WO2006034459A1 - Alkoxylated alkylamines / alkyl ether amines with peaked distribution - Google Patents
Alkoxylated alkylamines / alkyl ether amines with peaked distribution Download PDFInfo
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- WO2006034459A1 WO2006034459A1 PCT/US2005/034186 US2005034186W WO2006034459A1 WO 2006034459 A1 WO2006034459 A1 WO 2006034459A1 US 2005034186 W US2005034186 W US 2005034186W WO 2006034459 A1 WO2006034459 A1 WO 2006034459A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
Definitions
- the present invention relates to an alkali-catalyzed process for preparation of alkoxylated alkyl amines or alkoxylated alkyl ether amines with peaked distribution.
- Alkoxylated alkyl amines and alkyl ether amines have many applications in industry. They can be usefully employed as adjuvants in pesticide formulations, textile processing aids, dye transfer inhibitors, acid thickeners, detergent boosters, degreasers, anti-static agents and the like.
- Alkoxylated alkyl amines and alkoxylated alkyl ether amines are materials possessing the following general structures (I), respectively:
- R is typically selected from a linear or branched, saturated or non-saturated alkyl group containing 8 - 22 carbon atoms.
- R corresponds to the formula:
- R 1 is typically a linear or branched, saturated or non-saturated alkyl group containing 8-22 carbon atoms
- a and B are alkylene oxide groups containing 2 - 4 carbon atoms
- C is alkylene group containing 3 - 4 carbon atoms
- a, b each vary from O - 5
- c is 1
- X, Y, Z are alkylene oxide groups containing 2 - 4 carbon atoms
- x is 1
- y and z each independently vary from 0 - 15.
- the alkoxylated alkyl amines/ alkoxylated alkyl ether amines possess a surfactant structure which is composed of the
- SUBSTITUTE SHEIET (RULE 26) lipophilic groups (R or R 1 ) and the hydrophilic groups (polyalkylene oxide).
- R or R 1 lipophilic groups
- hydrophilic groups polyalkylene oxide
- the performance of the alkoxylated alkyl amines / alkoxylated alkyl ether amines is not necessarily optimal.
- these materials are prepared from the base- catalyzed alkoxylation of the corresponding alkyl amines / alkyl ether amines.
- Such an alkoxylation reaction is actually the polymerization reaction of alkylene oxide that includes the characteristic propagation and chain transfer steps of the polymerization process. For this reason, the resulting alkoxylated alkylamine / alkyl ether amine is not a pure compound, but a mixture of many homologs.
- Figure 1 Homolog distribution of tallow amine prepared with 5 moles of ethylene oxide by the regular hydroxide-catalyzed process.
- Figure 1 illustrates the homolog distribution of ethoxylated tallow amine prepared from the regular hydroxide-catalyzed ethoxylation of tallow amine with 5 moles of ethylene oxide.
- Homologs with shorter EO chain length ( ⁇ 3EO) or longer EO chain length (> 5EO) are not desirable for the applications for which a 5 EO/amine ratio surfactant is ordinarily prescribed, since such longer and shorter homologs are either too lipophilic or too hydrophilic for the applications utilizing this product.
- the presence of especially long species is particularly disadvantageous, e.g., species having an EO/amine ratio of more than about 1.5x the target ratio. Therefore, it is advantageous to develop an alkoxylation process that results in alkoxylated products with peaked distribution.
- U.S. patent 4,483 ,941 describes the preparation of ethoxylated organic materials comprising a peaked distribution of homologs, as prepared by ethoxylation in the presence of BF 3 and metal alkyls or metal alkoxides, SiF 4 and metal alkyls or metal alkoxides, or mixtures of all these catalysts.
- the reference lists alcohols, alkyl phenols, polyols, aldehydes, ketones, amines, amides, organic acids and mercaptans as substrates that may be ethoxylated.
- the patent includes a long list of amines that are subject to ethoxylation, particularly including octylamine and hexadecylamine.
- Working examples describe ethoxylation of Cn to 0 .4 alcohols.
- East German patent DD 219,478 describes the ethoxylation of amines in the presence of Lewis acid catalysts.
- a number of working examples are included which embody reactions with C 12 primary amine at ethylene oxide to amine ratios in the ranges of about 2, 3 and 6. At ratios of about 3 and about 6, final reaction temperatures range from 179° to 207 0 C.
- WO 02/38269 describes a catalyst comprising Ca sulfate, Ca acetate, low molecular weight Ca alcoholate and a crystalline phase in the form of organic Ca and sulfur compounds as a catalyst in the ethoxylation of alcohols to obtain a narrow distribution of homologs, and the use of such catalyst in the ethoxylation of organic substrates.
- alkoxylated alkyl(ether) amines that impart improved functional properties to formulations in which they are incorporated.
- herbicidal formulations such as aqueous liquid glyphosate formulations comprising a salt of glyphosate, wherein they may serve to increase the efficacy of the herbicide in controlling or destroying unwanted vegetation.
- N-phosphonomethylglycine otherwise known as glyphosate
- Glyphosate is well known in the art as an effective post-emergent foliar applied herbicide.
- Glyphosate is an organic compound that at neutral PH, contains three acidic protonatable groups, and in its acid form is relatively insoluble in water. Glyphosate is, therefore, normally formulated and applied as a water-soluble salt.
- monobasic, dibasic and tribasic salts of glyphosate can be made, it has generally been preferred
- SUBSTITUTE SHE 4 ET (RULE 26) to formulate and apply glyphosate, in the form of a monobasic salt, for example as a mono-(organic ammonium) salt such as the mono (isopropylamine), often abbreviated to IPA, salt, or as either monobasic or dibasic ammonium salt.
- a monobasic salt for example as a mono-(organic ammonium) salt such as the mono (isopropylamine), often abbreviated to IPA, salt, or as either monobasic or dibasic ammonium salt.
- ammonium When the terms “ammonium”, “monoammonium” and “diammonium” are used herein to refer to salts of glyphosate, these terms apply strictly to inorganic ammonium, i.e., NH 4 + , unless the context demands otherwise. Glyphosate rates and concentrations given herein, even where the glyphosate is present as a salt or salts, are expressed as acid equivalent (a.e.) unless the context demands otherwise.
- glyphosate salts generally require the presence of a suitable surfactant for best herbicidal performance.
- the surfactant may be provided in the concentrate formulation, or it may be added by the end user to the diluted spray solution.
- the choice of surfactant can be very important since there are wide variations among surfactants in their ability to enhance the herbicidal efficacy of glyphosate for particular applications.
- ammonia and potassium are low in cost, readily available, low in molecular weight, relatively soluble in water. Additionally, they are natural nutrients for the growth of plants and other organisms. Both potassium salts and ammonium salts have been used in substantial commercial volumes. Not all surfactants are as compatible with the potassium and ammonium salts at higher concentrations as they typically are with the isopropylamine salt, especially in concentrated aqueous liquid formulations.
- ammonium salts of glyphosate for preparing aqueous concentrate formulations of glyphosate suitable for killing and controlling weeds and other plants has, however, been somewhat limited due to difficulties arising from chemical and physical properties thereof, lack of suitable surfactants for preparing high-loaded liquid concentrates of such salts, reduced weed control, and requirement for complex processes for preparing liquid ammonium glyphosate compositions.
- Potassium salts have recently been introduced to the market and have been highly successful. However, potassium salts are not as easy to formulate as
- SUBSTITUTE SHE ⁇ T (RULE 26) isopropylamine salts, for example.
- the constraints on selection and concentration of surfactants in high load potassium salt solutions are generally more limiting than in the case of isopropylamine salts.
- the economical preparation of high efficacy glyphosate salt solutions depends on selecting a suitable surfactant or combination of surfactants, and providing an optimal concentration of the surfactant(s), often the highest concentration(s) that can be achieved without sacrifice of stability.
- Ethoxylated alkylamines have proven excellent bioefficacy in enhancing the herbicidal potency of glyphosate.
- the formulation may not be stable at elevated temperature. Above a threshold glyphosate concentration, any substantial increase in the concentration of surfactant is typically only achievable at the expense of reducing glyphosate a.e.
- a Ce to C 22 alkylamine substituted by reaction with two moles of alkylene oxide i.e., a bis(hydroxyalkyl)amine has a high degree of compatibility with a glyphosate salt, but limited value as an adjuvant to enhance the efficacy of the herbicide.
- Cs to C 22 alkylamines having longer chain alkylene oxide substituents are more effective as adjuvants but are not as compatible with concentrated aqueous solutions of glyphosate salts, and may cause the formulation
- the optimal surfactant may typically have an average alkylene oxide to amine ratio between about 3 and about 6. But even where the surfactant possesses such an average ratio, it may contain some unavoidable fractions of ⁇ 3:1 (EO to amine ratio) and >6:1 species, the presence of which can detract from either performance properties or stability of the formulation. In this case, species having a ratio of >8:1 may have a particularly adverse effect on stability.
- glyphosate formulations may typically include a surfactant wherein the average alkylene oxide to amine ratio is in the range of about 8 to about 12, or about 12 to about 18.
- Aqueous liquid concentrates comprising the latter surfactants are formulated in a manner which preserves stability despite the relatively long alkylene oxide chains, but it remains preferable to minimize the concentration of homolog species that are well above the target, e.g., in the case of a surfactant designed to have a ratio between 8 and 12, it may be preferable to minimize the fraction of homologs having an alkylene oxide/amine ratio >12:1, or in the case of a surfactant designed to have a ratio between 12 and 18, it may be preferable to minimize the fraction wherein the ratio is greater than about 20:1 or 22:1.
- the present invention generally relates to an alkoxylation process for the preparation of alkoxylated alkyl amines / alkoxylated alkyl ether amines with peaked distribution, to the products prepared therefrom and applications of same. Specific processes are described for the preparation of ethoxylated alkylamines including a Lewis acid catalyzed process and a process of the present invention while promoting the peaked distribution of the ethoxylated products.
- the present invention particularly relates to ethoxylated alkylamines and alkyletheramines that exhibit favorable compatibility with glyphosate and to glyphosate formulations comprising same.
- the specific ethoxylated alkylamines and alkyletheramines of the invention possess a relatively high concentration of the mid- range homologs that enables them to be compatible with glyphosate herbicide actives while retaining their characteristic adjuvancy.
- the ethoxylated alkylamines possess a relatively high concentration of the mid- range homologs that enables them to be compatible with glyphosate herbicide actives while retaining their characteristic adjuvancy.
- SUBSTITUTE SHE 7 ET (RULE 26) of the invention may further be useful in the preparation of glyphosate formulations of enhanced compatibility as compared to similar formulations which incorporate alkoxylated alkylamines of the prior art having a relatively flat or wide distribution of homologs.
- Alkoxylated alkyl amines and ethoxylated alkyl ether amines of the invention are materials possessing the following general structure (I):
- R is selected from a linear or branched, saturated or non-saturated alkyl group containing 8 - 22 carbon atoms or a group of the formula
- R 1 is selected from a linear or branched, saturated or non-saturated alkyl group containing 8 - 22 carbon atoms
- a and B are alkylene oxide groups containing 2 - 4 carbon atoms
- C is alkylene group containing 2 - 4 carbon atoms
- a, b each vary from 0 - 5
- c is 1
- X, Y, Z are alkylene oxide groups containing 2 - 4 carbon atoms
- x is 1
- y, y', z and z 1 each independently vary from 0 - 15.
- alkoxylated alkyl(ether)amine By utilizing the terminology “alkoxylated alkyl(ether)amine”, it is to be understood herein that the present inventors intend either or both of alkoxyfated alkyl amines and alkoxylated alkyl ether amines.
- the alkoxylated alkyl amine / alkyl ether amine compositions of the invention are not single compounds as suggested by their general structure (I), but rather, they comprise a mixture of several homologs having varied polyalkylene oxide chain length.
- homologs only those with the number of total alkylene oxide units per mole of amine closer to the most prevalent alkylene oxide adduct are preferred; homologs whose number of total alkylene oxide units is much lower or much higher than the most prevalent alkylene oxide adduct are undesirable since they are too liphophilic or too hydrophilic to be suitable for the application for which the alkoxylated alkylamine / alkyl ether amine are designed.
- the homologs having alkylene oxide chains significantly longer than average are particularly disadvantageous with respect to stability.
- Alkoxylated alkyl amines and alkoxylated alkyl ether amine are prepared from the reaction of the corresponding primary alkyl amine / alkyl ether amine with a selected number of moles of alkylene oxide.
- ethoxylated alkylamines (V) as an example, the prior art generally describes the synthesis of ethoxylated alkyl amines in a two-stage process:
- the catalyst is a base, preferably a hydroxide such as sodium hydroxide or potassium hydroxide.
- R a hydroxide
- the rate of the ethoxylation reaction is fast, and the formation of by-products, e.g., oxygenated hydrocarbons such as dioxane, and various (poly)ethylene glycol derivatives (EGDs), is minimal.
- the catalyzed ethoxylation in the second stage follows a polymerization mechanism that includes its characteristic propagation and chain transfer steps. As a result, the ethoxylated product obtained does not have a peaked distribution of total ethylene oxide substitution and possesses higher concentration of the undesired (too lipophilic / too hydrophilic) homologs.
- the prior art also describes another ethoxylation process designed to obtain a preferred peaked distribution of alkoxylated alcohols, aldehydes, ketones, or alkylamines.
- S ethoxylation
- the ethoxylation is catalyzed by a Lewis acid, preferably Boron Trifluouide, and follows a different mechanism.
- the resulting ethoxylated product possesses a peaked distribution, with highest concentration is of the homologs generally in the middle of the distribution range, or in any event more concentrated in a desired region than the homologs of an alkoxylated alkylamine.
- the peaked distribution alkoxylated alkylamines and etheramines of the present invention can be prepared by any process which provides the favorable distribution and/or favorable properties described herein.
- alkoxylation is conducted according to one or the other of two novel processes.
- S utilizes a Lewis acid catalyst of the type taught by the prior art, but under conditions which differ from those employed in known prior art processes for alkoxylation of alkylamines.
- the other and generally preferred process which we denote as the "N” process, optionally uses an alkaline catalyst of the type used in the conventional ("regular") process for the commercial manufacture of alkoxylated alkylamines, but proceeds under a set of conditions which nonetheless affords a peaked distribution by comparison to the commercially available surfactants.
- an alkylamine or etheramine is reacted with an alkylene oxide in the presence of a Lewis acid catalyst, preferably boron trifluoride, within a preferred temperature range.
- a Lewis acid catalyst preferably boron trifluoride
- Alternative catalyst systems promoting the peaked distribution can also be employed, and it is believe that the products prepared from the ethoxylation utilizing these alternative catalyst systems may also be useful in the context of the present invention.
- An example of such a system can be found in, for example, U.S. Patent No. 6,376,721 which utilizes a rare earth triflimide catalyst.
- the typical "S" ethoxylation process according to the invention also involves two stages.
- Stage 1 the formation of the intermediate (V) ( N,N-bis(2- hydroxyethyl)-N-alkylamine or etheramine), is the same as that for the regular "R” process.
- the intermediate (V) is prepared via the reaction of one mole of the selected alkyl (or alkylether) amine with two moles of the ethylene oxide or other alkylene oxide at temperature that varies preferably in the range from 160 - 190 0 C and at pressure that preferably varies from 40 -90 psig.
- the intermediate (V) is prepared immediately prior to its catalyzed ethoxylation.
- the Stage 1 can be by ⁇ passed by using the commercially available N,N-bis(2-hydroxyethyl)-N-alkylamine based on coco amine (Ethomeen C/12 from Akzo Nobel, Varonic K-202 from Degussa) or based on tallow amine (Ethomeen T/12 or Varonic T-202).
- the intermediate (V) is reacted with additional quantity of ethylene oxide or other alkylene oxide in the presence of a catalyst.
- This catalyzed ethoxylation stage involves the mixing of the intermediate (V) with the desired catalyst in a pressure vessel, followed by the slow addition of the desired quantity of the ethylene oxide to the vessel while the temperature of the mixture in the vessel is carefully maintained in a certain range.
- the catalyzed ethoxylation of the intermediate (V) is an exothermic reaction and cooling is required to maintain the temperature in the preferred range.
- Stage 2 of the "S” process utilizes a Lewis Acid catalyst.
- Boron trifluoride is the preferred catalyst, although other Lewis acid catalysts could be employed.
- said Lewis Acid catalyst can be tin fluoride (SnF 4 ), or a boron trifluoride complex.
- Examples of a boron trifluoride complexes useful in the context of the present invention include, but are not limited to members selected from the group consisting of boron trifluoride - ethylene oxide, boron trifluoride - diethyl ether, boron trifluoride - dibutyl ether, boron trifluoride - tetrahydrofuran, boron trifluoride- methanol, boron trifluoride - phosphoric acid and boron trifluoride - acetic acid and mixtures thereof.
- boron trifluoride is the catalyst for the ethoxylation of alkylamine, and it is most effective when used at the BF 3 concentration ranging from 0.04 - 0.07% of the weight of the final ethoxylated product.
- temperature is a critical factor in the new "S" ethoxylation process.
- the temperature can be anywhere between 110 - 19O 0 C.
- the normal catalyzed ethoxylation reaction of the intermediate (IV) does not occur at temperature higher than about 130 0 C (possibly due to the destruction of the catalyst - ethylene oxide complex) or lower than about 95 0 C.
- the catalyst (Boron Trifluoride) is not only expensive, but also a hazardous material. The use of this catalyst requires elaborated equipment for its storage and charging to the reactor.
- the process also enhances the formation of undesired by-products, most noticeably dioxane and (poly)ethylene glycol derivatives (EGDs).
- dioxane is perceived as a hazardous material and it is desirable that it be removed or minimized in the ethoxylated product.
- dioxane can be removed, e.g., by sparging the ethoxylation reaction product with nitrogen.
- removal of such a high concentration of dioxane requires additional equipment, greatly prolongs the cycle time and reduces the product yield.
- the concentration of EGDs may typically range from about 5% to about 10% by weight, much higher than that of dioxane. While it is not a hazardous material, the high content of EGDs lowers the concentration of the desired ethoxylated alkylamine, and thus may adversely affect the performance or effectiveness of the ethoxylated product in its application. Moreover, the EGDs are of substantially lower volatility than dioxane, and thus more difficult to separate from the alkoxylated amine surfactant.
- the preferred process of the present invention possesses the advantages of the above-described base-catalyzed and acid-catalyzed processes while eliminating or greatly reducing the drawbacks inherent in same.
- the "N” process enables the preparation of alkoxylated alkylamine / alkyl ether amine with the desired peaked alkoxylation distribution, thus ensuring optimum performance in their respective applications.
- the "N” process utilizes a base catalyst, preferably a hydroxide or may in some embodiments proceed without a catalyst.
- the present inventors have discovered that polymerization can be conducted without the necessity of utilizing a catalyst, such as a Lewis acid, calcium-based or rare earth catalyst while achieving a more favorable peaked distribution of homologs than is found in otherwise identical commercially available surfactants having the same average total of alkylene oxide substituents.
- a catalyst such as a Lewis acid, calcium-based or rare earth catalyst
- the preferred process, the "N" process may optionally use an alkaline catalyst while still preserving the favorable peaked distribution that distinguishes the surfactant of the invention from the products of commerce.
- the novel process achieves the desired result by control of the conditions of the reaction and especially the temperature thereof.
- alkoxylated alkylamines of modest average number of alkylene oxide units it has surprisingly been discovered that the reaction can be conducted entirely in the absence of any catalyst. Because the reactivity of the growing alkylene oxide chain declines with chain length, it is preferred that an alkaline catalyst be used during a portion of the conversion where the target average alkylene oxide to amine ratio is greater than about 6. Depending on the selection of amine, selection of alkylene oxide, exact process conditions and nature of the process equipment available, it may be preferable to conclude the alkoxylation in the presence of an alkaline catalyst at average alkylene oxide/amine ratios of about greater than about 6 or 7.
- Stage 1 of the "N” process Uncatalyzed ethoxylation of the primary alkylamine
- the starting primary alkylamine (II) is reacted with u moles of alkylene oxide, typically about 2 moles of ethylene oxide at high temperature to yield the same tertiary intermediate (III) (N,N-bis-(2-hydroxyethyl) N- alkylamine)
- the reaction temperature varies from 160 - 190 0 C and pressure varies from 40 - 90 psig.
- the intermediate (III) is prepared immediately prior to its further alkoxylation.
- the Stage 1 can be by-passed by using the commercially available N,N-bis(2-hydroxyethyl)-N-alkylamine based on coco amine (Ethomeen C/12 from Akzo Nobel, Varonic K-202 from Degussa) or based on tallow amine (Ethomeen T/12 or Varonic T-202).
- reaction product characterized as "intermediate (IV)" may constitute the final reaction product of the process. Where the ultimate target average number of alkylene oxide units exceeds about 6 or 7, the process preferably proceeds to stage 3.
- the peaked distribution obtained in the "N" process is possible in the stage 2 by reacting the tertiary intermediate (III) with alkylene oxide at certain temperature in the absence of a catalyst.
- the alkoxylation can proceed, and the absence of the catalyst facilitates the chain transfer between a newly alkoxylated molecule and another molecule of the tertiary intermediate (III), and results in the peaked distribution.
- the number of the moles of ethylene oxide used in this stage is preferred to be in the range of 1-8, typically between about 2 - 7, for example, in the range of 2 - 5. It is possible to use many sub-stages within stages 1 and 2 and end up with the same total EO addition. It is also possible to combine stages 1 and 2. However one must be mindful that ethoxylation performed in this stage with less than 2 moles of ethylene oxide normally results in final product without peaked ethoxylation distribution, while on the other hand, ethoxylation performed in this stage with more than 7 moles of ethylene oxide results in significant formation of by-products.
- the temperature is preferably maintained in the range of about 90 to about 130 0 C, more preferably in the range of about 100 to about 120 0 C.
- Ethoxylation performed at lower than 90 0 C or higher than 130 0 C normally stops before all the ethylene oxide is consumed.
- This stage is optional.
- the second intermediate (IV) is reacted with the remaining quantity of alkylene oxide to yield the final product (V).
- a catalyst is required to facilitate the ethoxylation in this stage.
- u, v and w represent the moles of alkylene oxide employed.
- the alkoxylation is performed using the remaining quantity of alkylene oxide in the presence of a catalyst.
- the catalyzed alkoxylation in this stage can be performed at temperature in the range of 100 - 190 0 C, and pressure between 40 -90 psig.
- the number of moles of alkylene oxide used in this stage varies, depending on the total number of moles of alkylene oxide used in the preparation (i.e., in all three stages).
- the number of moles of EO used in the third stage is maintained at the same or less than the number of moles of EO used in the second stage.
- Sodium hydroxide and potassium hydroxide are the preferred catalysts, though other hydroxide catalysts, including but not limited to lithium hydroxide, tetramethylammonium hydroxide, barium hydroxide, aluminum hydroxide, magnesium hydroxide, or complexes containing barium, magnesium and/or aluminum hydroxides, could be used.
- the sodium hydroxide or potassium hydroxide is most effective when the concentration of their active in the product mixture is 0.05% of the batch weight or higher.
- ethylene oxide or propylene oxide is preferably employed.
- Ethylene oxide is the alkylene oxide of choice in stage 2 of the "N” process.
- the number of moles (u) is preferably about 1-3, in another embodiment 1.5-2.4, and in still another embodiment about 2.0.
- the number of moles (v) is generally from about 0 to about 9, in another embodiment 1-7, and in still another embodiment about 2-5. It is generally preferred that u+v is greater than or equal to 4, for example, greater than or equal to about 5 or 6.
- u + v + w is generallyl5 or less.
- the first stage and optional third stage are similar to the two stages of the regular (the "R” process), base- catalyzed ethoxylation processes.
- the second stage of the "N” process according to this invention is, however, the most important, because it provides the desired peaked alkoxylation distribution.
- the preferred starting alkylamines include, but are not limited to, those derived from tallow, coconut oil, soybean oil, palm kernel oil, and mixtures thereof.
- the preferred starting ether amines include, but are not limited to, decyl ether amine, undecyl ether amine, dodecyl ether amine, tridecyl ether amine, tetradecyl ether amine, hexadecyl ether amine, octadecyl ether amine and mixtures thereof.
- R-NH 2 wherein R selected from a linear or branched, saturated or non-saturated alkyl group containing an average of 8 - 22 carbon atoms; for example, 12-22 carbon atoms; or 16-22 carbon atoms.
- R selected from a linear or branched, saturated or non-saturated alkyl group containing an average of 8 - 22 carbon atoms; for example, 12-22 carbon atoms; or 16-22 carbon atoms.
- the number of carbons is expressed as an average because amines derived from natural oils comprise a mixture of alkyl groups of somewhat varying length. It is generally preferred that the weight average value of R, R 1 or R 2 be between about C12 and about C2 2 .
- the average value is between about Cw and about C22 or between about Ci 6 and about C 22 -
- the alkoxylated alkyl(ether)amines used in the formulations of the invention be derived from primary amines having a molecular weight greater than about 200.
- Amines wherein the alkyl substituent contains between 16 and 18 carbon atoms may be especially advantageous, e.g., tallowamines which offer significant economic and commercial advantages in applications such as herbicidal formulations.
- Alkoxylated alkylamine and alkoxylated etheramine surfactants as prepared by the preferred W N" process of the invention have not only a peaked distribution of desired homologs but also relatively low concentrations of dioxane, EGDs and other
- the dioxane content after a stripping step is typically not greater than 400 ppm, more typically not greater than 300 ppm, and still more typically not greater than 200 ppm, while the total EGDs content, including a vinyl polyethylene glycol component, is less than about 5% by weight, more typically not greater than about 4% by weight, and most typically not greater than about 3% by weight, of the resulting ethoxylated product.
- degree of peaking is helpful.
- the degree of peaking ( ⁇ 3) is defined as the sum of the areas for the adjacent three most prevalent peaks.
- the relative degrees of peaking of ethoxylates prepared according to the process of the present invention was measured and compared to their counterparts prepared via conventional base- catalyzed ethoxylation.
- the alkoxylated alkyl amines having peaked distribution of the present invention are further characterized in having peaked distribution defined by a degree of peaking at least 5% greater than the degree of peaking in the distribution of a conventional alkoxylated amine composition prepared via conventional base catalysis.
- the degree of peaking may be at least 6% greater, preferably at least 7% greater than the degree of peaking in the distribution of a conventional alkoxylated amine composition prepared via conventional base catalysis, for which the conditions are described in Table A.
- the degree of peaking at least 10% greater than that found in the distribution of a conventional peaked alkoxylated amine compositions prepared via conventional base catalysis.
- PI is greater than 100, more preferably greater than about 102.
- the preferred alkoxylated alkylamines with peaked distribution include, but are not limited to ethoxylated tallow amine with 3 to 15 EO, ethoxylated coco amine with 3 to 15 EO, and mixtures thereof.
- Preferred alkoxylated alkyl ether amines with peaked distribution include, but are not limited to ethoxylated dodecyl ether amine with 3 to 15 EO, ethoxylated tridecyl ether amine with 3 to 15 EO, ethoxylated tetradecyl ether amine with 3 to 15 EO, ethoxylated hexadecyl etheramine with 3 to 15 EO, ethoxylated octadecyl etheramine with 3 to 15 EO and mixtures thereof.
- a surfactant having a relatively low ratio in the range of about 3 to about 6 EO/amine, most typically about 5 e.g.: (i) a surfactant having an intermediate EO/amine ratio in the range between about 8 and about 12 EO/amine, more typically about 9 to about 11, most typically about 10; and (iii) a surfactant having a relatively high EO/amine ratio in the range between about 12 and about 18 EO/amine, more typically between about 13 and about 17, most typically about 15.
- a solvent that is inert toward the reaction with ethylene oxide can also be used to improve the handling of the starting alkylamine or the resulting ethoxylated product, or to meet the minimum initial volume of material that is required for proper mixing action with ethylene oxide as required for each ethoxylation reactor.
- Aromatic solvents such as xylene, toluene, alkylbenzenes such as ethylbenzene, hexylbenzene, dodecylbenzene, alkylnaphthalenes such as methyl and dimethylnaphthalene, isopropyl- and di-isopropylnaphthalene, or commercial aromatic solvents, such as Aromatic Solvent 100, 150 or 200 available at ExxonMobil, or organic ethers, such as dibutyl ether... and the like are suitable solvents for the process of this invention.
- Glyphosate formulations generally require one or more adjuvants in order to boost their herbicidal efficacy.
- the proportion of adjuvant employed in the formulation is typically 10% or higher, in order to achieve significant boosting effect.
- the cost associated with the use of the adjuvants in glyphosate formulations is significant. Therefore, there is an ever increasing need to find a more effective and economical adjuvant for glyphosate.
- Glyphosate is an acid with a very limited solubility in water while salts of glyphosate have very high solubility in water. Therefore, glyphosate formulations usually employ salts of glyphosate.
- Many types of counterions have been used commercially in glyphosate products. They include isopropylammonium (IPA + ), monoethanolammonium (MtEA + ), diethanolammonium (DEA + ), triethanolammonium (TEA + ), sodium, trimethylsulfonium (TMS + ), potassium (K + ), and ammonium (NH 4 + ).
- Potassium glyphosate is a preferred glyphosate salt employable in the context of the invention.
- glyphosate loading is preferably 360 g ae/l or higher. It is known to those skilled in the art that many biologically useful surfactants cannot be reliably incorporated into glyphosate formulations at glyphosate, a.e., concentrations greater than 360 g/L without risk of phase separation at elevated temperatures. For such aqueous concentrates, therefore, an objective is to select a highly efficacious surfactant that can be used at relatively low concentration in glyphosate formulations to improve significantly the herbicidal efficacy of glyphosate. It is particularly preferred to identify and select a surfactant that can be formulated into stable glyphosate formulations including potassium and ammonium salts of glyphosate, at 470 - 600 g ae/l.
- the present invention meets such objective in providing glyphosate formulations having favorable and/or improved stability and herbicidal efficacy comprising, as an adjuvant, at least one peaked distribution alkoxylated alkylamine surfactant.
- the aforementioned adjuvant can be employed at low concentration and is stable in various salts of glyphosate even at very high glyphosate concentration.
- the total number of moles (2x + y + y' + z + z') of alkylene oxide used for the alkoxylation of the alkyl (or alkylether) amine varies from 3 - 15; typically from 3-12, in many instances from 3-9.
- ethoxylated alkylamines are ethoxylated versions based on cocoamine, tallow amine, soya amine, oleyl amine, palm amine and mixtures thereof.
- the ethoxylated amine of the invention is selected from the group consisting essentially of ethoxylated tallowamine, ethoxylated cocoamine, ethoxylated alkyletheramine such as tridecyletheramine, each having from 3 to 15 moles of EO, and mixtures thereof.
- a typical stable liquid glyphosate formulation according to the invention has a concentration of glyphosate in the range of 360 - 600 g ae/l, preferably 450 - 580 g ae/l, and the ratio of glyphosate (wt% ae) to the ethoxylated alkylamine surfactant with peaked distribution is between 2:1 to 25:1.
- ratio of glyphosate (wt% ae) to the ethoxylated alkylamine surfactant with peaked distribution is between 2.5:1 to 20:1, more typically between 3:1 to 15:1.
- the ethoxylated alkylamine with peaked distribution of the invention is exemplified by having an enhanced cloud point of about 8 degrees in 54.8% K- glyphosate formulation with 10% peaked cocoamine-5EO surfactant when compared to the regular cocoamine-5EO having the same carbon chain length and average EO chain length prepared via conventional base catalysis.
- the present invention encompasses not merely formulations of glyphosate, but also relates to other herbicidal compositions comprising at least one herbicidal active, and at least one surfactant, wherein said at least one surfactant comprises the alkoxylated alkylamine and/or alkylether amine with peaked distribution of the invention.
- a herbicidal composition according to the invention can optionally comprise other additives such as ammonium sulfate, potassium sulfate, potassium chloride, sodium sulfate, urea, glycols, or mixtures thereof.
- a contemplated composition can optionally include a synergist, quick-burn additive, humectant, co- herbicide, dye, pigment, corrosion inhibitor, thickener, dispersing agent, calcium sequestrant, defoamer, antifreeze, pour-point depressant, process aids, or mixture thereof.
- glyphosate salts and co-herbicide salts are specifically contemplated by the present invention.
- additives used in glyphosate compositions of the present invention possess sufficient solubility or dispersibility in a concentrated aqueous potassium glyphosate solution at a pH of from about 4 to about 7 to allow desired concentrations to be attained.
- co-herbicide is included in the formulation, it is preferred that the co-herbicide be water-soluble, and more preferred that it be included in the form of an ammonium or potassium salt.
- suitable co-herbicides are the ammonium salts of acifluorfen, asulam, benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, clopyralid, 2,4-D, 2,4-DB, pelargonic acid, dalapon, dicamba, dichlorprop, diclofop, endothall, fenac, fenoxaprop, flamprop, fluazifop, fluoroglycofen, fomesafen, fosamine, glufosinate, haloxyfop, imazameth, imazamethabenz, imazamox, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA 7 MCPB, meco
- Formulations of the present invention may be generally prepared by mixing the glyphosate salt solution, prepared as outlined above, together with other ingredients in a suitable mixing vessel with agitation, such as a blender.
- a typical aqueous concentrate according to the invention contains glyphosate acid equivalent in the range of from 30 to 45%, and from about 1.2 to about 22.5% surfactant.
- a typical formulation according to the invention contain glyphosate acid equivalent in the range of from about 0.1 to 18%, typically 0.1 to 5 wt. %, more typically 0.2 to 3%, most commonly 0.5 to 2 wt. %.
- stronger mixtures e.g., in the range from about 2 to about 15% surfactant may be desirable for some applications.
- This invention also relates to a herbicidal method of using a contemplated composition in an amount effective to kill or control unwanted vegetation by diluting the composition in water and applying the diluted composition to foliage of the vegetation to be killed or controlled.
- the glyphosate formulation of the invention should be applied to plant foliage at an application rate sufficient to give the desired effect.
- Application rates are usually expressed as amount of glyphosate a.e. per unit area of land treated, e.g. grams a.e. per hectare (g a.e./ha).
- What constitutes a "desired effect" varies according to the standards and practice of those who investigate, develop, market and use glyphosate products.
- the amount of glyphosate a.e. applied per unit area to give, consistently and reliably, at least 85% control of a plant species as measured by growth reduction or mortality is often used to define a commercially effective rate.
- compositions of the invention provide enhanced herbicidal efficacy by comparison with commercial standard formulations of glyphosate
- Herbicidal efficacy refers to any observable measure of control of plant growth, which can include one or more of the actions of (1) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying, or otherwise diminishing the occurrence and activity of plants.
- the glyphosate application rate is a herbicidally effective amount of about 0.1 to about 10 kg a.e./ha and preferably from about 0.25 to about 2.5 kg a.e./ha, although greater or lesser amounts may be applied.
- the alkoxylated alkylamine with peaked distribution of the invention is preferably selected so that an aqueous concentrate containing K- glyphosate wt% a.i. of 54.8 ("wt% a.i.” means weight percent active ingredient, in this case K glyphosate) and the peaked distribution alkoxylated alkylamine at a concentration of 10 wt% exhibits a cloud point greater than about 66°C.
- a formulation containing 10 wt% of a peaked distribution cocoamine 5EO surfactant has a cloud point approximately 8 0 C higher than the otherwise identical formulation containing 10 wt% of a conventional cocoamine 5EO surfactant made by conventional base catalysis.
- Other otherwise identical K glyphosate solutions containing conventional alkoxylated alkylamine surfactants typically possess a cloud point of room temperature, or slightly above room temperature.
- a typical stable liquid glyphosate formulation according to the invention has a concentration of glyphosate in the range of 360 - 600 g ae/l, preferably 450 - 580 g ae/l, and the ratio of glyphosate (wt% ae) to the ethoxylated alkylamine surfactant with peaked distribution is between 2:1 to 25:1.
- ratio of glyphosate (wt% ae) to the ethoxylated alkylamine surfactant with peaked distribution is between 2.5:1 to 20:1, more typically between 3:1 to 15:1.
- the ratio of glyphosate (wt% ae) to the alkoxylated amine surfactant with peaked distribution may be between 3.5:1 to 8:1, or in particular instances between 4:1 to 6:1.
- surfactants suitable for producing stable high load aqueous liquid concentrates comprising potassium and ammonium glyphosate can also be used in solid glyphosate acid and glyphosate salt formulations.
- Ammonium and diammonium glyphosate in particular are often supplied in dry, solid granular form. Dry formulations comprising sodium salts of glyphosate and or comprising glyphosate acid are also known.
- stable applies in the sense that formulations comprising the surfactants of the invention are formulated so as to avoid excessive stickiness and/or syneresis.
- the present inventors have established that superior properties are exhibited by the surfactants prepared by the novel processes described herein, and in particular that surfactants of the invention are distinguished by the distinctly higher cloud points compared to the cloud points exhibited by exemplary aqueous glyphosate salt concentrates which contain these surfactants.
- the surfactants of the invention may be characterized by reference to an aqueous concentrate containing potassium glyphosate salt in a concentration of 54.8 wt.% of the active ingredient salt ("a.i.”).
- SUBSTITUTE SHE ⁇ IT (RULE 26) alkylamine or alkoxylated etheramine of the invention has a cloud point at least 3 0 C higher, preferable at least 5°C higher, and In another embodiment at least 7°C higher than that of substantially similar glyphosate formulations containing conventional non-peaked ethoxylated alkylamines having the same distribution of carbon-chain length, and the same average EO chain length, prepared by conventional base catalysis, which is hereinafter defined as catalysis according to the conditions described in Table A, as the surfactant component.
- the surfactants of the invention contain relatively lower amounts of dioxane and EGDs including, but not limited to vinyl polyethylene glycols.
- the surfactants of the invention may be characterized by comparison of the cloud points exhibited by a pair of reference aqueous concentrates, each consisting of potassium glyphosate salt in a concentration of 540 g/L, a.e., 5.5 wt.% alkoxylated alkyl(ether)amine surfactant having >3 EO groups, and 4.5 wt.% bis(2-hydroxyethyl)cocoamine.
- a first such reference formulation containing an adjuvant surfactant of the invention exhibits a cloud point at least about 3°C higher than the cloud point of a second reference formulation of identical composition but containing 5.5 wt.% of a reference surfactant rather than the adjuvant surfactant of the invention.
- the surfactant of the invention and the reference surfactant are each derived from a primary amine having a molecular weight of at least 200 (thus have the same distribution of carbon chain length), and have the same value of W 0 as defined herein.
- the reference surfactant is prepared by an NaOH-catalyzed reaction of the amine with alkylene oxide conducted under conventional conditions described hereinbelow.
- the surfactants of the invention preserves a relatively low concentration of dioxane, vinyl PEGs, and other EGDs.
- the frequency distribution of homologs in the surfactants of the invention typically differs in various ways from the frequency distribution for the homologs of the conventional alkoxylated alkylamine and alkoxylated etheramine surfactants of commerce.
- the degree of peaking is higher in the surfactants of the invention.
- the degree of peaking is defined as the sum of the number percentages of the three most prevalent homologs.
- this sum is in most instances higher by an increment of at least about 2 wt.%, more typically at least about 3%, often at least about 4 wt.%, 5 wt.%, or 6 wt.%, basis the entire surfactant, than the ⁇ 3 value for a reference mixture of homologs having the same value of W 0 , the same frequency distribution with regard to the number of carbon atoms in the substituent R, and the same identity of X, Y and Z as the surfactant of the invention.
- the ratio of the degree of peaking for the surfactants of the invention to the corresponding reference mixture is typically at least about 1.05, more typically at least about 1.07 or 1.08, and in a majority of cases at least about 1.10.
- the reference mixture is an alkoxylated alkylamine or etheramine characteristic of the prior product of commerce, and is prepared by NaOH-catalyzed reaction of RNH2 with alkylene oxide conducted entirely under autogenous pressure up to 90 psig at a temperature of 160° to 180 0 C and an NaOH concentration of 0.2 wt. %.
- a surfactant of the invention which has a degree of peaking at least about 3 wt.% higher (or even 2 wt.% higher) than this reference composition will in at least most instances also have a degree of peaking higher than known commercially available alkoxylated amine surfactants which have the same values of Wo and ⁇ 3 as the inventive and reference surfactants, the same frequency distribution with regard to the number of carbon atoms in the substituent R, and the same identify of X, Y and Z.
- the degree of peaking varies with value of Wo, generally inversely therewith,
- the degree of peaking may be normalized across a range of values for W 0 by definition of a "peaking index,” computed by multiplying ⁇ 3 by a function of Wo.
- a peaking index may conveniently be defined as (W 0 /2) 1/2 ( ⁇ 3).
- the peaking index for the surfactant of the invention is typically greater than the peaking index for the corresponding reference mixture by an increment of at least about 3, more typically at least about 5, 6, or 8%.
- the ratio of the peaking index for the surfactants of the invention to the peaking index for the corresponding reference surfactants is typically at least about 1.05, more typically at least about 1.07 or 1.08, and in most instances at least about 1.10.
- the homolog frequency distribution pattern varies somewhat among the surfactants of the invention, as it also does among the surfactants of the commerce.
- analyses of the surfactants of the invention have indicated a degree of peaking and peaking index that have appeared to be actually lower than those of the comparative reference mixture, yet the novel surfactants still exhibit superior properties with respect to the cloud point of glyphosate salt concentrates. It is possible that these aberrant results have been attributable to analytical error, but also possible that they accurately reflect the samples analyzed.
- the homolog distribution for the surfactants of the invention also typically differs from the distribution for conventional alkoxylated surfactants of the prior art with respect to certain other characteristics. Among these are what may referred to as the "tailing index” and the "tilt ratio.”
- a surfactant of given value for Wo have a relatively low concentration of homologs whose degree of substitution, i.e., the value of (2x + y+ y' + z +t), is significantly greater than Wo.
- ⁇ 23 ⁇ 3 + [(k+1) - Wo3W k+ i;
- k is an integer such (Wo -1) ⁇ k ⁇ . (Wo ) ⁇ (k+1).
- ct ⁇ fe may preferably be greater than about 1.42.
- the tilt ratio varies with the value of W 0 , so that: where Wo is between 3 and 4.5, the tilt ratio cW ⁇ 2 3 is at least about 1.90; where W 0 is between 4.5 and 5.5, the tilt ratio ⁇ 2 3/ ⁇ 23 is at least about 1.85; where W 0 is between 5.5 and 6.5, the tilt ratio c_23/ ⁇ 23 is at least about 1.75; where W 0 is between 6.5 and 8.5, the tilt ratio ⁇ 2 3/ ⁇ 23 is at least about 1.40; where W 0 is above 8.5, the tilt ratio ⁇ 23 / ⁇ 23 is at least about 1.42.
- Other empirical f ⁇ nctions may provide alternative definitions of tailing index, tilt ratio and peaking index.
- the tilt ratio ⁇ 2 3/ ⁇ 2 3 differs from the same ratio for the corresponding reference mixture by an increment of at least about + 0.08, more typically at least about +0.10, and in most instances at least about 0.15.
- the ratio of the tilt ratio for the surfactant of the invention to the tilt ratio for the reference mixture is ordinarily at least about 1.05, more typically at least about 1.0, and in a majority of cases 1.15.
- the peaking indices, tailing indices and tilt ratios reflect empirical observations of the surfactants of the invention vs. the comparative reference mixtures that are indicative of the alkoxylated alkylamines and etheramines of commerce, it will be understood that there are variations from specimen to specimen whereby the range of values for the novel surfactants and the range of values for the reference mixtures and commercial surfactants can at least potentially be found to overlap with regard to at least one of these indices and perhaps in some instances with all of them. At the time of this application, that matter has not been fully explored.
- the surfactants of the invention also differ from prior art surfactants prepared by Lewis acid catalysis with respect to the concentration of dioxane, vinyl PEG and other EGDs.
- the surfactants of the invention differ from the reference mixtures, and therefore from the prior art commercial surfactants, with respect to at least one of the parameters discussed above, i.e., the degree of peaking, the peaking index, the tailing index, and/or the tilt ratio, or by some combination thereof; at that these parameters have value in helping to characterize the surfactants of the invention.
- Distilled coco amine (52Og, 2.6 moles) was charged to a one-gallon stainless steel pressure vessel and then heated at 130 0 C under nitrogen purging for 30 minutes to reduce its moisture content to less than 0.1%.
- Ethylene Oxide (23Og, 5.23 moles) was then added to the pressure vessel over a period of 40 minutes while the temperature was maintained at 150 - 160 0 C.
- the reaction mixture was purged with nitrogen to remove the trace of ethylene oxide and analyzed. Its Total Amine Value is 194 mg KOH/g, indicating that the 2.00 moles of ethylene oxide has been consumed for the ethoxylation of 1 mole of coco amine.
- the product mixture was then cooled to 100 0 C. Boron Trifluoride - Phosphoric Acid complex (1.7Og) was then injected to the reactor. The mixture was then heated to HO 0 C, then ethylene oxide (33Og, 7.5 moles) was added to the reactor over a 90 minutes period while the pressure was maintained at 50 psig. An exothermic reaction occurred; cooling was applied to maintain the temperature in the range of 110 - 120 0 C throughout the addition of ethylene oxide. Upon completion of the ethylene oxide addition, the reaction mixture was digested for one hour at the same temperature and pressure. Analysis showed that the product mixture contains about 2000 ppm of dioxane.
- Figure 2 illustrates the homologs distribution of the resulting product (C/15S) and of the Ethomeen C/15, its commercially available counterpart that is prepared by the regular, hydroxide-catalyzed ethoxylation of the cocoamine with the same number of moles (5) of the ethylene oxide.
- the peaked distribution of the homologs is indicated by their higher concentration (weight %) at the middle of the distribution range.
- weight % concentration at the middle of the distribution range.
- the most prevalent EO adduct is 4 in both processes even though 5 EO is added.
- the degree of peaking is 68 for C/15S and 60 for C/15.
- the first stage (ethoxylation of distilled cocoamine with 2 moles of ethylene oxide) was by-passed.
- the commercially available Ethomeen C/12 was used as the starting material.
- the ethoxylated of the Ethomeen C/12 with 4 moles of ethylene oxide in this example was catalyzed by Boron Trifluoride - Diethyl Ether Complex.
- Ethomeen C/12 (75Og, 2.59 moles) was charged to a one-gallon stainless steel pressure vessel and then heated at 130 0 C under nitrogen purging for 30 minutes to reduce its moisture content to less than 0.1%. It was then cooled 100 0 C.
- Boron Trifluoride - Diethyl Ether complex (1.56g) was then injected to the reactor.
- ethylene oxide 46Og, 10.45 moles
- the mixture was then heated to HO 0 C, then ethylene oxide (46Og, 10.45 moles) was added to the reactor over a 60 minutes period while the pressure was maintained at 50 psig. An exothermic reaction occurred; cooling was applied to maintain the temperature in the range of 110 - 120 0 C throughout the addition of ethylene oxide.
- the reaction mixture was digested for one hour at the same temperature and pressure. Analysis showed that the product mixture contains about 3000 ppm of dioxane.
- a combination of nitrogen purging and the in injection of water (4 % of batch weight, to generate steam in situ) was then applied for two hours to strip the dioxane from the product mixture.
- the product mixture was then dried by nitrogen purging at 120 0 C for one hour to reduce its moisture content to less than 0.5%. Its TAV is 123.7 mg KOH/g, indicating that a total of 5.8 moles of ethylene oxide have been consumed for the ethoxylation each mole of the coco amine.
- Figure 3 illustrates the homologs distribution of the resulting product (C/16S) and of the Ethomeen C/16, its commercially available counterpart that is prepared by the regular, hydroxide-catalyzed ethoxylation of the cocoamine with the same number of moles (6) of the ethylene oxide.
- the peaked distribution of the homologs is indicated by their higher concentration (weight %) at the middle of the distribution range.
- weight % concentration at the middle of the distribution range.
- the most prevalent EO adduct is 4 in both processes even though 6 EO is added.
- the degree of peaking is 58 for C/16S and 49 for C/16.
- a sample of a stable, transparent formulation is first heated in a 90+ 0 C water bath. As the temperature of the sample increases "cloudiness" is usually observed. Heating is continued until the cloudiness of the solution is maximized, i.e., the polymeric components dissolved in the formulation precipitate out of solution.Jf the temperature exceeds 9O 0 C and no cloudiness is apparent, the result is recorded as CP>90°C.
- the solution is slowly cooled by removing the formulation sample from the water bath while gently agitating the sample (e.g., by stirring with a thermometer) and monitoring the dissolution of the suspended polymeric material.
- the cloud point temperature is reached the transition increases dramatically due to the remixing or dissolution of the precipitated or polymeric phase.
- the temperature at which the formulation sample returns to transparency is recorded as the cloud point for that sample. This analysis is repeated on several different samples. The average observed cloud point of these samples is calculated and reported as the cloud point of the particular formulation tested.
- Table 1 Cloud Point of concentrated glyphosate formula containing ethoxylated alkylmines prepared from the regular and the peaked processes.
- Stage 1 Distilled coco amine (52Og, 2.6 moles) was charged to a one-gallon stainless steel pressure vessel and then heated at 130 0 C under nitrogen purging for 30 minutes to reduce its moisture content to less than 0.1%. Ethylene Oxide (23Og, 5.23 moles) was then added to the pressure vessel over a period of 40 minutes while the temperature was maintained at 150 - 160 0 C. Following a 30-minute period of digestion, the reaction mixture sampled and analyzed. Its Total Amine Value is 194 mg KOH/g, indicating that the 2.00 moles of ethylene oxide has been consumed for the ethoxylation of 1 mole of coco amine.
- Stage 2 The product mixture was then cooled to 115 0 C. Ethylene oxide (32Og, 7.27 moles) was then added to the pressure vessel over a period 50 minutes, while the temperature was maintained at 115-125 0 C. Following a 60- minute period of digestion, the reaction mixture was purged with nitrogen, then samples and analyzed. Its Total Amine Value is 138 mg KOH/g, indicating that in this stage, 2.7 moles of ethylene oxide has been consumed for the ethoxylation of 1 mole of coco amine.
- Ethylene oxide 32Og, 7.27 moles
- Stage 3 Potassium hydroxide (2.5Og, 0.02moles) was charged to the pressure vessel.
- the reaction mixture was purged with nitrogen, then heated at 150 0 C for 30 minutes under nitrogen purging to reduce its moisture content to less than 0.1%.
- Ethylene Oxide (15Og, 3.4 moles) was then added to the pressure vessel over a period of 20 minutes while the temperature was maintained at 150 - 160 0 C. Following a 30-minute period of digestion, the reaction mixture was purge with nitrogen to remove the trace of unreacted ethylene oxide, then cooled to 50 0 C and discharged. Its TAV is 120 mg KOH/g, indicating that a total of 6.1 moles of ethylene oxide have been consumed for the ethoxylation each mole of coco amine.
- FIG. 4 illustrates the homologs distribution of the resulting ethoxylated product (6NP) and of its counterpart that is prepared by the regular, hydroxide- catalyzed ethoxylation of the coco amine with the same number of moles (6) of the ethylene oxide (6RP) that has the same Total Amine Value.
- the degree of peaking is 60 for 6NP and 49 for 6RP, indicating that the 6NP product made by the new process possesses a peaked ethoxylation distribution.
- Figure 4 Homolog distribution of the 6-mole EO adduct of coco amine prepared by the regular ethoxylation process (6RP) and the new ethoxylation process (6NP).
- the degree of peaking is 60 for 6NP and 49 for 6RP.
- Stage 1 Distilled coco amine (52Og, 2.6 moles) was charged to a one-gallon stainless steel pressure vessel and then heated at 130 0 C under nitrogen purging for 30 minutes to reduce its moisture content to less than 0.1%. Ethylene Oxide (23Og, 5.23 moles) was then added to the pressure vessel over a period of 40 minutes while the temperature was maintained at 150 - 160 0 C. Following a 30-minute period of digestion, the reaction mixture sampled and analyzed. Its Total Amine Value is 194 mg KOH/g, indicating that the 2.00 moles of ethylene oxide has been consumed for the ethoxylation of 1 mole of coco amine.
- Stage 2 The product mixture was then cooled to 115 0 C. Ethylene oxide (46Og, 10.46 moles) was then added to the pressure vessel over a period 75 minutes, while the temperature was maintained at 115-125 0 C. Following a 60- minute period of digestion, the reaction mixture was purged with nitrogen, then samples and analyzed. Its Total Amine Value is 122 mg KOH/g, indicating that in this stage, 3.9 moles of ethylene oxide has been consumed for the ethoxylation of 1 mole of coco amine.
- Ethylene oxide 46Og, 10.46 moles
- Stage 3 Potassium hydroxide (3.0g, 0.025 moles) was charged to the pressure vessel.
- the reaction mixture was purged with nitrogen, then heated at 150 0 C for 30 minutes under nitrogen purging to reduce its moisture content to less than 0.1%.
- Ethylene Oxide (465g, 6.02 moles) was then added to the pressure vessel over a period of 20 minutes while the temperature was maintained at 150 - 160 0 C.
- the reaction mixture was purge with nitrogen to remove the trace of unreacted ethylene oxide, then cooled to 50 0 C and discharged. Its TAV is 101 mg KOH/g, indicating that a total of 8.08 moles of ethylene oxide have been consumed for the ethoxylation each mole of coco amine.
- the content of dioxane (about 200ppm) and EGDs (about 2.7%) of the final product are much lower than the content of dioxane (about 8000 ppm) and EGDs (about 9.0%) made by the acid-catalyzed process.
- Figure 5 illustrates the homologs distribution of the resulting ethoxylated product (8NP) and of its counterpart that is prepared by the regular, hydroxide- catalyzed ethoxylation of the coco amine with the same number of moles (8) of the ethylene oxide (8RP).
- the degree of peaking is 51 for 8NP and 42 for 8RP, indicating that the 8NP product made by the new process possesses a peaked ethoxylation distribution.
- Figure 5 Homolog distribution of 8-mole EO adduct of coco amine prepared by the regular ethoxylation process (8RP) and the new ethoxylation process (8NP). The degree of peaking is 51 for 8NP and 42 for 8RP.
- Example 6 Preparation of Ethoxylated Coco amine using 9 Moles of Ethylene Oxide
- the Stage 1 Ethoxylation non-catalyzed reaction of coco amine with 2 moles of ethylene oxide
- the commercially available Ethomeen C/12 having a Total Amine Value of 195 mg KOH/g, was used as the starting material.
- Stage 2 Ethomeen C/12 (70Og, 2.43 moles) containing less than 0.1% water was charged to a one-gallon stainless steel pressure vessel, purged with nitrogen then heated to 115 0 C. Ethylene oxide (45Og, 10.22 moles) was then added to the pressure vessel over a period 75 minutes, while the temperature was maintained at 115-125 0 C. Following a 60-minute period of digestion, the reaction mixture was purged with nitrogen, then samples and analyzed. Its Total Amine Value is 120 mg KOH/g, indicating that in this stage, 4.1 moles of ethylene oxide has been consumed for the ethoxylation of 1 mole of coco amine.
- Stage 3 Potassium hydroxide (3Jg, 0.03 moles) was charged to the pressure vessel.
- the reaction mixture was purged with nitrogen, then heated at 150 0 C for 30 minutes under nitrogen purging to reduce its moisture content to less than 0.1%.
- Ethylene Oxide (33Og, 7.50 moles) was then added to the pressure vessel over a period of 20 minutes while the temperature was maintained at 140 - 150 0 C.
- the reaction mixture was purge with nitrogen to remove the trace of unreacted ethylene oxide, then cooled to 50 0 C and discharged. Its TAV is 93 mg KOH/g, indicating that total of 9.2 moles of ethylene oxide have been consumed for the ethoxylation each mole of coco amine in this preparation.
- the content of dioxane (about 200ppm) and EGDs (about 3.0 %) of the final product are much lower than the content of dioxane (about 12000 ppm) and EGDs (about 11.0%) of its counterpart made by the acid-catalyzed process.
- Figure 6 illustrates the homologs distribution of the resulting ethoxylated product (9NP) and of its counterpart that is prepared by the regular, hydroxide- catalyzed ethoxylation of the coco amine with the same number of moles (9) of the ethylene oxide (9RP).
- the degree of peaking is 50 for 9NP and 43 for 9RP, indicating that the 9NP product made by the new process according possesses a peaked ethoxylation distribution.
- Figure 6 Homolog distribution of 9-mole EO adduct of coco amine prepared by regular ethoxylation process (9RP) and new ethoxylation process (9NP). The degree of peaking is 50 for 9NP and 43 for 9RP.
- Example 7 Effect of reduction of higher EO adduct on the cloud point of ⁇ lyphosate formulations.
- Figure 7 Homolog distribution of 9-mole EO adduct of tallowamine prepared by regular ethoxylation process (9R) and new W N" ethoxylation process (9N). The degree of peaking is 53 for T/19N and 43 for T/19R.
- Product T/19N was produced using a very similar process as outlined in example 6. General conditions have been also listed in Table A. The final Total Amine value i 1.50 for T/19N and 1.51 forT/19R.
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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EP05800809A EP1793667A1 (en) | 2004-09-23 | 2005-09-23 | Alkoxylated alkylamines / alkyl ether amines with peaked distribution |
BRPI0515898-2A BRPI0515898A (en) | 2004-09-23 | 2005-09-23 | processes for preparing maximum distribution alkoxylated alkyl ether amines / alkylamines, their compositions, surfactants and stable herbicidal formulations |
AU2005286666A AU2005286666B2 (en) | 2004-09-23 | 2005-09-23 | Alkoxylated alkylamines / alkyl ether amines with peaked distribution |
MX2007003478A MX2007003478A (en) | 2004-09-23 | 2005-09-23 | Alkoxylated alkylamines / alkyl ether amines with peaked distribution. |
JP2007533657A JP2008514619A (en) | 2004-09-23 | 2005-09-23 | Alkoxylated alkyl amine / alkyl ether amine with peak distribution |
CA002581342A CA2581342A1 (en) | 2004-09-23 | 2005-09-23 | Alkoxylated alkylamines / alkyl ether amines with peaked distribution |
US11/575,847 US8034979B2 (en) | 2004-09-23 | 2005-09-23 | Alkoxylated alkylamines/alkyl ether amines with peaked distribution |
US13/230,281 US8357636B2 (en) | 2004-09-23 | 2011-09-12 | Alkoxylated alkylamines/alkyl ether amines with peaked distribution |
US13/648,715 US20130116120A1 (en) | 2004-09-23 | 2013-01-18 | Alkoxylated alkylamines/alkyl ether amines with peaked distribution |
Applications Claiming Priority (4)
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US61259704P | 2004-09-23 | 2004-09-23 | |
US60/612,597 | 2004-09-23 | ||
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US13/230,281 Division US8357636B2 (en) | 2004-09-23 | 2011-09-12 | Alkoxylated alkylamines/alkyl ether amines with peaked distribution |
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AR (1) | AR053767A1 (en) |
AU (1) | AU2005286666B2 (en) |
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WO2007109791A2 (en) * | 2006-03-23 | 2007-09-27 | Akzo Nobel N.V. | Alkoxylated alkylamines or alkyl ether amines with peaked distribution |
WO2007147866A1 (en) * | 2006-06-23 | 2007-12-27 | Akzo Nobel N.V. | Process for preparation of alkoxylated alkylamines / alkyl ether amines with peaked distribution |
EP2128112A1 (en) * | 2008-04-08 | 2009-12-02 | Air Products and Chemicals, Inc. | Molecular de-airentrainer compositions and methods of use of same |
WO2009154772A2 (en) * | 2008-06-18 | 2009-12-23 | Stepan Company | Ultra-high loading glyphosate concentrate |
WO2010020599A2 (en) * | 2008-08-19 | 2010-02-25 | Akzo Nobel N.V. | Thickening glyphosate formulations |
WO2010026127A1 (en) * | 2008-09-04 | 2010-03-11 | Akzo Nobel N.V. | Viscoelastic system for drift reduction |
WO2010105047A2 (en) | 2009-03-11 | 2010-09-16 | Monsanto Technology Llc | Herbicidal formulations comprising glyphosate and alkoxylated glycerides |
US20110039703A1 (en) * | 2009-08-17 | 2011-02-17 | Pedro Brito Correia | Herbicide consisting of a glyphosate formulation containing as a surfactant a branched alkylamine where the nitrogen atom is connected to a chain of polypropylenoxide or to a copolymer of ethylene oxide and propylene oxide |
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US8618179B2 (en) | 2010-01-18 | 2013-12-31 | Basf Se | Composition comprising a pesticide and an alkoxylate of 2-propylheptylamine |
US8987172B2 (en) | 2009-06-14 | 2015-03-24 | Pedro Manuel Brito da Silva Correia | Herbicide containing glyphosate and a surfactant consisting essentially of a polyalkoxylated alkylamine wherein the alkyl group is branched |
US9192158B2 (en) | 2008-12-11 | 2015-11-24 | Monsanto Technology Llc | Herbicide formulations containing an etheramine and alkylamine alkoxylate surfactant system |
US9258996B2 (en) | 2010-03-17 | 2016-02-16 | Basf Se | Composition comprising a pesticide and an alkoxylate of iso-nonylamine |
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4456697A (en) * | 1982-09-23 | 1984-06-26 | Conoco Inc. | Catalysts for alkoxylation reactions |
US4483941A (en) * | 1982-09-02 | 1984-11-20 | Conoco Inc. | Catalysts for alkoxylation reactions |
DD219478A1 (en) * | 1983-11-17 | 1985-03-06 | Akad Wissenschaften Ddr | METHOD FOR THE PRODUCTION OF ODORLESS N-ALKYL SUBSITUTED TERTIAER ALKANOLAMINES |
EP0339426A2 (en) * | 1988-04-25 | 1989-11-02 | Henkel Kommanditgesellschaft auf Aktien | Use of calcined hydrotalcites as ethoxylation or propoxylation catalysts |
EP0354993A2 (en) * | 1988-07-18 | 1990-02-21 | Henkel Kommanditgesellschaft auf Aktien | Process for the preparation of addition products of ethylene oxide and/or propylene oxide for amines or amides |
US5012012A (en) * | 1987-09-29 | 1991-04-30 | Lion Corporation | Alkoxylation catalyst |
US5292910A (en) * | 1990-04-02 | 1994-03-08 | Henkel Kommanditgesellschaft Auf Aktien | Use of hydrophobized hydrotalcites as catalysts for ethoxylation or propoxylation |
WO1995032272A1 (en) * | 1994-05-25 | 1995-11-30 | The Procter & Gamble Company | Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents |
EP0826715A1 (en) * | 1995-03-28 | 1998-03-04 | Lion Corporation | Method for producing an alkylene oxide adduct of a compound having one more active hydrogen |
US6235940B1 (en) * | 1997-12-23 | 2001-05-22 | Basf Aktiengesellschaft | Method for producing oxalkylated amines or alcohols |
US6376721B1 (en) * | 2001-01-19 | 2002-04-23 | Rhodia, Inc. | Process for alkoxylation in the presence of rare earth triflimides |
WO2003067983A1 (en) * | 2002-02-11 | 2003-08-21 | Imperial Chemical Industries Plc | Surfactants and surfactant compositions |
WO2005104774A2 (en) * | 2004-04-27 | 2005-11-10 | Harcros Chemicals Inc. | Method of preparing alkoxylation catalysts and their use in alkoxylation processes |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE219478C (en) | 1900-01-01 | |||
US5703015A (en) | 1990-08-09 | 1997-12-30 | Monsanto Company | Pesticidal compositions of polyoxyalkylene alkylamine surfactants having reduced eye irritation |
US5731266A (en) | 1993-03-17 | 1998-03-24 | Ciba-Geigy Corporation | Herbicidal compositions comprising diamino-1,3,5-triazine and chloroacetanilide herbicides and a surfactant system |
US5389598A (en) | 1993-12-17 | 1995-02-14 | Monsanto Company | Aqueous concentrate formulations having reduced eye irritancy |
US5750468A (en) * | 1995-04-10 | 1998-05-12 | Monsanto Company | Glyphosate formulations containing etheramine surfactants |
US5916863A (en) | 1996-05-03 | 1999-06-29 | Akzo Nobel Nv | High di(alkyl fatty ester) quaternary ammonium compound from triethanol amine |
US6245713B1 (en) | 1996-10-25 | 2001-06-12 | Monsanto Company | Plant treatment compositions having enhanced biological effectiveness |
JP2002530304A (en) | 1998-11-23 | 2002-09-17 | モンサント カンパニー | Storage and transport systems for glyphosate herbicides |
US6235300B1 (en) | 1999-01-19 | 2001-05-22 | Amway Corporation | Plant protecting adjuvant containing topped or peaked alcohol alkoxylates and conventional alcohol alkoxylates |
UA72760C2 (en) | 1999-04-23 | 2005-04-15 | Monsanto Technology Llc | Method to treat plant foliage |
US6521785B2 (en) | 1999-08-03 | 2003-02-18 | Syngenta Participations Ag | Pesticide formulations containing alkoxylated amine neutralized aromaticsulfonic acid surfactants |
US6713433B2 (en) | 1999-08-11 | 2004-03-30 | Monsanto Technology, Llc | Coformulation of an oil-soluble herbicide and a water-soluble herbicide |
US7135437B2 (en) | 2000-05-19 | 2006-11-14 | Monsanto Technology Llc | Stable liquid pesticide compositions |
MY158895A (en) | 2000-05-19 | 2016-11-30 | Monsanto Technology Llc | Potassium glyphosate formulations |
US6992045B2 (en) | 2000-05-19 | 2006-01-31 | Monsanto Technology Llc | Pesticide compositions containing oxalic acid |
PL343853A1 (en) | 2000-11-13 | 2002-05-20 | Inst Ciezkiej Syntezy Orga | Oxyalkylenation catalyst and method of obtaining same |
AUPR183200A0 (en) | 2000-12-01 | 2001-01-04 | Huntsman Corporation Australia Pty Ltd | Herbicidal compositions |
BRPI0117035A2 (en) | 2001-05-08 | 2018-04-17 | Monsanto Europe Sa | glyphosate compositions and their uses |
ATE532410T1 (en) | 2001-09-07 | 2011-11-15 | Syngenta Participations Ag | SURFACE ACTIVE SYSTEMS FOR AGRICULTURALLY ACTIVE COMPOUNDS |
JP2003096186A (en) * | 2001-09-27 | 2003-04-03 | Nof Corp | Method for producing aliphatic primary amine-alkylene oxide adduct |
AU2002358264A1 (en) | 2001-12-21 | 2003-07-30 | Dow Agrosciences Llc | High-strength low-viscosity agricultural formulations |
US20060194699A1 (en) | 2003-01-10 | 2006-08-31 | Moucharafieh Nadim C | Sprayable non-aqueous, oil-continuous microemulsions and methods of making same |
BRPI0514527B1 (en) | 2004-08-19 | 2014-12-02 | Monsanto Technology Llc | Herbicidal composition, batch process for preparing a glyphosate salt solution, continuous process for preparing a finished composition in the form of a glyphosate salt solution and tank mix herbicidal composition |
US8129564B2 (en) | 2005-03-04 | 2012-03-06 | Monsanto Technology Llc | Mitigating necrosis in transgenic glyphosate-tolerant cotton plants treated with herbicidal glyphosate formulations |
AR060328A1 (en) | 2006-03-23 | 2008-06-11 | Monsanto Technology Llc | HERBICIDAL FORMULATIONS BASED ON ALKYLAMINES / ALKYLETHERAMINES ALCOXILADAS. |
-
2005
- 2005-09-23 AU AU2005286666A patent/AU2005286666B2/en not_active Ceased
- 2005-09-23 WO PCT/US2005/034186 patent/WO2006034459A1/en active Application Filing
- 2005-09-23 MX MX2007003478A patent/MX2007003478A/en unknown
- 2005-09-23 US US11/575,847 patent/US8034979B2/en not_active Expired - Fee Related
- 2005-09-23 JP JP2007533657A patent/JP2008514619A/en active Pending
- 2005-09-23 SG SG200906295-1A patent/SG155954A1/en unknown
- 2005-09-23 CA CA002581342A patent/CA2581342A1/en not_active Abandoned
- 2005-09-23 BR BRPI0515898-2A patent/BRPI0515898A/en not_active IP Right Cessation
- 2005-09-23 EP EP05800809A patent/EP1793667A1/en not_active Ceased
- 2005-09-26 AR ARP050104011A patent/AR053767A1/en not_active Application Discontinuation
-
2011
- 2011-09-12 US US13/230,281 patent/US8357636B2/en not_active Expired - Fee Related
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4483941A (en) * | 1982-09-02 | 1984-11-20 | Conoco Inc. | Catalysts for alkoxylation reactions |
US4456697A (en) * | 1982-09-23 | 1984-06-26 | Conoco Inc. | Catalysts for alkoxylation reactions |
DD219478A1 (en) * | 1983-11-17 | 1985-03-06 | Akad Wissenschaften Ddr | METHOD FOR THE PRODUCTION OF ODORLESS N-ALKYL SUBSITUTED TERTIAER ALKANOLAMINES |
US5012012A (en) * | 1987-09-29 | 1991-04-30 | Lion Corporation | Alkoxylation catalyst |
EP0339426A2 (en) * | 1988-04-25 | 1989-11-02 | Henkel Kommanditgesellschaft auf Aktien | Use of calcined hydrotalcites as ethoxylation or propoxylation catalysts |
EP0354993A2 (en) * | 1988-07-18 | 1990-02-21 | Henkel Kommanditgesellschaft auf Aktien | Process for the preparation of addition products of ethylene oxide and/or propylene oxide for amines or amides |
US5292910A (en) * | 1990-04-02 | 1994-03-08 | Henkel Kommanditgesellschaft Auf Aktien | Use of hydrophobized hydrotalcites as catalysts for ethoxylation or propoxylation |
WO1995032272A1 (en) * | 1994-05-25 | 1995-11-30 | The Procter & Gamble Company | Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents |
EP0826715A1 (en) * | 1995-03-28 | 1998-03-04 | Lion Corporation | Method for producing an alkylene oxide adduct of a compound having one more active hydrogen |
US6235940B1 (en) * | 1997-12-23 | 2001-05-22 | Basf Aktiengesellschaft | Method for producing oxalkylated amines or alcohols |
US6376721B1 (en) * | 2001-01-19 | 2002-04-23 | Rhodia, Inc. | Process for alkoxylation in the presence of rare earth triflimides |
WO2003067983A1 (en) * | 2002-02-11 | 2003-08-21 | Imperial Chemical Industries Plc | Surfactants and surfactant compositions |
WO2005104774A2 (en) * | 2004-04-27 | 2005-11-10 | Harcros Chemicals Inc. | Method of preparing alkoxylation catalysts and their use in alkoxylation processes |
Non-Patent Citations (1)
Title |
---|
HRECZUCH W ET AL: "HIGH ETHOXYLATED ALCOHOLS EITH NARROW DISTRIBUTION OF HOMOLOGUES", JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY, WILEY & SONS, CHICHESTER, GB, vol. 67, no. 1, September 1996 (1996-09-01), pages 53 - 60, XP000637763, ISSN: 0268-2575 * |
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WO2007109791A3 (en) * | 2006-03-23 | 2008-09-04 | Akzo Nobel Nv | Alkoxylated alkylamines or alkyl ether amines with peaked distribution |
WO2007109791A2 (en) * | 2006-03-23 | 2007-09-27 | Akzo Nobel N.V. | Alkoxylated alkylamines or alkyl ether amines with peaked distribution |
US8049039B2 (en) | 2006-06-23 | 2011-11-01 | Akzo Nobel N.V. | Process for preparation of alkoxylated alkylamines/alkyl ether amines with peaked distribution |
WO2007147866A1 (en) * | 2006-06-23 | 2007-12-27 | Akzo Nobel N.V. | Process for preparation of alkoxylated alkylamines / alkyl ether amines with peaked distribution |
RU2460720C2 (en) * | 2006-06-23 | 2012-09-10 | Акцо Нобель Н.В. | Method of producing alkoxylated alkylamines/alkyl ether amines with narrow distribution |
EP2128112A1 (en) * | 2008-04-08 | 2009-12-02 | Air Products and Chemicals, Inc. | Molecular de-airentrainer compositions and methods of use of same |
WO2009154772A2 (en) * | 2008-06-18 | 2009-12-23 | Stepan Company | Ultra-high loading glyphosate concentrate |
US10993442B2 (en) | 2008-06-18 | 2021-05-04 | Stepan Company | Ultra-high loading glyphosate concentrate |
WO2009154772A3 (en) * | 2008-06-18 | 2010-04-22 | Stepan Company | Ultra-high loading glyphosate concentrate |
WO2010020599A3 (en) * | 2008-08-19 | 2011-03-24 | Akzo Nobel N.V. | Thickening glyphosate formulations |
US9426997B2 (en) | 2008-08-19 | 2016-08-30 | Akzo Nobel N.V. | Thickening glyphosate formulations |
WO2010020599A2 (en) * | 2008-08-19 | 2010-02-25 | Akzo Nobel N.V. | Thickening glyphosate formulations |
WO2010026127A1 (en) * | 2008-09-04 | 2010-03-11 | Akzo Nobel N.V. | Viscoelastic system for drift reduction |
US8993629B2 (en) | 2008-09-04 | 2015-03-31 | Akzo Nobel N.V. | Viscoelastic system for drift reduction |
US9907303B2 (en) | 2008-09-04 | 2018-03-06 | Akzo Nobel Chemicals International B.V. | Viscoelastic system for drift reduction |
US10159247B2 (en) | 2008-12-11 | 2018-12-25 | Monsanto Technology Llc | Herbicide formulations containing an etheramine and alkylamine alkoxylate surfactant system |
US9192158B2 (en) | 2008-12-11 | 2015-11-24 | Monsanto Technology Llc | Herbicide formulations containing an etheramine and alkylamine alkoxylate surfactant system |
WO2010105047A2 (en) | 2009-03-11 | 2010-09-16 | Monsanto Technology Llc | Herbicidal formulations comprising glyphosate and alkoxylated glycerides |
US9723841B2 (en) | 2009-03-11 | 2017-08-08 | Akzo Nobel N.V. | Herbicidal formulations comprising glyphosate and alkoxylated glycerides |
US8987172B2 (en) | 2009-06-14 | 2015-03-24 | Pedro Manuel Brito da Silva Correia | Herbicide containing glyphosate and a surfactant consisting essentially of a polyalkoxylated alkylamine wherein the alkyl group is branched |
US20110039703A1 (en) * | 2009-08-17 | 2011-02-17 | Pedro Brito Correia | Herbicide consisting of a glyphosate formulation containing as a surfactant a branched alkylamine where the nitrogen atom is connected to a chain of polypropylenoxide or to a copolymer of ethylene oxide and propylene oxide |
WO2011086115A3 (en) * | 2010-01-18 | 2012-02-23 | Basf Se | Compound comprising a pesticide and an alkoxylate of 2-propylheptyl amine |
EA022034B1 (en) * | 2010-01-18 | 2015-10-30 | Басф Се | Compound comprising a pesticide and an alkoxylate of 2-propylheptyl amine, alkoxylate or derivative thereof, method for production thereof, method for controlling phytopathogenic fungi and/or undesirable plant growth and/or undesirable insect or mite infestation and/or for regulating the growth of plants, seed material comprising said composition and use of the alkoxylate or derivative thereof as an auxiliary agent |
US8618179B2 (en) | 2010-01-18 | 2013-12-31 | Basf Se | Composition comprising a pesticide and an alkoxylate of 2-propylheptylamine |
WO2011101303A3 (en) * | 2010-02-16 | 2012-04-26 | Basf Se | Compound comprising a pesticide and an alkoxylate of isoheptadecylamine |
US9258996B2 (en) | 2010-03-17 | 2016-02-16 | Basf Se | Composition comprising a pesticide and an alkoxylate of iso-nonylamine |
US9814233B2 (en) | 2011-02-28 | 2017-11-14 | Basf Se | Composition comprising a pesticide, a surfactant and an alkoxylate of 2-propyheptylamine |
Also Published As
Publication number | Publication date |
---|---|
JP2008514619A (en) | 2008-05-08 |
CA2581342A1 (en) | 2006-03-30 |
MX2007003478A (en) | 2007-08-17 |
EP1793667A1 (en) | 2007-06-13 |
SG155954A1 (en) | 2009-10-29 |
AU2005286666B2 (en) | 2011-05-19 |
US20080261814A1 (en) | 2008-10-23 |
AU2005286666A1 (en) | 2006-03-30 |
US8034979B2 (en) | 2011-10-11 |
BRPI0515898A (en) | 2008-08-12 |
US8357636B2 (en) | 2013-01-22 |
US20120053054A1 (en) | 2012-03-01 |
AR053767A1 (en) | 2007-05-23 |
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