FI123683B - A process for the catalytic oxidation of a natural composition comprising unsaturated fatty acids and / or their esters and use of a mixture thereof for the preparation of mono-, oligo- and / or polyesters - Google Patents

A process for the catalytic oxidation of a natural composition comprising unsaturated fatty acids and / or their esters and use of a mixture thereof for the preparation of mono-, oligo- and / or polyesters Download PDF

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Publication number
FI123683B
FI123683B FI20116188A FI20116188A FI123683B FI 123683 B FI123683 B FI 123683B FI 20116188 A FI20116188 A FI 20116188A FI 20116188 A FI20116188 A FI 20116188A FI 123683 B FI123683 B FI 123683B
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Prior art keywords
acid
mixture
process according
oil
group
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FI20116188A
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Finnish (fi)
Swedish (sv)
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FI20116188A (en
Inventor
Salme Koskimies
Jukka Tulisalo
Pauliina Pitkaenen
Minni Pirttimaa
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Teknologian Tutkimuskeskus Vtt
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Priority to FI20116188A priority Critical patent/FI123683B/en
Priority to PCT/FI2012/051175 priority patent/WO2013079791A1/en
Priority to EP12815719.5A priority patent/EP2785677A1/en
Publication of FI20116188A publication Critical patent/FI20116188A/en
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Publication of FI123683B publication Critical patent/FI123683B/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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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
5
FIELD OF THE INVENTION
The invention relates to a method for producing a mixture comprising carboxylic, epoxy and/or hydroxyl acids and to its further use in a method for 10 producing mono-, oligo-, and/or polyesters for various applications. The invention further relates to a mixture comprising carboxylic, epoxy and/or hydroxyl acids and to mono-, oligo- and/or polyesters. The invention further relates to lubricants and plasticizers.
15
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 20 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 obtained by processing hydrocarbons of vegetable oil or 25 fossil origin.
For example azelaic acid (nonanedioic acid)
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^ and pelargonic acid (nonanoic acid) used for the above ^ applications can be industrially produced by ozonoly-
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o sis of oleic acid. However, a drawback of this method ^ 30 is the toxicity and unstability of ozone as well as g the used processing chemicals and the produced inter- 0- mediates. Further, ozone has to be continuously gener-oo ated on-site by electrical discharge in air. The ozone
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t- production is the limiting factor for large scale pro- ^ 35 duction of these acids.
2
Further, traditionally chemical plant oil conversion reactions are mainly carried out using separated and purified raw material, whereby several purification step of the raw material are needed during 5 which part of the raw material is lost. However, in many applications, such as lubricants and plasticizers, the optimal properties are achieved by using several starting materials, e.g. fatty acids with variable chain length. In industrial scale this means using 10 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 15 enabling large-scale production of mono-, oligo- and/or polyesters for e.g. lubricant or plasticizer applications. Especially environmentally friendly materials and methods are needed in order to replace fossil based products with renewable materials.
20
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 25 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 o hydroxyl acids as starting material and to provide es-
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^ ters to be used in various applications.
° 30
χ SUMMARY
cr Q.
The method according to the present invention °o $2 for producing oligo- and/or polyesters is character- co Ί- ized by what is presented m claim 1.
δ c\j 3
The oligo- and/or polyesters according to the present invention are characterized by what is presented in claim 16.
The use of the oligo- and/or polyesters ac-5 cording to the present invention is characterized by what is presented in claim 17.
The lubricant according to the present invention is characterized by what is presented in claim 18 .
10
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 15 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 20 the natural composition and the aqueous phase contains a water-soluble oxidizing agent and wherein the catalytic system comprises a catalyst and a phase-transfer agent for the catalyst.
According to one embodiment of the present 25 invention a mixture comprising carboxylic, epoxy and hydroxyl acids is produced by the method according to the present invention.
o In this specification, unless otherwise stat es ^ ed, the term "natural composition including unsaturat- o 1 30 ed fatty acids and/or esters thereof" should be under- ^ stood as a composition derived or originating from a
X
£ natural source. The natural composition may be ob- «30 tained or it may originate from e.g. an oil plant or a oo ^ tree. The composition and/or ratio of the fatty acids ^ 35 and/or esters thereof in the natural composition may ^ vary depending on the original source of the natural composition.
4
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 5 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 10 invention the natural composition includes unsaturated fatty acids and esters thereof. According to one embodiment of the present invention the natural composition includes unsaturated fatty acids or esters thereof .
15 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 manufacture process. Tall oil fatty acid mixture (TOFA) is a 20 product, which can be obtained e.g. as by-product from the Kraft process of wood pulp manufacture after distillation of tall oil. The advantage of tall oil fatty acid mixture as a raw material is that it is inexpensive and readily available during all seasons enabling 25 large scale production of mono-, oligo- and/or polyesters in accordance with the present invention.
According to one embodiment of the present ” invention the tall oil fatty acid mixture comprises o ^ about 43 - 66 weight-% of linoleic acid and other
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o 30 diunsaturated fatty acids with 18 carbon atoms mclud- ^ ing conjugated acids, about 20 - 50 weight-% of oleic * acid, about 2-10 weight-% of polyunsaturated fatty
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acids and about 0,5-3 weight-% of saturated fatty oo $2 acids and about 0,5-3 weight-% of rosin acids. Table
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f- 35 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.
5
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__ 5 Table 2. Typical composition of TOFA from USA__
Component (weight-%)_
Linoleic non-conjugated 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 co ^ 10 esterified form. According to one embodiment of the present invention the fatty acids of the vegetable oil
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? are in transesterified form. The transesterified form
Tj- ·- can be obtained by reacting the vegetable oil with an ir alcohol, such as methanol or ethanol, wherein fatty
CL
15 acid esters, such as fatty acid methyl esters or fatty acid ethyl esters, respectively, are produced. Fatty
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acid methyl esters and fatty acid ethyl esters can be ° used as biodiesel.
6
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.
5 Without limiting the present invention to any specific compositions of the vegetable oils it can be presented, as examples only, that linseed oil can comprise about 5-6 weight-% of palmitic acid, about 3 -5 weight-% of stearic acid, about 18 - 26 weight-% of 10 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 acid, about 2-6 weight-% of stearic acid, 23 - 32 weight-% of oleic acid, about 48 - 52 weight-% of lin-15 oleic acid, and about 2-12 weight-% of linolenic acid; 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-20 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, 25 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 o ^ olive oil can comprise about 7-16 weight-% of pal- o 30 mitic acid, about 64 - 86 weight-% of oleic acid, and ^ about 4-15 weight-% of linoleic acid.
χ According to one embodiment of the present invention the natural composition is a mixture of fat-oo $2 ty acids and/or esters thereof obtained from a vegeta- ^ 35 ble oil.
° According to one embodiment of the present invention the natural composition comprises in addi- 7 tion to the unsaturated fatty acids and/or esters thereof further components. According to one embodiment of the present invention the natural composition further comprises varying amounts of one or more satu-5 rated fatty acids depending on the type of natural composition used. Esters can also be mentioned as examples of such further components.
According to one embodiment of the present invention the unsaturated fatty acids are monounsatu-10 rated, diunsaturated and/or triunsaturated fatty acids .
According to one embodiment of the present invention the water-soluble oxidizing agent comprises hydrogen peroxide. According to one embodiment of the 15 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 20 invention the organic phase contains at least one inert solvent. According to one embodiment of the present invention the organic phase contains toluene, xylene or a combination thereof.
According to one embodiment of the present 25 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.
CO
1- According to one embodiment of the present o ^ invention step a) is carried out for 0,5 - 10 h, pref- o 30 erably 1 - 6 h.
^ According to one embodiment of the present ^ invention the catalyst comprises at least one metal
CL
selected from the elements of group 6 of the periodic °o table. According to one embodiment of the present in-
CD
1- 35 vention the catalyst is selected from a group consist- ° ing of tungstic acid, molybdic acid, alkaline salts of molybdic acid and any mixture thereof.
8
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, 5 phosphonium salts, crown ethers and any mixture thereof .
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. 10 Without limiting the present invention to any specific reaction schemes, the Reaction scheme 1 below shows, as a general example only, the oxidation reaction of TOFA (with only oleic acid presented) in accordance with step a): 15
Reaction scheme 1:
Oleic acid 0 Pelargonicacid 0 0 + H2O2
HWO5VPTA HWtyPTA
-H20 ·4Η2θ
H+/H20 °H
-» \/\/\/\Α|/\/\/\/γ0Η w 9,10-epoxystearic acid 0 0 9,10-dihydroxystearic acid ® δ c\j in 20 The inventors of the present invention sur- 0 ^ prisingly found that a natural source, such as tall ^ oil fatty acid mixture, as an environmentally friendly x £ and readily feasible raw material, can be oxidized di- 00 rectly without any prior fractionation or purification 00 ^ 25 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- 9 dation reaction in accordance with step a) is that it is readily controllable whereby different kinds of acids with properties suitable for the further use can be produced. The oxidation reaction in step a) can be 5 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-10 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 15 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.
2 0 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 components. Esters of at least one fatty acid, un-reacted 25 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, o ^ wherein the method comprises the following steps: b)
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o 30 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
CL
alcohol selected from a group consisting of monoalco- 00 hols, oligoalcohols, polyols, and any mixture thereof, co 1- 35 in the presence of an acid catalyst for producing a ° reaction mixture; and c) neutralizing the reaction mixture .
10
According to one embodiment of the present invention the at least one alcohol is selected from a group consisting of monoalcohols, oligoalcohols, polyols, and any mixture of monoalcohols and polyols.
5 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.
10 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 consisting of neopentyl glycol (NPG), trimethylolpropane 15 (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 20 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, 25 trimethylol propane and 2-butyl-2-ethyl-l,3-propanediol.
According to one embodiment of the present
CO
T- invention step b) is carried out in the presence of at o ^ least one additional starting material.
uS
o 30 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- 0.
ing to one embodiment of the present invention step b) oo ® is carried out in the presence of at least one addi- co Ί- 35 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- 11 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, 5 myristinic acid, stearic acid, oleic acid, amber acid, adipic acid, azelaic acid, pelargonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid.
According to one embodiment of the present 10 invention step b) is carried out in the presence of at least one of propionic acid, valeric acid, caproic acid, 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 15 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 20 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-25 bly 100 - 200 °C.
According to one embodiment of the present invention the acid catalyst in step b) is a protonic
CO
^ acid catalyst or a Lewis acid catalyst. According to ^ one embodiment of the present invention the acid cata- m o 30 lyst m step b) is selected from a group consisting of ^ sulfuric acid (H2S04) , methanesulfonic acid (MeS03H) , ^ hydrochloric acid (HC1), phosphoric acid (H3PO4) , p-
CL
toluenesulphonic acid, titanates, (RO)4Ti, stannous 00 $2 oxide (SnO), and ion exchange resins. Sulfonated poly- co >- 35 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).
12
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 5 invention step c) comprises treating the reaction mixture with a base selected from a group consisting of triethylamine, sodium carbonate (Na2C03) , sodium bicarbonate (NaHCCh) r sodium hydroxide (NaOH), potassium hydroxide (KOH) and any mixture thereof. The base can 10 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 15 for producing mono-, oligo- and/or polyesters:
Reaction scheme 2:
Hck/\/oH 1-r
OH
TMP ./ n 1 ηοί °
-------HO^/s---OH
Pelargonic acid I u>s Ο V
CO Caproicacid j[ ][ i— OO LOOJn W HO^ '
Azelaic acid O
t— HOn <N^OH \
NPG
00 O O O
00 L Jn $5 20 δ
CM
13
Reaction scheme 3:
CH3(CH2)7CH-CH(CH2)7COOH + R^OOH + HOOC(CH2)mCOOH
No + CH3(CH2)7CHOHCHOH(CH2)7COOH + (HO)nR2 wherein R-ι 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 5 The present invention further relates to mono-, oligo- and/or polyesters obtainable by the method according to the present invention. The obtained product has typically a viscous liquid or waxy form in room temperature and a melting temperature of 10 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.
15 The present invention further relates to a lubricant comprising the mono-, oligo- and/or polyesters according to the present invention. The lubricant can be used in motors, as oil for refrigerating machines, in cosmetic applications, as compatibilisator co 5 20 when producing polymer blends or composites. The lub-
C\J
^ ricant can also be used as an agent for modifying wood ? or a component in printing inks.
The present invention further relates to a ϊ plasticizer comprising the mono-, oligo- and/or polyol 25 esters according to the present invention, co T- The embodiments of the invention described co ^ hereinbefore may be used in any combination with each o ^ other. Several of the embodiments may be combined to gether to form a further embodiment of the invention.
14 A method, a product or a use, to which the invention is related, may comprise at least one of the embodiments of the invention described hereinbefore.
An advantage of the present invention is that 5 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 10 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 15 an inexpensive manner.
An advantage of the oxidation method according to the present invention is that no extreme reaction conditions or temperatures are needed and that no harmful side products are produced during the reac-20 tions. Further, the product resulting from the oxidation 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.
25 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- o ^ tion procedure to be used for producing mono-, oligo- o 30 and/or polyesters. As the reaction procedure requires ^ less steps to be performed the overall production Ξ costs reduce.
cc
CL
An advantage of the esterification method is oo that the mono-, oligo- and/or polyesters produced have
CD
I- 35 good viscosity values especially for lubricant applied cations.
15
With the products produced according to the method of the present invention, natural alternatives to known product blends normally produced from petrochemical starting materials, and to products based on 5 raw oil, potentially containing carcinogens, are achieved.
EXAMPLES
The description below discloses some embodi-10 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 embodiments are discussed in detail, as many of the steps will be obvious for the person skilled in the art 15 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 20 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. Thereafter sodium bicarbonate (1,0-1,5 g) and toluene (50 25 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-
CO
I- tate consisting of mainly azelaic acid was connected o ^ with toluene phase. Toluene phase was evaporated under LO 0 o 30 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
CL
product mixture was analysed by GC. The combined yield oo $2 of azelaic acid and pelargonic acid was 75 % and hexa- co >- 35 noic acid yield was 7 %. Total acid number (TAN) of ° the product was determined by titration method and it was 294.
16
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 5 (2,3 g) was heated to 60-70 °C. Aqueous hydrogen per oxide (50 %; 170 g) was then added within about 1 hour at 60-7 0 °C. The mixture was further heated to reaction temperature (95-100 °C) and stirred at that temperature for 6 h. Thereafter sodium bicarbonate (1,0— 10 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 filtered. The formed precipitate was connected with a toluene phase. The toluene phase was evaporated under 15 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-% 20 of azelaic acid, 10 weight-% of pelargonic acid and 12 weight-% of hexanoic acid.
Example 3. Oxidation of rapeseed oil (Finnish food grade) 25 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-
CO
^ drogen peroxide (50 %; 160 g) was added within about 2 ^ hours at 60-70 °C. The mixture was further heated to
LO
o 30 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
CL
for 10 min at 80 - 85 C, the phases were separated as oo $2 hot. Water phase was cooled to 5 - 10 °C overnight and
CD
Ί- 35 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- 17 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.
5
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-10 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 15 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 toluene phase. The toluene phase was evaporated under vacuum to bath temperature of 60 °C to remove sol-20 vents. The product was a clear/white viscous liquid (yield 7 6 g) . The conversion of the reaction was determined from NMR and it was > 99 %. Total acid number increased in the reaction from 2,3 to 200 mgKOH/g.
25 Example 5. Preparation of oligo/polyesters from oxidized rapeseed oil methyl ester
Oxidation mixture of rapeseed oil methyl es- ” ter (75 g) , TMP (Merck, 99 %; 20 g) and toluene o ^ (Rathburn, HPLC grade: 70 ml) were added to a 3-necked
LO
o 30 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
CL
minutes) and p-TsOH (Sigma-Aldrich, 98 %; 1,0 g) was oo $2 added. Reaction mixture was stirred and heated for 4 co I- 35 hours and cooled to room temperature. Reaction mixture ^ was neutralized with NEt3 (Fluka, >99,5; 2 ml). Organ ic layer was washed with water and saturated NaCl and 18 dried with anhydrous Na2SC>4 and the solvents were evaporated 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.
5
Example 6. Preparation of oligo/polyesters from oxidized tall oil fatty acid mixture
Oxidation mixture of tall oil fatty acid mixture (hexanoic acid 11 %, nonanoic acid 9 %, azelaic 10 acid 24 %, others 56 %; 75 g) , NPG (Aldrich, 99 %; 18 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 thermometer. The reaction mixture was 15 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 20 and organic layer washed with water. Organic layer was dried with anhydrous Na2S04 and solvents were evaporated 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 25 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 $2 determined according to ASTM D 2270. The analysis re- o ^ suits are presented in the below table 4.
s ^ Example 7. Preparation of oligo/polyesters from oxi- x dised rapeseed oil (Finnish food grade) Q_
Oxidation mixture of rapeseed oil (Finnish ® food grade) (75 g), NPG (Aldrich, 99 %; 25 g) and tol- ^ 35 uene (Rathburn, HPLC grade: 8 0 ml) were added to a 3- necked flask (250 ml) which was equipped with oil bath, Dean-Stark apparatus, magnetic stirrer, N2-inlet 19 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.
5 The reaction mixture was neutralized with NEt3 (Fluka, >99,5/ 2 ml) . The organic layer was washed with water and saturated NaCl and dried with anhydrous Na2S04 and the solvents were evaporated using rotary evaporator. The product was a brown oil and the yield was 77 g. 10 The analysis results are presented in the below table 4.
RESULTS
Table 3 below shows the reaction conditions 15 and the composition of the products produced as a result of the oxidation reaction.
Table 3. Oxidation of Rapeseed oil methyl ester (RME, Finnish food grade, example 1), TOFA (example 2), 20 Rapeseed oil (Finnish food grade, example 3) and Rape-seed oil (Brassica Rapa, example 4).
RME (Exam- TOFA* Rapeseed Rapeseed pie 1) (Example oil oil 2) (Example (Example ____3)__4)_
Reaction conditions : 5 TOFA (g)___80___ ™ RME (g) 80 LO----- S5 Rapeseed 80 ^ oil (g)_____ I Rapeseed 80 oo oil (g)_____ ^ Tungstic 1,7 1,5 1,7 1,7 ^ acid (g) o----- ™ Arquad 2HT- 3,0 2,3 3,2 3,1 75 (g) ____ 20 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- o 5 plaining the difference in the numerical values.
CM
LO
Table 4 below shows analysis results received ^ from the measurements with examples 5-7.
x
X
CL
oo 10 Table 4. Analysis results with examples 5-7.
oo
CO
δ
C\J
21
Exam- Po- Oxida- Reac- To- Vis- Vis- Vis- pie lyol tion tion tal cosity cosity cosity mixture time acid (40 °C) (100 index of (h) num- °C) (VI) ber (TAN ) 5 TMP Rapseed 4 48 77 12 153 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 measurements presented in table 4 show that the esters produced in accordance with the present invention can be 5 used as lubricants or a components in lubricants. It m was noticed from the results that the method in ac- o cordance with the present invention can be used to
CNJ
produce products with properties suitable for lubri-o cants or plasticizers.
^ 10 It is obvious to a person skilled in the art x £ that with the advancement of technology, the basic oo 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 ^ 15 may vary within the scope of the claims.

Claims (18)

1. Menetelmä oligo- ja/tai polyesterien valmistamiseksi, tunnettu siitä, että menetelmä käsittää seuraavat vaiheet: a) hapetetaan luonnollinen koostumus, joka sisältää tyydyttymättömiä rasvahappoja ja/tai niiden estereitä kaksifaasisessa vesi-orgaanisessa järjestelmässä katalyyttisen järjestelmän läsnä ollessa, jossa orgaaninen faasi sisältää luonnollisen koostumuksen ja vesifaasi sisältää vesiliukoisen hapettavan aineen ja jossa katalyyttinen järjestelmä käsittää katalyytin ja faasinsiirtoaineen katalyyttiä varten; b) saatetaan seos, joka käsittää karboksyyli-, epoksi- ja/tai hydroksyylihappoja ja joka on saatavissa vaiheesta a), reagoimaan vähintään yhden alkoholin kanssa, jossa alkoholi valitaan joukosta, joka koostuu polyoleista, happokatalyytin läsnä ollessa re-aktioseoksen valmistamiseksi; ja c) neutraloidaan reaktioseos.A process for the preparation of oligo- and / or polyesters, characterized in that the process comprises the following steps: a) oxidizing a natural composition containing unsaturated fatty acids and / or their esters in a two-phase aqueous organic system in the presence of a catalytic system; the composition and the aqueous phase comprising a water-soluble oxidizing agent and wherein the catalytic system comprises a catalyst and a phase transfer agent for the catalyst; b) reacting a mixture of carboxylic, epoxy and / or hydroxylic acids obtainable from step a) with at least one alcohol, wherein the alcohol is selected from the group consisting of polyols, in the presence of an acid catalyst, to prepare a reaction mixture; and c) neutralizing the reaction mixture. 2. Patenttivaatimuksen 1 mukainen menetelmä, tunnettu siitä, että luonnollinen koostumus on mäntyöljyn rasvahapposeos (TOFA).Process according to Claim 1, characterized in that the natural composition is tall oil fatty acid mixture (TOFA). 3. Patenttivaatimuksen 1 mukainen menetelmä, tunnettu siitä, että luonnollinen koostumus on kasviöljy, joka käsittää tyydyttymättömiä rasvahappoja triglyseridi- tai esteröityneessä muodossa. £2Process according to Claim 1, characterized in that the natural composition is a vegetable oil comprising unsaturated fatty acids in a triglyceride or esterified form. £ 2 4. Patenttivaatimuksen 1 tai 3 mukainen mene- o c\J telmä, tunnettu siitä, että luonnollinen koostu- o mus valitaan joukosta, joka koostuu seuraavista: pel- £2 lavaöljy, soijaöljy, rapsiöljy, rypsiöljy ja oliiviöl- x jy. CCProcess according to claim 1 or 3, characterized in that the natural composition is selected from the group consisting of: petroleum oil, soybean oil, rapeseed oil, rapeseed oil and olive oil. CC 5. Patenttivaatimusten 3 tai 4 mukainen mene-oo oo telmä, tunnettu siitä, että luonnollinen koostuit mus on kasviöljystä saatavien rasvahappojen ja/tai ° niiden esterien seos.Process according to claim 3 or 4, characterized in that the natural composition is a mixture of fatty acids and / or their esters obtained from vegetable oil. 6. Jonkin patenttivaatimuksista 1-5 mukainen menetelmä, tunnettu siitä, että vesiliukoinen hapettava aine käsittää vetyperoksidin.Process according to one of Claims 1 to 5, characterized in that the water-soluble oxidizing agent comprises hydrogen peroxide. 7. Jonkin patenttivaatimuksista 1-6 mukainen menetelmä, tunnettu siitä, että vaihe a) toteutetaan 50 - 90 °C:n lämpötilassa, edullisesti 60 -80 °C:n lämpötilassa.Process according to one of Claims 1 to 6, characterized in that step a) is carried out at a temperature of 50 to 90 ° C, preferably at a temperature of 60 to 80 ° C. 8. Jonkin patenttivaatimuksista 1-7 mukainen menetelmä, tunnettu siitä, että katalyytti valitaan joukosta, joka koostuu seuraavista: volframi-happo, molybdeenihappo, molybdeenihapon emäksiset suolat ja niiden mikä tahansa seos.A process according to any one of claims 1 to 7, characterized in that the catalyst is selected from the group consisting of tungstic acid, molybdenic acid, basic salts of molybdenic acid and any mixture thereof. 9. Jonkin patenttivaatimuksista 1-8 mukai nen menetelmä, tunnettu siitä, että faasinsiirto-aine katalyyttiä varten valitaan joukosta, joka koostuu seuraavista: di(hydrattu tali ) dimetyyliammoniumkloridi, pyridiniumsuolat, fos- foniumsuolat, kruunueetterit ja niiden mikä tahansa seos.Process according to one of Claims 1 to 8, characterized in that the phase transfer agent for the catalyst is selected from the group consisting of di (hydrogenated tallow) dimethylammonium chloride, pyridinium salts, phosphonium salts, crown ethers and any mixture thereof. 10. Jonkin patenttivaatimuksista 1-9 mukai nen menetelmä, tunnettu siitä, että vaihe b) toteutetaan liuottimen läsnä ollessa, jossa liuotin valitaan joukosta, joka koostuu seuraavista: tolueeni, ksyleeni ja niiden mikä tahansa seos.Process according to one of Claims 1 to 9, characterized in that step b) is carried out in the presence of a solvent, wherein the solvent is selected from the group consisting of toluene, xylene and any mixture thereof. 11. Jonkin patenttivaatimuksista 1-10 mukainen menetelmä, tunnettu siitä, että vaihe b) „ toteutetaan 60 - 280 °C:n, edullisesti 90 - 260 °C:n o ja edullisemmin 100 - 200 °C:n lämpötilassa. l0Process according to one of Claims 1 to 10, characterized in that step b) is carried out at a temperature of 60 to 280 ° C, preferably 90 to 260 ° C and more preferably 100 to 200 ° C. l0 12. Jonkin patenttivaatimuksista 1-11 mu- O ^ kainen menetelmä, tunnettu siitä, että happokata- lyytti valitaan joukosta, joka koostuu seuraavista: £ rikkihappo (H2SO4) , metaanisulfonihappo (MeS03H) , suo- 00 lahappo (HC1) , fosforihappo (H3PO4) , p- cö tolueenisulfonihappo, titanaatit, (RO)4Ti, ti- 5 na(II)oksidi (SnO) ja ioninvaihtohartsit. c\jThe process according to any one of claims 1 to 11, characterized in that the acid catalyst is selected from the group consisting of: sulfuric acid (H2SO4), methanesulfonic acid (MeSO3H), hydrochloric acid (HCl), phosphoric acid (H3PO4) ), p-c0 toluenesulfonic acid, titanates, (RO) 4 Ti, tin (II) oxide (SnO) and ion exchange resins. c \ j 13. Jonkin patenttivaatimuksista 1-12 mu kainen menetelmä, tunnettu siitä, että vähintään yksi alkoholi valitaan joukosta, joka koostuu seuraa-vista: neopentyyliglykoli, pentaerytritoli, trimetylo-lipropaani ja 2-butyyli-2-etyyli-l,3-propaanidioli .Process according to one of Claims 1 to 12, characterized in that at least one alcohol is selected from the group consisting of neopentyl glycol, pentaerythritol, trimethylolpropane and 2-butyl-2-ethyl-1,3-propanediol. 14. Jonkin patenttivaatimuksista 1-13 mu kainen menetelmä, tunnettu siitä, että vaihe b) toteutetaan vähintään yhden propionihaposta, valeri-aanahaposta, kapronihaposta, adipiinihaposta, pelar-gonihaposta ja lauriinihaposta läsnä ollessa.Process according to one of Claims 1 to 13, characterized in that step b) is carried out in the presence of at least one of propionic acid, valeric acid, caproic acid, adipic acid, pelagic acid and lauric acid. 15. Jonkin patenttivaatimuksista 1-14 mu kainen menetelmä, tunnettu siitä, että vaihe c) käsittää reaktioseoksen käsittelemisen emäksellä, joka valitaan joukosta, joka koostuu seuraavista: trietyy- liamiini, dinatriumkarbonaatti (Na2<303) , natriumkarbonaatti (NaHC03) , natriumhydroksidi (NaOH), kaliumhydrok-sidi (KOH) ja niiden mikä tahansa seos.Process according to one of Claims 1 to 14, characterized in that step c) comprises treating the reaction mixture with a base selected from the group consisting of triethylamine, disodium carbonate (Na2 <303), sodium carbonate (NaHCO3), sodium hydroxide (NaOH) ), potassium hydroxide (KOH) and any mixture thereof. 16. Oligo- ja/tai polyesterit, jotka ovat saatavissa jonkin patenttivaatimuksista 1-15 mukaisella menetelmällä.Oligo- and / or polyesters obtainable by the process according to any one of claims 1 to 15. 17. Oligo- ja/tai polyesterien, jotka ovat saatavissa jonkin patenttivaatimuksista 1-15 mukaisella menetelmällä, käyttö voiteluaineen valmistamiseksi .Use of oligos and / or polyesters obtainable by the process according to any one of claims 1 to 15 for the manufacture of a lubricant. 18. Voiteluaine, tunnettu siitä, että se käsittää patenttivaatimuksen 16 mukaisia oligo- ja/tai co polyestereitä. δ (M m o i CO X cc CL CO CO δ δ (MLubricant, characterized in that it comprises the oligo- and / or co-polyesters according to claim 16. δ {M m o i CO X cc CL CO CO δ δ {M
FI20116188A 2011-11-28 2011-11-28 A process for the catalytic oxidation of a natural composition comprising unsaturated fatty acids and / or their esters and use of a mixture thereof for the preparation of mono-, oligo- and / or polyesters FI123683B (en)

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FI20116188A FI123683B (en) 2011-11-28 2011-11-28 A process for the catalytic oxidation of a natural composition comprising unsaturated fatty acids and / or their esters and use of a mixture thereof for the preparation of mono-, oligo- and / or polyesters
PCT/FI2012/051175 WO2013079791A1 (en) 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
EP12815719.5A EP2785677A1 (en) 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

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