Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/64—Cationic compounds of unknown constitution, e.g. natural products

Definitions

• ester-linked quaternary ammonium compounds also known as ’’esterquats
• HRBFA rice bran fatty acids
• Esterquats are a class of cationic surfactants mainly used in laundry applications such as fabric softeners. Esterquats generally contain a long chain fatty acid group linked to a quaternary ammonium group via an ester linkage.
• esterquats are generally prepared by using triethanolamine esterified with long chain fatty acids (e.g. C16-C18), followed by quaternisation with a suitable quaternising agent, such as dimethyl sulfate.
• a suitable quaternising agent such as dimethyl sulfate.
• Other types of esterquat structures such as those mentioned in US 6,072,063 and US 5,811 ,385 are also known.
• esterquats can be prepared directly from triglyceride oils via a trans esterification step followed by a quaternisation step as described e.g. in WO 2014/069833.
• esterquat products are in particular defined by their activity, acid value, odour and colour, which are parameters affecting both product performance and customer acceptance.
• So called high quality esterquat products can be obtained by selecting proper parameters during the manufacturing process of the esterquats. For example, it was found that having a low acid value esterquat results in an esterquat composition having higher viscosity as compared to an esterquat having a high acid value. From a product performance perspective, a higher viscosity formulation is perceived as being more stable and often aesthetically more appealing to customers.
• EP-A 0981512 describes the use of a typical process to achieve acid values ⁇ 6.5 mg KOH/g.
• US 2009/286712 describes esterquats with low acid values ( ⁇ 6.7 mg KOH/g) for esterquats synthesised using methyl-diethanolamine.
• the applications JP 2003277334 A and JP 2003252838 A describe a process wherein no solvent is used during the quaternisation step, which leads to a better quality of the product.
• US 2017/275560 describes the use of an oxidising agent to achieve a light coloured esterquat product.
• Esterquats are generally prepared by using fatty acids based on tallow or vegetable oils such as palm oil. However, there are also other types of vegetable oils that have been reported, including sunflower, soybean and rice bran oil. However a renewable, non-edible (in particular for humans) and sustainable source for esterquats is highly desirable.
• Fatty acid esterquats for example based on palm oil fatty acids, and the use thereof in compositions for various uses, in particular as cationic surfactant in laundry products, have been known for more than 20 years (e.g. US 5,830,845).
• rice bran fatty acid esterquats can be prepared by esterification of rice bran fatty acids with hydroxyl-alkylamines, such as diethanolamine (DEA) or triethanolamine (TEA) at 140°C for 3 to 4 hours, and following “quaternisation” of the obtained di-ester using dimethyl sulfate (DMS).
• DEA diethanolamine
• TAA triethanolamine
• the publication also describes dilute esterquat products prepared using hydrolysed fatty acids from rice bran oil.
• Rice bran fatty acids in general are considered a sustainable resource produced in rice bran processing.
• rice bran fatty acids are prepared by hydrolysis of rice bran oil.
• rice bran oil as such is a by-product of rice bran processing and is considered sustainable, the cost of rice bran oil is high and the oil is categorized as an edible product. Thus, food-grade oil is often wasted for non-food purposes, when it is hydrolysed and used for the synthesis of esterquats.
• a substantial amount of oil undergoes degradation due to enzymatic activity, forming fatty acids in the non-edible crude rice bran oil. To make this oil edible, this oil is refined by separating the fatty acids by alkali refining or steam distillation.
• the resultant rice bran fatty acids generated as the by-product of rice bran oil are components of a non-edible portion of the oil and hence are more favourable for the production of products unrelated to food.
• the rice bran fatty acids used in the synthesis of the esterquats of the present invention are those separated from the edible oil in the non-edible portion of rice bran oil.
• esterquats prepared from rice bran fatty acids are often prone to oxidation and therefore can be unstable during further processing or in the final products to which they are added.
• An objective of the present invention is therefore to provide an esterquat based on rice bran fatty acids, which has an acceptable stability towards oxidation. This objective is reached by the ester-linked quaternary ammonium compound of the present invention.
• An aspect of the present invention is therefore an ester-linked quaternary ammonium compound comprising at least one hydrocarbon chain derived from at least one rice bran fatty acid from a non-edible source (RBFA), wherein the RBFA is an at least partially hydrogenated rice bran fatty acid (HRBFA) and has an iodine value from 0 to 75, in particular an iodine value from 1 to 70.
• RBFA non-edible source
• HRBFA at least partially hydrogenated rice bran fatty acid
• the RBFA is obtained from a non-edible source that is generated as a by-product during refinement of rice bran oil.
• the iodine value is determined according to American Oil Chemists’ Society (AOCS) Tg 1a-64 and is used to measure the degree of unsaturation of the fatty acids.
• AOCS American Oil Chemists’ Society
• a large fraction typically about 25 to 35 wt.-% of the total weight of RBFA
• Esterquats comprising hydrocarbon chains derived from such an RBFA are particularly prone to oxidation.
• the at least partially hydrogenated RBFA contains a small fraction (typically less than 6 wt.-%, preferably less than 3 wt.-%, more preferably less than 2 wt.-% of the total weight of HRBFA) of fatty acids with two or more unsaturated bonds in the hydrocarbon chain.
• the esterquats comprising hydrocarbon chains derived from such an HRBFA have been found to be significantly more stable towards oxidation. However, it has also been found that with increasing saturation of HRBFA, the viscosity of the esterquats comprising hydrocarbon chains derived therefrom increases, thus that they may become less suited for their specific surfactant applications.
• the HRBFA is preferably only partially hydrogenated. Accordingly, the iodine value of the HRBFA is preferably 75 or less but greater than 0, more preferably 1 to 70, more preferably 10 to 65, more preferably 15 to 60, more preferably 20 to 55, more preferably 25 to 50.
• ester-linked quaternary ammonium compound of the invention has a structure of formula (I) wherein
• R 1 represents -(C n H2n)R 5 or -(C n H2n-i)R 5 2;
• R 2 represents C 1 -C 4 alkyl, C 2 -C 4 alkenyl or C 2 -C 4 alkynyl
• R 3 and R 4 each independently represent -(C n H2n)R 6 , -(CnH2n-i)R 6 2, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl;
• R 5 represents an acyloxy group having a hydrocarbon chain derived from an HRBFA or an alkoxycarbonyl group having a hydrocarbon chain derived from an HRBFA; each R 6 independently represents OH, OR 2 , a C 12 -C 25 acyloxy group or a C 12 -C 25 alkoxycarbonyl group;
• X- represents an anionic counter-ion; each n independently represents a number from 1 to 4.
• the (C n H2n) moiety in -(C n H2n)R 5 and -(C n H2n)R 6 is to be understood as a hydrocarbon group with two attachment points, which is not limited to hydrocarbon groups having primary attachment points, such as 1,2-ethylene, 1,3-propylene and 1,4-butylene, but also includes alkylene groups having secondary and tertiary attachment points, such as 1 ,1 -ethylene,
• the (C n H2 n ) moiety is an alkylene group having a 1 ,2-attachment pattern, such as 1 ,2-ethylene, 1 ,2-propylene, 1 ,2-butylene or 1 ,2-isobutylene, more preferably, 1 ,2-ethylene or 1 ,2-propylene, more preferably 1 ,2-ethylene.
• the (C n H2n-i) moiety in -(C n H2n-i)R 5 2 and -(C n H2n-i)R 6 2 is to be understood as a hydrocarbon group with three attachment points.
• the (C n H2 n -i) moiety has a 1,2,3-attachment pattern, as found, e.g. in glycerol and derivatives thereof.
• C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl include both linear, branched and cyclic groups, but are preferably linear or branched groups, more preferably linear groups.
• R 1 represents -(C n H2n)R 5 or -(C n H2n-i)R 5 2, preferably -(C n H2n)R 5 which comprises at least one of the ester linkages of the ester-linked quaternary ammonium compound of the invention.
• R 1 is typically introduced into the ester- linked quaternary ammonium compound of the invention prior to quaternisation by, e.g. esterification of an alcohol derived from an HRBFA with an amino carboxylic acid.
• R 5 represents an alkoxycarbonyl group having a hydrocarbon chain derived from an HRBFA. Said alcohol derived from an HRBFA is obtainable e.g.
• R 5 represents an acyloxy group having a hydrocarbon chain derived from an HRBFA. Due to easier accessibility, R 1 is preferably obtained by esterification of an HRBFA with an amino alcohol, thus that R 5 preferably represents an acyloxy group having a hydrocarbon chain derived from an HRBFA.
• R 2 represents C 1 -C 4 alkyl, C 2 -C 4 alkenyl or C 2 -C 4 alkynyl, preferably C 1 -C 4 alkyl, more preferably methyl.
• R 2 is typically introduced into the ester-linked quaternary ammonium compound of the invention by quaternisation of the respective amine by treatment with a quaternising agent that is suitable for transferring a carbenium ion derived from R 2 .
• R 3 and R 4 each independently represent - (CnH2n)R 6 , -(CnH2n-i)R 6 2, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl, preferably C-i- C 4 alkyl or -(C n H 2 n)R 6 , more preferably methyl or -(C n H 2 n)R 6
• R 3 and R 4 often are already present in the amine used for the synthesis of the ester-linked quaternary ammonium compound of the invention prior to the introduction of R 1 .
• R 3 and R 4 may be C 1 -C 4 alkyl, it may be present in an alkyl-dialkanolamine such as N-methyl diethanolamine or both may be present in a dialkyl-alkanolamine such as N,N-dimethyl ethanolamine.
• R 3 and/or R 4 may be introduced into the ester-linked quaternary ammonium compound of the invention during quaternisation after the introduction of R 1 , if the amine used for the synthesis of the ester-linked quaternary ammonium compound comprises N-H bonds.
• R 3 and R 4 is -(C n H2n)R 6 or -(C n H2n-i )R 6 2 wherein R 6 is OH
• R 6 is OH
• it may be present as either of the alkanol moieties of an alkanolamine, such as dialkanolamine, trialkanolamine, alkyl-dialkanolamine, e.g. triethanolamine, or derivatives thereof having two hydroxyl groups.
• R 6 is OR 2 , it is typically obtained from said alkanol moieties during quaternisation of the respective amine by reaction of the respective alkanol moiety with the quaternising agent.
• R 3 and R 4 can be -(C n H2n)R 6 or -(C n H2n-i )R 6 2, preferably -(C n H2n)R 6 , wherein R 6 is a C12-C25 acyloxy group or a C12-C25 alkoxycarbonyl group.
• R 3 and/or R 4 is typically introduced into the ester-linked quaternary ammonium compound of the invention in the same way as R 1 , however with a C12-C25 carboxylic acid instead of HRBFA, which may be the same as the HRBFA or different.
• the use of the C12-C25 carboxylic acid results in a total iodine value of all fatty acids of from 0 to 75, more preferably 1 to 70 more preferably 10 to 65, more preferably 15 to 60, more preferably 20 to 55, more preferably 25 to 50.
• the C12-C25 carboxylic acid can be different from the HRBFA.
• it is preferably a saturated C12-C25 carboxylic acid, more preferably selected from saturated C14-C20 carboxylic acids, more preferably from saturated C16 and C18 carboxylic acids, more preferably a saturated C16 carboxylic acid, in which case it has an iodine value of 0.
• the C12-C25 carboxylic acid is typically admixed to said HRBFA before the HRBFA is further processed into the ester-linked quaternary ammonium compound of the invention.
• the C12-C25 carboxylic acid can be a HRBFA, preferably a HRBFA obtained from a non-edible source.
• the C12-C25 carboxylic acid, from which the hydrocarbon chain in R 6 is derived may be the HRBFA from which the hydrocarbon chain in R 5 is derived and/or may be obtained in the same process as said HRBFA and therefore itself has an iodine value of from 0 to 75, more preferably 1 to 70, more preferably 10 to 65, more preferably 15 to 60, more preferably 20 to 55, more preferably 25 to 50.
• R 1 represents -(C n H2n-i)R 5 2
• each of R 2 , R 3 and R 4 preferably represents C1-C4 alkyl.
• X- represents an anionic counter-ion.
• this counter-ion is introduced during quaternisation of the respective amine and originates from the quaternising agent used for introducing the R 2 group.
• Such quaternising agent may be selected from e.g. oxonium salts, halides, phosphates, carbonates, sulphonates and sulphates of the respective R 2 group.
• X- is thus the respective anion obtainable by removing an (R 2 ) + carbenium ion from the quaternising agent.
• X- is selected from halide and alkyl sulphate, more preferably chloride or methyl sulphate.
• each n independently represents a number from 1 to 4, preferably a number from 2 to 3, more preferably 2.
• each n is the same and represents 2.
• the ester-linked quaternary ammonium compound has a structure of formula (I) as defined above, wherein R 2 represents C1-C4 alkyl, preferably methyl;
• R 3 and R 4 each independently represent C1-C4 alkyl, preferably methyl, or -(CnH 2n )R 6 ;
• R 5 represents an acyloxy group having a hydrocarbon chain derived from an HRBFA; each R 6 independently represents OH, OR 2 or a C 12 -C 25 acyloxy group;
• X- represents halide or alkyl sulphate, preferably chloride or methyl sulphate.
• ester-linked quaternary ammonium compound has a structure of formula (I) as defined above, wherein each R 6 independently represents OH, OR 2 or an acyloxy group having a hydrocarbon chain derived from an RBFA, preferably from an FIRBFA.
• ester-linked quaternary ammonium compound has a structure of formula (I) as defined above, wherein
• R 3 is C1-C4 alkyl, preferably methyl, or -(C n H2n)R 6 , with R 6 being OH or OR 2 , and
• R 4 is -(C n H2n)R 6 , with R 6 being an acyloxy group having a hydrocarbon chain derived from an RBFA, preferably from an HRBFA.
• ester-linked quaternary ammonium compound has a structure of formula (I) as defined above, wherein R 3 and R 4 represent -(C n H2n)R 6 , wherein each R 6 independently represents OH or OR 2 .
• the ester-linked quaternary ammonium compound has a structure of formula (I) as defined above, wherein R 3 and R 4 represent -(C n H2n)R 6 , wherein each R 6 is an acyloxy group having a hydrocarbon chain derived from an RBFA, preferably from an HRBFA.
• ester-linked quaternary ammonium compound has a structure of formula (I) as defined above, wherein R 3 and R 4 each independently represents C1-C4 alkyl, preferably methyl.
• the ester-linked quaternary ammonium compound has a structure of one of following formulae (la), (lb), (lc), (Id), (le), (If), (Ig), (Ih), (Ij), (Ik), (Im), (In), (lo), (Ip), (Iq), (Ir), (Is), (It), (lu), (Iv) and (Iw), wherein R 5 and R 6 each represent an acyloxy group having a hydrocarbon chain derived from an HRBFA, and X represents halide or alkyl sulphate, preferably chloride or methyl sulphate.
• the ester-linked quaternary ammonium compound has a structure of one of formulae (la), (lc), (le), (Ig), (Ij), (Im), (lo), (Iq), (Is) and (lu).
• the ester-linked quaternary ammonium compound has a structure of one of formulae (lb), (Id), (If), (Ih), (Ik), (In), (Ip), (Ir), (It) and (lv).
• the ester-linked quaternary ammonium compound has a structure of formula (Iw).
• ester-linked quaternary ammonium compound has a structure of one of formulae (la) and (lb). In another preferred embodiment, the ester-linked quaternary ammonium compound has a structure of one of formulae (lc) and (Id).
• the ester-linked quaternary ammonium compound has a structure of one of formulae (le) and (If). In another preferred embodiment, the ester-linked quaternary ammonium compound has a structure of one of formulae (Ig) and (Ih). In another preferred embodiment, the ester-linked quaternary ammonium compound has a structure of one of formulae (Ij) and (Ik).
• the ester-linked quaternary ammonium compound has a structure of one of formulae (Im) and (In). In another preferred embodiment, the ester-linked quaternary ammonium compound has a structure of one of formulae (lo) and (Ip). In another preferred embodiment, the ester-linked quaternary ammonium compound has a structure of one of formulae (Iq) and (Ir). In another preferred embodiment, the ester-linked quaternary ammonium compound has a structure of one of formulae (Is) and (It). In another preferred embodiment, the ester-linked quaternary ammonium compound has a structure of one of formulae (lu) and (Iv).
• Another aspect of the present invention is a mixture of ester-linked quaternary ammonium compounds comprising at least one, preferably at least two ester linked quaternary ammonium compounds of the invention, as described above.
• the mixture of the invention can be a mixture of at least one ester-linked quaternary ammonium compound of the invention as described above with any other ester-linked quaternary ammonium compound, e.g. with one or more ester- linked quaternary ammonium compounds of formula (I) as described above, wherein R 5 and, if applicable, R 6 represent an acyloxy group or an alkoxycarbonyl group having a hydrocarbon chain derived from a fatty acid that is not an HRBFA.
• the hydrocarbon chain is preferably derived from a C12-C25 fatty acid having an iodine value of 0 to 75, more preferably 1 to 70, more preferably 10 to 65, more preferably 15 to 60, more preferably 20 to 55, more preferably 25 to 50. Also preferably, the hydrocarbon chain is derived from a C14-C20, more preferably from a C16 or C18, more preferably from a C16 fatty acid that is not an HRBFA.
• the mixture of the invention can be a mixture of at least two ester- linked quaternary ammonium compounds of the invention as described above, without other ester-linked quaternary ammonium compounds.
• the mixture of the invention is a mixture of ester-linked quaternary ammonium compounds having structures of at least two of formulae (la), (lb), (lc), (Id), (le), (If), (Ig), (Ih), (Ij), (Ik), (Im), (In), (lo), (Ip), (Iq), (Ir), (Is), (It), (lu), (Iv) and (Iw), wherein R 5 and R 6 each represent an acyloxy group having a hydrocarbon chain derived from an HRBFA, and X- represents halide or alkyl sulphate, preferably chloride or methyl sulphate.
• the mixture of the invention is a mixture of ester-linked quaternary ammonium compounds having structures of at least two of formulae (la), (lc), (le), (Ig), (Ij), (Im), (lo), (Iq), (Is) and (lu).
• the mixture of the invention is a mixture of ester-linked quaternary ammonium compounds having structures of at least two of formulae (lb), (Id), (If), (Ih), (Ik), (In), (Ip), (Ir), (It) and (Iv).
• the mixture of the invention is a mixture of ester- linked quaternary ammonium compounds having structures of at least two of formulae (la), (Is) and (lu). In another preferred embodiment, the mixture of the invention is a mixture of ester-linked quaternary ammonium compounds having structures of at least two of formulae (lb), (It) and (Iv). In another preferred embodiment, the mixture of the invention is a mixture of ester-linked quaternary ammonium compounds having structures of at least two of formulae (lb), (It) and (Iv). In another preferred embodiment, the mixture of the invention is a mixture of ester-linked quaternary ammonium compounds having structures of at least two of formulae (lc), (Ig), (Ij), (Im), (lo), and (Iq).
• the mixture of the invention is a mixture of ester- linked quaternary ammonium compounds having structures of at least two of formulae (Id), (Ih), (Ik), (Ip) and (Ir).
• Another aspect of the present invention is a process for the production of an ester- linked quaternary ammonium compound or of a mixture of ester-linked quaternary ammonium compounds, comprising the steps of:
• step (ii) optionally mixing the FIRBFA or FIRBFAs with one or more C12-C25 fatty acids thus that the overall iodine value of all fatty acids remains within the range of from 0 to 75, preferably 1 to 70, more preferably 10 to 65, more preferably 15 to 60, more preferably 20 to 55, more preferably 25 to 50; (iii) esterification of the HRBFA, HRBFAs or, if applicable, of the mixture obtained in step (ii) with an alkanolamine of formula (II) wherein
• R 11 represents -(C n Fl2n)OFI or -(C n Fl2n-i)(OFI)2, preferably -(C n Fl2n)OFI;
• R 31 and R 41 each independently represent -(C n Fl2n)OFI, -(C n Fl2n-i)(OFI)2, H, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl, preferably -(C n Fl2n)OFI, FI or C1-C4 alkyl; and each n independently represents a number from 1 to 4, to obtain an ester amine (EA) or a mixture of ester amines (EAs)
• step (i) of the process of the present invention a rice bran fatty acid from a non edible source (RBFA), or a mixture of several rice bran fatty acids from a non edible source (RBFAs), are used.
• RBFA non edible source
• RBFAs a rice bran fatty acid from a non edible source
• the rice bran oil from the refinement of which the non-edible source of rice bran fatty acids is generated, is not particularly limited. It is, however, desirable to select rice bran oil that is a side product of rice bran processing.
• the rice bran itself is also not limited to specific rice bran, but is preferably rice bran that is a by-product of rice processing.
• the rice bran fatty acids from non-edible sources are usually obtained as a mixture of several fatty acids and often contain impurities that prevent the formation of high quality esterquats. Therefore the rice bran fatty acids are preferably separated from impurities prior to or after catalytic hydrogenation. It may be beneficial to carry out the separation after catalytic hydrogenation, in order to remove residual metal catalysts and by products generated during catalytic hydrogenation. Separation techniques for rice bran fatty acids may include any known separation techniques that are applicable for the separation of fatty acids from each other and/or from further impurities.
• separation techniques include, but are not limited to crystallisation, winterisation, distillation, sublimation, filtration, adsorption on high surface materials such as activated carbon or bleaching earths, chromatography including column, flash, and high performance liquid chromatography, liquid-liquid extraction and solid-liquid-extraction.
• Preferable separation techniques are crystallisation, winterisation and/or distillation. If a single rice bran fatty acid from a non-edible source (RBFA) is used, at least one of the above separation techniques has to be applied after impurities have been removed and prior to catalytic hydrogenation, since the non-edible source typically contains a mixture of different rice bran fatty acids. If a mixture of rice bran fatty acids from a non-edible source (RBFAs) is used, the mixture may be used without separation of any individual RBFA, or after removal of certain RBFA.
• RBFA non-edible source
• the RBFA or RBFAs are subjected to catalytic hydrogenation.
• This step is typically carried out with hydrogen in the presence of a hydrogenation catalyst.
• the hydrogenation catalyst is a group 8, 9, 10 or 11 transition metal hydrogenation catalyst, e.g. a ruthenium hydrogenation catalyst, a cobalt hydrogenation catalyst, a rhodium hydrogenation catalyst, an iridium hydrogenation catalyst, a nickel hydrogenation catalyst, a palladium hydrogenation catalyst, a platinum hydrogenation catalyst or a copper hydrogenation catalyst.
• the hydrogenation catalyst is a nickel hydrogenation catalyst.
• the catalytic hydrogenation is typically carried out in the absence of oxygen, which may be obtained by e.g.
• the flushing is carried out for at least 20 min, preferably at least 40 min, more preferably at least 60 min.
• the reaction vessel can be flushed with hydrogen, which is used in the subsequent hydrogenation reaction.
• the absence of oxygen can be established by repeatedly applying vacuum to the vessel and flooding the vessel with inert gas or with hydrogen.
• the vacuum and flooding is carried out at least twice, preferably at least 3 times, more preferably at least 5 times.
• catalytic hydrogenation of step (i) can be carried out at a reaction temperature of from 60 to 300°C, preferably from 100 to 250°C, more preferably from 150 to 200°C, more preferably from 160 to 180°C, more preferably from 170 to 175°C.
• catalytic hydrogenation of step (i) can be carried out for example at a hydrogen gas pressure of from 3 to 15 kg/cm 2 , preferably from 5 to 12 kg/cm 2 , more preferably from 7 to 10 kg/cm 2 , more preferably from 7.5 to 8 kg/cm 2 .
• catalytic hydrogenation is carried out at a reaction temperature of from 100 to 250°C and a hydrogen gas pressure of from 3 to 15 kg/cm 2 .
• it is carried out at a reaction temperature of from 150 to 200°C and a hydrogen gas pressure of from 5 to 12 kg/cm 2 .
• the catalyst loading can for example be from 0.01 to 2 wt.-%, preferably from 0.05 to 1 wt.-%, more preferably from 0.1 to 0.8 wt.-%, more preferably from 0.3 to 0.5 wt.-%.
• the catalytic hydrogenation of step (i) is carried out until the RBFA or RBFAs are at least partially hydrogenated to an iodine value of from 0 to 75, preferably 1 to 70, more preferably 10 to 65, more preferably 15 to 60, more preferably 20 to 55, more preferably 25 to 50, in order to obtain an at least partially hydrogenated rice bran fatty acid (FIRBFA) or a mixture of at least partially hydrogenated rice bran fatty acids (FIRBFAs).
• FIRBFA at least partially hydrogenated rice bran fatty acid
• FIRBFAs contain mono and polyunsaturated fatty acids. Therefore, the catalytic hydrogenation of RBFAs typically results in mixtures of cis and trans fatty acids.
• FIRBFAs independent of their cis and trans content, can be used for the preparation of ester-linked quaternary ammonium compounds, it is preferred to use FIRBFAs with a trans-content of less than 20 wt.-%, more preferred less than 15 wt.-%, more preferred less than 10 wt.-% and even more preferred less than 5 wt.-%, based on the total weight of FIRBFAs.
• the FIRBFA or FIRBFAs can be mixed with one or more C12-C25 fatty acids thus that the overall iodine value of all fatty acids remains within the range of from 0 to 75, preferably 1 to 70, more preferably 10 to 65, more preferably 15 to 60, more preferably 20 to 55, more preferably 25 to 50.
• This step is typically carried out in order to adjust the distribution of hydrocarbon chains of the final ester-linked quaternary ammonium compound, if a specific distribution, which cannot be obtained by RBFAs from the employed non-edible source, is required for a specific application.
• fatty acids preferably are selected from saturated C14-C20 fatty acids, more preferably from saturated C16 or C18 fatty acids, more preferably are a saturated C16 fatty acid. In one embodiment, step (ii) is carried out. In another embodiment, step (ii) is not carried out. If step (ii) is carried out, the fatty acids are preferably obtained from a non-edible source.
• step (iii) the FIRBFA, FIRBFA or, if step (ii) was carried out, the mixture obtained in step (ii), is subjected to an esterification reaction with an alkanolamine of formula (II) wherein
• R 11 represents -(C n H2n)OH or -(C n H2n-i)(OH)2, preferably -(C n H2n)OH;
• R 31 and R 41 each independently represent -(C n H2n)OH, -(C n H2n-i)(OH)2, H, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl, preferably -(C n H2n)OH, H or C1-C4 alkyl; and each n independently represents a number from 1 to 4, to obtain an ester amine (EA) or a mixture of ester amines (EAs).
• EA ester amine
• EAs mixture of ester amines
• the esterification reaction of step (iii) is typically carried out at temperatures between 50 and 250°C, preferably between 100 and 220°C, more preferably between 150 and 200°C. If the temperature is too low, the reaction is significantly slowed down and thus is not applicable on an industrial scale. However, if the temperature is too high, decomposition products occur at a high rate, thus limiting the usefulness of the product mixture.
• the esterification reaction of step (iii) is preferably carried out under atmospheric pressure.
• the esterification step (i) is carried out under conditions in which generated water is continuously removed from the reaction vessel.
• water removal may be accomplished by adding molecular sieves to the reaction mixture, by attaching a Dean-Stark-apparatus or distillation apparatus to the reaction vessel, or by applying vacuum to the reaction vessel. More preferably, the reaction is carried out under vacuum and/or with a distillation apparatus attached.
• the alkanolamine of formula (II) is selected from those having structures of any of following formulae (I la), (Mb), (lie), (lid), (Me), (Ilf), (Mg), (llh), (Mj), (Ilk), (Mm), (Mn), (Mo), (lip) and (Mq). (llq).
• the alkanolamine is selected from those having structures of any of formulae (I la), (lie), (lie), (llg), (llj) and (llm). In another embodiment, the alkanolamine is selected from those having structures of any of formulae (Mb),
• the alkanolamine is selected from those having structures of any of formulae (Mo), (lip) and (llq). In another embodiment, the alkanolamine is selected from those having structures of any of formulae (lla), (Me) and (Mm). In another embodiment, the alkanolamine is selected from those having structures of any of formulae (Mb), (lid) and (lln).
• the alkanolamine used in the process according to the invention may be any alkanolamine, however tertiary alkanolamines are preferred due to potential side reactions of N-H amines with HRBFAs during the esterification step. Even more preferred are trialkanolamines, especially triethanolamine.
• the molar ratio of rice bran fatty acids to alkanolamine in the esterification step (iii) is typically from 1 :2 to 3: 1 , preferably 1 :1 to 3: 1 , more preferably from 1 :1 to 2: 1 . If the ratio is too low, the resultant ester amines are formed in an undesirably low concentration. However, if it is too high, the resultant product exceeds the desired acidity. Accordingly, depending on the ratio and the employed alkanolamine, the resultant ester amine (EA) or mixture of ester amines (EAs) may contain monoesters, diesters, triesters or mixtures thereof.
• the quaternisation step (iv) is typically carried out at temperatures from 0 to 180°C, preferably from 20 to 120°C, more preferably from 50 to 100°C. If the temperature is too low, the reaction is significantly slowed down and thus is not applicable on an industrial scale.
• the quaternising agent in the quaternization step (iv) is not particularly limited and may be selected, e.g. from trialkyl oxonium salts, alkyl halides, dialkyl phosphates, dialkyl carbonates, alkyl sulphonates and dialkyl sulphates, however dialkyl sulphates and alkyl halides are preferred, especially dimethyl sulphate and methyl chloride, in particular dimethyl sulphate.
• the molar ratio between the ester amine and the quaternising agent is typically from 2:1 to 1:3, preferably from 1.5:1 to 1:2, most preferably from 1.1:1 to 1 : 1.1. If the ratio is too low, the quaternisation of the ester amine or the mixture of ester amines is not complete after the reaction is finished.
• the quaternisation step (iv) is carried out in the absence of a solvent, because solvents may be alkylated by the quaternizing agent, which may result in increased odour of the final product.
• one or more solvents may be added to the resultant mixture after the quaternization is at least partially completed, or fully completed.
• the solvent is not particularly limited, and can be selected from, e.g.
• the solvent added after the at least partial completion of the quaternization step is the polyol propylene glycol or an alcohol, more preferably ethanol, isopropanol or propylene glycol.
• the solvent may comprise further solvent components, such as aromatic hydrocarbons, aliphatic hydrocarbons, ethers, esters, lactones, lactams, amides, amines, furans and others.
• the solvent does not contain any of these further solvent components.
• the process according to the present invention leads to an ester-linked quaternary ammonium compound or a mixture of ester-linked quaternary ammonium compounds that has high quality.
• the ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds has a low acid value, a low level of odour and a low level of coloured stain.
• the acid value of the ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds prepared by the process according to the invention is typically lower than 7 mg KOH/g of the sample, and usually originates from the content of amine salts and free fatty acids in the product.
• the acid value may be determined by the recent standard method DIN EN ISO 2114.
• the odour of the ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds mostly originates from the solvent employed in or after the quaternisation step (ii), which solvent is often alkylated by the quaternising agent to give compounds with unpleasant odour.
• the ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds acquired by the process of the invention typically contains alkylated solvents, preferably alkylated alcohols, in particular methyl ethyl ether or methyl isopropyl ether in an amount below 10000 ppm, preferably below 5000 ppm, more preferably below 2000 ppm, as determined by integration of the corresponding resonance signals, preferably of the signals arising from the methyl groups introduced by the quaternising agent, in the 1 H NMR spectrum of a sample of the ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds.
• alkylated solvents preferably alkylated alcohols, in particular methyl ethyl ether or methyl isopropyl ether in an amount below 10000 ppm, preferably below 5000 ppm, more preferably below 2000 ppm, as determined by integration of the corresponding resonance signals, preferably
• the colour of the ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds acquired by the process according to the invention typically has a value of less than 8, preferably less than 5, more preferably 4 or less on the Gardner colour scale according to the recent standard method ASTM D1544.
• the ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds acquired by the process according to the invention preferably has an active esterquat content of above 0.7 meq/g, more preferably of above 0.8 meq/g, most preferably of above 1.0 meq/g, measured by Epton titration according to the recent standard method DIN EN ISO 2871.
• Another aspect of the present invention is the use of an at least partially hydrogenated rice bran fatty acid (HRBFA) or a mixture of at least partially hydrogenated rice bran fatty acids (HRBFAs) from a non-edible source for the production of an ester-linked quaternary ammonium compound or a mixture of ester-linked quaternary ammonium compounds, wherein the FIRBFA or FIRBFAs have an iodine value from 0 to 75, preferably 1 to 70, more preferably 10 to 65, more preferably 15 to 60, more preferably 20 to 55, more preferably 25 to 50.
• a mixture of rice bran fatty acids (RBFAs) from the non-edible portion obtained during refinement of rice bran oil was subjected to catalytic hydrogenation using a pressure reactor and a Nickel catalyst for hydrogenation of fatty acids (SCAT 2234 obtained from Suhans Chemicals). 7000 kg of pre-melted RBFAs were charged to the pressure reactor and 28 kg of the catalyst was added.
• RBFAs rice bran fatty acids
• compositions of fatty acids in the HRBFAs obtained from hydrogenation are listed in Table 2.
• Table 2 C-16 and C-18 indicate the C-chain length, 1 ” and “:2” indicate the number of unsaturated bonds.
• ester-linked ammonium compounds of examples 4, 5 and 6 were evaluated by measuring the softness of towels using PhabrOmeter (Nu Cybertek Inc.) according to their standard procedure (AATCC Test method TM202) and compared to a commercially available product made from palm oil fatty acid-based esterquat Praepagen TQOV-IPA.
• White hand towels (100% cotton, brand: Rhema, Indonesia, 30 cm x 28 cm) were prewashed with a common detergent. 25 g of the ester-linked ammonium compound were dissolved in tap water and stirred for 1 minute. Prewashed towels were soaked in the solution for 30 minutes and spin dried. Dried towels were conditioned in a room with constant humidity and temperature. The softness was evaluated by relative hand value (RHV, AATCC Test method TM202, Nu Cybertek Inc.), with higher values indicating softer fabrics. The results are listed in Table 4.
• ester-linked quaternary ammonium compounds of the invention can be used to obtain softer fabrics than commercially available palm oil fatty acid-based esterquats, such as Praepagen TQOV-IPA (of Clariant).

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• 2021
  • 2021-12-23 EP EP21847949.1A patent/EP4274881A1/de active Pending
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