Lubricating grease compositions containing pentacyclic triterpenes as co-thickeners

Abstract

The invention relates to lubricating grease compositions containing: a base oil, a soap thickener or polyurea thickener, and at least one pentacyclic triterpene having at least one OH group. The invention also relates to the production of said compositions, and to the use thereof for lubricating lubrication points on machines that come into contact with foodstuffs and feedstuffs.

Description

[0001] The invention relates to lubricating grease compositions comprising a base oil, a soap thickener, and at least one pentacyclic triterpene with at least one OH group, and their use for lubricating lubrication points on machinery in contact with food and feed. The soap thickener is a calcium soap, a calcium complex soap, an aluminum complex soap, or a mixture thereof. Technical context of the invention

[0002] Lubricants serve to reduce friction and wear on the contact surfaces of moving parts, thereby increasing the service life of components and machines and minimizing power and energy losses due to friction. While lubrication with oils is possible in many applications, some require the use of a consistent lubricant, i.e., a grease. Consistency allows a grease, unlike oils, to remain in place. This consistency is achieved by the thickener, which absorbs and retains the liquid oil component. High-quality greases are characterized by consistent consistency over a long period, good mechanical stability, and a defined oil release behavior. A grease consists of a base oil, at least one thickener, and possibly additives that are added to increase the lubricant's service life and performance.

[0003] Common soap thickeners include calcium soaps, calcium complex soaps, calcium sulfonate complex soaps, lithium soaps, lithium complex soaps, and aluminum complex soaps. Polyurethanes, polyureas, bentonite, and pyrogenic SiO₂ are also used as thickeners. However, conventional thickeners and the raw materials used to produce them are often not based on renewable resources, or only partially so.

[0004] Betulin (CAS 473-98-3) is a pentacyclic triterpene that can be obtained by extraction from birch bark (compare US 7482383 B2).

[0005] It is therefore a biogenic and renewable raw material. Betulin is a diol derived from the structure of lupane (CAS 464-99-3). Birch bark extracts contain, in addition to betulin as the main component (e.g., approx. 80% w / w), betulinic acid (CAS 472-15-1, e.g., approx. 4%), oleanolic acid (CAS 508-02-1, e.g., approx. 2% w / w), lupeol (CAS 545-47-1, e.g., approx. 4% w / w), erythrodiol (CAS 545-48-2, e.g., approx. 2% w / w), and a number of other compounds (e.g., approx. 8% other).

[0006] Oleanolic acid and erythrodiol are derived from the oleana backbone, which differs from the lupane backbone in that the fifth ring is a six-membered ring instead of a five-membered ring.

[0007] In addition to extraction from birch bark, betulin and betulinic acid are also accessible by biosynthetic production according to WO 2015 / 121168 A1.

[0008] Betulin is attributed with pharmacological properties; for example, it is used as an anti-inflammatory agent in skin or wound healing ointments (trade names Episalvan and Filsuvez). This utilizes another property of betulin, namely its ability to form oleogels (compare US 8536380 B1 / EP 1758555 B2). Vegetable oils and mineral oils, for example, have been suggested as carrier fluids for the oleogels.

[0009] In patent literature, birch bark extracts, betulin, and / or betulinic acid are occasionally proposed as thickeners. DE 10 2019 110921 A1 discloses the possible addition of bio-based oligomers or polymers as solid lubricants or co-thickeners, such as triterpenes, cellulose or modified cellulose, chitin, and / or chitosan, to lubricating grease compositions. Purpose of the invention:

[0010] The object of the invention is to provide lubricating greases with an advantageous thickening effect. The thickening systems thus obtained should exhibit a synergistic interaction between thickener and co-thickener and, according to at least one embodiment, be suitable for use or approval in the food or feed processing industry according to the "NSF H1" standard as "food grade".

[0011] It has been found that betulin-thickened oleogels, without further thickener, exhibit strong shear thinning under mechanical stress and strong post-hardening at rest, which is disadvantageous for use as a lubricant. Therefore, the object of the present invention was to improve the mechanical stability and storage stability. Summary of the invention

[0012] The problem is solved by the subject matter of the independent claims. Preferred embodiments are the subject matter of the dependent claims or described below.

[0013] The lubricating grease composition according to the invention comprises: a) a base oil (optionally comprising a base oil mixture) in an amount of 55 to 95 wt.% and preferably 70 to 90 wt.%; b) at least one soap thickener in an amount of 1 to 20 wt.%, preferably 1.5 to 15 wt.% or 1.5 to 10 wt.%, wherein the soap thickener is a calcium soap, a calcium complex soap, an aluminum complex soap or mixtures thereof; and c) at least one pentacyclic triterpene with at least one hydroxy group, preferably from the lupane group, particularly preferably (3beta)-Lup-20(29)-ene-3,28-diol, in an amount of 0.5 to 10 wt.%, preferably 1 to 5 wt.% as a co-thickener.

[0014] The lubricating grease composition according to the invention exhibits a synergistic interaction between betulin and the soap thickener. The co-thickener can substitute for the soap thickener to a certain extent, so that, as a result, less soap thickener is required. The lubricating grease compositions are also characterized by improved mechanical stability. Furthermore, unlike greases thickened solely with betulin, they exhibit no or negligible post-hardening and no or negligible shear-thinning behavior. Detailed description of the invention

[0015] The derivatives of baueran, friedelan, gammaceran, glutinan, hopan, lupan, multifloran, oleanan, taraxeran, and ursan, containing at least one OH group, can be used as pentacyclic triterpenes. Rings A to D of these pentacyclic triterpenes have six members. Ring E can have five or six members. The derivatives of lupan and oleanan are preferred. Mixtures of such pentacyclic triterpenes are available in the form of birch bark extracts. The basic structure of the pentacyclic triterpenes always has at least one hydroxyl group, e.g., at the 3-position, and can—even independently of this—have one or more methyl groups, e.g., at positions 4, 4, 5, 8, 10, 13, 14, 17, 20, 20, 22, and / or 22. The pentacyclic triterpene can, for example, also have two hydroxy groups.

[0016] Lupanes are a class of triterpenes with a pentacyclic structure. Like all triterpenes, lupanes are composed of six isoprene units and therefore typically have 30 carbon atoms. Lupanes have a structure consisting of four six-membered rings and one five-membered ring. Lupane C30H52 (CAS number 464-99-3) has methyl groups at positions 4, 4, 8, 10, 14, and 17, as well as an isopropyl group at position 19. The diol derived from the monounsaturated compound (20(29)-lupane), with OH groups at positions 3 and 28, is betulin (3(beta)-lupan-20(29)-ene-3,28-diol), which is the main component of birch bark extracts. In addition, such extracts also contain other lupan derivatives such as the monool lupeol (Lup-20(29)-en-3(beta)-ol), as well as the various oxidation products of the diol, such as betulinaldehyde (3(beta)-hydroxy-20(29)-lupen-28-aldehyde), betulinic acid (3(beta)-hydroxy-20(29)-lupen-28-ic acid) and betulonic acid (3-oxo-20(29)-lupen-28-ic acid).

[0017] Oleanans have a pentacyclic structure, with all five rings containing six members. Leanan C30H52 (CAS number 471-67-0) has methyl groups at positions 4, 4, 8, 10, 14, 17, 20, and 20. The diol erythrodiol (3(beta)-olean-12-ene-3,28-diol, CAS number 545-48-2), derived from the monounsaturated compound (12-oleanes), and its oxidation product oleanolic acid (3(beta)-hydroxy-12-oleanene-28-acid) are also found in birch bark extracts.

[0018] The base oils are liquid at room temperature (20 °C). The base oil preferably has a kinematic viscosity of 18 to 2500 mm² / s, particularly 25 to 1500 mm² / s, and most preferably 40 to 500 mm² / s, in each case at 40 °C (measured according to DIN EN ISO 3104). The term "base oil" here also includes a mixture of different base oils. Suitable base oils for food-grade (NSF H1) greases include, for example, highly refined white oils, gas-to-liquid (GTL) oils, polyalphaolefins as oligomers of C8 to C12 alpha olefins with a degree of oligomerization of 2 to 25, particularly 3 to 18, polyisobutylenes, poly(C2 to C4)alkylene glycols, C4 to C18 alkylated naphthalenes, native and synthetic esters, polyethers, polydimethylsiloxanes, as well as alcohols and polyols. Preferably, the base oil is an oil made from polyalphaolefins and / or synthetic esters. More preferably, the base oil is a hydrocarbon oil and / or an ester oil.

[0019] Suitable soap thickeners include calcium soap, calcium complex soap, aluminum complex soap, or mixtures thereof.

[0020] Aluminum complex soaps are obtained by reacting a suitable aluminum source (aluminum complex precursor), e.g., aluminum oxyisopropoxylate (= oxo(propan-2-olato)aluminum), with at least one fatty acid and at least one aromatic carboxylic acid as a complexing agent. Suitable fatty acids are saturated or unsaturated monocarboxylic acids with 10 to 24 carbon atoms, such as lauric acid, myristic acid, palmitic acid, oleic acid, or stearic acid. Suitable aromatic carboxylic acids are monocarboxylic acids derived from a substituted or unsubstituted aromatic parent compound. Examples include benzoic acid, salicylic acid, p-toluic acid, phenylacetic acid, or 3-phenylpropionic acid.

[0021] Instead of the aluminum source, an aluminum fatty acid carboxylate (e.g., aluminum oxystearate) can also be used as the aluminum source, which is reacted with at least one aromatic carboxylic acid as a complexing agent. An idealized aluminum complex thickener containing equal amounts of stearate (as a fatty acid) and benzoate (as a complexing aromatic carboxylic acid) can be described as aluminum stearoyl benzoyl hydroxide (CAS 977098-49-9).

[0022] Calcium soaps They are obtained by reacting calcium hydroxide with suitable carboxylic acids and, if necessary, additional inorganic acids such as phosphoric acid, whereby for calcium complex soaps a complexing agent is also reacted during the reaction.

[0023] Calcium soaps are salts of calcium with one or more saturated or unsaturated monocarboxylic acids with 10 to 24 carbon atoms, optionally with corresponding substituted monocarboxylic acids, such as preferably corresponding hydroxycarboxylic acids, e.g., 12-hydroxystearic acid. Suitable carboxylic acids include, for example, lauric acid, myristic acid, or behenic acid. In addition to the aforementioned straight-chain fatty acids, saturated or unsaturated branched-chain fatty acids can also be used. Naphthenic acids, neodecanoic acids, or comparable neoacids can also be employed.

[0024] Complexing agents within the meaning of the present invention are: (a) the alkali and / or alkaline earth salt, in particular calcium salts, of a saturated or unsaturated mono-carboxylic acid or also hydroxycarboxylic acids with 2 to 8, in particular 2 to 4 carbon atoms, or alkali and / or alkaline earth salts of a di-carboxylic acid with 2 to 16, in particular 2 to 12 carbon atoms, each optionally substituted, and / or (b) the alkali or alkaline earth salt of boric acid and / or phosphoric acid, in particular as reaction products with NaOH and / or Ca(OH)₂, wherein the boric acid and / or phosphoric acid may also be in the form of an ester of boric acid or phosphoric acid with unbranched or branched alkyl groups having 2 to 32 carbon atoms, preferably 8 to 32 carbon atoms.

[0025] The preferred complexing agent is (a). Particularly suitable monocarboxylic acids for the complexing agent are acetic acid and propionic acid. Also suitable are hydroxybenzoic acids such as parahydroxybenzoic acid, salicylic acid, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gammaresorcylic acid), or 4-hydroxy-4-methoxybenzoic acid. Particularly suitable dicarboxylic acids are adipic acid (C₆H₁₀O₄), sebacic acid (C₁₀H₁₈O₄), azelaic acid (C₉H₁₆O₄), and / or 3-tert-butyladipic acid (C₁₀H₁₈O₄).

[0026] The borate (b) can be, for example, metaborate, diborate, tetraborate, or orthoborate, or an alkali or alkaline earth metal such as monosodium orthoborate. Suitable phosphates include alkali (preferably lithium) and alkaline earth (preferably calcium) dihydrogen phosphate, hydrogen phosphate, or pyrophosphate, or calcium or lithium hydroxyapatite. Esters of boric acid and phosphoric acid with unbranched or branched alkyl groups of 2 to 32, preferably 8 to 32, carbon atoms can be used.

[0027] The compositions according to the invention preferably further contain additives. Additives can be antioxidants, high-pressure additives, corrosion inhibitors, metal deactivators, viscosity index improvers, friction reducers or anti-wear additives, solid lubricants and / or dyes.

[0028] Examples of antioxidants include amine compounds such as alkylamines or 1-phenylaminonaphthalene, aromatic amines such as phenylnaphtylamines or diphenylamines, polymeric hydroxyquinolines such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer (TMQ), phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol, zinc dithiocarbamate or zinc dithiophosphate; phosphites such as tris(2,4-ditert-butylphenyl phosphite or bis(2,4-ditert-butylphenyl)-pentaerythritol diphosphite or thioethers such as cresol thioethers.

[0029] Examples of high-pressure additives and / or anti-wear additives include organic sulfur compounds such as polysulfides or sulfurized olefins, thiophosphates such as triphenyl thiophosphate and dithiophosphates, phosphites and phosphonates such as di-n-octylphosphonate, phosphates such as substituted triphenyl phosphates or amine-neutralized alkyl phosphates, inorganic or organic boron compounds, thiocarbamates and / or dithiocarbamates such as methylene bis(di-butyldithiocarbamate).

[0030] Examples of corrosion inhibitors include sulfonates such as petroleum sulfonate, dinonylnaphthalenesulfonate; neutral or hyperbasic calcium sulfonates, magnesium sulfonates, sodium sulfonates, calcium and sodium naphthalenesulfonates, sulfonic acid esters, amine phosphates and / or N -Methyl- N -(1-oxo-9-octadecenyl)glycine.

[0031] Examples of metal deactivators include benzotriazoles such as methylbenzotriazole dialkylamine, sterically hindered phenols and / or sodium nitrite.

[0032] Examples of viscosity index improvers include polymethacrylate, polyisobutylene and / or polystyrene.

[0033] Examples of friction modifiers include organic acids, such as isostearic acid, fatty acid esters, possibly ethoxylated polyols like glycerol or sorbitan, partial glycerides, animal or vegetable oils, molybdenum dialkyl dithiophosphates, molybdenum dialkyl dithiocarbamates, zinc dithiocarbamate, zinc dithiophosphate, functional polymers such as oleylamides, organic compounds based on polyethers and amides, such as alkyl polyethylene glycol tetradecylene glycol ethers, PIBSI (polyisobutylene succinic imide) or PIBSA (polyisobutylene succinic anhydride), dialkyl hydrogen phosphonates, and alkyl succinates. These friction modifiers can also act as anti-wear additives.

[0034] Solid lubricants that can be used include: polymer powders such as polyamides, polyimides, polyphenylene sulfide (PPS) or polytetrafluoroethene (PTFE), melamine cyanurate, melamine polyphosphate, graphite, metal oxides, boron nitride, silicates, e.g. magnesium silicate hydrate (talc), sodium tetraborate, potassium tetraborate, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc, inorganic salts of alkali and alkaline earth metals, such as calcium carbonate, sodium and calcium phosphates, as well as carbon black or other carbon-based solid lubricants such as nanotubes. Manufacturing process

[0035] The process for manufacturing the lubricating grease composition comprises at least the following steps: Base oil and aluminum complex precursor are heated to obtain a mixture. The aluminum complex precursor can be, for example, an aluminum oxyalkanolate (reaction product with an alcohol / alcohol mixture) or an aluminum oxyalkanoate (reaction product with a carboxylic acid / alcohol mixture). Fatty acid (e.g., saturated or unsaturated monocarboxylic acids with 10 to 24 carbon atoms) and complexing agent (e.g., aromatic monocarboxylic acids) are added to the mixture at at least 60°C, and the mixture is heated further to at least 80°C, preferably at least 90°C. If the aluminum complex precursor is an aluminum oxyalkanoate, the addition of the fatty acid is only an option, but in any case, the addition of the fatty acid is preferred. The pentacyclic triterpene, if applicable, is then added.The oleogel in a portion of the base oil is added to the mixture at at least 80°C, particularly 80-110°C, preferably at least 90°C, particularly 90-100°C, and is further heated to at least 180°C; the mixture is cooled to below 80°C, preferably below 60°C; any additives are preferably added at below 80°C, preferably below 60°C; the grease thus obtained is homogenized and, if necessary, ground to obtain the desired lubricating grease composition.

[0036] To produce the lubricating grease composition according to the invention, in a preferred embodiment the pentacyclic triterpene is added as a co-thickener after the formation of the primary thickener, particularly when the formation of the primary thickener is largely complete. The reaction to form the primary thickener takes place in at least a portion of the base oil, at temperatures between 60 and 100°C, preferably at temperatures between 70 and 90°C. In this process, at least one carboxylic acid is added to a solution or suspension of a reactive precursor compound (e.g., aluminum oxystearate) and reacted by thorough mixing, or a reactive precursor compound (e.g., calcium hydroxide) is added to a solution or suspension of at least one carboxylic acid and reacted by thorough mixing. Any water that may be formed is removed by heating the mixture to temperatures above 100°C.

[0037] The pentacyclic triterpene is added, preferably at a temperature between 80 and 110°C, and preferably between 90 and 100°C. The pentacyclic triterpene can be added in powder form or as an oleogel in a portion of the base oil. The pentacyclic triterpene and the primary thickener are heated together with stirring to a maximum temperature. This maximum temperature, depending on the type of primary thickener, is between 120 and 220°C, preferably between 150 and 210°C.

[0038] Once the upper final temperature is reached, the mixture is cooled to a temperature below 80°C, preferably below 60°C. Optionally, at least one additive can be added at this temperature.

[0039] The resulting lubricating grease is homogenized using a colloid mill or a three-roll mill. use

[0040] The lubricating grease composition according to the invention is particularly suitable for use in gears, plain and rolling bearings, sliding guides, spindle drives, linear drives and ball screws, especially those used in the food (including the beverage industry) or animal feed industry. The lubricating grease composition according to the invention can be used for lubricating lubrication points on machines or devices in contact with food and animal feed.

[0041] The grease composition is intended for applications where the lubricant may come into contact with food during the production process, regardless of whether this contact is unavoidable or only occasional. For this purpose, the grease composition must be approved according to international regulations as per "NSF H1," as granted by "NSF International." Another standard is DIN ISO 21469. Experimental examples

[0042] In the following examples, the characteristic data of the lubricating greases according to the invention, co-thickened by betulin, are compared with those based on a pure soap thickener.

[0043] Aluminum Complex Grease 1 (AX1): In a heated reaction vessel equipped with a stirrer, 1055.7 g of the polyalphaolefin Synfluid PAO 8 cSt (Chevron Phillips Chemical, PAO 8, kinetic viscosity at 40°C approx. 46 mm² / s) and 120.0 g of the aluminum complex precursor Komad 8418 VO (MOL, aluminum oxystearate in white oil) were placed and heated to 80–85°C with stirring. 6.2 g of stearic acid and 18.1 g of benzoic acid were added together. With continuous stirring and the activation of a rotor-stator homogenizer (4000 rpm), the mixture was maintained at 85°C for one hour (reaction phase). Subsequently, the mixture was heated at a rate of 1 K / min to a final temperature of 205°C (heating phase). Once the final temperature was reached, the rotor-stator homogenizer was switched off and the mixture was cooled to below 60 °C (cooling phase). The resulting grease was then homogenized by grinding it in a colloid mill.

[0044] The other aluminum complex greases AX2, AX3, and AX4 were produced analogously, i.e., using the same process but with correspondingly larger proportions of the thickening agents. In the case of AX4, the ester Linplast 810 TM (Sasol, a trimellitic acid ester of linear C8 / C10 alcohols, kinetic viscosity at 40°C approx. 50 mm² / s) was used instead of the base oil PAO 8.

[0045] The production of the model greases M1, M2 and M3 according to the invention was carried out analogously to the production of the pure aluminum complex greases, i.e. using the same process but with correspondingly lower proportions of the raw materials, and with the difference that a corresponding amount of birch bark extract with a betulin content of approximately 80%, hereinafter referred to as betulin, was added after the reaction phase. Table 1 Part 1: Reference and model greases. Key figure Unit / Method AX1 M1 AX2 M2 base oil PAO 8 PAO 8 PAO 8 PAO 8 Thickener type Al complex Al-complex / Betulin AI Complex Al-complex / Betulin Al complex soap content [Weight %] 7 7 8 7 Betulin content [Weight %] - 1 - 3 PW 60 [0.1 mm] / DIN ISO 2137 340 330 324 297 PW 100,000 398 383 388 332 Δ PW 58 53 64 35 Part 2: Reference and model greases Key figure Unit / Method AX3 AX4 M3 AX5 base oil PAO 8 Ester Ester Ester Thickener type Al complex Al complex Al-complex / Betulin AI Complex Al complex soap content [Weight %] 10 7 7 10 Betulin content [Weight %] - - 3 - PW 60 [0.1 mm] / DIN ISO 2137 260 363 358 291 PW 100,000 346 414 368 352 Δ PW 86 51 10 61

[0046] Due to the thickening effect of betulin, the model greases M1, M2 and M3 have an improved consistency compared to the reference greases AX1 and AX4, which is more or less pronounced depending on the amount used and the type of base oil.

[0047] In comparison with the reference greases AX1 and AX4 (same content of Al complex soap) and also compared to AX2, AX3 and AX5 (same total thickener content), the model greases M1, M2 and M3 according to the invention exhibit improved mechanical stability (lower Δ PW), measured as the difference in walking penetration PW 100,000 with 100,000 strokes minus PW 60 with 60 strokes.

Claims

1. A lubricating grease composition comprising a) a base oil in an amount of 55 to 95 wt.%; b) at least one soap thickener in an amount of 1 to 20 wt.%, wherein the soap thickener is a calcium soap, a calcium complex soap, an aluminium complex soap or mixture thereof; and c) at least one pentacyclic triterpene having at least one OH group in an amount of 0.5 to 10 wt.%.

2. The lubricating grease composition according to claim 1 comprising a) the base oil in an amount of 70 to 90 wt.%; b) the soap thickener in an amount of 1.5 to 15 wt.%; c) the pentacyclic triterpene with at least one OH group in an amount of 1 to 5 wt.% as a co-thickener.

3. The lubricating grease composition according to at least one of the preceding claims, wherein the pentacyclic triterpene is from the group of lupanes and is preferably betulin and / or lupeol.

4. The lubricating grease composition according to at least one of the preceding claims, wherein the base oil has a kinematic viscosity of 18 to 2500 mm2 / s, in particular 25 to 1500 mm2 / s, and most preferably 40 to 500 mm2 / s, in each case at 40 °C.

5. The lubricating grease composition according to at least one of the preceding claims, wherein the base oil is a hydrocarbon oil and / or an ester oil.

6. The lubricating grease composition according to at least one of the preceding claims, wherein the soap thickener is an aluminium complex soap.

7. The lubricating grease composition according to at least one of the preceding claims, wherein the lubricating grease composition further contains additives selected from antioxidants, extreme pressure additives, corrosion inhibitors, metal deactivators, viscosity index improvers, friction modifiers, anti-wear additives, solid lubricants, colourants and mixtures thereof.

8. A method for producing the lubricating grease composition according to at least one of claims 1 to 7, wherein the soap thickener is initially produced and only then is the pentacyclic triterpene added to the mixture at a temperature of at least 80°C.

9. A method for producing the lubricating grease composition according to at least one of claims 1 to 7, wherein the soap thickener is or comprises an aluminium complex soap, comprising the following steps, - base oil and aluminium complex precursor are heated to form a mixture; - complexing agent and, optionally fatty acid are added to the mixture at a temperature of at least 60°C and the mixture is further heated to at least 80°C; - the pentacyclic triterpene is added to the mixture at a temperature of at least 80°C, and it is further heated to at least 180°C; - the mixture is cooled to below 80 °C, preferably to below 60 °C; - the grease thus obtained is homogenised to obtain the lubricating grease composition.

10. The method according to claim 9, wherein the fatty acids are a C10 to C24 fatty acid and the complexing agent is an aromatic carboxylic acid.

11. The method according to claim 9 or 10, wherein the aluminium complex precursor is an aluminium oxy-alkanolate or an aluminium oxy-alkanoate.

12. Use of the lubricating grease composition according to at least one of the preceding claims 1 to 7 for the lubrication of lubrication points on machines or devices that come into contact with foodstuffs and animal feed.