WO2013079791A1 - Method for catalytic oxidation of a natural composition including unsaturated fatty acids and/or esters thereof and the use of a mixture obtained therefrom for the production of mono-, oligo- and/or polyesters - Google Patents

Method for catalytic oxidation of a natural composition including unsaturated fatty acids and/or esters thereof and the use of a mixture obtained therefrom for the production of mono-, oligo- and/or polyesters Download PDF

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Publication number
WO2013079791A1
WO2013079791A1 PCT/FI2012/051175 FI2012051175W WO2013079791A1 WO 2013079791 A1 WO2013079791 A1 WO 2013079791A1 FI 2012051175 W FI2012051175 W FI 2012051175W WO 2013079791 A1 WO2013079791 A1 WO 2013079791A1
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Prior art keywords
acid
mixture
oligo
oil
mono
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PCT/FI2012/051175
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French (fr)
Inventor
Salme Koskimies
Pauliina PITKÄNEN
Jukka Tulisalo
Minni PIRTTIMAA
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Teknologian Tutkimuskeskus Vtt
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Priority to EP12815719.5A priority Critical patent/EP2785677A1/en
Publication of WO2013079791A1 publication Critical patent/WO2013079791A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • C10M105/44—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
    • C10M2207/3025—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/04—Oxidation, e.g. ozonisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The invention relates to a method for producing a mixture comprising carboxylic, epoxy and/or hydroxyl acids and to its further use for producing mono-, oligo- and/or polyesters for various applications.

Description

METHOD FOR CATALYTIC OXIDATION OF A NATURAL COMPOSITION INCLUDING UNSATURATED FATTY ACIDS AND/OR ESTERS THEREOF AND THE USE OF A MIXTURE OBTAINED THEREFROM FOR THE PRODUCTION OF MONO-, OLIGO- AND/OR POLYESTERS
FIELD OF THE INVENTION
The invention relates to a method for produc¬ ing a mixture comprising carboxylic, epoxy and/or hy- droxyl acids and to its further use in a method for producing mono-, oligo-, and/or polyesters for various applications. The invention further relates to a mix¬ ture comprising carboxylic, epoxy and/or hydroxyl ac¬ ids and to mono-, oligo- and/or polyesters. The inven¬ tion further relates to lubricants and plasticizers .
BACKGROUND OF THE INVENTION
Mono-, oligo- and/or polyester structures are used for various applications e.g. for the production of lubricants or plasticizers. Prior art recognizes methods and starting materials for producing such mono-, oligo- and/or polyesters. Products typically used in lubricant and plasticizer applications are produced from carboxylic acids as pure compounds ob¬ tained by processing hydrocarbons of vegetable oil or fossil origin.
For example azelaic acid (nonanedioic acid) and pelargonic acid (nonanoic acid) used for the above applications can be industrially produced by ozonoly- sis of oleic acid. However, a drawback of this method is the toxicity and unstability of ozone as well as the used processing chemicals and the produced inter¬ mediates. Further, ozone has to be continuously gener¬ ated on-site by electrical discharge in air. The ozone production is the limiting factor for large scale pro- duction of these acids. Further, traditionally chemical plant oil conversion reactions are mainly carried out using sep¬ arated and purified raw material, whereby several pu¬ rification step of the raw material are needed during which part of the raw material is lost. However, in many applications, such as lubricants and plasticiz- ers, the optimal properties are achieved by using sev¬ eral starting materials, e.g. fatty acids with varia¬ ble chain length. In industrial scale this means using several tanks and pumping systems for each of the raw materials. The use of such a complex system increases the total costs.
The inventors have thus recognized the need for new starting materials and methods for especially enabling large-scale production of mono-, oligo- and/or polyesters for e.g. lubricant or plasticizer applications. Especially environmentally friendly ma¬ terials and methods are needed in order to replace fossil based products with renewable materials.
PURPOSE OF THE INVENTION
The purpose of the invention is to provide a new type of method for producing a mixture comprising carboxylic, epoxy and/or hydroxyl acids. The purpose of the invention is further to provide a method for producing mono-, oligo- and/or polyesters using the produced mixture comprising carboxylic, epoxy and/or hydroxyl acids as starting material and to provide es¬ ters to be used in various applications.
SUMMARY
The method according to the present invention is characterized by what is presented in claim 1.
The mixture according to the present inven- tion comprising carboxylic, epoxy and/or hydroxyl ac¬ ids is characterized by what is presented in claim 10. The method according to the present invention for producing mono-, oligo- and/or polyesters is char¬ acterized by what is presented in claim 11.
The mono-, oligo- and/or polyesters according to the present invention are characterized by what is presented in claim 18.
The use of the mono-, oligo- and/or polyes¬ ters according to the present invention is characterized by what is presented in claim 19.
The lubricant according to the present inven¬ tion is characterized by what is presented in claim 20.
The plasticizer according to the present invention is characterized by what is presented in claim 21.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a method for producing a mixture comprising carboxylic, epoxy and/or hydroxyl acids, wherein the method comprises the following step:
a) oxidizing a natural composition including unsaturated fatty acids and/or esters thereof in a two-phase aqueous-organic system in the presence of a catalytic system, wherein the organic phase contains the natural composition and the aqueous phase contains a water-soluble oxidizing agent and wherein the cata¬ lytic system comprises a catalyst and a phase-transfer agent for the catalyst.
According to one embodiment of the present invention a mixture comprising carboxylic, epoxy and hydroxyl acids is produced by the method according to the present invention.
In this specification, unless otherwise stat- ed, the term "natural composition including unsaturat¬ ed fatty acids and/or esters thereof" should be under¬ stood as a composition derived or originating from a natural source. The natural composition may be ob¬ tained or it may originate from e.g. an oil plant or a tree. The composition and/or ratio of the fatty acids and/or esters thereof in the natural composition may vary depending on the original source of the natural composition .
The term "natural composition" used in this specification does not include synthetically produced compositions, where essentially pure or fractionated fatty acids and/or esters thereof are mixed together in order to form a composition.
According to one embodiment of the present invention the natural composition is processed prior to step a) .
According to one embodiment of the present invention the natural composition includes unsaturated fatty acids and esters thereof. According to one em¬ bodiment of the present invention the natural composi¬ tion includes unsaturated fatty acids or esters there- of.
According to one embodiment of the present invention the natural composition is a tall oil fatty acid mixture (TOFA) . Tall oil is a product, which can be produced e.g. as a byproduct of wood pulp manufac- ture process. Tall oil fatty acid mixture (TOFA) is a product, which can be obtained e.g. as by-product from the Kraft process of wood pulp manufacture after dis¬ tillation of tall oil. The advantage of tall oil fatty acid mixture as a raw material is that it is inexpen- sive and readily available during all seasons enabling large scale production of mono-, oligo- and/or polyes¬ ters in accordance with the present invention.
According to one embodiment of the present invention the tall oil fatty acid mixture comprises about 43 - 66 weight-% of linoleic acid and other diunsaturated fatty acids with 18 carbon atoms includ¬ ing conjugated acids, about 20 - 50 weight-% of oleic acid, about 2 - 10 weight-% of polyunsaturated fatty acids and about 0,5 - 3 weight-% of saturated fatty acids and about 0,5 - 3 weight-% of rosin acids. Table 1 shows the distribution of different fatty acids pre- sent in one example of Nordic TOFA. Table 2 shows the typical composition of TOFA from USA.
Table 1. Fatty acid distribution of Nordic TOFA (For- chem, for2)
Component (weight-% )
C 16:0 Palmitic acid 1,2
C 17:0 Margaric acid 1,0
C 18:0 Stearic acid 1,5
C 18:1 Oleic acid 24, 9
C 18:2 Linoleic acid 52, 4
C 18:3 Linolenic acid 1,4
C 18:3 Pinolenic acid 7,7
C 20:0 Arakis acid 0,8
C 20:2,3,4 Eicosanoic acids 1,8
Others 3,4
Table 2. Typical composition of TOFA from USA
Component (weight-% )
Linoleic non -conj ugated 34-59
Linoleic conjugated 7-9
Oleic acid 28-50
Saturated fatty acids 2-5
Other fatty acids 2-8
Rosin acids 0,8-4,3
According to one embodiment of the present invention the natural composition is a vegetable oil comprising unsaturated fatty acids in triglyceride or esterified form. According to one embodiment of the present invention the fatty acids of the vegetable oil are in transesterified form. The transesterified form can be obtained by reacting the vegetable oil with an alcohol, such as methanol or ethanol, wherein fatty acid esters, such as fatty acid methyl esters or fatty acid ethyl esters, respectively, are produced. Fatty acid methyl esters and fatty acid ethyl esters can be used as biodiesel.
According to one embodiment of the present invention the natural composition is selected from a group consisting of linseed oil, soybean oil, rapeseed oil, rubseed oil and olive oil.
Without limiting the present invention to any specific compositions of the vegetable oils it can be presented, as examples only, that linseed oil can com¬ prise about 5 - 6 weight-% of palmitic acid, about 3 - 5 weight-% of stearic acid, about 18 - 26 weight-% of oleic acid, about 14 - 20 % of linoleic acid, and about 51 - 56 weight-% of linolenic acid; that soybean oil can comprise about 2 - 10 weight-% of palmitic ac¬ id, about 2 - 6 weight-% of stearic acid, 23 - 32 weight-% of oleic acid, about 48 - 52 weight-% of lin- oleic acid, and about 2 - 12 weight-% of linolenic ac¬ id; that rapeseed oil of high-erucic acid type can comprise about 1 - 5 weight-% of palmitic acid, about 1 - 4 weight-% of stearic acid, about 13 - 38 weight-% of oleic acid, about 10 - 22 weight-% of linoleic ac- id, about 1 - 10 weight-% of linolenic acid, about 5 - 8 weight-% of eicosenoic acid and about 40 - 64 weight-% of erucic acid; and that rapeseed oil of low- erucic acid type can comprise about 1 - 5 weight-% of palmitic acid, about 1 - 2 weight-% of stearic acid, about 50 - 65 weight-% of oleic acid, about 15 - 30 weight-% of linoleic acid, about 5 - 13 weight-% of linolenic acid, about 1 - 3 weight-% of eicosenoic ac¬ id and about 0 - 2 weight-% of erucic acid; and that olive oil can comprise about 7 - 16 weight-% of pal- mitic acid, about 64 - 86 weight-% of oleic acid, and about 4 - 15 weight-% of linoleic acid. According to one embodiment of the present invention the natural composition is a mixture of fat¬ ty acids and/or esters thereof obtained from a vegeta¬ ble oil.
According to one embodiment of the present invention the natural composition comprises in addi¬ tion to the unsaturated fatty acids and/or esters thereof further components. According to one embodi¬ ment of the present invention the natural composition further comprises varying amounts of one or more satu¬ rated fatty acids depending on the type of natural composition used. Esters can also be mentioned as ex¬ amples of such further components.
According to one embodiment of the present invention the unsaturated fatty acids are monounsatu- rated, diunsaturated and/or triunsaturated fatty ac¬ ids .
According to one embodiment of the present invention the water-soluble oxidizing agent comprises hydrogen peroxide. According to one embodiment of the present invention the water-soluble oxidizing agent is hydrogen peroxide. According to one embodiment of the present invention the water-soluble oxidizing agent is aqueous hydrogen peroxide.
According to one embodiment of the present invention the organic phase contains at least one in¬ ert solvent. According to one embodiment of the pre¬ sent invention the organic phase contains toluene, xy¬ lene or a combination thereof.
According to one embodiment of the present invention step a) is carried out at a temperature of 50 - 90 °C, preferably at a temperature of 60 - 80 °C . The reaction of step a) is exothermic in nature.
According to one embodiment of the present invention step a) is carried out for 0,5 - 10 h, pref¬ erably 1 - 6 h. According to one embodiment of the present invention the catalyst comprises at least one metal selected from the elements of group 6 of the periodic table. According to one embodiment of the present in- vention the catalyst is selected from a group consist¬ ing of tungstic acid, molybdic acid, alkaline salts of molybdic acid and any mixture thereof.
According to one embodiment of the present invention the phase-transfer agent for the catalyst is selected from a group consisting of di (hydrogenated tallow) dimethylammonium chloride, pyridinium salts, phosphonium salts, crown ethers and any mixture there¬ of.
According to one embodiment of the present invention the method comprises the step of converting at least one ester produced in step a) into acid form.
Without limiting the present invention to any specific reaction schemes, the Reaction scheme 1 below shows, as a general example only, the oxidation reac- tion of TOFA (with only oleic acid presented) in ac¬ cordance with step a) :
Reaction scheme 1 :
Figure imgf000010_0001
The inventors of the present invention sur¬ prisingly found that a natural source, such as tall oil fatty acid mixture, as an environmentally friendly and readily feasible raw material, can be oxidized di¬ rectly without any prior fractionation or purification steps in accordance with step a) of the present inven¬ tion for producing a mixture comprising carboxylic, epoxy and/or hydroxyl acids. An advantage of the oxi¬ dation reaction in accordance with step a) is that it is readily controllable whereby different kinds of ac¬ ids with properties suitable for the further use can be produced. The oxidation reaction in step a) can be stopped e.g. at the diol stage or continued as a one- step process to oxidative cleavage, which yields shorter chain diacids and monoacids .
According to one embodiment of the present invention the method comprises, after step a) , remov- ing at least one component from the produced mixture comprising carboxylic, epoxy and/or hydroxyl acids and/or adding at least one component to the produced mixture comprising carboxylic, epoxy and/or hydroxyl acids before said mixture is reacted with at least one alcohol in step b) .
The present invention further relates to a mixture comprising carboxylic, epoxy and/or hydroxyl acids obtainable by the method according the present invention .
According to one embodiment of the present invention the mixture comprising carboxylic, epoxy and/or hydroxyl acids produced by the method according to the present invention comprises also other compo¬ nents. Esters of at least one fatty acid, un-reacted starting material etc. can be mentioned as examples of such components.
The present invention further relates to a method for producing mono-, oligo- and/or polyesters, wherein the method comprises the following steps: b) reacting a mixture comprising carboxylic, epoxy and/or hydroxyl acids, obtainable by the method of the pre- sent invention comprising step a) , with at least one alcohol selected from a group consisting of monoalco¬ hols, oligoalcohols , polyols, and any mixture thereof, in the presence of an acid catalyst for producing a reaction mixture; and c) neutralizing the reaction mixture.
According to one embodiment of the present invention the at least one alcohol is selected from a group consisting of monoalcohols, oligoalcohols, poly¬ ols, and any mixture of monoalcohols and polyols.
According to one embodiment of the present invention the monoalcohol is selected from a group consisting of 1-, 2- and i-butanol, 1- and i- valeralcohol , 1-hexanol and 2-ethyl hexanol and any mixture thereof.
According to one embodiment of the present invention the oligoalcohol ((HO)nR) is C2_C6_diol.
According to one embodiment of the present invention the polyol is selected from a group consist¬ ing of neopentyl glycol (NPG) , trimethylolpropane (TMP) , 2-methyl-l, 3-propanediol, 2-butyl-2-ethyl-l , 3- propanediol, trimethylolethane, di-trimethylol- propane, pentaerythtritol , di-pentaerythtritol , eth- ylene glycol, di- and oligo-ethylene glycol, propylene glycol, di- and oligo-propylene glycol, 1 , 3-methyl propanediol, trimethylolpropane, 1, 4-butanediol, 1,6- hexanediol and any mixture thereof.
According to one embodiment of the present invention the at least one alcohol is selected from a group consisting of neopentyl glycol, pentaerytritol , trimethylol propane and 2-butyl-2-ethyl-l , 3- propanediol .
According to one embodiment of the present invention step b) is carried out in the presence of at least one additional starting material.
According to one embodiment of the present invention step b) is carried out in the presence of at least one monoacid and/or at least one diacid. Accord¬ ing to one embodiment of the present invention step b) is carried out in the presence of at least one addi¬ tional carboxylic acid selected from a group consist¬ ing C2-Ci8-monocarboxylic acids and any mixture of cor- responding monocarboxylic acids. According to one em¬ bodiment of the present invention step b) is carried out in the presence of at least one of the following: 1- or i-butyric acid, 1- or i-valeric acid, caproic acid, caprylic acid, 2-ethylhexyl acid, dodecyl acid, myristinic acid, stearic acid, oleic acid, amber acid, adipic acid, azelaic acid, pelargonic acid, oxalic ac¬ id, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid.
According to one embodiment of the present invention step b) is carried out in the presence of at least one of propionic acid, valeric acid, caproic ac¬ id, adipic acid, pelargonic acid and lauric acid.
According to one embodiment of the present invention step b) is carried out in the presence of a solvent. According to one embodiment of the present invention step b) is carried out in the presence of a solvent selected from a group consisting of toluene, xylene and any mixture thereof.
According to one embodiment of the present invention step b) is carried out in the absence of a solvent.
According to one embodiment of the present invention step b) is carried out at a temperature of 60 - 280 °C, preferably 90 - 260 °C, and more prefera¬ bly 100 - 200 °C.
According to one embodiment of the present invention the acid catalyst in step b) is a protonic acid catalyst or a Lewis acid catalyst. According to one embodiment of the present invention the acid cata¬ lyst in step b) is selected from a group consisting of sulfuric acid (H2SO4) , methanesulfonic acid (MeSOsH) , hydrochloric acid (HC1) , phosphoric acid (H3PO4) , p- toluenesulphonic acid, titanates, (RO)4Ti, stannous oxide (SnO) , and ion exchange resins. Sulfonated poly- styrene-divinylbenzene ion exchange resins or acidic Dowex resins can be mentioned as examples of ion ex¬ change resins that can be used in the step b) .
According to one embodiment of the present invention step b) is carried out for 1 - 24 h, preferably 2-12 h, more preferably 3-6 h.
According to one embodiment of the present invention step c) comprises treating the reaction mixture with a base selected from a group consisting of triethylamine, sodium carbonate ( a2C03) , sodium bicar¬ bonate ( aHCOs) , sodium hydroxide (NaOH) , potassium hydroxide (KOH) and any mixture thereof. The base can be used in solid form or as an aqueous solution.
Without limiting the present invention to any specific reaction schemes, the general reaction schemes 2 and 3 below show, as examples only, some manners on how the esterification reactions proceed for producing mono-, oligo- and/or polyesters: Reaction scheme 2 :
Reaction scheme 3:
CH3(CH2)7CH-CH(CH2)7COOH + R-, COOH + HOOC(CH2)mCOOH
+ CH3(CH2)7CHOHCHOH(CH2)7COOH + (HO)nR2 wherein
R is C1-C18-alkyl or alkenyl group
R2 is straight-chain or branched alkyl group
m is 0-16 and
n is 2-6
OLIGO-/polyester
The present invention further relates to mono-, oligo- and/or polyesters obtainable by the method according to the present invention. The ob¬ tained product has typically a viscous liquid or waxy form in room temperature and a melting temperature of below 100 °C.
The present invention further relates to the use of the mono-, oligo- and/or polyesters produced with the method according to the present invention for the production of a lubricant or a plasticizer.
The present invention further relates to a lubricant comprising the mono-, oligo- and/or polyes¬ ters according to the present invention. The lubricant can be used in motors, as oil for refrigerating ma¬ chines, in cosmetic applications, as compatibilisator when producing polymer blends or composites. The lub¬ ricant can also be used as an agent for modifying wood or a component in printing inks.
The present invention further relates to a plasticizer comprising the mono-, oligo- and/or polyesters according to the present invention.
The embodiments of the invention described hereinbefore may be used in any combination with each other. Several of the embodiments may be combined to¬ gether to form a further embodiment of the invention. A method, a product or a use, to which the invention is related, may comprise at least one of the embodi¬ ments of the invention described hereinbefore.
An advantage of the present invention is that a natural composition of fatty acids and/or esters thereof such as tall oil fatty acid mixture can be used directly without purification or fractionation as a starting material for the production of a mixture comprising carboxylic, epoxy and/or hydroxyl acids. An advantage of using e.g. tall oil fatty acid mixture as starting material in the method in accordance with the present invention is that tall oil fatty acid mixture is a readily available and inexpensive raw material enabling large scale production of the end products in an inexpensive manner. An advantage of the oxidation method accord¬ ing to the present invention is that no extreme reac¬ tion conditions or temperatures are needed and that no harmful side products are produced during the reac- tions. Further, the product resulting from the oxida¬ tion of step a) of the present invention can be used as such without pretreatments for producing mono-, ol- igo- and/or polyesters in the esterification method in accordance with the present invention.
An advantage of both the oxidation method and the esterification method is that no purification or fractionation steps are required for the material used in step a) or step b) thus enabling a simplified reac¬ tion procedure to be used for producing mono-, oligo- and/or polyesters. As the reaction procedure requires less steps to be performed the overall production costs reduce.
An advantage of the esterification method is that the mono-, oligo- and/or polyesters produced have good viscosity values especially for lubricant appli¬ cations .
With the products produced according to the method of the present invention, natural alternatives to known product blends normally produced from petro- chemical starting materials, and to products based on raw oil, potentially containing carcinogens, are achieved .
EXAMPLES
The description below discloses some embodi¬ ments of the invention in such a detail that a person skilled in the art is able to utilize the invention based on the disclosure. Not all steps of the embodi¬ ments are discussed in detail, as many of the steps will be obvious for the person skilled in the art based on this specification. Example 1. Oxidation of rapeseed oil methyl ester
Rapeseed oil methyl ester (80 g) , tungstic acid (1,7 g) and Arquad 2HT-75 (3,0 g) was heated to 60-70 °C. Aqueous hydrogen peroxide (50 %; 160 g) was added within 1-2 hours at 60-80 °C. The mixture was further heated to reaction temperature (95-100 °C) and stirred at that temperature for about 6 hours. There¬ after sodium bicarbonate (1,0-1,5 g) and toluene (50 ml) were added. After stirring for 10 min at 80 - 85 °C phases were separated as hot. Water phase was cooled to 5 - 10 °C and filtered. The formed precipi¬ tate consisting of mainly azelaic acid was connected with toluene phase. Toluene phase was evaporated under vacuum to bath temperature of 90 °C to remove sol- vents. The product was clear viscous liquid (85 g) . Conversion of the reaction was > 99 %. The obtained product mixture was analysed by GC . The combined yield of azelaic acid and pelargonic acid was 75 % and hexa- noic acid yield was 7 %. Total acid number (TAN) of the product was determined by titration method and it was 294.
Example 2. Oxidation of tall oil fatty acid mixture
A tall oil fatty acid mixture ( (Forchem, for2), (80 g) , tungstic acid (1,5 g) and Arquad 2HT-75 (2,3 g) was heated to 60-70 °C. Aqueous hydrogen per¬ oxide (50 %; 170 g) was then added within about 1 hour at 60-70 °C . The mixture was further heated to reac¬ tion temperature (95-100 °C) and stirred at that tem- perature for 6 h. Thereafter sodium bicarbonate (1,0- 1,5 g) and toluene (50 ml) were added. After stirring for 10 min at 80 - 85 °C, the phases were separated as hot. The water phase was cooled to 5 - 10 °C and fil¬ tered. The formed precipitate was connected with a toluene phase. The toluene phase was evaporated under vacuum to a bath temperature of 90 °C for removing solvents. The product was a white/yellow wax and the yield was 85 g. The distillation residue was analyzed by GC after silylating with BSTFA. The conversion of the reaction was > 99 %. The yields were: 26 weight-% of azelaic acid, 10 weight-% of pelargonic acid and 12 weight-% of hexanoic acid.
Example 3. Oxidation of rapeseed oil (Finnish food grade)
A mixture of rapeseed oil (Finnish food grade; 80,0 g) , tungstic acid (1,7 g) and Arquad 2HT- 75 (3,2 g) was heated to 60-70 °C. Then, aqueous hy¬ drogen peroxide (50 %; 160 g) was added within about 2 hours at 60-70 °C. The mixture was further heated to reaction temperature (95-100 °C) and stirred at that temperature for 6 h. Thereafter sodium bicarbonate (1,5 g) and toluene (50 ml) were added. After stirring for 10 min at 80 - 85 °C, the phases were separated as hot. Water phase was cooled to 5 - 10 °C overnight and filtered. The formed precipitate was added to the tol- uene phase. The toluene phase was evaporated under vacuum to bath temperature of 60 °C to remove sol¬ vents. The product was a clear viscous liquid (yield 87 g) . The conversion of the reaction was determined from NMR and it was > 99 %. Total acid number in- creased in the reaction from 2,1 to 265 mgKOH/g.
Example 4. Oxidation of rapeseed oil (Brassica Rapa)
Mixture of rapeseed oil (Brassica Rapa; 80,0 g) , tungstic acid (1,7 g) and Arquad 2HT-75 (3,1 g) was heated to 60-70 °C. Then, aqueous hydrogen perox¬ ide (50 %; 160 g) was added within about 2 hours at 60-70 °C. The mixture was further heated to reaction temperature (95-100 °C) and stirred at that tempera¬ ture for 6 h. Thereafter sodium bicarbonate (1,5 g) and toluene (50 ml) were added. After stirring for 10 min at 80 - 85 °C the phases were separated as hot. The water phase was cooled to 5 - 10 °C overnight and filtered. The formed precipitate was added to the tol¬ uene phase. The toluene phase was evaporated under vacuum to bath temperature of 60 °C to remove sol¬ vents. The product was a clear/white viscous liquid (yield 76 g) . The conversion of the reaction was de¬ termined from NMR and it was > 99 %. Total acid number increased in the reaction from 2,3 to 200 mgKOH/g.
Example 5. Preparation of oligo/polyesters from oxi- dized rapeseed oil methyl ester
Oxidation mixture of rapeseed oil methyl es¬ ter (75 g) , TMP (Merck, 99 %; 20 g) and toluene (Rathburn, HPLC grade: 70 ml) were added to a 3-necked flask (250 ml) which was equipped with oil bath, Dean- Stark apparatus, magnetic stirrer, N2-inlet and ther¬ mometer. Reaction mixture was heated to 110-120 °C (35 minutes) and p-TsOH ( Sigma-Aldrich, 98 %; 1,0 g) was added. Reaction mixture was stirred and heated for 4 hours and cooled to room temperature. Reaction mixture was neutralized with Et3 (Fluka, >99,5; 2 ml). Organ¬ ic layer was washed with water and saturated NaCl and dried with anhydrous a2S04 and the solvents were evap¬ orated using rotary evaporator. The product was a brown oil and the yield was 86 g. The analysis results are presented in the below table 4.
Example 6. Preparation of oligo/polyesters from oxidized tall oil fatty acid mixture
Oxidation mixture of tall oil fatty acid mix- ture (hexanoic acid 11 %, nonanoic acid 9 %, azelaic acid 24 %, others 56 %; 75 g) , NPG (Aldrich, 99 %; 18 g) and toluene (Rathburn, HPLC grade: 70 ml) were add¬ ed to a 3-necked flask (250 ml) which was equipped with oil bath, Dean-Stark apparatus, magnetic stirrer, N2-inlet and thermometer. The reaction mixture was heated to 110-120 °C (0,5 h) and p-TsOH (Sigma- Aldrich, 98 %; 1,2 g) was added. Reaction mixture was stirred and heated for 2,5 hours and cooled to room temperature. Reaction mixture was neutralized with NEt3 (Fluka, >99,5; 8 ml), toluene (100 ml) was added and organic layer washed with water. Organic layer was dried with anhydrous Na2SC>4 and solvents were evapo¬ rated using rotary evaporator. The product was a brown oil, the yield was 75 g and the conversion was 63 %. The product was characterized by NMR, Cone & Plate viscometer and total acid number (TAN) was measured. Kinematic viscosities were determined according to ASTM D 445 at 40 °C and 100 °C. Viscosity indexes were determined according to ASTM D 2270. The analysis re¬ sults are presented in the below table 4. Example 7. Preparation of oligo/polyesters from oxidised rapeseed oil (Finnish food grade)
Oxidation mixture of rapeseed oil (Finnish food grade) (75 g) , NPG (Aldrich, 99 %; 25 g) and tol¬ uene (Rathburn, HPLC grade: 80 ml) were added to a 3- necked flask (250 ml) which was equipped with oil bath, Dean-Stark apparatus, magnetic stirrer, N2-inlet and thermometer. Reaction mixture was heated to 110- 120 °C (30 minutes) and p-TsOH ( Sigma-Aldrich, 98 %; 1,1 g) was added. Reaction mixture was stirred and heated for 13 hours and cooled to room temperature. The reaction mixture was neutralized with Et3 (Fluka, >99,5; 2 ml) . The organic layer was washed with water and saturated NaCl and dried with anhydrous a2S04 and the solvents were evaporated using rotary evaporator. The product was a brown oil and the yield was 77 g. The analysis results are presented in the below table 4.
RESULTS
Table 3 below shows the reaction conditions and the composition of the products produced as a re¬ sult of the oxidation reaction. Table 3. Oxidation of Rapeseed oil methyl ester (RME, Finnish food grade, example 1), TOFA (example 2), Rapeseed oil (Finnish food grade, example 3) and Rape- seed oil (Brassica Rapa, example 4) .
RME (ExamTOFA* Rapeseed Rapeseed ple 1) (Example oil oil
2) (Example (Example
3) 4)
Reaction
conditions :
TOFA (g) 80
RME (g) 80
Rapeseed 80
oil (g)
Rapeseed 80 oil (g)
Tungstic 1,7 1,5 1,7 1,7 acid (g)
Arquad 2HT- 3, 0 2,3 3,2 3,1 75 (g)
50 % H202 160 170 160 160
(g)
Temperature 95-100 95-100 95-100 95-100 (°C)
Time (h) 6 6 6 6
Yield (g) 85 85 87 76
Conversion >99 >99 >99 >99 (%)
Composition
of prod¬ ucts :
Hexanoic 7 11,5 8 6 acid
(weight-% ) Pelargonic 75 10,1 77 70 acid
(weight-% )
Azelaic ac¬ 26, 3
id (weight-
%)
Others 18 52, 1 15 24 (weight-% )
*The mixture of acids produced starting from TOFA (example 2) was analyzed using a different method than for the other examples (examples 1, 3 and 4) ex- plaining the difference in the numerical values.
Table 4 below shows analysis results received from the measurements with examples 5-7. Table 4. Analysis results with examples 5-7.
Exam Po- Oxida¬ Reac¬ To¬ Vis¬ Vis¬ Vis¬ pie lyol tion tion tal cosity cosity cosity mixtu¬ time acid (40 (100 index re of (h) num°C) °C) (VI) ber
(TAN
)
5 TMP Rap- 4 48 77 12 153 seed
oil
methyl
ester
6 NPG TOFA 2,5 78 118 14 121 7 NPG Rape- 13 21 244 25 130 seed
oil
(Finnish
food
grade)
The viscosity and viscosity index measure¬ ments presented in table 4 show that the esters pro¬ duced in accordance with the present invention can be used as lubricants or a components in lubricants. It was noticed from the results that the method in ac¬ cordance with the present invention can be used to produce products with properties suitable for lubri¬ cants or plasticizers.
It is obvious to a person skilled in the art that with the advancement of technology, the basic idea of the invention may be implemented in various ways. The invention and its embodiments are thus not limited to the examples described above; instead they may vary within the scope of the claims.

Claims

1. A method for producing a mixture compris¬ ing carboxylic, epoxy and/or hydroxyl acids, c h a r ¬ a c t e r i z e d in that the method comprises the fol- lowing step:
a) oxidizing a natural composition including unsaturated fatty acids and/or esters thereof in a two-phase aqueous-organic system in the presence of a catalytic system, wherein the organic phase contains the natural composition and the aqueous phase contains a water-soluble oxidizing agent and wherein the cata¬ lytic system comprises a catalyst and a phase-transfer agent for the catalyst.
2. The method of claim 1, c h a r a c t e r - i z e d in that the natural composition is tall oil fatty acid mixture (TOFA)
3. The method of claim 1, c h a r a c t e r i z e d in that the natural composition is a vegetable oil comprising unsaturated fatty acids in triglyceride or esterified form.
4. The method of claim 1 or 3, ch a r a c ¬ t e r i z e d in that the natural composition is se¬ lected from a group consisting of linseed oil, soybean oil, rapeseed oil, rubseed oil and olive oil.
5. The method of claims 3 or 4, c h a r a c ¬ t e r i z e d in that the natural composition is a mix¬ ture of fatty acids and/or esters thereof obtained from a vegetable oil.
6. The method of any one of claims 1 - 5, c h a r a c t e r i z e d in that the water-soluble oxi¬ dizing agent comprises hydrogen peroxide.
7. The method of any one of claims 1 - 6, c h a r a c t e r i z e d in that step a) is carried out at a temperature of 50 - 90 °C, preferably at a tem- perature of 60 - 80 °C .
8. The method of any one of claims 1 - 7, c h a r a c t e r i z e d in that the catalyst is select- ed from a group consisting of tungstic acid, molybdic acid, alkaline salts of molybdic acid and any mixture thereof .
9. The method of any one of claims 1 - 8, c h a r a c t e r i z e d in that the phase-transfer agent for the catalyst is selected from a group con¬ sisting of di (hydrogenated tallow) dimethylammonium chloride, pyridinium salts, phosphonium salts, crown ethers and any mixture thereof.
10. A mixture comprising carboxylic, epoxy and/or hydroxyl acids obtainable by the method of any one of claims 1 - 9.
11. A method for producing mono-, oligo- and/or polyesters, c h a r a c t e r i z e d in that the method comprises the following steps:
b) reacting a mixture comprising carboxylic, epoxy and/or hydroxyl acids obtainable by the method of any one of claims 1 - 9 with at least one alcohol selected from a group consisting of monoalcohols, oli- goalcohols, polyols, and any mixture thereof, in the presence of an acid catalyst for producing a reaction mixture; and
c) neutralizing the reaction mixture.
12. The method of claim 11, c h a r a c t e r - i z e d in that step b) is carried out in the presence of a solvent selected from a group consisting of tolu¬ ene, xylene and any mixture thereof.
13. The method of any one of claims 11 - 12, c h a r a c t e r i z e d in that step b) is carried out at a temperature of 60 - 280 °C, preferably 90 - 260 °C, and more preferably 100 - 200 °C .
14. The method of any one of claims 11 - 13, c h a r a c t e r i z e d in that the acid catalyst is selected from a group consisting of sulfuric acid (H2SO4) , methanesulfonic acid (MeSOsH) , hydrochloric acid (HC1) , phosphoric acid (H3PO4) , p-toluenesulphonic acid, titanates, (RO)4Ti, stannous oxide (SnO) , and ion exchange resins.
15. The method of any one of claims 11 - 14, c h a r a c t e r i z e d in that the at least one alco- hoi is selected from a group consisting of neopentyl glycol, pentaerytritol , trimethylol propane and 2- butyl-2 -ethyl- 1 , 3-propanediol .
16. The method of any one of claims 11 - 15, c h a r a c t e r i z e d in that step b) is carried out in the presence of at least one of propionic acid, va¬ leric acid, caproic acid, adipic acid, pelargonic acid and lauric acid.
17. The method of any one of claims 11 - 16, c h a r a c t e r i z e d in that step c) comprises treating the reaction mixture with a base selected from a group consisting of triethylamine, disodium carbonate ( a2C03) , sodium carbonate (NaHCOs) , sodium hydroxide (NaOH) , potassium hydroxide (KOH) and any mixture thereof.
18. Mono-, oligo- and/or polyesters obtaina¬ ble by the method of any one of claims 11 - 17.
19. Use of the mono-, oligo- and/or polyes¬ ters obtainable by the method according to any one of claims 11 - 17 for the production of a lubricant or a plasticizer.
20. Lubricant, c h a r a c t e r i z e d in that it comprises the mono-, oligo- and/or polyesters ac¬ cording to claim 18.
21. Plasticizer, c h a r a c t e r i z e d in that it comprises the mono-, oligo- and/or polyesters according to claim 18.
PCT/FI2012/051175 2011-11-28 2012-11-28 Method for catalytic oxidation of a natural composition including unsaturated fatty acids and/or esters thereof and the use of a mixture obtained therefrom for the production of mono-, oligo- and/or polyesters WO2013079791A1 (en)

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