|Publication number||US1970578 A|
|Publication date||Aug 21, 1934|
|Filing date||Nov 24, 1931|
|Priority date||Nov 29, 1930|
|Publication number||US 1970578 A, US 1970578A, US-A-1970578, US1970578 A, US1970578A|
|Inventors||Schoeller Conrad, Wittwer Max|
|Original Assignee||Ig Farbenindustrie Ag|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (339), Classifications (63)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Patented Aug. 21, lose I 1,970,578
UNITED STATES PATENT OFFICE ASSISTANTS FOR THE TEXTILE AND RELATED INDUSTRIES Conrad Schoeller and Max Wittwer, Ludwigshafen-on-the-Rhine, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankiort-on-the-Main, Germany No Drawing. Application November 24, 1931, Serial No. 577,148. In Germany November 29, 1930 15 Claims. (Cl. 260-98) The present invention relates to assistants for icles into the carboxylic acids correspond to the the textile and related industries. eneral formula We have found that valuable products are obtained by introducing into any water-insoluble R'CO OC2H4*) OCH2CH2 OH Organic mp nd c nt n at least one rcin which RC0 is the acid radicle of the carboxylic 55 active hydrogen atom, i. e. at least one hydroxyl, acid and is 3 or any integral number greater carboxyl amino group, polyglycol Tadiclesi than 3. Instead of the acids their esters with having at a t ur I XY polyhydric alcohols may be employed in which O p a f0 e a p e the t tra-ethylene glyc case a reesterification occurs, or the esters may radiclei be employed which still contain free hydroxyl 60 groups in a polyhydric alcohol radicle of such -e r 2- zz z ester, as for example monoor di-glycerides. In-
stead of the said acids or esters the carboxylic any free hydroxyl groups still present being neuhalides of the aforesaid acids may be employed if tralized with reactive compounds, if desired, as an alkaline condensing agent be used, or an al- 5 for example with carboxylic acids, polybasic minkaline condensing agent capable of assisting the oral acids such as sulphuric acid or phosphoric splitting ofi of halogen in the form of halogen acid, acid halides, alkyl or aryl halogen hydracid hydracids may be employed in the case of emor sulphuric acid esters or aldehydes. As initial ploying ethylene halogenhydrins instead of materials may be mentioned all water-insoluble ethylene oxide. Alcohols coming into considera- 7 organic compounds which contain one'or more tion are those containing at least 6 carbon atoms equal or difierent groups of the said kind. For and especially those corresponding to, or preexample water-insoluble carboxylic acids, alcopared by reduction. from, the aforesaid vegetal hols, phenols, hydroxy carboxylic acids, carboxcarboxylic acids or their glycerol esters, as for ylic acid amides, amines containing at least one example hexyl, octyl, decyl, undecyl, dodecyl, reactive hydrogen atom and any water-insoluble tetradecyl or octodecyl, cetyl or oleyl alcohols, hydroxy-alkyl amines and their water-insoluble cholesterol, and glycols of high molecular weight derivatives are suitable. of the type of octodecandiol, such as octomethyl Specific examples of the said compounds conglycol or decamethyl glycol, as well as water-intaining a reactive hydrogen atom are aliphatic soluble alkyl, or also cycloalkyl, aralkyl or aryl, u carboxylic acids insoluble in water such as those others of the diiferent polyhydric alcohols as for containing at least 6 carbon atoms and especially example the cresylic, phenylic, benzylic, cyclothe saturated, unsaturated and/ or hydroxylated hexylic or naphthylic ethers of glycol or of glycerrboxylic a ids of veg al, i. e. animal and v 01. The products obtainable by introducing the l in. and oth r m n o p ly-carboxylic said polyglycol radicles into the said alcohols acids containing from 6 to say 30 carbon atoms as correspond to the general formula for example caproic acid, lauric acid, oleic acid, ricinoleic acid, linoleic acid, palmitic acid, stearic C"H2+1 O C2H4) O Gib-CH2 acid, hydroxy stearic acid, montanic acid and in which n is 6 or any integral number greater 40 naphthenic acids, as well as analogous synthetic than 6 and :c is 3 or any integral number greater mixtures, obtainable by the destructive oxidation than 3. Water-insoluble phenols may also be of D fi WaX 0 parafiin oil or like non-aroemployed as for example the isomeric xylenols matic high molecular hydrocarbons and fractions and xylorcins (dimethyl dihydroxy benzene). of such oxidation products, as for example the Amines may be chosen from any water-insoluble 45 hydrozwcarboxylic acid fraction, insoluble in peamines provided theycontain at least one reactive troleum ether, and the acids of waxes of vegetal hydrogen atom connected to a nitrogen or oxygen and mineral origin such as of beeswax or Montan atom, as for example decylamine, undecylamine, wax which contain esters of carboxylic acids with dodecylamine, tetradecylamine, cetylamine, 0cmup to about 30 carbon atoms. The products obdecylamine, pentadecylamine, di-heptylamine, di- 50 tainable by introducing the said polyglycol radbutyl amine and diphenylamine. The products obtainable by introducing the said polyglycol raderalformula' I I I R.NH- (-O.C2H4-.) :-OCH2-CH2+-OH in whichRNHis theradicle of the amine and a:
icles' into the said amines correspond to. the genis B'orany integral number greater than 3. 'The amines containing a reactive hydrogen atom may contain the latter connected to oxygen as is the case with the alkylol amines which therefore need not contain a hydrogen atom connected to nitrogen. Suitable amines of this class are for example N-cyclohexyl-N-monoor di-alklyol amines such as N-cyclohexyl-N-monoor (ii-ethanol or propanol amines or the corresponding monoor water-insoluble amides may be chosen from those prepared from ammonia or water-soluble primary amines and from alkylol amines, asior'example. from those of mono-, dior tri-ethanol or -pro-.
panol amines or of 'mixtures thereof. Waterinsoluble esters of these alkylol amines with the aforesaid high molecular acids may be employed provided they still'contain a reactive hydrogen 7 atom as is the case for example with esters of the type of tri-ethanol amine or (ii-ethanol amine.
di-stearic or -pa1mitic-'esters, the former of which ed to the nitrogen atom.
' I The long chain polyglycol radicles may beadded on to the said initial materials by treatment with corresponding quantities of ethylene oxide or substances forming the same, such as alkylene halogenhydrins, if desired with the employment of condensation catalysts such as surface ac tive substances as for example bleaching earths or active charcoal, strongly acid substances as for example sulphuric or phosphoric acids or sodium or potassium bisulphates, or also strongly alkaline agents suchas caustic soda or alkali metal alcoholates and/ or with the employment of increased pressure, if desired at elevated temperatures such as from about to 200 0., preferably between and 150 C. whereby the ethylene oxide molecules arrange themselves with the formation of long chain polygylcols. Depending on the amount of ethylene oxide employed it is possible to add on four or more -C2H4-- groups to each other by means of ether linkages. On the other hand the quadruple polyglycol ethers or the ethers containing more than 4 polyglycol radicles may be first formed in known manner and then condensed in known manner with the compounds containing reactive hydrogen atoms to form therewith esters, ethers and so on. If desired mono-alkyl or -aryl ethers or esters of the at least quadruple polyglycol ethers may be employed for this step so that a further conversion of the products with acids, acid halides, alkyl or aryl halides or polybasic mineral acids described above may be dispensed with. .The quantities of the polyglycol forming agents e. g. of ethylene oxide, or of an equivalent compound such as the glycol chlorhydrins, generally correspond to from one half molecular proportion of polyglycol forming agent per carbon atom of the water-insoluble comcompounds.
pound,the quantity of polyglycol forming agent being,however, at least 4 molecular proportions of the water-insoluble initial material even it the latter should contain less than 8 carbon atoms so that products with at least quadruple polyglycol radicles are formed. In most cases, however, from 6 to 20 and up to 50 molecular proportions or'the polyglycol forming agent are employed per molecularproportion of the water insoluble initial material, or the corresponding polyglycols themselves.
By employing initial materials containl ing several reactive hydrogenatoms such as glyools, for example octodecandiol,octomethyl gly I I col, decamethyl glycol, or hydroxy carboxylic acids, for example hydroxy stearic acid and mono-,
glycerol esters thereof, dicarboxylic acids such as I p I sebacid or pimelic acids, or primaryaminesprodc ucts may be obtained containing not only one but several, at least quadrauple, polyglycol radicles 5 in the molecule. I
' The products obtainable by adding the polygly col radicles on to water-insoluble organic compounds containing at least two of the said reac- I tive groups usually contain one or two free hydroxyl groups at the end of the chains and-these may be converted as mentioned with. reactive I As such reactive compounds may be mentioned in particular acids which reactto form esters, as for example sulphuric, chlorsulphonic, phosphoric, phthalic or fatty acids for example with from 8 to 1'8 carbon atoms and their derivatives, such as chlorides, or halogenatedparaffin wax.- Such products as contain a halogen at the end of the polyglycol etherchain 10 as for example those prepared with ethylene ox- ,ide andhalogen 'hydrins, or those prepared by substituting the hydroxyl group at the end of the chain'by iodineor bromine according to the persing in water and have in many cases excellent wetting, foaming and cleansing power so that they may find a wide field of employment for example in the textile, leather, paper, wax and polish industries, as for example in carbonizing, mercerizing, dressing, bucking, washing, finishing, dyeing, printing or polishing. In dyeing and printing they exert an excellent levelling action. For example in dyeing with vat dyestuifs, or with azo dyestuffs from fi-naphthoic acid arylides on the fibre, the dyeings are rendered uniform or, respectively, fast to rubbing. A special advantage of the said products consists in the fact that they are generally speaking practically neutral so that the fibres are in no way attacked. Moreover, the formation of insoluble calcium or magnesium compounds such as is frequently the case in hard water with soaps or Turkey red oils does, not take place with these products.
The compounds containing the at least quad ruple polyglycol radicles are also suitable as disusual methods, may be brought into reaction with 'basic compounds, such as amines, acid amides, 115.
black, solid and liquid hydrocarbons, and they may also be advantageously used as softening agents as for example for films, bands and lacquers prepared from cellulose esters and ethers or from artificial resins. Most of the said condensation products may also be advantageously compounds, such as azo dyestuffs, are prepared in the presence-of the said products, the said insoluble compoundsare much more finely divided than when produced in the absence of the said products.
For treatments of textiles in aqueous baths, such as dyeing, washing, scouring, stripping, vivifying or degumming, the amount of the said condensation products is usually from 0.05 to 10 grams per each litre of the bath.
For the production of pastes, creams, cosmetic preparations, emulsions or suspensions, the amount of the'said condensation products may be from about 5 to about 1000 per cent of the weight of the other ingredients, or more, according to the nature ofthe substances treated and the required consistency of the final mixture.
The products according to the present invention may be used alone or together with other agents, such as alkali metal, ammonia or amine soaps or soap-like substances, for example sulphonic acids of high molecular aliphatic or aromatic hydrocarbons, which may also contain hydroxy and/or carboxylic groups or sulphuric esters of high molecular alcohols, fatty, i. e. vegetable and animal, oils and fats, natural and synthetic waxes or cellulose esters and ethers. For example preparations from the said products and soaps, Turkey red oils, saponine, organic aliphatic or aromatic sulphonic acids, glue, vegetable mucilages, dextrin and other colloids, salts, such as common salt, Glaubers salt, magnesium sulphate or organic solvents, bleaching agents, such as perborates have very valuable properties.
The following examples will further illustrate how this invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight, if not otherwise stated.
Example 1 200 parts of a mixture of higher alcohols, such as "is obtained by the catalytic hydrogenation of vegetal, i. e. animal and vegetable, oils or fats by means of hydrogen at a temperature from about 250 to 300 C. in the presence of a finely divided nickel catalyst, consisting mainly of alcohols of the formula CsHr'iOH to C1sH37OH, whereby about 50 per cent of dode'cyl alcohol is present, are heated to about 180 C. in an autoclave with about 400 parts of ethylene oxide which is introduced a little at a time. The ether prepared in this way has wetting, washing and emulsifying action as well as protective colloid properties and is eminently suitable for washing suint wool and woolen piece goods. For example if 10 grams of suint wool are treated for hour at 45 C. in a bath containing 3 grams of the said condensation product per litre of water, a very well cleansed wool having an agreeable soft touch is obtained.
The product is also miscible with solvents, as for example ethylene glycol mono-cresyl ether, tetrahydronaphthalene, carbon tetrachloride and like organic water-insoluble solvents, and by the addition of water to the mixtures, very good emulsions of the said solvents are obtained. Likewise by adding the said products, as for example 10 per cent, to mineral lubricating oil, paraflin oil or other mineral or fatty oils which are insoluble in water, they-may readily be rendered capable of being emulsified in water. I
The wetting action of the product may be still further increased by the introduction of sulphonic groups for example by means of chlorsulphonic acid. The product may also be advantageously employed, inter alia, in carbonizing baths.
Example 2 1.06 kilograms of diethylene glycol are heated to 150 C. in an autoclave and then 8.8 kilograms of ethylene oxide are added a little at a time. The pressure is about 10 atmospheres. After the whole of the ethylene oxide has been introduced, the autoclave is heated until the pressure has practically disappeared. A quantitative yield of a colourless water-soluble condensation product is obtained.
A mixture of 3 parts of the condensation product and 1 part of oleic or ricinoleic acid is I.
heated to about 130 C. The resulting ester is soluble in water and is not precipitated from aqueous solutions by salts of calcium, aluminium, copper, zinc or by organic and mineral acids. It has a good foaming power and washing, wetting and emulsifying action. For example if the condensation product be mixed with olive oil, whereby the addition may be less than 10 per cent, a fine and stable emulsion is obtained after dilution with water.
The product has an excellent washing action and isespecially suitable for washing suint wool or woolen piece goods. It may also be advantageously employed, inter alia, as an addition to desizing liquors. The usual desizing agents, as for example vegetable amylases, such as malt amylase, for example that known in the trade under the registered trade-mark Diastafor, or animal amylases, such as an extract from the pancreas gland, for example that known in the I trade under the registered trade-mark "Degomma, have an optimum effect in acid or neutral baths. Alkaline baths are disadvantageous, and it is only with a consequent injury to the desizing effect that alkaline washing agents such as soap can be added. The addition of a washing agent in addition to the ferment for degrading the starch is often desirable, however, when the material concerned contains fats and oils as well as starch and this requirement of practice is met by the products according to the present invention, such as that described in the foregoing.
5 parts of the said product are added to a desizing bath which contains 1 part of an extract from the pancreas gland for example that known in the trade under the registered trademark Degomma DL for each 1000 parts of water and which has a pH value of from about 6 to 7. The washing action of the product is fully exerted without the starch-degrading action of the pancreas gland extract being checked.
' When the same amount of soap is added to the bath it assumes a pH value of from 9.0 to 9.3 and the desizing efiect is consequently considerably impaired.
Example 3 10 molecular proportions of ethylene oxide are added on to one molecular proportion of the mono-ethyl ether of di-ethylene glycol (C2H5O.CH2.CH2.O.CH2.CH2.OH, obtainable by acting with ethylene oxide on the mono-ethyl ether of ethylene glycol) in the manner as described in Example 2. 100 parts of the resulting ether are heated with 30 parts of palmitic acid for about 12 hours at 150 C. A reaction product of the consistency of ointment is obtained which is soluble in fats and water and which is the palmitic ester of the aforesaid ether. For example if 2 parts of Japan wax be fused with 1 part of the said palmitic ester of the corresponding stearic ester until a clear solution is formed, an emulsion is obtained by slowly adding about 15 parts of hot water while stirring or shaking, which contrasted with the emulsions prepared with the aid of soda and soaps has the advantage of being neutral. Moreover no saponification of the wax takes place.
Example 4 An acetate silk fabric is treated at room temperature for about 10 minutes with 2 parts of the substance specified in Example 3 and 1 part of 10 per cent of formic acid for each 1000 parts of water. The fabric is centrifuged or squeezed and dried at from about 45 to 60 C. The fabric acquires a soft, and at the same time crisp, silky touch by this treatment. contrasted with the usual process for producing the crisp touch, which consists in treating the fabric in a soap bath with subsequent treatment in a bath of formic or lactic acid, the said method has the advantage of comprising only one operation.
Example 5 4 parts of the ester obtained according to Example 2 or the analogous ricinoleic ester, are added to a mixture of 30 parts of oleic and parts of arachis oil. After the emulsifying agent has been well dissolved in the oil mixture, preferably by warming, the whole is poured into 80 parts of water which contains 4 parts of hydroxyethyl methyl cellulose dissolved therein while diluted with water to form a 10 per cent emulsion. example for greasing wool.
The said ester or the ether alcohol obtained according to Example 1 may be employed as such or in conjunction with for example petroleum, by reason of their fatty character, their solubility in water and their washing and emulsifying action, as a textile oil in the working up of artificial silk without giving rise to subsequent inconvenience during dyeing. Similarly, by reason of the said properties, they are eminently suitable as such or in conjunction with other oils as greasing agents for the working up of animal or vegetable fibres.
Example 6 3 parts of a condensation product from 1 molecular proportion of diethylene glycol and 10 molecular proportions of ethylene oxide are esterified with 1 part of oleic acid in the manner described in Example 2, 10 parts of the ester thus obtained are added to 100 parts of neatsfoot oil, the whole being made into a 30 per cent emulsion with water by means of a stirring apparatus. The emulsion which may be diluted to any desired extent, possesses very good properties and is suitable, inter alia, for greasing leather. The first-mentioned product may also be employed as such as a softening agent for leather.
In the preparation of the emulsion of neats-foot oil, the inverse order may be followed by dissolving the emulsifying agent in water and allowing the oil to flow into the solution while stirring continuously.
Example 7 Cotton yarn is mordanted in the usual manner with tannin and tartar emetic and dyed in the usual manner with 1.5 per cent of Auramine O (Schultz, Farbstofftabellen 6th Edition No. 493) with an addition to each litre of the dye-bath of 1 gram of the ether obtained by the adding on of molecular proportions of ethylene oxide to 1 molecular proportion of 7.18-octodecandiol in the presence of 1 per cent, byweight of the octodecandiol, of caustic soda, in the manner described in Example 2. The 7.18-octodecandiol may be obtained for example by catalytic reduction of castor oil. The addition of the wax-like water-soluble product obtained by the adding on of ethylene oxide imparts to the bath an excellent capacity for wetting and in no way injuriously affects the dyeing by reason of the formation of lakes with the dyestuil' such as is usually the case with wetting agents containing sulphonic groups, as for example alkylated naphthalene sulphonic acids.
'The condensation product is eminently stable to lime and alumina. It may be added to indigozinc-lime vats or other indigo vats or to coupling baths for naphthols, for example to coupling salts which contain aluminium compounds in addition to the diazonium compounds, without the formatlon of precipitates. The resulting dyeing is considerably improved as regards its fastness to rubbing, so that the usual subsequent treatment with soap may be dispensed with. Likewise it remains in solution in acid baths, even in those of high concentration. The good stability of the product to all k'nds of electrolytes allows of its employment not only in neutral, but also in acid or alkaline printing pastes and in dyeing with aniline black.- Since the product does not form insoluble precipitates with basic dyestuffs, it may v.gorously moving the bath, the whole then being b added most advantageously to Solutions of The emulsion is eminently suitable for dyestuffs Example 8 molecular proportions of ethylene oxide are added on to the mono-ethyl ether of di-ethylene glycol in the manner described in Example 3. 100 parts of the reaction product are heated with parts of castor oil and 3.5 parts of the resulting oily ester are added to a solution of '7 parts of a collodion cotton (the solutions of which in organic solvents have a high viscosity) in 40 parts of butyl acetate, 20 parts of butanol, 20 parts of ethyl alcohol and 20 parts of benzene. The resulting solution is employed for pouring films, the resulting films having very good mechanical properties and very good fastness to light.
Example 9 10 parts of a collodion cotton which dissolves in organic solvents with the formation of solutions of low viscosity are dissolved in a mixture of 40 parts of butyl acetate, 10 parts of butanol and 30 parts of toluene. To this solution are added 5 parts of a conversion product from equal amounts of castor oil and the ester obtained from 1 molecular proportion of diethylene glycol and 10 molecular proportions of ethylene oxirle in the manner described in Example 2, and 2.5 parts of an artificial resin obtained from methylcyclohexanone by polymerization with methylalco- Example 10 150 parts of water containing 30 parts of the ester obtained from equal parts of coconut fatty acids and the condensation product from 1 molecular proportion of diethylene glycol and 10 molecular proportions of ethylene oxide (obtainable as described in Example 2) and also containing 10 parts of ethylene glycol monocresyl ether are introduced into a homogenizing appa ratus such as a turbo-mixer of colloid mill. A solution of 200 parts of an ethylene glycol ester of the acids of oxidation-bleached Montan wax (obtainable for example according to the U. S. application No. 247,454 filed January 17th, 1928) in 400 parts of oil of turpentine are added and the whole is emulsified for from 2 to 5 minutes while adding 450 parts of water, the temperature being kept near the melting point of the wax. A good emulsion is obtained which may be applied to leather, wood or other materials and yields a highly glossy coating on the said materials after polishing or brushing. I
Example 11 water containing 20 parts of the reaction product described in Example 2, and then a further 200 parts of water are added. The resulting emulsion is suitable as a basis for intaglio printing inks.
The emulsion may also be prepared by dissolving the emulsifying agent together with the asphalt in xylene and emulsifying the said solution with the necessary amount of water in a homogenizing apparatus. A
Alternatively, a part of the emulsifying agen may be dissolved in the asphaltic xylene solution and the remainder in water.
Example 1 18 molecular proportions of ethylene oxide are added onto 1 molecular proportion of octodecylamine by heating in an autoclave to about 150 C. A Water-soluble product having a very good wetting power is obtained, which possesses also a good levelling effect in dyeing with vat or acid dyestufis. Thus for example an addition of from 0.1 to 0.2 gram to each litre of a dyebath from Indanthren blue green B furnishesuniform shades on bleached mercerized cotton fabrics,
whereas without the addition bad dyeings are obtained.
Hydroxyethyl octodecylamine, obtainable for example by the conversion of the sulphuric ester of octodecyl alcohol with hydroxyethylamine, may also be used as the initial material and the salicylic salt of the product may be used as an addition to dressing preparations.
If one molecular proportion of the mono-oleic or -stearic esters of triethanolamine or of oleic or naphthenic amides be brought into reaction with from 4 to 10 molecular proportions of ethylene oxide, water-soluble products are obtained which may be employed as sizing or dressing agents or in bowking.
If about 12 molecular proportions of ethylene oxide are added on to for example triethanol amine and the resulting product is esterifled for example with oleic acid a product is obtained which may be added for example to machine oils as an emulgator.
Example 13 From6 to 9 molecular proportions of ethylene oxide are added on to 1 molecular proportion of octodecyl alcohol, the product being sulphonated with equimolecular proportions of chlorsulphonic acid while cooling to from 0 to 25 C.
If 3 parts of one of the resulting acid sulphuric esters in the form of its neutral sodium salt be added to 1000 parts of water, an excellent washing effect is obtained with suint wool when treating the same for ,4; hour at from 45 to 50? C. in the said bath while keeping the ratio of wool tobath at 1:50. The same result is obtained even after using the bath several times. When artificial silk is treated with water containing from 1 to 2 parts of the said product per 1000 parts, it acquires a pleasant supple touch. I
10 parts of crude Milan tram silk are degummed at 65 C. with 0.5 part of papain, 1.5 100 parts of sodium thiosulphate, 0.5 part of hydrosulphite and 1 part of the condensation product described in Examples 7 or 2 in 1000 parts of Water. The addition of the wetting agent efiects a more rapid wetting and dissolution of the dif- 105 ficultly soluble papain without checking its action, such as is the case for example with Turkey red oils or naphthalene sulphonic acids or other wetting agents containing sulphonic groups.
Example 15 From 5 to 10 per cent of the reaction product obtainable according to Example 2 are dissolved in 100 parts of boiling linseed oil, which may also contain siccatives, the solution being slowly 115 diluted with warm water while stirring. The resulting emulsion is very stable and is eminently suitable for example for sizing or dressing artificial silk or for the preparation of coatings on wood and other materials.
Example 16 From 3 to 5 per cent of the product obtained according to Example 7 are added to a commercial Marseilles soap. The soap becomes stable to lime after this addition and is not precipitated even in water for example of 20 hardness (German scale).
Emample 17 Example 18 of oleic acid, castor oil, ricinoleic acid or Montan wax carboxylic acids may be employed whereby waxy, from easily emulsifiable to water-soluble products are obtained.
Example 19 From 660 to 880 parts (from 15 to 20 molecular proportions) of ethylene oxide are led, while stirring at a temperature between 130 and 140 0., into 270 parts (1 molecular proportion) of octodecyl alcohol containing 2.7 parts of an aqueous caustic soda solution of 40 Be. The ether thus prepared solidifies into a waxy mass on cooling; the product is soluble in most of the usual organic solvents and dissolves very readily in water.
The ether possesses an excellent leveling power in dyeing with vat dyes and particularly promotes the thorough dyeing of mercerized pearl yarn and of silk yarn for embroideries in dyeing the said materials with vat dyes. If, for example, mercerized pearl yarn or strongly twisted viscose yarns be dyed in the usual manner with 5.5 per cent, calculated with reference to the weight of the yarn, of Indanthren blue RS double paste (Schultz, Farbstofitabellen, 1931, No. 1228) with an addition of 5 grams of the said wax-like ether per each litre of the dyebath, very evenly and thoroughly dyed yarns are obtained.
If, for example, artificial silk, for example cupro-ammonium silk, be dyed in the usual manner with 0.5 per cent, by weight of the silk, of Indanthren brilliant violet RR double paste (Schultz, Farbstofltabellen, 1931, No. 1265), or with a combination of 0.5 per cent, by weight of the silk, of Indanthren blue RS double paste (Schultz, Farbstofftabellen, 1931, No. 1228) and of 0.5 per cent of Indanthren yellow 3 RT double paste (Schultz, Farbstoffstabellen, 1931, No. 1242), with an addition of from 0.1 to 0.5 gram of the said ether per each litre of the dyebath, very evenly and thoroughly dyed silk is obtained, the quality of the dye-bath being moreover maintained through a long period of time.
If the said ether be added to diazo-solutions in fixing azo dyestuffs on fibres, the solidity to rubbing of the dyes is considerably improved.
The said wax-like ether dissolves in warm oleic acid to form a limpid solution. If a solution of, say, 2 to 5 parts of the ether in 100 parts of oleic aicd be slowly stirred into water, a stable emulsion is obtained which may be employed for example for oiling textiles.
If from about 8 to 12 molecular proportions of ethylene oxide be added on, similarly as described ,above, to 1 molecular proportion of decanol or dodecanol or of a mixture of alcohols obtainable by catalytically reducing coconut oil or palm 'oil by means of hydrogen, colourless water-soluble oils or semi-solid masses are obtained, which possess a good wetting power in alkaline, neutral or acid aqueous baths and which are not precipi-' tated from aqueous solutions by calcium, magnesium or heavy metal salts. The said oils or semisolid masses may be employed Whenever a wetting agent is needed; they may also be employed as additions to moistening preparations, for example for moistening cotton-yarn before weaving, or to preparations for combating pests. The said oils and masses act as protective colloids and possess a considerable dispersing power; if the said oils or masses be added to soap solutions in which calcium salts of the water have precipitated calcium soaps, the said calcium soaps are completely dissolved.
By adding from 5 to 6 molecular proportions of ethylene oxide on to 1 molecular proportion of cetyl alcohol, products are obtained which may be usefully employed for imparting to artificial silk, such as that prepared from viscose, the crisp touch of natural silk. If the said products be heated at 120 C. for 2 to 3 hours in vacuo with their own weight of a wax-like product, obtained by polymerizing ethylene oxide at a temperature between about 50 and 60 C. by means of an aqueous solution of caustic potash a product is obtained which possesses a very good levelling power in dyeing with vat dyes.
1 part of the mixture of alcohols of high molecular weight, obtained by separating the unsaponifiable constituents of a product of the destructive oxidation of parafi'in wax according to Example 1 of the British specification No. 303,281 is heated with 2 parts of ethylene oxide and 0.5 per cent, by weight of the alcohols, of the bleaching earth traded under the registered trade-mark Tonsil 3B in an autoclave to from to C. until the product has become soluble in water. A thick oil is obtained which possesses a good wetting-out power.
Example 21 ,1 part of wool fat is heated for 3 hours with 2 parts of ethylene oxide and 0.5 per cent, by weight of the fat, of a powdered bleaching earth consisting of aluminium hydrosilicate which contains small amounts of calcium hydroxide in an autoclave to 100 C. A salve-like, water-soluble product is obtained which may be used as an eflicient dressing agent.
Example 22 1 part of glycerol mono-oleic ester is heated at from 100 to 150 C. in a closed vessel with 2 parts of ethylene oxide. The resulting ether of the ester, which is a yellowish rather thick oil, forms a colloidal solution with water and may be employed in oiling textile materials of any kind in spinning, carding, weaving or other processes and as a lubricant. In the place of the oleic ester the corresponding ester mixture of the acids of Montan wax may be employed, masses resembling bees wax being thus obtained.
Example 23 88 parts of ethylene oxide are introduced at 120 C. into 51 parts of the mixture of alcohols obtained by the saponification of sperm oil and containing 1 per cent of caustic soda or of sodium ethylate. A product is obtained which possesses a high wetting and levelling power and which is capable of easily emulsifying waxes or waxy compounds as for example Japan wax or esters of the acids of crude or bleached Montan wax as for example the glycol esters.
If 25 or 12 parts of the alcohol mixture be employed instead of 51 parts valuable products are equally obtained the solubility of which in water is still higher than that of the aforesaid product. Mixtures of the aforesaid products with natural waxes, paraffin wax or like waxy materials can be easily emulsified in water, especially in conjunction with organic solvents, such as turpentine oil or benzene. The emulsions obtained in this manner may be employed as boot or fioor polishes or similar polishing preparations.
Eztample 24 20 molecular proportions of ethylene oxide are added on to 1 molecular proportion of octodecylalcohol containing 0.5 per cent, by weight, of caustic soda. After leading 1 per cent of hydrochloric gas into the condensation product, 0.5 molecular proportion of acetaldehyde is dropped in for each molecular proportion of the condensation product in the course of about 4 to 6 hours, while stirring under a reflux condenser. The water formed by the reaction and any hydrochloric acid present are removed by distillation in vacuo, and the remaining product is neutralized, if necessary, by means of soda. An oil is obtained which is a good plastifying agent for textiles.
Example 25 From 4 to 6 molecular proportions of ethylene oxide are added on to 1 molecular proportion of octodecyl alcohol in the presence of 1 per cent of caustic soda. The product obtained is very useful for the production of pastes and creams.
12 parts of the said condensation product are mixed at from 50 to 60 C. with 18 parts of vaseline and 10 parts of paraffin oil; 60 parts of water are slowly stirred into the mixture while cooling to room temperature. An excellent skin cream is thus obtained. A skin cream may also be prepared for example by mixing 10 parts of the said condensation product with 20 parts of paraffin oil, 3 parts of peanut oil and 6'? parts of water. i
Example 26 By acting with 1 molecular proportion of chlorosulphonic acid on 1 molecular proportion of the condensation product obtained according to Example 25 from 1 molecular proportion of octodecylalcohol and 4 molecular proportions of ethylene oxide, the water-soluble, acid sulphuric ester is obtained which is neutralized with caustic soda or potash, ammonia or an alkylol amine, such as mono-ethanolamine. The salts are excellent scouring agents for loose wool.
What we claim is:-
1. The process which comprises condensing a water-insoluble, monomeric, organic compound, selected from the group consisting of hydroxyl, carboxyl and amino compounds containing at least 6 carbon atoms and one reactive hydrogen atom, with a polyglycol compound containing at least four ethenoxy groups.
2. The process which comprises condensing a water-insoluble, monomeric, organic compound, selected from the group consisting of hydroxyl, carboxyl and amino compounds containing at least 6 carbon atoms and one reactive hydrogen atom, with a polyglycol compound containing from 6 to 50 ethenoxy groups.
3. From readily to difficultly water-soluble derivatives of water-insoluble, monomeric, organic compounds, selected from the group consisting of hydroxyl, carboxyl and amino compounds containing at least 6 carbon atoms, which derivatives contain a polyglycol radicle with at least four ethenoxy groups.
4. From readily to difficultly water-soluble derivatives of water-insoluble, monomeric, organic compounds, selected from the group consisting of hydroxyl, carboxyl and amino compounds containing at least 6 carbon atoms, which derivatives contain a reactive hydrogen atom, which derivatives contain the group (-OC2H4)n-OX in which OX denotes either a hydroxyl group, an
ether radicle or an ester radicle and n denotes an integral number above 3.
5. From readily to difficultly water-soluble derivatives of water-insoluble, monomeric, organic compounds, selected from the group consisting of water-insoluble alcohols, carboxylic acids and amino compounds containing at least 6 carbon atoms and one reactive hydrogen atom, which derivatives contain the group (O-CzH4)n-OX in which OX denotes either a hydroxyl group, an ether radicle or an ester radicle and n denotes an integral number above 3.
6. From readily to diflicultly water-soluble derivatives of water-insoluble aliphatic organic compounds selected from the group consisting of water-insoluble alcohols, carboxylic acids and amino compounds containing at least 6 carbon atoms and one reactive hydrogen atom, which derivatives contain the group (O-C2H4) n-OX in which OX denotes either a hydroxyl group, an ether radicle or an ester radicle and n denotes an integral number above 3.
'7. Readily water-soluble derivatives of water-insoluble aliphatic organic compounds selected from the group consisting of water-insoluble alcohols, carboxylic acids and amino compounds containing at least 6 carbon atoms and one reactive hydrogen atom, which derivatives contain the group (o-C2H4)n-OX in which X denotes a radicle of a polybasic mineral acid and n denotes an integral number above 3.
8. From readily to diflicultly water-soluble derivatives of water-insoluble, aliphatic organic compounds selected from the group consisting of water-insoluble alcohols, carboxylic acids and amino compounds containing at least 6 carbon atoms and one reactive hydrogen atom, which derivatives contain the group in which OX denotes either a hydroxyl group, an ether radicle or an ester radicle and n denotes an integral number from 6 to 50.
9. From readily to difiicultly water-soluble ethers of water-insoluble, aliphatic alcohols containing at least 6 carbon atoms, which ethers contain the group (O-C2H4)nOX in which OX denotes either a hydroxyl group, a monoalkyl or arylether or ester radical and n denotes an integral number above 3.
10. From readily to difiicultly water-soluble ethers of water-insoluble, aliphatic polyhydrlc alcohols containing at least 6 carbon atoms, which ethers contain the group (-OC2H4)n-OX in which OX denotes either a hydroxyl group, a monoalkyl or arylether or ester radical and n denotes an integral number above 3.
11. From readily to difiicultly water-soluble ethers of water-insoluble mixtures of aliphatic alcohols containing from 10 to 30 carbon atoms, which ethers contain the group in which OX denotes either a hydroxyl group, a monoalkyl or arylether or ester radical and 11. denotes an integral number above 3.
12. From readily to difiicultly water-soluble ethers of water-insoluble aliphatic alcohols containing from 10 to 30 carbonatoms, which ethers contain the group (--OCzH4)n-OX in which OX denotes either a hydroxyl group, a monoalkyl or arylether or ester radical and n denotes an integral number above 3.
13. From readily to difiicultly water-soluble ethers of water-insoluble aliphatic alcohols containing at least 6 carbon atoms, which ethers contain the group (OC:H4)OH. inrwhich n denotes an integral number from 6 to 50.
14. Neutralized from readily to difflcultly watersoluble ethers of water-insoluble aliphatic alcohols containing at least 6 carbon atoms, which ethers contain the group (-O-C2H4)-.OX, in
which X denotes a radicle or an acid and 11 denotes an integral number from 6 to 50.
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2417299 *||Aug 6, 1943||Mar 11, 1947||U S Vitamin Corp||Fat-soluble vitamin solutions|
|US2418752 *||Apr 24, 1943||Apr 8, 1947||American Viscose Corp||Yarn having the twist set therein with an unctuous solid|
|US2422145 *||Feb 21, 1942||Jun 10, 1947||Atlas Powder Co||Essential oil compositions|
|US2437261 *||Oct 9, 1944||Mar 9, 1948||Cons Royal Chemical Corp||Condensation products of cholesteryl esters with polyethylene glycol and process for producing same|
|US2447475 *||Nov 29, 1945||Aug 17, 1948||Monsanto Chemicals||Emulsifiable oils|
|US2450079 *||Apr 23, 1943||Sep 28, 1948||Atlas Powder Co||Waxy polyol ether-esters|
|US2451149 *||Nov 27, 1943||Oct 12, 1948||Nipa Lab Ltd||Manufacture of materials resistant to or active against microorganisms|
|US2451558 *||Nov 6, 1944||Oct 19, 1948||Rayonier Inc||Chemically treated wood pulp and a method of producing a cellulosic product|
|US2454643 *||Jul 18, 1945||Nov 23, 1948||Ici Ltd||Gelatine blasting explosive compositions containing water-soluble salts|
|US2460400 *||Jul 13, 1944||Feb 1, 1949||American Viscose Corp||Methods for the treatment of regenerated cellulose thread|
|US2461043 *||Nov 10, 1944||Feb 8, 1949||American Viscose Corp||Process of conditioning cellulose ester filaments|
|US2466212 *||Feb 28, 1945||Apr 5, 1949||Universal Oil Prod Co||Polymerization of conjugated diolefins and vinyl compounds|
|US2469493 *||Jul 2, 1947||May 10, 1949||Atlas Powder Co||Synthetic detergent composition|
|US2476609 *||Feb 20, 1946||Jul 19, 1949||Cons Royal Chemical Corp||Manufacture of condensation products|
|US2489310 *||Jan 12, 1946||Nov 29, 1949||American Viscose Corp||Spinning assistants|
|US2499551 *||Feb 7, 1947||Mar 7, 1950||Genesee Res Corp||Hydraulic pressure transmitting fluid|
|US2500349 *||Apr 17, 1948||Mar 14, 1950||Petrolite Corp||Process for breaking petroleum emulsions|
|US2501145 *||Jun 18, 1947||Mar 21, 1950||Nathan Smith||Composition for release of oxygen|
|US2501988 *||May 17, 1946||Mar 28, 1950||Lea Fabrics Inc||Method for the treatment of fabric, yarns, threads, strands, and the like to render rubberized articles made therefrom more durable|
|US2503665 *||Feb 2, 1950||Apr 11, 1950||American Machinery Corp||Coloration of fresh citrus fruits|
|US2509233 *||Sep 11, 1946||May 30, 1950||Monsanto Chemicals||Emulsifiable oil concentrates of biological toxicants|
|US2517091 *||Nov 26, 1945||Aug 1, 1950||Petrolite Corp||Monopyridinium derivatives of esterified oxyalkylated diphenylol methanes|
|US2517092 *||Nov 26, 1945||Aug 1, 1950||Petrolite Corp||Monopyridinium derivatives of esters of oxyalkylated diphenylol methanes|
|US2517094 *||Nov 26, 1945||Aug 1, 1950||Petrolite Corp||Dipyridinium derivatives of esterified oxyalkylated diphenylol methanes|
|US2518230 *||Nov 15, 1947||Aug 8, 1950||U S Vitamin Corp||Aqueous solutions of lipoid-soluble vitamins|
|US2519227 *||May 28, 1947||Aug 15, 1950||American Viscose Corp||Manufacture of yarns and the like|
|US2522155 *||Oct 18, 1946||Sep 12, 1950||Shell Dev||Lubricating compositions|
|US2528136 *||Oct 2, 1948||Oct 31, 1950||Sun Chemical Corp||Surface active compositions|
|US2541285 *||Mar 24, 1945||Feb 13, 1951||Parke Davis & Co||Aqueous solutions of vitamin a esters|
|US2543419 *||May 11, 1949||Feb 27, 1951||Rohm & Haas||Polycyclic di-epoxy ethers|
|US2543744 *||Apr 4, 1946||Mar 6, 1951||Gen Aniline & Film Corp||Nonfoaming soap composition|
|US2552187 *||Dec 28, 1946||May 8, 1951||Monsanto Chemicals||Emulsion concentrate of a biological toxicant|
|US2555285 *||Dec 27, 1948||May 29, 1951||General Aniline a Film Corporation||Detergent composition|
|US2556146 *||Nov 5, 1948||Jun 5, 1951||Gen Aniline & Film Corp||Di-(beta-hydroxyalkyl)-2-(alkyl carbamyl-oxy)- alkylamines|
|US2556820 *||Sep 21, 1945||Jun 12, 1951||Gen Aniline & Film Corp||Aqueous dispersions of dichlorodiphenyl-trichloroethane|
|US2559583 *||Jan 23, 1948||Jul 10, 1951||Atlas Powder Co||Solid compositions containing polyoxyethylene esters|
|US2560839 *||Jul 24, 1947||Jul 17, 1951||Gen Aniline & Film Corp||Detergent composition|
|US2563328 *||Sep 19, 1949||Aug 7, 1951||Procter & Gamble||Cottonseed oil refining process|
|US2577503 *||May 6, 1947||Dec 4, 1951||Ici Ltd||Detergent composition|
|US2580277 *||Jun 22, 1948||Dec 25, 1951||Monsanto Chemicals||Polymerization of vinyl chloride in aqueous suspension to produce granular polymers|
|US2585826 *||Nov 5, 1948||Feb 12, 1952||Gen Aniline & Film Corp||Carbamate-quaternary ammonium compounds and their preparation|
|US2588318 *||Feb 7, 1949||Mar 4, 1952||Monsanto Chemicals||Water emulsifiable soil-poison concentrate|
|US2588771 *||Jun 21, 1949||Mar 11, 1952||Hart Products Corp||Method of making polyoxyalkylene ethers|
|US2592234 *||Feb 16, 1949||Apr 8, 1952||Eastman Kodak Co||Plasticized cellulose acetate-butyrate and cellulose acetatepropionate|
|US2594258 *||May 12, 1949||Apr 22, 1952||Monsanto Chemicals||Detergent composition|
|US2599803 *||Nov 1, 1948||Jun 10, 1952||Shell Dev||Lubricating composition|
|US2602087 *||Nov 12, 1948||Jul 1, 1952||Petrolite Corp||Oxyalkylation of the esters of certain amino alcohols|
|US2611485 *||Apr 21, 1949||Sep 23, 1952||Dow Chemical Co||Frothing agents for flotation of ores|
|US2617830 *||Jun 30, 1950||Nov 11, 1952||Monsanto Chemicals||Polyglycol ethers of 7-ethyl-2-methyl-undecanol-4|
|US2618605 *||Feb 4, 1949||Nov 18, 1952||Procter & Gamble||Detergent compositions containing metal discoloration inhibitors|
|US2618606 *||Feb 4, 1949||Nov 18, 1952||Procter & Gamble||Detergent compositions containing metal discoloration inhibitors|
|US2619467 *||Apr 16, 1949||Nov 25, 1952||Detergent mixtures containing|
|US2624762 *||May 4, 1949||Jan 6, 1953||Monsanto Chemicals||Hydroxy aliphatic derivatives of symmetrical di-aromatic thioureas|
|US2624766 *||Oct 15, 1949||Jan 6, 1953||Monsanto Chemicals||Tridecenyl alcohols|
|US2628883 *||Nov 23, 1949||Feb 17, 1953||Pacific Mills||Continuous chrome mordanting and dyeing of wool|
|US2637677 *||Jan 10, 1951||May 5, 1953||Standard Oil Co||Aryl mercuric fungicide and the method of using the same|
|US2637740 *||Oct 20, 1950||May 5, 1953||Monsanto Chemicals||Branched higher alkanol sulfates|
|US2643211 *||Nov 30, 1949||Jun 23, 1953||Rayette Inc||Hair color-rinse concentrate|
|US2644831 *||Apr 16, 1951||Jul 7, 1953||Monsanto Chemicals||Alkali metal and ammonium sulfates of hydroxy ethers|
|US2644832 *||Apr 16, 1951||Jul 7, 1953||Mon||Alkanol amine sulfates|
|US2644833 *||Apr 16, 1951||Jul 7, 1953||Monsanto Chemicals||Alkanolamine sulfates of hydroxy ethers|
|US2645555 *||Jan 27, 1949||Jul 14, 1953||Courtaulds Ltd||Manufacture and production of artificial threads from viscose|
|US2645615 *||Nov 24, 1948||Jul 14, 1953||Ici Ltd||Thickened aqueous detergent solutions|
|US2648693 *||Jan 27, 1951||Aug 11, 1953||Universal Oil Prod Co||Polyalkylene glycol esters of alkyltetrahydrophenylalkanoic acids|
|US2649415 *||Dec 30, 1949||Aug 18, 1953||Gen Aniline & Film Corp||Corrosion inhibitor composition|
|US2652409 *||Oct 17, 1951||Sep 15, 1953||Petrolite Corp||Oxyalkylation of the amides of secondary amines|
|US2660575 *||Oct 2, 1950||Nov 24, 1953||Celanese Corp||Polymerization process for polyurethanes utilizing water, a water miscible solvent, and a water immiscible solvent|
|US2663989 *||Mar 19, 1949||Dec 29, 1953||Schlatter Carl||Coated articles and textiles and emulsions for producing them|
|US2664360 *||Aug 20, 1951||Dec 29, 1953||Int Paper Canada||Manufacture of cellulose|
|US2665256 *||Jan 23, 1948||Jan 5, 1954||Atlas Powder Co||Solid compositions containing polyoxyethylene ethers and urea|
|US2667268 *||Mar 22, 1951||Jan 26, 1954||Atlas Powder Co||Aqueous solution inert to gelatin|
|US2671115 *||Mar 2, 1954||Ethers of z-butyloc|
|US2671116 *||Oct 20, 1950||Mar 2, 1954||Polyglycol ethers of z|
|US2683087 *||Feb 10, 1948||Jul 6, 1954||American Cyanamid Co||Absorbent cellulosic products|
|US2686757 *||Jan 15, 1953||Aug 17, 1954||Int Nickel Co||Suppression of honeycombing in cathode nickel|
|US2689815 *||Nov 15, 1950||Sep 21, 1954||Lever Brothers Ltd||Opaque hair treating compositions|
|US2690259 *||Nov 14, 1951||Sep 28, 1954||Bethlehem Steel Corp||Froth flotation of iron sulfide ore|
|US2690426 *||Mar 7, 1950||Sep 28, 1954||Atlas Powder Co||Lubricating compositions|
|US2690427 *||Dec 14, 1949||Sep 28, 1954||American Viscose Corp||Textile composition|
|US2690978 *||Oct 4, 1950||Oct 5, 1954||Atlas Powder Co||Bituminous emulsion|
|US2692180 *||Aug 25, 1951||Oct 19, 1954||Bohme Fettchemie Gmbh||Processing of hides and stabilized tanning solution therefor|
|US2694021 *||Mar 30, 1951||Nov 9, 1954||Atlas Powder Co||Textile bearing a starch size|
|US2694629 *||Apr 18, 1951||Nov 16, 1954||American Cyanamid Co||Production of sized alkaline paper|
|US2694630 *||May 31, 1952||Nov 16, 1954||American Cyanamid Co||Sized waterlaid glass fiber products and process of preparing the same|
|US2695101 *||Dec 10, 1952||Nov 23, 1954||American Cyanamid Co||Frothing agents for the flotation of ores and coal|
|US2695270 *||Mar 22, 1951||Nov 23, 1954||Atlas Powder Co||Oil soluble cationic textile antistatic agent|
|US2702796 *||May 31, 1950||Feb 22, 1955||Atlas Powder Co||Textile size comprising a partially neutralized polymethacrylic acid|
|US2706713 *||Jun 13, 1952||Apr 19, 1955||Exxon Research Engineering Co||Textile oil|
|US2709683 *||Mar 8, 1951||May 31, 1955||Composition for producing detergent|
|US2710861 *||Aug 20, 1951||Jun 14, 1955||Int Paper Canada||Treatment of cellulose with the reaction product of primary aliphatic amines and ethylene oxide|
|US2712994 *||Jan 27, 1949||Jul 12, 1955||Monsanto Chemicals||Process for improving paper and product|
|US2714109 *||Oct 9, 1951||Jul 26, 1955||o||Process for the production of|
|US2714607 *||Feb 13, 1951||Aug 2, 1955||Ciba Pharm Prod Inc||Polyethoxy esters of p-butylaminobenzoic acid|
|US2716058 *||Jun 24, 1950||Aug 23, 1955||Int Paper Canada||Deresination of wood pulp|
|US2717214 *||Sep 30, 1950||Sep 6, 1955||Monsanto Chemicals||Coating compositions and methods of preparing same|
|US2717270 *||Sep 3, 1953||Sep 6, 1955||Geigy Ag J R||Basic polyglycol ethers|
|US2724694 *||Oct 17, 1951||Nov 22, 1955||American Cyanamid Co||Mineral oils containing alkoxyalkylolamine epichlorhydrin condensation products|
|US2727004 *||Oct 2, 1952||Dec 13, 1955||Monsanto Chemicals||Chemical compounds and process of treating textile materials therewith|
|US2731338 *||Jan 5, 1951||Jan 17, 1956||Monsanto Chemicals||Emulsifying and dispersing agents|
|US2738059 *||Apr 24, 1952||Mar 13, 1956||Kendall & Co||Packaged surgical sutures and method of preparing same|
|US2743208 *||Mar 6, 1951||Apr 24, 1956||West Disinfecting Co||Dry free-flowing iodine compositions|
|US2744874 *||May 24, 1952||May 8, 1956||Monsanto Chemicals||Detergent compositions|
|US2745855 *||Apr 14, 1951||May 15, 1956||Sinclair Oil & Gas Co||Alkylene oxide condensate of discard palm oil|
|US2755296 *||Feb 13, 1953||Jul 17, 1956||Visco Products Co||Inorganic esters of aliphatic polyoxyalkylene compounds|
|US2759839 *||Jul 29, 1952||Aug 21, 1956||Standard Oil Co||Asphalt compositions|
|US2763269 *||Feb 1, 1952||Sep 18, 1956||Rayette Inc||Foaming hair coloring compositions comprising basic dyes, and method of use|
|US2766212 *||Sep 16, 1952||Oct 9, 1956||Gen Aniline & Film Corp||Detergents|
|US2769684 *||Feb 24, 1953||Nov 6, 1956||Ciba Ltd||Process for stripping and lightening wool dyeings|
|US2778854 *||Apr 21, 1953||Jan 22, 1957||Olin Mathieson||Purified polyethenoxy alkylphenyl ethers|
|US2782151 *||Sep 20, 1951||Feb 19, 1957||Petrolite Corp||Method of testing oils|
|US2783270 *||Dec 8, 1950||Feb 26, 1957||Union Oil Co||Polyhydric alcohol esters of acids formed by oxidation of hydrocarbons|
|US2784091 *||Apr 29, 1954||Mar 5, 1957||Eastman Kodak Co||4-hydroxy-6-alkyl-1, 3, 3alpha, 7-tetrazaindene stabilizers for photographic emulsions sensitized with polyalkylene esters, amides, and ethers|
|US2786080 *||Nov 25, 1953||Mar 19, 1957||Wyandotte Chemicals Corp||Stabilized polyoxyalkylene compositions|
|US2789093 *||Sep 28, 1953||Apr 16, 1957||California Research Corp||Filter adhesives|
|US2790764 *||Feb 17, 1954||Apr 30, 1957||Bohme Fettchemie Gmbh||Composition for preventing textile materials from becoming electrically charged|
|US2792308 *||Apr 9, 1953||May 14, 1957||Monsanto Chemicals||Alkylene oxide condensates and use thereof as defoaming agents|
|US2794825 *||Sep 15, 1953||Jun 4, 1957||Ciba Pharm Prod Inc||Polyethylene glycol esters of isocyclic organic carboxylic acids|
|US2800487 *||Dec 31, 1952||Jul 23, 1957||Universal Oil Prod Co||Polyoxyalkylene substituted heterocyclic amines and their ammonium salt derivatives|
|US2802789 *||Dec 21, 1954||Aug 13, 1957||California Research Corp||Polyoxypropylene glycol disulfate detergent compositions|
|US2803565 *||Sep 8, 1955||Aug 20, 1957||Ici Ltd||Processing of fibres|
|US2810694 *||Oct 12, 1954||Oct 22, 1957||Exxon Research Engineering Co||Textile oil|
|US2820808 *||May 7, 1954||Jan 21, 1958||Us Rubber Co||Organic esters of sulfurous acid|
|US2824832 *||Oct 21, 1953||Feb 25, 1958||Nopco Chem Co||Textile lubricating compositions|
|US2828243 *||Aug 28, 1953||Mar 25, 1958||Vick Chemical Company||Oxyethylated lauryl alcohol steam inhalation composition|
|US2829077 *||Oct 30, 1956||Apr 1, 1958||Du Pont||Galvanizing flux|
|US2831013 *||Dec 30, 1953||Apr 15, 1958||Universal Oil Prod Co||Sulfo-esters of alcohols bearing a hydrophilic substituent|
|US2834731 *||Jan 11, 1956||May 13, 1958||Exxon Research Engineering Co||Hydrocarbon oil meulsifier|
|US2839464 *||Feb 16, 1954||Jun 17, 1958||Exxon Research Engineering Co||Textile oil|
|US2841521 *||Jul 8, 1954||Jul 1, 1958||Armour & Co||Insecticidal compositions and method of combating insects|
|US2842462 *||Dec 16, 1954||Jul 8, 1958||Bohme Fettchemie Gmbh||Antistatic synthetic textile material|
|US2849474 *||Sep 1, 1954||Aug 26, 1958||Universal Oil Prod Co||Alkylaryl thio-urethans|
|US2852474 *||Sep 4, 1951||Sep 16, 1958||Exxon Research Engineering Co||Impregnation procedure for manufacturing hydroforming catalysts|
|US2854410 *||Aug 3, 1953||Sep 30, 1958||Exxon Standard Sa||Soap-thickened lubricating greases containing an alcohol-substituted amide|
|US2861108 *||Jun 30, 1953||Nov 18, 1958||Olin Mathieson||Production of polyethyenoxy alkyl phenate ethers|
|US2861956 *||Feb 25, 1953||Nov 25, 1958||Monsanto Chemicals||Liquid detergent compositions|
|US2868686 *||Nov 19, 1956||Jan 13, 1959||West Laboratories Inc||Iodine bromine preparations for controlling microorganisms|
|US2871266 *||Jan 7, 1957||Jan 27, 1959||Rohm & Haas||Tert-carbinamines|
|US2876263 *||Dec 31, 1952||Mar 3, 1959||Universal Oil Prod Co||Polyoxyalkylene cyclic hydrocarbon substituted amines and their ammonium salt derivatives|
|US2877178 *||Dec 20, 1955||Mar 10, 1959||Gen Aniline & Film Corp||Ampholytic compositions in wet treatments|
|US2887460 *||Dec 27, 1955||May 19, 1959||Dow Chemical Co||Stabilized latex coating compositions containing reactive pigments and glycolamine stabilizers and method for preparing same|
|US2889297 *||Jun 29, 1953||Jun 2, 1959||Atlas Powder Co||Polyvinyl acetate adhesive compositions containing a polyethylene glycol monoether of a monohydric phenol|
|US2890983 *||Jul 30, 1957||Jun 16, 1959||Monot Pierre Louis Victor||Excipient|
|US2892818 *||Mar 26, 1956||Jun 30, 1959||California Research Corp||Detergent copolymers|
|US2907670 *||Mar 22, 1957||Oct 6, 1959||Gen Aniline & Film Corp||Pigment dispersions|
|US2910441 *||Nov 2, 1954||Oct 27, 1959||Bohme Fettchemie Gmbh||Dispersing agents and dispersions produced therewith|
|US2911372 *||May 22, 1956||Nov 3, 1959||Austin Sr Harry G||Lanolin-ammonia composition|
|US2914477 *||Aug 29, 1955||Nov 24, 1959||Standard Oil Co||Emulsifiable oil|
|US2921920 *||Jul 3, 1956||Jan 19, 1960||Union Carbide Corp||Polyethylene telomer-polyalkylene oxide block copolymer and method of preparing same|
|US2932616 *||Feb 19, 1957||Apr 12, 1960||Monsanto Chemicals||Detergent compositions|
|US2932670 *||Sep 16, 1957||Apr 12, 1960||Monsanto Chemicals||Derivatives of glycerol 1, 3-dialkyl ethers and their preparation|
|US2934568 *||Feb 6, 1950||Apr 26, 1960||Atlas Powder Co||Detergent reaction products of branched chain aliphatic alcohols and ethylene oxide|
|US2938887 *||Nov 15, 1955||May 31, 1960||Colgate Palmolive Co||Water-soluble copolymers|
|US2941950 *||Sep 30, 1954||Jun 21, 1960||Procter & Gamble||Concentrated liquid detergent|
|US2943979 *||Jun 23, 1959||Jul 5, 1960||Nathaniel M Elias||Concentrated foam-producing spermicides|
|US2953526 *||Dec 20, 1955||Sep 20, 1960||Gen Aniline & Film Corp||Ampholytic compositions in wet treatments|
|US2964470 *||Mar 19, 1956||Dec 13, 1960||American Viscose Corp||Tire cord fiber lubricant|
|US2965678 *||Dec 28, 1951||Dec 20, 1960||Gen Aniline & Film Corp||Polyoxyethylene ethers of branched chain alcohols|
|US2968541 *||May 7, 1957||Jan 17, 1961||Atlas Powder Co||Nitrostarch composition and method of making the same|
|US2968621 *||Jun 28, 1955||Jan 17, 1961||Sinclair Refining Co||Acid-tolerating soluble oil composition|
|US2971920 *||Feb 25, 1957||Feb 14, 1961||Wurmbock Egon||Finger nail polish remover|
|US2980588 *||Jul 18, 1957||Apr 18, 1961||Lab Francais Chimiotherapie||Multivitamin preparation and method of making same|
|US2986542 *||Dec 30, 1958||May 30, 1961||Ciba Ltd||Pigmented artificial resin lacquers dispersible in aqueous media and process for their manufacture|
|US2993003 *||Sep 25, 1957||Jul 18, 1961||California Research Corp||Asphalt emulsion|
|US2995523 *||Feb 17, 1958||Aug 8, 1961||Grace W R & Co||Detergent-softener compositions|
|US2999045 *||Jul 22, 1953||Sep 5, 1961||Rayonier Inc||Deresination of wood pulp|
|US3010907 *||Apr 9, 1957||Nov 28, 1961||Pennsalt Chemicals Corp||Alkaline cleaning compositions|
|US3024198 *||Apr 28, 1958||Mar 6, 1962||Nopco Chem Co||Emulsifier composition|
|US3025127 *||May 28, 1959||Mar 13, 1962||Du Pont||Acid dyeing of polyamides using quaternary ammonium salts|
|US3029205 *||May 5, 1958||Apr 10, 1962||Lever Brothers Ltd||Light duty liquid detergent|
|US3030197 *||Nov 22, 1960||Apr 17, 1962||Petrolite Corp||Thermally stable distillate fuels|
|US3034984 *||Oct 8, 1958||May 15, 1962||Texaco Inc||Drilling fluid|
|US3037875 *||Feb 16, 1959||Jun 5, 1962||Universal Oil Prod Co||Paint compositions|
|US3038794 *||Nov 4, 1958||Jun 12, 1962||Plant Products Corp||Plant growth regulator|
|US3044898 *||Oct 21, 1960||Jul 17, 1962||Deering Milliken Res Corp||Textile sizing composition, applicating method and resulting product|
|US3048539 *||Jun 29, 1959||Aug 7, 1962||American Cyanamid Co||Antistatic textile lubricant finishes|
|US3049392 *||Aug 14, 1962||Process for dyeing nitrogenous mate-|
|US3056644 *||Oct 14, 1960||Oct 2, 1962||Mayborn Products Ltd||Dyeing compositions|
|US3061547 *||Jan 17, 1955||Oct 30, 1962||Atlas Chem Ind||Hydraulic fluid composition and thickening agent therefor|
|US3061548 *||Nov 26, 1958||Oct 30, 1962||Standard Oil Co||Method of cleaning alcl3-hydrocarbon complex from metals|
|US3062749 *||Sep 2, 1958||Nov 6, 1962||Herrling Robert F||Composition and method for removing postage stamps|
|US3063819 *||Dec 12, 1958||Nov 13, 1962||Shell Oil Co||Fuel composition|
|US3068058 *||Nov 27, 1959||Dec 11, 1962||Ciba Company||Process for printing polyhydroxylated|
|US3076508 *||Jan 11, 1960||Feb 5, 1963||Petrolite Corp||Well reactivation|
|US3079348 *||Dec 1, 1958||Feb 26, 1963||Rohm & Haas||Surfactants|
|US3079416 *||Dec 1, 1958||Feb 26, 1963||Rohm & Haas||Surfactant compositions|
|US3096300 *||Jul 10, 1958||Jul 2, 1963||Dow Chemical Co||Polymeric compositions of monovinyl aromatic hydrocarbons and synthetic rubber containing high molecular weight polyethylene glycols or monoesters of such glycols|
|US3097039 *||Mar 28, 1960||Jul 9, 1963||Hoas oh|
|US3097040 *||Feb 1, 1960||Jul 9, 1963||Ciba Company Inc||Process for dyeing nitrogenous fibers|
|US3101301 *||May 11, 1962||Aug 20, 1963||Bristol Myers Co||Transparent water and mineral oil gels as hair conditioners|
|US3101323 *||Sep 12, 1960||Aug 20, 1963||Montedison Spa||Compositions imparting antistatic properties to fibers and method of making same|
|US3104443 *||Dec 4, 1957||Sep 24, 1963||Monsanto Chemicals||Method and composition for fulling fabrics|
|US3104931 *||Mar 9, 1959||Sep 24, 1963||Ciba Geigy Corp||Process for dyeing wool|
|US3118000 *||Aug 10, 1959||Jan 14, 1964||Rohm & Haas||Polyoxyalkylene surface-active agents|
|US3122508 *||Jul 28, 1960||Feb 25, 1964||Gen Aniline & Film Corp||Heavy duty detergent compositions|
|US3123565 *||May 10, 1960||Mar 3, 1964||Process for tinting laundry chemicals|
|US3145180 *||Apr 19, 1960||Aug 18, 1964||Rohm & Haas||Process of cleaning metal surfaces|
|US3146059 *||Nov 10, 1958||Aug 25, 1964||Nikken Chemicals Co Ltd||Evaporation-suppressing agents and method of their production|
|US3154498 *||Dec 6, 1960||Oct 27, 1964||Calgon Corp||Water treating composition|
|US3155470 *||Oct 13, 1960||Nov 3, 1964||Bohme Fettchemie Gmbh||Process for the separation of suspended particles from gases|
|US3158484 *||Oct 24, 1961||Nov 24, 1964||Gevaert Photo Producten N V Mo||Light-sensitive colloid silver halide photographic elements|
|US3162604 *||May 10, 1960||Dec 22, 1964||Stamford Chemical Ind Inc||Dry cleaning solvent compositions|
|US3168478 *||Jul 28, 1960||Feb 2, 1965||Gen Aniline & Film Corp||Highly alkaline surface active compositions|
|US3170877 *||Dec 21, 1961||Feb 23, 1965||Gen Aniline & Film Corp||Antistatic treating solution for polyacrylonitrile fibers and method|
|US3173877 *||Sep 9, 1957||Mar 16, 1965||Wyandotte Chemicals Corp||Detergent compositions comprising inorganic esters of epoxyhydrocarbon polymers|
|US3174943 *||Aug 8, 1960||Mar 23, 1965||I C I Organics Inc||Plasticized urea-formaldehyde resins|
|US3188292 *||May 29, 1961||Jun 8, 1965||Ucb Sa||Pickling inhibiting compositions|
|US3197333 *||Aug 11, 1961||Jul 27, 1965||Berol Aktiebolag||Processes of treating textile fibres before forming the same into a yarn|
|US3199942 *||Mar 12, 1962||Aug 10, 1965||Bayer Ag||Divinyl sulfone, diisocyanate, dicarboxylic acid or dihydroxysulfide reaction products with polyethylene ethers in high temperature pad dyeing and printing|
|US3206410 *||Jul 11, 1961||Sep 14, 1965||Scholten Chemische Fab||Water-in-oil emulsions|
|US3206420 *||Apr 28, 1961||Sep 14, 1965||Celanese Corp||Blends of a vinylidene cyanide polymer and a polyalkylene glycol or derivative thereof|
|US3210191 *||Nov 3, 1961||Oct 5, 1965||Gevaert Photo Prod Nv||Silver halide emulsions sensitized with alkylene oxide polymers|
|US3215200 *||Oct 31, 1960||Nov 2, 1965||Nalco Chemical Co||Production of aqueous foams and compositions therefor|
|US3218116 *||Jan 22, 1963||Nov 16, 1965||Ciba Geigy Corp||Process for dyeing wool|
|US3219697 *||Dec 29, 1961||Nov 23, 1965||Union Carbide Corp||Tricyclodecane amino polyols|
|US3223471 *||Mar 12, 1962||Dec 14, 1965||Process fgr dyeing textile materials|
|US3229777 *||Mar 22, 1961||Jan 18, 1966||Swift & Co||Method of transporting water from a well as a substantially stable foam|
|US3233961 *||May 15, 1963||Feb 8, 1966||Celanese Corp||Process for dyeing cellulose acetate having an acetyl value of at least 59% in the presence of hydroxyalkylamine-fatty acid condensation products|
|US3243402 *||Dec 5, 1960||Mar 29, 1966||Montedison Spa||Highly stable halogenated polyvinyl plastisols|
|US3244624 *||Aug 28, 1962||Apr 5, 1966||Bayer Ag||Treatment of synthetic filaments and composition therefor|
|US3250719 *||Sep 30, 1963||May 10, 1966||Wyandotte Chemicals Corp||Foaming detergent compositions|
|US3250808 *||Oct 31, 1963||May 10, 1966||Du Pont||Fluorocarbon ethers derived from hexafluoropropylene epoxide|
|US3257233 *||Apr 8, 1963||Jun 21, 1966||Gen Mills Inc||Textile fabric treated with ditertiary amine obtained from a secondary amine and polyoxyethylene glycol and the quaternary obtained therefrom|
|US3268593 *||Jun 26, 1961||Aug 23, 1966||Cumberland Chemical Corp||Ethylene oxide adducts of tertiary acetylenic alcohols|
|US3272899 *||Apr 3, 1964||Sep 13, 1966||Hagan Chemicals & Controls Inc||Process for producing a solid rinse block|
|US3281341 *||Apr 18, 1963||Oct 25, 1966||United States Steel Corp||Method of improving solderability of tin plate|
|US3282728 *||May 1, 1962||Nov 1, 1966||Aquitaine Petrole||Process for suppressing electrostatic charges on sulphur|
|US3291556 *||Nov 18, 1963||Dec 13, 1966||Ciba Ltd||Process for dyeing wool yarn and preparations for use therein|
|US3291692 *||May 26, 1965||Dec 13, 1966||Grace W R & Co||Germicidal compositions containing complexes of iodine|
|US3293191 *||Oct 29, 1964||Dec 20, 1966||Cumberland Chemical Corp||Ethylene oxide adducts of tertiary acetylenic alcohols|
|US3294693 *||Mar 12, 1965||Dec 27, 1966||Rohm & Haas||Phosphorylated surfactants as hydrotropes|
|US3296019 *||Apr 19, 1962||Jan 3, 1967||Fmc Corp||Poly (ethylene oxide) adducts of fatty oils and fatty amines as antistatic coating for polyolefin fibers|
|US3296065 *||Oct 7, 1963||Jan 3, 1967||Monsanto Co||Paper products containing carboxylic acid esters and process for preparing such products|
|US3310496 *||Mar 12, 1965||Mar 21, 1967||Rohm & Haas||Alkali stable and soluble surfactants|
|US3312624 *||Mar 12, 1965||Apr 4, 1967||Rohm & Haas||Stable alkali soluble surfactants|
|US3317609 *||May 6, 1964||May 2, 1967||Jefferson Chem Co Inc||Epoxide addition reaction with amino alcohol|
|US3333983 *||Aug 29, 1966||Aug 1, 1967||Nopco Chem Co||Antistatic polymeric materials containing ethylene oxide condensation products of phenolic derivatives|
|US3341467 *||Mar 3, 1967||Sep 12, 1967||Grace W R & Co||Method of inhibiting foaming in aqueous systems|
|US3342542 *||Nov 22, 1965||Sep 19, 1967||Ho o nhx c chax c chjx o oh|
|US3347805 *||Feb 21, 1963||Oct 17, 1967||Montedison Spa||Process for producing synthetic polyvinyl ester latices, particularly suitable for water paints and latices thus obtained|
|US3352790 *||Feb 21, 1964||Nov 14, 1967||Gen Aniline & Film Corp||Process and compositions for dry cleaning|
|US3354209 *||Feb 19, 1964||Nov 21, 1967||Hercules Inc||Poly(dihydroxyalkyl) tertiary amines|
|US3359205 *||Jul 8, 1965||Dec 19, 1967||Monsanto Co||Detergent composition containing substituted benzyl ether non-ionic detergents|
|US3364142 *||Dec 6, 1965||Jan 16, 1968||Northern Petro Chem Co||Composition for reconstituting frozen aqueous systems and method for making|
|US3365402 *||Feb 25, 1964||Jan 23, 1968||Chem Y||Process for eliminating the harmful effects of an alkaline catalyst in capillary-active products|
|US3380925 *||Oct 17, 1966||Apr 30, 1968||Henkel & Cie Gmbh||Polyglycol ethers suitable for detergent preparations|
|US3384443 *||Feb 4, 1963||May 21, 1968||Bayer Ag||Dyeing cellulose and wool fibers with a polyethylene glycol ether of a styrene-propenylphenol copolymer containing dye solution|
|US3389205 *||Mar 24, 1964||Jun 18, 1968||Celanese Corp||Method of improving the dye receptivity of fibers of vinylidene cyanide copolymers|
|US3391750 *||Aug 9, 1965||Jul 9, 1968||Union Carbide Corp||Surfactant composition|
|US3398201 *||May 7, 1965||Aug 20, 1968||Gaf Corp||Reaction products from 2-alkoxybutanols and 3, 5,x - polyalkoxyalkanols with alkylene oxides|
|US3406208 *||Dec 16, 1966||Oct 15, 1968||Henkel & Compagnie G M B H||Polyglycol ethers suitable for detergent preparations, and process for preparing the same|
|US3428692 *||Feb 28, 1966||Feb 18, 1969||Continental Oil Co||Preparation of nonionic detergents|
|US3442999 *||Jul 19, 1966||May 6, 1969||Cassella Farbwerke Mainkur Ag||Process for the production of chipboards|
|US3471297 *||Dec 22, 1966||Oct 7, 1969||Gaf Corp||Photomechanical emulsions containing a polyethylene glycol dicarboxylic acid ester|
|US3472605 *||Jul 31, 1964||Oct 14, 1969||Sandoz Ag||Process for dyeing or printing leather|
|US3472783 *||Feb 2, 1966||Oct 14, 1969||Winston B Smillie||Nonionic detergent compositions|
|US3489690 *||Dec 13, 1965||Jan 13, 1970||Oreal||Water-in-oil emulsion|
|US3490918 *||Oct 11, 1968||Jan 20, 1970||Ashland Oil Inc||Shortenings containing ethoxylated partial glycerol esters|
|US3499876 *||Apr 21, 1967||Mar 10, 1970||Gaf Corp||Novel anhydride interpolymers|
|US3509048 *||Oct 3, 1966||Apr 28, 1970||American Cyanamid Co||Softening agent for cotton and for synthetic textile substrates|
|US3519006 *||Dec 5, 1966||Jul 7, 1970||Ralph Simon||Pipelining oil/water mixtures|
|US3619271 *||Oct 15, 1968||Nov 9, 1971||Ciba Ltd||Process for improving fabrics containing cellulosic fibers|
|US3634017 *||Dec 10, 1968||Jan 11, 1972||Hoechst Ag||Oxazine dye concentrate with polyethylene oxide|
|US3639154 *||Jul 9, 1969||Feb 1, 1972||Kanegafuchi Spinning Co Ltd||Process for manufacturing fibrous structure having excellent recovery from extension by treatment with polyorganosiloxane and a polyethylene glycol or derivative thereof|
|US3639255 *||Apr 24, 1968||Feb 1, 1972||Ici Ltd||Process of dispersing oil slicks|
|US3770495 *||Oct 28, 1971||Nov 6, 1973||K Bernklau||Non-adhesive high elastic elastomer threads|
|US3773463 *||Apr 18, 1972||Nov 20, 1973||Sybron Corp||Lubricating, antistat and dye leveling agent and process for textile materials|
|US3776766 *||Nov 17, 1971||Dec 4, 1973||Hoechst Ag||Process for improving the processing properties of polyester filaments and fibres|
|US3779934 *||Dec 7, 1971||Dec 18, 1973||Henkel & Cie Gmbh||Process and agents for the clear rinse in mechanical dishwashing|
|US3780860 *||May 17, 1971||Dec 25, 1973||Stephan Chem Co||Flotation of copper sulfide ores|
|US3827557 *||May 17, 1971||Aug 6, 1974||Stepan Chemical Co||Method of copper sulfide ore flotation|
|US3846546 *||Jul 13, 1971||Nov 5, 1974||Oreal||New emulsions, and cosmetic products made from such emulsions|
|US3860540 *||May 17, 1972||Jan 14, 1975||Ciba Geigy Ag||Agent for rendering wool non-felting|
|US3897208 *||Jun 9, 1969||Jul 29, 1975||Ici America Inc||Textile treating compositions, process of treating textiles, and textile articles|
|US3910972 *||Feb 28, 1974||Oct 7, 1975||Henkel & Cie Gmbh||Fatty acid ester mixtures liquid at low temperatures and process|
|US3925009 *||Jun 9, 1969||Dec 9, 1975||Ici America Inc||Fatty group containing methylolated, polyoxyalkylene carbamates and textile materials softened by treatment therewith|
|US3954399 *||Mar 26, 1973||May 4, 1976||Sumitomo Chemical Company, Limited||Process for dyeing nitrogen-containing fibers|
|US3994826 *||Nov 27, 1974||Nov 30, 1976||The Richardson Company||Method of emulsification|
|US4060387 *||Nov 10, 1975||Nov 29, 1977||Sandoz Ltd.||Aromatic carboxylic acid esters and amides as fixing agents|
|US4063886 *||Jun 1, 1976||Dec 20, 1977||Westvaco Corporation||Mercerizing compositions|
|US4071458 *||Sep 17, 1976||Jan 31, 1978||Texaco Inc.||Oil displacement fluid containing a solubilizing agent|
|US4082506 *||Oct 15, 1975||Apr 4, 1978||Union Carbide Corporation||Printing formulations|
|US4120358 *||Apr 11, 1977||Oct 17, 1978||Texaco Inc.||Surfactant oil recovery method for use in high temperature formations containing water having high salinity and hardness|
|US4126702 *||May 28, 1976||Nov 21, 1978||L'oreal||Novel derivatives of glycerol|
|US4169062 *||Jul 3, 1978||Sep 25, 1979||Southern Sizing Co.||Random copolymers of polyoxyethylene polyoxypropylene glycol monoester, process of making the same and textile fiber containing the same|
|US4194565 *||Mar 27, 1978||Mar 25, 1980||Texaco Inc.||Surfactant oil recovery method for use in high temperature formations containing water having high salinity and hardness|
|US4200733 *||Mar 29, 1979||Apr 29, 1980||Basf Aktiengesellschaft||Iodine-containing block copolymers of 1,4-butylene oxide and ethylene oxide|
|US4210572 *||Aug 29, 1978||Jul 1, 1980||Nl Industries, Inc.||Coupling agents for thermosetting composites|
|US4210700 *||Sep 15, 1978||Jul 1, 1980||Allied Chemical Corporation||Production of polyester yarn|
|US4224311 *||Aug 8, 1975||Sep 23, 1980||L'oreal||Disubstituted derivatives of glycerol and cosmetic compositions containing the same as an oily excipient therefor|
|US4238331 *||Jul 27, 1979||Dec 9, 1980||The British Petroleum Company Limited||Process for treating sea water containing waxy lipids|
|US4288331 *||Jun 13, 1979||Sep 8, 1981||Shell Oil Company||Lubricating compositions for primary backing fabrics used in the manufacture of tufted textile articles|
|US4297262 *||Aug 31, 1979||Oct 27, 1981||E. I. Du Pont De Nemours And Company||Polyvinyl butyral plasticized with tetraethyleneglycol di-n-heptanoate|
|US4312973 *||Apr 11, 1980||Jan 26, 1982||Union Carbide Corporation||Polyurethane elastomers prepared from polyol or polymer/polyol-chain extender mixtures|
|US4384978 *||Aug 26, 1980||May 24, 1983||Henkel Kommanditgesellschaft Auf Aktien||Aqueous concentrates of a tenside of the sulfate and sulfonate type and process for the improvement of the flow behavior of difficultly pourable aqueous tenside concentrates|
|US4410508 *||Jun 19, 1981||Oct 18, 1983||The United States Of America As Represented By The Secretary Of The Army||Novel aqueous foam formulation and method|
|US4416868 *||Aug 8, 1975||Nov 22, 1983||Societe Anonyme Dite: L'oreal||Cosmetic excipient|
|US4422879 *||Jul 26, 1982||Dec 27, 1983||Akzona, Inc.||Paper sizing agent and process for the preparation thereof|
|US4461729 *||Aug 23, 1982||Jul 24, 1984||Mobil Oil Corporation||Method for the selective preparation of secondary alcohols and derivatives thereof|
|US4461730 *||Aug 23, 1982||Jul 24, 1984||Mobil Oil Corporation||Method for the selective preparation of secondary alcohols and derivatives thereof|
|US4472294 *||Jan 29, 1982||Sep 18, 1984||Daikin Kogyo Co., Ltd.||Fluorine-containing compounds, and surface-tension lowering agent containing same|
|US4476037 *||Feb 24, 1983||Oct 9, 1984||Henkel Kommanditgesellschaft Auf Aktien||Free flow, readily dilutable aqueous concentrates of a tenside of the sulfate and sulfonate type|
|US4532125 *||Jul 9, 1979||Jul 30, 1985||L'oreal||New surface-active statistical oligomers, a process for their preparation and compositions in which they are present|
|US4568351 *||May 17, 1984||Feb 4, 1986||Sandoz Ltd.||Use of certain esters as pH regulators in textile finishing processes|
|US4594366 *||Dec 7, 1984||Jun 10, 1986||Union Carbide Corporation||Connected branched polyols and polyurethanes based thereon|
|US4816336 *||Apr 2, 1987||Mar 28, 1989||Hoechst Celanese Corporation||Synthetic fiber having high neutralized alkyl phosphate ester finish level|
|US4832865 *||Jan 5, 1988||May 23, 1989||Ppg Industries, Inc.||Composition containing non-ionic surfactant|
|US5007489 *||Apr 27, 1990||Apr 16, 1991||Baker Hughes Incorporated||Drilling fluid methods and composition|
|US5099930 *||Jan 25, 1991||Mar 31, 1992||Baker Hughes Incorporated||Drilling fluid methods and composition|
|US5181276 *||Sep 9, 1991||Jan 26, 1993||Baxter International Inc.||Infection resistant products|
|US5213700 *||Feb 21, 1992||May 25, 1993||Texaco Inc.||Method of lubricating a textile machine|
|US5273683 *||Jun 26, 1992||Dec 28, 1993||Asphalt Technology & Consulting, Inc.||Emulsifier for use in mixing grade emulsions|
|US5276204 *||Oct 23, 1992||Jan 4, 1994||Henkel Kommanditgesellschaft Auf Aktien||Fatty alcohol mixtures and ethoxylates thereof showing improved low-temperature behavior|
|US5279677 *||Jun 17, 1991||Jan 18, 1994||Coral International, Inc.||Rinse aid for metal surfaces|
|US5466725 *||Dec 4, 1991||Nov 14, 1995||Baxter International, Inc.||Anti-viral materials|
|US5780043 *||Oct 18, 1995||Jul 14, 1998||Dane; Greg||Infection resistant thermoplastic polyurethane|
|US5858281 *||Feb 27, 1997||Jan 12, 1999||Clariant Finance (Bvi) Limited||Textile treatment processes and compositions therefor|
|US6849751 *||Dec 16, 2002||Feb 1, 2005||The Procter & Gamble Company||Alkyl-capped alkoxylated esters and compositions comprising same|
|US7081541||Nov 17, 2004||Jul 25, 2006||The Procter & Gamble Company||Alkyl-capped alkoxylated esters and compositions comprising same|
|US7662982||Mar 28, 2006||Feb 16, 2010||The Procter & Gamble Company||Alkyl-capped alkoxylated esters and compositions comprising same|
|US7910759||Mar 28, 2006||Mar 22, 2011||The Procter & Gamble Company||Synthesis of alkyl-capped alkoxylated esters useful as suds-controlling surfactants|
|US7915435||Mar 28, 2006||Mar 29, 2011||The Procter & Gamble Company||Alkyl-capped alkoxylated esters and compositions comprising same|
|US8143208||Mar 28, 2006||Mar 27, 2012||The Procter & Gamble Company||Alkyl-capped alkoxylated esters and compositions comprising same|
|US20030158438 *||Dec 16, 2002||Aug 21, 2003||The Procter & Gamble Company||Alkyl-capped alkoxylated esters and compositions comprising same|
|US20050090421 *||Nov 17, 2004||Apr 28, 2005||The Procter & Gamble Company||Alkyl-capped alkoxylated esters and compositions comprising same|
|US20060167293 *||Mar 28, 2006||Jul 27, 2006||Gray Lon M||Alkyl-capped alkoxylated esters and compositions comprising same|
|US20060275244 *||Mar 28, 2006||Dec 7, 2006||Gray Lon M||Alkyl-capped alkoxylated esters and compositions comprising same|
|US20060276664 *||Mar 28, 2006||Dec 7, 2006||Gray Lon M||Alkyl-capped alkoxylated esters and compositions comprising same|
|US20060276665 *||Mar 28, 2006||Dec 7, 2006||Gray Lon M||Alkyl-capped alkoxylated esters and compositions comprising same|
|DE762219C *||Jan 3, 1937||Oct 29, 1951||Henkel & Cie Gmbh||Verfahren zur Herstellung von wasserloeslichen alkylierten cycloaliphatischen Aminen|
|DE973985C *||Jun 26, 1953||Aug 11, 1960||Boehme Fettchemie Gmbh||Verfahren zur Herstellung von als Dispergiermittel dienenden esterartigen Produkten|
|DE974767C *||Aug 10, 1954||May 18, 1961||Union Carbide Corp||Verfahren zur Herstellung von Polyglykolaethern hoeherer Alkohole|
|DE1054239B *||Aug 31, 1956||Apr 2, 1959||Union Carbide Corp||Verfahren zur Herstellung eines oberflaechenaktiven, hydrophilen Polyglykolaethers|
|DE1060595B *||Jul 10, 1956||Jul 2, 1959||Ciba Geigy||Verfahren zur Herstellung von Egalisiermitteln fuer das Faerben von Textilien|
|DE1064717B *||Jul 10, 1956||Sep 3, 1959||Ciba Geigy||Verfahren zur Herstellung von wasserloeslichen, stickstoffhaltigen Polyglykolaetherderivaten|
|DE1132123B *||Jun 7, 1956||Jun 28, 1962||Inst Francais Du Petrole||Verfahren zur Herstellung von als Schmieroele geeigneten Ricinusoelfettsaeurepolyaethylenglykolestern|
|DE1149907B *||Feb 25, 1959||Jun 6, 1963||Basf Ag||Verfahren zur Herstellung von hoehermolekularen Alkoholen, die die Gruppierung -CH-CH-O- enthalten|
|DE1168077B *||Jul 7, 1960||Apr 16, 1964||Geigy Ag J R||Verfahren zur Herstellung von Polyaddukten|
|DE102010034331A1||Aug 14, 2010||Feb 16, 2012||Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.||Polymer-gestützte Kultursysteme|
|EP2418233A1||Jul 21, 2011||Feb 15, 2012||Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.||Polymer-supported culture systems|
|U.S. Classification||558/48, 252/8.83, 564/468, 8/129, 516/DIG.700, 516/51, 564/433, 554/223, 504/363, 564/505, 516/45, 564/462, 435/263, 8/138, 8/127, 564/475, 516/DIG.600, 8/595, 554/227, 504/365, 568/622, 209/901, 558/179, 564/180, 558/29, 568/623, 558/174, 435/272, 8/94.2, 516/76, 558/34, 516/DIG.400, 8/139, 564/477, 558/52, 516/71, 507/136, 252/8.86, 554/149, 568/618, 252/62.2, 560/1, 558/51, 162/DIG.300, 252/73, 554/167, 560/263, 516/73, 508/501, 554/219, 558/186, 558/32|
|International Classification||C09B67/46, C08K5/06|
|Cooperative Classification||C09B67/0085, Y10S162/03, Y10S209/901, Y10S516/06, Y10S516/07, C08K5/06, Y10S516/04|
|European Classification||C08K5/06, C09B67/00P10B|