Plasticizer composition containing tripentyl esters of 1,2,4-cyclohexanetripropionic acid and a 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester

Abstract

The present invention relates to a plasticizer composition comprising a compound of formula (1) (1) in which the alkyl groups R each have 5 carbon atoms, of which 45 to 97 mol%, preferably 55 to 97 mol% are n-pentyl radicals, and at least one 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester, wherein the two alkyl groups in the 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester each have 8, 9 or 10 carbon atoms.

Description

[0001] 202500055 Abroad

[0002] 1

[0003] Plasticizer composition containing tripentyl ester of 1,2,4-cyclohexanetripropionic acid and a 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester

[0004] The invention relates to a plasticizer composition containing a compound of formula (1)

[0005] COOR

[0006]

[0007] COOR (1),

[0008] in which the alkyl groups R each have 5 carbon atoms, of which 45 to 97 mol% are n-pentyl groups, and at least one 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester, wherein the two alkyl groups in the 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester each have 8, 9 or 10 carbon atoms.

[0009] Dialkyl esters of 1,2- or 1,4-cyclohexanedicarboxylic acid have been known for some time and are established in the market. Relevant representatives are the diisononyl esters, which are commercially available as DINCH (diisononyl-1,2-cyclohexanedicarboxylic acid ester) and DINCD (diisononyl-1,4-cyclohexanedicarboxylic acid ester) as esters of 1,4-cyclohexanedicarboxylic acid. The corresponding di-2-ethylhexyl esters have also been described.

[0010] The dialkyl esters of 1,2- or 1,4-cyclohexanedicarboxylic acid generally exhibit good viscosity properties and good cold flexibility, but show weaknesses in plasticizing efficiency, gelation, and volatility. Therefore, it would be desirable to reduce the disadvantages of the dialkyl esters of 1,2- or 1,4-cyclohexanedicarboxylic acid.

[0011] Trialkyl esters of 1,2,4-cyclohexanetripropionic acid according to formula (1), wherein the three alkyl groups each have 5 carbon atoms, are also generally known and have been described, for example, in EP 3838888 A1. It was also mentioned there that these esters of 1,2,4-cyclohexanetripropionic acid can be used as plasticizers for polymers. However, these products exhibit increased viscosity in plastisols and poorer cold flexibility.

[0012] The present invention was based on the objective of providing a plasticizer composition containing dialkyl esters of 1,2- or 1,4-cyclohexanedicarboxylic acid, but exhibiting better application-related properties than plasticizer compositions containing only dialkyl esters of 1,2- or 1,4-cyclohexanedicarboxylic acid, which, although generally suitable for international applications,

[0013] 2

[0014] While gelling and efficiency can be improved, disadvantages often result, particularly regarding volatility.

[0015] This problem is solved by the plasticizer composition according to claim 1. The subject matter of the invention is therefore a plasticizer composition containing a compound of formula (1) COOR

[0016] COOR

[0017]

[0018] COOR (1)

[0019] in which the alkyl groups R each have 5 carbon atoms, of which 45 to 97 mol% are n-pentyl groups, preferably 55 to 97 mol% are n-pentyl groups, and at least one 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester, wherein the two alkyl groups in the 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester each have 8, 9, or 10 carbon atoms, preferably 8 or 9 carbon atoms. Preferred embodiments of the present invention are specified in the dependent claims. The R groups are therefore pentyl groups with a certain proportion of the n-pentyl isomer. The percentage mol% here refers to 100 mol% of all R groups of the compound according to formula (1).

[0020] Within the scope of the present invention, the terms "pentyl", "pentyl groups" or similar are used. This emphasizes that the esters according to the invention contain various pentyl isomers, in particular 2-methylbutyl and / or 3-methylbutyl and / or n-pentyl.

[0021] 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 pentyl groups are present. The most important representatives of the isomers of the pentyl group are the linear n-pentyl group and the simply branched 2-methylbutyl and 3-methylbutyl groups.

[0022] The composition according to the invention comprises mixed esters of the tripentyl esters of 1,2,4-cyclohexanetripropionic acid, wherein at least 45 mol%, preferably at least 55%, particularly preferably at least 75 mol%, and in each case a maximum of 97 mol% of the pentyl groups in the mixed ester are n-pentyl groups. The percentage mol% refers here as well to 100 mol%, i.e., to all pentyl groups in the mixed ester.

[0023] The sum of all pentyl groups present in the mixed ester naturally yields 100 mol%. The remaining pentyl groups are then necessarily distributed among 2-methylbutyl and / or 3-methylbutyl groups. It is preferred to keep the proportion of 3-methylbutyl groups low. Preferably, in the tripentyyl esters of 1,2,4-cyclohexanetripropionic acid, less than 10 mol%, preferably less than 5 mol% of the 202500055 foreign

[0024] 3

[0025] Pentyl groups and 3-methylbutyl groups. In a particularly preferred embodiment, the 1,4-dipentylcyclohexanedicarboxylic acid ester contains less than 0.1 mol% or no 3-methylbutyl groups. The percentage (mol%) refers to 100 mol%, i.e., all pentyl groups in the mixed ester.

[0026] In contrast, it has proven advantageous if the tripentyl ester of 1,2,4-cyclohexanetripropionic acid contains 2-methylbutyl groups. Preferably, up to 55 mol% of the pentyl groups in the tripentyl esters of 1,2,4-cyclohexanetripropionic acid are 2-methylbutyl groups, more preferably up to 45 mol% of the pentyl groups are 2-methylbutyl groups, and particularly preferably 3 to 25 mol% of the pentyl groups are 2-methylbutyl groups. The percentage (mol%) refers to 100 mol%, i.e., all pentyl groups in the mixed ester. These mixtures are also preferred because industrially available pentanoias are usually mixtures of pentanol and 2-methylbutanol, containing > 90 mol% n-pentanol and < 10 mol% 2-methylbutanol.

[0027] In addition to the tripentyle esters of 1,2,4-cyclohexanetripropionic acid, the plasticizer composition according to the invention contains 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid esters, wherein the two alkyl groups each independently have 8, 9 or 10 carbon atoms, preferably 8 or 9 carbon atoms.

[0028] The corresponding 1,4-dialkylcyclohexanedicarboxylic acid esters can be described by the following Markush formula:

[0029]

[0030] wherein the two residues T are each independently alkyl groups with 8, 9 or 10 carbon atoms, preferably 8 or 9 carbon atoms.

[0031] The two alkyl groups can each be selected independently of one another from the group consisting of a normal octyl group, an isooctyl group, a 2-ethylhexyl group, a normal nonyl group, an isononyl group, an n-decyl group, an isodecyl group, or a 2-propylheptyl group, preferably from the group consisting of a normal octyl group, an isooctyl group, a 2-ethylhexyl group, a normal nonyl group, and an isononyl group. For the purposes of the present invention, an isooctyl group is understood to be a mixture of linear and branched primary C8 alkyl groups. Similarly, an isononyl group and an isodecyl group are each understood to be a mixture of linear and branched primary C9 alkyl groups and C10 alkyl groups, respectively.

[0032] 4

[0033] In a preferred embodiment of the present invention, the two alkyl groups of the 1,4-dialkylcyclohexanedicarboxylic acid ester each have the same number of carbon atoms. This means that both alkyl groups have 8, 9, or 10 carbon atoms, but not that both alkyl groups must always be identical with respect to the respective isomers.

[0034] However, it is particularly preferred that the 1,4-dialkylcyclohexanedicarboxylic acid ester in the composition according to the invention is 1,4-di-isononyl-cyclohexanedicarboxylic acid ester (1,4-DINCH or DINCD) or 1,4-di-2-ethylhexyl-cyclohexanedicarboxylic acid ester (1,4-DEHCH).

[0035] The preparation of the 1,4-dialkylcyclohexanedicarboxylic acid esters according to the invention can be carried out by direct esterification of the 1,4-cyclohexanedicarboxylic acid with an alcohol having 8, 9, or 10 carbon atoms, preferably 8 or 9 carbon atoms. The alcohol is preferably used in excess, i.e., in an amount of more than 2 moles per mole of acid component. The direct esterification is further preferably carried out over an acidic catalyst, for example, inorganic, organic, or Lewis acids. Corresponding processes are known to those skilled in the art.

[0036] The 1,4-dialkylcyclohexanedicarboxylic acid esters according to the invention can also be produced by transesterification, wherein a 1,4-dialkylcyclohexanedicarboxylic acid ester with alkyl groups having fewer than 8 carbon atoms is used and transesterified with an alcohol having 8, 9, or 10 carbon atoms, preferably with 8 or 9 carbon atoms. Here too, the alcohol with 8, 9, or 10 carbon atoms, preferably with 8 or 9 carbon atoms, can be used in excess. Transesterification is also a process known to those skilled in the art.

[0037] Preferably, the preparation is carried out by the esterification of terephthalic acid with an alcohol having 8, 9, or 10 carbon atoms, preferably with 8 or 9 carbon atoms, or by transesterification of a terephthalic acid ester whose alkyl group has fewer than 8 carbon atoms, preferably dimethyl terephthalate. This yields dialkyl terephthalic acid esters whose alkyl groups have 8, 9, or 10 carbon atoms, preferably 8 or 9 carbon atoms. The dialkyl terephthalic acid esters thus prepared are then undergoed nuclear hydrogenation to obtain the desired 1,4-dialkylcyclohexanedicarboxylic acid esters. Processes for nuclear hydrogenation are described in the literature and are known to those skilled in the art.

[0038] The corresponding 1,2-dialkylcyclohexanedicarboxylic acid esters can be described by the following Markush formula: 202500055 Abroad

[0039] 5

[0040]

[0041] wherein the two residues T are each independently alkyl groups with 8, 9 or 10 carbon atoms, preferably with 8 or 9 carbon atoms.

[0042] The two alkyl groups can each be selected independently from the group consisting of a normal octyl group, an isooctyl group, a 2-ethylhexyl group, a normal nonyl group, an isononyl group, an n-decyl group, an isodecyl group, or a 2-propylheptyl group, preferably from the group consisting of a normal octyl group, an isooctyl group, a 2-ethylhexyl group, a normal nonyl group, and an isononyl group. For the purposes of the present invention, an isooctyl group is understood to be a mixture of linear and branched primary C8 alkyl groups. Similarly, an isononyl group and an isodecyl group are understood to be mixtures of linear and branched primary C9 alkyl groups and C10 alkyl groups, respectively.

[0043] In a preferred embodiment of the present invention, the two alkyl groups of the 1,2-dialkylcyclohexanedicarboxylic acid ester each have the same number of carbon atoms. This means that both alkyl groups have 8, both alkyl groups have 9, or both alkyl groups have 10 carbon atoms, but not that both alkyl groups must always be identical with respect to the respective isomers.

[0044] However, it is particularly preferred that the 1,2-dialkylcyclohexanedicarboxylic acid ester in the composition according to the invention is 1,2-di-isononyl-cyclohexanedicarboxylic acid ester (DINCH) or 1,2-di-2-ethylhexyl-cyclohexanedicarboxylic acid ester (DEHCH).

[0045] The 1,2-dialkylcyclohexanedicarboxylic acid esters according to the invention can be prepared by direct esterification of the 1,2-cyclohexanedicarboxylic acid or the corresponding anhydride with an alcohol having 8, 9, or 10 carbon atoms, preferably with 8 or 9 carbon atoms. The alcohol is preferably used in excess, i.e., in an amount of more than 2 moles per mole of acid component. The direct esterification is further preferably carried out over an acidic catalyst, for example, inorganic, organic, or Lewis acids. Alternatively, the 1,2-dialkylcyclohexanedicarboxylic acid esters according to the invention can also be prepared via a reaction sequence that includes a Diels-Alder reaction of butadiene and maleic anhydride. The resulting tetrahydrophthalic anhydride is then esterified with alcohols, and the double bond is hydrogenated. Corresponding processes are known to those skilled in the art.

[0046] 6

[0047] The 1,2-dialkylcyclohexanedicarboxylic acid esters according to the invention can also be produced by transesterification, wherein a 1,2-dialkylcyclohexanedicarboxylic acid ester with alkyl groups having fewer than 8 carbon atoms is used and transesterified with an alcohol having 8, 9, or 10 carbon atoms, preferably with 8 or 9 carbon atoms. Here too, the alcohol with 8, 9, or 10 carbon atoms, preferably with 8 or 9 carbon atoms, can be used in excess. Corresponding processes are also known to those skilled in the art.

[0048] Preferably, the preparation is carried out by the esterification of phthalic acid, particularly preferably with phthalic anhydride, with an alcohol having 8, 9, or 10 carbon atoms, preferably with 8 or 9 carbon atoms, or by transesterification of a phthalic acid ester whose alkyl group has fewer than 8 carbon atoms. This yields dialkylphthalic acid esters whose alkyl groups have 8, 9, or 10 carbon atoms, preferably 8 or 9 carbon atoms. The dialkylphthalic acid esters thus prepared are then undergoed nuclear hydrogenation to obtain the desired 1,2-dialkylcyclohexanedicarboxylic acid esters. Processes for nuclear hydrogenation are described in the literature and are known to those skilled in the art.

[0049] 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 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester are present in the plasticizer composition in a weight ratio (compound according to formula (1) : 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester) of 1 : 99 to 99 : 1, preferably 10 : 90 to 90 : 10, and particularly preferably 20 : 80 to 80 : 20.In a particularly preferred embodiment of the present invention, the compound according to formula (1) and the 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid esters are present in the plasticizer composition in a weight ratio (compound according to formula (1) : 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester) of 40 : 60 to 10 : 90. By selectively adjusting the mixing ratios, specific application-related properties can be improved without having to make significant compromises in the other properties.

[0050] 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 thermal stability and mechanical properties and, depending on their proportion, also exhibit plasticizing properties.

[0051] 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 preferred for export.

[0052] 7

[0053] The plasticizer composition according to the invention is used. Epoxidized soybean oil, also known by the acronym ESBO, is particularly preferred.

[0054] The epoxidized fatty acid esters can be produced by transesterification of the above epoxidized oils with alcohols in the range of 1 to 10 carbon atoms, preferably 4 to 9 carbon atoms.

[0055] Alternatively, the natural oil can first be transesterified and the double bonds of the fatty acid subsequently epoxidized.

[0056] 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 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester. 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 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester.

[0057] 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, isosorbide esters, furane dicarboxylates, phosphates, succinates, sulfonamides, alkyl sulfonic acid esters of phenol, phthalates, terephthalates, isophthalates, cyclohexanedicarboxylates, with the exception of the already existing esters, trimellites, as well as polyol esters and oligomeric or polymeric esters based on adipic, succinic or sebacic acid.

[0058] 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 the dialkyl esters of 1,2- or 1,4-cyclohexanedicarboxylic acid, with the exception of the already present esters with 8 or 9 carbon atoms and dialkyl esters of 1 ,3-Cyclohexanedicarboxylic acid, is selected.

[0059] In a further preferred embodiment, the at least one additional plasticizer that may be contained 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 C4 to C9 alkyl groups, C4 to C10 trialkyl trimellites, C4 to C9 dialkyl terephthalates, C4 to C13 dialkyl phthalates, in particular C9-202500055 Abroad

[0060] 8

[0061] selected up to C13 dialkyl phthalates and C4 to C10 dialkyl esters of 1,3-cyclohexanedicarboxylic acid, as well as the C4-C7 dialkyl esters of 1,2- or 1,4-cyclohexanedicarboxylic acid.

[0062] 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. This group also includes acetylated or non-acetylated esters of citric acid, in which the alkyl chains may have different chain lengths, such as C4 / C8 or C5 / C9. 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), triisononyl trimellite (TINTM) and the trimellitic acid ester with linear C8 and C10 alcohols (T810TM) are preferred.

[0063] A further object of the present invention is a plastic composition comprising a plastic and the plasticizer composition comprising the compound of formula (1) and at least one 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester, wherein the two alkyl groups each have 8, 9 or 10 carbon atoms, preferably each 8 or 9 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.

[0064] 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), 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. 202500055 Foreign,

[0065] 9

[0066] In a preferred embodiment, the plastic is a polymer 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] In addition, fillers, pigments, blowing agents, UV stabilizers and lubricants may also be included in the plastic composition as additives.

[0071] 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.

[0072] 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, 202500055 Abroad

[0073] 10

[0074] 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, especially in hoses or blood bags.

[0075] 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.

[0076] Example 1 - Preparation of the various pentyl esters of 1,2,4-cyclohexanetripropionic acid

[0077] Trimethylcyclohexane-1,2,4-tripropionate (Me-Tc) was prepared according to Example 0 of EP 3 838 888 A1 and transesterified with 2-methylbutanol (Mb) and n-pentanol (Pe) (molar ratio see Table 1) to give the product MbPe-Tc in a transesterification apparatus. The transesterification apparatus consisted of a glass flask equipped with a stirrer, temperature sensor, distillation column, vacuum divider, and distillation setup.

[0078] First, the mixtures of n-pentanol and 2-methylbutanol listed in Table 1, along with the amount of Me-Tc specified 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 Me-Tc). The reaction was then initiated by heating. The reaction temperature ranged from 130 to 240°C, increasing 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. Once no further distillate was observed, the reaction progress was monitored by GC analysis.The reaction was terminated when the tripentyl ester accounted for >98.8% of the GC surface area, based on the sum of the surface areas of the reactant, mono-, di- and triesters.

[0079] 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.

[0080] 11

[0081] Table 1: Pentanol mixtures for the preparation of the cyclohexane-1,2,4-tripropionic acid tripentyl ester mixture (molar amount Me- amount n- amount 2- ratio of an Tc / g (mol) pentanol / g methylbutanol /

[0082] Pentanol (Pe) and 2- (mol) g (mol)

[0083] Methylbutanol (Mb)

[0084] A) (Pe / Mb = 50 / 50) 1543 (4.5) 743 (8.4) 743 (8.4)

[0085] B) (Pe / Mb = 65 / 35) 1710 (5.0) 1071 (12.2) 577 (6.6)

[0086] C) (Pe / Mb = 93 / 7) 1883 (5.5) 1690 (19.2) 127 (1.4)

[0087]

[0088] Example 2 - Production of plastisols

[0089] 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 2-4.

[0090] Table 2: Overview of the plastisols produced with DINCH or DINCD and MbPe-Tc (50:50). Plastisol 1 2 3* 4* 5* 6 7* 8* 9* 10*

[0091] phr phr phr phr phr phr phr phr phr phr

[0092] PVC (Vestolit® P

[0093] 1430 K 70 Ultra; Fa. 100 100 100 100 100 100 100 100 100 100 Vestolit)

[0094] ELATUR® CH, (Di- isononyl-1 ,2- cyclohexanoat, Fa. 50 37,5 33,33 25 16,67

[0095] Evonik Oxeno & Co.

[0096] KG)

[0097] ELATUR® DINCD,

[0098] (Di-isononyl-1 ,4- cyclohexanoat, Fa. 50 37,5 33,33 25 16,67 Evonik Oxeno & Co.

[0099] KG)

[0100] A) MbPe-Tc (50:50)

[0101] (2-Methylbutyl-n- pentyl-3,3',3"- 12,5 16,67 25 33,33 12,5 16,67 25 33,33 (cyclohexan-1 ,2,4- triyl)proprionat)

[0102] epoxidiertes

[0103] Sojabohnenöl als 3 3 3 3 3 3 3 3 3 3

[0104] Co-Stabilisator

[0105]

[0106] 202500055 Ausland

[0107] 12

[0108] (Edenol® D81 , Fa.

[0109] Emery)

[0110] Thermostabilisator

[0111] based on Ca / Zn

[0112] 2 2 2 2 2 2 2 2 2 2 (Reagent MBL

[0113] 197 / 9 PF)

[0114]

[0115] * = composition according to the invention

[0116] phr = parts per hundred parts resin

[0117] Table 3: Overview of the plastisols produced with DINCH or DINCD and MbPe-Tc (35:65). Plastisol 11* 12* 13* 14* 15* 16* 17* 18*

[0118] phr phr phr phr phr phr phr phr PVC (Vestolit® P 1430 K 70

[0119] 100 100 100 100 100 100 100 100 Ultra; Vestolit)

[0120] ELATUR® CH, (di-isononyl-1,2-cyclohexanoate, Evonik 37.5 33.33 25 16.67

[0121] Oxeno & Co. KG)

[0122] ELATUR® DINCD, (di-isononyl-1,4-cyclohexanoate, 37.5 33.33 25 16.67 from Evonik Oxeno & Co. KG)

[0123] B) MbPe-Tc (35:65) (2-methylbutyl-n-pentyl-3,3',3"- 12.5 16.67 25 33.33 12.5 16.67 25 33.33 (cyclohexane-1,2,4-triyl)propionate)

[0124] epoxidized soybean oil as

[0125] Co-stabilizer 3 3 3 3 3 3 3 3 (Edenol® D81, Emery)

[0126] Ca / Zn-based thermostabilizer 2 2 2 2 2 2 2 2 (Reagent MBL 197 / 9 PF)

[0127]

[0128] * = composition according to the invention

[0129] phr = parts per hundred parts resin202500055 abroad

[0130] 13

[0131] Table 4: Overview of the plastisols produced with DINCH or DINCD and MbPe-Tc (7:93). Plastisol 19* 20* 21* 22* 23* 24* 25* 26*

[0132] phr phr phr phr phr phr phr phr

[0133] PVC (Vestolit® P 1430 K 70

[0134] 100 100 100 100 100 100 100

[0135] Ultra; Vestolit company)

[0136] ELATUR® CH, (di-isononyl-1,2-cyclohexanoate, Evonik 37.5 33.33 25 16.67

[0137] Oxeno & Co. KG)

[0138] ELATUR® DINCD, (di-isononyl-1,4-cyclohexanoate, 37.5 33.33 25 16.67

[0139] (Evonik Oxeno & Co. KG)

[0140] C) MbPe-Tc (7:93) (2-methylbutyl-n-pentyl-3,3',3"- 12.5 16.67 25 33.33 12.5 16.67 25 33.33 (cyclohexane-1,2,4-triyl)propionate)

[0141] epoxidized soybean oil as

[0142] Co-stabilizer 3 3 3 3 3 3 3 3

[0143] (Edenol® D81, Emery)

[0144] Ca / Zn-based thermostabilizer 2 2 2 2 2 2 2 2

[0145] (Reagent MBL 197 / 9 PF)

[0146]

[0147] * = composition according to the invention

[0148] phr = parts per hundred parts resin

[0149] Example 3 - Gelation of plastisols

[0150] 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.

[0151] The following parameters were set:

[0152] Mode: Temperature gradient

[0153] Starting temperature: 25 °C

[0154] Final temperature: 180 °C

[0155] Heating / cooling rate: 5 °C / min

[0156] Oscillation frequency: 4 to 0.1 Hz, logarithmic ramp

[0157] Omega angular frequency: 10 s- 1

[0158] Number of measuring points: 63

[0159] Measurement point duration: 0.5 min 202500055 Abroad

[0160] 14

[0161] Automatic gap tracking F: 0 N

[0162] Constant measurement point duration

[0163] Gap width 0.5 mm

[0164] Performing the measurement

[0165] 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 Memmert temperature control chamber) as a function of temperature.

[0166] 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 5.

[0167] Table 5: Gelation of the plastisols after 24 hours, temperature in °C at reaching a paste viscosity of 1000 Pa*s.

[0168] Plasticizer composition Gelling temperature

[0169] Recipe

[0170] according to Tables 1-3 [°C]

[0171] 1 DINCH 88.7

[0172] 2* DINCH / MbPe-Tc (50:50) (3:1) 83.6

[0173] 3* DINCH / MbPe-Tc (50:50) (2:1) 82.7

[0174] 4* DINCH / MbPe-Tc (50:50) (1:1) 80.7

[0175] 5* DINCH / MbPe-Tc (50:50) (1:2) 79.9

[0176] 6 DINCD 85.2

[0177] 7* DINCD / MbPe-Tc (50:50) (3:1) 82.2

[0178] 8* DINCD / MbPe-Tc (50:50) (2:1) 81,2

[0179] 9* DINCD / MbPe-Tc (50:50) (1 :1) 80,2

[0180] 10* DINCD / MbPe-Tc (50:50) (1 :2) 79,0

[0181] 11* DINCH / MbPe-Tc (35:65) (3:1) 83,4

[0182] 12* DINCH / MbPe-Tc (35:65) (2:1) 82,5

[0183] 13* DINCH / MbPe-Tc (35:65) (1 :1) 80,5

[0184] 14* DINCH / MbPe-Tc (35:65) (1 :2) 79,3

[0185] 15* DINCD / MbPe-Tc (35:65) (3:1) 82,0

[0186] 16* DINCD / MbPe-Tc (35:65) (2:1) 80,9

[0187] 17* DINCD / MbPe-Tc (35:65) (1 :1) 79,9

[0188] 18* DINCD / MbPe-Tc (35:65) (1 :2) 78,4

[0189] 19* DINCH / MbPe-Tc (7:93) (3:1) 83,4

[0190]

[0191] 202500055 Ausland

[0192] 15

[0193] 20* DINCH / MbPe-Tc (7:93) (2:1) 82,5

[0194] 21* DINCH / MbPe-Tc (7:93) (1:1) 80,5

[0195] 22* DINCH / MbPe-Tc (7:93) (1:2) 79.3

[0196] 23* DINCD / MbPe-Tc (7:93) (3:1) 82.0

[0197] 24* DINCD / MbPe-Tc (7:93) (2:1) 81.2

[0198] 25* DINCD / MbPe-Tc (7:93) (1:1) 79.9

[0199] 26* DINCD / MbPe-Tc (7:93) (1:2) 78.4

[0200]

[0201] * Experiment with plasticizer composition according to the invention

[0202] Increasing the MbPe-Tc content, regardless of the MbPe composition, significantly reduces the gelling temperature compared to the primary plasticizers DINCH and DINCD. Furthermore, it becomes apparent that a higher n-pentyl content further improves the gelling temperature.

[0203] Example 4 - Production of films

[0204] 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 to the front of the doctor blade, and the doctor blade was spread across the clamped release paper by pulling the guide frame (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.

[0205] Example 5 - Determination of mass loss (activated carbon method)

[0206] 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.

[0207] The filled tin cans were placed in the pre-heated heating cabinet (120 °C) in such a way that the fan in the cabinet was not obstructed and the cans did not touch each other. Air exchange and 202500055 abroad

[0208] 16

[0209] The exhaust dampers were set to 10% each. After 72 hours, the cans were removed from the cabinet, cooled, and then the individual samples were taken from the baskets, conditioned for another 16 hours in the desiccator, and then weighed again on the 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 6 shows the results of the volatility tests.

[0210] Table 6: Mass loss of the test specimens after three days at 120 °C.

[0211] Film no. Plasticizer composition after mass loss after 3 days in

[0212] Tables 1-3 Mass%

[0213] 1 DINCH -5.01

[0214] 2* DINCH / MbPe-Tc (50:50) (3:1) -4.28

[0215] 3* DINCH / MbPe-Tc (50:50) (2:1) -3.64

[0216] 4* DINCH / MbPe-Tc (50:50) (1:1) -3.57

[0217] 5* DINCH / MbPe-Tc (50:50) (1 :2) -2,70

[0218] 6 DINCD -3,10

[0219] 7* DINCD / MbPe-Tc (50:50) (3:1) -2,84

[0220] 8* DINCD / MbPe-Tc (50:50) (2:1) -2,56

[0221] 9* DINCD / MbPe-Tc (50:50) (1 :1) -2,40

[0222] 10* DINCD / MbPe-Tc (50:50) (1 :2) -2,10

[0223] 11* DINCH / MbPe-Tc (35:65) (3:1) -4,62

[0224] 12* DINCH / MbPe-Tc (35:65) (2:1) -3,96

[0225] 13* DINCH / MbPe-Tc (35:65) (1 :1) -3,71

[0226] 14* DINCH / MbPe-Tc (35:65) (1 :2) -3,05

[0227] 15* DINCD / MbPe-Tc (35:65) (3:1) -2,94

[0228] 16* DINCD / MbPe-Tc (35:65) (2:1) -2,76

[0229] 17* DINCD / MbPe-Tc (35:65) (1 :1) -2,43

[0230] 18* DINCD / MbPe-Tc (35:65) (1 :2) -2,14

[0231] 19* DINCH / MbPe-Tc (7:93) (3:1) -4,73

[0232] 20* DINCH / MbPe-Tc (7:93) (2:1) -4.00

[0233] 21* DINCH / MbPe-Tc (7:93) (1:1) -3.79

[0234] 22* DINCH / MbPe-Tc (7:93) (1:2) -3.08

[0235] 23* DINCD / MbPe-Tc (7:93) (3:1) -2.78

[0236] 24* DINCD / MbPe-Tc (7:93) (2:1) -2.66

[0237] 25* DINCD / MbPe-Tc (7:93) (1:1) -2.42

[0238] 26* DINCD / MbPe-Tc (7:93) (1:2) -1.92

[0239]

[0240] * = composition according to the invention 202500055 Abroad

[0241] 17

[0242] Increasing the MbPe-Tc content reduces the volatility of the plastisols. For the compounds according to formula (1) with a high n-pentanol content, the volatility can be reduced even further.

[0243] Example 6 - Determination of Shore A hardness

[0244] The sheets produced according to Example 4 yielded 4.8 x 4.8 cm pieces. 2Large pieces were cut. These were stacked in a press frame in 6-8 layers, depending on the film thickness, and pressed at 170 °C and 200 bar. The test specimens were then conditioned for at least 16 hours in a climate chamber under standard conditions (25 °C, 50% relative humidity) and subsequently measured using a Shore A measuring device from Zwick-Roell, in accordance with DIN 48-4. The readings were taken after 3 seconds. Measurements were taken at three different points on each test specimen, and the average was calculated. The results are listed in Table 7.

[0245] Table 7: Shore A hardness of the pressed test specimens.

[0246] Plasticizer composition according to Table 1-3 Shore A

[0247] 1 DINCH 86.0

[0248] 2* DINCH / MbPe-Tc (50:50) (3:1) 83.7

[0249] 3* DINCH / MbPe-Tc (50:50) (2:1) 82.8

[0250] 4* DINCH / MbPe-Tc (50:50) (1:1) 81.7

[0251] 5* DINCH / MbPe-Tc (50:50) (1 :2) 81.0

[0252] 6 DINCD 83.6

[0253] 7* DINCD / MbPe-Tc (50:50) (3:1) 82.2

[0254] 8* DINCD / MbPe-Tc (50:50) (2:1) 81.6

[0255] 9* DINCD / MbPe-Tc (50:50) (1 :1) 81.0

[0256] 10* DINCD / MbPe-Tc (50:50) (1 :2) 80.2

[0257] 11* DINCH / MbPe-Tc (35:65) (3:1) 83.8

[0258] 12* DINCH / MbPe-Tc (35:65) (2:1) 83.3

[0259] 13* DINCH / MbPe-Tc (35:65) (1 :1) 81.9

[0260] 14* DINCH / MbPe-Tc (35:65) (1 :2) 81.2

[0261] 15* DINCD / MbPe-Tc (35:65) (3:1) 82.7

[0262] 16* DINCD / MbPe-Tc (35:65) (2:1) 82.0

[0263] 17* DINCD / MbPe-Tc (35:65) (1 :1) 81.5

[0264] 18* DINCD / MbPe-Tc (35:65) (1 :2) 80.6

[0265] 19* DINCH / MbPe-Tc (7:93) (3:1) 83.1

[0266] 20* DINCH / MbPe-Tc (7:93) (2:1) 82.3

[0267] 21* DINCH / MbPe-Tc (7:93) (1:1) 80.8

[0268] 22* DINCH / MbPe-Tc (7:93) (1:2) 80.3

[0269] 23* DINCD / MbPe-Tc (7:93) (3:1) 82.0

[0270] 24* DINCD / MbPe-Tc (7:93) (2:1) 81.4

[0271]

[0272] 202500055 Abroad

[0273] 18

[0274] 25* DINCD / MbPe-Tc (7:93) (1:1) 80.5

[0275] 26* DINCD / MbPe-Tc (7:93) (1:2) 79.5

[0276]

[0277] * = composition according to the invention

[0278] The efficiency, measured by a decreasing Shore A hardness, is improved by the addition of the MbPe-Tc esters.

Claims

202500055 Abroad 19 Patent claims 1. Plasticizer composition containing a compound of formula (1) in which the alkyl groups R each have 5 carbon atoms, of which 45 to 97 mol% are n-pentyl groups, preferably 55 to 97 mol% are n-pentyl groups, and at least one 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester, wherein the two alkyl groups of the 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester each have 8, 9 or 10 carbon atoms.

2. Plasticizer composition according to claim 1, wherein the two alkyl groups of the 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester are each selected independently of one another from the group consisting of a normal octyl group, an isooctyl group, a 2-ethylhexyl group, a normal nonyl group, an isononyl group, an n-decyl group, an isodecyl group and a 2-propylheptyl group.

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

4. Plasticizer composition according to any of the preceding claims, wherein the 1,4-dialkylcyclohexanedicarboxylic acid ester is the 1,4-di-isononyl-cyclohexanedicarboxylic acid ester (1,4-DINCH or DINCD) or the 1,4-di-2-ethylhexylcyclohexanedicarboxylic acid ester (1,4-DEHCH) and / or the 1,2-dialkylcyclohexanedicarboxylic acid ester of the 1,2-di-isononyl-cyclohexanedicarboxylic acid ester (DINCH) or the 1,2-di-2-ethylhexylcyclohexanedicarboxylic acid ester (DEHCH).

5. Plasticizer composition according to one of the preceding claims, wherein the compound according to formula (1) and the 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester are present in the plasticizer composition in a weight ratio (compound according to formula (1) : 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester) of 1 : 99 to 99 : 1, preferably 10 : 90 to 90 : 10, particularly preferably 20 : 80 to 80 :

20. 20 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.

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 1,2- or 1,4-dialkylcyclohexanedicarboxylic acid ester in the plasticizer composition.

10. Plasticizer composition according to any of the preceding claims, wherein the plasticizer composition is a mixture of esters of the compound of formula (1) comprising, wherein at least 75 mol% and at most 97 mol% of the pentyl groups in the mixed ester are n-pentyl groups.

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 as a polymer 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 13 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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