amine ester, derivative, water-soluble herbicide composition or agricultural dispersant, rough surfa

专利摘要:

公开号:BR112013009964B1
申请号:R112013009964
申请日:2011-10-25
公开日:2018-10-16
发明作者:Brown Aaron；A Dameshek Anatoliy；D Malec Andrew；Holland Brian；R Allen Dave；Lee Whitlock Laura；J Nepras Marshall；Shane Wolfe Patrick；Skelton Patti；J Bernhardt Randal；A Masters Ronald
申请人:Stepan Co；
IPC主号:

专利说明:

(54) Title: AMINE ESTER, DERIVATIVE, COMPOSITION OF WATER SOLUBLE HERBICIDE OR AN AGRICULTURAL DISPERSANT, ROUGH SURFACE CLEANER, SHAMPOO OR CONDITIONER, OR PERSONAL CLEANING PRODUCT OR SOAP AND CORROSION INHIBITOR FOR PETROLEUM USE ) lnt.CI .: C07C 229/00 (30) Unionist Priority: 10/25/2010 US 61 / 406,547, 10/25/2010 US 61 / 406,556, 10/25/2010 US 61 / 406,570 (73) Holder ( es): STEPAN COMPANY (72) Inventor (s): DAVE R. ALLEN; RANDAL J. BERNHARDT; AARON BROWN; ANATOLIY A. DAMESHEK; BRIAN HOLLAND; ANDREW D. MALEC; RONALD A. MASTERS; MARSHALL J. NEPRAS; PATTI SKELTON; LAURA LEE WHITLOCK; PATRICK SHANE WOLFE (85) National Phase Start Date: 24/04/2013
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AMINE ESTER, DERIVATIVE, COMPOSITION OF WATER SOLUBLE HERBICIDE OR AN AGRICULTURAL DISPERSANT, ROUGH SURFACE CLEANER, SHAMPOO OR CONDITIONER, OR PERSONAL CLEANING PRODUCT OR SOAP AND CORROSION INHIBITOR FOR USE IN
PETROLEUM FIELD APPLICATIONS
FIELD OF THE INVENTION
The Invention refers to amine ester and derivative compositions that originate from renewable resources, particularly from natural oils and their metathesis products.
BACKGROUND OF THE TECHNIQUE "Ester amines" are typically reaction products of fatty acid esters, fatty esters, or triglycerides and a tertiary alkanolamine (for example, triethanolamine or Ν, Ν-dimethylethanolamine). Although ester amines have value inside and outside themselves, they are most commonly quaternized to make "ester quats", cationic surfactants that are useful in a wide range of end-use applications, including fabric softening (see Pat. Nos. US5. 670,677; 5,750,492; 6,004,913; 6,737,392; and Publ. Ped. Pat. No. US2001 / 0036909), cosmetics (Pat. No. US6,914,146), hair conditioning (Pat. No. US5,939,059) , detergent additives for fuel (Pat. No. US5.964.907), antimicrobial compositions (Pat. No.US6.420.330), agricultural dispersants (Publ. Ped. Pat. No. US2010 / 0016163), and improved oil recovery (Pat. No.US7.163.056).
Esters or fatty acids, used to make ester amines and their derivatives, are usually made through hydrolysis or transesterification of triglycerides, which are typically animal or vegetable fats. Consequently, the greasy portion of the acid or ester will typically have 6-22 carbons with a mixture of saturated and internally unsaturated chains. Depending on the source, the ester or fatty acid often has a preponderance of component Ci6 to C22. For example, soybean oil methanolysis provides the saturated methyl esters of palmitic (C16) and stearic (Cie) acids and the unsaturated methyl esters of oleic (mono-unsaturated Cis), linoleic (di-unsaturated Cie), and α-linolenic (tri-unsaturated Cis) ). Unsaturation in these acids has an exclusively or predominantly cis- configuration.
Recent improvements in metathesis catalysts (see J.C. Mol,
Green Chem. 4 (2002) 5) provide an opportunity to generate short chain length, monounsaturated raw materials, which are valuable for making
Petition 870180072225, of 08/17/2018, p. 12/15
2/49 detergents and surfactants, from natural oils rich in Ci6 to C22- such as soybean oil or palm oil. Soy oil and palm oil can be more economical than, for example, coconut oil, which is a traditional starting material for making detergents. As Professor Mol explains, metathesis refers to the conversion of olefins into new products by breaking and reforming carbon-carbon double bonds mediated by transition metal - carbene complexes. Auto-metathesis of an unsaturated fatty ester can provide a balanced mixture of starting material, an internally unsaturated hydrocarbon and an unsaturated diester. For example, methyl oleate (methyl c / s-9-octadecenoate) is partially converted to dimethyl 9-octadecene and 9octadecene-1,18-dioate, with both products predominantly consisting of trans- isomer. Metathesis effectively isomerizes the cis- double bond of methyl oleate to provide a balance mixture of cis- and trans-isomers both in the “unconverted” starting material and in the metathesis products, with the trans-predominant isomers.
Cross-metathesis of unsaturated fatty esters with olefs generates new olefins and new unsaturated esters that may have reduced chain length and this can be difficult to do otherwise. For example, cross-metathesis of methyl oleate and 3-hexene provide 3-dodecene and methyl 9-dodecenoate (see also U.S. Pat. No. 4,545,941). Terminal olefins are particularly desirable synthetic targets, and Elevance Renewable Sciences, Inc. recently described and refined the means of preparing them by cross-methosing an internal olefin and an α-olefin in the presence of a ruthenium alkylidene catalyst (see Publ. Ped. No. US2010 / 0145086). A variety of cross-metathesis reactions involving an α-olefin and an unsaturated fatty ester (as the source of internal olefin) are described. Thus, for example, reaction of soy oil with propylene followed by hydrolysis provides, among other things, 1decene, 2-undecenes, 9-decenoic acid, and 9-undecenoic acid. Despite the availability (cross-metathesis of natural oils and olefins) of unsaturated fatty esters having reduced chain length and / or predominantly trans unsaturated configuration, amine esters and their derivatives made from these raw materials, seem to be unknown. In addition, amine esters and their derivatives were not made from the Cw unsaturated diester, which can be readily done through auto-metathesis of a natural oil.
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In short, traditional sources of esters and fatty acids used to make ester amines and their derivatives, generally have predominantly (or exclusively) cis- isomers and are devoid of unsaturated fatty portions of relatively short chain (for example, Cio or C12). Metathesis chemistry provides an opportunity to generate precursors having shorter chains and mainly trans- isomers, which could provide improved performance when the precursors are converted to downstream compositions (for example, in surfactants). Ester dysfunctional amines Ci ₈ new and derivatives are also potentially available from auto-metathesis of natural oil or C10 unsaturated acid or ester auto-metathesis. In addition to an increased variety of precursors, the unsaturation present in the precursors allows for additional functionalization, for example, through sulfonation or sulfitation.
SUMMARY OF THE INVENTION
In one aspect, the invention relates to amine ester compositions. The amine esters comprise a reaction product of a metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or its ester derivatives with a tertiary alkanolamine. The invention includes derivatives made by quaternization, sulfonation, alkoxylation, sulfation, and / or ester ester amines. In one aspect, the ester derivative of C10-C17 monounsaturated acid or octadecene-1,18-dioic acid is a lower alkyl ester. In another aspect, the ester derivative is a modified triglyceride made by auto-metathesis of a natural oil or an unsaturated triglyceride made by cross-metathesis of a natural oil with an olefin. Ester amines and their derivatives are valuable for a wide variety of end uses, including cleansers, tissue treatment, hair conditioning, personal care (liquid cleansers, conditioning bars, oral care products), antimicrobial compositions, agricultural uses and cosmetic applications. oilfield.
DETAILED DESCRIPTION OF THE INVENTION
In one aspect, the invention relates to amine ester compositions which comprise reaction products of a metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or its ester derivatives with a tertiary alkanolamine.
C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or its ester derivatives used as a reagent is derived from the metathesis of a natural oil. Traditionally, these materials, particularly chain acids
4/49 short and derivatives (eg 9-decylenic acid or 9-dodecylenic acid) have been difficult to obtain except in laboratory scale quantities at considerable cost. However, because of recent improvements in metathesis catalysts, these acids and their ester derivatives are now available in bulk at a reasonable cost. Thus, C10-C17 esters and monounsaturated acids are conventionally generated through cross-metathesis of natural oils with olefins, preferably α-olefins, and particularly ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like. Auto-metathesis of natural oil or a precursor of ester or C10 acid (for example, methyl 9-decenoate) provides the diester or C ₈ diacid in optimal yield when it is the desired product.
Preferably, at least a portion of the C10C17 monounsaturated acid has "Δ ⁹ " unsaturation, that is, the carbon-carbon double bond in C-ioC- | ₇ is in the 9- position with respect to acid carbonyl. In other words, there are preferably seven carbons between the acid carbonyl group and the C 9 and C 10 olefin group. For Cn to C17 acids, an alkyl chain of 1 to 7 carbons, respectively, is attached to C10. Preferably, the unsaturation is at least 1 mol% of trans-Δ ⁹ , more preferably at least 25 mol% of trans-Δ ⁹ , more preferably at least 50 mol% of trans-Δ ⁹ , and even more preferably at minus 80% trans-Δ ⁹ . Unsaturation can be greater than 90% by mol, greater than 95% by mol, or even 100% trans-Δ ⁹ . In contrast, naturally occurring fatty acids that have Δ ⁹ unsaturation, for example oleic acid, usually have -100% cis- isomers.
Although a high proportion of trans- geometry (particularly trans-Δ ⁹ geometry) may be desirable in metastatic-derived amines and derivatives of the invention, the person skilled in the art will recognize that the exact configuration and location of the carbon-carbon double bond will depend on reaction conditions, catalyst selection, and other factors. Metathesis reactions are commonly accompanied by isomerization, which may or may not be desirable. See, for example, G. Djigoué and M. Meier, Appl. Catai. A: General 346 (2009) 158, especially Fig. 3. In this way, the person skilled in the art can modify the reaction conditions to control the degree of isomerization or change the proportion of cis- and trans- generated isomers. For example, heating a metathesis product in the presence of an inactivated metathesis catalyst may allow the person skilled in the art to induce double bond migration to provide a lower proportion of product having trans-Δ ⁹ geometry.
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A high proportion of trans- isomer content (in reference to the all-in-one configuration of the natural monounsaturated ester or acid) gives different physical properties to the amine ester compositions made from them, including, for example, modified physical form, melting range, compactability, and other important properties. These differences should allow formulators using ester amines and esters quat, greater latitude or increased chances as they use amine esters in cleaners, tissue treatment, personal care, agricultural uses, and other end uses.
Suitable monosaturated acid C10-C17 derived from metathesis includes, for example, 9-decylenic acid (9-decenoic acid), 9-undecenoic acid, 9-dodecylenic acid (9-dodecenoic acid), 9-tridecenoic acid, 9tetradecenoic acid, 9-pentadecenoic acid, 9-hexadecenoic acid, 9heptadecenoic acid, and the like, and their ester derivatives.
Usually, cross metathesis or auto-metathesis of natural oil is followed by separation of an olefin stream from a modified oil stream, typically by eliminating the most volatile olefins through distillation. The stream of modified oil is then reacted with a lower alcohol, typically methanol, to provide glycerin and a mixture of alkyl esters. This mixture usually includes saturated C6-C22 alkyl esters, predominantly C ₁₆ -Ci8 alkyl esters, which are essentially spectators in the metathesis reaction. The rest of the product mixture depends on whether automatic or cross metathesis is used. When the natural oil is self-metatized and then transesterified, the alkyl ester mixture will include an unsaturated C-is diester. When the natural oil is cross-metatized with an α-olefin and the product mixture is transesterified, the resulting alkyl ester mixture includes a C10 unsaturated alkyl ester and one or more Cn to C17 unsaturated alkyl ester co-products in addition to glycerin by-product. The terminally unsaturated C ₁₀ product is accompanied by different co-products, depending on which olefin (s) is used as a cross metathesis reagent. Thus, 1-butene gives one C ₂ alkyl unsaturated ester, 1-hexene provides one unsaturated C ₄ alkyl ester , and so on. As shown in the examples below, the C ₁₀ unsaturated alkyl ester is readily separated from the C 17 to C 17 unsaturated alkyl ester and each is easily purified by fractional distillation. Such alkyl esters are excellent starting materials for making the amine ester compositions of the invention.
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Natural oils suitable for use as a raw material to generate C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or their ester derivatives from auto-metathesis or cross-metathesis with olefins, are known. Suitable natural oils include vegetable oils, algae oil, animal fat, pine oils, oil derivatives, and combinations thereof. Thus, suitable natural oils include, for example, soybean oil, palm oil, rapeseed oil, coconut oil, palm kernel oil, sunflower oil, safflower oil, sesame oil, corn oil, olive oil , peanut oil, cottonseed oil, canola oil, castor oil, tallow, lard, chicken fat, fish oil, and the like. Soy oil, palm oil, rapeseed oil, and their mixtures are preferred natural oils.
Genetically modified oils, for example, soybean oil rich in oleate or genetically modified algae oil, can also be used. Preferred natural oils have substantial unsaturation, as this provides a reaction site for the metathesis process for generating olefins. Particularly preferred are natural oils that have a high content of unsaturated fatty groups derived from oleic acid. Thus, preferred natural oils particularly include soybean oil, palm oil, seaweed oil, and rapeseed oil.
A modified natural oil, such as a partially hydrogenated vegetable oil, can be used instead of or in combination with natural oil. When a natural oil is partially hydrogenated, the unsaturation site can migrate to a variety of positions in the main hydrocarbon structure of the fatty ester moiety. Because of this trend, when the modified natural oil is self-metatized or cross-metatized with the olefin, the reaction products will have a different and generally more extensive distribution compared to the product mixture generated from a non-natural oil. modified. However, products generated from modified natural oil are converted similarly to the amine ester compositions of the invention.
An alternative to using a natural oil as a raw material to generate C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or its ester derivatives from auto-metathesis or cross-metathesis with olefins, is an acid monounsaturated fat obtained by the hydrolysis of a vegetable oil or animal fat, or an ester or salt of such an acid obtained by esterification of a fatty acid or carboxylate salt, or by transesterification of a natural oil with an alcohol. Also useful as starting compositions are carboxylate salts,
7/49 polyunsaturated fatty acids and esters. The salts can include an alkali metal (for example, Li, Na, or K); an alkaline earth metal (for example, Mg or Ca); a Group 13-15 metal (for example, B, Al, Sn, Pb, or Sb), or a transition metal, lanthanide or actinide. Additional suitable starting compositions are described on p. PCT application 7-17 WO 2008/048522, the contents of which are incorporated by reference herein.
The other reagent in the cross metathesis reaction is an olefin. Suitable olefins are internal or α-olefins having one or more carbon-carbon double bonds. Mixtures of olefins can be used. Preferably, the olefin is a C2-C10 monounsaturated α-olefin, more preferably a C2-C ₈ monounsaturated aolefin. Preferred olefins also include C4-C9 internal olefins. Thus, olefins suitable for use include, for example, ethylene, propylene, 1-butene, cis- and Zrans-2-butene, 1-pentene, isohexylene, 1hexene, 3-hexene, 1-heptene, 1-octene, 1 -nonene, 1-decene, and the like, and mixtures thereof.
Cross-metathesis is performed through the reaction of natural oil and olefin in the presence of a homogeneous or heterogeneous metathesis catalyst. Olefin is omitted when natural oil is self-metatized, but the same types of catalysts are generally used. Suitable homogeneous metathesis catalysts include combinations of an oxide halide or transition metal halide (eg WOCI4 or WCU) with an alkylation co-catalyst (eg Me ₄ Sn). Preferred homogeneous catalysts are well-defined alkylidene (or carbene) complexes of transition metals, particularly Ru, Mo, or W. These include first and second generation Grubbs catalysts, Grubbs-Hoveyda catalysts, and the like. Suitable alkylidene catalysts have the general structure:
M [X ¹ X ² L ¹ L ² (L ³ ) _n ] = C _m = C (R ¹ ) R ² where M is a transition metal of Group 8, L ¹ , L ² , and L ³ are binders neutral electron donors, n is 0 (such that L ³ may not be present) or 1, m is 0, 1, or 2, X ¹ and X ² are anionic ligands, and R ¹ and R ² are independently selected from of H, hydrocarbyl, substituted hydrocarbyl, hydrocarbyl containing heteroatom, substituted hydrocarbyl containing heteroatom, and functional groups. Any two or more of X ¹ , X ² , L ¹ , L ² , L ³ , R ¹ and R ² can form a cyclic group and either group can be attached to a support.
First generation Grubbs catalysts fall into this category where m = n = 0 and particular selections are made for η, X ¹ , X ² , L ¹ , L ² , L ³ ,
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R ¹ and R ² as described in Publ. Ped. Pat. No. US2010 / 0145086 (“the Ό86 publication”), whose teachings that refer to all metathesis catalysts are incorporated in this by reference.
Second generation Grubbs catalysts also have the general formula 5 described above, but L ¹ is a carbene linker where the carbene carbon is flanked through N, O, S, or P atoms, preferably through two N atoms. The carbene ligand is usually part of a cyclic group. Examples of second generation Grubbs catalysts also appear in publication '086.
In another class of suitable alkylidene catalysts, L ¹ is a highly coordinating electron neutral donor as in the first and second generation Grubbs catalysts, and L ² and L ³ are weakly coordinating electron donor ligands in the form of optionally substituted heterocyclic groups. . Thus, L ² and L ³ are pyridine, pyrimidine, pyrrole, quinoline, thiophene, or the like.
In yet another class of suitable alkylidene catalysts, a pair of substituents is used to form a bi or tridentate linker, such as a bisphosphine, dialkoxide, or alkyl diketonate. Grubbs-Hoveyda catalysts are a subset of this type of catalyst in which L ² and R ² are coupled.
Typically, a nitrogen or neutral oxygen coordinates with the metal although it is also bonded to a carbon that is α-, β-, or y- with reference to the carbene carbon to provide the bidentate ligand. Examples of suitable Grubbs-Hoveyda catalysts appear in publication '086.
The structures below provide only a few illustrations of suitable catalysts that can be used:
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Heterogeneous catalysts suitable for use in the reaction of self-synthesis or cross-metathesis include certain compounds of rhenium and molybdenum as described, for example, by JC Mol in Green Chem. 4 (2002) 5 on p. 1112. Particular examples are catalytic systems that include Re ₂ O ₇ on alumina promoted through an alkylation co-catalyst such as a lead-tin, germanium, or silicon compound tetraalkyl. Others include MoCI ₃ or M0CI5 on silica activated via tetraalkyl-tin.
For additional examples of catalysts suitable for self-metathesis or cross-metathesis, see Pat. No. U.S.4.545.941, whose teachings are incorporated into this by reference and cited references.
The amine esters are made by reacting one to metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or its ester derivatives with a tertiary alkanolamine.
In one aspect, the ester derivative is a lower alkyl ester, especially a methyl ester. The lower alkyl esters are preferably generated by transesterification of a metathesis-derived triglyceride. For example, cross metathesis of a natural oil with an olefin, followed by removal of unsaturated hydrocarbon metathesis product by stripping, and then transesterification of the modified oil component with a lower alkanol under basic conditions provides a mixture of unsaturated lower alkyl esters. . The unsaturated lower alkyl ester mixture can be used "as is" to make an amine ester mixture of the invention or can be purified to isolate particular alkyl esters before making amine esters.
In another aspect, the ester derivative to be reacted with tertiary alkanolamine is the metathesis-derived triglyceride discussed in the preceding paragraph. Instead of transesterifying the metathesis-derived triglyceride with a lower alkanol to generate lower alkyl esters as previously described, the metathesis-derived triglyceride, following olefin stripping, is reacted directly with the tertiary alkanolamine to make a mixture of the amine ester of the invention.
The person skilled in the art will appreciate that "ester derivative" here encompasses other equivalents of acyl, such as acid chlorides, acid anhydrides, or the like, in addition to the lower alkyl esters and glyceryl esters discussed above.
Suitable tertiary alkanolamine have a tertiary amine group and one to three primary or secondary hydroxyl groups. In alkanolamines
10/49 preferred, tertiary nitrogen is attached to zero, one, or two C ₁ -C ₄ alkyl groups, preferably C ₁ -C ₄ alkyl groups, and one to three hydroxyalkyl groups having 2 to 4 carbons each, where the total number of alkyl and hydroxyalkyl groups is three. Suitable alkanolamines are known and commercially available from BASF, Dow Chemical and other suppliers. They include, for example, triethanolamine, N-methyldiethanolamine, Ν, Ν-dimethylethanolamine, N, Ndimethylpropanolamine, Ν, Ν-dimethylisopropanolamine, N-methyldiisopropanolamine, Ν, Ν-diethylethanolamine, triisopropanolamine, and the like, and mixtures thereof. Particularly preferred alkanolamines are triethanolamine, Nmethyldiethanolamine, and Ν, Ν-dimethylethanolamine, which are economically and readily available.
Suitable alkanolamines include alkoxylated derivatives of the compounds described above. Thus, for example, the alkanolamine used to make the amine ester can be a reaction product of an alkanolamine with 0.1 to 20 moles of ethylene oxide or propylene oxide per mole of OH groups in the alkanolamine.
The amine esters are made using a known process that provides a unique product mixture because of the unconventional starting mixture of acid or ester derivatives. Reagents are typically heated, with or without a catalyst under conditions effective to esterify or transesterify the starting ester or acid with tertiary alkanolamine. The reaction temperature is typically within the range of 80 ° C to 300 ° C, preferably from 150 ° C to 200 ° C, and more preferably from 165 ° C to 180 ° C.
The amounts in reference to alkanolamine and acid or ester reagents used depend on the desired stoichiometry and is left to the discretion of the person skilled in the art. Preferably, however, the equivalent ratio between acyl groups (in metathesis-derived or ester-derived acid) and hydroxyl groups (in tertiary alkanolamine) is within the range of 0.1 to 3, preferably from 0.3 to 1. As the examples below illustrate, the ratio is often about 1 (see preparation of C10-2 or C10-4), but equivalent lower acyl: hydroxyl ratios are also common (see, for example, the preparation of C10-6, acyl: OH = 0.56).
Some ester amines have the formula:
(R ¹ ) 3-mN - [(CH2) n- (CHCH3) zO-CO-R ² ] m where:
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R ¹ is C- | -C6 alkyl; R ² is -C9H16-R ³ or -Ci6H ₃ o-CO ₂ R ⁴ ; R ³ is hydrogen or C1-C7 alkyl; R ⁴ is glyceryl ester, polyoxyalkylene, oxyalkylene, alkenyl, aryl, substituted or unsubstituted alkyl, or a mono or divalent cation; m = 1-3; n = 1-4; z = 0 or 1; and when z = 0, n = 2-4.
Preferably, R ² is - (CH2) 7-CH = CHR ³ or - (CH2) 7-CH = CH- (CH ₂ ) 7CO ₂ R ⁴ .
General note regarding chemical structures:
As the skilled person will recognize, products made according to the invention are typically mixtures of cis- and trans- isomers. Unless otherwise stated, all structural representations provided herein show only one trans- isomer. The knowledgeable person will understand that this convention is used for convenience only, and that a mixture of cis- and trans- isomers is understood unless the context dictates otherwise. (The “C18” series of products in the examples below, for example, is nominally 100% trans isomers while the “Mix” series is nominally mixtures of trans- / cis- 80:20 isomers.) Structures shown often refer to a product that can be accompanied by a smaller proportion of other components or positional isomers. For example, reaction products from modified triglycerides are complex mixtures. As another example, sulfonation or sulfitation processes often provide mixtures of sultones, alkanesulfonates, and alkenesulfonates, in addition to isomerized products. Thus, the structures provided represent likely or predominant products. Charges may or may not be shown, but they are understood, as in the case of amine oxide structures. Counterions, as in quaternized compositions, are not usually included, but they are understood by a person versed from the context.
Some specific examples of ester amines with bases C10, C ₁₂ , C14, and Cw appear below:
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ο
Some specific examples of ester amines based on C ₁₈ :
OH
The mixture of amine ester product can be complex when the ester derivative reacted with alkanolamine is a modified triglyceride made by auto-metathesis of a natural oil and separation to remove olefins (see, for example, the MTG and PMTG products described below ) or an unsaturated triglyceride made by cross-metathizing a natural oil and an olefin and separating to remove olefins (see, for example, the UTG and PUTG products described below). As is evident from the reaction schemes, the products
MTG and PMTG include a C ₈ unsaturated amine diester as a major component, although UTG and PUTG products include a C ₀ unsaturated amine ester component and one or more Cn to Cv unsaturated amine ester components. (For example, with 1-butene as the cross-methane reagent, as illustrated, results in an unsaturated Ci ₂ ester ester component.) Other components of the product mixture are glycerin and saturated or unsaturated mono, di or triesters
13/49 that incorporate alkanolamine. Despite the complexity, purification to isolate a particular species is often neither economical nor desirable for good performance.
Thus, in one aspect, the amine ester is produced by reacting an alkanolamine with a modified triglyceride made by auto-synthesis of a natural oil. Auto-metathesis of natural oil provides a mixture of olefins and a modified triglyceride that is enriched in an unsaturated Ci ₈ diester component together with saturated diesters C16-C18. The olefins are subjected to stripping, usually with heat and reduced pressure. When the auto-metathesis product is reacted directly with alkanolamine, it results in a complex mixture in which hydroxyl groups of the alkanolamine completely or partially displaces glycerin from glyceryl esters to form amine ester functionalities. Below, representative amine ester products are made by reacting alkanolamines with MTG-0 (triglyceride modified from soybean oil) or PMTG-0 (triglyceride modified from palm oil). An example is the MTG ester 2: 1 TEA:
R '= C16, C18 Sat. + Insat.
In another aspect, the amine ester is produced by reacting an alkanolamine with an unsaturated triglyceride made by cross-methosing a natural oil with an olefin. Cross-synthesis of natural oil and olefin provides a mixture of olefins and an unsaturated triglyceride that is rich in C10 and C12 unsaturated esters as well as saturated esters C ₁₆ -C ₁₈ . The olefins submitted to stripping, usually with heat and reduced pressure. When the cross-metathesis product is reacted with alkanolamine, it results in a complex mixture in which hydroxyl groups of alkanolamine completely or partially displace glycerin from glyceryl esters to form
14/49 amine ester functionalities. Below, representative amine ester products are made by reacting alkanolamines with UTG-0 (unsaturated triglyceride from cross-linked soy oil and 1-butene) or PUTG-0 (unsaturated triglyceride from cross-linked oil synthesis) palm with 1butene). One example is the PUTG 2: 1 TEA ester product:
R = C16, C18Sat. + Insat.
The reaction to form the amine esters can be carried out under a spray of nitrogen or under vacuum to remove released alcohol. When glyceride esters are reactive, the released glycerin must not be removed from the product. The reaction is considered complete when the residual glyceride content of the product reaches the desired level.
The invention includes derivatives made through one or more of quaternization, sulfonation, alkoxylation, sulfation, and amine ester suffitation. Methods for quaternizing tertiary amines are known in the art. Quaternization of amine esters is performed by heating them with a quaternization agent such as an alkyl halide or dialkyl sulfate. Specific examples include dimethyl sulfate, methyl chloride, epichlorohydrin, benzyl chloride, alkali metal chloroacetate, and the like. Dimethyl sulfate is particularly preferred. The reaction is generally carried out at a temperature within the range of 30 ° C to 150 ° C, preferably from 65 ° C to 100 ° C, or more preferably from 80 ° C to 90 ° C. The amount of quaternization agent used is typically 0.8 to 1.0 mol equivalent based on the tertiary nitrogen content. The reaction is considered to be complete when the free amine value is in the desired range as determined by perchloric acid titration. Suitable methods for quaternizing the amine esters are described in U.S. Pat. We. US 5,750,492; 5,783,534; 5,939,059; and 6,004,913, whose teachings are incorporated into this by reference.
Examples of quaternized amine esters with suitable C ₁₀ , C12, C14, and Ci ₆ bases ("esters quat"):
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Examples of C ₁₈ -quat ester ester-suitable:
OH
An exemplary ester quat based on a mixture of amine ester and 10 base PUTG:
R = C16, C 18 Sat + Insat
The amine esters and esters quat have unsaturation which can be sulphonated or sulphited if desired. Sulphonation is performed using known methods, including reaction of olefin with sulfur trioxide. Sulphonation can optionally be conducted using an inert solvent. Non-limiting examples of suitable solvents include liquid SO2, hydrocarbons, and hydrocarbons
Halogenated 16/49. In a commercial approach, a falling film reactor is used to continuously sulfonate oiefin using sulfur trioxide. Other sulfonating agents can be used with or without the use of a solvent (for example, chlorosulfonic acid, fuming sulfuric acid), but sulfur trioxide is generally the most economical. Sultones which are the immediate reaction products of olefins with SO3, chlorosulfonic acid, and the like can subsequently be subjected to a hydrolysis reaction with aqueous caustic to allow mixtures of alkane sulfonates and hydroxyalkane sulfonates. Suitable methods for sulphonating olefins are described in Pat. We. US3,169,142; 4,148,821; and Publ. Ped. Pat. No. US2010 / 0282467, the teachings of which are incorporated herein by reference.
Sulfitation is accomplished by combining an oiefin in water (and usually a co-solvent such as isopropanol) with at least one molar equivalent of a sulphiting agent using known methods. Suitable sulphiting agents include, for example, sodium sulfite, sodium bisulfite, sodium metabisulfite, or the like. Optionally, a catalyst or initiator is included, such as peroxides, iron, or other free radical initiators. Typically, the reaction mixture is conducted at 15-100 ° C until the reaction is reasonably complete. Suitable methods for sulphiting olefins appear in Pat. We. US2,653,970; 4,087,457; 4,275,013, whose teachings are incorporated into this by reference.
When the amine ester has hydroxyl functionality, it can also be alkoxylated, sulfated, or both using known techniques. For example, a hydroxyl-terminated amine ester can be alkoxylated by reacting it with ethylene oxide, propylene oxide, or a combination of them to produce an alkoxylated alcohol. Alkoxylations are usually catalyzed through a base (for example, KOH), but other catalysts such as double metal cyanide complexes (see. Pat. No. US5.482.908) can also be used. Oxyalkylene units can be incorporated randomly or in blocks. The hydroxyl-functional amine ester can be sulfated, with or without alkoxylation before, and neutralization to provide an alcohol sulfate according to known methods (see, for example, Pat. No. US 3,544,613, the teachings of which are incorporated into it through of reference).
The amine esters and their quaternized, sulfonated, alkoxylated, sulfated, and sulphited derivatives can be incorporated into various compositions for use, such as surfactants, emulsifiers, skin sensory agents,
17/49 film-forming, rheological modifiers, biocides, biocide enhancers, solvents, release agents, and conditioners. Compositions find value in several end uses, such as personal care (liquid cleansers, conditioning bars, oral care products), household products (liquid and powder laundry detergents, liquid or sheet fabric softeners, surface cleaners rough and smooth, sanitizers and disinfectants), and industrial or institutional cleaners.
The amine esters and derivatives can be used in emulsion polymerization, including processes for latex production. They can be used as surfactants, humidifiers, dispersants, or solvent agricultural applications, as inert ingredients in pesticides, or as adjuvants for pesticide delivery for crop protection, home and garden, and professional applications. Amine esters and derivatives can also be used in oilfield applications, including gas and oil transport, chemical production, stimulation and drilling, reservoir improvement and compliance uses, and special sparkling. The compositions are also valuable as foam moderators or dispersants for the production of gypsum, cement wall board, fire foams and concrete additives. The compositions are used as coalescents for paints and coatings, and as adhesives based on polyurethane.
In food and beverage processing, amine esters and derivatives can be used to lubricate the transport systems used to fill containers. When combined with hydrogen peroxide, amine esters and derivatives can function as low-foam disinfectants and sanitizing, odor-reducing agents, and as antimicrobial agents to clean and protect food or beverage processing equipment. In industrial, institutional and laundry applications, amine esters and derivatives, or their combinations with hydrogen peroxide, can be used to remove debris and sanitize and disinfect fabrics and as film-forming antimicrobial compositions on rough surfaces.
The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.
Syntheses of Raw Material:
Preparation of 9-Methyl Decenoate (“C10-0”) and 9-Methyl Dodecenoate (“C12-0”)
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Publ. Ped. Pat. No. US 2011/0113679, the teachings of which are incorporated into this by reference, are used to generate raw materials C10-0 and C12-0 as follows:
Example 1A: Cross Metathesis of Soy Oil and 1-Butene. A clean, dry 5-gallon stainless steel Parr reactor equipped with an immersion tube, overhead stirrer, internal cooling / heating coils, temperature probe, sampling valve and exhaust valve is purged with argon at 15 ° C. psig. Soybean oil (SBO, 2.5 kg, 2.9 mol, Costco, M _n = 864.4 g / mol, 85% by weight of unsaturation, sprinkled with argon in a 5 gal container for 1 hour) is added to the Parr reactor. The reactor is sealed, and the SBO is purged with argon for 2 hours while cooling to 10 ° C. After 2h, the reactor is ventilated at 10 psig. The dip tube valve is connected to a 1-butene cylinder (Airgas, CP grade, 33 psig headspace pressure,> 99% by weight) and re-pressurized to 15 psig with 1-butene. The reactor is again vented to 10 psig to remove residual argon. The SBO is stirred at 350 rpm and 9-15 ° C under 18-28 psig of 1-butene until 3 moles of 1-butene per SBO olefin bond are transferred to the reactor (~ 2.2 kg of 1-butene to the 4-5h).
A toluene solution of [1,3-bis- (2,4,6-trimethylphenyl) -2imidazolidinylidene] -dichlororutene (3-methyl-2-butenylidene) (tricyclohexylphosphine) (C827, Matter) is prepared in a Fischer pressure vessel -Porter by dissolving 130 mg of catalyst in 30 g of toluene (10 mol ppm per mol of SBO olefin binding). The catalyst mixture is added to the reactor via the reactor dip tube by pressurizing the headspace inside the Fischer-Porter vessel with argon to 50-60 psig. The Fischer-Porter vessel and immersion tube are rinsed with additional toluene (30 g). The reaction mixture is stirred for 2.Oh at 60 ° C and is then allowed to cool to room temperature while the gases in the headspace are vented.
After the temperature is released, the reaction mixture is transferred to a round bottom flask containing bleaching clay (B80 CG PureFlo® clay, product of Oil-Dri Corporation of America, 2% w / w SBO, 58 g) and a magnetic stir bar. The reaction mixture is stirred at 85 ° C under argon. After 2 hours, during which time any remaining 1-butene is allowed to vent, the reaction mixture cools to 40 ° C and is filtered through a fleet of
19/49 glass. An aliquot of the product mixture is transesterified with 1% w / w NaOMe in methanol at 60 ° C. Through gas chromatography (GC), it contains: 9-Methyl Decenoate (22% by weight), 9-Methyl Dodecenoate (16% by weight), 9-dimethyl octadecenedioate (3% by weight), and 9 -methyl octadecenoate (3% by weight).
The results compare favorably with yields calculated for a hypothetical equilibrium mixture: 9-Methyl Decenoate (23.4% by weight), 9-Methyl Dodecenoate (17.9 by weight /%), 9-dimethyl octadecenedioate (3.7% by weight) and 9 -methyl octadecenoate (1.8% by weight).
Example 1B. The procedure of Example 1A is generally followed with 1.73 kg of SBO and 3 mol of 1-butene / SBO double bond. An aliquot of the product mixture is transesterified with sodium methoxide in methanol as described above. The products (by GC) are: Methyl 9-decenoate (24% by weight), Methyl 9-dodecenoate (18% by weight), dimethyl 9-octadecenedioate (2% by weight) and methyl 9-octadecenoate ( 2% by weight).
Example 1C. The procedure of Example 1A is generally followed with 1.75 kg of SBO and 3 mol of 1-butene / SBO double bond. An aliquot of the product mixture is transesterified with sodium methoxide in methanol as described above. The products (by GC) are: Methyl 9-decenoate (24% by weight), Methyl 9-dodecenoate (17% by weight), dimethyl 9-octadecenedioate (3% by weight) and methyl 9-octadecenoate ( 2% by weight).
Example 1D. The procedure of Example 1A is generally followed with 2.2 kg of SBO and 3 mol of 1-butene / SBO double bond. In addition, the toluene used to transfer the catalyst (60 g) is replaced with SBO. An aliquot of the product mixture is transesterified with sodium methoxide in methanol as described above. The products (by GC) are: Methyl 9-decenoate (25% by weight), Methyl 9-dodecenoate (18% by weight), dimethyl 9-octadecenedioate (3% by weight) and methyl 9-octadecenoate ( 1% by weight).
Example 1E. Separation of Modified Triglyceride Olefins. A 12-L round-bottom flask equipped with a magnetic stir bar, heating mantle and temperature controller is loaded with the combined reaction products from Examples 1A-1D (8.42 kg). A cooling condenser with a vacuum inlet is attached to the middle neck of the bottle and a receiver bottle is connected to the condenser. Volatile hydrocarbons (olefins) are removed from the reaction product via vacuum distillation. Pot temperature: 22 ° C-130 ° C; head temperature
Distillation 20/49: 19 ° C-70 ° C; pressure: 2000-160 ptorr. After removing the volatile hydrocarbons, 5.34 kg of non-volatile residue remain. An aliquot of the non-volatile product mixture is transesterified with sodium methoxide in methanol as described above. The products (by GC) are: Methyl 9-decenoate (32% by weight), Methyl 9-dodecenoate (23% by weight), dimethyl 9octadecenedioate (4% by weight) and methyl 9-octadecenoate (5% by weight). This mixture is also called "UTG-0." (An analogous product made from palm oil is called “PUTG-0.”).
Example 1F. Modified Triglyceride Methanolysis. A 12L round-bottom flask coupled with a magnetic stir bar, condenser, heating mantle, temperature probe and gas adapter is charged with sodium methoxide in methanol (1% w / w, 4.0 L) and the mixture of non-volatile product produced in Example 1E (5.34 kg). The resulting light yellow heterogeneous mixture is stirred at 60 ° C. After 1h, the mixture becomes homogeneous and has an orange color (pH = 11). After 2 hours of reaction, the mixture is cooled to room temperature and forms two layers. The organic phase is washed with aqueous methanol (50% v / v, 2 x 3 L), separated and neutralized by washing with glacial acetic acid in methanol (1 mol of HOAc / mol of NaOMe) to pH = 6.5. Yield: 5.03 kg.
Example 1G. Isolation of Methyl Ester Raw Materials. A 12L round bottom flask coupled with a magnetic stirrer, filled column and temperature controller is charged with the methyl ester mixture produced in example 1F (5.03 kg), and the flask is placed in a heating mantle. The glass column is 2 ”x 36” and contains 0.16 ”Pro-Pak ™ stainless acid seals (Cannon Instrument Co.). The column is attached to a fractional distillation head to which a pre-weighed 1-L flask is attached to collect fractions. Distillation is performed under vacuum (100-120 ptorr). A reflux ratio of 1: 3 is used to isolate methyl 9-decenoate (“C10-0”) and methyl 9dodecenoate (“C12-0”). Samples collected during distillation, distillation conditions and fraction composition (by GC) are shown in Table 1. A reflux ratio of 1: 3 refers to 1 drop collected for every 3 drops sent back to the column of distillation. Combination of appropriate fractions yields 9-Methyl Decenoate (1.46 kg, 99.7% pure) and 9-Methyl Dodecenoate (0.55 kg,> 98% pure).
Table 1. Isolation of C10-0 and C12-0 by Distillation Distillation Fractions # Temp. head (° C) Temp. pot (° C) Vacuum Weight (g) C10-0 C12-0 (% in
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(% inWeight) Weight) 1 40-47 104-106 110 6.8 80 0 2 45-46 106 110 32.4 99 0 3 47-48 105-110 120 223.6 99 0 4 49-50 110-112 120 283 99 0 5 50 106 110 555 99 0 6 50 108 110 264 99 0 7 50 112 110 171 99 0 8 51 114 110 76 97 1 9 65-70 126-128 110 87 47 23 10 74 130-131 110 64 0 75 11 75 133 110 52.3 0 74 12 76 135-136 110 38 0 79 13 76 136-138 100 52.4 0 90 14 76 138-139 100 25.5 0 85 15 76-77 140 110 123 0 98 16 78 140 100 426 0 100
Preparation of fatty acids from methyl esters
Methyl esters C10-0, C12-0, and Mix-0 are converted to their respective fatty acids (C10-36, C12-39, and Mix-67) as follows.
Glycerin / Potassium hydroxide solution (16-17% by weight KOH) is added to a flask equipped with a suspended stirrer, thermocouple, and nitrogen sparging, and the solution is heated to ~ 100 ° C. The methyl ester is then added to the KOH / glycerin solution. An excess of KOH (2-4 moles KOH per mole of methyl ester) is used; for monoesters the mol ratio is about 2, and for diesters about 4. The reaction temperature is increased to 140 ° C and heating continues until analysis by gas chromatography indicates complete conversion. Deionized water is added so that the weight ratio of reaction mixture to water is about 1.5. The solution is heated to 90 ° C to melt any fatty acid salt that may have solidified. Sulfuric acid (30% solution) is added and mixed well to convert the salt to free fatty acid, and the layers are allowed to be separated. The aqueous layer is drained, and the fatty acid layer is washed with water until the aqueous washings are neutral. Unrefined fatty acids are used "as is" to make some of the ester amines.
Analysis of unreacted amines in ester amines
Several grams of ester amines are dissolved in 100ml of a mixture of toluene and isopropanol 70/30 (vol / vol) and this solution is extracted with a 50ml portion and two 25ml portions of 20% aqueous NaCI. The combined aqueous layers are then titrated with 0.1 N aqueous HCL. The amount of amine extracted is interpreted to be the amount of unreacted amine. IS
22/49 calculated from the volume of endpoint titration and the molecular weight of the starting amine used to prepare the amine ester composition.
C10-2: C10 TE A Ester
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C10-36 fatty acid (176.7 g, 0.984 mol), the basic catalyst and triethanolamine (49.0 g, 0328 mol) are loaded into a 4-necked flask under a nitrogen blanket. A subsurface nitrogen sparse is maintained. The mixture is stirred (170 rpm) and heated without vacuum to 185 ° C and kept for 21 h. Free fatty acid content is found through titration to be 0.078meq / g. The reaction temperature is increased to 190 ° C under vacuum (50 mm Hg) and heating continues for an additional 4 hours. After cooling, the amine ester product, C10-2, has a fatty acid content of 0.0651 meq / g and an unreacted triethanolamine value of 0.77%.
C10-4: C10 MDEA Ester
O
C10-36 fatty acid (168.5g, 0.939 mol), basic catalyst and N-methyldiethanolamine (55.9g, 0.469 mol) are loaded into a 4-neck flask under a nitrogen blanket. A subsurface sparse (200m / min) is maintained. The mixture is stirred (170 rpm) and heated without vacuum to 185 ° C and kept for 20 hours. Free fatty acid content is found through titration: 0.133 meq / g. Reaction temperature is reduced to 180 ° C (200 mm Hg) and heating continues for another 8 hours. Fatty acid content: 0.123 meq / g. Additional methidiethanolamine (7.2 g) is added and heating continues at 180 ° C (200 mm Hg) for another 3 hours. After cooling, the amine ester product, C10-4 has a fatty acid content of 0.0649 meq / g and a value of 1.11% of unreacted Nmethyldiethanolamine.
.C10-6: C10 DMEA Ester
Fatty acid C10-36 (153 g, 0890 mol) and N, N-dimethylethanolamine (142.7 g, 1.60 mol) are loaded into a flask equipped with heating blanket, temperature controller, mechanical stirrer, nitrogen sparse, Oldershaw column of five plates and condenser. The mixture is gradually heated to 180 ° C, while the temperature of the distillate in suspension is kept below
23/49 of 105 ° C. After the reaction mixture temperature reaches 180 ° C, it is kept at that temperature overnight. Free fatty acid content through ¹ H NMR: 5% (essentially complete). The mixture is cooled to 90 ° C and the column, condenser and nitrogen sparge are removed. Vacuum is applied in increments of 20 mm Hg over ~ 1h, kept at 20 mm Hg for 0.5h, then improved to full vacuum for 1.5h. The amine ester product, C106, has an unreacted dimethylethanolamine value of 0.41%. Purity is confirmed by a satisfactory ¹ H NMR spectrum.
C12-2: C12TEA Ester
O
Methyl ester C12-0 (193.9 g, 0.912 mol), basic catalyst, and triethanolamine (45.5 g, 0.305 mol) are loaded into a 4-neck flask under a nitrogen blanket. A subsurface nitrogen sparse (200 ml / min) is maintained. The mixture is stirred (170 rpm) and heated without a vacuum to 165 ° C and kept for 16h. ¹ H NMR indicates essentially complete reaction with a trace of unreacted ester medium. After cooling, the amine ester product,
C12-2, has a unreacted triethanolamine value of 0.06%.
C12-4: C12 MDEA Ester
C12-0 methyl ester (185.9 g, 0.875 mol), basic catalyst and N-methyldiethanolamine (54.9 g, 0.460 mol) are loaded into a 4-necked flask under a nitrogen blanket. A subsurface nitrogen sparse (200 ml / min) is maintained. The mixture is stirred (170 rpm) and heated without a vacuum to 165 ° C and kept for 16h. The temperature is raised to 170 ° C (at 200 mm Hg) and heating continues for 3 hours. After cooling, the amine ester product, C12-4, has an unreacted N-methyldiethanolamine value of 3.22%. Purity is confirmed by a satisfactory ¹ H NMR spectrum.
C12-6: C12 DMEA Ester
Fatty acid C12-39 (187.2 g, 0.917 mol) and N, N-dimethylethanolamine (147.1 g, 1.65 mol) are loaded into a flask equipped with heating blanket, temperature controller, mechanical stirrer, nitrogen sparge, Oldershaw column of five plates, and condenser. The mixture is gradually heated
24/49 to 180 ° C while the temperature of the distillate in suspension is kept below 105 ° C. After the reaction mixture temperature reaches 180 ° C, it is kept at that temperature overnight. Free fatty acid content: 1.59%. The mixture is cooled to 90 ° C and the column, the condenser, and the nitrogen sparse are removed. After usual vacuum stripping, the amine ester product, C12-6, has an unreacted dimethylethanolamine value of 0.084%. Purity is confirmed by a satisfactory ¹ H NMR spectrum.
Preparation of raw material of methyl 9-hexadecenoate (“C16-0”)
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The procedures in Example 1A are generally followed except that 1-octene is cross-metatized with soybean oil instead of 1-butene. Combined reaction products are then stripped removed as described in Example 1E to remove the most volatile unsaturated hydrocarbon fraction from the modified oil fraction. The procedure of Example 1F is used to convert the modified oil fraction to a methyl ester mixture that includes methyl 9-hexadecenoate. Fractional distillation under reduced pressure is used to isolate the desired product, methyl 9-hexadecenoate from other methyl esters.
C16-3: C16 Fatty acid
O
Potassium hydroxide (20 g) and glycerol (112 g) are added to a round-bottom flask equipped with a Dean-Stark trap. The mixture is mechanically stirred and heated to 100 ° C under nitrogen until homogeneous. Unsaturated methyl ester C16-0 (80 g) is added and the mixture is heated to 120 ° C, then kept for 3 hours. Gas chromatography indicates complete conversion to the desired acid. Deionized water (100 g) and 30% aqueous sulfuric acid solution (132 g) are added to the reaction mixture. The layers are separated and the organic phase is washed with deionized water (3 x 220 ml) at 60 ° C. Short distillation is performed to remove water (100 ° C, total vacuum, 2h). The product, C16-3, obtained in 92% yield, is analyzed: acid value: 219.7 mg KOH / g; % humidity: 0.1%; isomer ratio: 18.8 c / s- / 81.2 trans-.
¹ H NMR (DMSO), δ (ppm): 5.36 (CH = CH); 2.34 (-CH ₂ -C (O) -OH).
C16-6: C16 MDEA Ester
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Ο
The procedure used to make C12-4 is generally followed using C16-0 methyl fatty ester (162.5 g) and N-methyldiethanolamine (35.7 g). The product, C16-6, has an unreacted N-methyldiethanolamine value of 0.88% and provides a satisfactory ¹ H NMR spectrum.
Formation of ester quat from ester amines C10 and C12
Each of the amine esters prepared as described above is quaternized as follows. Table 2 summarizes the products, amount of dimethyl sulfate ("DMS," quaternizing agent), reaction time, temperature, and amount of isopropyl alcohol solvent ("IPA"). The amount of DMS used for all reactions is determined by titrating perchloric acid (“PAT” value) from the amine ester.
The amine ester is loaded into a round-bottom flask equipped with a reflux condenser, heating blanket / thermocouple, and nitrogen inlet. The sample is heated to 65 ° C if IPA is used to help solubilize the amine ester; otherwise, it is heated to 75-80 ° C. DMS is added dropwise via addition funnel. Temperature is maintained at or below 70 ° C if IPA is included or at or below 85 ° C if not used. After the DMS is added, the temperature is raised to 70 ° C (if IPA is included) and stirred for 2-3 hours; otherwise, the temperature is raised to 85 ° C and stirred for 1h. The reaction is considered complete if the PAT value indicates <5% permanence of quaternizable amine based on the original PAT value of the amine ester. IPA (—10% by weight) is added (unless previously added) to help eliminate residual DMS. The reaction mixture is also heated to 80-85 ° C for 1h to ensure complete DMS removal; contents are also tested with a Dràger apparatus for residual DMS.
Table 2: Synthesis of ester Quat C10 and C12 Ester Quat Product Esterthe mine(g) DMS(g) Time(H) TempRxn.(° C) %ValueinQuatperPAT IPA(g) O 147.5 30.5 3 70 98.5 20.0
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Ester quat C10-3: C10 TEA h ₃ co ' 2 148.9 46.5 1 85 98.7 22.0 Ester quat C10-5: C10 MDEA CH, ^H 3 ^C / O h ₃ c 98.9 49.6 3 70 98.2 26.2 Ester quat C10-7: C10 DMEA ^{H 3} ° 'n ⁺ ° 0 154.0 26.6 3 70 98.0 20.0 Ester quat C12-3: C12 TEA ch ₃ 0 162.4 38.6 1 85 98.4 23.0 Ester quat C12-5: C12 MDEA H, C ³ O. H C '^ ³ ch ₃ 0 99.8 44.6 3 70 98.8 24.0 Ester quat C12-7: C12 DMEA
C16-7: C16 MDEA Quat ester
Ester MDEA C16-6 (127.8 g) is placed in a round bottom flask equipped with a condenser, thermocouple, heating mantle, and nitrogen inlet. The contents are heated to 80 ° C. Dimethyl sulfate (27.7 g) is added via an addition funnel. The amount of DMS is added to achieve> 95% quaternization as determined from the perchloric acid (PAT) titration value. After adding DMS, the temperature is raised to 85 ° C. Two hours after the addition of DMS is complete, the quaternization percentage is -97%. Isopropyl alcohol (17.0 g) is added and the temperature is maintained at 85 ° C. After 1h, the mixture is cooled to room temperature. The product, C16-7, is removed and tested with a Dráger apparatus for residual DMS.
Synthesis of Raw Material:
Preparation of Dimethyl 9-Octadecene-1,18-dioate (“Mix-0” or “C18-0”)
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ο
Eight samples of methyl 9-dodecenoate (10.6 g each, see Table 3) are heated to 50 ° C and degassed with argon for 30 minutes. A metathesis catalyst ([1,3-bis- (2,4,6-trimethylphenyl) -25 imidazolidinylidene] dichlororutene (3-methyl-2-butenylidene) - (tricyclohexylphosphine), product of Matter) is added to 9-dodecenoate methyl (quantity shown in Table 3) and vacuum is applied to provide a pressure of <1 mm Hg. The reaction mixture is allowed to auto-metatize for the reported time. Analysis using gas chromatography indicates that dimethyl 9-octadecene-1,18-dioate is produced in the yields reported in Table 3. “Mix-0” is an 80:20 mixture of trans-cis-isomer obtained from the mixture of reaction. Crystallization provides the all-trans, “C18-0” isomer feed ._
Table 3. Auto-Metathesis of Methyl 9-Dodecanoate Sample Load catalyst (ppm mol / mol) * Reaction Time (h) C18-0(GC% area) THE 100 3 83.5 B 50 3 82.5 Ç 25 3 83.0 D 10 3 66.2 AND 15 4 90.0 F 13 4 89.9 G 10 4 81.1 H 5 4 50.9 * ppm mol catalyst / mol methyl 9-dodecenoate
Ester amines are prepared from C18, "Mix-0" or "Mix-0-2" diesters (80:20 trans-lys- mixtures) or "C18-0" (100% trans-) as described below.
MIX-3: C18 TEA Ester (2: 1) Mix (80:20 trans- / cis-)
OH
O
Mix-0-2 methyl ester (246.0 g, 0.720 mol), basic catalyst, and triethanolamine (107.4 g, 0.720 mol) are loaded into a 4-neck flask equipped with a distillation head and condenser. The contents are heated to 80 ° C, then to 135 ° C, under a flow of nitrogen (150 ml / min). Methanol is distilled as the reaction proceeds, and the temperature is gradually increased to 175 ° C over 2 hours. The nitrogen flow is then directed below the liquid surface. After 3.5h at 175 ° C, the mixture is
Cooled 28/49. The methanol collected is 77.4% of the theoretical amount. The mixture has become viscous and the reaction is considered complete. The amine ester product, Mix-3, has an unreacted triethanolamine value of 3.46%.
MIX-5: C18 TEA Ester (1: 1) Mix (80:20 trans-lcis-)
OH
OH
Mix-0-2 methyl ester (167.0 g, 0.489 mol), basic catalyst, and triethanolamine (145.9 g, 0.978 mol) are loaded into a 4-neck flask under a nitrogen blanket. A subsurface nitrogen sparse (200 ml / min) is maintained. The mixture is stirred (170 rpm) and heated without a vacuum to 150 ° C and kept for 1h, after which the temperature is increased to 180 ° C and kept for 22h. The temperature is reduced to 175 ° C (400 mm Hg) for another 4 hours. After cooling, the amine ester product, Mix-5, has an unreacted triethanolamine value of 14.6%.
MIX-7: C18 TEA Ester (3: 1) Mix (80:20 trans-lcis-) o
Mix-0-2 methyl ester (293.0 g, 0.858 mol), basic catalyst, and triethanolamine (85.3 g, 0.572 mol) are loaded into a 4-neck flask equipped with a distillation head and a condenser. The contents are heated to 130 ° C under a flow of nitrogen (150 ml / min). Methanol is distilled as the reaction proceeds, and the temperature is gradually increased to 175 ° C over 2 hours. The nitrogen flow is then directed below the liquid surface. After 2h at 175 ° C, the mixture is cooled. The methanol collected is 62.0% of the theoretical amount. The mixture has become viscous and the reaction is considered complete. The amine ester product, Mix-7, has an unreacted triethanolamine value of 0.99%.
C18-9: C18 MDEA Ester (2: 1) Mix (100% trans-)
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Methyl ester C18-0 (258.2 g, 0.758 mol), basic catalyst, and N-methyldiethanolamine (90.4 g, 0.758 mol) are loaded into a 4-neck flask under a nitrogen blanket. A sparse of subsurface nitrogen (175 ml / min) is maintained. The mixture is stirred (170 rpm) and heated without a vacuum to 130 ° C and kept for 1 h, after which the temperature is increased to 150 ° C and kept for 3 h. Methanol evolves quickly, then slows down. Additional methyldiethanolamine (0.68 g) is added and heating continues at 170 ° C (50 mm Hg) for 7h, then at 180 ° C (50 mm Hg) for another 7h. Because the analysis through ¹ H NMR shows 35% unreacted methyl ester content, heating continues up to 180 ° C (760 mm Hg) for another 70h. NMR shows that the reaction is 93% complete. More N-methyldiethanolamine (5.5 g) is added, and the mixture is heated to 180 ° C and kept overnight. After cooling, the amine ester product, C18-9, has an unreacted N-methyldiethanolamine value of 0.53%.
MIX-9: C18 MDEA Ester (2: 1) Mix (80:20 trans- / cis-)
O
Mix-0-2 methyl ester (266.0 g, 0.779 mol), basic catalyst, and N-methyldiethanolamine (92.8 g, 0.779 mol) are loaded into a 4-neck flask under a nitrogen blanket. A sparse of nitrogen above the surface (50-75 ml / min) is maintained. The mixture is stirred (170 rpm) and heated without vacuum to 130 ° C and kept for 6.75h. The temperature is gradually increased over 9h to 175 ° C and kept at 175 ° C (400 mm Hg) for 4h, then at 175 ° C (760 mm Hg) for 20.5h. After cooling, the amine ester product, Mix-9, has an unreacted N-methyldiethanolamine value of 1.25%.
MIX-11: C18 MDEA Ester (1: 1) Mix (80:20 trans-tcis-)
Mix-0-2 methyl ester (186.4 g, 0.546 mol), basic catalyst, and N-methyldiethanolamine (130.0 g, 1.09 mol) are loaded into a 4-neck flask under a nitrogen blanket. A sparse of nitrogen above the surface (50-75 ml / min) is maintained. The mixture is stirred (170 rpm) and heated without a
30/49 vacuum with a gradual temperature ramp as follows: up to 130 ° C and kept for 4.75h; up to 140 ° C and kept for 16.5h; up to 150 ° C and kept for 6.5h; up to 160 ° C and kept for 18h. Thereafter, heating continues at 170 ° C for 8h with a sparse of subsurface nitrogen (50 to 75 ml / min). After cooling, the amine ester product, Mix-11, has an unreacted N-methyldiethanolamine value of 10.6%.
MIX-13: C18 MDEA Ester (3: 1) Mix (80:20 trans- / cis-)
O
Mix-0-2 methyl ester (311.0 g, 0.910 mol), basic catalyst, and N-methyl10 diethanolamine (72.3 g, 0.607 mol) are loaded into a 4-neck flask under a nitrogen blanket. A sparse of nitrogen above the surface (50-75 mi / min) is maintained. The mixture is stirred (170 rpm) and heated, initially without a vacuum, with a gradual temperature ramp as follows: up to 130 ° C and kept for 6.5 hours; up to 140 ° C and kept for 2h; up to 150 ° C and kept for 2h; up to 160 ° C and kept for 1h; up to 170 ° C and kept for 2.5 hours; up to 175 ° C (400 mm Hg) and kept for 2.5 hours; up to 175 ° C (760 mm Hg) and kept for 20.5h; up to 160 ° C (760 mm Hg) and kept for 16h. After cooling, the amine ester product, Mix-13, has an unreacted N-methyldiethanolamine value of 0.45%.
MIX-67: C18 fatty diacid (80:20 trans- / cis ~)
O
MIX-15: C18 diDMEA Ester Mix (80:20 trans- / cis-)
Mix-67 fatty acid (170.7 g, 0.546 mol), prepared by hydrolysis of 25 Mix-0, and Ν, Ν-dimethylethanolamine (175.3 g, 1,967 mol) are loaded into a flask equipped with a heating blanket, temperature controller temperature, mechanical stirrer, nitrogen sparse, five-plate Oldershaw column and condenser. The mixture is gradually heated to 145 ° C while the
31/49 suspension distillate temperature is kept below 105 ° C. The reaction temperature is kept at 145-150 ° C for 4 h, then increased over 2 h to 180 ° C, then kept at 180 ° C overnight. The free fatty acid content is 3.30%, and the reaction is considered complete. The mixture is cooled to 90 ° C and the product is subjected to vacuum stripping (20 mm Hg, 0.5h, then in total vacuum, 1.5h). The amine ester, Mix-15, has an unreacted dimethylethanolamine value of 0.23% and provides a satisfactory ¹ H NMR spectrum.
Ester Quat formation from C18 and MIX C18 amines
Each of the amine esters prepared as described above is categorized as follows. Table 4 summarizes the products, amount of dimethyl sulfate ("DMS," quaternizing agent), reaction time, temperature, and amount of isopropyl alcohol solvent ("IPA"). The amount of DMS used for all reactions is determined by titrating perchloric acid (“PAT” value) from the amine ester.
The amine ester is loaded into a round-bottom flask equipped with a reflux condenser, thermocouple / heating mantle, and nitrogen inlet. The sample is heated to 50-65 ° C if IPA is used to help solubilize the amine ester; otherwise, it is heated to 75-80 ° C. DMS is added dropwise via addition funnel. Temperature is kept below 70 ° C if IPA is included or at or below 85 ° C if not used. After the DMS is added, the temperature is raised to 70 ° C (if IPA is included) and stirred for 2-3 hours; otherwise, the temperature is raised to 85 ° C and stirred for 1h. The reaction is considered complete if the PAT value indicates <5% permanence of quaternizable amine based on the original PAT value of the amine ester. IPA (10-50% by weight) is added (unless added previously) to help eliminate residual DMS. The reaction mixture is also heated to 80-85 ° C for 1h to ensure complete DMS removal; contents are also tested with a Dráger apparatus for residual DMS.
Table 4: C18 and MIX C18 Synthesis of ester Quat Ester Quat Product Esterthe mine(9) DMS(g) Time(H) Temp.InRxn.(° C) Value in% ofQuatthroughinPAT IPA(g)
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OHO -Í 0 ''MIX-4: C18TE OiA Ester (2: 1) Mix Quat 156.7 43.4 3 70 97.6 50.0 HO ---- 'ν' ηO OH0 116.0 48.5 3 70 97.4 41.1 MIX-6: C18TEA Ester (1: 1) Mix Quat 0O'·'-·-<0 0 -X / γ; _η 0 181.3 36.5 3 70 98.0 72.5 MIX-8: C18 TEA Ester (3: 1) Mix Quat 0• i 0 - oC18-10: C18 Quat OMDEA Ester (2: 1) Mix 143.5 38.0 3 70 98.4 45.3 0- ·. MIX-10: C18 Quat OMDEA Ester (2: 1) Mix 146.7 37.5 3 70 98.5 35.0 0 * j 0 - ^N '—0 ^{J <} _v ]; · MIX-12: C18 Quat 0MDEA Ester (1: 1) Mix 113.3 51.3 1 85 98.5 18.0 0I 0 i 0 0 186.3 36.3 1 80 98.0 39.3 MIX-14: C18 MDEA Ester (3: 1) Quat N * °0 9; 91.8 46.6 2 70 97.8 30.0 MIX-16: C18 diDMEA DiQuat
Modified triglyceride based on soybean oil (“MTG-0”) ο, _η
The procedures in Examples 1A and 1E are generally followed, except that 1-butene is omitted.
Triglyceride Mod. From Cross Metathesis of Soybean Oil and 1Butene (“UTG-0”)
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Ο
Ο
Unsaturated triglycerides (enriched with C10 and C12, also containing saturated C16 and C18)
The procedures of Examples 1A and 1E are generally followed to produce UTG-0 from soybean oil and 1-butene.
Modified triglyceride based on palm oil (“PMTG-0”)
The procedure used to make MTG-0 is followed, except that palm oil is used instead of soy oil.
Triglyceride Mod. From cross-metathesis of palm oil and 1Butene (“PUTG-0”) o
O
Unsaturated triglycerides (enriched with C10 and C12, also containing saturated C16 and C18)
The procedure used to make UTG-0 is followed, except that palm oil is used instead of soy oil.
MTG-0 Derived raw materials
Table 5. Summary of modified products and unsaturated triglycerides Soy oil Palm oil Auto-met.MTG-0 Met.crusadeUTG-0 Auto-met.PMTG-0 Met.crusadePUTG-0 TEA Ester, 1: 1 MTG-3 UTG-3 PMTG-3 PUTG-3 TEA Ester, 1: 1 quat MTG-7 UTG-7 PMTG-7 PUTG-7
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TEA Ester, 2: 1 MTG-1 UTG-1 PMTG-1 PUTG-1 TEA Ester, 2: 1 quat MTG-2 UTG-2 PMTG-2 PUTG-2 TEA Ester, 3: 1 MTG-4 UTG-4 PMTG-4 PUTG-4 TEA Ester, 3: 1 quat MTG-8 UTG-8 PMTG-8 PUTG-8 MDEA Ester, 2: 1 MTG-9 UTG-9 PMTG-9 PUTG-9 MDEA Ester, 2: 1 quat MTG-10 UTG-10 PMTG-10 PUTG-10 TEA = triethanolamine; MDEA = N-methyldiethanolamine.
Ester amines from modified and unsaturated triglycerides: general procedures
Ester amines are prepared from modified triglycerides (MTG-0, PMTG-0) or unsaturated triglycerides (UTG-0, PUTG-0) using the following general procedure. Details of the preparation for MTG products (MTG-1, -3, 4, and -9) appear in Table 6. The corresponding PMTG products are prepared analogously. Details of the preparation for PUTG products (PUTG1, -3, -4, and -9) also appear in Table 6, and the corresponding UTG products are prepared analogously.
In general, triglyceride, alkanolamine (triethanolamine or N-methyldiethanolamine) and a basic catalyst are combined in a 4-necked flask. The mixture is moved (180 rpm) and heated quickly to 175 ° C under nitrogen. The mixture is allowed to react overnight and is then cooled to room temperature to provide the amine ester. Residual unreacted alkanolamine is determined by titration of water-extractable amine with aqueous HCI. Amounts of selected amine ester reagents appear in Table 6. Target product mixtures are also summarized below.
Table 6. Preparation of Ester Amines from Unsaturated or Modified Triglycerides Amine ester MTG-0,g PUTG-0, g TEA, g MDEA, g alkanolamineresidual,% MTG-1 230.6 70.4 - 3.88 MTG-3 187.2 - 112.7 - 14.2 MTG-4 249.8 - 51.1 - 1.38 MTG-9 239.4 - - 60.6 3.88 PUTG-3 - 187.1 115.3 - 14.3
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PUTG-1 - 230.4 69.8 - 3.68 PUTG-4 - 249.7 50.6 - 1.33 PUTG-9 - 239.3 - 59.8 2.84
5.
CH ⁺ FLO
R
CH
Ι-Ό'Ύ'CH R = C16-C18 Sat. and Insat.
CH
R '= C16, C18 Sat. + Insat.
MTG-3: MTG TEA Ester (1: 1)
OH
R = 06, 08 Sat. + Insat.
MTG-4: MTG TEA Ester (3: 1)
R = 06, 08 Sat. + Insat.
MTG-9: MTG MDEA Ester (2: 1)
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R = C16, C18Sat. + Insat.
PUTG-3: PUTG TEA Ester (1: 1)
OH
O
R = C16, C18 Sat. + Insat.
PUTG-1: PUTG TEA Ester (2: 1) o
O

R = C16, C18 Sat + Insat.
PUTG-4: PUTG TEA Ester (3: 1)

R O
O
O
THE.
R = C10, C12-C18 Sat. and Insat.
HO
OH
OH
R = C16, C18 Sat. + Insat.
PUTG-9: PUTG MDEA Ester (2: 1)
Ο I o
Jk X + HO '
R, / o O R
HO
OH
R = C10, C12-C18 Sat. and Insat. R '= C10, C12-C18 Sat and Insat.
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Quaternization of Ester Amines from Modified and Unsaturated Triglycerides: General Procedure
The amine esters prepared from modified or unsaturated triglycerides are quaternized using the general procedures below. Details of the preparation for MTG products (MTG-2, -7, -8, and -10) appear in Table7. The corresponding PMTG products are prepared analogously. Details of the preparation for the PUTG products (PUTG-2, -7, -8, and -10) also appear in Table 7, and the corresponding UTG products are prepared analogously.
In general, the amine ester is loaded into a round-bottom flask equipped with a condenser, thermocouple, heating blanket, and nitrogen inlet, and the contents are heated to 80 ° C. Dimethyl sulphate (“DMS”) is added via an addition funnel. Sufficient DMS is added to achieve quaternization> 95% as determined from the perchloric acid (PAT) titration value. After adding DMS, the temperature is raised to up to 85 ° C. One hour after the addition of DMS is complete, the% quaternization is ~ 98%. Isopropyl alcohol (IPA) is added and the temperature is raised to 86 ° C. After 1h, the mixture is cooled to room temperature and the quat of ester is removed and tested with a Dràger apparatus for residual DMS. For the preparation of PUTG-8, IPA is included in the initial charge, and the reaction temperature is adjusted down to 65 ° C-70 ° C accordingly. Amounts of reagents for quat of selected esters are shown in Table 7. Target product mixtures are also summarized below.
Table 7. Quaternization of Ester Amines from Modified or Unsaturated Triglycerides Ester quat Amine ester Amine ester, g DMS, g IPA, g MTG-2 MTG-1 143.1 27.4 19.1 MTG-7 MTG-3 138.9 43.2 20.2 MTG-8 MTG-4 141.2 19.4 17.8 MTG-10 MTG-9 147.6 29.4 19.7 UTG-2 UTG-1 157.3 32.1 21.0 PUTG-7 PUTG-3 151.4 48.1 22.1 PUTG-2 PUTG-1 147.7 28.1 19.5 PUTG-8 PUTG-4 150.6 20.5 19.1
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PUTG-10 PUTG-9 148.3 27.4
19.6
MTG-2 MTG TE A Esther (2: 1) Quat o
r ^A oo
R = C16-C18 Sat. and Insat.
MTG-7: MTG TEA Ester (1: 1) Quat
OH
R = C16-C18 Sat. and Insat.
MTG-8: MTG TEA Ester (3: 1) Quat
R = C16-C18 Sat. and Insat.
MTG-10: MTG MDEA Ester (2: 1) Quat
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ο ¹ ο
R ’= C16, C18 Sat. + Insat.
PUTG-7: PUTG TEA Ester (1: 1) Quat
OH
O
ZoOH
R ’= C16, C18 Sat. + Insat.
PUTG-2 PUTG TEA Ester (2: 1) Quat o
O
X
R
R ’= C16, C18 Sat. + Insat.
PUTG-8: PUTG TEA Ester (3: 1) Quat
R ’= C16, C18 Sat. + Insat.
PUTG-10: PUTG MDEA Ester (2: 1) Quat
O
O
+
R = C10, C12-C18 Sat. and Insat. R '= C10, C12-C18 Sat. and Insat.
Water Soluble Herbicide Formulation Test
40/49
Surfactant candidates for water-soluble herbicide applications are examined as a replacement for the anionic, nonionic portion or anionic / nonionic blend portion and compared to a known industry adjuvant standard for use in paraquat, a concentrated soluble herbicide formulation. in water. A standard dilution test is conducted whereby the concentrates are diluted with water to determine whether solubility is complete.
Control: Paraquat (9.13 g of 43.8% active material) is added to a 20 ml glass ampoule. A known industry paraquat adjuvant (2.8 g) is added and mixed vigorously for 30 s. Deionized water (8.07 g) is added, and the mixing continues for 30s. Standard water of 342 ppm (47.5 ml) is added to a 50 ml cylinder of Nessler, which is capped and equilibrated in a water bath at 30 ° C. Once the test water is balanced, the formulated paraquat (2.5) is added via pipette to the cylinder. The cylinder is capped and inverted ten times. Solubility is recorded as complete or incomplete. Cylinders are allowed to stand and the amount (in ml) and type of separation is recorded after 30min, 1h, 2h and 24h. Results of the solubility test appear in Table 8 below.
Anionic test sample: Paraquat (4.57 g of 43.8% active material) is added to a 20 ml glass ampoule. An alkyl phenol ethoxylate surfactant of eight to ten moles (0.7 g) is added and vigorously mixed for 30s. Test sample (0.7 g) is added and mixing continued for 30s. Deionized water (4.03 g) is added, and mixing continues for 30s. A 2.5 ml sample of the formulated paraquat is added to 47.5 ml of 342 ppm hard water, and the test continues as described above for the control sample.
Non-ionic test sample: Paraquat (4.57 g of 43.8% active material) is added to a 20 ml glass ampoule. Test sample (0.7 g) is added and vigorously mixed for 30 seconds. Linear sodium alkylbenzene sulfonate (“NaLAS,” 0.7 g) is added and mixing continued for 30s. Deionized water (4.03 g) is added, and mixing continues for 30 s. A 2.5 ml sample of the formulated paraquat is added to 47.5 ml of 342 ppm hard water, and testing continues as described above for the control sample.
Adjuvant test sample (anionic / nonionic): Paraquat (4.57 g of 43.8% active material) is added to a 20 ml glass vessel. Test sample (1.4 g) is added and vigorously mixed for 30 seconds. Deionized water (4.03 g) is added, and mixing is continued for 30 s. A sample
41/49 of 2.5 ml of the formulated paraquat is added to 47.5 ml of 342 ppm of hard water, and testing continues as described above for the control sample.
Criteria for emulsion solubility: test samples should be as good or better than the control with no separation after one hour.
Three test samples perform as well as, or better than, the control in the emulsion stability test. Results appear in Table 8.
Table 8: Water-soluble herbicidal formulation:Emulsion stability, separation by ml Anionic Nonionic Adjuvant Classification Test sample Sun 1 am 24h Sun 1 am 24h Sun 1 am 24h C10-7 s 0 0 s 0 0 s 0 0 Good C12-7 s 0 0 D 0 0 s 0 0 Good Mix-16 s 0 0 D Tr Tr s 0.25 0.25 Good D = dispersible; S = soluble; l = insoluble; Tr = dashControl result: Solubility: D; 1 h: 0 ml; 24h: Tr.
Selection of Agricultural Dispersant:
The potential of a composition for use as an agricultural dispersant is assessed through its performance with five active ingredients typical of pesticides: Atrazine, Chlorotalonil, Diuron, Imidacloprid and Tebuconazole. The performance of each dispersant sample is evaluated against five standard Stepsperse® dispersants: DF-100, DF-200, DF-400, DF-500, and DF600 (all Stepan Company products), and each is tested with and without a nonionic or anionic wetting agent. General results versus controls are summarized in Table 9; four ester amines perform at least as well as controls. Details of the individual tests are reported in Table 10 (wetting agent included) and Table 11 (without wetting agent). Note that sample C12-3 receives an overall rating of “good” when results with and without the wetting agent are taken into account.
A selection sample is prepared as shown below for each asset. Humidifying agents, clays, and various additives are included or excluded from the selection process as needed. The percentage of pesticide weight ("technical material") in the formulation depends on the desired level of active in the final product. The chosen asset level is similar to other products on the market. If this is a new active ingredient, then the highest active level is used.
Samples are evaluated in water of varying hardness, in this case 342 ppm and 1000 ppm. Initial assessments are performed at room temperature. Other temperatures can be assessed as desired. The water of 342
42/49 ppm is made by dissolving anhydrous calcium chloride (0.304 g) and magnesium chloride hexahydrate (0.139 g) in deionized water and dilution in 1 L. The water of 1000 ppm is made similarly using 0.89 g of chloride calcium and 0.40 g of magnesium chloride hexahydrate.
Technical material (60-92.5% by weight), wetting agent (0.5-1.0% by weight when used), silica (0.5-1.0% by weight), and clay (balance) are mixed in a suitable container. The blend is ground to a particle size of at least d (90) of <20 μ using a hammer and air / jet mill as needed. Test dispersant (0.1 g) is added to the test water (50 ml) in a beaker and stirred for 1-2min. Ground powder containing the chemical material (1.0 g) is added to the dispersing solution and stirred until all the powder is moist (2-5min.). The mixture is transferred to a 100 ml cylinder using additional test water to sweeten the beaker and is then diluted to volume. The cylinder is capped and inverted ten times, then allowed to rest. Visual inspection is performed at t = 0.5, 1.0, 2.0, and 24 hours, and the amount of sediment observed (in ml) is recorded. Sediment trace = "Tr" (see Tables 10-11).
Table 9. Overall performance as an agricultural dispersant Sample Classification C10-5 Higher C12-3 Good C12-5 Good C12-7 Good Control Good
Table 10. Agricultural Dispersant Test: Nonionic Wetting Agent Includedor Anionic Sedimentation result in 1h; 24h (ml) Waterintest,PPm DF-200(anionic) DF-500(anionic) C12-3(nonionic) C12-5(nonionic) C12-7(anionic) Diuron 342 0.25-0.5; 1 Tr; 1 0.75; 1.25 0.5-1; 1 1.5; 2 1000 0.5-1; 1-1.25 2-2.5; 2 0.25-0.5;0.75 0.5-1; 1 2.25; 2 Chlorothalonil 342 0.25; 1.5 Tr; 1.25 0.5; 2 0.5; 1 Tr; 1 1000 Tr; 1.75 5; 3.5 Tr-0.5; 1-1.25 0.5; 1 Tr; 0.75
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Imidacloprid 342 Tr; 1-1.5 Tr; 1.5-2 Tr-0.25; 1 0.75-1; 1-1.5 1; 1.75-2 1000 Tr; 2 1-1.5; 3 Tr-0.25; 1 0.75-1; 2 0.5-1; 1.5-2 Tebuconazole 342 0; 1 Tr; 1 Tr; 0.5 Tr; 1 3; 3.5 1000 0.5-1; 3.5-4 12; 5 5.25; 3 Tr; 1 3.5; 3.5-3.75 Atrazine 342 Tr; 1 Tr; 1 Tr-0.25; 1.5 0.25-0.5; 1-1.5 0.25-0.5;1.75-2 1000 Tr; 2 7; 4 0.25; 1 0.5-1; 2 0.25-0.5; 1 Classification control control good good good
Table 11. Agricultural Dispersant Test: Without Wetting Agent Sedimentation result in 1 h; 24h (ml) Waterintest,PPm DF-200 DF-500 C10-5 C12-3 Diuron 342 1; 2 0.5; 1-1.5 0.25-0.5; 1 0.75-1; 1.5 1000 1; 2-2.5 0.5-0.75; 2 0.25-0.5; 0.75-1 2.5-3; 2-2.5 Chlorothaionil 342 0.25; 1-1.25 0.25; 1-1.25 0.25-0.5; 1.25-1.5 5-5.5; 4 1000 0.25-0.5;1.25-1.5 2; 3 0.25-0.5; 1-1.25 5-5.25; 4 Imidacloprid 342 Tr; 1-1.5 0.5-1; 2 0.75-1; 1-1.25 0.5-0.75; 1.5-2 1000 Tr; 1-1.5 0.5-1; 2-2.5 0.5-0.75; 1-1.25 2-2.25; 2 Tebuconazole 342 Tr; 1.25 Tr; 1.5 0; 0.25-0.5 0.5-0.75; 2-2.5 1000 Tr; 3 Tr; 3 0; 0.5-0.75 5; 4.5-5 Atrazine 342 Tr-0.25; 1-1.5 0.5; 1 Tr-0.25; 0.75-1 1.5-2; 3 1000 Tr-0.25; 1-1.5 6; 3 Tr-0.25; 0.75-1 3; 4 Rating control control higher bottom
Rough Surface Cleaners: Aqueous Degreaser
This test measures the ability of a cleaner to remove greasy dirt debris from a white vinyl tile. The test is automated and uses an industry-standard Gardner direct washable apparatus. A camera and controlled lighting are used to make a real-time video of the cleaning process. The machine uses a moistened sponge
44/49 with a known quantity of the test product. As the machine rubs the sponge along the tile with debris, the video records the result, from which a cleaning percentage can be determined. A total of 10 attempts are made using test formulation diluted 1:32 with water, and cleaning is calculated for each of attempts 1-10 to provide a profile of the cleaning efficiency of the product. The test sample is used as a component of different control formulations depending on whether it is anionic, amphoteric or non-ionic.
A neutral, dilutable, all-purpose cleaner is prepared from 10 propylene glycol n-propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate (4.0 g), Stepanol® WA-Extra PCK (lauryl sodium sulfate, Stepan, 1.0 g), test sample (0.90 g if 100% active material), and deionized water (for 100.0 g of solution). The control sample for nonionic / amphoteric testing replaces the test sample with Bio-Soft® EC-690 (ethoxylated alcohol, Stepan, 1.0 g, nominally 90% active material).
Debris composition:
Tiles are exposed to debris with a particulate medium (50 mg) and an oil medium (5 drops). The particulate medium is composed of (in parts by weight) hyperhumus (39), paraffin oil (1), used motor oil (1.5), Portland cement (17.7), silica 1 (8), molacca black (1.5) , iron oxide (0.3), black clay bandy (18), stearic acid (2) and oleic acid (2). The oil medium is composed of kerosene (12), Stoddard solvent (12), paraffin oil (1), SAE-10 engine oil (1), Crisco® vegetable fat (product of JM Smucker Company) (1) , olive oil (3), linoleic acid (3), and squalene (3).
Four samples, Mix-3, Mix-5, Mix-15 and UTG-7, perform in the same way as their corresponding controls in the test (see Tables 12A and 12B).
Table 12A. Table 9. Control runs for Gardner's Direct Washability Test Ave.% cleaning after 2, 4, 6, 8, or 10 rubs 2 4 6 8 10 Control 4 52.5 58.2 59.5 60.9 63.3 Control 18 62.2 67.6 70.4 71.7 71.7 Control 19 60.8 68.0 70.6 71.4 71.5
Table 12B. Nonionic / amphoteric Test Samples: Examples of the Invention Ave.% cleaning Sample Con. # Compound Class 2 4 6 8 10 Classifiedaction Mix-3 19 TEA ester 55.0 61.6 63.3 65.6 66.7 equal Mix-5 4 TEA ester 60.1 62.0 64.7 66.3 67.1 equal
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Mix-15 18 DMEA ester 47.0 60.9 62.8 64.3 65.5 equal UTG-7 4 TEA ester quat 59.5 62.7 63.7 66.0 66.4 equal
Hair Conditioners: Procedure for Combing Assessment
Moist
Strands of hair (10 ”length, 2-3 g) are prepared using a uniform and consistent hair type (double bleached, blond). The strands are collectively washed with shampoo with a 15% solution of active sodium lauryl sulfate. Care is taken to avoid excessive embarrassment when washing with shampoo. The wicks are rinsed clean with tap water at 40 ° C. The process is repeated to simulate double application of shampoo. The strands are separated and marked for testing. The conditioner preparation (2.0 cm ³ ), either the test or the control, is applied to each damp wick, cleaned using a syringe. When the test material is a non-quaternized amine ester, the base conditioner used as a control for the test contains cetyl alcohol (2.0%), hydroxyethyl cellulose (0.7%), cetrimonium chloride (1.0%), potassium chloride (0.5 %), and water (100% qs). The non-quaternized amine ester is formulated as an additive of 2% by weight (active) to the base conditioner. When the test material is a quaternized amine ester, the conditioner used as a test control contains cetyl alcohol (3%), cetrimonium chloride (1%), and water (100% qs). The quaternized amine ester is formulated active at 1% in a conditioner that contains cetyl alcohol (3%) and water (100% qs).
The conditioner is processed by touching fingers down for a minute on the hair. The wicks are rinsed thoroughly under 40 ° C tap water. Excess water is squeezed from each strand to simulate towel drying. The hair is combed, first, in the wet state. It is assessed that it is easy to comb through the test samples and the base or control conditioner, and qualitative ratings are assigned to the test samples compared to the results with only base or control conditioner.
When the material is a non-quaternized amine ester, improvement of conditioning of the base through the amine ester additive is the criterion of technical success at this stage and is the basis for a higher classification. Equal to inferior performance versus the base conditioner yields a lower rating.
When the material is a quaternized amine ester, the classification system is as follows: “superior” is a wet hairstyle enhancement above that of the conditioner used as a test control; “Equal” is a
46/49 wet hairstyle comparable to the conditioner used as a test control; and “bottom” is a wet hairstyle worse than the conditioner used as a test control. Results appear in Table 13.
Table 13. Wet combing performance in hair conditioners Higher Good MTG-1 PUTG-1 Base conditioner UTG-4 PUTG-4 PMTG-7 * PMTG-1 PUTG-7 * PMTG-4 PUTG-9 PMTG-9 * ester quaternized amines
Personal Care: Cleaning Application
Tests of mechanical foam balance and viscosity are used to assess the probable value of a particular surfactant as a secondary surfactant in personal care cleaning applications.
All experimental samples are evaluated for their performance versus a control (either MEA cocamide or cocamidopropyl betaine).
Viscosity curves are generated by preparing aqueous solutions of the test or control material with 12% sodium lauryl ether (1) sulfate (SLES-1), then measuring viscosity using a Brookfield DV-1 + viscometer. The active content of test material is 1.5% if the material is an amidoamine, and 3% if the material is an amidoamine oxide. Sodium chloride is added incrementally (1-3% by weight) and viscosity is recorded as a function of increasing NaCI concentration. A “good” result is a curve that shows a viscosity construction comparable to the control sample. A “higher” rating indicates that the sample builds up viscosity more quickly than the control.
Foaming properties are assessed using a mechanical foam agitation test. Aqueous solutions composed of 12% active SLES-1 and the control or test material (1.5% active content if material is an amidoamine, 3% active content if material is an amidoamine oxide) are prepared. Sample solutions calculated at 0.2% total surfactant active are thereafter made from aqueous solutions using tap water at 25 ° C. A 100.0-g portion of the solution is carefully transferred to a 500 ml graduated cylinder. Castor oil (2.0 g) is added. The cylinder is capped and mechanically inverted ten times, then allowed to adjust for 15 s. Foam height is recorded. After 5min., Foam height is recorded
47/49 again. The experiment is repeated without castor oil. In a set of experiments, the cleaning base contains SLES-1 both in the control and in the experimental execution. In a second set of experiments, the cleaning base contains another widely used anionic surfactant, that is, a mixture of sodium methyl 2-sulfolaurate and disodium 2-sulfolaurate, instead of SLES-1. A “good” result is recorded when the solution containing the test material results in a foam height that is within +/- 25 ml of the control run. Results> 25 ml of the control mark a higher classification; results <25 ml of the control are rated lower.
MTG-1, when tested against cocamidopropyl betaine, demonstrates equal viscosity and foam building properties, and is generally classified as “good”.
Personal care / antibacterial soap:
Method for Determining Foam Reinforcement Benefit
Foam volume, which signals “cleanliness” to consumers, is a desirable attribute in an antibacterial soap. Because cationic antibacterial actives are not compatible with anionic surfactants (the best foaming agents), achieving sufficient foam volume with them is challenging. The method below identifies surfactants that provide more foam volume than cocamidopropyl betaine (active / active bases) in an antibacterial soap base. Formulation: deionized water (qs to 100% by weight), cocoglycoside (3.0% by weight), lauramine oxide (3.0% by weight), benzalkonium chloride (0.1% by weight), and test molecule or cocamidopropyl betaine (3.0% by weight).
Solutions are prepared by combining ingredients in the order prescribed above, stirring with a stir bar or mixing gently using a suspended stirrer or manually using a spatula. Heat can be applied if the test molecule is a solid at room temperature. Mixing is maintained to ensure a homogeneous solution. The pH is adjusted to 6.5 +/- 0.5.
Test and control solutions are compared, with and without 2% castor oil, to 0.2% total surfactant active concentration (2.22 g of solution for 100 ml with Lake Michigan tap water, -150 ppm of Ca hardness) / Mg) for foam volume using the cylinder inversion test. Initial and delayed measurements (5min.) Are taken.
48/49
Classification system: Superior: a result> 25 ml on the control of cocamidopropyl betaine in both oil and non-oil systems. Good: a result within 25 ml of the cocamidopropyl betaine control for both oil and non-oil systems. Lower: a result> 25 ml below that of the cocamidopropyl betaine control in both oil and non-oil systems.
Compared to the controls, three samples, C10-5, C12-7 and UTG-2 all performed well in the antibacterial soap tests.
The previous examples are considered as illustrations only. The following 10 claims define the invention.
Oil Field Corrosion Inhibition: Polarization Resistance Procedure
Polarization resistance is performed in diluted NACE brine (3.5% by weight NaCI; 0.111% by weight CaCÍ2.2H2O; 0.068% by weight MgCÍ2 * 6H2O) under sweet conditions (pulverized CO ₂ ) at 50 ° C. The functional electrode is cylindrical, made of C1018 iron and rotates at 3000 rpm. The opposite electrode is a platinum wire. The reference is a calomel electrode with an internal salt bridge. A baseline corrosion rate is established over at least a 3-h period. Once the baseline has been established, the corrosion inhibitor is injected and data is collected for the remainder of the test period. The desired inhibitor concentration is 0.00011-0.0010 meq / g active. Software details', initial delay is at 1800 s with 0.05 mV / s stability; range: -0.02 to + 0.02V; scanning speed: 0.1mV / s; sample period: 1 s; data collection: ~ 24h. The final corrosion range is an average of the last 5-6 hours of data collection. Protection range is calculated from:
Protection Range = (Initial Protection Range [without inhibitor - Final Protection Range (with inhibitor!) * 100 Initial Protection Range [without inhibitor]
As shown in Table 14, twenty-one of the samples tested show overall performance as a corrosion inhibitor that is equal to or exceeds that of the control.
Table 14. EOR Corrosion Inhibitor Performance Protection Range (%) ClassificationGeneral Sample Low dose Average dose High dose IndustryStandard A 85 85 80 Control B 66 83 76 Control C 97 98 97
49/49
Control D 90 98 85 C10-5 90 72 61 good C12-5 80 89 90 good C16-7 80 73 78 good Mix-4 84 88 89 good Mix-6 91 90 80 good Mix-10 79 85 82 good MTG-2 59 95 89 good MTG-7 80 89 81 good MTG-8 16 77 95 good MTG-10 72 72 50 good PMTG-2 71 85 90 good PMTG-7 98 84 73 good PMTG-8 96 98 99 good PMTG-10 93 85 89 good UTG-2 95 91 89 good UTG-7 92 86 90 good UTG-10 87 95 93 higher PUTG-2 93 91 90 good PUTG-7 94 87 63 good PUTG-8 71 90 83 good PUTG-10 94 76 70 good
The preceding examples are intended as illustrations only. The following claims define the invention.
1/2

权利要求:
Claims (14)
[1]
1. Amine ester comprising a reaction product of a metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or its ester derivatives with a tertiary alkanolamine, said amine ester
[2]
2/2 the fact that the equivalent ratio of acyl groups in C10-C17 monosaturated acid derived from metathesis, octadecene-1,18-dioic acid, or ester derivative for hydroxyl groups in tertiary alkanolamine is within the range of 0.1 to 3, preferably within the range of 0.3 to 1.
2. Derivative, characterized by the fact that it is made through one or 15 more among quaternization, sulfonation, alkoxylation, sulfation and sulfation of amine ester, as defined in claim 1.
[3]
3. Amine ester according to claim 1, characterized by the fact that alkanolamine is selected from the group consisting of triethanolamine, N-methyldiethanolamine, Ν, Ν-dimethylethanolamine, and their alkoxylated derivatives.
20
[4]
4. Amine ester according to claim 1, characterized by the fact that the ester derivative is a modified triglyceride made through the automatic synthesis of a natural oil.
[5]
10. Amine ester according to claim 1, characterized in that the C10-C17 monounsaturated acid or ester derivative comprises (i) a C10 ester or monounsaturated acid derivative and a C12; (ii) a C10 ester or monounsaturated acid derivative and a Cu; or (iii) a C10 ester or monounsaturated acid derivative and a C16.
10
5. Amine ester, according to claim 4, characterized by the fact that the natural oil is selected from the group consisting of soybean oil,
25 palm, rapeseed oil, seaweed oil, and mixtures thereof.
5 characterized by the fact that it has the formula:
(R ¹ ) 3-mN - [(CH2) n- (CHCH ₃ ) zO-CO-R ² ] m where:
R ¹ is C ¹ -C 6 alkyl; R ² is - (CH2) 7-CH = CHR ³ or - (CH2) 7-CH = CH- (CH ₂ ) 7CO2R ⁴ ; R ³ is hydrogen or C1-C7 alkyl; R ⁴ is glyceryl ester, polyoxyalkylene,
[6]
6. Amine ester, according to claim 1, characterized by the fact that the ester derivative is an unsaturated triglyceride made by cross-metathizing a natural oil with an olefin.
[7]
7. Amine ester according to claim 6, characterized by the fact that the natural oil is selected from the group consisting of soybean oil, palm oil, rapeseed oil, algae oil, and mixtures thereof, and olefin it is a C2-C8 aolefin or a C4-C9 internal olefin.
[8]
8. Derivative, characterized by the fact that it is made through one or more of quaternization, sulfonation, alkoxylation, sulfation and sulfitation of
Amine ester as defined in either of claims 4 or 6.
[9]
Amine ester according to claim 1, characterized by
Petition 870180072225, of 08/17/2018, p. 13/15
[10]
10 oxyalkylene, alkenyl, aryl, substituted or unsubstituted alkyl, or a mono or divalent cation; m = 1-3; n = 1-4; z = 0 or 1; and when z = 0, n = 2-4;
and where, when R ³ is C 1 -C 7 alkyl, the amine ester has at least 25 mol% trans-Δ ⁹ unsaturation.
[11]
11. Composition of water-soluble herbicide or an agricultural dispersant, characterized in that it comprises 0 amine ester, as defined in claim 1, or 0 derivative, as defined in claim 2.
[12]
12. Rough surface cleaner, shampoo or conditioner, or personal cleanser or soap, characterized by the fact that each
15 comprises the amine ester, as defined in claim 1, or the derivative, as defined in claim 2.
[13]
13. Corrosion inhibitor for use in oilfield applications, characterized by the fact that it comprises 0 amine ester, as defined in claim 1, or 0 derivative, as defined in claim 2.
Petition 870180072225, of 08/17/2018, p.
[14]
14/15

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法律状态:
2018-05-22| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2018-09-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2018-10-16| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US40654710P| true| 2010-10-25|2010-10-25|

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US40657010P| true| 2010-10-25|2010-10-25|

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US40655610P| true| 2010-10-25|2010-10-25|

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PCT/US2011/057596|WO2012061093A1|2010-10-25|2011-10-25|Esteramines and derivatives from natural oil metathesis|

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