CN116783274A - Hydrogenated ester quaternary ammonium salt from rice bran fatty acid and preparation thereof - Google Patents

Hydrogenated ester quaternary ammonium salt from rice bran fatty acid and preparation thereof Download PDF

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CN116783274A
CN116783274A CN202180089572.XA CN202180089572A CN116783274A CN 116783274 A CN116783274 A CN 116783274A CN 202180089572 A CN202180089572 A CN 202180089572A CN 116783274 A CN116783274 A CN 116783274A
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quaternary ammonium
ester
rice bran
hrbfa
linked quaternary
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C·科尔斯
K·J·穆特奇
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Clariant International Ltd
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    • 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

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Esterquats are mainly used as fabric softeners. After tallow fatty acid and palm oil fatty acid, fatty acids from sustainable sources such as Rice Bran Fatty Acid (RBFA) are desired. RBFA is formed as a by-product during refining of rice bran oil and is therefore contained in the non-edible part of the oil. However, esterquats from RBFA are often prone to oxidation, which leads to undesirable properties in the final product. The present invention relates to esterquats derived from rice bran fatty acids, wherein the rice bran fatty acids are at least partially Hydrogenated Rice Bran Fatty Acids (HRBFA). This results in higher oxidative stability of the esterquat and thus in an overall higher acceptance of the final product.

Description

Hydrogenated ester quaternary ammonium salt from rice bran fatty acid and preparation thereof
The present invention relates to ester-linked quaternary ammonium compounds obtained from at least partially Hydrogenated Rice Bran Fatty Acids (HRBFA), also known as "esterquats", and the preparation of these products. Esterquats are a class of cationic surfactants that are primarily used in laundry applications such as fabric softeners. Esterquats typically contain long chain fatty acid groups linked to a quaternary ammonium group through an ester linkage.
The structure and composition of esterquats are described, for example, in EP-A1806392. Esterquats are typically prepared by using triethanolamine esterified with a long chain fatty acid (e.g., C16-C18) followed by quaternization with a suitable quaternizing agent such as dimethyl sulfate. Other types of esterquat structures are also known, such as those mentioned in US 6,072,063 and US 5,811,385. In general, esterquats may be prepared directly from triglyceride oils via a transesterification step followed by a quaternization step, as described for example in WO 2014/069833.
The quality of esterquat products is specifically defined by their activity, acid number, odor and color, which are parameters affecting product performance and customer acceptance. So-called high quality esterquat products can be obtained by selecting appropriate parameters during the manufacture of the esterquat. For example, it was found that esterquats having a low acid number result in esterquat compositions having a higher viscosity than esterquats having a high acid number. From a product performance standpoint, higher viscosity formulations are considered more stable and generally more aesthetically attractive to the consumer.
EP-A0981512 describes the use of conventional methods to achieve an acid number of <6.5mg KOH/g. US 2009/286712 describes esterquats with low acid number (< 6.7mg KOH/g), which are esterquats synthesized using methyl-diethanolamine. Applications JP 2003277334A and JP 2003252838a describe a process in which no solvent is used during the quaternization step, which results in a better quality of the product. US 2017/275560 describes the use of an oxidizing agent to achieve a light colored esterquat product.
Cold workability of esterquat and/or dispersibility of esterquat at low temperatures are additional desirable properties of high quality products due to better energy economy and ease of production.
US 2013/196894 describes the use of synthetic esterquat composition products of fatty acids (e.g. from tallow, canola oil (canola), soybean oil or palm oil) with iodine values between 65-85 and good ester distribution to promote dispersibility at low temperatures.
Esterquats are typically prepared by using fatty acids based on tallow or vegetable oils such as palm oil. However, other types of vegetable oils have also been reported, including sunflower oil, soybean oil, and rice bran oil. However, renewable, non-edible (especially for humans) and sustainable sources of esterquats are highly desirable.
Fatty acid ester quaternary ammonium salts have been known, for example based on palm oil fatty acids and their use in compositions for various uses, in particular as cationic surfactants in laundry products for over 20 years (e.g. US 5,830,845). The use of quaternary ammonium salts of rice bran fatty acid esters as cationic surfactants in fabric softeners is reported in publications Gunjan and Vinod K.Tyagi (2014) ("Synthesis of Rice Bran Fatty Acids (RBFAs) Based Cationic Surfactants and Evaluation of Their Performance Properties in Combination wi th Nonionic Surfactant", tenside Surfactants Detergents: vol. 51, 6 th, pages 497-505). It describes the preparation of rice bran fatty acid ester quaternary ammonium salts by esterifying rice bran fatty acids with hydroxy-alkylamines such as Diethanolamine (DEA) or Triethanolamine (TEA) at 140 ℃ for 3 to 4 hours, and then "quaternizing" the obtained diester with dimethyl sulfate (DMS). The publication also describes diluted esterquat products prepared using hydrolyzed fatty acids from rice bran oil.
Rice bran fatty acids are generally considered to be a sustainable resource generated in rice bran processing. Typically, rice bran fatty acids are prepared by hydrolysis of rice bran oil. Although rice bran oil itself is a byproduct of rice bran processing and is considered sustainable, rice bran oil is costly and the oil is classified as an edible product. Thus, food grade oils are often wasted for non-food purposes when they are hydrolyzed and used in the synthesis of esterquats. However, during extraction of rice bran oil, a large amount of oil undergoes degradation due to enzymatic activity, forming fatty acids in the non-edible crude rice bran oil. In order to make the oil edible, the oil is refined and the fatty acids are separated by alkali refining or steam distillation. The resulting rice bran fatty acids produced as rice bran oil by-products are components of the non-edible part of the oil and thus are more advantageous for the production of food independent products. The rice bran fatty acids used in the synthesis of the esterquats of the present invention are those that are separated from the edible oil in the non-edible portion of the rice bran oil.
It has now been found that esterquats prepared from rice bran fatty acids are often prone to oxidation and thus may be unstable during further processing or in the final product to which they are added. It is therefore an object of the present invention to provide esterquats based on rice bran fatty acids which have acceptable oxidative stability. This object is achieved by the ester-linked quaternary ammonium compounds according to the invention.
Accordingly, one aspect of the present invention is an ester-linked quaternary ammonium compound comprising at least one hydrocarbon chain derived from at least one Rice Bran Fatty Acid (RBFA) from a non-edible source, wherein RBFA is an at least partially Hydrogenated Rice Bran Fatty Acid (HRBFA) and has an iodine value of 0-75, particularly an iodine value of 1-70.
Preferably, the RBFA is obtained from a non-edible source produced as a by-product during refining of rice bran oil.
The iodine number was determined according to american society of oleochemists (AOCS) Tg 1a-64 and was used to measure the unsaturation of fatty acids. At iodine values of 96 or greater, a majority (typically about 25 to 35 weight percent of the total weight of the RBFA) of the RBFAs has two or more unsaturated bonds in the hydrocarbon chain. Esterquats comprising hydrocarbon chains derived from such RBFAs are particularly prone to oxidation. Hydrogenation of RBFA results in saturation of unsaturated bonds in the hydrocarbon chain, thus lowering the iodine value. At iodine values of 75 or less, the at least partially hydrogenated RBFA (=hrbfa) contains a small fraction (typically less than 6 wt%, preferably less than 3 wt%, more preferably less than 2 wt%, based on the total weight of HRBFA) of fatty acids having two or more unsaturated bonds in the hydrocarbon chain. Esterquats comprising hydrocarbon chains derived from such HRBFAs have been found to be significantly more stable to oxidation. However, it has also been found that as the saturation of HRBFA increases, the viscosity of esterquats comprising hydrocarbon chains derived from HRBFA increases, and therefore they may become less suitable for their particular surfactant application.
Therefore, 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.
In one embodiment, the ester-linked quaternary ammonium compounds of the present invention have the structure of formula (I)
Wherein the method comprises the steps of
R 1 Representation- (C) n H 2n )R 5 Or- (C) n H 2n-1 )R 5 2 ；
R 2 Represent C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl;
R 3 and R is 4 Each independently represents- (C) n H 2n )R 6 、-(C n H 2n-1 )R 6 2 、C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl;
R 5 represents an acyloxy group having a hydrocarbon chain derived from HRBFA or an alkoxycarbonyl group having a hydrocarbon chain derived from HRBFA;
each R 6 Independently represent OH, OR 2 、C 12 -C 25 Acyloxy groups or C 12 -C 25 An alkoxycarbonyl group;
X – represents an anionic counterion;
each n independently represents a number of 1 to 4.
In the context of the present invention, - (C) n H 2n )R 5 And- (C) n H 2n )R 6 (C) n H 2n ) The structural moiety is understood to be a hydrocarbon group having two points of attachment, which is not limited to hydrocarbon groups having primary points of attachment, such as 1, 2-ethylene, 1, 3-propylene and 1, 4-butylene, but also includes alkylene groups having secondary and tertiary points of attachment, such as 1, 1-ethylene, 1-propylene, 1-butylene, 1, 2-propylene, 1, 2-butylene, 1, 3-butylene, 2-propylene, 2-butylene, 2, 3-butylene and1, 2-isobutyl group.
Preferably, (C) n H 2n ) The moiety is an alkylene group having a 1, 2-linkage, such as 1, 2-ethylene, 1, 2-propylene, 1, 2-butylene or 1, 2-isobutylene, more preferably 1, 2-ethylene or 1, 2-propylene, still more preferably 1, 2-ethylene. Thus, - (C) n H 2n-1 )R 5 2 And- (C) n H 2n-1 )R 6 2 (C) n H 2n-1 ) A moiety is understood to be a hydrocarbon group having three points of attachment. Preferably, (C) n H 2n-1 ) The moiety has a 1,2, 3-linkage, such as found in glycerol or derivatives thereof.
In addition, C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl and C 2 -C 4 Alkynyl groups include linear, branched and cyclic groups, but linear or branched groups are preferred, with linear groups being more preferred.
In formula (I), R 1 Representation- (C) n H 2n )R 5 Or- (C) n H 2n-1 )R 5 2 Preferably- (C) n H 2n )R 5 Comprising at least one of the ester linkages of the ester-linked quaternary ammonium compounds of the present invention. R is typically reacted with an alcohol derived from HRBFA, for example by esterification with an aminocarboxylic acid, prior to quaternization 1 The ester-linked quaternary ammonium compounds of the present invention are incorporated. In this case, R 5 Represents an alkoxycarbonyl group having a hydrocarbon chain derived from HRBFA. The HRBFA-derived alcohol may be prepared, for example, by using LiAlH 4 Selectively reducing the carboxylic acid of HRBFA. Aminocarboxylic acids such as glycine, iminodiacetic acid and nitrilotriacetic acid and their derivatives are commercially available. Alternatively, R can be obtained by esterifying HRBFA with alkanolamines (=aminoalcohols) such as ethanolamine, diethanolamine, triethanolamine and their derivatives, for example 1 . In this case, R 5 Represents an acyloxy group having a hydrocarbon chain derived from HRBFA. R is relatively easily obtained 1 Preferably obtained by esterifying HRBFA with an amino alcohol, so R 5 Preferably represents hydrocarbons with a derivative of HRBFAAcyloxy groups of the chain.
In formula (I), R 2 Represent C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl, preferably C 1 -C 4 Alkyl groups, more preferably methyl groups. Derived from R by suitable conversion 2 Quaternizing the corresponding amine by treatment with a carbonising agent which is a carbonium of R 2 The ester-linked quaternary ammonium compounds of the present invention are incorporated.
In formula (I), R 3 And R is 4 Each independently represents- (C) n H 2n )R 6 、-(C n H 2n-1 )R 6 2 、C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl, preferably C 1 -C 4 Alkyl or- (C) n H 2n )R 6 More preferably methyl or- (C) n H 2n )R 6 . At the introduction of R 1 Before, R 3 And R is 4 Often already in the amine used to synthesize the ester-linked quaternary ammonium compounds of the present invention. For example, if R 3 And R is 4 Any one of which is C 1 -C 4 Alkyl, it may be present in an alkyl-dialkanolamine, such as N-methyldiethanolamine, or both may be present in a dialkyl-alkanolamine, such as N, N-dimethylethanolamine. Alternatively, if the amine used to synthesize the ester-linked quaternary ammonium compound contains an N-H bond, R can be incorporated during quaternization 1 Thereafter R is taken 3 And/or R 4 The ester-linked quaternary ammonium compounds of the present invention are incorporated.
Alternatively, if R 3 And R is 4 Any one of which is- (C) n H 2n )R 6 Or- (C) n H 2n-1 )R 6 2 Wherein R is 6 Is OH, it may be present as any of the alkanol moieties of the alkanolamine, such as dialkanolamine, trialkanolamine, alkyl-dialkanolamine, such as triethanolamine or derivatives thereof having two hydroxyl groups.
If R is 6 Is OR (OR) 2 It is usually at the correspondingThe quaternization of the amine is obtained from the corresponding alkanol moiety by reaction of the alkanol moiety with a quaternizing agent.
Alternatively, R 3 And R is 4 Any one of them may be- (C) n H 2n )R 6 Or- (C) n H 2n-1 )R 6 2 Preferably- (C) n H 2n )R 6 Wherein R is 6 Is C 12 -C 25 Acyloxy groups or C 12 -C 25 An alkoxycarbonyl group. In this case, R is generally as follows 1 R is defined in the same manner as 3 And/or R 4 The incorporation of the ester-linked quaternary ammonium compounds of the present invention, however, uses C 12 -C 25 The carboxylic acid replaces HRBFA, which may be the same as or different from HRBFA. Preferably, C is used 12 -C 25 The carboxylic acid results in a total iodine value of all fatty acids 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. For example, C 12 -C 25 The carboxylic acid may be different from HRBFA. In this case, saturated C is preferred 12 -C 25 Carboxylic acids, more preferably selected from saturated C 14 -C 20 Carboxylic acids, more preferably from saturated C 16 And C 18 Carboxylic acids, more preferably saturated C 16 Carboxylic acids, in this case having an iodine value of 0. If this is the case, C will typically be present before further processing by HRBFA into the ester-linked quaternary ammonium compounds of the present invention 12 -C 25 Carboxylic acid is blended to the HRBFA. Alternatively, C 12 -C 25 The carboxylic acid may be HRBFA, preferably HRBFA obtained from a non-edible source. In this case, R 6 C from which the hydrocarbon chain in (B) is derived 12 -C 25 The carboxylic acid may be R 5 HRBFA from which the hydrocarbon chains of (a) are derived, and/or obtainable in the same process as said HRBFA, and thus have an iodine value of from 0 to 75, more preferably from 1 to 70, more preferably from 10 to 65, more preferably from 15 to 60, more preferably from 20 to 55, more preferably from 25 to 50, by themselves.
Wherein R is 1 Representation- (C) n H 2n-1 )R 5 2 In embodiments of (2), R 2 、R 3 And R is 4 Each of (3)Each preferably represents C 1 -C 4 An alkyl group.
In formula (I), X – Represents an anionic counterion. Typically, such counter ions are incorporated during quaternization of the corresponding amine and are derived from the process used to introduce R 2 Quaternizing agents for the groups. Such quaternizing agents can be selected, for example, from the corresponding R 2 Oxygen of radicalsSalts, halides, phosphates, carbonates, sulfonates and sulfates. X is X - Thus can be removed by removing (R) 2 ) + Carbocations obtain the corresponding anions. Preferably X - Selected from the group consisting of halides and alkylsulfates, more preferably chloride or methylsulfate.
Furthermore, in formula (I), each n independently represents a number from 1 to 4, preferably a number from 2 to 3, more preferably 2. Preferably, each n is the same and represents 2.
In an embodiment of the invention, the ester-linked quaternary ammonium compound has the structure of formula (I) as defined above, wherein
R 2 Represent C 1 -C 4 Alkyl, preferably methyl;
R 3 and R is 4 Each independently represents C 1 -C 4 Alkyl, preferably methyl or- (C) n H 2n )R 6 ；
R 5 Represents an acyloxy group having a hydrocarbon chain derived from HRBFA;
each R 6 Independently represent OH, OR 2 Or C 12 -C 25 An acyloxy group;
X - represents a halide or alkylsulfate, preferably chloride or methylsulfate.
In another embodiment, the ester-linked quaternary ammonium compound has the structure of formula (I) as defined above, wherein each R 6 Independently represent OH, OR 2 Or an acyloxy group having a hydrocarbon chain derived from RBFA, preferably HRBFA.
In another embodiment, the ester-linked quaternary ammonium compound has the structure of formula (I) as defined above, wherein
R 3 Is C 1 -C 4 Alkyl, preferably methyl, or- (C) n H 2n )R 6 Wherein R is 6 Is OH OR OR 2 A kind of electronic device
R 4 Is- (C) n H 2n )R 6 Wherein R is 6 Is an acyloxy group having a hydrocarbon chain derived from RBFA, preferably HRBFA.
In another embodiment, the ester-linked quaternary ammonium compound has the structure of formula (I) as defined above, wherein R 3 And R is 4 Representation- (C) n H 2n )R 6 Wherein each R is 6 Independently represents OH OR OR 2 。
In another embodiment, the ester-linked quaternary ammonium compound has the structure of formula (I) as defined above, wherein R 3 And R is 4 Representation- (C) n H 2n )R 6 Wherein each R is 6 Is an acyloxy group having a hydrocarbon chain derived from RBFA, preferably HRBFA.
In another embodiment, the ester-linked quaternary ammonium compound has the structure of formula (I) as defined above, wherein R 3 And R is 4 Each independently represents C 1 -C 4 Alkyl groups, preferably methyl groups.
In one embodiment, the ester-linked quaternary ammonium compound has the structure of one of the following formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ij), (Ik), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu), (Iv) and (Iw), wherein R 5 And R is 6 Each representing an acyloxy group having a hydrocarbon chain derived from HRBFA, and X - Represents a halide or alkylsulfate, preferably chloride or methylsulfate.
In a preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Ia), (Ic), (Ie), (Ig), (Ij), (Im), (Io), (Iq), (Is) and (Iu). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Ib), (Id), (If), (Ih), (Ik), (In), (Ip), (Ir), (It) and (Iv). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of formula (Iw). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Ia) and (Ib). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Ic) and (Id).
In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Ie) and (If). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Ig) and (Ih). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Ij) and (Ik). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Im) and (In). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Io) and (Ip). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Iq) and (Ir). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Is) and (It). In another preferred embodiment, the ester-linked quaternary ammonium compound has the structure of one of formulas (Iu) and (Iv).
Another aspect of the 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 invention is thatThe 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 Represents an acyloxy group or an alkoxycarbonyl group having a hydrocarbon chain derived from a fatty acid other than HRBFA. In this case, the hydrocarbon chain is preferably derived from C having an iodine value of from 0 to 75, more preferably from 1 to 70, more preferably from 10 to 65, more preferably from 15 to 60, more preferably from 20 to 55, more preferably from 25 to 50 12 -C 25 Fatty acids. Also preferably, the hydrocarbon chain is derived from C 14 -C 20 More preferably derived from C 16 Or C 18 More preferably derived from C 16 Fatty acids, which are not HRBFA.
Alternatively, the mixture of the present invention may be a mixture of at least two of the ester-linked quaternary ammonium compounds of the present invention as described above, without other ester-linked quaternary ammonium compounds.
In one embodiment, the mixture of the present invention Is a mixture of ester-linked quaternary ammonium compounds having the structure of at least two of formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ij), (Ik), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu), (Iv) and (Iw), wherein R 5 And R is 6 Each representing an acyloxy group having a hydrocarbon chain derived from HRBFA, and X - Represents a halide or alkylsulfate, preferably chloride or methylsulfate. In a preferred embodiment, the mixture of the present invention Is a mixture of ester-linked quaternary ammonium compounds having the structure of at least two of formulas (Ia), (Ic), (Ie), (Ig), (Ij), (Im), (Io), (Iq), (Is) and (Iu). In another preferred embodiment, the mixture of the present invention is a mixture of ester-linked quaternary ammonium compounds having the structure of at least two of formulas (Ib), (Id), (If), (Ih), (Ik), (In), (Ip), (Ir), (It) and (Iv).
In another preferred embodiment, the mixture of the present invention Is a mixture of ester-linked quaternary ammonium compounds having the structure of at least two of formulas (Ia), (Is) and (Iu). In another preferred embodiment, the mixture of the present invention is a mixture of ester-linked quaternary ammonium compounds having the structure of at least two of formulas (Ib), (It) and (Iv). In another preferred embodiment, the mixture of the present invention is a mixture of ester-linked quaternary ammonium compounds having the structure of at least two of formulas (Ib), (It) and (Iv). In another preferred embodiment, the mixture of the present invention is a mixture of ester-linked quaternary ammonium compounds having the structure of at least two of formulas (Ic), (Ig), (Ij), (Im), (Io) and (Iq).
In another preferred embodiment, the mixture of the present invention is a mixture of ester-linked quaternary ammonium compounds having the structure of at least two of formulas (Id), (Ih), (Ik), (Ip) and (Ir).
Another aspect of the invention is a process for preparing an ester-linked quaternary ammonium compound or a mixture of ester-linked quaternary ammonium compounds comprising the steps of:
(i) Catalytically hydrogenating Rice Bran Fatty Acids (RBFAs) or mixtures of Rice Bran Fatty Acids (RBFAs) from a non-edible source to an iodine value of 0-75, preferably 1-70, more preferably 10-65, more preferably 15-60, more preferably 20-55, more preferably 25-50, so as to obtain at least partially Hydrogenated Rice Bran Fatty Acids (HRBFA) or mixtures of at least partially Hydrogenated Rice Bran Fatty Acids (HRBFAs);
(ii) Optionally mixing HRBFA or HRBFAs with one or more C 12 -C 25 Fatty acids such that the total iodine value of all fatty acids is in the range of 0-75, preferably 1-70, more preferably 10-65, more preferably 15-60, more preferably 20-55, more preferably 25-50;
(iii) Esterifying HRBFA or HRBFAs or (if applicable) the mixture obtained in step (II) with an alkanolamine of formula (II)
Wherein the method comprises the steps of
R 11 Representation- (C) n H 2n ) OH or- (C) n H 2n-1 )(OH) 2 Preferably- (C) n H 2n )OH；
R 31 And R is 41 Each independently represents- (C) n H 2n )OH、-(C n H 2n-1 )(OH) 2 、H、C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl, preferably- (C) n H 2n ) OH, H or C 1 -C 4 An alkyl group; and
each n independently represents a number of 1 to 4,
to obtain an Esteramine (EA) or a mixture of Esteramines (EAs),
(iv) EA or EAs is quaternized with a quaternizing agent, preferably dimethyl sulfate.
In step (i) of the method of the present invention, rice Bran Fatty Acids (RBFAs) from non-edible sources or a mixture of several Rice Bran Fatty Acids (RBFAs) from non-edible sources are used.
There is no particular limitation on the rice bran oil of non-edible origin from which the rice bran fatty acid is refined. However, it is desirable to select rice bran oil that is a byproduct of rice bran processing. The rice bran itself is not limited to specific rice bran, but rice bran which is a byproduct of rice processing is preferable.
Rice bran fatty acids from non-food sources are often obtained as a mixture of several fatty acids and often contain impurities that prevent the formation of high quality esterquats.
Therefore, it is preferable to separate the rice bran fatty acid from impurities before or after the catalytic hydrogenation. It may be advantageous to conduct the separation after catalytic hydrogenation in order to remove residual metal catalyst and by-products generated during catalytic hydrogenation. The separation technique of the rice bran fatty acids may include any known separation technique suitable for separating the fatty acids from each other and/or from additional impurities. Such separation techniques include, but are not limited to, crystallization, winterization, distillation, sublimation, filtration, adsorption onto high surface materials such as activated carbon or fuller's earth, chromatography, including columns, flash and high performance liquid chromatography, liquid-liquid extraction, and solid-liquid extraction.
Preferred separation techniques are crystallization, winterization and/or distillation. If a single Rice Bran Fatty Acid (RBFA) from a non-edible source is used, at least one of the above separation techniques has to be applied after removal of impurities and before catalytic hydrogenation, as the non-edible source typically contains a mixture of different rice bran fatty acids. If a mixture of Rice Bran Fatty Acids (RBFAs) from non-edible sources is used, the mixture may be used without isolation of any single RBFA or after removal of a certain RBFA.
In step (i) of the process of the invention, the RBFAs or RBFAs are subjected to catalytic hydrogenation. This step is typically carried out using hydrogen in the presence of a hydrogenation catalyst. Preferably, the hydrogenation catalyst is a group 8, 9, 10 or 11 transition metal hydrogenation catalyst, such as 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. Preferably, the hydrogenation catalyst is a nickel hydrogenation catalyst. Catalytic hydrogenation is generally carried out in the absence of oxygen, which can be obtained, for example, by flushing the reaction vessel with an inert gas such as nitrogen, argon or helium. In this case, the flushing is performed for at least 20min, preferably at least 40min, more preferably at least 60min. Alternatively, the reaction vessel may be flushed with hydrogen for use in a subsequent hydrogenation reaction.
Alternatively, oxygen-free may be achieved by repeatedly applying a vacuum to the container and filling the container with an inert gas or with hydrogen. In this case, the vacuum and filling are performed at least twice, preferably at least 3 times, more preferably at least 5 times.
For example, the catalytic hydrogenation of step (i) may be carried out at a reaction temperature of from 60 to 300 ℃, preferably from 100 to 250 ℃, more preferably from 150 to 200 ℃, more preferably from 160 to 180 ℃, more preferably from 170 to 175 ℃. Furthermore, the catalytic hydrogenation of step (i) may be carried out, for example, in the range of from 3 to 15kg/cm 2 More preferably 5-12kg/cm 2 More preferably 7-10kg/cm 2 More preferably 7.5-8kg/cm 2 Is carried out under hydrogen pressure. In one embodiment, the reaction temperature is in the range of 100 to 250℃and 3 to 15kg/cm 2 Catalytic hydrogenation is carried out under hydrogen pressure. In another embodiment, the reaction temperature is in the range of 150 to 200℃and 5 to 12kg/cm 2 Catalytic hydrogenation is carried out under hydrogen pressure.
In another oneIn embodiments, the reaction temperature is between 160 and 180℃and between 7 and 10kg/cm 2 Catalytic hydrogenation is carried out under hydrogen pressure. In another embodiment, the reaction temperature is in the range of 170-175℃and 7.5-8kg/cm 2 Catalytic hydrogenation is carried out under hydrogen pressure. The catalyst loading may be, for example, from 0.01 to 2 wt%, preferably from 0.05 to 1 wt%, more preferably from 0.1 to 0.8 wt%, and even more preferably from 0.3 to 0.5 wt%, based on the total weight of the RBFA.
The catalytic hydrogenation of step (i) is carried out until the RBFA or RBFAs is at least partially hydrogenated to an iodine value of 0-75, preferably 1-70, more preferably 10-65, more preferably 15-60, more preferably 20-55, more preferably 25-50, so as to obtain at least partially Hydrogenated Rice Bran Fatty Acids (HRBFA) or a mixture of at least partially Hydrogenated Rice Bran Fatty Acids (HRBFAs).
RBFA contain mono-and polyunsaturated fatty acids. Thus, catalytic hydrogenation of RBFA typically results in a mixture of cis and trans fatty acids. Although all HRBFAs, independent of their cis and trans content, may be used to prepare the ester-linked quaternary ammonium compounds, preferably HRBFAs having a trans content of less than 20 wt%, more preferably less than 15 wt%, more preferably less than 10 wt% and even more preferably less than 5 wt%, based on the total weight of HRBFAs, are used.
In optional step (ii), the HRBFA or HRBFAs may be combined with one or more C 12 -C 25 The fatty acids are mixed such that the total iodine value of all fatty acids is in the range of 0-75, preferably 1-70, more preferably 10-65, more preferably 15-60, more preferably 20-55, more preferably 25-50. If a specific distribution is desired for a particular application, which is not available through RBFA from a non-edible source being used, this step is typically performed in order to adjust the distribution of the hydrocarbon chains of the final ester-linked quaternary ammonium compound.
These fatty acids are preferably selected from saturated C 14 -C 20 Fatty acids, more preferably selected from saturated C 16 Or C 18 Fatty acids, more preferably saturated C 16 Fatty acids. In one embodiment, step (ii) is performed. In another embodiment, step (ii) is not performed. If step (ii) is carried out, the fatty acid is preferably obtained from a non-edible source.
In step (iii), HRBFA, HRBFAs or (if step (II)) the mixture obtained in step (II) is subjected to an esterification reaction with an alkanolamine of formula (II)
Wherein the method comprises the steps of
R 11 Representation- (C) n H 2n ) OH or- (C) n H 2n-1 )(OH) 2 Preferably- (C) n H 2n )OH；
R 31 And R is 41 Each independently represents- (C) n H 2n )OH、-(C n H 2n-1 )(OH) 2 、H、C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl, preferably- (C) n H 2n ) OH, H or C 1 -C 4 An alkyl group; and
each n independently represents a number of 1 to 4,
to obtain an Esteramine (EA) or a mixture of Esteramines (EAs).
The esterification reaction of step (iii) is typically carried out at a temperature of between 50 and 250 ℃, preferably between 100 and 220 ℃, more preferably between 150 and 200 ℃. If the temperature is too low, the reaction is considerably retarded and thus unsuitable for 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 at ambient pressure.
Preferably, the esterification step (i) is carried out under conditions such that the water produced is continuously removed from the reaction vessel. For example, water removal may be accomplished by: molecular sieves are added to the reaction mixture, a Dean-Stark apparatus (Dean-Stark-appaatus) or a distillation apparatus is connected to the reaction vessel, or a vacuum is applied to the reaction vessel. More preferably, the reaction is carried out under vacuum and/or using a connected distillation apparatus.
In one embodiment, the alkanolamine of formula (II) is selected from those having the structure of any one of formulas (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIg), (IIh), (IIj), (IIk), (IIm), (IIn), (IIo), (IIp) and (IIq) below.
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In another embodiment, the alkanolamine is selected from those having the structure of any of formulas (IIa), (IIc), (IIe), (IIg), (IIj), and (IIm). In another embodiment, the alkanolamine is selected from those having the structure of any of formulas (IIb), (IId), (IIf), (IIh), (IIk), and (IIn). In another embodiment, the alkanolamine is selected from those having the structure of any one of formulas (IIo), (IIp) and (IIq). In another embodiment, the alkanolamine is selected from those having the structure of any one of formulas (IIa), (IIe) and (IIm). In another embodiment, the alkanolamine is selected from those having the structure of any one of formulas (IIb), (IId), and (IIn).
The alkanolamine used in the process according to the present invention may be any alkanolamine, however tertiary alkanolamines are preferred due to possible side reactions of the N-H amine with HRBFA during the esterification step. Even more preferred are trialkanolamines, especially triethanolamine.
The molar ratio of rice bran fatty acid to alkanolamine in the esterification step (iii) is generally in the range of from 1:2 to 3:1, preferably 1:1 to 3:1, more preferably 1:1 to 2:1. If the ratio is too low, the resulting esteramine is formed at an undesirably low concentration. However, if the ratio is too high, the resulting product exceeds the desired acidity. Thus, depending on the ratio and alkanolamine used, the resulting Esteramine (EA) or mixture of Esteramines (EAs) may contain mono-, di-, tri-or mixtures thereof.
The quaternization reaction of step (iv) is generally carried out at a temperature of from 0 to 180 ℃, preferably from 20 to 120 ℃, more preferably from 50 to 100 ℃. If the temperature is too low, the reaction is considerably retarded and thus unsuitable for industrial scale.
However, if the temperature is too high, the decomposition products occur at a higher rate and undesired methylation of other functional groups may occur.
The quaternizing agent in quaternization step (iv) is not particularly limited and may be selected from, for example, trialkyloxySalts, alkyl halides, dialkyl phosphates, dialkyl carbonates, alkyl sulfonates and dialkyl sulfates, however dialkyl sulfates and alkyl halides are preferred, especially dimethyl sulfate and methyl chloride, especially dimethyl sulfate.
The molar ratio between esteramine and quaternizing agent in quaternization step (iv) is generally 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, quaternization of the esteramine or the mixture of esteramines is incomplete after the reaction is complete. If the ratio is too high, there is a risk that other functional groups of the product are alkylated.
Preferably, at least a portion of the quaternization step (iv), often the complete quaternization step (iv), is carried out in the absence of solvent, as the solvent may be alkylated by the quaternizing agent, which may result in an increased odor of the final product. However, the solvent or solvents may be added to the resulting mixture after the quaternization is at least partially or fully completed. The solvent is not particularly limited, and the solvent may be selected from, for example, lower alcohols having 1 to 6 carbon atoms such as ethanol, propanol, isopropanol, etc.; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, and glycerin, and they may be used alone or in combination thereof. Preferably, the solvent added after the quaternization step is at least partially completed is the polyol propylene glycol or alcohol, more preferably ethanol, isopropanol or propylene glycol.
The solvent may comprise additional solvent components such as aromatic hydrocarbons, aliphatic hydrocarbons, ethers, esters, lactones, lactams, amides, amines, furans, and the like. Preferably, the solvent does not contain any of these additional solvent components.
The process according to the invention results in an ester-linked quaternary ammonium compound or a mixture of ester-linked quaternary ammonium compounds having a high quality. The ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds has a low acid number, a low odor level and a low colored stain level.
The acid number of the ester-linked quaternary ammonium compound or the mixture of ester-linked quaternary ammonium compounds prepared by the process according to the invention is generally below 7mg KOH/g of the sample and is generally derived from the content of free fatty acids and amine salts in the product. The acid number can be determined by the latest standard method DIN EN ISO 2114.
The odor of the ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds results mainly from the solvent used in or after quaternization step (ii), which is often alkylated by quaternizing agents to give compounds with unpleasant odor. The ester-linked quaternary ammonium compound or mixture of ester-linked quaternary ammonium compounds obtainable by the process of the present invention generally comprises an alkylated solvent, preferably an alkylated alcohol, in particular methylethyl ether or methylisopropyl ether, in an amount of less than 10000ppm, preferably less than 5000ppm, more preferably less than 2000ppm, as a sample of the mixture of ester-linked quaternary ammonium compounds or ester-linked quaternary ammonium compounds 1 The corresponding resonance signal in the H NMR spectrum is preferably determined by integration of the signal of the presence of the methyl group introduced by the quaternizing agent.
The color of the ester-linked quaternary ammonium compound or the mixture of ester-linked quaternary ammonium compounds obtained by the process according to the invention generally has a value of less than 8, preferably less than 5, more preferably less than 4 on the gardner color, according to the latest standard method ASTM D1544.
The ester-linked quaternary ammonium compound or the mixture of ester-linked quaternary ammonium compounds obtained by the process according to the invention preferably has an active ester quaternary ammonium salt content of more than 0.7meq/g, more preferably more than 0.8meq/g, most preferably more than 1.0meq/g, measured by Epton titration according to the latest standard method DIN EN ISO 2871.
Another aspect of the 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 producing an ester-linked quaternary ammonium compound or a mixture of ester-linked quaternary ammonium compounds, wherein the HRBFA or HRBFAs has an iodine number of 0-75, preferably 1-70, more preferably 10-65, more preferably 15-60, more preferably 20-55, more preferably 25-50.
The invention is disclosed in more detail in the following examples and claims.
Examples
Examples 1,2 and 3 (hydrogenation of RBFA)
Mixtures of Rice Bran Fatty Acids (RBFAs) from the non-edible fraction obtained during refining of rice bran oil were subjected to catalytic hydrogenation using a pressure reactor and a nickel catalyst for fatty acid hydrogenation (SCAT 2234 obtained from Suhans Chemicals). 7000kg of premelted RBFAs are charged into the pressure reactor and 28kg of catalyst are added.
The mixture was purged of oxygen by nitrogen and heated to 170-175 ℃. Introducing hydrogen into the reactor and maintaining the pressure of the hydrogen at 7.5-8kg/cm 2 . The hydrogenation reaction (gas chromatography) was monitored by analysis of iodine number and composition. Three 50kg HRBFA samples, each having an iodine value of 49.0 (example 1), 38.8 (example 2) and 30.4 (example 3), were separated after 120min, 180min and 240min, respectively, and filtered through a filter press for additional use. The parameters of the hydrogenation reaction are listed in table 1.
TABLE 1
Hydrogenation parameters Value of
Reaction temperature (. Degree. C.) 170–175
Reaction time (min) 240
Reaction pressure (kg/cm) 2 ) 7.5–8.0
Catalyst SCAT 2234
Catalyst loading (wt%) 0.4
The composition of the fatty acids in HRBFA obtained from hydrogenation is listed in table 2.
TABLE 2
C-16 and C-18 represent the C chain length, ":1" and ":2" represent the number of unsaturated bonds.
Examples 4, 5 and 6 (transformations)
The HRBFA samples from examples 1,2 and 3 were further converted to ester-linked ammonium compounds by the following method.
2250g (8 moles) of HRBFAs were subjected to a reaction with 787g of triethanolamine (5.28 moles) at 180℃for 6 hours at atmospheric pressure, with 0.2g of catalyst hypophosphorous acid (25 ppm) and water was continuously removed by distillation. 2900g of a mixture of esteramines (5.28 mol) are separated off and cooled to room temperature.
2800g (5.11 moles) of EA was heated to 80℃and 628g (4.9 moles) of dimethyl sulphate (DMS) were added over a 105 minute period and the reaction continued for a further 10 minutes to allow DMS to react. The formation of highly viscous material indicates a reaction with DMS. Thereafter, 380g of ethanol was continuously added over a period of 80 minutes and the reaction was continued at 80℃for two further hours. Approximately 3810g of a pale yellow mixture of ester-linked ammonium compounds was obtained. The results are set forth in Table 3.
TABLE 3 Table 3
The ester-linked ammonium compounds of examples 4, 5 and 6 were evaluated by measuring softness of towels using PharbOmetter (Nu Cybertek Inc.) according to their standard procedure (AATCC test method TM 202) and compared to commercially available products made from palm oil fatty acid based esterquat Praetagen TQOV-IPA.
Cleaning procedure:
the white towel (100% cotton, brand: rhema, indonesia, 30 cm. Times.28 cm) was pre-cleaned with a conventional cleaning agent. 25g of the ester-linked ammonium compound were dissolved in tap water and stirred for 1 minute. The pre-cleaned towel was immersed in the solution for 30 minutes and dried. The dried towels were conditioned in a room with constant humidity and temperature. Softness was evaluated by relative hand values (RHV, AATCC test method TM202, nu Cybertek inc.) where higher values indicate softer fabrics. The results are set forth in Table 4.
TABLE 4 Table 4
Sample name RHV
Untreated reference 0
Example 4 6.28
Example 5 6.44
Example 6 6.45
Praepagen TQOV-IPA 5.52
From the results it is evident that the ester-linked quaternary ammonium compounds of the present invention can be used to obtain softer fabrics than commercially available palm oil fatty acid based ester quaternary ammonium salts such as Praepagen TQOV-IPA (belonging to Clariant).

Claims (15)

1. An ester-linked quaternary ammonium compound comprising at least one hydrocarbon chain derived from at least one Rice Bran Fatty Acid (RBFA) from a non-edible source, wherein RBFA is an at least partially Hydrogenated Rice Bran Fatty Acid (HRBFA) and has an iodine value of 0-75.
2. The ester-linked quaternary ammonium compound according to claim 1, wherein HRBFA is a partially hydrogenated rice bran fatty acid having an iodine number of 1-70, in particular 10-65.
3. The ester-linked quaternary ammonium compound according to claim 1 or 2, having the structure of formula (I)
Wherein the method comprises the steps of
R 1 Representation- (C) n H 2n )R 5 Or- (C) n H 2n-1 )R 5 2 Preferably- (C) n H 2n )R 5 ；
R 2 Represent C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl;
R 3 and R is 4 Each independently represents- (C) n H 2n )R 6 、-(C n H 2n-1 )R 6 2 、C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl;
each R 5 Independently represents an acyloxy group having a hydrocarbon chain derived from HRBFA or an alkoxycarbonyl group having a hydrocarbon chain derived from HRBFA;
each R 6 Independently represent OH, OR 2 、C 12 -C 25 Acyloxy groups or C 12 -C 25 An alkoxycarbonyl group;
X – represents an anionic counterion;
each n independently represents a number of 1 to 4.
4. The ester-linked quaternary ammonium compound of claim 3, wherein
R 2 Represent C 1 -C 4 Alkyl, preferably methyl;
R 3 and R is 4 Each independently represents C 1 -C 4 Alkyl, preferably methyl or- (C) n H 2n )R 6 ；
R 5 Represents an acyloxy group having a hydrocarbon chain derived from HRBFA;
each R 6 Independently represent OH, OR 2 Or C 12 -C 25 An acyloxy group;
X - represents a halide or alkylsulfate, preferably chloride or methylsulfate.
5. The ester-linked quaternary ammonium compound of claim 3 or 4, wherein each n is 2.
6. The ester-linked quaternary ammonium compound of any one of claims 3 to 5, wherein each R 6 Independently represent OH, OR 2 Or derived from RBFA, preferably derived fromAcyloxy groups from the hydrocarbon chain of HRBFA.
7. The ester-linked quaternary ammonium compound according to any one of claims 3 to 6, wherein
R 3 Is C 1 -C 4 Alkyl, preferably methyl, or- (C) n H 2n )R 6 Wherein R is 6 Is OH OR OR 2 A kind of electronic device
R 4 Is- (C) n H 2n )R 6 Wherein R is 6 Is an acyloxy group having a hydrocarbon chain derived from RBFA, preferably HRBFA.
8. The ester-linked quaternary ammonium compound according to any one of claims 3 to 6, wherein R 3 And R is 4 Representation- (C) n H 2n )R 6 Wherein each R is 6 Independently represents OH OR OR 2 。
9. A mixture of ester-linked quaternary ammonium compounds comprising at least one, preferably at least two ester-linked quaternary ammonium compounds according to any one of claims 1 to 8.
10. A process for preparing an ester-linked quaternary ammonium compound or a mixture of ester-linked quaternary ammonium compounds comprising the steps of:
(i) Catalytically hydrogenating Rice Bran Fatty Acids (RBFAs) or mixtures of Rice Bran Fatty Acids (RBFAs) from non-edible sources to an iodine value of 0-75 to obtain at least partially Hydrogenated Rice Bran Fatty Acids (HRBFA) or mixtures of at least partially Hydrogenated Rice Bran Fatty Acids (HRBFAs);
(ii) Optionally mixing HRBFA or HRBFAs with one or more C 12 -C 25 Fatty acids such that the total iodine value of all fatty acids is in the range of 0-75;
(iii) Esterifying HRBFA or HRBFAs with alkanolamine of formula (II) or, if applicable, the mixture obtained in step (II)
Wherein the method comprises the steps of
R 11 Representation- (C) n H 2n ) OH or- (C) n H 2n-1 )(OH) 2 Preferably- (C) n H 2n )OH；
R 31 And R is 41 Each independently represents- (C) n H 2n )OH、-(C n H 2n-1 )(OH) 2 、H、C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl or C 2 -C 4 Alkynyl, preferably- (C) n H 2n ) OH, H or C 1 -C 4 An alkyl group; and
each n independently represents a number of 1 to 4,
to obtain an Esteramine (EA) or a mixture of Esteramines (EAs),
(iv) EA or EAs is quaternized with a quaternizing agent, preferably dimethyl sulfate.
11. The process according to claim 10, wherein the alkanolamine in esterification step (iii) is a trialkanolamine, a dialkanolamine or an alkyl-dialkanolamine, preferably triethanolamine.
12. The process according to claim 10 or 11, wherein at least a part, preferably the complete quaternization step (iv) is performed in the absence of solvent, and the solvent is optionally added only after at least a partial, preferably complete, completion of the quaternization step (iv).
13. The process according to any one of claims 10 to 12, wherein a solvent is added after the quaternization step (iv) and is propylene glycol or an alcohol, preferably ethanol, isopropanol or propylene glycol.
14. The process according to any one of claims 10 to 13, wherein the catalytic hydrogenation in step (i) is carried out using hydrogen in the presence of a group 8, 9, 10 or 11 transition metal hydrogenation catalyst, preferably a nickel catalyst.
15. 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 producing an ester-linked quaternary ammonium compound or a mixture of ester-linked quaternary ammonium compounds, wherein the HRBFA or the HRBFAs have an iodine value of 0-75.
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