COMPOSITION CONTAINING A GREASE AMIDE, 5 AMIDE SULPHONATE, ANONIC AND NON-IONIC DISPERSANT AND EMULS

专利摘要:
COMPOSITION CONTAINING A GREASE STARCH, AMIDE SULPHONATE, ANIONIC AND NON-IONIC DISPERSANT AND EMULSIFIERS FOR AGRICULTURAL COMPOSITIONS, HERBICIDAL COMPOSITION IN WATER, AGRICULTURAL SOLVENT, ANTIMICROBIAL COMPOSITION, DEAMORINION, SHAMPOO, EIDOROROIN compositions of grease amide and its derivatives are disclosed. The fatty amides comprise a reaction product of a metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid or its ester derivatives with a primary or secondary amine. Derivatives made through reduction, quaternization, sulfonation, alkoxylation, sulfation and sulfitation of amine grease are also included. The amine reagent can be diethylenetriamine or (2-aminoethyl) ethanolamine, which come from imidazoline amides or esters, respectively. In one aspect, the ester derivative of C10-C17 monounsaturated acid or octadecene-1,18-dioic acid is a lower alkyl ester. In other respects, the ester derivative is a modified triglyceride made by auto-metathesis of a natural oil or is an unsaturated triglyceride made by cross-metathesis of a natural oil with an olefin. The compositions are valuable for cleaners, for fabric treatment, for hair conditioning, personal care, antimicrobial compositions, agricultural uses and applications in the field (...).
公开号:BR112013009940B1
申请号:R112013009940-2
申请日:2011-10-25
公开日:2020-07-07
发明作者:Dave R. Allen；Marcos Alonso；Randal J. Bernhardt；Aaron Brown；Kelly Buchek；Sangeeta Ganguly-Mink；Brian Holland；Gary Luebke；Renee Luka；Andrew D. Malec；Ronald A. Masters；Dennis S. Murphy；Irene Shapiro；Patti Skelton；Brian Sook；Michael R. Terry；Gregory Wallace；Laura Lee Whitlock；Michael Wiester；Patrick Shane Wolfe；Lena Titievsky
申请人:Stepan Company；
IPC主号:

专利说明:

FIELD OF THE INVENTION
The invention relates to fatty amides and derivative compositions that originate from renewable resources, particularly natural oils and their metathesis products. BACKGROUND OF THE INVENTION
Fatty amides are reaction products of fatty acids or esters (including oils and glycerides) and an amine. The amine can be ammonia or a primary or secondary amine (for example, dimethylamine, ethanolamine, isopropanolamine or diethanolamine). Another important class of grease amine products are imidazolines produced by reacting a fatty acid or ester with diethylenetriamine (DETA), (2-aminoethyl) ethanolamine (AEEA), or the like. Imidazolines are particularly interesting because they are quaternized to improve solubility in water and have their applicability extended. Fatty amides, including imidazolines and their quats, are useful in a wide range of end-use applications, including fabric softeners (see US Patent Nos. 7,304,026 and Patent Application Publication No. US 2007/0054835), hair (US Patent No. 3,642,977 and 6,306,805, and Patent Application Publication No. US 2006/0128601), detergents (US Patent No. 3,696,043; 3,759,847; and 6,057,283), soaps ( US Patent No. 4,668,422), agricultural adjuvants (US Patent No. 5,622,911 and Patent Application Publication No. US 2011/0124505), functionalized monomers (Patent Application No. US 2009/0143527).
The fatty acids or esters used to make fatty amines are usually made by hydrolysis or transesterification of triglycerides, which are usually animal or vegetable fats. Consequently, the greasy portion of the acid or ester will normally have 6-22 carbons with a mixture of saturated and internally unsaturated chains. Depending on the source, the fatty acid or ester often has a preponderance of components C16 to C2. For example, soy oil methanolysis provides the saturated methyl esters of palmitic (Cie) and stearic acids (C18) and the unsaturated methyl esters of oleic acid (Cis monounsaturated), linoleic acid (C18 di-unsaturated) and a- linoleic (Ci8 tri-unsaturated). Saturation in these acids has, either exclusively or predominantly, a c / s configuration.
Recent improvements in metathesis catalysts (see JC Mol, Green Chem. 4 (2002) 5) provide an opportunity to generate reduced chain lengths, monounsaturated raw materials, which are valuable for making detergents and surfactants, from natural oils rich in Ci6a C22, such as soybean oil or palm oil. Soy oil or palm oil can be more economical than, for example, coconut oil, which traditionally is a starting material for making detergents. As Professor Mol explains, metathesis is based on the conversion of olefins into new products by breaking and reforming carbon-carbon double bonds mediated by the transition of metal-carbon complexes. Auto-metathesis of an unsaturated fatty ester can provide a balanced mixture of the starting material, an internally unsaturated hydrocarbon and an unsaturated diester. For example, methyl oleate (methyl c / s-9-octadeceonate) is partially converted to 9-octadecene and dimethyl 9-octadecene-1,18-dioate, with both products predominantly consisting of the trans isomer. Metathesis effectively isomerizes the double c / s- bonding of methyl oleate in order to yield an equilibrium mixture of c / s- and trans-isomers both in the “unconverted” starting material and in the metathesis products, with the predominance of trans-,
Cross-metathesis of unsaturated fatty esters with olefin generates new olefins and new unsaturated esters, which may have reduced chain length and which may be difficult to make otherwise. For example, cross-metathesis of methyl oleate and 3-hexene provides 3-dodecene and methyl 9-dodecenoate (see also U.S. Patent No. 4,545,941). Terminal olefins are particularly desirable synthetic targets, and Elevance Renewable Sciences, Inc. recently described an improved way to prepare them by cross-methosing an internal olefin and an olefin in the presence of a ruthenium alkylidene catalyst (see Publication of US Patent Application No. 2010/0145086). A variety of cross-metathesis reactions involving an α-olefin and an unsaturated fatty ester (as the internal source of olefin) are described. Thus, reacting soybean oil with propylene, for example, followed by hydrolysis, yields, among other things, 1-decene, 2-decene, 9-decenoic acid and 9-undecenoic acid. Despite the availability (from the cross metathesis of natural oils and olefins) of unsaturated fatty esters having reduced chain length and / or predominantly trans-unsaturation configuration, fatty amides and their derivatives made from these raw materials seem to be unknown . In addition, fatty amides and their derivatives have not been made from C-is unsaturated diesters, which can be readily made through the auto-metathesis of a natural oil.
In short, natural sources of fatty acids and esters used to make fatty amides and their derivatives generally have, predominantly (or exclusively) cis- isomers and the absence of a relatively short chain (for example, C10 or C12) of unsaturated fatty portions. Metathesis chemistry provides an opportunity to generate precursors having shorter chains and predominantly trans- isomers, which could offer improved performance when the precursors are converted into downstream compositions (for example, in surfactants). New difunctional Ci8 fatty amides and derivatives are also potentially available from auto-metathesis of oil, Ci0 unsaturated acid or ester. In addition to an expanded variety of precursors, the present unsaturation in the precursors allows for other functionalizations, for example, sulfonation or sulfitation. SUMMARY OF THE INVENTION
In one aspect, the invention relates to grease amide compositions. The amides comprise a reaction product of a metathesis-derived Cr C17 monounsaturated acid, octadecene-1,18-dioic acid or its ester derivatives with ammonia or a primary or secondary amine. The invention includes derivatives made by means of one or more of reduction, quaternization, sulfonation, alkoxylation, sulfation and sulfitation of the grease amide. In particular aspects, the amine reagent is diethylenethriemine or (2-aminoethyl) -ethanolamine, which comes from imidazoline amides or esters, respectively. In one aspect, the ester derivative of C10-C17 monounsaturated acid or octadecene-1,18-dioic acid is a lower alkyl ester. In other respects, the ester derivative is a modified triglyceride made by auto-metathesis of a natural oil or an unsaturated triglyceride made by auto-metathesis of a natural oil with a natural olefin. Fatty amides and their derivatives are valuable for a wide variety of end uses, including cleansers, tissue treatment, hair conditioning, personal care (cleaning products, conditioner bars, personal care products), antimicrobial compositions, agricultural uses and oilfield applications. DETAILED DESCRIPTION OF THE INVENTION
In one aspect, the invention relates to grease amide compositions, which comprise reaction products of metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid or its ester derivatives with ammonia or a primary or secondary amine .
Cio-C17 monounsaturated acid, octadecene-1,18-dioic acid or its ester derivatives, used as a reagent, are derived from the metathesis of a natural oil. Traditionally, these materials, particularly short-chain acids and derivatives (for example, 9-decylenic acid or 9-dodecylenic acid), have been difficult to obtain, except in quantities of laboratory scale with considerable costs. However, due to recent improvements in metathesis catalysts, these acids and their ester derivatives are now available in quantities at reasonable prices. Thus, C10-C17 monounsaturated acids and esters are conveniently generated by auto-metathesis of natural oils with olefins, preferably a olefins and, in particular, ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like. Auto-metathesis of natural oil, a C10 acid or an ester precursor (for example, methyl 9-decenoate) provides the C18 diacid or diester in optimal yield, when it is the desired product.
Preferably, at least a portion of the C10-C17 monounsaturated acid has "A9" unsaturation, i.e., the carbon-carbon double bond in the C10-C17 acid is in the 9- position with respect to the carbonyl acid. In other words, there are preferably seven carbons between the carbonyl acid group and the C 9 and C 10 olefin group. For Cu to C- | 7 acids, an alkyl chain of 1 to 7 carbons, respectively, is attached to Cw. Preferably, the unsaturation is at least 1 mol% trans-A9, more preferably at least 25 mol% trans-A9, more preferably at least 50% mol trans-A9 and even more preferably at least 80% in mol trans-A9. Unsaturation can be greater than 90% by weight, greater than 95% by mol or even 10% by mol trans-A9. In contrast, naturally occurring fatty acids, which have A9 unsaturation, for example, oleic acid, have -100% in cis- isomers.
Although a high proportion of trans- geometry (particularly trans-A9 geometry) may be desirable in fatty starches derived from metathesis 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 reaction conditions, catalyst selection and other factors. Metathesis reactions are commonly accompanied by isomerization, which may or may not be desired. See, for example, G. Djigoué and M. Meier, Appl. Catai. A: General 346 (2009) 158, especially figure 3. Therefore, the person skilled in the art must modify the reaction conditions in order to control the degree of isomerization or change the proportion of cis- and trans-isomers. For example, heat a metathesis product, in the presence of an inactive metathesis catalyst, can allow the person skilled in the art to induce the migration of the double bond to yield a low proportion of product having trans-A9 geometry.
A high proportion of trans- isomer content (relative to any usual cis- configuration of natural monounsaturated acid or ester) gives different physical properties to the grease amide compositions made from it, including, for example, modified physical form, melting range , compactability and other important properties. These differences should allow formulators to use fatty amides of greater latitude or greater choice, since they use fatty amides or derivatives in cleaners, tissue treatment, personal care, agricultural uses and other end uses.
Suitable C10-C-17 monosaturated acids derived from metathesis include, for example, 9-decylenic acid (9-decenoic acid), 9-undecenoic acid, 9-dodecylenic acid (9-dodecenoic acid), 9-tridecenoic acid, 9 -tetradecenoic acid, 9-pentadecenoic acid, 9-hexadecenoic acid, 9-heptadecenoic 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 removing the most volatile olefins by 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 normally includes saturated C6-C22 alkyl esters, predominantly C1-6 alkyl esters, which are essentially spectators in the metathesis reaction. The rest of the product mixture depends on whether auto-metathesis or cross-metathesis is used. When the natural oil is self-metatized and then transesterified, the alkyl ester mixture will include an unsaturated C18 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 C1 to C7 unsaturated alkyl ester co-products. to the glycerin by-product. The terminally unsaturated Cw product is accompanied by different co-products, depending on which olefin (s) is used as a cross-metathesis reagent. Thus, 1-butene provides an unsaturated C1 alkyl ester, 1-hexene provides an C14 unsaturated alkyl ester, and so on. As shown in the examples below, the unsaturated alkyl ester Cw is readily separated from the unsaturated alkyl ester Cu to C17 and each is easily purified by fractional distillation. These alkyl esters are excellent starting materials for making the alkoxylated grease amide compositions of the invention.
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 well 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 mixtures of these 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 to generate olefins. Particularly preferred are natural oils that have a rich content of unsaturated fatty groups derived from oleic acid. Thus, particularly preferred natural oils 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 the modified natural oil are converted similarly to the alkoxylated grease amide 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 a fatty acid monounsaturated 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 transesteretification of a natural oil with an alcohol. Also useful as starting compositions are polyunsaturated fatty esters, acids and carboxylate salts. 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 a-olefins having one or more carbon-carbon double bonds. Mixtures of olefins can be used. Preferably, the olefin is a mono-unsaturated C2-C10 α-olefin, more preferably a mono-unsaturated C2-C8 α-olefin. Preferred olefins also include C4-C9 internal olefins. Thus, olefins suitable for use include, for example, ethylene, propylene, 1-butene, cis and trans-2-butene, 1-pentene, isohexylene, 1-hexene, 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 a transition metal halide or oxohalide (for example, W0CI4 or WCI6) with an alkylating co-catalyst (for example, Me4Sn). Preferred homogeneous catalysts are well defined as 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 [X1X2L1L2 (L3) n] = Cm = C (R1) R2 where M is a transition metal of Group 8, L1, L2, and L3 are binders for neutral electron donors , n is 0 (such that L3 may not be present) or 1, m is 0, 1, or 2, X1 and X2 are anionic binders, and R1 and R2 are independently selected from H, hydrocarbyl, substituted hydrocarbyl, hydrocarbyl containing heteroatom, hydrocarbil containing substituted heteroatom, and functional groups. Any two or more of X1, X2, L1, L2, L3, R1 and R2 can form a cyclic group and any one of these groups can be attached to a support.
First generation Grubbs catalysts fall into this category where m = n = 0 and particular selections are made for n, X1, X2, L1, L2, L3, R1 and R2 as described in Ruby. Ped. Pat. No. US2010 / 0145086 (“the publication‘ 086 ”), whose teachings that refer to all metathesis catalysts are incorporated into this by reference.
Second generation Grubbs catalysts also have the general formula described above, but L1 is a carbene linker where the carbene carbon is flanked by N, O, S, or P atoms, preferably by two N. atoms. carbene is part of a cyclic group. Examples of second-generation Grubbs catalysts also appear in ‘086.
In another class of suitable alkylidene catalysts, L1 is a strongly coordinating neutral electron donor as in the first and second generation Grubbs catalysts, and L2 and L3 are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups. Thus, L2 and L3 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 L2 and R2 are coupled. Typically, a nitrogen or neutral oxygen coordinates the metal although it is also attached to a carbon that is a-, 0-, or y- with reference to the carbene carbon to provide the bidentate binder. Examples of suitable Grubbs-Hoveyda catalysts appear in publication ‘086.
The structures at the front provide only a few illustrations of suitable catalysts that can be used:
Heterogeneous catalysts suitable for use in the auto-metathesis or cross-metathesis reaction include certain rhenium and molybdenum compounds as described, for example, by J.C. Mol in Green Chem. 4 (2002) 5 on p. 11-12. Particular examples are catlitic systems that include Re2O7 on alumina promoted through an alkylation co-catalyst such as a lead-tin, germanium, or silicon compound tetraalkyl. Others include MOCI3 or M0CI5 on silica activated via tetraalkyl-tin. For additional examples of catalysts suitable for self-metathesis or cross-metathesis, see Pat. No. US 4,545,941, the teachings of which are incorporated into this by references and references cited here.
Fatty amides are made by reacting a metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid or its ester derivatives with ammonium or a primary or secondary amine.
In one aspect, the ester derivative is a lower methyl ester, especially a methyl ester. 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 the removal of unsaturated hydrocarbon metathesis products 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 the grease amide mixtures of the invention or can be purified to isolate particular alkyl esters before making fatty amides.
In another aspect, the ester derivative to be reacted with the primary or secondary ammonia or amine is the metathesis-derived triglyceride discussed in the previous paragraph. Instead of transesterification of the metathesis-derived triglyceride with a lower alkanol to generate alkyl esters as described above, the metathesis-derived triglyceride, followed by olefin stripping, is reacted directly with ammonia or with a primary or secondary amine to make an amide mixture. grease of the invention.
The person skilled in the art will appreciate that the "ester derivative" here incorporates 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 primary or secondary amines have one or two hydrogens attached to the amine group. The remaining groups are typically alkyl or substituted alkyl groups, preferably C1-C10 alkyl, more preferably, C1 -C4 alkyl. Thus, suitable primary or secondary amines include ethylamine, isopropylamine, N, N-dimethylamine, N, N-diethylamine, N, N-diisopropylamine and the like. In a preferred class of primary and secondary amines, an N or O atom is attached to a carbon that is beta or gamma with respect to the N atom of the amine. In some preferred primary or secondary amines, nitrogen is attached to a C1-C10 alkyl group, preferably a C1-C4 alkyl group and a hydroxyalkyl group having 2 to 4 carbons. In other preferred primary or secondary amines, nitrogen is attached to one hydrogen and two hydroxyalkyl groups having 2 to 4 carbons each. Alcanolamines that have a beta oxygen atom in relation to amine nitrogen are particularly preferred. Suitable alkanolamines are well known and are commercially available from BASF, Dow
Chemical and other suppliers. They include, for example, ethanolamine, propanolamine, isopropanolamine, diethanolamine, N-methylethylamine, N-methylisopropanolamine, N-ethylethhanolamine and the like and mixtures thereof. Particularly preferred alkanolamines are ethanolamine, diethanolamine and N-methylethylamine, which are economical and readily available.
Suitable primary and secondary amines include alkoxylated derivatives of the compounds described above. Thus, for example, the amine used to make grease amide can be an amine-terminated polyether comprising 0.1 to 20 moles of ethylene oxide or propylene oxide per mole of -OH group in alkanolamine.
The primary or secondary amine is advantageously diethylene triamine (DETA), (2-aminoethyl) ethanolamine (AEEA) or an alkoxylated derivative thereof. DETA and AEEA can react with two equivalents of a C10-C17 monounsaturated acid, octadecene-1,18-dioic acid or its ester derivatives to yield an imidazoline or ester amide, respectively, which have a tertiary nitrogen available for quaternization.
Fatty amides are made using a well-known process that provides a unique product mixture, depending on the conventional starting mixture of acid or ester derivatives (including lower alkyl esters or triglycerides). The reagents are typically heated, under conditions effective to convert the starting acid or ester to an amide. No catalyst is required, but a basic catalyst, such as an alkoxide, is optionally included. The reaction temperature is typically within the range of 40 ° C to 300 ° C, preferably between 50 ° C to 250 ° C and, more preferably, from 50 ° C to 200 ° C. The reaction mixture is heated until the starting ester, acid or triglycerides are substantially consumed. The amide product can be purified by distillation, washing with water or other normal means, if desired. Alternatively, the product is used "as is" and converted to other derivatives.
When imidazolines are targeted, reaction temperatures tend to be higher, a two-step process is used, and an acid catalyst is used to promote cyclization. The starting ester is normally heated with a tertiary amine catalyst (eg DABCO, 1,4-diazabicyclo [2.2.2] octane), and DETA or AEEA at 80 ° C to 250 ° C. Additional AEEA or DETA is added to the reactor as needed. When the initial reaction is complete (as is generally indicated by no distillate with more than one alcohol), an acid catalyst, such as p-toluenesulfonic acid, is added and the mixture is heated to an elevated temperature (for example, 150 ° C to 300 ° C, preferably between 180 ° C to 250 ° C) to close the desired ring. Examples of procedures are provided below.
The relative amounts of primary or secondary amine and ester or acid reagents used depend on the desired stoichiometry and are left to the qualified person. When the primary or secondary amine is ethanolamine, diethanolamine, isopropanolamine or the like, it is preferable to use one mole of C-io or C12 acid or ester derivative per mole of amine. With DETA or AEEA, it is preferable to use two moles of C10 to C17 of acid or ester derivative per mole of DETA or AEEA to allow the production of an imidazoline. The examples below illustrate the variety of possible fatty amides available from a C18 diester or diacid. In general, the molar ratio of amino groups in the primary or secondary amine to the available acid or ester groups is within the range of 0.1: 1 to 3: 1, preferably 0.5: 1 to 3: 1, and most preferably from 1: 1 to 3: 1. Some amides have the formula: R1CO-NR2R3 where R1 is R4-CgHi6- or R5O2C-CI6H30-, R4 is hydrogen or C1-C7 alkyl; R5alkyl is substituted or unsubstituted, aryl, alkenyl, oxyalkylene, polyoxyalkylene, glyceryl ester or a mono or divalent cation; and each R2 and R3 is independently H, CrC6alkyl, or -CH2CH2OR6, where R6 is H or CrC6 alkyl. Preferably, R1 is R4CH = CH- (CH2) 7- or R5O2C- (CH2) 7-CH = CH- (CH2) 7-. General note concerning chemical structures:
As the skilled person will recognize, products made in accordance with the invention are typically mixtures of cis and trans isomers. Unless otherwise stated, all structural representations provided here show only one trans isomer. The skilled person will understand that this convention it 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 80:20 trans / cis isomers). Structures shown often refer to a main product that may 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 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 fatty amides based on C10, C12, C14 and C16 appear below:
Some specific examples of imidazolines based on C10, C12> C14 and C16-

The mixture of grease amide product can be complex when the ester derivative reacted with the primary or secondary amine is a modified triglyceride 5 made by auto-metathesis of a natural oil and separation to remove olefins (see, for example, products MTG and PMTG described below) or an unsaturated triglyceride made using cross-metathesis of a natural oil and an olefin and separation to remove olefins (see, for example, the UTG and PUTG products described below). As is evident from the 10 reaction schemes, MTG and PMTG products include an unsaturated C-is diamide as a major component, while UTG and PUTG products include a C10 unsaturated amide component and one or more C11 unsaturated amide components. to C17. (For example, with 1-butene as the cross-methane reagent, as illustrated, results in a C12 unsaturated amide component). Other components of the product mixes are glycerin and saturated or unsaturated fatty amides derived from the primary or secondary amine. Despite the complexity, purification to isolate a particular species is often neither economical nor desirable for good performance.
Thus, in one aspect, grease amide is produced by reacting ammonia or a primary or secondary amine with a modified triglyceride by auto-metathesis of a natural oil. Auto-metathesis of natural oil provides a mixture of olefins and a modified triglyceride which is enriched in a C18 unsaturated diester component over saturated diesters C16-C18- Olefins are normally subjected to stripping with heat and reduced pressure. When the auto-metathesis product is reacted directly with the ammonia or primary or secondary amine, a complex mixture results, in which the amine groups of the ammonia or primary or secondary amine displaces partially or completely the glycerin from the glycerol esters to form amide functionalities. Representative grease amide products below are made by reacting a primary or secondary amine with MTG-0 (triglyceride modified from soybean oil) or PMTG-0 (triglyceride modified from palm oil). An example is MTG-17, a reaction product of MTG-0 and ethanolamine:
In another aspect, grease amide is produced by reacting ammonia or a primary or secondary amine with an unsaturated triglyceride made from the auto-metathesis of a natural oil with an olefin. Cross metathesis of natural oil and olefin provides a mixture of olefins and an unsaturated triglyceride that is rich in C10 and Ci2 unsaturated esters, as well as saturated esters C16-Cis- The olefins are subjected to stripping, usually under reduced pressure and heat. When the cross-metathesis product is reacted with ammonia or primary or secondary amine, a complex mixture results, in which the amine groups of the ammonia or primary or secondary amine displaces partially or completely the glycerin from the glycerol esters to form the functionalities of the amide. Representative grease amide products below are made by reacting primary or secondary amine with UTG-0 (unsaturated triglyceride from cross-linked soy oil and 1-butene) or PUTG-0 (unsaturated triglyceride from cross-linked oil methane) palm with 1-butene). An example is the reaction of MTG-17 with isopropanolamine to make the MIPA PUTG-17 amide product: R = C16, C18Sat.
The reaction to form the fatty amides from lower alkyl esters can be formed by spraying nitrogen or vacuum to remove released alcohol. When esters are reactive, the released glycerin must 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 from one or more of reduction, quaternization, sulfonation, alkoxylation, sulfation and sulfitation of the grease amide product. Methods for quaternizing tertiary amines are well known in the art. Quaternization of imidazolines is performed by heating them with a quaternizing 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 quaternizing agent is normally 0.8 to 1.2 moles equivalent to the tertiary nitrogen content base. The reaction is considered complete when the free amine value is within the desired range, as determined by titration of perchloric acid or another suitable analytical method. Suitable methods for quaternization imidazolines are disclosed in Patent Nos. US 5,750,492; 5,783,534; 5,939,059; and 6,004,913, the teachings of which are incorporated into this report by reference.
Examples of quaternized imidazolines based on C10, C12, C14 and C16

The fatty amides and quaternized fatty amides have unsaturation that can be sulfonated or sulphited, if desired. Sulphonation is performed using well-known methods, including reacting the olefin with sulfuric trioxide. Sulphonation can optionally be conducted using an inert solvent. Non-limiting examples of suitable solvents include liquid SO2, hydrocarbons and halogenated hydrocarbons. In a commercial approach, a descending film reactor is used to continuously sulfonate the olefin, using sulfuric trioxide. Other sulfonating agents can be used with or without the use of a solvent (eg, chlorosulfonic acid, fuming sulfuric acid), but sulfuric trioxide is generally the most economical. The sultones that are the immediate products of the olefin reaction with SO3, chlorosulfonic acid and the like can subsequently be subjected to the hydrolysis reaction with aqueous caustic soda to obtain mixtures of alkene sulfonates and hydroxyalkane sulfonates. Suitable methods for sulfonation of olefins are described in Patent Nos. US 3,169,142; 4,148,821; and Patent Application Publication No. US 2010/0282467, the teachings of which are incorporated into this report by reference.
Sulfitation is accomplished by combining an olefin in water (and usually a cosolvent, such as isopropanol) with at least one molar equivalent of a sulphiting agent using well-known methods. Suitable sulphiting agents include, for example, sodium sulfide, sodium bisulfide, sodium metabisulfide or the like. Optionally, a catalyst or initiator is included, such as peroxides, iron or another free radical initiator. Normally, the reaction mixture is conducted at 15-100 ° C until the reaction is reasonably complete. Suitable methods for sulfating olefins appear in Patent Nos. US 2,653,970; and 74,087,457; 4,275,013, the teachings of which are incorporated into this report by reference.
When the grease amide has hydroxyl functionality, it can also be alkoxylated, sulfated or both, using well-known methods. For example, a hydroxyl ready grease amide can be alkoxylated by reacting it with ethylene oxide, propylene oxide or a combination of these to produce an alkoxylated alcohol. Alkoxylations are usually catalyzed by means of a base (for example, KOH), but other catalysts, such as double metal cyanide complexes (see US Patent No. 5,482,908) can also be used. Oxyalkylene units can be incorporated randomly or in blocks. The hydroxyl functional grease amide can be sulfated with or without prior alkoxylation and neutralized to yield an alcohol sulfate according to known methods (see, for example, Patent No. US 3,544,613, the teachings of which are incorporated in this report through reference).
Fatty amides and their reduced, quaternized, sulphonated, alkoxylated, sulphated and sulphited derivatives can be incorporated into various compositions, for use, for example, surfactants, emulsifiers, skin sensory agents, film-forming, rheological modifiers, biocides, highlighters biocides, solvents, release agents and conditioners. The compositions have value in several end uses, such as personal care (liquid cleaning products, conditioners, oral care products), household cleaning products (liquid detergents and powder detergents for dirty clothes) and industrial or household cleaners.
Fatty amides and derivatives can be used in emulsion polymerizations, including processes for making latex. They can also be used as surfactants, wetting agents, dispersants or solvents in agricultural applications, as inert ingredients in pesticides, or as adjuvants for pesticide supplies for crop protection, houseplants and gardens, in addition to professional applications. Fatty amides and derivatives can also be used in oil field applications, including oil and gas transportation, chemical production, stimulation and exploration, reservoir shaping and improved uses, and especially foaming. The compositions are also valuable as foam moderators or dispersants for the manufacture of gypsum, cement wall boards, additives for concrete and anti-fire foams. The compositions are used as coalescents for paints and coatings and as adhesives based on polyurethane.
In food and beverage processing, fatty amides and derivatives can be used to lubricate the conversion systems used to fill containers. When combined with hydrogen peroxide, fatty amides and derivatives can function as low foam disinfectants and sanitizing agents, other reducing agents and as antimicrobial agents for cleaning and protecting food or beverage processing equipment. In industrial, domestic and dirty clothing applications, fatty amides and derivatives or their combinations with hydrogen peroxide can be used to remove debris and sanitize and disinfect fabrics or as antimicrobial film-forming compositions on hard surfaces.
The following examples merely illustrate the invention. Those skilled in the art will recognize several variations within the spirit of the invention and the scope of the claims. Synthesis of raw material: Preparation of methyl 9-decenoate (“C10-0”) and methyl 9-dodecenoate (“C12-0”)
Publ. Ped. Pat. No. US2011 / 0113679, whose teachings are hereby incorporated 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, suspended stirrer, internal cooling / heating coils, temperature probe, sampling valve and exhaust valve is purged with argon at 15 psig. Soybean oil (SBO, 2.5 kg, 2.9 mol, Costco, Mn = 864.4 g / mol, 85% by weight of unsaturation, sprinkled with argon in a 5-gal container for 1 h) is added to the Parr reactor. The reactor is sealed, and the SBO is purged with argon for 2 h while cooling to 10 ° C. After 2 h, 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 1-butene until 3 mol of 1-butene per SBO olefin bond is transferred to the reactor (~ 2.2 kg of 1- butene over 4-5 h.
A toluene solution of [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] -dichlororutene (3-methyl-2-butenylidene) (tricyclohexylphosphine) (C827, Matter) is pre-continued in Fischer-Porter pressure vessel 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 immersion tube by pressurizing the headspaced 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 2.0 hours 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 rounded bottom flask containing bleaching clay (B80 CG Pure-Flo® clay, product of the 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 h, during which time any remaining 1-butene is allowed to vent, the reaction mixture cools to 40 ° C and is filtered through a glass frit. An aliquot of the product mixture is transesterified with 1% w / w NaOMe in methanol at 60 ° C. Through gas chromatography (GC), it contains: methyl 9-decenoate (22% by weight), methyl 9-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: methyl 9-decenoate (23.4% by weight), methyl 9-dodecenoate (17.9 by weight /%), dimethyl 9-octadecenedioate (3 , 7% by weight) and methyl 9-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 by vacuum distillation. Pot temperature: 22 ° C-130 ° C; distillation head temperature: 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 9-octadecenedioate (4% by weight) and methyl 9-octadecenoate ( 5% by weight). This mixture is also called "UTG-0." (An analog 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 non-volatile product mixture produced in Example 1E (5.34 kg). The resulting light yellow heterogeneous mixture is stirred at 60 ° C. After 1 h, the mixture becomes homogeneous and has an orange color (pH = 11). After 2 h 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 loaded 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 9-Methyl Decenoate (“C10-0”) and 9-Methyl Dodecenoate (“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 methyl 9-decenoate (1.46 kg, 99.7% pure) and methyl 9-dodecenoate (0.55 kg,> 98% pure). SYNTHESIS OF AMIDA C10-28: C10 MEA Amida

A round-bottom flask equipped with nitrogen sprinkler, thermocouple, heating mantle, shaker, and Dean-Stark apparatus is loaded with raw material of methyl ester C10-0 (129.8 g, 0.703 mol) and monoethanolamine (" MEA ", 43.8 g, 0.718 mol). The mixture is heated to 60 ° C. Sodium methoxide (2.22 ml_ of 30% after methanol solution, 0.012 mol) is added to the flask, and the reaction becomes exothermic at ~ 80 ° C. The mixture is then heated to 100 ° C and maintained for 2.5 h. The reactor is cooled to 90 ° C and the Dean-Stark apparatus is removed. Vacuum is gradually applied up to 20 mm Hg over 0.5 h. Vacuum was maintained at 20 mm Hg for 0.5 h and then at 1.4 mm Hg for 1.0 hour to remove residual methanol. 1H NMR spectroscopy indicates reasonably complete conversion, as is readily judged with the loss of methyl ester CH3O-signal of about 3.6 ppm. Free MEA, determined by titration, is 0.61%. C12-25: C12 DMA Amide
A round bottom flask is loaded with C12-0 methyl ester raw material (900.0 g, 4.22 mol) and the material is heated to 60 ° C. The reactor is sealed and vacuum is applied for 0.5 hours to dry / degas the raw material. The reactor is refilled with nitrogen and then sodium methoxide (30 g of 30% methanol solution) is added via a syringe. A static vacuum (-30 "Hg) is established, and then dimethylamine (" DMA ", 190.3 g, 4.22 mol) is slowly added through the sub-surface immersion tube. When the pressure if equalized, the reactor is opened for nitrogen overload and the temperature is increased to 70 ° C for 1.0 hour. The reactor is then cooled to room temperature and the addition of DMA is discontinued. Heating is restarted at 80 ° C and DMA is slowly introduced by sub-surface spray and held for 2.0 hours, the temperature is then increased to 90 ° C and maintained for 1.0 hour. 1H NMR spectroscopy indicates> 98% conversion The mixture is cooled to 75 ° C and a full vacuum is applied to remove excess methanol and DMA The catalyst is quenched by the addition of 50% aqueous sulfuric acid (16.3 g), and the mixture is stirred vigorously for 10 minutes Deionized water (200 ml_) is added, and all contents are transferred to a bottom drain pan. The aqueous layer is removed. The wash is repeated with 300 ml and then 150 ml of deionized water. Approximately 50 ml of a 20% NaCl solution is added and the mixture is set up overnight. The bottom layer is removed, and the product is transferred back to the reactor. The product is heated to 75 ° C and a vacuum is applied to remove residual water. The amide is recovered by vacuum distillation at 120 ° C. The starch fraction is placed under full vacuum at 135 ° C until the ester content is less than 1%. The final ester content: 0.7%. Yield: 875 g (91.9%). C12-30: C12 MEA Amide
The procedure used to make C10-C28 is generally followed when using C12-0 ester raw material (125.1g, 0.596 mol), monoethanolamine (37.2 g. 0.608 mol) and sodium methoxide (2.14 mL of 30% by weight of solution in methanol, 0.011 mol). 1H NMR spectroscope indicates reasonably complete conversion. Free MEA: 0.71%. C12-31: C12 DEA Amide
The procedure used to make C10-28 is generally followed when using raw material of C12-0 methyl ester (124.7 g., 0.587 mol), diethanolamine (62.9 g., 0.598 mol) and sodium methoxide ( 2.14 ml - 30% by weight of solution in methanol (0.011 mol). The reaction time is increased by 9.5 hours at 100 ° C. 1H NMR spectroscope indicates reasonably complete conversion. Free DEA: 4.99%. C12-38: C12 MIPA Amide
The procedure used to make C10-28 is generally followed when using C12-0 methyl ester raw material (126.7 g., 0.604 mol),
monoisopropanolamine (46.3 g, 0.616 mol) and sodium methoxide (2.17 ml - 30% by weight of 0.012 mol solution in methanol). 1H NMR spectroscope indicates that the product has the expected structure. Free DEA: 1.15%. C10-25: C10 DMA Amide
A round bottom flask is loaded with C10-0 methyl ester raw material (235 g) and the mixture is degassed with nitrogen. Sodium methoxide (5 g of 30% methanol solution) is added via syringe and the mixture is stirred for 5 min. Dimethylamine (67 g) is slowly added via a sub-surface immersion tube. After the addition, the mixture is heated to 60 ° C and kept overnight. The amide, C10-25, is recovered by vacuum distillation (120 ° C, 20 mm Hg). Yield: 241.2 g (96.3%). Iodine value = 128.9 g of l2 / 100 g of sample. 1H NMR (CDCl3), δ (ppm) = 5.8 (CH2 = C / 7-); 4.9 (CH2 = CH-); 2.8-3.0 (-C (O) -N (CH3) 2); 2.25 (-CW2-C (O) -). Ester content (through 1H NMR): 0.54%. C10-27: C10 DEA Amide
The procedure used to make C10-28 is generally followed when using C10-0 methyl ester raw material (96.8 g., 0.524 mol), diethanolamine (53.2 g., 0.50 mol) and sodium methoxide ( 1.68 ml of 30% by weight solution in methanol (0.0080 mol). 1H NMR spectroscope indicates reasonably complete conversion. Free DEA: 5.54%. IMIDAZOLINE SYNTHESIS:
Imidazolines are synthesized from fatty acids (C10-36 and C12-39) and DETA or AEEA, as described below. C10-36: C10 Fatty acid
C10-0 methyl ester (390.2 g) is loaded into a round bottom flask equipped with an overhead stirrer, and the contents are heated to 70 ° C. Potassium hydroxide (16% glycerin solution, 523 g) is added. The mixture is heated to 100 ° C and KOH pellets (35.10 g) are added. After stirring 17 h, gas chromatography indicates conversion of ~ 94% to fatty acid. Additional KOH (10 g) is added and stirring is continued at 100 ° C for 4 hours. GC conversion is> 97%. The mixture is stirred at 100 ° C for an additional 4 hours, and is then cooled to 80 ° C. Water (400 ml) and 30% sulfuric acid solution (500 ml) are added, and the mixture is stirred for 1 hour. The aqueous phase is then removed. Water (500 ml) is added, and heating / stirring is resumed (at 80 ° C) for 0.5 hour. The aqueous phase is removed again. The water washing process is repeated two more times (2 x 500 mL). The crude fatty acid product is degassed under vacuum at 80 ° C for 2 hours to remove water, and is used without further purification. Yield: 357 g. C10-12: C10 DETA Amide
A round bottom flask is loaded with C10-36 fatty acid (310 g) and the raw material is degassed with nitrogen. Diethylenetriamine ("DETA", 62.6 g) is added, and the mixture is heated from 130 ° C to 170 ° C for 4 hours and stirred (170 rpm) under a flow of nitrogen (175 mL / min.) . After 18 h, the titration reveals 0.097 meq / g of free fatty acid. The temperature is raised to 200 ° C for 4 hours. Titration indicates 96% ring closure to form C10-12. C10-15: C10 AEEA Ester
A round-bottom flask is loaded with half the required amount of C10-36 fatty acid (117.5 g) and the raw material is degassed with nitrogen. 2-aminoethyl-ethanolamine ("AEEA", 69.5 g) and xylene (20.8 g) are added and the mixture is quickly heated to 180 ° C. The water is removed using a Dean-StarkO apparatus and a sub-surface nitrogen purge (175 mL / min.) At atmospheric pressure. The mixture is heated for 18 hours at 180 ° C. The remaining fatty acid (117.5 g) is added, and the temperature is raised to 190 ° C. After 6 hours, the titration indicates a complete reaction. Yield: 94.6%. C12-39: C12 Fatty Acid
The procedure used to produce C10-36 fatty acid is generally followed. Thus, the flask is loaded with glycerin (749 g) and KOH pellets (142 g) and heated to 100 ° C until the KOH dissolves. After cooling to 75 ° C, C12-0 methyl ester (384 g, 2.084 mol) is added, and the mixture is heated to 120 ° C. Heating continues for 4 hours. GC indicates complete conversion. After cooling to 85 ° C, 30% H2SO4 (1000 mL) is added in one portion. The two-phase mixture is stirred at 85 ° C for 0.5 hour, and the aqueous phase is removed. The fatty acid (C12-39) is washed with water (3 x 1000 ml) at 85 ° C and dried as previously described. It is used without further purification. Yield: 346.2 g. C12-15: C12 AEEA Ester
A round-bottomed flask is loaded with C12-39 fatty acid (250.0 g) and the raw material is degassed with nitrogen. AEEA (63.9 g) is added, and the mixture is heated from 130 ° C to 170 ° C for 4 hours and stirred (170 rpm), under a flow of nitrogen (175 ml / min.). After 22 hours, titration of free fatty acid indicates conversion of 93% to C12-15. C12-12: C12 DETA Amide
9-Methyl dodecenoate ("C12-0", 273.3 g), DABCO (0.3450 g) and DETA (66.48 g) are loaded into a round bottom flask, and the liquid mixture is sparged with nitrogen ( 175 ml / min). The mixture is heated from 100 ° C to 170 ° C for 2 hours at atmospheric pressure. After 4.5 hours at 170 ° C, a vacuum 15 (90 mmHg) is applied, and the mixture is heated for an additional 6 hours. The resulting distillate (44.3 g) comprises about 2 g of DETA. Additional DETA (2 g) is added to the reactor, and heating continues at 170 ° C for 5 hours at 400 mm Hg. The temperature is increased to 200 ° C at a higher vacuum (50 mm Hg). After 4 hours there is no distillate. P-Toluenesulfonic acid is added (to induce ring closure for imidazoline), and the mixture is reheated (200 ° C, 50 mm Hg) for 22 hours. The analysis by titration shows that the ring closure is 81%. QUATERNIZATION OF IMIDAZOLINS C10-13: C10 DETAQuat
A round-bottomed flask is loaded with imidazoline C10-12 (202.1 30 g), which is degassed with nitrogen and heated to 75 ° C. Dimethyl sulfate ("DMS", 60.6 g) is added via addition funnel, with cooling to maintain the reaction temperature at ~ 80 ° C. After the DMS addition is complete, the mixture is maintained at 80 ° C for 1 hour. Free amine (by perchloric acid titration): 0.067 meq / g. Isopropyl alcohol (IPA) (13.9 g) is added, and the mixture is heated to 85 ° C for 1 hour to destroy any unreacted DMS. C10-16: C10 AEEAQuat
The procedure used to make C10-13 is generally followed with C10-15 imidazoline (109.6 g), DMS (12.15 g) and IPA (6.4 g). Free amine: 0.08 meg / g. C12-16: C12 AEEAQuat
The procedure used to make C10-13 is generally followed with C12-15 imidazoline (112.3 g), DMS (11.0 g) and IPA (6.5 g). DMS is added in two portions (10.8 g and 0.2 g) with a total heating time of 3 hours at 80 ° C. Free amine: 0.067 meg / g. C12-13: C12 DETAQuat
A flask equipped with a condenser, nitrogen inlet, thermocouple and a port for an addition flask is loaded with imidazoline C12-12 (212.1 g). The contents are heated to 80 ° C, and DMS (59.3 g) is added via the addition flask with a 0.065 perchloric acid target value (PAT) titer. The temperature is raised to 85 ° C, and stirring is continued for 1 hour. A sample is removed and titrated to the PAT (found: 0.045). Isopropyl alcohol (30.4 g) is added, and the mixture is stirred for 1 hour. SULFITATION REACTIONS C10-14: C10 DETA Quat Sulphonate
A round bottom flask is loaded with sodium metabisulfite (78.48 g) and deionized water (176 g). The pH is adjusted to 6.6 with 50% sodium hydroxide. The mixture is heated to 75 ° C, and isopropyl alcohol (117 g) and t-butylperoxybenzoate (BTB, 0.2 ml) are added at the same time. After 10 minutes, C10-13 olefin (117.4 g) is added, followed by the remaining TBB (0.58 ml). After 1 hour, the pH rises to 7.7 and is reduced to 6.6 by the addition of SO2 gas. After 0.5 hour, the pH rises to 7.1 and is reduced to 6.5 with SO2. The mixture is stirred at 75 ° C for 1.5 days, adjusting the pH two more times with SO2 to 6.5. The 1H NMR spectrum shows the disappearance of the olefin signals, which indicates a complete conversion to the disulfonate. C12-14: C12 DETA Quat SULPHONATE
DETA C12 quat (012-13, 126.1 g), IPA (126.1 g) and t-butylperoxybenzoate (2.5 g) are loaded into a round bottom flask. The mixture is heated to 75 ° C. A solution of sodium metabisulfite (37.5 g), sodium sulfite (7.2 g), deionized water (190.0 g) and t-butylperoxybenzoate (1.2 g) is loaded into an addition funnel, and then they are added dropwise to the reaction mixture, which is carried out at 75 ° C for 16 hours. IPA is removed by means of rotary evaporation. The 1H NMR spectrum indicates 75% conversion. Moisture content is adjusted to ~ 50% by adding water. (Note: the structure indicated above suggests single-site sulfonation, but the person skilled in the art will understand at least part of the product, with the result of being sulfonated on both carbon-carbon double bonds). C12-29: C12 DMA Amide Sulphonate
Sodium metabisulfite (43.9 g), sodium sulfite (1.45 g), isopropyl alcohol (656.5 g), C12-25 amide (101.0 g) and water (606 g) are loaded into a round bottom flask and the pH is adjusted to 6.5 with caustic, t-butylperoxybenzoate (BTB, 0.43 ml) is added and the mixture is heated to 75 ° C. After 16 hours, the conversion is about 50% by 1 H NMR. More TBB (0.44 ml) is added and the mixture is heated to 75 ° C for 8 hours. After 2 days at room temperature, more TBB (0.2 ml) is added and the mixture is heated to 75 ° C. The pH (5.8) is adjusted to 7.2 with caustic soda and then with SO2 to 7.0. After 16 hours, the conversion is about 70%. IPA is removed and the resulting two layers are separated. The upper phase (unreacted amide, ~ 52 g) is removed. A lower phase NMR spectrum shows that the starting olefin sulfonate product ratio is 94: 6 mol%. C10-26: C10 DMA Sulphonate
Sulfur trioxide (23.6 g) is added dropwise to the C10-25 unsaturated amide (48.6 g) with a vaporizer at a rate effective to maintain the reaction temperature between 35-40 ° C. Initial vaporization in the upper space of the reactor is minimal. About halfway through the addition of SO3, the reaction product becomes too viscous to be stirred properly. The reactor is equipped with an acetone / dry ice apparatus and the product is diluted with methylene chloride (50 ml) to aid stirring. The reaction temperature is maintained between 20oC-25 ° C. Additional methylene chloride (20 ml) is added during the addition of SO3 to maintain fluidity. At the end of the addition, the reactor is purged with nitrogen for 5 minutes. Total addition time: 45 min. The yellow-brown product (104.76 g) is transferred to a round bottom flask and the solvent is removed under vacuum (~ 40 ° C, 2 hours). The resulting sulfonic acid is digested at 45 ° C for 30 minutes. Yield: 71.4 g.
Aqueous sodium hydroxide (75 g of a 10.7% solution) is added to the dry sulfonic acid. The pH is adjusted, if necessary. Once dissolved, the mixture is transferred to a flask equipped with a mechanical stirrer. Water (78.4 g) and aqueous NaOH (24.6 g of 50% solution) are added. The mixture is heated to 95 ° C overnight, maintaining the pH = 7 with 50% aqueous NaOH solution and then is cooled. Preparation of raw material of methyl 9-hexadeceonate (“C16-0”)
The procedures of Example 1A are generally followed, except that 1-octene is cross-metallized with soybean oil instead of 1-butene. Reaction products are then stripped 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, which includes methyl 9-hexadecenoate. Fractional distillation at reduced pressure is used to isolate the desired product, methyl 9-hexadecenoate from other methyl esters. C16-14: C16 DMA Amide o
C16-0 methyl ester (502 g, 1.8 mol) is loaded into a vessel equipped with a mechanical stirrer, thermocouple, vacuum manometer and side distillation arm. The material is heated to 50 ° C and a total vacuum is applied for 30 minutes to dry and degas the system. The vessel is refilled with nitrogen and sodium methoxide (30% methanol solution, 20 g) is loaded using a syringe. The mixture is stirred for 5 minutes and then the pressure is reduced to about -25 "Hg. The vessel is sealed under a static vacuum and addition of dimethylamine (DMA) through the sub-surface depth tube is initiated. When the pressure in the container is equalized, the side distillation arm is connected to a water / bubbler apparatus, and the loading continues, at atmospheric pressure, adjusting the addition speed to minimize blowing (indicated by bubbling in the washer). a slight excess of DMA was charged, the vessel is stirred for 3 hours at 60 ° C under nitrogen.1H NMR analysis indicates complete consumption of the methyl ester, and the mixture is cooled to room temperature overnight. The mixture is reheated at 65 ° C and vacuum stripping to remove excess DMA and MeOH. When the stripping is complete, the container is filled with nitrogen. Concentrated HCI is added in portions until a wet pH test strip indicates a v slightly acid pH value. After stirring for 15 minutes, the neutralized mixture is washed with water (3 x 200 mL), adding 20% NaCI as necessary to facilitate phase separation. The washed product is heated to 65 ° C and the vacuum is applied slowly to remove water. When the stripping is complete, the vessel is refilled with nitrogen and the removed product is filtered through a plug of silica gel in a glass to remove a fine precipitate. The product remains obscure and is diluted with ethyl acetate and filtered again through a pad of Celite, which gives a light yellow liquid. Volatiles are removed via rotary evaporator and then under high vacuum, producing dimethylamide C16-14 as a light yellow oil (509.4 g, 96.8% yield). 1H NMR analysis is consistent with the target structure and shows the remaining 0.8% methyl ester. Additional analysis shows: humidity: 0.04%; iodine value: 89.3 g of sample l2 / 100 g. Synthesis of raw material: Preparation of 9-octadecene-1,18-dioate dimethyl (“Mix-0” or “C18-0”)
Eight samples of methyl 9-dodecenoate (10.6 g each, see table 2) are heated to 50 ° C and degassed with argon for 30 minutes. A metathesis catalyst ([1,3-bis- (2) 4,6-trimethylphenyl) -2-imidazolidinylidene] dichlororutene (3-methyl-2-butenylidene) - (tricyclohexylphosphine), product of matter) is added to methyl- 9 dodecenoate (amount shown in Table 2) and the vacuum is applied to provide a pressure of <1 mm Hg. The reaction mixture is allowed to self-metatise for the reported time. Analysis by gas chromatography indicates that dimethyl 9-octadecene-1,18-dioate is produced in the yields shown in table 2. "Mix-0" is a mixture of 80:20 trans- / cis- isomers obtained from the mixture of reaction. Crystallization provides the feed for all-trans-isomer, "C18-0".
Amides from C18: MIX-39: C18 DiDMA Amide diacids (80:20 trans- / cis-)
A round-bottom flask is charged with Mix-0 methyl ester (250.0 g, 0.73 mol) and the raw material is heated to 50 ° C. Sodium methoxide (10 g of 30% methanol solution) is added via a syringe. The reactor is sealed and a static aspirator (-25 "Hg) is established. Dimethylamine (80 g) is slowly added through the tube dipped below the surface. The reaction temperature is raised to 55 ° C and maintained for ~ 9 hours. Residual ester (per 1H NMR): <0.8%. Total vacuum is applied to remove excess methanol and DMA. The catalyst is quenched by the addition of 50% aqueous sulfuric acid (5.4 g). vacuum to remove water. The product is diluted with chloroform and filtered through Celite. The chloroform is removed by rotary evaporation and the product is dried overnight under full vacuum. 1H NMR indicated reasonably complete conversion of the ester groups methyl, for dimethyl amide groups as evidenced by negligible methyl ester CH3O-, a signal of about 3.6 ppm, and the expected amide CH3 simply at 2.9-3 ppm. C18-41: C18 DiMEA Amide (100% trans- )
A round-bottom flask equipped with nitrogen spray, thermocouple, heating mantle, shaker and Dean-Stark apparatus is loaded with dibasic ester C18-0 (129.9 g, 0.763 mol) and monoethanolamine (47.5 g, 0.778 mol). The mixture is heated to 60 ° C. Sodium methoxide (2.23 ml_ of 30% by weight of methanol solution, 0.012 mol) is added to the vial. The reactor is heated to 70 ° C, the temperature peaks to ~ 90 ° C and the mixture forms a solid mass. The reactor is heated to 155 ° C and, after melting the solid, the reactor is kept at 155 ° C for 1 hour. The apparatus is removed and the vacuum is improved in increments at 50 mm Hg over 0.5 hour, then maintained for 1.5 hours. The product is divided into flakes by pouring the melted amide onto an aluminum foil, allowing it to harden, and then breaking it out of the foil. 1H NMR indicated reasonably complete conversion. Free MEA (by titration): 1.70%. MIX-41: C18 DiMEA Amide (80:20 trans- / cis-)
The apparatus used to make C18-41 is loaded with dibasic ester Mix-0 (129.9 g, 0.760 mol) and monoethanolamine (47.4 g, 0.776 mol). The mixture is heated to 150 ° C and kept overnight. Additional monoethanolamine (1.0 g) is added and reacted for 1 hour. Total reaction time: 24 hours. Full vacuum is applied for 3.0 hours to remove methanol and residual MEA excess. The product is divided into flakes as described above. 1H NMR indicated reasonably complete conversion. Free DEA: 0.92%. C18-42: C18 DiDEA Amide (100% trans-)
The procedure used to make C18-41 is generally followed with dibasic ester C18-0 (106.1 g, 0.623 mol) and diethanolamine (66.8 g, 0.636 mol). The mixture is heated to 60 ° C, and sodium methoxide (1.82 ml of 30% by weight of a solution in methanol, 0.010 mol) is added. The mixture is heated to 100 ° C and maintained for 8.5 hours. After cooling to 70 ° C, a total vacuum is applied for 0.5 hour to remove residual methanol. 1H NMR indicated reasonably complete conversion. Free DEA: 6.71%. MIX-42: C18 DiDEA Amide (80:20 trans- / cis-)
The procedure used to make C18-42 is generally followed with dibasic ester Mix-0 (109.7 g., 0.644 mol) and diethanolamine (69.1 g., 0.657 mol). The mixture is heated to 100 ° C for 5 hours, then cooled and stripping as described above. 1H NMR indicates reasonably complete conversion. Free DEA: 6.71%. C18-66: C18 DiMPA Amide (100% trans-)
The apparatus used to make C18-41 is loaded with monoisopropanolamine (54.1 g, 0.720 mol), which is heated to 80 ° C. Dibasic ester C18-0 (120.2 g, 0.706 mol) is loaded into the reactor through a powder funnel while increasing the reactor temperature to 100 ° C. Nitrogen sparging is used to aid methanol removal. The temperature of the reactor is raised to 130 ° C and maintained for 5 hours, left to cool and then reheated to 135 ° C and maintained overnight. After vacuum extraction, the product is divided into flakes by pouring the molten amide onto the sheet, as previously described. 1H NMR indicated reasonably complete conversion. Free MIPA: 0.33%. MIX-66: C18 DiMIPA Amide (80:20 trans- / cis-)
The procedure used to make C18-66 is generally followed with dibasic ester Mix-0 (128.1 g., 0.750 mol) and monoisopropanolamine (57.5 g., 0.765 mol). The mixture is heated to 130-135 ° C and kept overnight. 1H NMR spectroscope indicates reasonably complete conversion. Free DEA: 0.65%. Imidazolines and derivatives from C18 Dibasic ester: MIX-21: C18 DiDETA (80:20 trans- / cis ~)
A round-bottom flask is loaded with C18-0 dibasic ester (267 g) and the raw material is degassed with nitrogen. DETA (131 g) and DABCO (0.24 g) are added and the mixture is heated to 140 ° C. Methanol is collected using a Dean-Stark apparatus, with nitrogen sparging. After 18 hours, the reaction temperature is increased to 197 ° C for 4 hours. Vacuum (10 mm Hg) is applied and p-toluenesulfonic acid (0.5 g) is added. The temperature is reduced to 175 ° C and the vacuum is replaced by a nitrogen purge. Heating continues for 18 hours. The analysis by titration shows that the ring closure is 77%. MIX-22: C18 DiDETA DiQuat (80:20 trans- / cis-)
Mix-21 (79.5 g) is loaded into a bottle equipped with a condenser, nitrogen inlet, thermocouple and addition bottle. Imidazoline is heated to 65 ° C, and DMS (35.8 g) is added. Methanol (34 g) is added to decrease viscosity. After 2 hours, the temperature is raised to 78 ° C and maintained for 3 hours. Titration confirms the disappearance of DMS from the reaction mixture and the desired product with a good yield. MIX-23: C18 DIDETA DIQuat Sulphonate
A round bottom flask is loaded with Mix-22 diquat (127.9 g), isopropyl alcohol (100 g) and water (300 g). Sodium bisulfate (40.98 g), sodium sulfite (2.7 g) and t-butylperoxybenzoate are added, and the mixture is heated to 75 ° C and maintained overnight. The 1H NMR analysis confirms complete disappearance of the olefin protons. Isopropyl alcohol is removed by means of rotary evaporation to obtain the final product. MIX-69: C18 Ester / Acid (80:20 trans- / cis-)
The Mix-69 ester / acid medium is prepared from the mixture of dibasic ester-0 (used as received), as described in Organic Synthesis: Col. Vol. IV (1963) 635. Thus, Mix-0 (1 kg) is added to methanol (-9 L) and the mixture is mechanically stirred. In a separate container, Ba (OH) 2 (274.4 g) is dissolved in methanol (-4 L), and the solution is added in portions over 2 hours to the stirred diester solution, resulting in the formation of a white precipitate. The solid is isolated by filtration, washed several times with methanol and air dried. The solid is then transferred to a 12 L reaction vessel and slurried in ethyl acetate (~ 3.5 L). Aqueous HCI (32%, Aldrich, 1248.6 g) is added in portions to the stirred suspension, resulting in the dissolution of the solid and the formation of a clear solution. The solution is washed three times with water, and the aqueous layers are removed and collected in a separate vessel. The combined aqueous layers are extracted once with ethyl acetate, and the organic phase is combined with the washed product solution. The mixture is dried (Na2SO4), filtered and concentrated by means of a rotary evaporator. Complete drying, under high vacuum, gives a waxy, crystalline solid after cooling (655 g, -70% yield). Analysis of the product (following derivatization) by gas chromatography shows that it contains 94% acid / ester and 6% diacid. Quantitative 13C NMR shows a trans-cis isomer ratio: 86:14. MIX-59: C18 DMA Amide Ester
The mixed acid / ester (Mix-69, 315.2 g) is converted to the acid / ester chloride by reaction with a slight excess of thionyl chloride (SOCI2, 1.2 eq., 147.5 g) in solution chloroform, and the product is isolated by removing the solvents, and the excess SOCI2 under reduced pressure. NMR analysis of the isolated product shows an essentially quantitative conversion with the acid / ester chloride, and the material is used without further purification.
The acid / ester chloride is diluted with CHCl3 (250 ml) in the same 1 liter reaction vessel equipped with a mechanical stirrer, nitrogen inlet, stainless steel with dipping leg and thermocouple. The mixture is heated to 40 ° C and dimethylamine (DMA), is introduced slowly, through sub-surface spray, through the stainless steel dipping leg. During the addition, the temperature rises moderately and is maintained at a maximum of 50 ° C by external cooling, as needed. The addition of DMA is stopped when a little more than 2 molar equivalents are introduced, and the mixture is stirred at 50 ° C for 1 hour. The vessel is then equipped with a side arm and an ice-cooled dry distillation apparatus, and the excess DMA and CHCl3 is removed by applying a gentle vacuum. The volatiles are condensed in the apparatus, and the vacuum is increased in increments until full vacuum is achieved. Total vacuum is maintained for 30 minutes, and then the device is refilled with nitrogen. The dark, viscous liquid thus obtained is diluted with ethyl acetate (EtOAc, 500 mL), causing a fine solid to precipitate. The solid is removed by filtration, and the hygroscopic solid is washed with additional EtOAc (2 x 250 ml). The deep red filtrate is evaporated to dryness by means of a rotary evaporator, giving a dark red oil with moderate viscosity. The oil is taken up in an equivalent volume of EtOAc, and the solution is filtered through a plug of silica gel, resulting in a color whitening. The filtrate is then evaporated to dryness by rotary evaporation and dried completely under high vacuum, giving a red oil (332.1 g, 98.7% yield). The 1H NMR analysis of the product is consistent with the target structure (õ 3.6 ppm, s, 3H, ester-OCH3; õ 3.0 ppm, 2s, 6H, N (CH3) 2 amide). Iodine value: 70.7 g l2 / 100 g of sample. C18-26: C18 DiDMAPA Amide (100% trans-)
A round-bottom flask equipped with a mechanical stirrer is loaded with C18-0 diester (545.6 g) and DMAPA (343.3 g). A Dean-Stark apparatus is turned on, and sodium methoxide (20 g of 30% by weight of MeOH solution) is added. The temperature is raised to 110 ° C over 1.5 hours, and methanol is collected. The temperature is increased to 150 ° C, as the distillation decreases. The mixing is carried out at 150 ° C for 6.5 hours and then cooled to room temperature. 1 H NMR analysis indicated a small amount of unreacted methyl ester. The mixture is heated to 180 ° C for several hours and additional DMAPA and sodium methoxide are added. The mixture is cooled and neutralized with concentrated hydrochloric acid. When the mixture has cooled to 90 ° C, the deionized water is added slowly, with vigorous stirring, resulting in the precipitation of the amide to obtain a suspension. The solids are isolated by vacuum filtration and washed with water. The solid product, trans-C18-26 amide, is dried in vacuo. Yield: 92.2%. 1H NMR (CDCI3) confirms the formation of the amide, based on the disappearance of the methyl ester peak at 3.65 ppm and the appearance of DMAPA CH2 signals at 3.31,2,12 and 1,62 ppm and the N (C / 73) 2 to 2.20 ppm. C18-68: C18 DiDMAPA Amide Sulphonate
DiDMAPA amidoamine C18-26 (82.9 g) is added to isopropyl alcohol (IPA, 500 g), and the mixture is heated to 60 ° C and stirred, giving a homogeneous solution. Sodium sulfite (9.3 g) is dissolved in water (250 g), and the solution is added to the amidoamine solution. The pH is adjusted from 9.2 to 6.5 with gaseous SO2 and t-butylperoxybenzoate (BTB, 0.90 ml) is added. The mixture is stirred at 75 ° C, and more IPA (50 g) is added to aid solubility. Eventually, the mixture thickens and more IPA (50 g) and water (50 g) are added. The mixture is stirred at night. Water (75 g) and more TBB (0.25 ml) are added to the cloudy mixture. Analysis by 1H NMR after several hours indicates 50% conversion. The mixture is stirred overnight and, after analysis, shows the conversion of 59%. A slow spray of O2 is introduced to expel IPA, and the temperature is increased to 80 ° C. After approximately 6 hours, heating is discontinued and the mixture is stirred at room temperature over the weekend. The analysis shows the 97% conversion. Residual IPA is removed to give the sulfonate, C18-68. Humidity: 62.6%; inorganic sulfate: 7.28%. Modified triglyceride based on soy oil (“MTG-0”)
The procedures of examples 1A and 1E are generally followed to produce UTG-0 from soybean oil and 1-butene.
Triglyceride modified from cross metathesis of soy oil and 1-butene (“UTG-0”)
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 for the fact that palm oil is used instead of soy oil.
Triglyceride modified from cross-metathesis of palm oil 1-butene (“PUTG-0”)
Unsaturated triglycerides (enriched C10 and C12, also containing saturated C16 and C18)
The procedure used to make UTG-0 is followed, except for the fact that palm oil is used instead of soy oil. MTG-0 Raw material derivatives
Fatty amides are prepared from modified triglycerides (MTG-0, PMTG-0) or unsaturated triglycerides (UTG-0, PUTG-0). Details of the preparation for MTG products. (MTG-15, -16 and -18) appear below. The corresponding PMTG products are prepared analogously. Details of the preparation for PUTG products (PUTG-15, -16, -17 and -18) also appear below, and the corresponding UTG products are prepared analogously. MTG-15: MTG DMA Amide R = C16, C18 Saturated + unsaturated
A round-bottom flask is charged with MTG-0 (175.0 g, 0.71 mol) and the raw material is heated to 60 ° C. The reactor is sealed and a vacuum is applied to dry / degas the raw material. The reactor is refilled with nitrogen and then sodium methoxide (7.5 g of 30% methanol solution) is added via a syringe. The reactor temperature is increased to 90 ° C. The static vacuum (-30 "Hg) is established, and dimethylamine (87 g) is slowly added through the tube dipped below the surface. When the pressure in the reactor is equalized, it is opened up by nitrogen, and the temperature is increased to 110 ° C for 3.0 hours The progress of the reaction is verified by infrared (IR) spectroscopy. The temperature is increased to 150 ° C and maintained for an additional 8.5 hours. IR indicates a reasonably complete reaction.
The catalyst is extinguished by the addition of 50% aqueous sulfuric acid (4.1 g). Deionized water (100 ml) is added, and the mixture is stirred vigorously for ~ 15 minutes. The reactor contents are washed with water, with the application of heat to assist the separation of the phases. Aqueous sulfuric acid is added until the acidic aqueous phase is tested. A solution of aqueous NaCI (20%) is also used to aid phase separation. The amide product is washed two more times with aqueous saline solution and is then returned to the reaction vessel. The reactor is heated to 70 ° C and a full vacuum is applied for 0.5 hour to remove residual water. The hot product is then filtered through silica gel over a porous glass. MTG-16: MTG DEA Amide
A round-bottom flask equipped with a nitrogen inlet, thermocouple, heating mantle and a stirrer is charged with MTG-0 (133.8 g, 0.477 mol) and the raw material is heated to 65 ° C. Sodium borohydride (0.067 g, 0.0018 mol) is added, and the contents are stirred at 65 ° C for 1 hour. Diethanolamine (52.2 g, 0.497 mol) and sodium methoxide (2.29 ml of 30% by weight of solution in methanol, 0.012 mol) are loaded into the mixture. After adding the catalyst, the reaction becomes exothermic at ~ 80 ° C. After the exotherm has disappeared, the reactor is heated to 90-95 ° C and maintained overnight. Total vacuum is applied for 5.0 hours. 1H NMR indicated reasonably complete conversion. Free DEA: 3.89%. MTG-17: MTG MEA Amide R = C16, C18 Saturated + Unsaturated
The procedure used to make MTG-16 is generally followed with MTG-0 (134.2 g., 0.488 mol), sodium borohydride (0.067 g., 0.0018 mol), monoethanolamine (30.4 g., 0.498 mol) and sodium methoxide (2.30 ml of 30% by weight of methanol solution, 0.012 mol). Full vacuum was applied for 1 hour to the residual free amine strip. 1H NMR indicates reasonably complete conversion. Free MEA: 0.53%. MTG-18: MTG MIPA Amide R = C16, C18 Saturated + Unsaturated
The procedure used to make MTG-16 is generally followed with MTG-0 (130.5 g., 0.527 mol), sodium borohydride (0.065 g., 0.0017 mol), monoisopropanolamine (40.35 g., 0.537 mol) and sodium methoxide (2.24 ml of 30% by weight of solution in methanol, 0.012 mol). Full vacuum was applied for 1 hour to the residual free amine strip. 1H NMR indicates reasonably complete conversion. Free MEA: 0.64%. PUTG-15: PUTG DMA Amide
The procedure used to make MTG-15 is generally followed when using PUTG-0 (250.0 g., 0.91 mol), sodium methoxy (5.0 g of 30% methanol solution) and dimethylamine (43 g). When the pressure in the reactor becomes equal, the reactor is opened to suspended nitrogen and the mixture is kept overnight at 80 ° C. IR analysis shows that significant glyceride remains. The temperature is raised to 120 ° C and the addition of DMA is maintained via sub-surface spray for 4 hours. Then the temperature is raised to 140 ° C and the addition of DMA is kept continuous for 2 hours. The reaction mixture is cooled to room temperature. Total loaded DMA: 43 g. The reactor is reheated to 140 ° C and more sodium methoxide (5 g of 30% methanol solution) is added. The addition of DMA continues for 2 hours. The temperature is reduced to 80 ° C and maintained for 7 hours.
The mixture is heated to 50 ° C, and deionized water (100 ml) is added. The catalyst is extinguished by adding 50% aqueous sulfuric acid (9.1 g), and the mixture is worked up as described previously. 1H NMR indicates reasonably complete conversion. PUTG-16: PUTG DEA Amide
The procedure used to make MTG-16 is generally followed with PUTG-0 (133.1 g „0.444 mol), sodium borohydride (0.067 g„ 0.0017 mol), diethanolamine (51.9 g., 0.494 mol) ) and sodium methoxide (2.28 ml_ of 30% by weight of solution in methanol, 0.012 mol). 1H NMR indicates reasonably complete conversion. Free MEA: 2.04%. PUTG-17: PUTG MEA Amida
The procedure used to make MTG-16 is generally followed with PUTG-0 (136.6 g., 0.477 mol), sodium borohydride (0.068 g., 0.0018 mol), monoethanolamine (31.0 g., 0.507 mol) and sodium methoxide (2.34 mL of 30% by weight of solution in methanol, 0.013 mol). 1H NMR indicates reasonably complete conversion. Free MEA: 0.96%. PUTG-18: PUTG MIPA Amide
The procedure used to make MTG-16 is generally followed with PUTG-0 (136.1 g., 0.495 mol), sodium borohydride (0.068 g., 0.0018 mol), monoisopropanolamine (38.0 g., 0.50 mol) and sodium methoxide (2.34 ml of 30% by weight of solution in methanol, 0.013 mol). 1H NMR indicates reasonably complete conversion. Free MEA: 0.90%. Agricultural products: Anionic Emulsifiers
Samples of anionic surfactant contain a relatively high amount of water (> 20%) and are prepared as oil-in-water (EW) concentrates. They are tested against controls containing a standard surfactant or a blank. Enough is formulated to test two water roughnesses (34 ppm and 1000 ppm) for each of the three samples.
Sample preparation: piraflufen (97.8% active, 0.30 g) is combined with Stepan® C-25 (caprylate / methyl caprate, 7.20 g) and N-methyl-2-pyrrolidone (1.20 g) , and the mixture is magnetically stirred until dissolved. In a separate container, Toximul® 8242 (castor oil ethoxylate, POE 40, Stepan product) 0.96 g), Ninex® MT-630F (fatty acid ethoxylate, POE 30, Stepan, 0.19 g), Ninex ® MT-615 (fatty acid ethoxylate, POE 15, Stepan, 0.17 g), 150 Aromatic solvent (Exxon Mobil, 0.37 g) and the anionic sample to be tested (0.71 g) are mixed. If necessary, the anionic sample is melted in an oven at 50-60 ° C before combining with the other surfactants. When the piraflufene is dissolved, the entire surfactant mixture is added and magnetically stirred until homogeneous. Deionized water (0.90 g) is added slowly, with mixing, to avoid gelation. Turbidity changes are noted and recorded.
Control sample 1: The same procedure is followed, except that the anionic sample is replaced with 60L of Ninate® (calcium alkylbenzenesulfonate, Stepan, 0.71 g).
Control sample 2: None of the 60L of Ninate® (or anionic sample) is included, and the amount of aromatic 150 is increased to 1.08 g. Emulsion stability test
ASTM E1116-98 (2008) is modified as follows. Graduated cylinders of 100 mL, with flat bottom, are loaded with 34 ppm or 1000 ppm of water (95 mL). A Mohr pipette is used to feed EW concentrate to each cylinder. The cylinders are covered and inverted ten times, then allowed to stand for 0.5, 1 and 24 hours, while recording stability at each tempp, such as type and% of separation.
Spontaneity is recorded according to the following criteria: (1) poor: very fine cloudy emulsion with great oil droplet separation, (2) reasonable: fine cloudy emulsion, with less oil droplet separation, (3) good: emulsion fine cloudy reaches the bottom of the cylinder, without separation of any kind, (4) excellent: thick cloudy emulsion reaches the bottom of the cylinder, without separation of any kind.
The results are shown in Table 4. The three examples given below are classified as "good", in general as anionic surfactants.
Agricultural products: Nonionic emulsifiers
Non-ionic samples contain a small amount of water (<1%) and are prepared as emulsifiable concentrates (EC) with three pesticides, using two different solvent systems. In the aromatic solvent series, the non-ionic sample replaces Toximul® 8240 (castor oil ethoxylate, POE 36, Stepan), and in the Hallcomid ™ solvent series (N, N-dimethylcaprilamide / N, N-dimethylcapramide, Stepan), the non-ionic sample replaces Ninex® MT-630F. The values are sufficiently prepared to test two water hardnesses (34 ppm and 1000 ppm) for each of the three samples. Aromatic solvent series.
Sample preparation: Ninate® 60E (calcium alkylbenzenesulfonate, Stepan) and the test sample are stirred until they are homogeneous. If necessary, the nonionic surfactant is melted in an oven at 50-60 ° C, before being combined with 60E Ninate. Controls 1-3 are performed when using Toximul 8240 in the amounts indicated, instead of the non-ionic sample. Formulations: 1. Bifenthrin, 240 g / L (2.99 g), Aromatic 100 (Exxon Mobil, 8.05 g), Ninate 60E (0.38 g) and a non-ionic sample or Toximul 8240 (0.58 g) ). 2. 2,4-D ester, 480 g / L (8.90 g), Exxsol® D-110 (Exxon Mobil, 2.50 g), Ninate 60E (0.36 g) and a non-ionic sample or Toximul 8240 (0.24 g). 3. Tebuconazole, 360 g / L (4.45 g), N-methyl-2-pyrrolidone (6.35 g), Ninate 60E (0.48 g), non-ionic sample or Toximul 8240 (0.72 g) . Hallcomid solvent series.
Sample preparation: The surfactants are combined and agitated until they are homogeneous, with the nonionic sample being melted, if necessary, before the combination. Controls 1-3 are performed using Ninex MT-630F in the amounts indicated, instead of the non-ionic sample. Formulations: 1. Bifenthrin, 240 g / L (2.99 g), Hallcomid M-8-10 (8.29 g), Ninate 60E (0.09 g), Toximul 8320 (0.22 g), Toximul 8242 (0.29 g) and a non-ionic sample or Ninex MT-630F (0.13 g). 2. 2,4-D diester, 480 g / L (8.90 g), Hallcomid M-8-10 (2.38 g), Ninate 60E (0.09 g), Toximul 8320 (0.22 g) , Toximul 8242 (0.29 g), and non-ionic samples or Ninex MT-630F (0.13 g). 3. Tebuconazole, 360 g / L (4.45 g), Hallcomid M-8-10 (6.83 g), Ninate 60E (0.09 g), Toximul 8320 (0.22 g), Toximul 8242 (0 , 29 g) and a non-ionic sample or Ninex MT-630F (0.13 g). Emulsion stability test
ASTM E1116-98 (2008) is modified as follows. Graduated cylinders of 100 mL, with flat bottom, are loaded with 34 ppm or 1000 ppm of water (95 mL). A Mohr pipette is used to feed EW concentrate to each cylinder. The cylinders are covered and inverted ten times, then they are left to rest for 0.5, 1 and 24 hours during the recording of each 10 moment of stability, such as the type and% of separation. Spontaneity is assessed as described for testing anionic emulsifiers.
The results with both solvent systems are provided in Table 5. Based on the results of general testing, C10-27 is classified as "good" as a nonionic surfactant.
Screening of agricultural dispersant:
The potential of a composition for use as an agricultural dispersant is assessed by its performance with five typical active pesticidal ingredients: atrazine, chlorotalonil, diuron, imidacloprid and tebuconazole. The performance of each dispersant sample is assessed against five standard Stepsperse® dispersants: DF-100, DF-200, DF 400, DF-500 and DF-600 (all Stepan Company products), and each is optionally tested with and without a nonionic or anionic wetting agent.
A screening sample is prepared as shown below for each asset. Wetting agents, clays and various additives are included or excluded from the screening process, as needed. The weight percentage of insecticide ("technical material") in the formulation depends on the desired active level of the final product. The active level chosen is similar to that of other products on the market. If this is a new active ingredient, then the highest active level is used.
The samples are evaluated in water of variable hardness, in this case, 342 ppm and 1000 ppm. Initial assessments are carried out at room temperature. Other temperatures can be evaluated as desired. The 342 ppm water is made by dissolving anhydrous calcium chloride (0.304 g) and magnesium chloride hexahydrate (0.139 g) in deionized water and diluting to 1 L. The water of 1000 ppm is made in a similar way, using 0.89 g of calcium chloride and 0.40 g of magnesium chloride hexahydrate are used.
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 mixture is ground to a particle size of at least d (90) of <20 p using a hammer and air / jet mills as needed. Test dispersant (0.1 g) is added to test water (50 ml) in a container and stirred for 1-2 minutes. Ground powder containing the technical material (1.0 g) is added to the dispersing agent solution and stirred until all the powder is wetted (2-5 min.). The mixture is transferred to a 100 ml cylinder, using additional test water to rinse the container, and is then diluted to volume. The cylinder is capped and inverted ten times, then allowed to stand. Visual inspection is performed at time 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 7 and 8).
General results versus controls are summarized in Table 6; four amidaa perform at least as well as the controls. Details of the individual tests are shown in Table 7 (wetting agent included) and Table 8 (without wetting agent).
Water Soluble Herbicide Formulation Test
Candidate surfactants for water-soluble herbicide applications are examined as a replacement for the anionic, nonionic or anionic / nonionic blend portion and compared to an industry adjuvant standard known for use in paraquat, a concentrated soluble herbicide 15 formulation. in water. A standard dilution test is conducted by means of which the concentrates are diluted in water to determine whether the solubility is complete.
Control: Paraquat (9.13 g of 43.8% active material) is added to a small 20 ml glass ampoule. A paraquat adjuvant known in the industry (2.8 g) is added and mixed vigorously for 30 seconds. Deionized water (8.07 g) is added, and the mixture is resumed for 30 seconds. Standard water with 342 ppm (47.5 mL) is added to a 50 mL Nessler cylinder, which is capped and equilibrated in a 30 ° C water bath. Once the test water is balanced, the formulated paraquat (2.5 mL) is added by 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 quantity (in mL) and type of separation are recorded after 30 min., 1 h, 2 h and 24 h. Results of the solubility test appear in Table 9 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 30 seconds. Test sample (0.7 g) is added and mixing is resumed for 30 seconds. Deionized water (4.03 g) is added, and the mixture is resumed for 30 seconds. 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 the mixture is resumed for 30s. Deionized water (4.03 g) is added, and the mixture is resumed for 30 s. 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.
Adjuvant test sample (anionic / nonionic): Paraquat (4.57 g of 43.8% active material) is added to a 20 mL glass ampoule. Test sample (1.4 g) is added and vigorously mixed for 30 seconds. Deionized water (4.03 g) is added, and the mixture is resumed for 30 s. 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.
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 or better than the control in the emulsion stability test. Results appear in table 9.
Agrochemical solvent analysis: Active solubility
Solvency strength of potential agrochemical solvents is assessed by identifying the solubility level of the four standard pesticides in the solvent by weight percentage: 2,4-D acid, imidacloprid, trifluralin and tebuconazole. The test is performed using a small 4 ml flask with a magnetic panel stirrer and a sample weighing 2 to 2.2 g of the solvent. The active material is also accurately weighed prior to addition. Initial amounts of the active material are approximately: 2.4-D: 0.3 g; imidacloprid: 0.02 g; trifluralin: 0.5 g; tebuconazole: 0.3 g. Solvent and active pesticide are combined, left to mix for 1 hour at room temperature and then inspected for the presence of undissolved active material. Active material is added in small increments, properly until they do not dissolve completely. This mixture is then stirred for 24 hours at room temperature, and if the active substance has completely dissolved, the active ingredient is added and the mixture is stirred for another 24 hours at room temperature. The percentage of solubility is recorded, and the performance is compared to that of a standard agricultural solvent.
When the method described above is followed, five amide compositions perform as the control in this assay, and one (Mix-59) is superior, as noted in Table 10 below.
Detailed results appear in table 11 below:
Rough surface cleaners: Aqueous degreasers
This test measures the ability of a cleaner to remove a greasy soil debris from a white vinyl tile. The test is automated and uses an industry-standard Gardner Straight Line Washability device. A camera and controlled lighting are used to record a live video of the cleaning process. The device uses a sponge moistened with a known amount of test product. As the machine cleans the sponge between the dirty tile, the video records the result, from which a cleaning percentage can be determined. A total of 10 strokes are taken using the test formulation diluted 1:32 with water, and cleaning is calculated for each of the strokes 1-10 to provide a profile of the cleaning efficiency of the product. The test sample is used as a control component of different formulations, depending on whether it is anionic, amphoteric or non-ionic. Anionic samples:
A neutral and dilutable multipurpose cleaner is prepared from propylene glycol n propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate (4.0 g), Bio-Soft® EC-690 alcohol ethoxylated (1.0 g, Stepan product), test sample (0.29 g, if 100% active material) and deionized water (100.0 g of solution). The control sample for the anionic test replaces the test sample with Stepanol WA-Extra® PCK (sodium lauryl sulfate, Stepan, 1.0 g, nominally 30% active material). Nonionic and amphoteric test samples:
A neutral and dilutable multipurpose cleaner is prepared from propylene glycol n-propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate (4.0 g), Stepanol® WA-Extra PCK ( sodium lauryl sulfate, 1.0 g), the test sample (0.90 g, if 100% active material) and deionized water (100.0 g of solution). The control sample for non-ionic / amphoteric tests replaces the test sample with Bio-Soft® EC-690 (ethoxylated alcohol, Stepan, 1.0 g, nominally, 90% active material). Waste composition (using the Gardner ASTM D4488-95 method):
The tiles are dirty with a particulate medium (50 mg) and an oily medium (5 drops). The particle medium (in parts by weight) is composed of hyperhumus (39), paraffin oil (1), used motor oil (1.5), Portland cement (17.7), silica (8), black molacca (1 , 5), iron oxide (0.3), arched black clay (18), stearic acid (2), oleic acid (2). The oil medium is composed of kerosene (12), Stoddard solvent (12), paraffin oil (1), SAE-10 engine oil (1), Crisco® shortening, product of JM Smucker Co. (1), olive oil (3), linoleic acid (3) and squalene (3).
Table 13 shows the results of six amphoteric or nonionic test samples (quat sulfonates and amides) and an anionic sample (an amide sulfonate) that performed as well or better than the control in the Gardner direct line washability test. Control performs as summarized in table 12. Industrial Degreaser Formulations
This test measures the ability of a solvent to clean greasy debris from a white vinyl tile. The debris is the same as that used in the Gardner ASTM D4488-95 A5 method, only applied to the part with a brush. The test consists of placing a drop of the test solvent on the dirty tile, waiting 10 seconds (pure samples) or 30 seconds (diluted) and then adding a second drop adjacent to the first, wait the prescribed time and add a third drop , etc. After a few minutes, the drop is stopped and the tile is rinsed, photographed and judged to be clean versus pure control in the diluted formulation.
The pure samples are tested against STEPOSOL® M8-10, a mixture of N, N-dimethylcapramide and N, N-dimethylcaprilamide, a product from Stepan.
The diluted samples are made from test assets (5.0 g), AMMONYX® LMDO (lauramidopropylamine oxide, Stepan product, 10.0 g), and deionized water (qs for 100 g). The control for diluted samples replaces the active test agents with STEPOSOL M8-10 (5.0 g).
The results are shown in Table 14. In general, Cio-Ci2 amides outperformed control as a degreasing solvent when tested pure and diluted.
Personal Care: Cleaning Application
Viscosity and mechanical stirring foam tests are used to assess the likely value of a particular surfactant, as a secondary surfactant, in cleaning applications for personal care.
All experimental samples are evaluated for their performance compared to a control (cocamide MEA).
Viscosity curves are produced by preparing diluted aqueous solutions of the test or control material (1.5% active content) 12% active with sodium lauryl ether (1) sodium sulfate (SLES-1), in then measuring viscosity using a Brookfield DV-1 + viscometer. Sodium chloride is added incrementally (1-3% by weight) and the viscosity is recorded as a function of increasing the concentration of NaCl. A "good" result is a curve that shows a viscosity development comparable to that of the control sample. A "higher" rating means that the sample forms viscosity substantially faster than the control.
Foaming properties are assessed using a mechanical stirring foam test. Aqueous solutions composed of 12% active SLES-1 and test or control material (1.5% active amide) are prepared. Sample solutions calculated at 0.2% total active surfactant material are subsequently 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 is added (2.0 g). The cylinder is capped and inverted mechanically ten times, then allowed to settle for 15 seconds. The height of the foam is recorded. After 5 minutes the height of the foam is recorded again. The experiment is repeated without the castor oil. In a set of experiments, the cleaning base contains SLES-1 in both experimental and control tests. In a second set of experiments, the cleaning base contains another anionic solvent used, 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 materials results in foam heights that are within +/- 25 mL of control. Results greater than 25 mL of the control bring a higher classification; results below 25 mL of control are classified as inferior.
Fourteen test materials, identified in Table 15, perform well overall in both foam and viscosity tests.
Personal Care / Antibacterial Soap: Method for determining the foam improvement benefit
Foam volume, which signals "clean" to consumers, is a desirable attribute in an antibacterial soap. Because the antibacterial cationic assets are not compatible with anionic surfactants (the best foaming agents), achieving sufficient foam volume with them is a challenge. The method below identifies surfactants that provide more volume of foam than cocamidopropyl betaine (active / active base) in an antibacterial soap base. Formulation: Deionized water (qs to 100% by weight.), Cocoglucoside (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.).
The solutions are prepared by combining ingredients in the order prescribed, stirring with a stir bar and mixing gently using a top stirrer, or manually using a spatula. Heat can be applied if the test molecule is a solid at room temperature. The mixture is maintained to ensure a homogeneous solution. The pH is adjusted to 6.5 +/- 0.5.
The test and control solutions are compared with and without 2% castor oil, at 0.2% total concentration of active surfactant (2.22 g of 100 ml solution with Lake Michigan tap water, -150 ppm Ca / Mg hardness) for the foam volume using the inversion test cylinder. (5 min.) Initial and late measurements are taken.
Classification system: Superior: A result> 25 mL on cocamidopropyl betaine control in both non-petroleum and petroleum systems. Good: A result of a 25 mL radius of the cocamido-propyl betaine control in both non-oil and oil systems. Lower: A result> 25 mL below that of the cocamidopropylbetains control in both non-oil and oil systems.
Three test materials, identified in Table 16, show good overall performance in tests with antibacterial soaps.
Hair conditioners: Procedure for assessing wet combing
Hair braids (10 "in length, 2-3 g) are prepared using a consistent and uniform hair type (bleached, blond, double). The hair curls are collectively washed with a 15% solution of active sodium lauryl sulfate Care is taken to avoid excessive embarrassment during washing. Hair is washed with clean tap water at 40 ° C. The process is repeated to simulate a twice-shampoo application. The hair curls are separated and marked for The preparation conditioner, either the test or control material (ie the base conditioner), is applied (2.0 cm3) to each clean wet braid using a syringe. The base conditioner contains cetyl alcohol (2.0%), hydroxyethyl cellulose (0.7%), cetrimonium chloride (1.0%), potassium chloride (0.5%) and water (qs to 100%). Test samples are formulated as an additive of 2% by weight (active) of the conditioner-based additive.
The conditioner is worked through the hair for one minute with fingers moving downwards. The hair is washed thoroughly and cleaned in running water at 40 ° C. Excess water is squeezed from each strand to simulate hair with a dry towel. The hair is first combed in the wet state. Combing ease is assessed for the test samples and the base conditioner and qualitative ratings are assigned to the test samples, compared to the results obtained with only base conditioners. Improvement of conditioning of the base by the amide additive is the criterion of technical success at this stage and is the basis for a higher classification. Equal to a lower performance compared to the base conditioner, it gains a lower rating. The results are shown in Table 17.
Cold water cleaning performance of compacting laundry detergents
This method assesses the general cold water cleaning performance (55 ° F) of a laundry detergent formula that comprises a concentrated blend of anionic and non-ionic surfactants, a builder, Ci6 MES and an experimental sample. The formulations are prepared as described below. The experimental sample is tested for its ability to improve the overall cleaning performance compared to cocoamide DEA. Preparation of Concentrated Blend
Deionized water (90% of the total amount required) is first combined and mixed at 50 ° C with Bio-Soft® S-101 (dodecylbenzene sulfonic acid, 3.27% by weight, Stepan product). Sodium hydroxide (50% aq. Solution) is added to pH 11 (around 24% of the total amount of 4% by weight required). Citric acid (50% aq. Solution, 6.2% by weight) is added, followed by triethanolamine (3.45% by weight). Bio-Soft® EC-690 (laureth-7, 90% active, 27.8% by weight, Stepan product) is slowly added. The pH is adjusted to the range of 7.8 to 8.4, targeting 8.1 with the remaining aqueous sodium hydroxide solution. Sodium xylene sulfonate (40% active, 4.30% by weight) is added, followed by a preservative and the remaining deionized water (q.s. to 100% by weight). Preparation of an ultra-detergent for dirty clothes with Cig MES and the mixture:
Deionized water (q.s. to 100% by weight) is charged at 55-60 ° C. The concentrated mixture prepared above (58.0% by weight) is added while maintaining a temperature between 50 ° C and 60 ° C. MES C16 (87% active, 10.34% by weight) is slowly added and allowed to dissolve. The mixture is then allowed to cool to 35 ° C. The experimental sample or standard DEA cocamide (5.0% by weight) is then added slowly and the mixing continues until the batch is homogeneous. Cold water cleaning assessment
Powdered soap (30 g, see Part A) is loaded into the washing machine, followed by dirty / stained fabric samples that are attached to pillowcases. Wash temperature: 55 ° F. Rinse: 55 ° F. The samples are detached from the pillowcases, dried, and ironed. Samples are scanned to measure L * a * b * values, which are used to calculate a debris removal index (IRS) for each type of sample. Finally, the ASRI is calculated, which equals the SRI experimental sample minus the SRI of a predetermined standard (or control) dirty laundry detergent formula. When | ASRI | > 1, differences are noticeable to the naked eye. If the ASRI value is greater than or equal to 1, the sample is greater. If ASRI is less than or equal to -1, the sample is less. If ASRI is greater than 1 and less than 1, the sample is considered to be equal to the standard.
The following fabric samples exposed to standard debris / stains are used: dirt on cotton (DSC); bovine tallow (BT); kaolin clay and wool fat on (WFK 30C); grass on cotton (GC); blueberry on cotton (BC); cocoa on cotton (EMPA 112); and blood / ink / milk on cotton (EMPA 116). At least three of each type of sample are used per wash. Samples are stapled to the pillowcases for washing, and extra pillowcases are included to complete a six-pound load (2.72).
The same procedure is used to wash all pillowcases / samples, with care taken to ensure that water temperature, washing time, manner of addition, etc. are kept constant for the cold water washing process. When the cycle is complete, samples are removed from the pillowcases, dried over low heat in a rack and pressed briefly with a dry iron.
A Hunter Labscan® XE spectrophotometer is used to determine the L * a * b * values to calculate the SRI for each type of sample, and the stain removal index (SRI) is calculated as follows:
A test sample, C12-30, performs the control in the cold water cleaning test (see table 18).
Oilfield Products: Paraffin Dispersant Asphaltene Scan Test
During the stimulation of acid from an oil well, a mixture of HCI, HF and corrosion inhibitor is pumped into a well, left to stand and then pumped out. During the transfer of the acid, small amounts of iron chloride are developed in the acidic solution. Once the acid mixture dissolves scales and deposits in the well bore, the oil begins to flow and mixes with the acid solution in the well. Crude oil can solidify after acidification, and asphaltenes have been associated with the problem. Thus, dispersants are often added to the acid to prevent solidification. Test method:
A stock solution of iron-contaminated acid is made by adding 1% FeCh to a 15% HCI acid solution. The sample dispersant to be tested (0.2% by weight) is added to the acid solution (7.5 ml). A 15 ml bottle is charged with the acid / dispersing agent mixture and the crude oil (2.5 ml), and the bottle is shaken vigorously for 30 seconds. The initial appearance is recorded. After standing at room temperature for 1 hour, the appearance is observed again. The vial is placed in an oven (50 ° C) for 24 hours and its appearance is recorded. The flask is allowed to cool to room temperature and the appearance is observed again. Finally, after 24 hours at room temperature, the appearance is observed again. The blank sample containing oil and acid solution, but not dispersant, is run. A control sample containing trimethylammonium chloride starch soy amine as the dispersant is also run. Yet another example is performed containing a 1: 1 mixture of soybean starch trimethylammonium chloride test dispersant mixture.
One example, C18-66, provides superior performance as a paraffin dispersant. Oil Field Corrosion Inhibition: Polarization Resistance Procedure
Polarization resistance is carried out in diluted NACE brine (3.5% by weight of NaCI; 0.111% by weight of CaCl2.2H2O; 0.068% by weight of MgCl2 * 6H2O) under sweet conditions (CO2 sprayed) at 50 ° C. The working electrode is cylindrical, made of C1018 steel, and rotates at 3000 rpm. The counter electrode is a platinum wire. The reference is a calomel electrode with an internal salt bridge. The corrosion rate of the baseline is established for at least a period of 3 hours. Once the baseline is established, the corrosion inhibitor is injected and data is collected for the remainder of the test period. The desired inhibitor concentration is 00011-, 0010 meq / g active. Software details: initial delay is at least 1800 seconds with 0.05 mV / s stability; range: -0.02 to +0.02 V; scan rate: 0.1 mV / s; sampling period: 1 second; data collection: ~ 24 hours. The average final corrosion rate is the last 5-6 hours of data collection. Protection fee is calculated from:
As shown in table 19, two test samples show overall performance as corrosion inhibitors that are the same as those in the control.
Performance as a tub additive Paint formulation:
The titanium dioxide sludge (Dupont Ti-Pure® R746) is loaded into a container, followed by deionized water and propylene glycol, and the contents are mixed (500 rpm). Latex (49% solids) and preservative (Acticide® GA, Thor's product) are added. Thickener (Dow AcrysolTM SCT-275 product, 0.3%) is slowly loaded under the liquid surface by means of a syringe. The pH is adjusted to 9.0 using ammonium hydroxide solution. The batch is mixed for 30 minutes and then left to stand for at least 2 hours. The batch is remixed gently, and a portion (240 g) is transferred to a 400 ml beaker. Solvent (C- | 8 amide) and derivative (1.76% active based on latex solids) are added and mixed at 650 rpm. Viscosity is adjusted to an initial KU of 90 with more thickener. The ink is covered and the final KU is measured after 24 hours. Its value falls within the range of 93-100 KU and varies from the original measurement by no more than 5 KU.
Formulation example: TiO2 (solids base): 24.35% by weight, water: 46.39% by weight; propylene glycol 2.59% by weight; latex (solid based) 22.76%, ammonium hydroxide: 0.04% by weight; preservative: 0.10% by weight; control additive (with solvent): 1.14% by weight; derivative (100% solids). 0.40% by weight; thickener: 2.23% by weight. PVC: 22.1%. VOC: <50 g / L. Final KU: 98.6. Resistance to wet friction / modified ASTM 2486
Resistance to wet friction based on a modified version of ASTM- 2486-00, method B; modified to% weight loss, is performed for each ink formulation. The paints are applied on plastic panels Leneta P-121- 10N, using a width of 13 cm, wet film applicator of 10 mil. and is dried under ambient conditions for five days before testing. The coated panels are then cut into strips (16.5 cm x 5.7 cm, two per undercut). The strips are weighed before testing. Two samples at a time are placed in a friction tester from Gardner Company with a gap of approximately 2 "of space between samples and taped to secure the panels to the apparatus. A spacer is placed over the samples to maintain friction via brush and protect further samples. A friction brush (8 cm x 3 cm), preconditioned in water at room temperature is inserted in the support. Friction compound (10 g, supplied by Leneta Company as "friction compound ASTM-2486" ) is applied evenly to the brush. Water (5 g) is placed in the space between samples. Samples are tested in 1200 cycles. Additional friction compound (10 g) and water (5 g) are reapplied every 300 cycles. strips are then washed with warm water and dried for 24 hours, the strips are weighed again and the percentage of coating removed is determined. Wet rub resistance / ASTM 2486 Correction method
The procedure described above is used, except that a correction (ASTM accepted) is added before applying strips of coated panel. Failure cycles are determined visually. Brightness Determination - 60 ° / 20 ° - ASTM D523
Paints are applied to the Leneta P-121-10N plastic panels using a wet film applicator (13 cm x 10 mil) and dried under ambient conditions for 5 days before testing. Brilo is measured with an ASTM accepted gloss meter (Gardco).
Results: one sample, C10-12, is superior as an ink additive (see Table 20)
Performance as a coalescing solvent for a fully acrylic latex
An acrylic latex polymer (49% solids) is loaded into a flask and mixed with a test sample at the level of 5% solids based on latex (0.6 g of a 100% active sample) for at least 16 hours. A film is launched on a RHOPOINT MFFT 90 instrument that is adjusted to a gradient from 0 ° C to 180 ° C at the surface temperature. The minimum film-forming temperature (TMFP) of the mixture is determined. The test samples are evaluated either as the sole solvent or as 60:40 mixtures (control solvent to test the sample). Control samples are also analyzed, including latex alone and latex in addition to the control solvent. The results are shown in Table 21.
Performance as a coalescing solvent in a latex paint
The titanium dioxide sludge (Dupont Ti-Pure® R746) is loaded into a container, followed by deionized water and propylene glycol, and the contents are mixed (500 rpm). Latex (49% solids) and preservative (Acticide® GA, Thor's product) are added. Thickener (Acrysol ™ SCT-275, 0.3% Dow product) is slowly loaded under the liquid surface using a syringe. The pH is adjusted to 9.0 using ammonium hydroxide solution. The batch is mixed for 30 minutes and then left to stand for at least 2 hours. The batch is remixed gently, and a portion (240 g) is transferred to a 400 ml beaker. The derivatives are added as the solvent, at a level of 2-5% based on the latex solids and mixed at 650 rpm. Viscosity is adjusted to 90KU with more thickener. The paint is covered and the viscosity is measured after 24 hours. Its value falls within the range of 93-100 KU and varies from the original measurement by no more than 5 KU.
Formulation example 2% co-solvent with C18 amide: TiO2 (solids base): 24.50% by weight; water: 46.66% by weight; propylene glycol, 2.60% by weight; latex (based on solids) 22.89%; ammonium hydroxide: 0.04% by weight; preservative: 0.10% by weight; control additive: 0.68%; derivative (100% solids): 0.46% by weight; thickener: 2.07% by weight. PVC: 22.1%. VOC: <50 g / L. Final KU: 103.7.
Formulation example, 5% solvent, derivative only: TiO2 (solids base): 24.43% by weight; water: 46.54% by weight; propylene glycol, 2.60% by weight; latex (based on solids) 22.84%; ammonium hydroxide: 0.05% by weight; preservative: 0.10% by weight; derivative: 1.14% by weight; thickener: 2.30% by weight. PVC: 22.1%. VOC: <50 g / L. Final KU: 97.7.
Results: four of the tested samples perform as the control solvent (s) in a latex paint. See table 22.
In another type of test to assess coalescent solvents, thermogravimetric analysis (TGA) is used to determine the VOC content of a test sample, compared to that of a control solvent. The instrument is configured to measure weight loss over 60 minutes at 110 ° C. The C12-25 test sample has a 4.49% VOC value, compared to 4.20% for the control sample, a C12 dimethylamide. This indicates a performance equal to C12-25 versus the control. Antimicrobial Products: Biocidal Assets
Biocidal efficiency is assessed using the rapid screening assay, an ATP-based method that measures the relative mortality% of bacteria over a period of 5 minutes. The control used is the first generation ADBAC BTC 835 (benzyl dimethylammonium chloride). Test organisms: Pseudomonas aeruginosa and Staphylococcus aureas.
Test organism cultures aged twenty-four hours are prepared in Mueller Hinton broth and incubated. The samples are accurately weighed in deionized water or 400 ppm of water to produce a 1000 ppm solution, taking into account the active levels of the sample. The 24 hour culture is diluted to 10% volume to obtain a cell concentration of ~ 107 cfu / ml (colony forming units per ml). The reagents are prepared using the instructions provided in the Microbial Cell Viability Assay Kit (Promega product) and calibrated at room temperature for 15 minutes. Each type of formulation is dispensed (90 mL at 1000 ppm) in each row of a 96-well plate. Blank medium, that is, Mueller Hinton broth (10 mL) is dispensed into three replicated wells (1-3) to determine the baseline, while the organism to be tested (10 mL) is dispensed into nine experimental replicated wells (4-12). The timer is started, and the assay plate (baseline and experimental) is shaken for 30 seconds. After an adequate contact time (for example, 5 or 10 minutes), an equal amount of BacTiter-GIo ™ reagent mixture is added to each reaction mixture, starting with the experimental samples and ending with the baseline samples . After shaking to ensure thorough mixing, the relative luminescence units (RLU) for each well are measured and recorded. The mortality rate of 107 cfu / mL, after 5 minutes of contact time for each organism in Dl or hard water, is calculated from:% mortality = [1- (average RLU of experimental wells - Average RLU of WELLS baseline controls)] / 80000
As shown in Table 23, a tested composition performs as the control when tested as an antimicrobial asset.
The previous examples are taken as illustrations only. The following claims define the invention.

权利要求:
Claims (10)
[0001]
1. Composition comprising a grease amide, characterized by the fact that the grease amide has a structure selected from the group consisting of:
[0002]
2. Amide sulfonate, characterized by the fact that it is made by sulfonation of the composition as defined in claim 1.
[0003]
3. Composition according to claim 1, characterized by the fact that the grease amide has the structure
[0004]
4. Composition comprising a grease amide, characterized by the fact that the grease amide has a structure selected from the group consisting of:
[0005]
5. Amide sulfonate, characterized by the fact that it is made by sulfonation of the composition as defined in claim 4.
[0006]
6. Anionic emulsifier for agricultural compositions, non-ionic emulsifier for agricultural compositions, dispersant for agricultural compositions, water-soluble herbicidal composition or an agricultural solvent, characterized (a) in that it comprises the composition or sulfonate as defined in any of the claims 1 to 5.
[0007]
7. Antimicrobial composition, aqueous rough surface cleaner, industrial rough surface cleaner or a dirty laundry detergent formulation, characterized by the fact that it comprises the composition or sulfonate as defined in any of claims 1 to 5.
[0008]
8. Shampoo, hair conditioner, personal cleanser or soap, characterized by the fact that it comprises the composition or sulfonate as defined in any one of claims 1 to 5.
[0009]
9. Corrosion inhibitor or paraffin dispersant for use in oil field applications, characterized by the fact that it comprises the composition or sulfonate as defined in any one of claims 1 to 5.
[0010]
10. Additive coating or paint composition, characterized by the fact that it comprises the composition or sulfonate as defined in any one of claims 1 to 5.

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EP2632256B1|2017-02-01|

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法律状态:
2017-03-01| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-01-23| B07D| Technical examination (opinion) related to article 229 of industrial property law [chapter 7.4 patent gazette]|

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2018-08-21| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2018-10-30| B07B| Technical examination (opinion): publication cancelled [chapter 7.2 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 7.4 NA RPI NO 2455 DE 23/01/2018 POR TER SIDO INDEVIDA. |

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2019-10-22| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-04-22| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-05-19| B07B| Technical examination (opinion): publication cancelled [chapter 7.2 patent gazette]|

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2020-05-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-07-07| 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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US40655610P| true| 2010-10-25|2010-10-25|

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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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US61/406,547|2010-10-25|

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US61/406,570|2010-10-25|

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US61/406,556|2010-10-25|

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PCT/US2011/057597|WO2012061094A1|2010-10-25|2011-10-25|Fatty amides and derivatives from natural oil metathesis|

---