Oleyl alcohol and production method

Abstract

The present invention relates to oleyl alcohol, wherein the oleyl chain is obtained from a mixture of oils (1): oils (2) from 1:9 to 6:4, preferably 2:8 to 5:5, wherein oil (1) is selected from palm oil, cottonseed oil or mixtures thereof, and oil (2) is selected from tall oil, olive oil, canola oil, sunflower oil variants containing more than 60 wt% oleic acid or mixtures thereof, by hydrogenation of a fatty acid, a fatty acid methyl ester or a combination thereof to provide a fatty alcohol; and to a process for preparing said oleyl alcohol.

Description

Technical Field

[0001] This invention relates to a method for producing oleyl alcohol, which is a useful intermediate in the production of surfactants. Background Technology

[0002] Oil-based surfactants such as oleyl ether carboxylates, oleyl ether sulfates, oleyl alcohol ethoxylates, and oleyl sulfates can be used in laundry detergents. Surfactants can be synthesized from oleyl alcohol, which is obtained from palm oil or palm kernel oil by converting triglycerides to fatty acids or methyl esters, followed by distillation to obtain the oleic acid fraction, and then reducing (hydrogenating) the carboxylic acid or methyl ester to an alcohol. The resulting oleyl alcohol is primarily a mixture of oleyl alcohol with significant levels of palmitol and stearyl alcohol. The balance of these components is important in controlling the detergency and physical form of the surfactant.

[0003] US5,672,781 (Henkel) discloses a fatty alcohol produced from palm kernel oil, wherein the palm kernel oil is transesterified to methyl ester, followed by fractional distillation and then hydrogenation to obtain the fatty alcohol. A similar method is also disclosed for producing fatty alcohols from a 70:30 wt% mixture of palm kernel oil methyl ester and rapeseed oil methyl ester. This method requires fractional distillation to high temperatures, which demands considerable energy for heating. The method also produces waste fractions.

[0004] There is a need for an improved method for producing oleyl alcohols and surfactants synthesized from them, using simpler chemical processes that involve fewer high-energy steps and produce fewer waste fractions.

[0005] Surprisingly, this problem can be solved by the method of the present invention and by oleic alcohol. Summary of the Invention

[0006] This invention relates to oleyl alcohols, wherein the oil-based chain is obtained by hydrogenation of fatty acids, fatty acid methyl esters or combinations thereof to provide fatty alcohols in a mixture of oil (1): oil (2) ranging from 1:9 to 6:4, preferably 2:8 to 5:5, wherein oil (1) is selected from palm oil, cottonseed oil or mixtures thereof, and oil (2) is selected from tall oil, olive oil, low erucic acid rapeseed oil, sunflower oil variants containing more than 60% by weight of oleic acid, or mixtures thereof.

[0007] Preferably, oil (1) is palm oil, and oil (2) is selected from low erucic acid rapeseed oil and sunflower seed oil variants containing more than 60% by weight of oleic acid, or mixtures thereof, more preferably low erucic acid rapeseed oil.

[0008] Preferably, an oil-based surfactant derived from oleyl alcohol is present, wherein the oil-based chain is obtained by hydrogenation of fatty acids, fatty acid methyl esters or combinations thereof to provide fatty alcohol in a mixture of oil (1): oil (2) ranging from 1:9 to 6:4, preferably 2:8 to 5:5, wherein oil (1) is selected from palm oil, cottonseed oil or mixtures thereof, and oil (2) is selected from tall oil, olive oil, low erucic acid rapeseed oil, sunflower oil variants containing more than 60% by weight of oleic acid, or mixtures thereof.

[0009] Preferably, the surfactant is selected from oleyl sulfate, oleyl alcohol ethoxylate, oleyl ether sulfate, oleyl ether carboxylate and oleyl sulfosuccinate, and more preferably from oleyl alcohol ethoxylate, oleyl ether sulfate and oleyl ether carboxylate.

[0010] Preferably, the surfactant as described above is part of the liquid detergent composition, and more preferably, the liquid laundry detergent composition contains 0.5-50% by weight of the oil-based surfactant.

[0011] In a second aspect of the invention, a method for producing oleyl alcohol is provided, comprising the steps of: -

[0012] a) Hydrogenation of fatty acids, fatty acid methyl esters, or combinations thereof to provide fatty alcohols;

[0013] The fatty acid, fatty acid methyl ester oil or combination thereof contains an oil-based chain obtained from a mixture of oil (1) and oil (2) in a ratio of 1:9 to 6:4, preferably 2:8 to 5:5, wherein oil (1) is selected from palm oil, cottonseed oil or a mixture thereof, and oil (2) is selected from tall oil, olive oil, low erucic acid rapeseed oil, sunflower oil variant containing more than 60% by weight of oleic acid, or a mixture thereof.

[0014] Preferably, in this method, oil (1) is palm oil, and oil (2) is selected from low erucic acid rapeseed oil and sunflower oil variants containing more than 60% by weight of oleic acid, or mixtures thereof, preferably wherein oil (2) is low erucic acid rapeseed oil.

[0015] Preferably, in this method, oleyl alcohol is converted into a surfactant, more preferably into a surfactant selected from the following: oleyl sulfate, oleyl alcohol ethoxylate, oleyl ether sulfate, oleyl ether carboxylate and oleyl sulfosuccinate, more preferably oleyl alcohol ethoxylate, oleyl ether sulfate and oleyl ether carboxylate.

[0016] Preferably, in this method, fatty acid methyl esters are produced by triglyceride transesterification to fatty acid methyl esters, followed by the removal of glycerol. Detailed Implementation

[0017] Unless otherwise stated, the indefinite article “a” or “one” and its corresponding definite article “the” as used herein refer to at least one or more.

[0018] Weight % refers to the amount of an ingredient by weight based on the total weight of the composition. For anionic surfactants, weight % is calculated based on the protonated form of the surfactant.

[0019] The production of oleyl alcohol

[0020] This article provides a method for producing oleyl alcohol, which includes the following steps: -

[0021] a) Hydrogenation of fatty acids, fatty acid methyl esters, or combinations thereof to provide fatty alcohols;

[0022] The fatty acid, fatty acid methyl ester oil or combination thereof contains an oil-based chain obtained from a mixture of oil (1) and oil (2) in a ratio of 1:9 to 6:4, preferably 2:8 to 5:5, wherein oil (1) is selected from palm oil, cottonseed oil or a mixture thereof, and oil (2) is selected from tall oil, olive oil, low erucic acid rapeseed oil, sunflower oil variants containing more than 60% by weight of oleic acid, or a mixture thereof.

[0023] Surfactants are generated from oleyl alcohol.

[0024] Oil alcohols are useful intermediates in the production of various surfactants. Examples of oil-based surfactants are as follows.

[0025] hydrogenation

[0026] Fatty alcohols are typically prepared by reducing the corresponding fatty acids or esters, usually via catalytic hydrogenation. They can be produced from fatty acid methyl esters by hydrogenation typically at 250–350 °C and 200–275 bar hydrogen pressure in the presence of a mixed catalyst containing chromium or zinc.

[0027] For example, using a CuCrO4 catalyst, fatty acid methyl esters can be hydrogenated to alcohols in a typical hydrogenation reactor at a pressure of about 225 bar and a temperature of 275 to 330 °C. The use of copper chromite is described by Homer Adkins in Catalytic Hydrogenation of Esters to Alcohols (2011 Organic Reactions, Inc. Published by John Wiley and Sons, Inc.). Its method is also discussed in Sanchez MA et al. J. Chem. Technol. Biotechnol 2017; 92: 27-92; Thakur, DS et al. JAOCS vol 76 (1999) 995-1000 and Ullmann's Enzyclopaedie der technischen Chemie, Verlag Chemie, Weinheim, 4th Edition, Vol. 11, 436, et seq. Other catalysts based on transition metals such as Ru or Fe can be used as described in Organometallics 2015, 34, 1, 335–339; Chimica Oggi Catalysis & Biocatalysis 2019, 37(4), 10. Lindlar catalysts (palladium on calcium carbonate; lead-poisoned) can also be used, ACS Omega 2020, 5, 36, 22901-22913.

[0028] Preferably, the cis configuration of the double bonds on the oil base chain is maintained.

[0029] Preferably, the alcohol of the present invention has a C16 fraction of 10 to 28 wt% and a C18 fraction of greater than 70 wt%. Preferably, the C18 fraction is greater than 50 wt%, more preferably greater than 70 wt% monounsaturated.

[0030] The content of conjugated olefins is preferably less than 6% by weight, more preferably less than 4% by weight, and most preferably less than 2% by weight. The content of linoleic acid is preferably less than 6% by weight, more preferably less than 4% by weight, and most preferably less than 2% by weight. The content of linolenic acid is preferably less than 4% by weight, more preferably less than 1% by weight, and most preferably less than 0.4% by weight.

[0031] Formation of fatty acids

[0032] Fatty acids can be hydrolyzed by alkali or enzymes, and then glycerol can be removed to form triglycerides.

[0033] Ester exchange

[0034] The transesterification reaction of triglycerides to fatty acid methyl esters and glycerol is discussed in Fattah et al. (Front. Energy Res., June 2020, Vol. 8, Chapter 101) and its references. In this transesterification process, glycerides react with methanol in the presence of a catalyst to form fatty acid methyl esters and glycerol. Strong bases or strong acids can be used as catalysts, such as NaOH, KOH, sodium methoxide, or potassium methoxide.

[0035] In a typical process, the alcohol, base catalyst, and oil are combined in a reactor and stirred at 60°C for approximately 1 hour. Batch reactors or continuous flow processes involving continuous stirred tank reactors (CSTRs) or plug flow reactors can be used. After the reaction, glycerol is removed from the methyl ester. Due to the low solubility of glycerol in the ester, this separation usually occurs rapidly and can be accomplished using a settling tank or centrifuge.

[0036] After separation from glycerol, the methyl ester is passed through a methanol stripper, typically a vacuum flash evaporator or a falling film evaporator, before proceeding to the neutralization and water washing steps. Acid is added to neutralize any residual catalyst and decompose any soaps that may have formed during the reaction. The soaps react with the acid to form water-soluble salts and free fatty acids. The salts are removed during the water washing step, and the free fatty acids remain in the methyl ester.

[0037] Triglyceride source

[0038] The palm oil used in this invention is selected from crude palm oil and refined bleached and deodorized palm oil derived therefrom, or neutralized bleached and deodorized palm oil, including fractionated derivatives stearin and olein.

[0039] Crude palm oil is extracted from the pulp (mesocarp) of the fruit of the oil palm, preferably the African oil palm (Elaeis guineensis). Palm oil is preferably from non-logged, non-peat, and non-mined palm oil.

[0040] Palm oil is discussed in Palm Oil (1st Edition), Production, Processing, Characterization, and Uses, edited by Oi-Ming Lai Chin-Ping Tan Casimir Akoh (Academic Press and AOCS Press 2012).

[0041] Low-erucic acid rapeseed oil (canola oil) is discussed in Canola and Rapeseed, edited by F. Shahidi (Springer 1990). High-oleic acid variants may be used. The oil may be partially hydrogenated to reduce its content of polyunsaturated fatty acids; however, the oleic acid fraction should not be significantly reduced. Preferably, low-erucic acid rapeseed oil contains up to 2% by weight, preferably 0.5% by weight, of erucic acid.

[0042] Standard sunflower seed oil is naturally rich in polyunsaturated linoleic acid, comprising approximately 70% of the total sunflower seed oil content, and monounsaturated oleic acid, comprising 20%. Medium-oleic, high-oleic, and high-stearic / high-oleic sunflower seed oils are variants in which the oil contains more than 60% by weight of oleic acid. High-oleic and high-stearic / high-oleic variants are more preferred, with the high-oleic variant being the most preferred. The fatty acid composition of high-oleic sunflower seed oil is typically 82% oleic acid, 9% linoleic acid, and 9% saturates. The fatty acid composition of high-stearic / high-oleic sunflower seed oil is typically 72% oleic acid, 5% linoleic acid, 18% stearic acid, and 5% other saturates.

[0043] Cottonseed oil is produced from the seeds of various cotton plants, primarily upland cotton (Gossypium hirsutum) and herbaceous cotton (Gossypium herbaceum).

[0044] Olive oil is obtained from the fruit of the olive tree, belonging to the Oleaceae family. Linton olive oil, a non-edible olive oil, is the preferred type.

[0045] The oleyl alcohol of the present invention, wherein the oil-based chain is obtained by hydrogenation of fatty acids, fatty acid methyl esters or combinations thereof to provide a fatty alcohol in a mixture of oil (1): oil (2) ranging from 1:9 to 6:4, preferably 2:8 to 5:5, wherein oil (1) is selected from palm oil, cottonseed oil or mixtures thereof, and oil (2) is selected from tall oil, olive oil, low erucic acid rapeseed oil, sunflower oil variants containing more than 60% by weight of oleic acid, or mixtures thereof.

[0046] Preferably, oil (1) is palm oil, and oil (2) is selected from low erucic acid rapeseed oil and sunflower seed oil variants containing more than 60% by weight of oleic acid, or mixtures thereof, more preferably low erucic acid rapeseed oil.

[0047] The preferred iodine value is 65 to 85, more preferably 65 to 75, and most preferably 70 to 75.

[0048] Oil-based surfactants

[0049] Oleols are converted into surfactants by chemically attaching water-soluble head groups to OH groups, preferably selected from sulfates, ethoxylates, ether sulfates, ether carboxylates, and sulfosuccinates, more preferably ethoxylates, ether sulfates, and ether carboxylates.

[0050] Anionic surfactants are discussed in Helmut W.'s edited book, Anionic Surfactants Organic Chemistry (Marcel Dekker 1996).

[0051] The integers “q”, “m”, and “n” are the mole averages.

[0052] oleyl alcohol ethoxylate

[0053] Oleyl alcohol ethoxylates can be synthesized via the ethoxylation of oleyl alcohol R1-OH through the following reaction:

[0054] R1-OH + q-ethylene oxide → R1-O-(CH2CH2O) q -H

[0055] The oleyl alcohol ethoxylate preferably has a q of 4-20, more preferably 5-14, and most preferably 8, 9, 10, 11, or 12.

[0056] The ethoxylation reaction is described in Non-Ionic Surfactant Organic Chemistry (NMvan Osed), Surfactant Science Series Volume 72, CRC Press.

[0057] Preferably, the ethoxylation reaction is catalyzed by a base, using NaOH, KOH, or NaOCH3. Even more preferably, catalysts providing a narrower ethoxy group distribution than NaOH, KOH, or NaOCH3 are preferred. These narrower distribution catalysts preferably include Group II bases, such as barium dodecanoate; Group II metal alkoxides; and Group II hydrotalcites, as described in WO2007 / 147866. Lanthanides may also be used.

[0058] Preferably, the narrow ethoxy group distribution has a concentration of greater than 70% by weight, more preferably greater than 80% by weight in RO-(CH2CH2O). x -H to RO-(CH2CH2O) y Alcohol ethoxylates in the -H range RO-(CH2CH2O) q -H, where q is the molar average degree of ethoxylation, and x and y are absolute numbers, where x = q - (q / 2) and y = q + (q / 2). For example, when q = 10, then more than 70% by weight of alcohol ethoxylates should consist of ethoxylates having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 ethoxylate groups.

[0059] Oil-based ether sulfate

[0060] Oil-based ether sulfates preferably have the following formula:

[0061] R1-O-(CH2CH2O) m -SO3H

[0062] Wherein m is preferably 3 to 20, more preferably 4 to 12, and even more preferably 5, 6, 7, or 8.

[0063] Ether sulfates are discussed in *Anionic Surfactants: Organic Chemistry* (Marcel Dekker 1996), edited by Helmut W. Stache, published in the Surfactant Science Series by CRC Press. Ether sulfates can be synthesized by sulfonation of the corresponding alcohol ethoxylates.

[0064] Oil-based ether carboxylates

[0065] Oil-based ether carboxylates preferably have the following formula:

[0066] R1-O-(CH2CH2O) n -CH2COOH

[0067] Preferably, n is 5-20, more preferably 6-14, and most preferably 8, 9, 10, 11, or 12.

[0068] The synthesis of alkyl ether carboxylic acids is discussed in *Anionic Surfactants Organic Chemistry*, edited by Helmut W. Staache. They can be synthesized by reacting the corresponding alcohol ethoxylates with chloroacetic acid or sodium monochloroacetate in the presence of NaOH.

[0069] Liquid laundry detergent

[0070] In one embodiment, the invention takes the form of a detergent composition, preferably a liquid laundry detergent composition. Such compositions are explained in more detail in the following paragraphs.

[0071] In the context of this invention, the term "laundry detergent" refers to a formulation intended for and capable of wetting and cleaning household garments such as clothing, linens, and other home textiles. The aim is to provide compositions that, upon dilution, form a liquid laundry detergent composition and in the manner now described.

[0072] The term "linen products" is commonly used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles can include woven, nonwoven, and knitted fabrics; and can include natural or synthetic fibers such as silk, linen, cotton, polyester, polyamide fibers such as nylon, acrylic, acetate, and their blends, including cotton and polyester blends.

[0073] Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine-wash and liquid color-protecting detergents, such as those suitable for hand washing or washing delicate garments (e.g., those made of silk or wool) in the wash cycle of an automatic washing machine.

[0074] In the context of this invention, the term "liquid" means that the continuous phase or main component of the composition is liquid, and that the composition is flowable at 15°C and above. Therefore, the term "liquid" can include emulsions and suspensions, but not compositions having a flowable but stiffer consistency (referred to as gels or pastes). The viscosity of the composition at 25°C and 21 seconds... -1 The shear rate is preferably from 100 to about 1000 mPa·s. This shear rate is the shear rate typically applied to the liquid when poured from the bottle. The pourable liquid detergent composition preferably has a viscosity of 200 to 500 mPa·s, more preferably 200 to 300 mPa·s.

[0075] Preferably, the liquid laundry detergent composition comprises 50% by weight of water, more preferably 70% by weight of water, and most preferably 75% by weight of water. Preferably, the water used has a French hardness of less than 5 degrees, and most preferably, it is demineralized. Preferably, the water is treated with a disinfectant, preferably selected from chlorine-based disinfectants, ozone, or UV treatment, to disinfect the water.

[0076] Liquid laundry detergent compositions may suitably have an aqueous continuous phase. "Aqueous continuous phase" refers to a continuous phase based on water. Preferably, the formulation has a pH of 5 to 10, more preferably 6 to 8, and most preferably 6.1 to 7.0.

[0077] The liquid laundry detergent composition suitably contains 5 to 60%, preferably 10 to 40% (based on the total weight of the composition) of one or more detergency surfactants. Preferably, more than 50% by weight, more preferably more than 80% by weight, and most preferably more than 95% by weight of the detergency surfactant is selected from oil-based surfactants, more preferably oil-based ethoxylates, oil-based ether sulfates, and oil-based ether carboxylates, and most preferably oil-based ethoxylates and oil-based ether sulfates.

[0078] In the context of this invention, the term "stain-removing surfactant" refers to a surfactant that provides a stain-removing (i.e. cleaning) effect on clothing treated as part of a household laundry process.

[0079] Preferably, the choice and amount of surfactant make the composition and the diluted mixture is isotropic in nature.

[0080] Preferably, the weight ratio of nonionic surfactant to alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate) is 0.5 to 2, more preferably 0.7 to 1.5, and most preferably 0.9 to 1.1.

[0081] Preferably, the weight ratio of the nonionic surfactant to the linear alkylbenzene sulfonate (if present) (weight of nonionic surfactant / weight of linear alkylbenzene sulfonate) is 0.1 to 2, more preferably 0.3 to 1, and most preferably 0.45 to 0.85.

[0082] Defoamer

[0083] The composition may also contain an antifoaming agent. Antifoaming materials are well known in the art and include siloxanes and fatty acids.

[0084] Preferably, the fatty acid soap is present in the composition at 0-3.0% by weight, more preferably 0-0.5% by weight, and most preferably 0%.

[0085] In the context of this invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight-chain or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, and most preferably 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid, or stearic acid; and fatty acid mixtures wherein 50-100% by weight (based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures are typically derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil, or tallow).

[0086] Fatty acids can exist in the form of their sodium, potassium, or ammonium salts and / or as soluble salts of organic bases such as mono-, di-, or triethanolamine.

[0087] A mixture of any of the above materials may also be used.

[0088] For formulation purposes, fatty acids and / or their salts (as defined above) are not included in the surfactant or builder levels in the formulation.

[0089] Polymer cleaning enhancer

[0090] Anti-redeposition polymers stabilize dirt in washing solutions, thereby preventing redeposition of dirt. Suitable detergency polymers for this invention include alkoxylated polyethyleneimine. Polyethyleneimine is a material composed of ethyleneimine units -CH2CH2NH-, and in the case of branching, the hydrogen on the nitrogen atom is replaced by the chain of another ethyleneimine unit. Preferred alkoxylated polyethyleneimines used in this invention have a weight-average molecular weight (M) of about 300 to about 10,000. w The polyethyleneimine backbone is a polymer consisting of a linear or branched structure. It can be branched to the extent that it is a dendritic polymer. Alkoxylation can typically be ethoxylation or propoxylation, or a mixture of both. When nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10-30 per modification, preferably 15-25 alkoxy groups. A preferred material is ethoxylated polyethyleneimine, wherein the average degree of ethoxylation is 10-30 per ethoxylated nitrogen atom in the polyethyleneimine backbone, preferably 15-25 ethoxy groups.

[0091] A mixture of any of the above materials may also be used.

[0092] The liquid laundry detergent composition will preferably contain 0.025% to 8% by weight of one or more anti-redeposition polymers, such as, for example, alkoxylated polyethyleneimine as described above.

[0093] Decontamination polymer

[0094] Stain-removing polymers (SRPs) help improve the removal of dirt from fabrics by modifying the fabric surface during the washing process. The adsorption of SRPs on the fabric surface is promoted by the affinity between the chemical structure of the SRP and the target fibers.

[0095] The SRP used in this invention may include various charged (e.g., anionic) and uncharged monomer units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include end-capping groups to control molecular weight or modify polymer properties such as surface activity. The weight-average molecular weight (M) of the SRP... w The range can be from about 1,000 to about 20,000, preferably from about 1,500 to about 10,000.

[0096] The SRP used in this invention may suitably be selected from copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid, or terephthalic acid), glycols (e.g., ethylene glycol or propylene glycol), and polyglycols (e.g., polyethylene glycol or polypropylene glycol). The copolyester may also include monomer units substituted with anionic groups, such as sulfonated isophthaloyl units. Examples of such materials include oligomers produced by transesterification / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”), and poly(ethylene glycol”) (“PEG”); partially and fully anionic-terminated oligomers, such as oligomers derived from ethylene glycol (“EG”), PG, DMT, and Na-3,6-dioxa-8-hydroxyoctanesulfonic acid; nonionic-terminated block polyester oligomers, such as those produced by combinations of DMT, Me-terminated PEG and EG and / or PG, or Me-terminated PEG and Na-dimethyl-5-sulfoisophthalic acid; and copolymer blocks of ethylene glycol terephthalate or propylene glycol terephthalate with polyethylene oxide or polypropylene glycol terephthalate.

[0097] Other types of SRPs used in this invention include cellulose derivatives, such as hydroxy ether cellulose polymers, C1-C4 alkyl celluloses, and C4 hydroxyalkyl celluloses; polymers having hydrophobic poly(vinyl ester) segments, such as graft copolymers of poly(vinyl ester), for example, C1-C6 vinyl esters grafted onto a polyepoxide backbone (e.g., poly(vinyl acetate)); poly(vinyl caprolactam) and related copolymers with monomers such as vinylpyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensation of adipic acid, caprolactam, and polyethylene glycol.

[0098] Preferred SRPs used in this invention comprise those formed by the condensation of terephthalate and glycol, preferably 1,2-propanediol, and further comprise a terminally capped copolyester formed from repeating units of alkyl-terminated epoxy compounds. Examples of such materials have structures corresponding to general formula (I):

[0099]

[0100] Where R 1 and R 2 They are independent of each other as X-(OC2H4) n -(OC3H6) m ;

[0101] Where X is C 1-4 Alkyl groups, preferably methyl groups;

[0102] n is between 12 and 120, preferably between 40 and 50;

[0103] m is between 1 and 10, preferably between 1 and 7; and

[0104] a is a number between 4 and 9.

[0105] Because they are averages, m, n, and a are not necessarily integers for a large number of polymers.

[0106] A mixture of any of the above materials may also be used.

[0107] When included, the overall level of SRP can range from 0.1% to 10%, depending on the level of polymer intended for final dilution of the composition, and ideally from 0.3% to 7%, more preferably from 0.5% to 5% (based on the total weight of the diluted composition by weight).

[0108] Suitable detergency polymers are described in more detail in US Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO 2007 / 079850, and WO2016 / 005271. When used, the detergency polymer is typically incorporated into the liquid laundry detergent compositions herein at a concentration ranging from 0.01% to 10%, more preferably from 0.1% to 5%, based on the weight of the composition.

[0109] Water-soluble substances

[0110] Liquid laundry detergent compositions may incorporate non-aqueous carriers such as water-soluble co-solvents and phase stabilizers. These materials are typically low molecular weight, water-soluble or water-miscible organic liquids, such as C1-C5 monohydric alcohols (e.g., ethanol and n-propanol or isopropanol); C2-C6 diols (e.g., monopropylene glycol and dipropylene glycol); C3-C9 triols (e.g., glycerol); weight-average molecular weight (M... w The range is approximately 200 to 600 for polyethylene glycol; C1-C3 alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine; and alkyl aryl sulfonates (e.g., xylene, toluene, ethylbenzene and sodium and potassium isopropylbenzene (cumene) sulfonate) having up to 3 carbon atoms in the lower alkyl group.

[0111] A mixture of any of the above materials may also be used.

[0112] When included, the presence of a non-aqueous carrier can range from 0.1% to 20%, preferably 2% to 15%, more preferably 10% to 14% (by weight based on the total weight of the composition). The level of the co-water-soluble agent used is related to the level of the surfactant, and ideally, the level of the co-water-soluble agent is used to control the viscosity in such a composition. Preferred co-water-soluble agents are monopropylene glycol and glycerin.

[0113] Co-surfactants

[0114] In addition to the aforementioned non-soap anionic and / or nonionic detergency surfactants, liquid laundry detergent compositions may contain one or more co-surfactants (such as amphoteric (amphoionic) and / or cationic surfactants).

[0115] Specific cationic surfactants include C8-C18 alkyl dimethyl ammonium halides and their derivatives, wherein one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof. When included, the amount of the cationic surfactant may range from 0.1% to 5% (by weight based on the total weight of the composition).

[0116] Specific amphoteric (ampholy) surfactants include alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkyl sulfobetaine (sulfobetaine), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoteric acetates, alkyl amphoteric propions, alkyl amphoteric glycinates, alkylamidopropyl hydroxysulfobetaine, acyl taurates, and acyl glutamates, having an alkyl group containing about 8 to about 22 carbon atoms, preferably selected from C12, C14, C16, C18, and C18:1. The term "alkyl" is used for alkyl moiety comprising a higher acyl group. When an amphoteric (ampholy) surfactant is included, its presence may be 0.1-5% (by weight based on the total weight of the composition).

[0117] A mixture of any of the above materials may also be used.

[0118] Detergent builders and chelating agents

[0119] The detergent composition may also optionally contain relatively low levels of organic detergent builders or chelating agents. Examples include alkali metals, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates, and polyacetylated carboxylates. Specific examples include sodium, potassium, and lithium salts of oxadiosuccinic acid, phenylhexacarboxylic acid, benzene polycarboxylic acids, and citric acid. Other examples are DEQUEST. TM Organophosphonate chelating agents and alkane hydroxyphosphonates are sold by Monsanto.

[0120] Other suitable organic builders include higher molecular weight polymers and copolymers known to possess builder properties. For example, such materials include suitable polyacrylic acid, polymaleic acid, and polyacrylic acid / polymaleic acid copolymers and their salts, such as those produced by BASF under the name SOKALAN. TMThose sold. If used, the organic detergent-building substance may constitute about 0.5% to 20% by weight, preferably 1% to 10% by weight, of the composition. Preferably, the detergent-building content is less than 10% by weight of the composition, preferably less than 5% by weight. More preferably, the liquid laundry detergent formulation is a non-phosphate-based laundry detergent formulation, i.e., containing less than 2% by weight, preferably less than 1% by weight, of phosphate. Most preferably, the laundry detergent formulation is not a detergent-building agent, i.e., containing less than 1% by weight of detergent-building agent. A preferred chelating agent is HEDP (1-hydroxyethylidene-1,1,-diphosphonic acid), for example, sold as Dequest 2010. Also suitable but less preferred (due to poorer cleaning effect) is Dequest® 2066 (diethylenetriaminepenta (methylenephosphonic acid) or heptasodium DTPMP).

[0121] polymer thickener

[0122] Liquid laundry detergent compositions may contain one or more polymer thickeners. Polymer thickeners suitable for use in this invention include hydrophobically modified alkali-swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in this invention comprise linear or crosslinked copolymers prepared by addition polymerization of a monomer mixture comprising at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e., methacrylic acid and / or acrylic acid); and at least one associating monomer. In the context of this invention, the term "associating monomer" refers to a monomer having an olefinically unsaturated portion (for addition polymerization with other monomers in the mixture) and a hydrophobic portion. Preferred types of associating monomers comprise a polyoxyethylene portion between the olefinically unsaturated portion and the hydrophobic portion. Preferred HASE copolymers for use in this invention comprise those prepared by addition polymerization of (meth)acrylic acid with (i) at least one linear or branched C8-C monomer. 40 Alkyl (preferably straight-chain C) 12 -C 22 (i) an associating monomer of alkyl)polyethoxylated (meth)acrylate; and (ii) a linear or crosslinked copolymer prepared by addition polymerization of at least one other monomer selected from C1-C4 alkyl (meth)acrylates, polybasic acid vinyl monomers (such as maleic acid, maleic anhydride and / or salts thereof) and mixtures thereof. The polyethoxylated portion of the associating monomer (i) typically contains about 5 to about 100, preferably about 10 to about 80, and more preferably about 15 to about 60 oxyethylene repeating units.

[0123] A mixture of any of the above materials may also be used.

[0124] When included, the liquid laundry detergent composition preferably contains 0.01% to 5% by weight of the composition, but depends on the amount intended for use in the final diluted product, and is ideally 0.1% to 3% by weight based on the total weight of the diluted composition.

[0125] fluorescent agents

[0126] Including a fluorescent agent in the composition may be advantageous. These fluorescent agents are typically provided and used in the form of their alkali metal salts, such as sodium salts. The total amount of one or more fluorescent agents used in the composition is typically 0.005-2% by weight, more preferably 0.01-0.5% by weight.

[0127] Preferred types of fluorescent agents are: stilbene biphenyl compounds, such as Tinopal (trademark) CBS-X; diamine distilbene disulfonic acid compounds, such as Tinopal DMS pure Xtra, Tinopal 5BMGX and Blankophor (trademark) HRH; and pyrazoline compounds, such as Blankophor SN.

[0128] Preferred fluorescent agents are: sodium 2-(4-styryl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N-methyl-N-2-hydroxyethyl)amino-1,3,5-triazin-2-yl)]amino}stilbene-2-2'disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2'disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.

[0129] Most preferably, the fluorescent agent is a stilbene biphenyl compound, preferably sodium 2,2'-([1,1'-biphenyl]-4,4'-dimethylbis(ethylene-2,1-dimethyl))diphenylsulfonate (CAS-No 27344-41-8).

[0130] Toning dyes

[0131] Tinting dyes can be used to improve the properties of a composition. Preferred dyes are purple or blue. It is believed that depositing low levels of these shades of dye on fabrics masks yellowing. A further advantage of tinting dyes is that they can be used to mask any yellow tints in the composition itself.

[0132] Color dyes are well-known in the field of laundry liquid formulations.

[0133] Suitable and preferred types of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes, and dye conjugates.

[0134] Preferred examples include Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bonded to ethoxylated or propoxylated polyethyleneimine as described in WO2011 / 047987 and WO2012 / 119859, alkoxylated monoazothiophene, dyes having CAS-No 72749-80-5, Acid Blue 59, and phenazine dyes selected from the following:

[0135]

[0136] in:

[0137] X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and -OC2H5;

[0138] X4 is selected from: -H; -CH3; -C2H5; -OCH3; and -OC2H5;

[0139] Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and C(O)OCH3.

[0140] Alkoxylated thiophene dyes are discussed in WO2013 / 142495 and WO2008 / 087497.

[0141] The tinting dye is preferably present in the composition in an amount of 0.0001-0.1% by weight. Depending on the nature of the tinting dye, there exists a preferred range depending on the effectiveness of the tinting dye, which depends on the species and the specific effectiveness within any particular species.

[0142] External structuring agent

[0143] Liquid laundry detergent compositions can have their rheological properties further modified by using one or more external structuring agents that form a structured network within the composition. Examples of such materials include hydrogenated castor oil, microfibrillated cellulose, and citrus pulp fibers. The presence of external structuring agents can provide shear-thinning rheology and also allow materials such as encapsulants and visual cues to remain stably suspended in the liquid.

[0144] enzymes

[0145] Liquid laundry detergent compositions may contain an effective amount of one or more enzymes selected from pectinase, protease, amylase, cellulase, lipase, mannanase, and mixtures thereof. The enzymes are preferably present together with a corresponding enzyme stabilizer.

[0146] preservative

[0147] The composition preferably contains a preservative.

[0148] Preferably, the composition contains a preservative to inhibit microbial growth. For example, the preservative may optionally be included in various embodiments as a means of further enhancing protection against microbial contamination by the consumer, such as from contaminated ingredients, contaminated storage containers, equipment, processing steps, or other sources, involving total bacteria, viruses, and / or fungi. Any conventional preservative known in the art can be used. Some of the listed preservatives include: potassium sorbate, sodium benzoate, benzoic acid, phenoxyethanol, benzyl alcohol, dehydoxyacetic acid, sodium borate, boric acid, lichenic acid, phenols, quaternary ammonium compounds, glycols, isothiazolinones (methylisothiazolinone, benzylisothiazolinone, chloroisothiazolinone), DMDM ​​hydantoin, hexocide, ethanol, IPBC, polyaminopropyl biguanide, phenylphenol, imidazolidinyl urea, parabens, formaldehyde, salicylic acid or its salts, caprylyl glycol, D-glucono-1,5-lactone, sodium isoascorbate, sodium hydroxymethylglycinate, peroxides, sodium sulfite, bisulfite, glucose oxidase, lactoperoxidase, and other preservatives compatible with cleaning ingredients. Other natural substances may also be considered, such as cinnamon, fruit acids, essential oils such as thyme and rosemary, willow bark, poplar bark, tocopherol, curry, citrus extracts, honeysuckle, and amino acid-based preservatives. Preservatives that do not compete with the cleaning ingredients and have not been reported to cause health or environmental problems are particularly preferred. Some more preferred preservatives are: phenoxyethanol, benzoic acid / potassium sorbate, enzymes, borates, isothiazolinones such as MIT, BIT, and CIT, and the aforementioned natural solutions. In one embodiment, the preservative is present in an amount of less than about 5% by weight based on the total weight of the cleaning composition. In another embodiment, the preservative is present in an amount of about 0.01 to about 2% by weight. In yet another embodiment, the fragrance is present in an amount of about 0.01 to about 1% by weight.

[0149] More preferably, the composition comprises BIT and / or MIT at a combined level not exceeding 550 ppm, more preferably 300-450 ppm. Preferably, the MIT level does not exceed 95 ppm. Preferably, the BIT level does not exceed 450 ppm.

[0150] Most preferably, the composition contains benzoate as a preservative. Preferably, the benzoate is present in the composition at 0.01-3% by weight, more preferably 0.1-2% by weight, and most preferably 0.5-1.5% by weight.

[0151] Fragrance

[0152] Fragrances are well known in the art and can be incorporated into the compositions described herein.

[0153] Microcapsules

[0154] One type of microparticle suitable for this invention is a microcapsule.

[0155] Microencapsulation can be defined as the process of encapsulating or sealing one substance within another on a very small scale, resulting in capsules with sizes ranging from less than 1 micrometer to several hundred micrometers. The encapsulated material can be referred to as the core, active ingredient or activator, filler, effective load, core, or internal phase. The material encapsulating the core can be referred to as a coating, membrane, shell, or wall material.

[0156] Microcapsules typically have at least one generally spherical continuous shell surrounding a core. Depending on the materials and encapsulation techniques used, the shell may contain pores, vacancies, or gap openings. Multiple shells may be made of the same or different encapsulating materials and may be arranged in layers of varying thicknesses around the core. Alternatively, microcapsules may be asymmetrically and variably shaped, with a certain amount of smaller core material droplets embedded throughout the microcapsule.

[0157] The shell can function as a barrier protecting the core material from the external environment of the microcapsule, but it can also serve as a means of regulating the release of the core material, such as fragrances. Therefore, the shell can be water-soluble or water-swellable and can initiate fragrance release in response to microcapsule exposure to a humid environment. Similarly, if the shell is temperature-sensitive, the microcapsule may release fragrance in response to increased temperature. Microcapsules can also release fragrance in response to shear forces applied to their surface.

[0158] The preferred type of polymer microparticles suitable for this invention are polymer core-shell microcapsules, wherein at least one generally spherical shell of polymeric material surrounds a core containing the fragrance formulation (f2). The shell typically comprises up to 20% by weight based on the total weight of the microcapsules. The fragrance formulation (f2) typically comprises about 10-about 60% by weight, preferably about 20-about 40% by weight based on the total weight of the microcapsules. The amount of fragrance (f2) can be determined by taking a slurry from the microcapsules, extracting it into ethanol, and measuring it by liquid chromatography.

[0159] The polymer core-shell microcapsules used in this invention can be prepared using methods known to those skilled in the art, such as aggregation, interfacial polymerization, and polycondensation.

[0160] Coagulation methods typically involve encapsulating a core material that is generally insoluble in water by depositing a colloidal material onto the surface of a material droplet. Coagulation can be simple, for example, using a single colloid such as gelatin, or complex, in which two or possibly more colloids with opposite charges, such as gelatin and gum arabic or gelatin and carboxymethyl cellulose, are used under carefully controlled pH, temperature, and concentration conditions.

[0161] Interfacial polymerization typically utilizes the formation of fine dispersions of oil droplets (oil droplets containing core material) in an aqueous continuous phase. The dispersed droplets form the core of the future microcapsule, and the size of the dispersed droplets directly determines the size of the subsequent microcapsule. A microcapsule shell-forming material (monomer or oligomer) is contained within both the dispersed phase (oil droplets) and the aqueous continuous phase, and they react together at the phase interface to build a polymer wall around the oil droplet, thereby encapsulating the droplet and forming a core-shell microcapsule. An example of a core-shell microcapsule produced by this method is a polyurea microcapsule having a shell formed by the reaction of a diisocyanate or polyisocyanate with a diamine or polyamine.

[0162] Polycondensation involves forming a dispersion or emulsion of a core material in an aqueous solution of a precondensate of a polymer material under appropriate stirring conditions to produce capsules of the desired size, and adjusting the reaction conditions to induce condensation of the precondensate via acid catalysis, thereby causing the condensate to separate from the solution and surround the dispersed core material to produce an adhesive film and the desired microcapsules. An example of core-shell microcapsules produced by this method is an amino-plastic microcapsule having a shell formed from the polycondensation product of melamine (2,4,6-triamino-1,3,5-triazine) or urea with formaldehyde. Suitable crosslinking agents (e.g., toluene diisocyanate, divinylbenzene, butanediol diacrylate) can also be used, and secondary wall polymers, such as acid anhydrides and their derivatives, particularly polymers and copolymers of maleic anhydride, can also be used appropriately.

[0163] An example of a preferred polymer core-shell microcapsule used in this invention is an amino-plastic microcapsule having an amino-plastic shell surrounding a core containing a fragrance formulation (f2). More preferably, this amino-plastic shell is formed from a condensation product of melamine and formaldehyde.

[0164] The polymer microparticles suitable for use in this invention typically have an average particle size of 100 nanometers to 50 micrometers. Particles larger than this fall into the visible range. Examples of submicron-sized particles include latexes and microemulsions with typical sizes ranging from 100 to 600 nanometers. Preferred particle size ranges are in the micrometer range. Examples of micrometer-sized particles include polymer core-shell microcapsules (as further described above) with typical sizes ranging from 1 to 50 micrometers, preferably 5 to 30 micrometers. The average particle size can be determined using a Malvern Mastersizer by light scattering, where the average particle size is taken as the median particle size D (0.5) value. The particle size distribution can be narrow, broad, or multimodal. If desired, the initially produced microcapsules can be filtered or sieved to produce a product with higher size uniformity.

[0165] The polymer microparticles suitable for use in this invention may have a deposition aid on the outer surface of the microparticles. The deposition aid is used to modify the external properties of the microparticles, for example, to make the microparticles more compatible with a desired matrix. The desired matrix includes cellulosic products (including cotton) and polyesters (including those used to manufacture polyester fabrics).

[0166] Deposition aids can be appropriately provided on the outer surface of particles via covalent bonding, entanglement, or strong adsorption. Examples include polymer core-shell microcapsules (such as those further described above), wherein the deposition aid is preferably attached to the exterior of the shell via covalent bonding. While it is preferred that the deposition aid is directly attached to the exterior of the shell, it can also be attached via a connecting material.

[0167] The deposition aids used in this invention may suitably be selected from polysaccharides that have an affinity for cellulose. Such polysaccharides may be naturally occurring or synthetic, and may have an inherent affinity for cellulose, or may be derivatized or otherwise modified to have an affinity for cellulose. Suitable polysaccharides have a 1-4 linked β-glycan (generalized sugar) backbone structure having at least 4, preferably at least 10, β1-4 linked backbone residues, such as a dextran backbone (composed of β1-4 linked glucose residues), a mannan backbone (composed of β1-4 linked mannose residues), or a xylan backbone (composed of β1-4 linked xylose residues). Examples of such β1-4 linked polysaccharides include xyloglucan, glucomannan, mannan, galactomannan, β(1-3),(1-4)glucan, and the xylan family, including glucuronic acid-, arabinose-, and glucuronic acid-arabinose-xylan. Preferred β1-4 linked polysaccharides used in this invention can be selected from plant-derived xyloglucans, such as pea xyloglucan and tamarind xyloglucan (TXG) (which has a β1-4 linked glucan backbone and α-D-pyranoylpyranose and β-D-galactopyranosyl-(1-2)-α-D-xylanose side chains, both of which are 1-6 linked to the backbone); and plant-derived galactomannans, such as locust bean gum (LBG) (which has a β1-4 linked mannan backbone, wherein a single-unit galactose side chain α1-6 is linked to the backbone).

[0168] Also suitable are polysaccharides that can be hydrolyzed to obtain cellulose affinity, such as cellulose monoacetate; or modified polysaccharides that have cellulose affinity, such as hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, hydroxypropyl guar gum, hydroxyethyl ethyl cellulose and methylcellulose.

[0169] The deposition aids used in this invention can also be selected from phthalate-containing polymers that have an affinity for polyesters. Such phthalate-containing polymers may have one or more nonionic hydrophilic segments containing oxyolefin groups (such as ethylene oxide, polyoxyethylene, oxypropylene, or polyoxypropylene groups) and one or more hydrophobic segments containing terephthalate groups. Typically, the degree of polymerization of the oxyolefin groups is from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. Suitable examples of this type of phthalate-containing polymer are copolymers having random block copolymers of polyethylene terephthalate and polyethylene oxide terephthalate.

[0170] Any mixture of the above materials may also be suitable.

[0171] The weight-average molecular weight (M) of the deposition aid used in this invention w Typically, it is in the range of about 5kDa to about 500kDa, preferably about 10kDa to about 500kDa, and more preferably about 20kDa to about 300kDa.

[0172] An example of a particularly preferred polymer core-shell microcapsule for use in this invention is an amino-plastic microcapsule having a shell formed by the condensation polymerization of melamine and formaldehyde; surrounding a core containing a fragrance formulation (f2); wherein a deposition aid is covalently bonded to the exterior of the shell. Preferred deposition aids are selected from β1-4 linked polysaccharides, particularly plant-derived xyloglucan, as further described above.

[0173] The inventors have surprisingly observed that the total amount of fragrances contained in liquid laundry detergent compositions can be reduced without sacrificing the overall fragrance experience provided to consumers during key stages of the laundry process. Reducing the total amount of fragrances is advantageous for both cost and environmental reasons.

[0174] Therefore, the total amount of fragrance formulation (f1) and fragrance formulation (f2) in the liquid laundry detergent composition is suitably 0.5 to 1.4%, preferably 0.5 to 1.2%, more preferably 0.5 to 1%, and most preferably in the range of 0.6 to 0.9% (based on the total weight of the composition by weight).

[0175] The weight ratio of fragrance formulation (f1) to fragrance formulation (f2) in the liquid laundry detergent composition is preferably in the range of 60:40 to 45:55. Particularly good results were obtained at a weight ratio of approximately 50:50 for fragrance formulation (f1) to fragrance formulation (f2).

[0176] Fragrance (f1) and flavoring (f2) are typically incorporated at different stages of the formation of liquid laundry detergent compositions. Typically, discrete polymeric microparticles (e.g., microcapsules) encapsulating the fragrance formulation (f2) are added in slurry form to a warm base formulation containing other components of the composition, such as surfactants and solvents. Fragrance (f1) is typically added post-concentrated after the base formulation has cooled.

[0177] Other optional ingredients

[0178] Liquid laundry detergent compositions may contain additional optional ingredients to enhance performance and / or consumer acceptability. Examples of such ingredients include foam promoters, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, draping agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or opacifiers, and tinting dyes. Each of these ingredients will be present in an amount sufficient to effectively achieve its purpose. Typically, these optional ingredients are contained individually in amounts of up to 5% (by weight, based on the total weight of the diluted composition) and adjusted according to the dilution ratio with water.

[0179] Preferably, the composition contains less than 1% alcohol, more preferably less than 0.1% alcohol.

[0180] Many of the ingredients used in embodiments of the invention can be obtained from so-called black charcoal sources or more sustainable green sources. A list of alternative sources for several of these ingredients and how they can be formulated into the raw materials described herein is provided below.

[0181] Alkyl ether sulfates

[0182] SLES and other such alkali metal alkyl ether sulfate anionic surfactants are typically obtained by sulfated alcohol ethoxylates. These alcohol ethoxylates are typically obtained by ethoxylating straight-chain alcohols. Similarly, primary alkyl sulfate surfactants (PAS) can be obtained directly from straight-chain alcohols by sulfated straight-chain alcohols. Therefore, the formation of straight-chain alcohols is the central step in obtaining PAS and alkali metal alkyl ether sulfate surfactants.

[0183] Straight-chain alcohols suitable as an intermediate step in the manufacture of alcohol ethoxylates and therefore anionic surfactants such as sodium lauryl ether sulfate can be obtained from many different sustainable sources. These include:

[0184] Primary sugar

[0185] Primary sugars are obtained from sugarcane or sugar beets and can be fermented to form bioethanol. The bioethanol is then dehydrated to form bioethylene, which then undergoes olefin metathesis to form alkenes. These alkenes are then processed into straight-chain alcohols via hydroformylation or oxidation.

[0186] An alternative method can be used, which also involves the formation of straight-chain alcohols from primary sugars, where the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are then hydrolyzed into straight-chain fatty acids, which are then reduced to form straight-chain alcohols.

[0187] biomass

[0188] Biomass, such as forestry products, rice husks, and straw, can be gasified into syngas. These are then processed into alkanes via the Fischer-Tropsch reaction, which subsequently dehydrogenate to form alkenes. These alkenes can be processed in the same manner as the chain alkenes described above [primary sugars].

[0189] An alternative method involves converting the same biomass into polysaccharides via steam explosion, which can then be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol, which is subsequently dehydrated to form bioethylene. This bioethylene is then processed into a straight-chain alcohol as described above [primary sugars].

[0190] waste plastics

[0191] Waste plastics are pyrolyzed to form pyrolysis oil. This oil is then fractionated to form straight-chain alkanes, which are dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].

[0192] Alternatively, the pyrolysis oil is cracked to form ethylene, which is then subjected to olefin metathesis to form the desired chain olefins. These are then processed into straight-chain alcohols as described above [primary sugars].

[0193] Urban solid waste

[0194] MSW is converted into syngas via gasification. From the syngas, it can be processed as described above [primary sugars] or converted into ethanol via an enzymatic process before dehydrogenation to ethylene. Ethylene can then be converted into straight-chain alcohols via the Ziegler process.

[0195] MSW can also be converted into pyrolysis oil by gasification, and then fractionated to form alkanes. These alkanes are then dehydrogenated to form alkenes and then straight-chain alcohols.

[0196] Ocean carbon

[0197] There are various carbon sources from marine communities, such as seaweed and kelp. From these marine communities, triglycerides can be separated from the source and then hydrolyzed to form fatty acids, which are then reduced to straight-chain alcohols in the usual way.

[0198] Alternatively, the raw materials can be separated into polysaccharides, which are then enzymatically degraded to form secondary sugars. These can be fermented to form bioethanol, and then processed as described above for [primary sugars].

[0199] waste oil

[0200] Waste oils, such as used cooking oils, can be physically separated into triglycerides, which are then broken down to form straight-chain fatty acids and then, as described above, straight-chain alcohols.

[0201] Alternatively, used cooking oil can be subjected to the Neste process, whereby the oil undergoes catalytic cracking to produce bio-ethylene. It is then processed as described above.

[0202] Methane capture

[0203] Methane capture methods capture methane from landfills or fossil fuel production. Methane can be gasified to form syngas. Syngas can be processed as described above, thereby converting syngas into methanol (Fischer-Tropsch reaction), then into olefins, and subsequently into straight-chain alcohols via hydroformylation oxidation.

[0204] Alternatively, the syngas can be converted into alkanes and then into alkenes via the Fischer-Tropsch process and subsequent dehydrogenation.

[0205] Carbon capture

[0206] Carbon dioxide can be captured by any of a variety of well-known methods. Carbon dioxide can be converted to carbon monoxide via a reverse water-gas shift reaction, which can then be converted to syngas using hydrogen in an electrolytic reaction. The syngas is then processed as described above and converted to methanol and / or alkanes before reacting to form olefins.

[0207] Alternatively, the captured carbon dioxide is mixed with hydrogen before enzymatic treatment to form ethanol. This is a process developed by Lanzatech. The ethanol is then converted to ethylene, which is then processed into olefins as described above, and subsequently into straight-chain alcohols.

[0208] The above method can also be used to obtain C16 / 18 chains of C16 / 18 alcohol ethoxylates and / or C16 / 18 ether sulfates.

[0209] LAS

[0210] One of the other major surfactants commonly used in cleaning compositions, especially laundry compositions, is LAS (linear alkylbenzene sulfonate).

[0211] The key intermediate compounds in LAS production are the relevant chain olefins. These chain olefins (olefins) can be produced by any of the methods described above, and can be derived from, for example, primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, and marine carbon formation.

[0212] Unlike the methods described above, where olefins are processed through hydroformylation and oxidation to form straight-chain alcohols, olefins react with benzene and then sulfonate to form LAS.

[0213] The invention will be further described through the following non-limiting embodiments.

[0214] Example

[0215] Crude palm oil and low-erucic acid rapeseed (canola) oil were obtained from agricultural sources. The oils were blended in various ratios and transesterified to the corresponding methyl esters, which were then separated from glycerol and residual methanol. The methyl esters were reduced to the corresponding alcohols, and the carbon chain length distribution was measured by GC. The values ​​are given below.

[0216]

[0217] PKO is palm kernel oil;

[0218] RSO is low-erucic acid rapeseed oil;

[0219] CPO is crude palm oil.

[0220] The iodine value of all samples was measured, and if necessary, further hydrogenation was performed until a value of 70-75 was obtained. Under these conditions, the dominant C18 fraction was oil-based.

[0221] The mixture of RSO and CPO of the present invention provides a matched carbon chain distribution without the need for distillation and removal of waste fractions.

[0222] Fatty acid methyl esters (FAMEs) of rapeseed oil were prepared by transesterification catalyzed by potassium hydroxide (KOH). The reaction was carried out in a 2-1 three-necked round-bottom flask equipped with a stirrer and a condenser. The amount of catalyst used was 1% by weight, compared with the starting rapeseed oil having a methanol to oil molar ratio of 9:1. KOH and methanol were added to the rapeseed oil and stirred at 60 °C for 2 h and then cooled. Subsequently, the lower glycerol phase was removed. The upper phase was washed several times with distilled water at 60 °C to remove any remaining KOH, methanol, and possible soaps. Finally, the mixture was dried at 60 °C using a rotary evaporator to remove any remaining wash water. The composition of FAMEs was determined by GC.

Claims

1. A method for producing oleyl alcohol, comprising the following steps: a) Hydrogenation of fatty acids, fatty acid methyl esters, or combinations thereof to provide fatty alcohols; The fatty acid, the fatty acid methyl ester or combination thereof contains an oil-based chain obtained from a mixture of oil (1) and oil (2) in a ratio of 1:9 to 6:4, wherein oil (1) is palm oil and oil (2) is low erucic acid rapeseed oil; and wherein the method does not include distillation.

2. The method according to claim 1, wherein the fatty acid, the fatty acid methyl ester or combination thereof comprises an oil-based chain obtained from a mixture of oil (1) and oil (2) in a ratio of 2:8 to 5:

5.

3. The method according to any one of claims 1 to 2, wherein the oleyl alcohol is converted into a surfactant.

4. The method according to any one of claims 1 to 2, wherein the oleyl alcohol is converted into a surfactant selected from the group consisting of oleyl sulfate, oleyl alcohol ethoxylate, oleyl ether sulfate, oleyl ether carboxylate, and oleyl sulfosuccinate.

5. The method according to any one of claims 1 to 2, wherein the oleyl alcohol is converted into a surfactant selected from the group consisting of oleyl alcohol ethoxylate, oleyl ether sulfate, and oleyl ether carboxylate.

6. The method according to any one of claims 1 to 2, wherein the fatty acid methyl ester is generated by triglyceride transesterification to fatty acid methyl ester, followed by removal of glycerol.

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