Tripentyl esters of 1,2,4-cyclohexanetripropionic acid and plasticizer compositions containing same

Abstract

The invention relates to trialkyl esters of 1,2,4-cyclohexanetripropionic acid of the formula [I], wherein each of the three alkyl groups R has 5 carbon atoms, and 55 to 95 mol% of the trialkyl esters are n-pentyl radicals. The invention further relates to a plasticizer composition comprising the aforementioned trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula [I].

Description

[0001] 202400193

[0002] 1

[0003] Tripentyl esters of 1,2,4-cyclohexanetripropionic acid and plasticizer compositions containing it

[0004] The invention relates to trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) in which the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. Another item is a plasticizer composition comprising the aforementioned trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1).

[0005] The compounds according to formula (1) of the invention are trialkyl esters of 1,2,4-cyclohexanetripropionic acid, wherein the three alkyl groups each have 5 carbon atoms. Trialkyl esters of 1,2,4-cyclohexanetripropionic acid are generally known and have been described, for example, in EP 3 838 888 A1. It was also mentioned there that these esters of 1,2,4-cyclohexanetripropionic acid can be used as plasticizers for polymers.

[0006] Although the trialkyl esters of 1,2,4-cyclohexanetripropionic acid are known and their use as plasticizers has been mentioned, there is a continuous need to improve their properties when used as plasticizers. Depending on the application, the requirements for the plasticizer to be used can vary.

[0007] The present invention was based on the objective of providing a compound that exhibits improved properties compared to known trialkyl esters of 1,2,4-cyclohexanetripropionic acid. Furthermore, a plasticizer composition was to be provided that contains trialkyl esters of 1,2,4-cyclohexanetripropionic acid but has better application-related properties than compositions with known trialkyl esters of 1,2,4-cyclohexanetripropionic acid.

[0008] This problem is solved by the specific trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to claim 1, and by the plasticizer composition according to claim 1. The problem is further solved by the plasticizer composition according to claim 5. Preferred embodiments are specified in the dependent claims. 202400193

[0009] 2

[0010] One object of the present invention is trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) in which the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. In a preferred embodiment, 60 to 95 mol% of the alkyl groups R are n-pentyl groups. The percentage mol% here also refers to 100 mol% of the groups R, i.e., all groups R of the compound according to formula (1).

[0011] The compounds according to formula (1) of the invention are therefore tripentyl esters of 1,2,4-cyclohexanetripropionic acid, in which a certain proportion of one or more isomers of the pentyl group is present. The most important representatives of the isomers of the pentyl group are the linear n-pentyl group and the simply branched 2-methylbutyl group and 3-methylbutyl group.

[0012] According to the invention, it is preferred that the trialkyl ester of 1,2,4-cyclohexanetripropionic acid comprises, in addition to the n-pentyl groups, exclusively 2-methylbutyl and / or 3-methylbutyl groups. Thus, preferably 5 to 45 mol%, preferably 5 to 40 mol% of the alkyl groups R in the trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) are 2-methylbutyl groups and / or 3-methylbutyl groups.

[0013] Particularly preferably, the alkyl groups of the trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) contain only 2-methylbutyl groups in addition to the n-pentyl groups. Thus, preferably 5 to 45 mol%, more preferably 5 to 40 mol% of the alkyl groups R in the trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) are 2-methylbutyl groups.

[0014] Another object of the present invention is a plasticizer composition containing the previously described trialkyl esters of 1,2,4-cyclohexanetripropionic acid. This corresponds to a plasticizer composition containing trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) 202400193

[0015] 3 in which the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol%, preferably 60 to 95 mol%, are n-pentyl groups. The percentage mol% here also refers to 100 mol% of the R groups, i.e., all R groups of the compound according to formula (1).

[0016] According to the invention, it is preferred that the trialkyl ester of 1,2,4-cyclohexanetripropionic acid in the plasticizer composition comprises, in addition to the n-pentyl groups, exclusively 2-methylbutyl and / or 3-methylbutyl groups. Thus, preferably 5 to 45 mol%, preferably 5 to 40 mol% of the alkyl groups R in the trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) are 2-methylbutyl groups and / or 3-methylbutyl groups.

[0017] Particularly preferably, the alkyl groups of the trialkyl esters of 1,2,4-cyclohexanetripropionic acid in the plasticizer composition according to formula (1) contain, in addition to the n-pentyl groups, only 2-methylbutyl groups. Thus, preferably 5 to 45 mol%, preferably 5 to 40 mol% of the alkyl groups R in the trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) are 2-methylbutyl groups.

[0018] 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.

[0019] In a preferred embodiment of the present invention, the plasticizer composition comprises at least one further plasticizer selected 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. 202400193

[0020] 4

[0021] The two substances, i.e., the trialkyl esters of 1,2,4-cyclohexanetripropionic acid and the further plasticizer, 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 further plasticizers are present in the plasticizer composition in a weight ratio (compound according to formula (1) : further plasticizer) of 1 : 99 to 99 : 1, preferably 10 : 90 to 90 : 10, and particularly preferably 30 : 70 to 70 : 30.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] The epoxidized oil or the corresponding epoxidized fatty acid alkyl esters may be used in amounts of 1 to 150 parts by weight per 100 parts by weight of the total amount of the compound according to formula (1) and the additional plasticizer. 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, each based on 100 parts by weight of the total amount of the compound according to formula (1) and the additional plasticizer.

[0026] 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, 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 1,3-cyclohexanedicarboxylic acid.

[0027] An object of the present invention is a plasticizer composition comprising

[0028] Tributyl citrate and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to the formula shown above (1), 202400193

[0029] 5 in which the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1 : 99 to 99 : 1, preferably 10 : 90 to 90 : 10, more preferably 30 : 70 to 70 : 30 or 50 : 50.

[0030] Another object of the present invention is a plasticizer composition comprising tripentyl citrate and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0031] Another object of the present invention is a plasticizer composition comprising tri-n-hexyl citrate and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0032] Another object of the present invention is a plasticizer composition comprising tri-2-ethylhexyl citrate and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0033] Another object of the present invention is a plasticizer composition comprising triisononyl citrate and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0034] Another object of the present invention is a plasticizer composition comprising acetyltributyl citrate (ATBC) and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0035] Another object of the present invention is a plasticizer composition comprising acetyltripentyl citrate and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to above 202400193

[0036] 6 shown in formula (1), wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1 : 99 to 99 : 1, more preferably 10 : 90 to 90 : 10, and more preferably 30 : 70 to 70 : 30 or 50 : 50.

[0037] Another object of the present invention is a plasticizer composition comprising diethylhexyl adipate (DEHA) and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0038] Another object of the present invention is a plasticizer composition comprising diisononyl adipate (DINA) and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0039] Another object of the present invention is a plasticizer composition comprising diethylhexyl terephthalate (DEHT or DOTP) and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0040] Another object of the present invention is a plasticizer composition comprising triethylhexyl trimellitate (TEHTM or TOTM) and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0041] Another object of the present invention is a plasticizer composition comprising triisononyl trimellitate (TINTM) and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50. 202400193

[0042] 7

[0043] Another object of the present invention is a plasticizer composition comprising tripentyl trimellitate (TPTM) and tripentyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0044] A further object of the present invention is a plasticizer composition comprising 1,4-diethylhexylcyclohexanedicarboxylic acid ester (1,4-DEHCH) and tripentyl ester of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0045] A further object of the present invention is a plasticizer composition comprising 1,2-diethylhexylcyclohexanedicarboxylic acid ester (1,2-DEHCH) and tripentyl ester of 1,2,4-cyclohexanetripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0046] A further object of the present invention is a plasticizer composition comprising a glycol dibenzoate from the group consisting of diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, and mixtures thereof, and tripentyl esters of 1,2,4-cyclohexane tripropionic acid according to formula (1) shown above, wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups. The two plasticizers are preferably present in a weight ratio of 1:99 to 99:1, more preferably 10:90 to 90:10, and more preferably 30:70 to 70:30 or 50:50.

[0047] Another object of the present invention is a plastic composition comprising a plastic and the plasticizer composition comprising the compound of formula (1) and optionally a further plasticizer. 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-mentioned list.

[0048] 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 residues 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 202400193

[0049] 8

[0050] 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), 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), polyester, starch, cellulose and cellulose derivatives, in particular nitrocellulose (NC), ethylcellulose (EC),Cellulose acetate (CA), cellulose acetate / butyrate (CAB), rubber and silicones are selected.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] Additional additives, such as fillers, pigments, blowing agents, and lubricants, may also be included in the plastic composition. 202400193

[0056] 9

[0057] 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, a wire insulation, a hose, an extruded article, a film, an object in the automotive interior, a wallpaper, an ink, a toy, a contact film, a food packaging or a medical article, in particular a hose or a blood bag.

[0058] 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.

[0059] 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.

[0060] Examples

[0061] Example 1 - Preparation of cyclohexane-1,2,4-tripropionic acid trimethyl ester (Me-Tc) 202400193

[0062] 10

[0063] [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. The reaction was carried out for 10 h at 110 °C. Afterward, the autoclave was cooled to room temperature and depressurized. The desired product was obtained by distillation (165 °C at 10 -3 bar) cleaned and with 1 H-, 13 Characterized by C-NMR and HR-MS (15.6 g, 91% yield).

[0064] Example 2 - Preparation of various cyclohexane-1,2,4-tripropionic acid tripentyl esters (MbPe-Tc)

[0065] The trimethyl ester (Me-Tc) prepared according to Example 1 was transesterified to the product MbPe-Tc in a typical laboratory transesterification apparatus with 2-methylbutanol and n-pentanol (molar ratio see table). The transesterification apparatus consists of a glass flask equipped with a stirrer, temperature sensor, distillation column, vacuum divider, and distillation setup.

[0066] First, the mixtures of n-pentanol / 2-methylbutanol and M-Tc listed in Table 1 were placed in the transesterification apparatus. The entire apparatus was then purged with nitrogen, and tetra(n-butyl)titanate (TNBT) was added as a catalyst (0.15 mol% based on M-Tc). The reaction was then initiated by heating. The reaction temperature was 130–240°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 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 >98.8% of the GC surface area, based on the sum of the surface areas of the reactant, mono-, di- and triester.

[0067] 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 it was neutralized by adding three times the stoichiometric amount of 10% NaOH. Next, the mixture was heated to 202400193 °C.

[0068] 11

[0069] The product is stripped at 160 °C with nitrogen for 2 hours. In the final step, it is filtered through a 0.5 dm PTFE filter with perlite as a filter aid until clear.

[0070] Table 1: Pentanol mixtures for the preparation of cyclohexane-1,2,4-tripropionic acid tripentyl esters * 1 As in EP 3 838 888 A1

[0071] * 2 according to the invention

[0072] Example 3 - Production of Plastisols 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 Table 2.

[0073] Table 2: Overview of the produced plastisols * = according to invention phr = parts per hundred parts resin 202400193

[0074] 12

[0075] 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.

[0076] Example 4 - Viscosities of Plastisols

[0077] The viscosity of the plastisols produced in Example 3 was measured using a Physica MCR 101 rheometer (Anton Paar Germany GmbH) with the help of the associated software, using the rotation mode and the CC27 measuring system.

[0078] The following points were targeted during the measurement:

[0079] Pre-shear of 100 s-1 for a period of 60 seconds, during which no measurements were recorded.

[0080] Shear rate down-ramp from 200 s⁻¹ to 0.1 s⁻¹. 30 measurement points were recorded with a measurement duration of 10 seconds each.

[0081] The measurements were performed at room temperature. The results of the viscosity measurements of the plastisols produced in Example 3 with the respective plasticizers or plasticizer mixtures are shown in Table 3.

[0082] Table 3: Viscosity of plastisols in Pa*s after 24 hours at a shear rate of 200 s -1

[0083] * according to the invention

[0084] Example 5 - Gelation of plastisols

[0085] 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. 202400193

[0086] 13

[0087] The following parameters were set:

[0088] Mode: Temperature gradient

[0089] Starting temperature: 25 °C

[0090] Final temperature: 180 °C

[0091] Heating / cooling rate: 5 °C / min

[0092] Oscillation frequency: 4 to 0.1 Hz, logarithmic ramp

[0093] Omega angular frequency: 10 s 1

[0094] Number of measuring points: 63

[0095] Measurement duration: 0.5 min

[0096] Automatic gap tracking F 0 N

[0097] Constant measurement point duration

[0098] Gap width 0.5 mm

[0099] Performing the measurement

[0100] 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.

[0101] 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 4.

[0102] Table 4: Gelation of the plastisols after 24 hours, temperature in °C at reaching a paste viscosity of 1000 Pa*s.

[0103] * according to the invention

[0104] When using the tripentyl esters according to the invention, the gelling temperature can be lowered. 202400193

[0105] 14

[0106] Example 6 - Production of films

[0107] The plastisols produced in Example 3 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 (at a speed of 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.

[0108] Example 7 - Determination of the glass transition temperature using DMTA

[0109] The glass transition temperature was determined using DMTA measurements according to DIN 65583 with an Anton Paar MCR 302 rheometer. Under constant dynamic mechanical conditions (1 Hz, 0.3% deformation), the viscoelastic properties of the films (1 mm thick) were recorded as a function of temperature (temperature ramp from -100 to +50 °C), and the storage modulus, loss modulus, and loss factor were determined. The maximum loss modulus is used as the glass transition temperature. Table 5 below shows the mean value from two separate measurements.

[0110] Table 5: Mass loss of the test specimens after three days at 120 °C.

[0111] * = according to the invention

[0112] The glass transition temperatures of the samples according to the invention are lower than in the comparison example.

Claims

202400193 15 Patent claims 1. Trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1) wherein the three alkyl groups R each have 5 carbon atoms, of which 55 to 95 mol% are n-pentyl groups.

2. Trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to claim 1, wherein 60 to 95 mol% of the alkyl groups R are n-pentyl groups.

3. Trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to claim 1 or 2, wherein 5 to 45 mol%, preferably 5 to 40 mol% of the alkyl groups R are 2-methylbutyl residues and / or 3-methylbutyl residues.

4. Trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to claim 2, wherein 5 to 45 mol%, preferably 5 to 40 mol% of the alkyl groups R are 2-methylbutyl residues.

5. Plasticizer composition, wherein the plasticizer composition comprises the trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to any one of claims 1 to 4.

6. Plasticizer composition according to claim 5, wherein the plasticizer composition comprises at least one further plasticizer selected 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 the polyadipates, dialkyl esters of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid.

7. Plasticizer composition according to one of the preceding claims, wherein the compound according to formula (1) and the further plasticizer (compound according to formula (1) : further 202400193 16 Plasticizers) in proportions of 1:99 to 99:1, preferably 10:90 to 90:10, particularly preferably 30:70 to 70:30 in the plasticizer composition.

8. 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.

9. 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.

10. Plasticizer composition according to claim 9, wherein the epoxidized oil is epoxidized soybean oil or epoxidized linseed oil, preferably epoxidized soybean oil.

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 automotive interiors, in wallpapers, inks, toys, contact films, food packaging or medical articles, in particular in hoses or blood bags.

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