Plasticizer composition containing trimethyl ester of 1,2,4-cyclohexanetripropionic acid and the longer-chain derivatives thereof

Abstract

The invention relates to a plasticizer composition containing a compound of formula (1) and at least one longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid, wherein each of the three alkyl groups in the trialkyl ester of 1,2,4-cyclohexanetripropionic acid has 4 to 9 carbon atoms.

Description

[0001] 202300217

[0002] 1

[0003] Plasticizer composition containing trimethyl esters of 1,2,4-cyclohexanetripropionic acid and its longer-chain derivatives

[0004] The invention relates to a plasticizer composition containing a compound of

[0005] Formula 1) and at least one longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid, wherein the three alkyl groups in the trialkyl ester of 1,2,4-cyclohexanetripropionic acid each have 4 to 9 carbon atoms.

[0006] The compounds according to formula (1) of the invention are trimethyl esters of 1,2,4-cyclohexanetripropionic acid. Trimethyl esters of 1,2,4-cyclohexanetripropionic acid are generally known and have been described, for example, in EP 3 838 886 A1. It was also mentioned there that these esters of 1,2,4-cyclohexanetripropionic acid can be used as plasticizers. In this context, the trimethyl ester was described as a product with a low gelling temperature.

[0007] These esters do not always exhibit only positive properties when used as plasticizers in plastics. If trimethyl ester were used as the sole plasticizer, for example in a PVC-based plastisol formulation, the plastisol would have a rather high viscosity. Furthermore, a significant portion of the trimethyl ester would evaporate during processing and thus no longer remain in the final product. It therefore makes sense to use the aforementioned trimethyl esters in mixtures with other plasticizers.

[0008] The present invention was based on the objective of providing a plasticizer composition containing trialkyl esters of 1,2,4-cyclohexanetripropionic acid, but exhibiting better application-related properties than mixtures with other plasticizers.

[0009] This problem is solved by the plasticizer composition according to claim 1. The invention therefore relates to a plasticizer composition containing a compound of formula (1) 202300217

[0010] 2 and at least one longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid, wherein the three alkyl groups each have 4 to 9 carbon atoms. Preferred embodiments of the present invention are specified in the dependent claims.

[0011] The trimethyl ester of 1,2,4-cyclohexanetripropionic acid, i.e., the substance that constitutes part of the plasticizer composition according to the invention, is not currently commercially available. However, a process for the preparation of these esters is described, for example, in EP 3 842411 A1. The esters of 1,2,4-cyclohexanetripropionic acid are therefore generally accessible.

[0012] In addition to the trimethyl esters of 1,2,4-cyclohexanetripropionic acid, the plasticizer composition according to the invention contains longer-chain trialkyl esters of 1,2,4-cyclohexanetripropionic acid, wherein the three alkyl groups each independently have 4 to 9 carbon atoms. The corresponding compounds can be described by the following Markush formula: where the three R groups are each independently alkyl groups with 4 to 9 carbon atoms.

[0013] The three alkyl groups can each be selected independently from the group consisting of a normal butyl group, an isobutyl group, a normal pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a normal hexyl group, an isohexyl group, a normal heptyl group, an isoheptyl group, a normal octyl group, an isooctyl group, a normal nonyl group, or an isononyl group. An isononyl group is defined as 202300217

[0014] 3 in the sense of the present invention is understood to be a mixture of linear and branched primary C9 alkyl groups.

[0015] In a preferred embodiment of the present invention, the three alkyl groups of the longer-chain trialkyl esters of 1,2,4-cyclohexanetripropionic acid each have the same number of carbon atoms. This means that the three alkyl groups have 4, 5, 6, 7, 8, or 9 carbon atoms, but not that the three alkyl groups must always be identical.

[0016] However, it is particularly preferred that the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid in the composition according to the invention is a tripentyl ester of 1,2,4-cyclohexanetripropionic acid or a triisononyl ester of 1,2,4-cyclohexanetripropionic acid. The term tripentyl ester of 1,2,4-cyclohexanetripropionic acid includes trialkyl esters of 1,2,4-cyclohexanetripropionic acid in which each of the three alkyl groups is a 2-methylbutyl group, a 3-methylbutyl group, or an n-pentyl group. Preferably, the proportion of n-pentyl groups is at least 55% and at most 95% based on all (= 100%) of the pentyl groups in the tripentyl ester of 1,2,4-cyclohexanetripropionic acid. The term triisononyl ester of 1,2,4-cyclohexanetripropionic acid also includes mixed esters containing different isononyl groups. This is due to their preparation using commercially available isononanol (e.g., from Evonik Oxeno GmbH & Co. KG).KG), which typically represents a mixture of different C9 alcohols (linear and branched).

[0017] The preparation of the longer-chain trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to the invention can be carried out by transesterification of the trimethyl ester of 1,2,4-cyclohexanetripropionic acid with an alcohol having 4 to 9 carbon atoms, or by direct esterification of 1,2,4-cyclohexanetripropionic acid with an alcohol having 4 to 9 carbon atoms. The alcohol is used in excess, i.e., in an amount of more than 3 mol per mol of ester component, preferably 3.75 to 5.25 mol of alcohol per mol of ester component. The transesterification and the direct esterification are preferably carried out over an acidic catalyst, for example, inorganic or organic Brønsted or Lewis acids.

[0018] The two substances can be present in different amounts in the plasticizer composition according to the invention. It should be clear that the two substances must be present in an amount at which they exert an effect, i.e., where a plasticizing effect occurs. In a preferred embodiment of the present invention, the compound according to formula (1) and the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid are present in the plasticizer composition in a weight ratio (compound according to formula (1) : the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid) of 1 : 99 to 99 : 1, preferably 10 : 90 to 90 : 10, and particularly preferably 30 : 70 to 70 : 30.In a particularly preferred embodiment of the present invention, the compound according to formula (1) and the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid are present in the plasticizer composition in a weight ratio (compound according to formula (1) : the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid) of 30 : 70 to 5 : 95. 202300217.

[0019] 4

[0020] The plasticizer composition according to the present invention can additionally contain an epoxidized oil or an epoxidized alkyl ester of a fatty acid. Epoxidized oils or corresponding esters can improve the thermal stability and mechanical properties.

[0021] The epoxidized oil can be selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized tall oil, and mixtures thereof. Epoxidized soybean oil or epoxidized linseed oil are preferably used in the plasticizer composition according to the invention. Epoxidized soybean oil, also known by the acronym ESBO, is particularly preferred.

[0022] The epoxidized fatty acid esters can be prepared by transesterification of the aforementioned epoxidized oils with alcohols in the range of 1 to 10 carbon atoms, preferably 4 to 9 carbon atoms. Alternatively, the natural oil can first be transesterified and the double bonds of the fatty acid subsequently epoxidized.

[0023] The epoxidized oil or the corresponding epoxidized fatty acid alkyl esters may be used in amounts of 1 to 150 parts by weight, based on 100 parts by weight of the total sum of the compound according to formula (1) and the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid. The epoxidized oil or the epoxidized fatty acid esters may also be included in the plasticizer composition in amounts of 2 to 125 parts by weight, 5 to 100 parts by weight, 10 to 80 parts by weight, or 20 to 70 parts by weight, respectively, based on 100 parts by weight of the total sum of the compound according to formula (1) and the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid.

[0024] The plasticizer composition according to the invention may additionally contain at least one further plasticizer selected from the group consisting of adipates, benzoates, for example monobenzoates or glycol dibenzoates, chlorinated hydrocarbons (so-called chlorinated paraffins), citrates, epoxidized fatty acid esters, epoxidized vegetable oils, epoxidized acylated glycerides, furane dicarboxylates, phosphates, succinates, sulfonamides, sulfonates, terephthalates, isophthalates, phthalates, trimellites, cyclohexane dicarboxylates and oligomeric or polymeric esters based on adipic, succinic or sebacic acid.

[0025] In a preferred embodiment of the present invention, the plasticizer composition comprises at least one further plasticizer from the group consisting of alkyl benzoates, alkyl sulfonic acid esters of phenol, dialkyl adipates, glycerol esters, C4 to C6 alkanoic acid esters of polyols, acetylated or non-acetylated trialkyl citric acid esters, glycol dibenzoates, trialkyl esters of trimellitic acid, dialkyl terephthalates, dialkyl phthalates, dialkyl isophthalates, esters of furandicarboxylic acid, dialkanoyl esters of dianhydrohexitols (e.g., isosorbide), epoxidized fatty acid alkyl esters, polymer plasticizers, for example, polyadipates, and dialkyl esters of 1,2-, 1,3-, or 1,4-cyclohexanedicarboxylic acid. 202300217

[0026] 5

[0027] In a further preferred embodiment, the at least one additional plasticizer that may be included in the plasticizer composition according to the invention is selected from the group consisting of C8 to C13 alkyl benzoates, C4 to C10 dialkyl adipates, pentaerythritol tetravalerate, acetylated or non-acetylated trialkyl citric acid esters with C2 to C9 alkyl groups, C4 to C10 trialkyl trimellites, C4 to C9 dialkyl terephthalates, C4 to C13 dialkyl phthalates, in particular C9 to C13 dialkyl phthalates and C4 to C10 dialkyl esters of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid.

[0028] Butyl, pentyl, or higher citrates, which may contain an acetyl group, are particularly preferred. These include tributyl citrate, tripentyl citrate, tri-n-hexyl citrate, tri-2-ethylhexyl citrate, triisononyl citrate, acetyltributyl citrate, and acetyltripentyl citrate. Of the C4 to C10 dialkyl adipates, diethylhexyl adipate (DEHA) and diisononyl adipate (DINA) are preferred. Of the C4 to C9 dialkyl terephthalates, dibutyl terephthalate (DBT), dipentyl terephthalate (DPT), and diethylhexyl terephthalate (DEHT or DOTP) are preferred. Of the C4 to C10 trialkyl trimellites, triethylhexyl trimellite (TEHTM or TOTM) and triisononyl terephthalate (TINTM) are preferred. Of the C4 to C10 dialkyl esters of 1,4-cyclohexanedicarboxylic acid, the 1,4-di-2-ethylhexylcyclohexanedicarboxylic acid ester (1,4-DEHCH) and the 1,4-diisononylcyclohexanedicarboxylic acid ester (1,4-DINCH or DINCD) are preferred.Of the C4 to C10 dialkyl esters of 1,2-cyclohexanedicarboxylic acid, the 1,2-di-2-ethylhexylcyclohexanedicarboxylic acid ester (1,2-DEHCH) and the 1,2-diisononylcyclohexanedicarboxylic acid ester (1,2-DINCH) are preferred.

[0029] A further object of the present invention is a plastic composition comprising a plastic and a plasticizer composition comprising the compound of formula (1) and at least one of the longer-chain trialkyl esters of 1,2,4-cyclohexanetripropionic acid, wherein the three alkyl groups each have 4 to 10 carbon atoms. The plastic composition may also include the epoxidized oil and / or an epoxidized fatty acid alkyl ester and / or at least one additional plasticizer from the above list.

[0030] Suitable plastics are polymeric substances, preferably from the group consisting of PVC (polyvinyl chloride), homo- or copolymers based on ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, ethyl acrylate, butyl acrylate or methacrylate with alkoxy groups of branched or unbranched alcohols with one to ten carbon atoms, acrylonitrile or cyclic olefins, polyvinylidene chloride (PVDC), polyacrylates, in particular polymethyl methacrylate (PMMA), polyalkyl methacrylate (PAMA), polyureas, silylated polymers, fluoropolymers, in particular polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetals, in particular polyvinyl butyral (PVB), polystyrene polymers, in particular polystyrene (PS), expandable polystyrene (EPS). Acrylonitrile styrene acrylate (ASA), styrene acrylonitrile (SAN), acrylonitrile butadiene styrene (ABS), styrene maleic anhydride copolymer (SMA),Styrene-methacrylic acid copolymer, polyolefins, in particular polyethylene (PE) or polypropylene (PP), 202300217,

[0031] 6 thermoplastic polyolefins (TPO), polyethylene vinyl acetate (EVA), polycarbonates, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPU), polysulfides (PSu), biopolymers, in particular polylactic acid (PLA), polyhydroxybutyral (PHB), polyhydroxyvaleric acid (PHV), polyesters, starch, cellulose and cellulose derivatives, in particular nitrocellulose (NC), ethylcellulose (EC), cellulose acetate (CA), cellulose acetate / butyrate (CAB), rubber and silicones, may be selected.

[0032] In a preferred embodiment, the plastic in the plasticizer composition is selected from the group consisting of polyvinyl chloride (PVC), polyalkyl methacrylate (PAMA), polyvinyl butyral (PVB), polyurethane, polysulfides, polylactic acid (PLA), polyhydroxybutyral (PHB), nitrocellulose, and copolymers of vinyl chloride with vinyl acetate or with butyl acrylate. PVC is particularly preferred as the plastic in the plastic composition according to the invention.

[0033] The amount of the plasticizer composition according to the invention in the plastic composition is preferably 5 to 150 parts by weight, preferably 10 to 120 parts by weight, particularly preferably 15 to 110 parts by weight and most preferably 20 to 100 parts by weight of the plastic.

[0034] The plastic composition may contain additional additives besides the aforementioned ingredients. Examples of additional additives are rheological additives, which can reduce the viscosity of the plastic composition. Examples of known rheological additives are the products available under the trade names VISCOBYKO-5120, VISCOBYKO-5130, and VISCOBYKO-4041. The additives may be present in a proportion of 1 to 12, preferably 2 to 10 parts by weight per 100 parts by weight of PVC in the plastic composition.

[0035] Furthermore, the plastic composition may contain one or more thermostabilizers. Suitable thermostabilizers include lead salts, organotin compounds, barium / zinc compounds, cadmium or zinc compounds, calcium / zinc stabilizers, and organic-based stabilizers (OBS). Preferred thermostabilizers are barium / zinc compounds, calcium / zinc stabilizers, and organic-based stabilizers (OBS). The proportion of the stabilizer(s) in the plastic composition is preferably 1 to 6 parts by weight per 100 parts by weight of PVC.

[0036] In addition, fillers, pigments, blowing agents and lubricants may also be included in the plastic composition as additives.

[0037] The plastic composition according to the invention is preferably a component of an adhesive, a sealant, a coating compound, a varnish, a paint, a plastisol, a dry blend, a foam, an artificial leather, a floor covering, in particular its top or foam layer, a roofing membrane, an underbody protection, a fabric coating, a cable, 202300217

[0038] 7 of a wire insulation, a hose, an extruded article, a film, an automotive interior item, a wallpaper, an ink, a toy, a contact film, a food packaging or a medical article, in particular a hose or a blood bag.

[0039] The present invention therefore also relates to the use of the plastic composition in adhesives, sealants, coatings, varnishes, paints, plastisols, foams, artificial leather, floor coverings, in particular top and foam layers, roofing membranes, underbody protection, fabric coatings, cables, wire insulation, hoses, extruded articles, films, in automotive interiors, in wallpapers, inks, toys, contact films, food packaging or medical articles, in particular in hoses or blood bags.

[0040] The present invention is illustrated below by means of examples. The following examples are intended to explain the invention without limiting its scope of application as set out in the description and the claims.

[0041] Examples

[0042] Example 1a - Preparation of cyclohexane-1,2,4-tripropionic acid trimethyl ester (Me-Tc)

[0043] [Pd(acac)₂] (15.2 mg, 0.1 mol%), catalyst L (103 mg, 0.4 mol%), and p-toluenesulfonic acid (PTSA) (143 mg, 1.5 mol%) were placed in a 100 mL steel autoclave under an argon atmosphere. Then, MeOH (30 mL) and trivinylcyclohexane (8.1 g, 50 mmol) were injected via syringe. The autoclave was purged three times with CO₂ and subsequently pressurized to 40 bar. 202300217

[0044] 8

[0045] The reaction took place over 10 hours at 110 °C. Afterwards, the autoclave was cooled to room temperature and depressurized. The desired product was obtained by distillation (165 °C at 10 hours). -3 bar) cleaned and with 1 H-, 13 Characterized by C-NMR and HR-MS (15.6 g, 91% yield).

[0046] Example 1b - Preparation of cyclohexane-1,2,4-tripropionic acid tripentyl ester (MbPe-Tc)

[0047] The trimethyl ester (Me-Tc) prepared according to Example 1a was transesterified to the product MbPe-Tc in a typical laboratory transesterification apparatus with 2-methylbutanol and n-pentanol (molar ratio 7:93). The transesterification apparatus consists of a glass flask equipped with a stirrer, temperature sensor, distillation column, vacuum divider, and distillation setup.

[0048] Initially, 127 g of 2-methylbutanol, 1690 g of n-pentanol, and 1880 g of M-Tc were placed in the transesterification apparatus. The entire apparatus was then purged with nitrogen, and subsequently, 2.72 g of tetra(n-butyl)titanate (TNBT) was added as a catalyst. The reaction was then initiated by heating. The reaction temperature ranged from 130 to 240°C, meaning it increased during the reaction. Methanol produced during the transesterification was removed from the system via the column and distillation apparatus (65°C head temperature). The C5 alcohols, separated from the methanol in the column, were refluxed back into the reaction mixture. When no further distillate was observed, the reaction progress was monitored via GC analysis. The reaction was terminated when the triester accounted for >99% of the GC surface area, based on the sum of the surface areas of the reactant, mono-, di- and triester.

[0049] Following the reaction, the excess alcohol was distilled off under vacuum at 160 °C. The acid number of the reaction mixture was then determined and neutralized by adding three times the stoichiometric amount of 10% NaOH. Next, the mixture was stripped with nitrogen at 160 °C for 2 hours. Finally, the product was filtered clear through a 0.5 pm PTFE filter with perlite as a filter aid.

[0050] Example 1c - Preparation of cyclohexane-1,2,4-tripropionic acid trisononyl ester (In-Tc)

[0051] The trimethyl ester (Me-Tc) prepared according to Example 1 a was transesterified in a typical laboratory transesterification apparatus analogously to Example 1 b), but now with isononanol to give the product In-Tc.

[0052] Initially, 1944 g of isononanol (INA, manufactured by Evonik Oxeno GmbH & Co. KG) and 1230 g of M-Tc were placed in the transesterification apparatus. The entire apparatus was then purged with nitrogen. Next, 2.03 g of tetra(n-butyl)titanate (TNBT) were added as a catalyst. The reaction was then initiated by heating. The reaction temperature ranged from 130 to 240°C, i.e., it increased during the reaction. Methanol, produced during the transesterification, was removed from the system via the column and distillation apparatus (65°C head temperature). The INA, separated from the methanol in the column, was refluxed back into the reaction mixture. 202300217

[0053] 9

[0054] A slight vacuum was occasionally applied to obtain sufficient distillate. When no further distillate was observed, the reaction progress was monitored by GC analysis. The reaction was complete when the triester accounted for >99% of the GC surface area, based on the sum of the surface areas of the reactant, mono-, di-, and triester.

[0055] Following the reaction, the excess alcohol was distilled off under vacuum at 180 °C. The acid number of the reaction mixture was then determined and neutralized by adding three times the stoichiometric amount of 10% NaOH. Next, the mixture was stripped with nitrogen at 180 °C for 2 hours. Finally, the product was filtered clear through a 0.5 pm PTFE filter with perlite as a filter aid.

[0056] Example 2 - Production of plastisols

[0057] PVC plastisols were produced, such as those used for manufacturing topcoat films for floor coverings. The plastisol formulations are given in parts by weight (phr). The polymer composition formulations are listed in Tables 1 and 2.

[0058] Table 1: Overview of the produced plastisols (MbPe-Tc / Me-Tc).

[0059] * = composition according to the invention phr = parts per hundred parts resin 202300217

[0060] 10

[0061] Table 2: Overview of the produced plastisols (In-Tc / Me-Tc).

[0062] * = composition according to the invention

[0063] First, the liquid and then the powdered components were weighed into a PE beaker. The mixture was stirred by hand with a spatula until no unwetted powder remained. The sealed beaker was placed in the holder in the speed mixer, mixed, and vented. After mixing was complete, the temperature of the plastisol was measured using an IR thermometer. The plastisol was then immediately tempered at 25.0 °C in a climate chamber for further analysis.

[0064] Example 3 - Gelation of plastisols

[0065] The gelling behavior of the plastisols from Example 2 was investigated using a Physica MCR 101 in oscillation mode with a plate-plate measuring system (PP25) operated under shear stress control. An additional temperature control hood was connected to the instrument to achieve homogeneous heat distribution and a uniform sample temperature. 202300217

[0066] 11

[0067] The following parameters were set:

[0068] Mode: Temperature gradient

[0069] Starting temperature: 25 °C

[0070] Final temperature: 180 °C

[0071] Heating / cooling rate: 5 °C / min

[0072] Oscillation frequency: 4 to 0.1 Hz, logarithmic ramp

[0073] Omega angular frequency: 10 s 1

[0074] Number of measuring points: 63

[0075] Measurement duration: 0.5 min

[0076] Automatic gap tracking F 0 N

[0077] Constant measurement point duration

[0078] Gap width 0.5 mm

[0079] Performing the measurement

[0080] A few grams of the paste to be measured were applied to the lower measuring system plate using a spatula, ensuring no air bubbles were present. Care was taken to allow some paste to ooze out evenly from the measuring system after it was closed (no more than 6 mm all around). The excess was removed with a spatula. The temperature control hood was then positioned over the sample and the measurement started. The complex viscosity of the paste was determined after 24 hours (storage of the paste at 25 °C in a temperature control chamber from Memmert) as a function of temperature.

[0081] A significant increase in complex viscosity was considered a measure of gelation. Therefore, the temperature at which a paste viscosity of 1000 Pa*s was reached was used as a reference value. The results obtained are listed in Table 3.

[0082] Table 3: Gelation of the plastisols after 24 hours, temperature in °C at reaching a paste viscosity of 1000 Pa*s.

[0083] * Test with plasticizer composition according to the invention 202300217

[0084] 12

[0085] Compared to other rapid gelling agents, the use of trimethyl cyclohexane-1,2,4-tripropionic acid (Me-Tc) in the plasticizer compositions significantly reduces the gelling temperature. Using more Me-Tc can lower the gelling temperature even further.

[0086] Example 4 - Production of films

[0087] The plastisols produced in Example 2 were each processed into 1 mm thick films. First, high-gloss release paper (Sappi, Italy) was cut to a size of 30 x 44 cm and placed in the tensioning frame of the LTSV coating unit for the Mathis oven. The tensioning frame was then placed on the guide frame, the Mathis oven (type LTF) was set to 200 °C, and the frame was preheated for 15 seconds after reaching this temperature. Next, the doctor blade was placed in the clamping device, and the blade gap was adjusted through preliminary tests so that the film thickness after gelation was 1 mm (+ / - 0.05 mm). An adhesive strip was applied to the leading edge of the paper to catch excess plastisol. The plastisol was then applied in front of the doctor blade, and the doctor blade was spread across the clamped release paper by pulling the guide frame along with the blade (speed 3 m / min).The squeegee was then removed and the adhesive strip with the excess plastisol was peeled off. The frame was then placed in the oven. After gelling (2 minutes at 200 °C), the frame was removed from the oven and, after cooling, the film was peeled off the paper.

[0088] Example 5 - Determination of mass loss (activated carbon method)

[0089] Following DIN EN ISO 176 (Method B), three circular discs with a diameter of 5 cm were punched out from the manufactured PVC films and initially conditioned for 16 hours in a desiccator at room temperature. The sample discs were weighed on an analytical balance, placed in a wire basket, and closed with a clamp. The wire baskets were then placed in a tin can filled with activated carbon, ensuring that there was approximately 130 ml of activated carbon between each basket, between the basket and the lid (perforated), and between the can and the base.

[0090] The filled tinplate cans were placed in a pre-heated oven (120 °C) in such a way that the oven fan was not obstructed and the cans did not touch each other. Air exchange and exhaust damper were each set to 10%. After 72 hours, the cans were removed from the oven, cooled, and then the individual samples were taken from the baskets, conditioned for another 16 hours in a desiccator, and then weighed again on an analytical balance. The resulting mass difference is due to the loss of plasticizer. The average of the three mass differences was calculated, and the percentage loss of plasticizer was determined. Table 4 shows the results of the volatility tests. 202300217

[0091] 13

[0092] Table 4: Mass loss of the test specimens after three days at 120 °C.

[0093] * = composition according to the invention

[0094] The mass loss of films with the plasticizer composition according to the invention is less than that of films produced with plasticizer compositions containing other rapid gelling agents.

Claims

202300217 14 Patent claims 1. Plasticizer composition containing a compound of formula (1) and at least one longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid, wherein the three alkyl groups each have 4 to 9 carbon atoms.

2. Plasticizer composition according to claim 1, wherein the three alkyl groups are each selected independently from the group consisting of a normal butyl group, an isobutyl group, a normal pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a normal hexyl group, an isohexyl group, a normal heptyl group, an isoheptyl group, a normal octyl group, an isooctyl group, a normal nonyl group or an isononyl group.

3. Plasticizer composition according to claim 1 or 2, wherein the three alkyl groups of the trialkyl ester of 1,2,4-cyclohexanetripropionic acid have the same number of carbon atoms.

4. Plasticizer composition according to any of the preceding claims, wherein the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid is a tripentyl ester of 1,2,4-cyclohexanetripropionic acid or a triisononyl ester of 1,2,4-cyclohexanetripropionic acid.

5. Plasticizer composition according to one of the preceding claims, wherein the compound according to formula (1) and the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid are present in the plasticizer composition in a weight ratio (compound according to formula (1) : 1,2-dialkylcyclohexanedicarboxylic acid ester) of 1 : 99 to 99 : 1, preferably 10 : 90 to 90 : 10, particularly preferably 30 : 70 to 70 :

30.

6. Plasticizer composition according to any of the preceding claims, wherein the plasticizer composition additionally comprises an epoxidized oil or an epoxidized alkyl ester of a fatty acid. 202300217 15 7. Plasticizer composition according to claim 6, wherein the epoxidized oil is selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, epoxidized oleate, epoxidized tall oil, epoxidized linoleate and mixtures thereof.

8. Plasticizer composition according to claim 7, wherein the epoxidized oil is epoxidized soybean oil or epoxidized linseed oil, preferably epoxidized soybean oil.

9. Plasticizer composition according to any one of claims 6 to 8, wherein the epoxidized oil is present in an amount of 1 to 150 parts by weight based on 100 parts by weight of the total sum of the compound according to formula (1) and the longer-chain trialkyl ester of 1,2,4-cyclohexanetripropionic acid in the plasticizer composition.

10. Plasticizer composition according to one of the preceding claims, wherein the composition further comprises a further plasticizer selected from the group consisting of adipates, benzoates, for example monobenzoates or glycol dibenzoates, chlorinated hydrocarbons (so-called chlorinated paraffins), citrates, epoxidized fatty acid esters, epoxidized vegetable oils, epoxidized acylated glycerides, furane dicarboxylates, phosphates, succinates, sulfonamides, sulfonates, terephthalates, isophthalates, trimellites, cyclohexane dicarboxylates and oligomeric or polymeric esters based on adipic, succinic or sebacic acid.

11. Plastic composition comprising the plasticizer composition according to any one of claims 1 to 10 and a plastic.

12. Plastic composition according to claim 11, wherein the proportion of the plasticizer composition is 5 to 150 parts by weight per 100 parts by weight of plastic.

13. Plastic composition according to claim 11 or 12, wherein the plastic is selected from the group consisting of polyvinyl chloride (PVC), polyalkyl methacrylate (PAMA), polyvinyl butyral (PVB), polyurethane, polysulfides, polylactic acid (PLA), polyhydroxybutyral (PHB), nitrocellulose and copolymers of vinyl chloride with vinyl acetate or with butyl acrylate.

14. Plastic composition according to claim 13, wherein the plastic is polyvinyl chloride (PVC).

15. Use of the plastic composition according to any one of claims 11 to 14 in adhesives, sealants, coatings, varnishes, paints, plastisols, foams, artificial leather, floor coverings, in particular top and foam layers, roofing membranes, underbody protection, fabric coatings, cables, wire insulation, hoses, extruded articles, films, in 202300217 16 Automotive interiors, in wallpaper, inks, toys, contact films, food packaging or medical articles, especially in hoses or blood bags.

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