option. The end result needs to be where ONLY admin posts the
question; the responses get rated, the top rated responses automatically keep
flowing to the top WITHIN each specific query.
4) rating system of a 1 thru 5 (not likes or thumbs etc...) with #1 being the best solution
and so on down. I see where some rating plugins use a % basis.
This could be used to auto-track where each solution lands within
each query. For instance, 25 solutions with the top rated one holding
top spot on down.
5) users can choose to either: 1) have their post rated or simply rate
other posts, up to a total of 5.
6) users must be able to adapt their solutions to the feedback being
offered. Possibly an icon indicating solution has been modified?
7) users must be able to readjust how they rate solutions. Possibly the %,
the individual users chosen rating preference, and the overall rating of each solution,
could all be consolidated and easily seen, located in the top right corner within each solution?
This way, users could keep track of their preferences and readjust them more easily.
Thank you.
Looking to make some money?
- Set your budget and the timeframe
- Outline your proposal
- Get paid for your work
Hire Freelancers who also bid on this project
Looking for work?
Work on projects like this and make money from home!Sign Up Now
- Forbes
- The New York Times
- Time
- Wall Street Journal
- Times Online


text:
Online Teaching Assistant Course£99 instead of £274 (from My Distance Learning College) for a Level 3 or Level 4 NCFE-accredited online teaching assistant course - save 64%
A Level 3 NCFE-accredited online teaching assistant course from My Distance Learning College (was £274) OR redeem towards another Wowcher deal.You save 64% (£175)
A Level 4 NCFE-accredited online teaching assistant course from My Distance Learning College (was £274) OR redeem towards another Wowcher deal.You save 64% (£175)
Save 64%
Time left to purchase
- A Level 3 or 4 NCFE-accredited teaching assistant course.
- 24/7 access for 12 months.
- Approx. 100hrs of study inc. child development, activities and more.
- No entry requirements and certificate upon completion.
- Perfect if you're looking for a career in teaching!
The Fine Print
- May buy multiples.
- Voucher valid for redemption until 4th March 2014.
- Subject to availability.
Full Details
Don't worry about teaching a man to fish, not when you can teach yourself to become a teaching assistant...
Today we're offering you a Level 3 NCFE-accredited online teaching assistant course or a Level 4 NCFE-accredited online teaching assistant course for only £99, saving you 64% off My Distance Learning College's price of £274 (correct as of 14.2.14).
With 24/7 access to the online teaching assistant course for one year, training to become a teaching assistant couldn't be easier no matter how busy your schedule is! There's even an online student portal where you can get tutor support if you're struggling. The Level 3 course covers approximately 100 hours' worth of material split into the following modules:
- Unit 1: Child Development
- Unit 2: Safeguarding Children
- Unit 3: Supporting Children and Young People's Health and Safety
- Unit 4: Personal Development
- Unit 5: Supporting Learning Activities
- Unit 6: Developing and Maintaining Positive Working Relationships
- Unit 7: Promoting Equality, Diversity and Inclusion
- Unit 8: Schools as Organisations
The Level 4 course also covers approximately 100 hours' worth of material and examines the core learning structure as well as more specific parts of the curriculum. For a full breakdown of the modules, click here and select the Snapshot tab.
Upon completion, you'll receive a NCFE-accredited Level 3 or Level 4 Teaching Assistant Certificate as proof of your newly found skills. And the best part? There are no entry requirements, so whatever you're currently doing in life, it's not too late to change for a more rewarding career!
How to Redeem
- When the deal ends we'll send you your unique wowcher code.
- Head to My Distance Learning College's site using the link we send you.
- Click to enrol.
- Enter your wowcher code when prompted.
Once purchased, you can redeem this wowcher towards another wowcher or claim a Wowcher Wallet Credit. Click here for more info.
Wentworth Castle Gardens, Playground & Parking for 2£8 instead of £15.50 for two adult tickets including parking to Wentworth Castle Gardens, Barnsley - save 48%
Teaching Assistant, SEN & Managing Behaviour Level 3 Course£29 instead of £299 for an online Level 3 SEN teaching and SEN teaching assistant course or £405 for a classroom taught course from Mary Kay Jenny - save up to 90%
Save 90%
Time left to purchase
10 EuroMillions Line Bets for the Massive £112 Million Jackpot!£9 instead of £20 (with Lottoland) for 10 EuroMillions line bets in Friday draws - try your luck on the gigantic £112 million jackpot and save 55%
Save 55%
Time left to purchase


text:
BB Dakota 'Colton' Faux Fur Vest
Women's Kyi Kyi Genuine Fox Pompom Hat -
A genuine fox-fur pompom adds a posh upgrade to a cozy knit hat hand-crafted in Canada. Color(s): black, black multi, black/ silver tip, blue, blush, bordo/ bordo, charcoal/ charcoal, cobalt, dusty blue/ teal, fuchsia, green, ivory, ivory w/ lynx dye, navy, rose/ rosewood, turquoise, wine. Brand: KYI KYI. Style Name:Kyi ... Learn More
Women's Nordstrom Cashmere & Silk Wrap, Size One
Delicate eyelash fringe travels the edge of a gauzy cashmere-blend scarf. Color(s): aqua plumage, beige rainy day, black, blue agiers, blue atal, blue cashmere, blue fog, blue horizon, blue kentucky, blue lapis, blue mazarine, blue merlin, blue regatta, blue sea, blue shadow, blue true, blue turquoise, blue wing, burgundy beauty, ... Learn More
Women's Echo Bouclé Cape, Size One Size - Black
A staple layering piece offers a long length of cozy softness in a plush bouclé knit that defines this fringe-trimmed cape. Color(s): baby camel, black, cream, deep denim, forest berry, light grey, navy, pomegranate. Brand: Echo. Style Name:Echo Bouclé Cape. Style Number: 1164778. Available in stores. Learn More
Women's Rag & Bone 'Tamara' Cashmere Scarf, Size
Faint speckles dapple a wide, lavish scarf knit from ultrasoft cashmere.Pre-order this style today! Add to Shopping Bag to view approximate ship date. You'll be charged only when your item ships. Color(s): black, grey. Brand: RAG AND BONE. Style Name:Rag & Bone 'Tamara' Cashmere Scarf. Style Number: 5177205. Available in ... Learn More
Women's Hide Society Hooded Plaid Cape With Genuine
The brushed surface of this woolen cape softens the lines of a magnified plaid, enhancing the cozy, warming feel of a whimsical alternative to the usual cold-weather fare. Silvery fox fur trims the edge of the hood, adding face-framing warmth and a touch of retro romance. Color(s): grey/ black plaid. ... Learn More
Women's Bun Maternity 'Cozy Up' Maternity/nursing Poncho, Size
An ultra-chic knit poncho with an asymmetrical hemline adds a versatile layering essential to your maternity wardrobe and perfectly transitions to post-pregnancy wear. When you're ready to nurse, just flip up the front layer for discreet access. Color(s): black, cocoa, grey, teal. Brand: Bun Maternity. Style Name:Bun Maternity 'Cozy Up' ... Learn More
Women's Halogen Faux Fur Pom Bag Charm -
A clip-on pom bag charm is made from soft, fluffy faux fur and adds a touch of whimsy to your look. Color(s): black, grey griffin, ivory pristine, pink cement, pink cyclamen, purple cosmic, tan hazel, tan praline, white snow. Brand: HALOGEN. Style Name:Halogen Faux Fur Pom Bag Charm. Style Number: 1174490. Available in stores. ... Learn More
Women's Ugg Australia Water Resistant Quilted Hat With Genuine
A plush sheep-fur pompom tops a cute diamond-quilted beanie cut from lustrous water-resistant fabric. The cuffed brim can be worn folded up or down for a slouchier, more relaxed look. Color(s): black multi, grey, white multi. Brand: UGG AUSTRALIA. Style Name:Ugg Australia Water Resistant Quilted Hat With Genuine Shearling Pompom. Style Number: 1175104. ... Learn More


text:
Small Bright Spot In J.J. Watt Injury"I think we played pretty good without (Watt)," Jadeveon Clowney said, "but that was preseason, this is the regular season, we're getting everyone's best right now."
With Run Game Slowed, Lamar Miller Knows He Needs To Be More Aggressive"I think we're very close, I think I have to do a good job at the second level, making guys miss," Lamar Miller said of the run game breaking out.
Texans Will Have A Tall Task Stopping The Run With The Titans In Town"(Murray) is doing an excellent job," Bill O'Brien said. "He's running hard, he breaks tackles, he's got good vision, he's an excellent running back."
Special Teams For The Texans Haven't Been Very Special"We just got to focus and improve on the little things that we can," Charles James said.
Daune Brown Say's "It's A Possibility" About A Return This Sunday"Feeling really good today, probably do a little more tomorrow and go from there," Duane Brown said.
Antonio Smith "Always Knew" He'd Be Back On The Texans"No replacement at all," Smith said of stepping in for Watt, "I'm just here to help the team out as best as I can."
Brian Cushing Practices And Is Close To A ReturnThe Houston Texans received a needed boost to the team with middle linebacker Brain Cushing returning back to practice Wednesday.
Robinson Cano Hands The Astros A 4-3 Loss"He's a great player everybody knows that," Jose Altuve said of Cano, "Luke (Gregerson) made a really good pitch and I don't know how Robbie hit that ball."
Former Tiger Alex Bregman "Shocked" By Les Miles Firing"I'm interested to see who they bring in that will be better than him," Alex Bregman said of the Tigers firing Les Miles.
Texans Defense Is Getting Hard To Game Plan For"I think we have a ton of guys who make plays and a ton of guys coming from all different ways," J.J. Watt said.
Jacoby Brissett Not A Total Unknown To The Texans"We spent a lot of time on Jacoby (Brissett) in the draft, we spent a lot of time on Jacoby in the preseason," head coach Bill O'Brien said
Bill O'Brien Says RB Jonathan Grimes Is An Unsung Hero"Probably one of the unsung hero's of our team," Bill O'Brien said of the contributions from Grimes


text:
Manufacturing Area
Category: Cabinet Handles
Finish: Polished with Lacquer Nickel Plated Chrome Plated Antique Brass Antique English Antique Silver/Pewter Antiqu ...
Category: Closet Organizers
1. Great for suits,coats,sweaters,shoes and other items storage 2. Eco-Friendly, Folding Hanging closet Organizer 3. closet Organizer can be folded up to save spaceKeyword : closet organizer | quilt closet organizer storage box | underwear sock closet organizer | closet organizer
1. Great for suits,coats,sweaters,shoes and other items storage 2. Eco-Friendly, Folding Hanging closet Organizer 3. closet Organizer can be folded up to save spaceKeyword : hanging closet organizer | hanging closet organizer
Category: Closet / wardrobe organizers
Our RIO closet system features a full steel construction and a soft touch extra closet cover. It is the answer to guest room and extra storage anywherKeyword : closet | storage closet | non woven closet
--Durable industrial plastic joints and steel construction --Extra storage shelf space --Heavy duty breathable TNT cover --Large capacity clothing storage Storage closet size:75WX50DX160H CM ma ...Keyword : closet | storage closet | non woven closet
Category: Furniture Knobs
Item No. AT408 Material: stainless steel Size: 16mmD x 20mmH Size: 20mmD x 24mmH Size: 25mmD x 30mmH Size: 30mmD x 37mmH Finish: brushed Keyword : knob | cylindrical knob
2 shelf mini closet, product size: 45x70x160cm, I set in one box, inner box size:72x48x6.5cm 5sets in one carton. . carton size:73.5x50x33cm,G.W/N.W:24/23kg.cover cloth with non-woven, oxford canvas f ...
DIY Walk-in Wardrobe Size, Color and Design can be customized (1)Material: High quality Aluminium alloy frame ensure durability (2)Elegant and graceful appearance enhance image. (3)Used for livin ...Keyword : Aluminium Closet
Beautiful granite knobs, drawer pulls, doorknobs, for kitchens & baths, custom made to match your counters by Highly skilled Craftsmen. Our high quality polished granite knobs, Natural granite cabinet ...
Item No. AB016 Material: brass Size: φ29.5mm*37mmH Finish: SL, SC, PL, DC, PC, DN Keyword : knob | cabinet knob | furniture knob | brass knob
Item No. AB014 Material: brass Size: φ31mm*32mmH Finish: SL, SC, PL, DC, PC, DN Keyword : knob | furniture knob | brass knob
Item No. AT407 Material: stainless steel Size: 25mmD x 26mmH x 2.5mmT Size: 30mmD x 33mmH x 2.5mmT Finish: polished / brushed Keyword : knob | stainless steel knob | door knob
good quality reasonable price Keyword : furniture knob
Category: Wardrobes / Closets
Wardrobe home wardrobe doors France style wardrobe wardrobe closet wood wardrobe FCD-128 Production Descroption: Wardrobe home wardrobe doors France style wardrobe wardrobe closet wood wardrobe ...Keyword : wardrobe closet
Category: Gear Shift Knobs
1. Auto parts gear shift knob description: 2.High quality walnut cover with microfiber leather ball shift knob. 3.Customized shift knobs for auto spare parts. 4.OEM order accepted, small order is also ...Keyword : Auto parts gear shift knob | ball shift knob
Quick Details Type:Bedroom Furniture, bedroom wardrobe Specific Use: Wardrobe Material:Wooden Brand Name:Yoochoice Place of Origin:Guangdong China Des ...Keyword : sliding closet doors
1. Suitable for furniture cabinet 2. Using raw material, enough weight 3. Professional design team provide you own customizKeyword : stainless steel knob | furniture knob | cabinet knob
1.Exquisite workmanship. 2.Use raw material, excellent stability, long life time. 3.Professional design team will make the private custom packing for you.Keyword : crystal knob


text:
Danial AhmedShared publicly -
View original post
The World is Not Enough: Eilean Donan Castle, Scotland. During this Bond adventure, the villains destroyed MI6 headquarters on the South bank of the Thames. However, as luck would have it the world's most secret spy agency had a standby office in what is one of Scotland's most beautiful locations.
Add a comment...


text:
Home > Sunglasses > Marc Jacobs > MJ 624/S (L2A/99)
New Releases
Size and availability
Free outbound and return shipping
30-day money-back guarantee
Low prices
Free outbound and return shipping
30-day money-back guarantee
Low prices
MJ 624/S/L2A/99 Ophthalmic Glasses
MJ 624/S is a fashion statement, for which sunshine is not necessarily required, because these sunglasses enhance your natural radiance turning night into day. The MJ 624/S is available in the Edel-Optics online shop in other styles from Marc Jacobs collections 2015 and 2016.
With no frills and state-of-the-art materials and craftsmanship, these men's glasses stand for stylish design and self-confidence. Minimalism, like rimless eyewear, never goes out of fashion. MJ 624/S comes paired with timeless elegance. 7. Eyeglass frames (shape) This epitome of aviator sunglasses from the house Marc Jacobs is distinguished by their characteristically large lenses and thin frame. The model a sure hit, not only in the cockpit of an airplane. The noble metal frame allows for filigree lines and creates an extraordinary lightness in appearance. In addition, metal eyeglasses are virtually indestructible - strong, flexible and corrosion resistant. The colour gold is absolutely hip in 2016. This Marc Jacobs lends any outfit a certain something. With gold, darker skin types can never go wrong. You can rely on the guaranteed UV400 protection, for all the sunglasses in our shop.
Even if this Marc Jacobs is presently not in stock, it is worth ordering now, because the current price can't be beaten. If you buy at Edel-Optics you get the best price, because "in the sale" is our standard.
New Releases
Need help?
Don't hesitate to call us at
payment methods


text:
realmagick.com The shrine of knowledge.
- 'Spotlight' Wins Big at Academy Awards
- Unfortunately Geigon used to go on trips with boys and one time he got in an accident and one of the sons got killed.
Geigon is described in multiple online sources, as addition to our editors' articles, see section below for printable documents, Geigon books and related discussion.
Suggested News Resources
Great care has been taken to prepare the information on this page. Elements of the content come from factual and lexical knowledge databases, realmagick.com library and third-party sources. We appreciate your suggestions and comments on further improvements of the site.
Geigon Topics
About - Contact - Advertising
© 2000 - 2016 Realmagick.com, All Rights Reserved.
© 2000 - 2016 Realmagick.com, All Rights Reserved.


text:
Pokój z widokiem na ogród świetlisty
Maks. liczba gości2
Rozmiar15 m²
- Przyjazny dla rodziny/dzieci
- Internet
- Wanna z jacuzzi
- Balkon/taras
- Ręczniki
- Łóżeczko dziecięce
|Greene Avenue, NY 11221 New York, Stany Zjednoczone
|Rodzaj nieruchomości
|Prywatny pokój
|Kod referencyjny
|Wskaźnik odpowiedzi
|Czas reakcji
|Kilka godzin
|Zaktualizowano kalendarz
|Tydzień temu
Mieszkanie znajduje się w pobliżu Manhattanu, jest tylko trzy przystanki pociągiem i łatwo dojechać z lotniska JFK.
Tu można łatwo znaleźć targowiskach takich jak Hattie Carthan Wspólnoty Garden, Marcy Avenue. między Lafayette i Clifton w soboty (9am-3pm) i Hattie Carthan po rynku kościół na 49 Van Buren między Throop. Poza tym, trzeba także Tompkins w niedziele (1-6pm) lokalnie uprawianych jedzenie jedzenie organiczne warzywa, owoce, jaja, surowe miód.
Nie nadużywanie alkoholu.
Brak strony lub zwierzęta domowe.
Absolutnie nie ma palenia w domu.
Nie przeszkadza sąsiedztwa. Domy tylko.
Brak buty noszone w domu. Przynieś kapcie.
Nie śniadanie, ale można kupić przyzwoite śniadanie na sklep spożywczy delikatesy rogiem: pozycje z kanapki, herbatę, kawę, ekologicznej gorącej czekolady.
W lecie lub wczesną jesienią można odpocząć i zjeść śniadanie w ogrodzie ogromne czerwone klony pełne śpiewu ptaków.
Opłata za sprzątanie w wysokości $ 15, jeśli pokój jest brudny zapewniamy miotłę, dzięki czemu można utrzymać pokój w idealnym stanie, jak jej otrzymaniu.
Kaucja w wysokości 20 dolarów za klucze.
Nic innego niż papier toaletowy w łazience proszę zapewniamy śmietnika produktów kobiece zabezpieczeń.
Upewnij się, zabrać śmieci codziennie. Recykling jest prawo. Zapewniamy wszystkie informacje na temat tego, co można oddać do recyklingu lub nie.
Proszę umieścić swoje torby na śmieci na zewnątrz.
Przewodnik turystyczny (francuskim i angielskim) dostępne książki i broszury.
|Opłata tygodniowa
|1749 zł
|Maks. liczba nocy
|3 tydzień
|Zameldowanie po
|Zameldowanie przed
|Do ustalenia
|Wymeldowanie przed
|Zasady Anulowania Rezerwacji
Our stay was amazing. The hosts were so friendly and helpful. The room was tidy and cozy. We had a great time.
My dad and I spent a really nice week in New York and our accommodation at Ceciles's was very nice!
The room was comfortable and bright. We had access to the garden, wifi and an own bathroom. Everything worked out well and I can recommend this place to any other visitor who has no big claims but want to stay at a pleasant family with a good connection to Manhattan. (The next train station is 10-15 minutes away.)
I will come back - not yet but anytime! :)
Kind regards from Germany - Hamburg!
We stayed for two weeks and Cecile and her family were perfect hosts, very helpful and kind. The apartment was located very close to the subway just a few stops away from Soho, Manhattan. The room and toilet was clean and as described in the information on Wimdu. This is a very good place to stay if you want to save some money and still have a place to crash near Manhattan.
This is a nice room in Brooklyn. Cecile and her husband are very kind en helpfull. We could rent for a small amount two bikes with which we cycled through Manhatten. The place is about half an hour from downtown Manhatten (10 minutes walk, 20 minutes metro)
We would like to thank Cecile, Ndong & their lovely family for having been so welcoming throughout our stay. The communication with them prior to our arrival was flawless. The room and the bed were extremely clean, as well as the bathroom. The apartment is well connected to public transportation which makes it possible to be in Soho within 25min. Supermarkets & restaurants are close by.
Unfortunately room and bathroom are on two different levels, with stairs leading downstairs to the bathroom were the family lives. Walking down the wooden stairs at night is definitely a safety issue - apart from the fact that it is simply not convenient! Another factor was the noise level which was described as being ´unusually high´ during the 3 nights of our stay (neighbors ringing the bell around midnight, loud conversations outside the room, alarms going off, etc.) - and here I´m explicitly taking out the three lovely kids!
In summary: A good place for first time NYC visitors who want to explore the city and simply need a clean place to crash.
We very much enjoyed our stay with Cecile and her family. They were friendly and helpful. The room was bright and clean, we even had our own bathroom.
We liked the neighborhood, it's safe to walk around and the subway is near by.
Cecile and her family were really nice and friendly. The room and bathroom were very clean.The neighbourhood was very safe and friendly. Walking distance to subway station is about 5 mins. Had a great time there. Thank you.
If you like to get to know a really nice and warm family and if you also want to sleep in a tidy, clean, silent room you should go to the house of Cécile and family. We had a great time there. The way to Manhattan is short by taking the subway near the house. The bathroom is also clean. You will like it. :-)
New York is always a good idea- crazy, different and nice. The people we've met there are so kind and friendly.
Thank you very much for your friendly welcome. We loved it to stay in your house.
The family is very pleasant and they made us feel welcome. Cecile and her husband were ever so helpful. The room and bathroom were spotlessly clean. We hope to be able to come back one day. Thank you again!
Staying with Cecile and her familie was just awesome. They were so nice, helpful and always interested in our activities. We really appreciated all their help, good advises and their good nature. The whole familiy has been always in a good mood and especially the kids are very well accomplished and so lovely. In addition,having your privacy is not a big deal, we felt all the time very well. All in all I can say that staying with that family has broaden our horizons and it has been a really worthwhile experience to us, which we would repeat immediately. Thank you very much....We will keep that time in mind :D
- Gwarancja jakości zakwaterowania
- Każdy gospodarz jest weryfikowany telefonicznie
- Bezpieczna płatność za pomocą szyfrowania SSL


text:
Have you visited Dr. Nicholas Soter? Rate you experience below.
Dermatologists in New York, NY
Dr. Nicholas Soter specializes in dermatology in New York, New York.
Dr. Nicholas Soter has been compared 77 times. Details of Dr. Soter's 51 years experience as an MD and education at University of Texas are available on your free doctor report.
Dr. Nicholas Soter has an average rating of 5 stars (out of 5) with a rating of Excellent based on 4 reviews.
Have you visited Dr. Nicholas Soter? Rate you experience below.
Dr. Nicholas Soter has been identified as specializing in Dermatology.
He is certified in Dermatology.
Dr. Soter attended medical school at University of Texas Southwestern Medical School and graduated in 1965 having 51 years experience.
While there is no proven correlation between the quality of one's educational institution and the quality of one's professional competence, it is often an indicator. Medical schools have various levels of selectivity (some are harder to get into than others), and both the quality of their clinical training and level of research are measured. Additional medical training in both residency and fellowships and the facilities they are conducted at also provide a history of the doctors' level of training and experience.
Patients may also know Dr. Nicholas Soter MD as:
156 E 79th St, Apartment 9A New York, NY 10075
Dermatology 315 West 57, 315 W 57th St, Suite 405 New York, NY 10019
250 W 57th St, New York, NY 10107
Adelle Quintana MD, 130 W 42nd St, Suite 1900 New York, NY 10036
153 E 88th St, New York, NY 10128
Are you Dr. Nicholas Soter?
Update your information


text:
Gery Woelfel: You knew this was inevitable: A source tells me a Western Conference team has had internal talks about possibly signing Larry Sanders.
Larry Sanders back to the NBA?
September 26, 2016 | 9:35 am EDT Update
Paul Pierce will retire after this season
Paul Pierce: This is it, my final season. It's time to move on from the game of basketball. Just like any difficult decision, I think you've got to be at peace with yourself. I'm at peace with retiring, but I've got one more ride left. One more season. One more opportunity.
Paul Pierce: With the Clippers, in the city where I grew up, I feel like I have that opportunity on a great team. We're hungry. We want to win a championship. After 18 NBA years, it's hard to believe I'll be playing in each arena for the last time. So I'm going to enjoy every practice, every bus ride, every team dinner, every time running out through the tunnel. I'm going to do my part to give us a shot at the ultimate goal.
Jake Fischer: Paul Pierce told me in July former Wizards teammate Marcin Gortat watched him play as a kid. 19 years will be quite the run for Pierce.
September 26, 2016 | 8:51 am EDT Update
Smith has been in town all weekend (he attended at least two Indians games) and the two sides have maintained dialogue on a new contract, but there was no deal as of Sunday night.
A small portion of Liggins' two-year, roughly $2 million contract is guaranteed, a team source told cleveland.com, and the second year of the deal is a team option. The significance is Liggins is the 14th player coming to camp with at least a portion of his salary guaranteed — it means the Cavs think he has a better chance to make their 15-man roster than the players in camp whose contracts aren't guaranteed.
Yormark, the CEO of Brooklyn Sports and Entertainment, the Nets parent company, didn't identify the brands nor give a timeline for when a deal could be done. According to Sports Business Journal, the Nets are seeking "high seven figures" from advertisers. The patch, which the NBA describes as Post-It note sized, won't be worn until the 2017-18 season. There has been only one deal since April. between StubHub and the 76ers. And SBJ notes, the market for the patches is much smaller than the league and teams had projected.