EP2964640A1 - Ester isononylique à base d'acides gras ou de mélanges d'acides gras obtenus à partir de tallöl ou d'huile de lin - Google Patents

Ester isononylique à base d'acides gras ou de mélanges d'acides gras obtenus à partir de tallöl ou d'huile de lin

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Publication number
EP2964640A1
EP2964640A1 EP14706517.1A EP14706517A EP2964640A1 EP 2964640 A1 EP2964640 A1 EP 2964640A1 EP 14706517 A EP14706517 A EP 14706517A EP 2964640 A1 EP2964640 A1 EP 2964640A1
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EP
European Patent Office
Prior art keywords
fatty acid
ester
reaction
isononyl
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14706517.1A
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German (de)
English (en)
Inventor
Benjamin WOLDT
Michael Grass
Andreas Gevers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
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Evonik Degussa GmbH
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Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2964640A1 publication Critical patent/EP2964640A1/fr
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    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids

Definitions

  • the invention relates to isononyl ester or a Isononylestergemisch an epoxidized fatty acid or an epoxidized fatty acid mixture, wherein the fatty acid
  • the invention relates to processes for their preparation, and their use as plasticizers for polymers.
  • epoxidized diesters of fatty acids of tall oil with glycerol, propylene glycol and ethylene glycol are described.
  • the oil is tall oil. In another embodiment, the oil is linseed oil.
  • the oil is a mixture of various vegetable oils wherein the proportion of linseed oil or tall oil is greater than 50 mass percent, preferably greater than 75 mass percent. In one embodiment, the average number of epoxide groups per fatty acid is greater than 1.20, preferably greater than 1.30, most preferably greater than 1.40. In one embodiment, the proportion of saturated fatty acids in the isononyl ester mixture is less than 12 area%, preferably less than 8 area%, particularly preferably less than 6 area%.
  • the proportion of saturated fatty acids in the isononyl ester mixture is greater than 1 area%.
  • method step c1) can also take place before method step b1).
  • the method step c2) transesterification of the fatty acid ester or fatty acid ester mixture with isononanol.
  • the method step c2) can also take place before the method step b2).
  • the fatty acid ester described in a2) is in a specific embodiment a methyl ester of the corresponding fatty acid or of the fatty acid mixture.
  • the fatty acid methyl ester is first prepared and epoxidized.
  • the epoxidized fatty acid methyl ester is then separated into a fraction rich in saturated fatty acid methyl esters and a fraction rich in epoxidized fatty acid methyl esters. This separation can be done for example by distillation.
  • ester or ester mixture as plasticizer for a polymer selected from: polyvinyl chloride, polyvinylidene chloride, polylactic acid,
  • Polyurethanes polyvinyl butyral, polyalkyl methacrylates or copolymers thereof.
  • Preferred here is the use of a previously described ester or ester mixture as a plasticizer for polyvinyl chloride.
  • esters or ester mixtures according to the invention can be used as plasticizers for the modification of polymers.
  • These polymers are, for example, selected from the group consisting of:
  • Polyvinyl chloride PVC
  • PVDC polyvinylidene chloride
  • polyacrylates in particular
  • PMMA Polymethyl methacrylate
  • PAMA polyalkyl methacrylate
  • fluoropolymers in particular polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc,
  • Polyvinyl alcohol PVA
  • polyvinyl acetals in particular polyvinyl butyral (PVB)
  • PVB polyvinyl butyral
  • Polystyrene polymers in particular polystyrene (PS), expandable polystyrene (EPS), and
  • ASA Acrylonitrile-styrene-acrylate
  • SAN styrene-acrylonitrile
  • ABS acrylonitrile-butadiene-styrene
  • SMA styrene-maleic anhydride copolymer
  • styrene-methacrylic acid copolymer polyolefins, in particular polyethylene (PE) or polypropylene (PP) , thermoplastic polyolefins (TPO), polyethylene-vinyl acetate (EVA), polycarbonates, polyethylene terephthalate (PET),
  • PBT Polybutylene terephthalate
  • POM polyoxymethylene
  • PA polyamide
  • PEG polyethylene glycol
  • PU polyurethane
  • TPU thermoplastic polyurethane
  • PSu polysulfides
  • Biopolymers in particular polylactic acid (PLA), polyhydroxybutyral (PHB),
  • Polyhydroxyvaleric acid PVC
  • polyester starch
  • cellulose and cellulose derivatives in particular nitrocellulose (NC), ethylcellulose (EC), cellulose acetate (CA), cellulose acetate / butyrate (CAB), rubber or silicones and mixtures or copolymers of have mentioned polymers or their monomeric units.
  • the polymers according to the invention preferably comprise PVC or homo- or copolymers based on ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, methacrylates,
  • the polymer preferably contains PVC, suspension, bulk, microsuspension or emulsion PVC.
  • the polymers preferably contain from 5 to 200, preferably from 10 to 150 parts by mass of plasticizer.
  • ester / ester mixtures according to the invention can also be combined with other plasticizers, for example with other esters of natural fatty acids, or with oil from vegetable sources.
  • a combination with a plasticizer can be selected from the following group: adipates, benzoates, citrates, cyclohexyandicarboxylates, epoxidized fatty acid esters, epoxidized vegetable oils, epoxidized acetylated glycerides, furandicarboxylates, phosphates, phthalates, sulfonamides, sulfonates, terephthalates, trimellitates or oligomers or polymeric esters based on adipic, succinic or sebacic acid.
  • the mixtures of PVC and the esters according to the invention may also contain other additives such as, for example, heat stabilizers, fillers, pigments, blowing agents, biocides, UV stabilizers, etc.
  • esters or ester mixtures described above can be used in adhesives, sealants, coating compositions, lacquers, paints, plastisols, foams, artificial leather,
  • Floor coverings eg cover layer
  • roofing membranes e.g cover layer
  • underbody protection e.g cover layer
  • Example 1 Isononyl fatty acid ester based on linseed oil
  • the apparatus was rinsed through the dip tube for one hour at 6 IN 2 / hour.
  • the reaction also proceeded under nitrogen injection.
  • the batch was slowly heated to 240 ° C with stirring. The temperature was kept constant at full reflux. The reaction time was 6 hours. The conversion was controlled by the decrease of the isononanol content by GC analysis. After the isononanol content stopped changing, the batch was turned off and cooled to 80 ° C.
  • the reaction product from the transesterification was transferred to a 4 L reaction flask and attached to a Ciaisen bridge with vacuum divider. In addition, a dip tube with nitrogen connection and a thermometer were attached. The reaction was purged with nitrogen while stirring. In order to remove the glycerol which had become free in the reaction, the batch was washed three times at 80 ° C. with 25% deionized water (based on the amount of reaction effluent), allowed to settle and then the aqueous phase was separated off. Subsequently, the still contained excess of isononanol, in the presence of 1% activated carbon, distilled off at up to 210 ° C ( ⁇ 1 mbar).
  • the vacuum was adjusted to 40 mbar via nitrogen sparging and the product was cooled to 90 ° C.
  • the ester was filtered through a Buchner funnel with filter paper and pre-pressed filter cake of filter aid (Perlite type D14) by means of vacuum in a suction bottle.
  • Filction bottle At the filtrate were Color number, acid number, water content, density and dyn. Viscosity determined and carried out a GC analysis.
  • Example 2 epoxidized isononyl fatty acid ester based on linseed oil
  • the fatty acid ester was placed in an epoxidation apparatus (3000 ml jacketed reactor with integrated cooling coil, stirrer, dip tube, dropping funnel, metering pump, thermometer, pH meter and attached reflux condenser). The apparatus was purged for 60 minutes at 6 IN 2 / hour via the dip tube. During the reaction, nitrogen was passed over the reactor contents to ensure gas phase inertization. The ester was slowly heated with stirring to 45 ° C. After reaching the target temperature, the pH was adjusted to pH 5 by means of the sodium hydroxide solution. Subsequently, the peracetic acid was added by means of metering pump within 2 hours. Over the entire time, the pH was kept constant by dropwise addition of sodium hydroxide solution.
  • the reaction temperature was kept constant over the entire reaction time (+/- 1, 5 ° C). After the start of the reaction, the heat of reaction was removed via the cooling coil. After complete addition, an after-reaction was carried out for 22 hours. After 10, 30 and 60 minutes, as well as after 2, 4, 8 and 24 hours of reaction time, samples were taken and analyzed to document the progress of the reaction. The sample volume was about 3 ml, which were then shaken out with 3 times the amount of VE-H 2 0. The organic phase was separated from the aqueous phase after about 30 minutes settling time, filled into an evaporating dish and dried for 12 hours in a desiccator. The conversion was monitored by NMR measurements.
  • reaction effluent was placed in a separatory funnel and allowed to sit for 30 minutes at room temperature.
  • the aqueous phase was drained and discarded.
  • the organic phase was filled into a 2 liter reaction flask and built with a dip tube, stirrer and thermometer to a Ciaisen Hampshire with vacuum connection.
  • the reaction was washed 3 times with 25% water based on the weight. It was then dried at 60 ° C under maximum vacuum for 15 minutes. After that was heated to 160 ° C. After reaching the temperature, the flask contents were stripped with nitrogen. For this purpose, the amount of nitrogen was adjusted so that the pressure of maximum vacuum increased to 40 mbar.
  • Example 3 Isononyl fatty acid esters based on tall oil fatty acids
  • the apparatus was purged over the dip tube for 1 hour at 6 lN2 / hr.
  • the reaction also proceeded by metering in nitrogen.
  • the conversion was controlled by the amount of water and the acid number. After no more water of reaction, a sample was taken and the acid number was determined. The approach was stopped when the acid number was ⁇ 0.1 mg KOH / g.
  • the reaction product from the esterification was transferred to a 4 l reaction flask and attached to a Ciaisen bridge with vacuum divider. In addition, a dip tube with nitrogen connection and a thermometer were attached. The reaction was purged with nitrogen while stirring. At maximum vacuum ( ⁇ 1 -5 mbar) was slowly heated and the Temperature corresponding to the distillation attack slowly increased to 190 ° C. The vacuum was adjusted to 40 mbar via nitrogen sparging and the product was cooled to 180.degree. After reaching the temperature was stripped for 2 hours at 180 ° C, 40 mbar, with nitrogen. Then the heater was turned off and the approach in
  • the ester was filtered through a Buchner funnel with filter paper and pre-pressed filter cake of filter aid (Perlite type D14) by means of vacuum in a suction bottle. On the filtrate, a color number, acid number and GC analysis are performed.
  • filter aid Perlite type D14
  • Example 4a / b / c epoxidized isononyl fatty acid ester based on tall oil fatty acids
  • the fatty acid ester was placed in an epoxidation apparatus (3000 ml jacketed reactor with integrated cooling coil, stirrer, dip tube, dropping funnel, metering pump, thermometer, pH meter and attached reflux condenser).
  • the apparatus was purged for 60 minutes at 6 IN 2 / hour via the dip tube. During the reaction, nitrogen was passed over the reactor contents to ensure gas phase inertization.
  • the product was slowly heated with stirring to 45 ° C. After reaching the target temperature, the pH was adjusted to pH 5 by means of the sodium hydroxide solution. Subsequently, the peracetic acid was added by means of metering pump within 2 hours. Over the entire time, the pH was kept constant by dropwise addition of sodium hydroxide solution.
  • the reaction temperature was kept constant over the entire reaction time (+/- 1, 5 ° C). After the start of the reaction, the heat of reaction was removed via the cooling coil. After complete addition, an after-reaction was carried out for 22 hours. After 10, 30 and 60 minutes, as well as after 2, 4, 8 and 24 hours of reaction time, samples were taken and analyzed to document the progress of the reaction. The sample volume was about 3 ml, which were then shaken out with 3 times the amount of demineralized water. (Example 4a) Lower degrees of epoxidation could be achieved by stopping the reaction after a lesser time (Examples 4b, 20 hours and Example 4c, 4.5 hours). The organic phase was separated from the aqueous phase after about 30 minutes settling time, filled into an evaporating dish and dried for 12 hours in a desiccator. The conversion was monitored by NMR measurements.
  • the reaction effluent was placed in a separatory funnel and allowed to sit for 30 minutes at room temperature.
  • the aqueous phase was drained and discarded.
  • the organic phase was filled into a 2 liter reaction flask and built with a dip tube, stirrer and thermometer to a Ciaisen Hampshire with vacuum connection.
  • the reaction was washed 3 times with 25% water based on the weight. It was then dried at 60 ° C under maximum vacuum for 15 minutes. Thereafter, it was heated to 160 ° C. After reaching the temperature, the flask contents were stripped with nitrogen. For this purpose, the amount of nitrogen was adjusted so that the pressure of maximum vacuum increased to 40 mbar. After 2 hours, the heating was switched off and the mixture, while introducing nitrogen, cooled to 90 ° C.
  • the ester was filtered through a Buchner funnel with filter paper and pre-pressed filter cake of filter aid (Perlite type D14) by means of vacuum in a suction bottle. On the filtrate, a color number and acid number were determined and GC analysis and NMR analyzes were performed.
  • filter aid Perlite type D14
  • Example 5 Isodecyl fatty acid ester based on tall oil fatty acids
  • the apparatus was purged over the dip tube for 1 hour at 6 lN2 / hr.
  • the reaction also proceeded by metering in nitrogen.
  • the conversion was controlled by the amount of water and the acid number. After no more water of reaction was collected and a sample was taken and the acid number determined. The approach was stopped when the acid number was ⁇ 0.1 mg KOH / g.
  • the reaction product from the esterification was transferred to a 4 l reaction flask and attached to a Ciaisen bridge with vacuum divider. In addition, a dip tube with nitrogen connection and a thermometer were attached. The reaction was purged with nitrogen while stirring. At maximum vacuum ( ⁇ 1 -5 mbar) was slowly heated and the temperature corresponding to the distillation slowly increased to 190 ° C. The vacuum was adjusted to 40 mbar via nitrogen sparging and the product was cooled to 180.degree. After reaching the temperature was stripped for 2 hours at 180 ° C, 40 mbar, with nitrogen. Then the heater was turned off and the approach in
  • the ester was filtered through a Buchner funnel with filter paper and pre-pressed filter cake of filter aid (Perlite type D14) by means of vacuum in a suction bottle. From the filtrate, a color number and acid number were determined and a GC analysis was performed.
  • filter aid Perlite type D14
  • Example 6 Epoxidized isodecyl fatty acid ester based on tall oil fatty acids
  • the fatty acid ester was placed in an epoxidation apparatus (3000 ml jacketed reactor with integrated cooling coil, stirrer, dip tube, dropping funnel, metering pump, thermometer, pH meter and attached reflux condenser).
  • the apparatus was purged for 60 minutes at 6 IN 2 / hour via the dip tube. During the reaction, nitrogen was passed over the reactor contents to ensure gas phase inertization.
  • the product was slowly heated with stirring to 45 ° C. After reaching the target temperature, the pH was adjusted to pH 5 by means of the sodium hydroxide solution. Subsequently, the peracetic acid was added by means of metering pump within 2 hours. Over the entire time, the pH was kept constant by dropwise addition of sodium hydroxide solution.
  • the reaction temperature was kept constant over the entire reaction time (+/- 1, 5 ° C). After the start of the reaction, the heat of reaction was removed via the cooling coil. After complete addition, an after-reaction was carried out for 22 hours. After 10, 30 and 60 minutes, as well as after 2, 4, 8 and 24 hours of reaction time, samples were taken and analyzed to document the progress of the reaction. The sample volume was about 3 ml, which were then shaken out with 3 times the amount of demineralized water. The organic phase was separated from the aqueous phase after about 30 minutes settling time, filled into an evaporating dish and dried for 12 hours in a desiccator. The conversion was monitored by NMR measurements.
  • the reaction effluent was placed in a separatory funnel and allowed to sit for 30 minutes at room temperature.
  • the aqueous phase was drained and discarded.
  • the organic phase was filled into a 2 liter reaction flask and built with a dip tube stirrer and thermometer to a Ciaisen Hampshire with vacuum connection.
  • the reaction was washed 3 times with 25% water based on the weight. It was then dried at 60 ° C. under maximum vacuum for 15 minutes. Thereafter, it was heated to 160 ° C. After reaching the temperature, the flask contents were stripped with nitrogen. For this purpose, the amount of nitrogen was adjusted so that the pressure of maximum vacuum increased to 40 mbar. After 2 hours, the heater was turned off and the experiment, while introducing nitrogen, cooled to 90 ° C.
  • the ester was filtered through a Buchner funnel with filter paper and pre-pressed filter cake of filter aid (Perlite type D14) by means of vacuum in a suction bottle. From the filtrate a color number and acid number were determined and GC and NMR analyzes were performed.
  • filter aid Perlite type D14
  • Example 7 Isononyl fatty acid ester based on rapeseed oil methyl ester
  • Raschigringkolonne vacuum divider and collecting flask submitted.
  • the apparatus was purged for one hour at 6 IN 2 / hour over the dip tube.
  • the conversion was controlled by GC analysis. The approach was stopped when the proportion of biodiesel was ⁇ 0.5 area%. After 4.5 hours, the 1. The reaction was periodically monitored by GC analyzes until the end of the reaction.
  • reaction effluent from the transesterification is transferred to a 4 l reaction flask and mixed with 2% activated carbon based on the mass of reaction effluent.
  • the flask was attached to a Ciaisen bridge with vacuum divider.
  • a dip tube with
  • Nitrogen connector inserted into the piston.
  • a thermometer was attached.
  • the reaction was purged with nitrogen while stirring.
  • Under maximum vacuum ( ⁇ 1 mbar) was slowly heated and the temperature corresponding to the distillation slowly increased to 222 ° C.
  • the main run was removed.
  • the light ( ⁇ 214 ° C) and high boilers (> 219 ° C) were discarded.
  • Example 8 epoxidized isononyl fatty acid ester based on rapeseed oil methyl ester
  • the fatty acid ester was placed in an epoxidation apparatus (1000 ml jacketed reactor with integrated cooling coil, stirrer, dip tube, dropping funnel, thermometer and attached reflux condenser). The apparatus was purged for 60 minutes at 6 IN 2 / hour via the dip tube. During the reaction, nitrogen was passed over the reactor contents to ensure gas phase inertization. The product was slowly heated with stirring to 55 ° C. Subsequently, the hydrogen peroxide was added by means of metering pump within 2 hours. After about 5 minutes, the temperature in the reactor increased. At 60 ° C, the temperature was trapped and kept constant over the cooling (+/- 1, 5 ° C). After the start of the reaction, the heat of reaction (strongly exothermic reaction) was removed via the cooling coil (cooling at intervals). After complete addition, a post-reaction was carried out for 5 hours.
  • epoxidation apparatus 1000 ml jacketed reactor with integrated cooling coil, stirrer, dip tube, dropping funnel, thermometer and attached reflux condens
  • reaction effluent was placed in a separatory funnel and allowed to sit for 30 minutes at room temperature.
  • the aqueous phase was drained and discarded.
  • the organic phase was filled in a 0.5 liter reaction flask and built with a dip tube stirrer and thermometer to a Ciaisen vite with vacuum connection. It was then dried at 60 ° C under maximum vacuum for 15 minutes. Thereafter, it was heated to 160 ° C. After reaching the temperature, the flask contents were stripped with nitrogen. For this purpose, the amount of nitrogen was adjusted so that the pressure of maximum vacuum increased to 40 mbar. After 2 hours, the heater was turned off and the experiment, while introducing nitrogen, cooled to 90 ° C.
  • the ester was filtered through a Buchner funnel with filter paper and pre-pressed filter cake of filter aid (Perlite type D14) by means of vacuum in a suction bottle.
  • the color number and acid number of the filtrate were determined, and GC and NMR analyzes were carried out.
  • the volatility of plasticizers is a central feature of many polymer applications. High volatilities lead to an exposure of the environment and due to reduced plasticizer levels in the polymer to deteriorated mechanical Properties. Volatile plasticizers are therefore often added only in small amounts to other plasticizer systems or not used at all. For example, volatility is of particular importance in interior applications (wallpapers, automobiles) or in accordance with guidelines and standards for cables or food packaging.
  • the volatility of the pure plasticizers was determined using the halogen dryer HB 43-S from Mettler Toledo. Before the measurement, an empty, clean aluminum tray was placed in the weighing pan. Thereafter, the aluminum tray was tared with a nonwoven and about five grams of plasticizer pipetted on the fleece and weighed exactly.
  • the measurement was started and the sample was heated from room temperature to 200 ° C at the maximum heating rate (default setting) and the corresponding loss of mass due to evaporation was automatically determined by weighing every 30 seconds. After 10 minutes, the measurement was automatically stopped by the device.
  • the Stabinger viscometer SVM 3000 is a combination device with which density and viscosity can be determined. These are in the device two measuring cells behind each other
  • a rotational viscometer with cylinder geometry is installed and, to determine the density, a density measuring cell according to the bending oscillator principle.
  • the samples are measured at 20 ° C.
  • the measuring cells are tempered by a Peltier element (reproducibility 0.02 ° C).
  • the samples are measured with the preset measurement mode "M0-ASTM (PRECISE)" measurement with highest accuracy and repetition, for tests according to the standard ASTM D7042 by adding 0.5 ml of sample for each measurement (to exclude air bubbles or impurities ).
  • the determination of the proportion of double bonds, epoxides and alcohols is carried out by 1 H NMR spectroscopy.
  • 1 H NMR spectroscopy To record the spectra, for example, 50 mg of substance are dissolved in 0.6 ml of CDCl 3 (containing 1% by mass of TMS) and filled into a 5 mm diameter NMR tube.
  • the NMR spectroscopic investigations can in principle be carried out with any commercially available NMR instrument.
  • an apparatus of the type Avance 500 from Bruker was used.
  • TMS tetramethylsilane
  • Other commercially available NMR devices give comparable results with the same operating parameters.
  • the corresponding signals in the NMR spectrum are first to be identified.
  • the signals used in the following are listed with their position in the spectrum and the assignment to the corresponding structural elements:
  • the signals in the range from 4.8 to 6.4 ppm were assigned to the 1 H nuclei of the double bonds.
  • the signals in the range 4.0 to 3.25 ppm were assigned to the 1 H nuclei of the alcohols.
  • the signals in the range 3.25 to 2.85 ppm were assigned to the 1 H nuclei of the epoxides.
  • reference signals of known size are needed. Methylene groups of the fatty acid residue or the alcohol residue of the fatty acid esters were used. In the case of the isononyl and isodecyl esters, the signal of the methylene group at 2.3 ppm is partially superimposed by signals from the alcohol, therefore the methylene group of the alcohol was used by 4 ppm.
  • the following signals were used:
  • the quantification is done by determining the area under the respective resonance signals, i. H. the area enclosed by the signal from the baseline.
  • Commercially available NMR devices have devices for integrating the signal surface. In the present NMR spectroscopic study, the integration was performed using the software "TOPSPIN", version 3.1. To calculate the proportion of double bonds, the integral value x of the double bond signals in the range from 4.8 to 6.4 ppm is divided by the integral value of the reference methylene group r.
  • the integral value y of the epoxide signals in the range 2.85 to 3.25 ppm is divided by the integral value of the reference methylene group r.
  • the integral value z of the epoxide signals in the range from 3.9 to 3.25 ppm is divided by half the integral value of the reference methylene group r / 2.
  • the relative proportions of the structural elements double bond, epoxide and alcohol per fatty acid residue are obtained.
  • 0.1 g NaOH solution (20 g NaOH / l anhydrous methanol) was added to 0.1 g sample and refluxed for 30 minutes. Subsequently, 2.0 ml of methanolic boron trifluoride solution (140 mg / ml) was added and heated under reflux for a further 30 minutes.
  • Capillary column 30 m DB-WAX; 0.32 mm ID; 0.5 ⁇ film
  • Carrier gas helium
  • Oven temperature 80 ° C - 10 ° C / min - 220 ° C (40 min)
  • Capillary column 30 m DB-5HT; 0.32 mm ID; 0.1 ⁇ film
  • Carrier gas helium
  • Injector cool on column, 80 ° C- 140 ° C / min - 400 ° C
  • Injection volume 1.0 ⁇
  • the procedure was as follows: First, the retention time range of the saturated and unsaturated fatty acid methyl esters was identified by means of a reference solution of relevant fatty acid methyl esters. A standardization of all signals of fatty acid methyl esters (saturated, unsaturated and epoxidized fatty acid methyl esters) as fatty acids to 100 area% was performed. The proportions of the individual fatty acid methyl esters in area% could then be calculated as follows:
  • Proportion of fatty acid methyl esters (saturated and unsaturated according to method II in area%) multiplied by the proportion of the particular fatty acid methyl ester (saturated and unsaturated according to method I in area% / 100%).
  • the proportion of saturated FS then results from summing up the proportions of myristic, palmitic and stearic fatty acid methyl esters.
  • Example WM No. 2 (Drapex 4.4) Method 1 yields the area percentages of the saturated and unsaturated fatty acid methyl esters (epoxidized fatty acid methyl esters are not taken into account):
  • Method 2 provides the area percent of epoxidized fatty acid methyl esters
  • Epoxidized fatty acid methyl esters 95, 15 area% The real proportion of saturated fatty acid methyl esters in WM No. 2 is then calculated as follows:
  • OH / FS mean number of alcohol groups per fatty acid
  • a PVC plastisol has been produced, such as used in the manufacture of top coat films for floor coverings.
  • the information in the Plastisolrezepturen are each in parts by weight.
  • Vestolit B 7021 -Ultra was used as PVC.
  • diisononyl phthalate (DINP, VESTINOL 9 from Evonik Industries) and epoxidized 2-ethylhexyl tallate (Drapex 4.4, from Chemtura), an epoxidized 2-ethylhexyl oxyate (PLS Green 8, Petrom), an epoxidized isononyl oxyate (PLS Green 9, from Petrom) and an isononyl fatty acid ester based on rapeseed oil fatty acids (Example 8), and an isodecyl fatty acid ester from tall oil fatty acids (Example 6).
  • EZ / FS average number of epoxide groups per fatty acid
  • the products correspond to those from the synthesis instructions of Examples 2, 4a, 4b, 4c, 6, 8.
  • each recipe contains 3 parts by weight of an epoxidized soybean oil as a co-stabilizer (Drapex 39, Galata), and 2 parts by weight of a Ca / Zn-based heat stabilizer (Mark CZ 149, Galata).
  • an epoxidized soybean oil as a co-stabilizer
  • a Ca / Zn-based heat stabilizer Mark CZ 149, Galata
  • the plasticizers were heated to 25 ° C prior to addition.
  • the liquid and then the powdered ingredients were weighed into a PE beaker.
  • the mixture was stirred with an ointment spatula so that no unwetted powder was present.
  • the mixing cup was then clamped in the clamping device of a dissolver stirrer. Before immersing the stirrer in the mixture, the speed was set to 1800 rpm. After switching on the stirrer, stirring was continued until the temperature at the digital indicator of the thermocouple reached 30.0 ° C. This ensured that the homogenization of the plastisol was achieved with a defined energy input. Thereafter, the plastisol was immediately heated at 25.0 ° C.
  • a shear rate down ramp starting at 200 s "1 and ending at 0.1 s " 1 , divided into a logarithmic series of 30 steps each with a 5 second measurement point duration.
  • the measurements were usually carried out (if not stated otherwise) after 24 h storage / maturation of the plastisols. Between measurements the plastisols were stored at 25 ° C.
  • Heating / cooling rate 5 ° C / min
  • Oscillation frequency 4-0.1 Hz ramp logarithmic
  • the cross-over temperature is determined. This method calculates the intersection of the two selected y variables. It is used to find the end of the linear viscoelastic region in an amplitude sweep (y: G ', G "; x: gamma) to obtain the crossing frequency in a frequency sweep (y: G', G"; x: frequency). or to determine the gel time or curing temperature (y: G ', G "; x: time or temperature).
  • the cross-over temperature documented here corresponds to the temperature of the first intersection of G 'and G ".
  • Pastes comprising an ester according to the invention Compared to the pastes consisting of DINP (1) and the isodecyl ester (5) pastes of the invention (3), (4) and (6) have a significantly decreased cross-over temperature. This is synonymous with accelerated gelation.
  • Pastes with epoxidized isononyl fatty acid esters which have an average number of epoxide groups per fatty acid smaller than 1 or whose fatty acids originate from other oils (7, 8, 9) have a significantly higher cross-over temperature.
  • gelled 1 mm polymer films were prepared from the corresponding plastisols (gelling conditions in the Mathis oven: 200 ° C./2 min.).
  • the thermal stability measurements were carried out on a thermal tester (type LTE-TS Fa. Mathis AG).
  • the sample frame for the thermal stability measurement is equipped with 14 aluminum rails.
  • the aluminum rails serve as sample holders, in which samples up to a
  • the sample length is 40 cm.
  • edges of the films to be examined were removed with the help of a shearing machine and the films were cut at right angles (dimensions: 20 cm x 30 cm). Then two strips (20 * 2 cm) were cut off. The strips were side by side in the aluminum rails from
  • Table 5 The test specimens which were produced from epoxidized fatty acid esters (2 to 10) did not show any blackening in the time interval in the thermal tester.
  • the thermal stability is significantly higher than the industry standard DINP (1). This is due to trapping of formed HCl by the epoxide function. 6. Softening effect
  • the Shore hardness is a measure of the softness of a specimen. The further a standardized needle can penetrate into the sample body during a certain measuring period, the lower the measured value will be.
  • the plasticizer with the highest efficiency gives the lowest value for the Shore hardness with the same amount of plasticizer. Since in practice formulations / formulations are often adjusted to a specific Shore hardness or can be optimized, with very efficient plasticizers therefore a certain proportion can be saved in the recipe, which means a cost reduction for the processor.
  • the pastes produced as described above were poured into circular molds made of brass with a diameter of 42 mm (weight: 20.0 g). The pastes in the molds were then gelled at 200 ° C. for 30 minutes in a convection oven, removed after cooling and stored in the climatic chamber (25 ° C.) for at least 24 hours before the measurement. The thickness of the discs was about 12 mm.
  • the hardness measurements were carried out in accordance with DIN 53 505 with a Shore A measuring device from Zwick-Roell, the measured value was read off in each case after 3 seconds. Measurements were taken at three different sites on each test specimen and an average was formed.
  • test specimen (1) In comparison to the industrial standard DINP, test specimen (1), the test specimens (3), (4) and (6) according to the invention have lower Shore hardnesses.
  • the plasticizers according to the invention can be used to produce PVC mixtures which have a better efficiency than when the corresponding DINP is used. As a result, plasticizer can be saved, which leads to lower formulation costs.
  • sample (7) a clear incompatibility of the plasticizer leads to a sticking out of the test piece.
  • samples (8), (9) and (10) show a slight exudation. This results in a lower proportion of plasticizer in the polymer and, associated therewith, an increased Shore hardness. Exudation of the plasticizer is unacceptable in all relevant applications.
  • the experiments described above have shown that the esters of the invention have good to very good plasticizer properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fats And Perfumes (AREA)
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Abstract

La présente invention concerne un ester isononylique ou un mélange d'ester isononylique d'un acide gras époxydé ou d'un mélange d'acides gras époxydé, lequel acide gras ou lequel mélange d'acides gras est obtenu à partir de tallöl ou d'huile de lin, et le nombre moyen de groupes époxyde par acide gras est supérieur à 1,00.
EP14706517.1A 2013-03-08 2014-02-14 Ester isononylique à base d'acides gras ou de mélanges d'acides gras obtenus à partir de tallöl ou d'huile de lin Withdrawn EP2964640A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013203972.7A DE102013203972A1 (de) 2013-03-08 2013-03-08 Isononylester auf Basis von Fettsäuren oder Fettsäuregemischen aus Tallöl oder Leinöl
PCT/EP2014/052910 WO2014135355A1 (fr) 2013-03-08 2014-02-14 Ester isononylique à base d'acides gras ou de mélanges d'acides gras obtenus à partir de tallöl ou d'huile de lin

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EP2964640A1 true EP2964640A1 (fr) 2016-01-13

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US (1) US20160009898A1 (fr)
EP (1) EP2964640A1 (fr)
KR (1) KR20150125718A (fr)
CN (1) CN105377839A (fr)
AR (1) AR095049A1 (fr)
BR (1) BR112015021821A2 (fr)
CA (1) CA2904118A1 (fr)
DE (1) DE102013203972A1 (fr)
TW (1) TW201500348A (fr)
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MX2020002771A (es) 2017-10-13 2020-07-20 Lg Chemical Ltd Composicion plastificante y composicion de resina que incluye lo mismo.
BE1026295B9 (nl) * 2018-05-22 2020-01-14 Proviron Holding N V Gebruik van een geëpoxideerde vetzuurester als weekmaker in gehalogeneerde harsen

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BE542386A (fr) 1954-10-29
GB1020866A (en) 1961-06-16 1966-02-23 British Celanese Epoxidised esters and their uses as plasticisers
US4486561A (en) * 1981-08-21 1984-12-04 Ethyl Corporation Injection-moldable thermoplastic polyester composition
US6797753B2 (en) * 2000-06-20 2004-09-28 Battelle Memorial Institute Plasticizers derived from vegetable oils
DE10217186A1 (de) * 2002-04-18 2003-11-13 Oxeno Olefinchemie Gmbh Benzoesäureisononylester und deren Verwendung
US8802877B2 (en) * 2009-12-17 2014-08-12 Npc Industrias Quimicas Ltda Process for modifying vegetable oils and primary plasticizer for vinyl polymers
WO2013003225A2 (fr) * 2011-06-29 2013-01-03 Dow Global Technologies Llc Plastifiant dérivé d'huile végétale

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TW201500348A (zh) 2015-01-01
DE102013203972A1 (de) 2014-09-11
BR112015021821A2 (pt) 2017-07-18
US20160009898A1 (en) 2016-01-14
CA2904118A1 (fr) 2014-09-12
CN105377839A (zh) 2016-03-02
WO2014135355A1 (fr) 2014-09-12
KR20150125718A (ko) 2015-11-09
AR095049A1 (es) 2015-09-16

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