Cyclohexanetripropropionic acid triester

Abstract

The present invention relates to triesters of cyclohexanetripropionic acid. In particular, the present invention relates to triesters of cyclohexanetripropionic acid and their preparation and use as plasticizers for polymers. The object of the present invention is to provide new plasticizers covering a wide range of properties. In high temperature applications such as cables, the new plasticizers are superior to trimellitic acid esters. This object is achieved by the triesters of cyclohexanetripropionic acid of the present invention, in which the three alcohol parts of the three ester groups each contain 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.

Description

Technical Field

[0001] The present invention relates to triesters of cyclohexanetripropionic acid and their preparation and use as plasticizers for polymers. Background Art

[0002] In order to improve the processability and also to adjust the application-related properties to the respective requirements, polymer plasticizers are added. In order to obtain the particularly desired properties, plasticizers with various effects can be used. Phthalate compounds are among the most important plasticizers for PVC and vinyl chloride-containing copolymers.

[0003] Phthalate esters have different properties and are therefore more or less suitable for different plasticizer applications, depending on factors including the number of carbons in the alcohol portion of the ester functionality. Phthalate esters with short-chain alcohol portions (e.g., dibutyl phthalate and diamyl phthalate) have lower and therefore favorable gelling temperatures, and are therefore used as fast gelling agents, whereas these phthalates are not suitable for other uses due to their high volatility. Phthalate esters with longer-chain alcohol portions (e.g., diisononyl phthalate (DINP)) do have poorer gelling properties than lighter homologues, but at the same time benefit from lower volatility, but are still too high for certain applications that must withstand high temperatures. Even the relatively low volatility of ditridecyl phthalate is not sufficient to allow the use of this phthalate in many high temperature applications. Since phthalates having more than 13 carbon atoms in the alcohol moiety have low polymer compatibility and corresponding polymer phthalate mixtures tend to separate, no representatives of the class of phthalate plasticizers having more than 13 carbon atoms in the alcohol moiety can be used as plasticizers, for example in high-temperature cables.

[0004] Because of its lower volatility compared to phthalates, trimellitate plasticizers are used for high temperature applications. The textbook "Plasticizers-Principles and Practice" by AS Wilson (The Institute of Materials, 1995, pp. 166-170) describes trimellitate esters with an alcohol moiety containing 7 to 9 carbon atoms or a mixture of C6- and C8-esters or C7-, C8- and C9-esters of commercially interesting trimellitic acid, wherein tri(2-ethylhexyl) trimellitate is emphasized as the most important trimellitate ester. Even these trimellitates are still generally too volatile for use in high temperature cables.

[0005] The published specification US 2018 / 0319954 A1 discloses trimellitic esters and at the same time also cyclohexane-1,2,4-tricarboxylic esters and their suitability as plasticizers. Summary of the invention

[0006] Now, the object of the present invention is to provide representatives of a new class of plasticizers covering a wide range of properties, that is, they can be used in many different applications. The new class of plasticizers should preferably contain agents with very good gelling power and agents with excellent high temperature properties. In high temperature applications such as cables, representatives of the new class of plasticizers should preferably be superior to trimellitates.

[0007] This object is achieved by the triesters of cyclohexanetripropionic acid according to the invention.The invention relates to triesters of cyclohexanetripropionic acid, wherein the three alcohol moieties of the three ester groups each contain 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.

[0008] Like all carboxylic acid esters, the triester of cyclohexanetripropionic acid is formed by carboxylic acid and alcohol formally, so this ester comprises acid part and alcohol part.The triester of cyclohexanetripropionic acid according to the present invention is composed of cyclohexanetripropionic acid part and three alcohol parts.These alcohol parts each comprise 2,3,4,5,6,7,8,9,10,11 or 12 carbon atoms.

[0009] The triester of cyclohexanetripropionic acid according to the invention is also referred to hereinafter as triester according to the invention for short.

[0010] Surprisingly, it has been found that representatives of this novel class of plasticizers are suitable for plastisol applications, have a lower gelling temperature and can be advantageously used as fast gelling agents, while other representatives of this class can be advantageously used in thermoplastic applications. In plastisol applications and thermoplastic applications, representatives of this class of plasticizers have low mass losses. Good low-temperature flexibility (low glass transition temperature) can also be achieved with representatives of this class.

[0011] Besides the desired suitability of the representatives of the novel plasticizer class for high-temperature applications, the representatives of this class also enable the low viscosity of the plastisols in question and also the advantageous thickening properties in plastisol applications.

[0012] The three propionate groups of the ester according to the invention can be bonded to various positions of the cyclohexane ring. However, the triester according to the invention is preferably a triester of cyclohexane-1,2,4-tripropropionic acid or a triester of cyclohexane-1,3,5-tripropropionic acid, in particular a triester of cyclohexane-1,2,4-tripropropionic acid.

[0013] The alcohol moiety of the triester of cyclohexanetripropionic acid can be a cyclic or acyclic alkyl group with or without a functional group comprising a multiple bond. It is insignificant here whether the functional group is derived from the alcohol used to prepare the triester according to the invention or is subsequently inserted into the triester molecule. It is also possible to have an alcohol moiety comprising an aromatic ring which rotates without a functional group or with one or more functional groups. In addition to the oxygen of the ester function, the alcohol moiety of the triester according to the invention preferably does not contain any other heteroatoms and does not contain multiple bonds. The advantage of these alcohol moieties (formally based on alkanols, preferably based on acyclic alkanols) is that, due to the availability of alkanols, the obtained triesters can be prepared at particularly low costs.

[0014] The present invention preferably relates to triesters of cyclohexanetripropionic acid, wherein the three alcohol moieties of the three ester groups each contain 2 to 9 (preferably 4 to 9 or 4, 5, 6, 7, 8 or 9) carbon atoms. These triesters have good gelling properties, and the plastisols prepared using them are characterized by low plastisol viscosities, which also increase only slightly over time. In plastisol applications, such as those consisting of thin films, only a small amount of mass loss occurs in air. It is obvious from the low glass transition temperature that the low-temperature flexibility of the test specimens containing these triesters is higher than in the case of the comparative compounds. However, the triesters according to the present invention are preferably triesters of cyclohexane-1,2,4-tripropionic acid or triesters of cyclohexane-1,3,5-tripropionic acid, in particular triesters of cyclohexane-1,2,4-tripropionic acid, the alcohol moieties of which are preferably formally derived from acyclic alkanols.

[0015] The present invention also preferably relates to triesters of cyclohexanetripropionic acid, wherein the three alcohol moieties of the three ester groups each contain 7 to 12 (preferably 8 to 10 and in particular 8 or 9) carbon atoms. These triesters are characterized by very low mass losses at high temperatures and are therefore very suitable for high temperature applications. In addition, the low-temperature flexibility of the test specimens containing these triesters is higher than in the case of the comparative compounds. However, the triesters according to the invention are preferably triesters of cyclohexane-1,2,4-tripropionic acid or triesters of cyclohexane-1,3,5-tripropionic acid, in particular triesters of cyclohexane-1,2,4-tripropionic acid, the alcohol moieties of which are preferably formally derived from acyclic alkanols.

[0016] Triesters according to the invention preferably contain two or three alcohol moieties with the same empirical formula in one molecule. In this case, the "same empirical formula" alcohol moieties in one triester have the same arrangement of atoms present or different structures, i.e., isomeric alcohol moieties. Preferably, all alcohol moieties present in one molecule of triester according to the invention have the same empirical formula and at the same time have the same or different structural formulas. Triesters according to the invention, in which the alcohol moieties have the same empirical formula and different structural formulas, contain isomeric alcohol groups. Such triesters are also advantageously liquid at low temperatures.

[0017] Preferred cyclohexanetripropionate triesters (ie triesters of cyclohexane-1,2,4-tripropionic acid) have the structure reproduced in formula I, wherein the radicals R have the same empirical formula and at the same time the same or different structural formulas.

[0018]

[0019] In one embodiment, the radical R of formula I is an acyclic alkyl radical having 2 to 8 or 9, in particular having 4, 5, 6 or 7, carbon atoms. In another embodiment, the radical R of formula I is an acyclic alkyl radical having 7 to 10, in particular having 8 or 9, carbon atoms.

[0020] The present invention further relates to a mixture of at least two cyclohexane tripropionate triesters according to the present invention. In this case, at least two triesters according to the present invention may differ in their empirical formula, their structural formula or both. An example of a mixture in which there is a difference in the empirical formula and the mixture contains at least two triesters according to the present invention is a mixture containing tri(n-pentyl)cyclohexane-1,2,4-tripropionate and tri(2-ethylhexyl)cyclohexane-1,2,4-tripropionate. If at least 2 esters according to the present invention are different in their structural formula, there may be, for example, at least one cyclohexane-1,2,4-tripropionate triester and at least one cyclohexane-1,3,5-tripropionate triester in the mixture. Alternatively or in addition to the possible difference in the position of the propionate group on the cyclohexane ring, the mixture may contain at least two triesters according to the present invention, which contain "empirical formulas are the same" alcohol parts with different structures, that is, isomeric alcohol parts. For example, the mixture may contain a triester according to the present invention, the alcohol part of which is always linear, and a triester according to the present invention, the alcohol part of which is uniformly branched. An example of such a mixture is a combination of tri(n-pentyl)cyclohexane-1,2,4-tripro[iota]nate and tri(2-methylbutyl)cyclohexane-1,2,4-tripro[iota]nate. Also possible are more complex mixtures comprising tri(n-butyl)cyclohexane-1,2,4-tripro[iota]nate, tri(isopentyl)cyclohexane-1,2,4-tripro[iota]nate, tri(n-butyl)cyclohexane-1,3,5-tripro[iota]nate and tri(isopentyl)cyclohexane-1,3,5-tripro[iota]nate.

[0021] The prefix "iso" refers to the fact that this is a mixture of isomers with a common number of carbon atoms. Thus, isopentyl ( iso The pentyl) group contains at least two isomeric alkyl groups having 5 carbon atoms, wherein the name contains no information about how many and which isomeric groups are present in what ratio. If the isomeric mixture of tri(isoalkyl)cyclohexane tripropionate does not only contain the same triester according to the invention, it is correspondingly a mixture of at least two triesters according to the invention whose structural formulae differ.

[0022] Preferred triesters according to the invention or mixtures according to the invention are

[0023] Tri(n-butyl)cyclohexane-1,2,4-triproinate, tri(methylpropyl)cyclohexane-1,2,4-triproinate, tri(n-pentyl)cyclohexane-1,2,4-triproinate, tri(isopentyl)cyclohexane-1,2,4-triproinate, tri(2-methylbutyl)cyclohexane-1,2,4-triproinate, tri(3-methylbutyl)cyclohexane-1,2,4-triproinate, tri(n-hexyl)cyclohexane-1,2,4-triproinate, tri(isohexyl)cyclohexane-1,2,4-triproinate, Tri(n-heptyl)cyclohexane-1,2,4-triproinate, tri(isoheptyl)cyclohexane-1,2,4-triproinate, tri(n-octyl)cyclohexane-1,2,4-triproinate, tri(isooctyl)cyclohexane-1,2,4-triproinate, tri(2-ethylhexyl)cyclohexane-1,2,4-triproinate, tri(n-nonyl)cyclohexane-1,2,4-triproinate, tri(isononyl)cyclohexane-1,2,4-triproinate, tri(n-decyl)cyclohexane-1,2,4-triproinate, tri(isodecyl)cyclohexane-1,2,4-triproinate, tri(2-propylheptyl)cyclohexane-1,2,4-triproinate;

[0024] Tri(n-butyl)cyclohexane-1,3,5-triproinate, tri(methylpropyl)cyclohexane-1,3,5-triproinate, tri(n-pentyl)cyclohexane-1,3,5-triproinate, tri(isopentyl)cyclohexane-1,3,5-triproinate, tri(2-methylbutyl)cyclohexane-1,3,5-triproinate, tri(3-methylbutyl)cyclohexane-1,3,5-triproinate, tri(n-hexyl)cyclohexane-1,3,5-triproinate, tri(isohexyl)cyclohexane-1,3,5-triproinate, Tri(n-heptyl)cyclohexane-1,3,5-triproinate, tri(isoheptyl)cyclohexane-1,3,5-triproinate, tri(n-octyl)cyclohexane-1,3,5-triproinate, tri(isooctyl)cyclohexane-1,3,5-triproinate, tri(2-ethylhexyl)cyclohexane-1,3,5-triproinate, tri(n-nonyl)cyclohexane-1,3,5-triproinate, tri(isononyl)cyclohexane-1,3,5-triproinate, tri(n-decyl)cyclohexane-1,3,5-triproinate, tri(isodecyl)cyclohexane-1,3,5-triproinate and tri(2-propylheptyl)cyclohexane-1,3,5-triproinate.

[0025] As already described, the esters according to the invention have advantageous properties when used as plasticizers for polymers. Therefore, the present invention further relates to a plasticizer for polymers, which comprises a triester according to the invention or a mixture according to the invention (comprising at least two of these triesters) and optionally at least one other compound that plasticizes the polymer. The plasticizer is particularly suitable for PVC.

[0026] The invention also relates to a composition comprising a triester according to the invention or a mixture according to the invention comprising at least two of these triesters or a plasticizer according to the invention and one or more polymers.

[0027] Suitable polymers are preferably selected from the group consisting of polyvinyl chloride (PVC), homopolymers or copolymers based on ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, ethyl acrylate, butyl acrylate or butyl methacrylate with alkoxy groups of branched or unbranched alcohols with 1 to 10 carbon atoms, acrylonitrile or cycloolefins, polyvinylidene chloride (PVDC), polyacrylates, in particular polymethyl methacrylate (PMMA), polyalkyl methacrylates (PAMA), polyureas, silylated polymers, fluoropolymers, in particular polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetal, 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 copolymers (SMA), styrene-methacrylic acid copolymers, polyolefins, in particular polyethylene (PE) or polypropylene (PP), thermoplastic polyolefins (TPO), polyethylene vinyl acetate (EVA), polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPU), polysulfide (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 silicone.

[0028] In a preferred embodiment, at least one polymer or preferably at least 90% by weight of the polymers in the composition are selected from the group consisting of polyvinyl chloride (PVC), polyalkyl methacrylates (PAMA), polyvinyl butyral (PVB), polyurethanes, polysulfides, polylactic acid (PLA), polyhydroxybutyral (PHB), nitrocellulose and copolymers of vinyl chloride with vinyl acetate or with butyl acrylate.

[0029] In the composition according to the invention comprising one or more polymers, the amount of triesters according to the invention is preferably 5 to 150 parts by mass per 100 parts by mass of polymer, preferably 10 to 120 parts by mass per 100 parts by mass of polymer, particularly preferably 15 to 110 parts by mass per 100 parts by mass of polymer and especially preferably 20 to 100 parts by mass per 100 parts by mass of polymer. However, compositions comprising one or more polymers may also conceivably contain less than 20 parts by mass of triesters according to the invention per 100 parts by mass of polymer.

[0030] The composition according to the invention is preferably a component of adhesives, sealing compounds, coating compositions, varnishes, paints, plastisols, dry mixes, foams, synthetic leathers, floor coverings, in particular the top layer or foam layer thereof, roofing membranes, underbody protection, textile coatings, cables, wire insulation, hoses, extruded or injection-moulded articles, films, articles for automotive interiors, wallpapers, inks, toys, contact sheets, food packaging or medical articles, in particular tubes or blood bags.

[0031] The invention further relates to the use of the triesters according to the invention or the mixtures according to the invention (comprising at least two of these triesters) as plasticizers for polymers. The triesters according to the invention or the mixtures according to the invention (comprising at least two of these triesters) are preferably used as plasticizers for the polymers already mentioned above, in particular polyvinyl chloride (PVC), polyalkyl methacrylates (PAMA), polyvinyl butyral (PVB), polyurethanes, polysulfides, polylactic acid (PLA), polyhydroxybutyral (PHB), nitrocellulose and copolymers of vinyl chloride with vinyl acetate or with butyl acrylate. Particular preference is given to the use as a plasticizer for polyvinyl chloride (PVC).

[0032] This use preferably results in the use of the triesters according to the invention or of the mixtures according to the invention comprising at least two of these triesters in adhesives, sealing compounds, coating compositions, varnishes, paints, plastisols, foams, synthetic leathers, floor coverings, in particular top layers or foam layers, roofing membranes, underbody protection, textile coatings, cables, wire insulation, hoses, extruded articles, films, articles for automotive interiors, wallpapers, inks, toys, contact sheets, food packaging or medical articles, in particular tubes or blood bags.

[0033] In a preferred embodiment, triesters of cyclohexanetripropionic acid, in which the three alcohol moieties of the three ester groups contain 7 to 12, preferably 8 to 10 and especially 8 or 9 carbon atoms, are used as compounds for plasticizing polymers in high temperature applications, especially in high temperature cables or dashboard components.

[0034] In another preferred embodiment, triesters of cyclohexanetripropionic acid, wherein the three alcohol moieties of the three ester groups contain 2 to 9, preferably 4 to 9 or 4, 5, 6, 7, 8 or 9 carbon atoms, are used as compounds for plasticizing polymers in plastisol applications. Preference is given to using them in textile coatings, wallpapers, synthetic leathers as well as films, roof waterproofing membranes and floor coverings.

[0035] The triesters according to the present invention can be prepared by:

[0036] - Cyclohydrogenation of the corresponding benzene tripropionate triester,

[0037] - transesterification of a trialkyl ester of cyclohexanetripropionic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, wherein the alcohol of the alcohol part of the trialkyl ester to be introduced in the transesterification has a higher boiling point than the alcohol of the alcohol part to be replaced,

[0038] - esterification of cyclohexanetripropropionic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, or

[0039] - Alkoxycarbonylation of trivinylcyclohexane with at least one alcohol comprising 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.

[0040] In the transesterification reaction preferably trimethyl ester or triethyl ester is used.

[0041] The present application preferably relates to the preparation of cyclohexane tripropionate triester according to the present invention by the following method:

[0042] - by ring hydrogenation of benzene tripropionate triesters, wherein the alcohol moieties of the ester groups each contain 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms,

[0043] - transesterification of a trialkyl ester of cyclohexanetripropionic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, wherein the alcohol of the alcohol part of the trialkyl ester to be introduced in the transesterification has a higher boiling point than the alcohol of the alcohol part to be replaced,

[0044] - by esterification of cyclohexanetripropropionic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, or

[0045] - by alkoxycarbonylation of trivinylcyclohexane with at least one alcohol comprising 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.

[0046] Particular preference is given to using the corresponding cyclohexane-1,2,4 compounds to prepare triesters of cyclohexane-1,2,4-tripropropionic acid.

[0047] In the transesterification reaction preferably trimethyl ester or triethyl ester is used.

[0048] The present invention particularly preferably relates to the preparation of the cyclohexane-1,2,4-tripropionic acid triester according to the invention by the following process:

[0049] - by ring hydrogenation of benzene-1,2,4-tripropropionic acid triesters, wherein the alcohol moieties of the ester groups each contain 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms,

[0050] - by transesterification of trimethyl or triethyl ester of cyclohexane-1,2,4-tripropropionic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms,

[0051] - by esterification of cyclohexane-1,2,4-triproic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, or

[0052] - by alkoxycarbonylation of 1,2,4-trivinylcyclohexane with at least one alcohol comprising 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.

[0053] The ring hydrogenation of benzene-1,2,4-tripropionic acid triester carried out to obtain the triester according to the invention can be carried out in one or more hydrogenation units connected in series. The hydrogenation units are preferably each composed of at least one, preferably two or more hydrogenation reactors. The at least one hydrogenation reactor can be a tubular reactor, a tube bundle reactor or preferably a shaft oven. The individual reactors can be operated adiabatically, polytropically or almost isothermally (i.e., the temperature increase is generally less than 10° C.). In particular in this case, the reactor operated in loop mode is quasi-isothermally driven, preferably operated at a temperature increase of less than 10° C., particularly preferably less than 5° C. One or more hydrogenation units can be operated in loop mode.

[0054] The hydrogenation of benzene trimesopropionate triester is preferably carried out continuously with a hydrogen-containing gas over a solid catalyst arranged in a fixed bed.

[0055] The hydrogenation gas used may be any hydrogen-containing gas mixture which does not contain any harmful amounts of catalyst poisons such as carbon monoxide or hydrogen sulfide. The use of an inert gas is optional, hydrogen preferably being used in a purity of greater than 95%, in particular greater than 98%. The inert gas portion may be, for example, nitrogen or methane.

[0056] Preferably, a solid hydrogenation catalyst comprising at least one metal of the eighth group of the transition group in the periodic table is used. The active metal of the eighth group of the transition group in the periodic table used is preferably platinum, rhodium, palladium, cobalt, nickel or ruthenium or a mixture of two or more thereof, and ruthenium as an active metal is particularly preferred. In addition to the metals already mentioned, at least one metal of the first group and / or the seventh group of the transition group in the periodic table may also be present in the catalyst. It is preferred to use rhenium and / or copper. The catalyst used is preferably a supported catalyst. Examples of carriers that can be used include the following: activated carbon, silicon carbide, aluminum oxide, silicon oxide, aluminosilicate, titanium dioxide, zirconium dioxide, magnesium oxide and / or zinc oxide or mixtures thereof. It is particularly preferred to use a catalyst with an aluminum oxide or titanium dioxide carrier. In addition, these carrier materials may contain alkali metals, alkaline earth metals and / or sulfur. It is preferred to use a ruthenium catalyst.

[0057] The hydrogenation process is preferably carried out in a three-phase reactor in a liquid / gas mixed phase or in a liquid phase in parallel flow, wherein the hydrogenation gas is distributed in a manner known per se in the liquid reactant / product stream. In order to achieve a uniform distribution of the liquid, to improve the removal of the heat of reaction and / or to obtain a high space-time yield, the reactor operated in loop mode is preferably operated with a high liquid load of 10 to 400 cubic meters, preferably 20 to 200 cubic meters and particularly preferably 40 to 150 cubic meters per square meter of empty reactor cross section and per hour.

[0058] The hydrogenation reaction can be carried out in the absence or preferably in the presence of a solvent. The solvent used can be a liquid that forms a homogeneous solution with all reactants and products, is inert under the hydrogenation conditions, and can be easily removed from the product. The solvent can also be a mixture of two or more substances, and optionally includes water. Most preferably, the product of the hydrogenation reaction is used as a solvent.

[0059] The transesterification of the trimethyl ester of cyclohexanetripropionic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms and the esterification of cyclohexanetripropionic acid with one or more of these alcohols are preferably carried out in the presence of a catalyst or two or more catalysts, for example, using a Bronsted acid or base or a Lewis acid or base as a catalyst. Particularly suitable catalysts have been found to be sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, metals or compounds thereof. Examples of particularly preferred metal catalysts are tin powder, tin(II) oxide, tin(II) oxalate, titanates such as tetraisopropyl orthotitanate or tetrabutyl orthotitanate and also zirconates such as tetrabutyl zirconate and sodium and potassium methoxide. Cyclohexanetripropionic acid can be obtained via hydroxycarbonylation, i.e., noble metal-catalyzed reaction of trivinylcyclohexane with CO and H2O.

[0060] The esterification process and the transesterification process can be carried out under conventional process conditions in typical esterification equipment known to those skilled in the art. The process is preferably carried out at a temperature equal to or higher than the boiling point of the alcohol formed in the reaction so that it can be distilled off from the reaction mixture. Examples of suitable transesterification processes are described in the experimental section.

[0061] The esterification process or transesterification process is preferably carried out at a temperature of 100 to 300° C., preferably 120 to 270° C. and in particular 140 to 250° C. The pressure in the esterification apparatus is preferably 0.1 to 20 bar or 15 bar, in particular 0.1 to 10 bar.

[0062] Preferred is an alkoxycarbonylation process comprising the following process steps:

[0063] a) first charging one of compounds (i), (ii), (iii) or a mixture of at least two of these compounds;

[0064]

[0065] b) adding a ligand (L) and a compound comprising Pd or a complex comprising Pd and a ligand (L);

[0066]

[0067] c) adding an alcohol having 1 to 12 carbon atoms;

[0068] d) supplying CO;

[0069] e) Heating the reaction mixture from a) to d), wherein the compound / mixture from a) is converted into a triester.

[0070] In one variant of the process, compound (i) is charged first in process step a), while in another variant, compound (ii) is charged first. The alcohol in process step c) preferably contains no further heteroatoms and no multiple bonds besides oxygen and is in particular selected from the group consisting of methanol, ethanol, n-butanol, methylpropanol, n-pentanol, isopentanol, 2-methylbutanol, 3-methylbutanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol, isodecanol and 2-propylheptanol.

[0071] Particular preference is given to preparing the trimethyl ester by methoxycarbonylation and then transesterifying it to the triester according to the invention or to the mixture of triesters according to the invention.

[0072] In the alkoxycarbonylation reaction, CO is added in process step d), preferably until the pressure is in the range of 20 to 60 bar and in particular 30 to 50 bar. The temperature in process step e) is preferably in the range of 90° C. to 130° C., in particular in the range of 100° C. to 120° C.

[0073] After the alkoxycarbonylation reaction, the triester is preferably purified in step f). DETAILED DESCRIPTION

[0074] Experimental Section

[0075] Acid value:

[0076] The acid number is determined according to DIN EN ISO 2114.

[0077] GC analysis:

[0078] GC analysis was performed using the following parameters:

[0079] Capillary column: 30m DB5; 0.25mm ID; 0.25μm film

[0080] Carrier gas: Helium

[0081] Column pressure:

[0082] Diversion: about 23.8ml / min

[0083] Oven temperature program (duration: 50°C (1 minute), heating at 7.5°C / min to 350°C (hold temperature for 30 minutes)

[0084] Injector: 350℃

[0085] Detector (FID): 400°C

[0086] Injection volume: 1.0 μl

[0087] The components in the sample chromatogram were identified using a reference solution of the relevant ester. The signals in the sample chromatogram were then normalized to 100 area %. The molar ratios were then determined sufficiently closely from the area ratios of the individual signals.

[0088] Purity was determined via the portion of the product signal as a proportion of the total area in the chromatogram.

[0089] Example 0: Preparation of cyclohexane-1,2,4-tripropionate trimethyl ester

[0090]

[0091] [Pd(acac)2] (15.2 mg, 0.1 mol%), (L) (see above formula, 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. Methanol (MeOH, 30 ml) and trivinylcyclohexane (i) (8.1 g, 50 mmol) were then injected through an injector. The autoclave was flushed with CO three times and then pressurized at a CO pressure of 40 bar. The reaction was carried out at 110°C for 10 hours. The autoclave was then cooled to room temperature and decompressed. The reaction mixture was purified by distillation (165°C, 10 -3 The desired product was purified by 1 H-, 13 The product was characterized by C-NMR and HR-MS (15.6 g, yield 91%, purity 98%).

[0092] 1 H-NMR (300MHz, C6D6) δ=3.39-3.37(m,9H), 2.24-1.86(m,7H), 1.48-0.27(m,14H).

[0093] 13 C-NMR(75MHz,C6D6)δ=173.68-173.54(m),51.04,40.60-40.47(m), 38.24,38.14,37.51,37.07,36.54,36.10,35.52,35.14,33.87,32.70,32.55, 32.51,32.38,32.29,32.23,32.08,31.97,31.86,31.76,31.68,31.63,31.43, 30.98,30.79,30.75,29.31,28.52,28.47,28.34,28.13,28.11,27.13,26.58, 25.12,20.79,19.74.

[0094] MS(EI):311(13.40),293(3.65),269(75.76),237(60.40),219(25.13), 205(100),191(17.62),177(14.83),145(24.59).

[0095] HR-MS(ESI): Calculation of C 18 H 30 O6[M+H] + : 343.21152, get : 343.21113.

[0096] Example 1-5: Preparation of cyclohexane-1,2,4-tripropionate trialkyl ester according to the present invention

[0097] In a distillation apparatus comprising an immersed tube, a thermometer and a Raschig ring column with a condenser attached, a quantity of m e Cyclohexane-1,2,4-tripropionate trimethyl ester and suspend it in an amount of m a Before adding 0.15% by mass (based on the mass of tripropionate) of tetra-n-butyl titanate (Sigma Aldrich, purity> 97%), the apparatus was purged with nitrogen (6 l / h) through an immersion tube for at least one hour. While bubbling with nitrogen (6 l / h) (this continued until the end of the reaction), the mixture was slowly heated to boiling under stirring. At a top temperature of 61 to 63° C., methanol was produced, which was continuously removed from the reaction via a distillation head. If the top temperature exceeded 68° C., no distillate was removed. During the transesterification, an amount of m m of methanol (reaction time t). Samples were taken every hour during the reaction and analyzed by gas chromatography. If less than 0.5 area % of monomethyl esters could be detected in the GC analysis, the heat medium was removed and the contents of the reaction flask were cooled to 80° C. by introducing nitrogen.

[0098] For work-up, the crude product was transferred to a distillation apparatus with a Claisen joint and a vacuum distributor. Excess alcohol was distilled off under reduced pressure (about 1 mbar) and at a bottom temperature of about 160° C. or about 180° C. (about 160° C. for tributyl and tripentyl esters, about 180° C. for tri(2-ethylhexyl) esters and tri(isononyl) esters) and then the mixture was cooled again under a nitrogen atmosphere. The acid number of the contents in the flask was determined and then, under nitrogen (6 l / h) bubbling, the contents were stirred at 80° C. for 15 minutes with three times the stoichiometric amount of base (10% aqueous NaOH solution, NaOH purchased from Merck, purity>99%). Subsequently, 2% by weight of activated carbon (Cabot Norit Nederland BV, CAP Super), based on the mass of the contents of the flask, was filled therein and stirred for 5 minutes. The remaining volatile fractions are removed again under vacuum and at about 160° C. or about 180° C. (see above) with the aid of nitrogen inlet, the nitrogen flow being adjusted so that the pressure does not exceed 20 mbar. If the residual alcohol content according to GC analysis is less than 0.025 area %, the resulting crude product is cooled and filtered through a Buchner funnel with filter paper and precompacted filter aid cake (Perlite D14 type) with the aid of reduced pressure into a suction flask.

[0099] The amount m obtained with the purity (%) specified in Table 1 is p The corresponding cyclohexane-1,2,4-tripropionic acid trialkyl ester (Tc ester).

[0100] Detailed features of each synthesis:

[0101] In the preparation of tri(2-ethylhexyl) ester, tri(isononyl) ester and tri(2-propylheptyl) ester, during the transesterification reaction (at a tower bottom temperature of 240° C.), reduced pressure was gradually applied while maintaining reflux. In this case, the tower top temperature slowly decreased as the pressure decreased.

[0102] Table 1: Details of the preparation of cyclohexane-1,2,4-tripropionate trialkyl ester according to the invention

[0103]

[0104] * Inventiveness

[0105] n-Butanol: Sigma Aldrich, purity >99.4%

[0106] Isoamyl alcohol: a mixture of n-pentanol (Sigma Aldrich, purity >99%) and 2-methylbutanol (Sigma Aldrich, purity >99%) in a 1:1 molar ratio

[0107] 2-Ethylhexanol: Sigma Aldrich, purity >99%

[0108] Evonik Performance Materials GmbH, purity >99%

[0109] Evonik Performance Materials GmbH, purity > 99.5%

[0110] Examples 6-10: Preparation of non-inventive cyclohexane-1,2,4-tricarboxylic acid trialkyl esters

[0111] In a distillation apparatus comprising an immersion tube, a thermometer and a condenser with an attached water separator, first charge a quantity m s Cyclohexane-1,2,4-tricarboxylic acid (Ct acid, >97%) and suspended in an amount of m a Before adding 0.15% by mass (based on the mass of cyclohexane-1,2,4-tricarboxylic acid) of tetrabutyl titanate (Sigma Aldrich, purity> 97%), the apparatus is purged with nitrogen (6 l / h) through the immersion tube for at least one hour. While bubbling with nitrogen (6 l / h) (this lasts until the end of the reaction), the mixture is slowly heated to boiling under stirring. The resulting reaction water is continuously removed from the reaction via a water separator. If continuous reflux no longer exists, an amount of m c Cyclohexane is used as an azeotropic agent. During the esterification process, an amount of m w After the theoretical amount of water reacted is reached, samples are taken every half hour to determine the acid value. If the measured acid value is <0.1 mg KOH / g, the contents of the reaction flask are cooled to 80° C. by removing the heat source and introducing nitrogen.

[0112] For workup, the crude product was transferred to a distillation apparatus comprising a Claisen adapter with a vacuum distributor. Excess alcohol was distilled off under reduced pressure (about 1 mbar) at a bottom temperature of about 160° C. or about 180° C. (about 160° C. for tri(n-butyl) ester and tri(isoamyl) ester, about 180° C. for tri(2-ethylhexyl) ester, tri(isononyl) ester and tri(2-propylheptyl) ester), and the mixture was then cooled again under a nitrogen atmosphere. The acid number of the contents in the flask was determined, and then the contents were stirred at 80° C. for 15 minutes with three times the stoichiometric amount of base (10% aqueous NaOH solution, NaOH purchased from Merck, purity>99%) under nitrogen bubbling (6 l / h). Subsequently, 2% by weight of activated carbon (Cabot Norit Nederland BV, CAP Super), based on the mass of the contents of the flask, was filled therein and stirred for 5 minutes. The remaining volatile fractions are removed again under vacuum and at about 160° C. or about 180° C. (see above) with the aid of nitrogen inlet, the nitrogen flow being adjusted so that the pressure does not exceed 20 mbar. If the residual alcohol content according to GC analysis is less than 0.025 area %, the resulting crude product is cooled and filtered through a Buchner funnel with filter paper and precompacted filter aid cake (Perlite D14 type) with the aid of reduced pressure into a suction flask.

[0113] The amount m was obtained with the purity percentage (%) specified in Table 2 p The corresponding cyclohexane-1,2,4-tricarboxylic acid trialkyl ester.

[0114] Specific features of each synthesis:

[0115] Preparation of tri(n-butyl) ester: In this experiment, 0.15 wt% (based on the mass of cyclohexane-1,2,4-tricarboxylic acid) of sulfuric acid (Sigma-Aldrich, purity 95-97%) was added together with tetra-n-butyl titanate. In addition, if the acid value was <1 g KOH / g (instead of <0.1 mg KOH / g), the contents of the reaction flask were cooled to 80° C. by introducing nitrogen.

[0116] Preparation of tri(n-butyl) and tri(isoamyl) esters: At the start of the reaction, only half of the amount of tetra-n-butyl titanate and the corresponding alcohol described above was initially charged, and the remainder was added only when a bottom temperature of 240° C. was reached.

[0117] Table 2: Preparation details of non-inventive cyclohexane-1,2,4-tricarboxylic acid trialkyl esters (Ct-esters)

[0118]

[0119] n-Butanol: Sigma Aldrich, purity >99.4%

[0120] Isoamyl alcohol: a mixture of n-pentanol (Sigma Aldrich, purity >99%) and 2-methylbutanol (Sigma Aldrich, purity >99%) in a 1:1 molar ratio

[0121] 2-Ethylhexanol: Sigma Aldrich, purity >99%

[0122] Isononanol: Evonik Performance Materials GmbH, purity >99%

[0123] 2-Propylheptanol: Evonik Performance Materials GmbH, purity >99.5%

[0124] Example 11: Intrinsic Viscosity of Esters of Examples 1-10

[0125] The viscosity is determined with the aid of a Stabinger viscometer (SVM3000 from Anton Paar), which is a modification of the classic Couette rotational viscometer. The esters are poured into the measuring cell separately and without bubbles according to the instruction manual and the measurement is carried out at 20°C.

[0126] Table 3 lists the intrinsic viscosities of these esters.

[0127] Table 3: Intrinsic viscosity of esters of Examples 1-10 at 20°C [mPa·s]

[0128] Cyclohexane-1,2,4-tripropionate trialkyl ester* Cyclohexane-1,2,4-tricarboxylic acid trialkyl ester n-Butyl 52.3 47.4 79.7 69.1 151.8 158.0 168.0 163.5 217.5 222.9

[0129] * Inventiveness

[0130] Example 12: Production of plastisol

[0131] PVC plastisols were produced, for example, as topcoat films for floor coverings. The figures in the plastisol formulations are in parts by mass. The formulations of the polymer compositions are listed in Table 4.

[0132] Table 4: Plastisol Formulations

[0133] PVC (Vestolit B 7021-Ultra; purchased from Vestolit) 100 Trisester of Example 1*, 2*, 3*, 6, 7 or 8 (mixture) 50 Epoxidized soybean oil (Drapex 39, purchased from Galata) as a co-stabilizer 3 Ca / Zn based heat stabilizer (reagent CLX / 759 / 6PF) 2

[0134] Figures are in phr (phr = parts per hundred parts of resin)

[0135] First, the liquid ingredients and then the powdered ingredients are weighed into a PE beaker. The mixture is stirred manually with an ointment spatula in such a way that unwetted powder no longer exists. The mixing beaker is then clamped into the clamping device of the dissolving stirrer. After turning on the stirrer, the speed is slowly increased to about 2000 rpm (revolutions per minute). At the same time, the plastisol is carefully degassed, and the pressure is kept below 20 mbar. After the plastisol reaches a temperature of about 30°C, the speed is reduced to about 350 rpm. Thereafter, the plastisol is degassed at this speed and a pressure below 20 mbar for 9 minutes. This ensures that the plastisol is homogenized under defined energy input conditions. Thereafter, the plastisol is immediately equilibrated to 25.0°C in a climate-controlled cabinet for further investigation.

[0136] Example 13: Determination of thickening behavior

[0137] The viscosity of the plastisol produced in Example 12 was measured with a Physica MCR 101 rheometer (Anton Paar Germany GmbH) using the rotational mode and a CC27 measuring system with the aid of the associated software.

[0138] The following points were controlled during the measurements:

[0139] 100s in a 60s period -1 of pre-shear, during which no measurements were made,

[0140] The shear rate was from 200 s -1 Down to 0.1s -1 . Take 30 measurement points, and the measurement point duration of each measurement point is 10 seconds.

[0141] The measurements were carried out after storage for 2 hours, 24 hours and 7 days. Between the measurements, the plastisols were stored at 25°C.

[0142] Based on the viscosity value after 2 hours, the percentage increase in viscosity after 24 hours and after 7 days was calculated as 1s -1 , 10s -1 and 100s -1 The thickening behavior of plastisols is determined by the shear rate.

[0143] Table 5: Plastisol of Example 12 at 1 s -1 Thickening behavior

[0144]

[0145] *According to the invention

[0146] Table 6: Plastisol of Example 12 at 10 s -1 Thickening behavior

[0147]

[0148] *According to the invention

[0149] Table 7: Plastisol of Example 12 at 100 s -1 Thickening behavior

[0150]

[0151] *According to the invention

[0152] The plastisol viscosity of the cyclohexane-1,2,4-tripropionate trialkyl esters according to the invention is lower than that of the comparative esters. In addition, the viscosity of the cyclohexane-1,2,4-tripropionate trialkyl esters increases less significantly over time than the comparative esters. Due to these favorable properties, the triesters according to the invention can be used without the addition of viscosity-reducing additives even after long-term storage, which, in addition to not using these additives, also saves time and effort associated with their use.

[0153] Example 14: Preparation of thin film

[0154] The plastisols prepared in Example 12 were each processed to give films 1 mm thick.

[0155] To this end, all high gloss release papers (purchased from Sappi, Italy) were first trimmed to a size of 30×44 cm and then inserted into the clamping frame of the LTSV coating device for the Mathis furnace. The clamping frame was then placed on a guide frame, the Mathis furnace (model LTF) was adjusted to 200° C., and the frame was preheated for 15 seconds when this temperature was reached. The blade coater was then inserted into the clamping device, and the blade gap was adjusted through preliminary experiments so that the film thickness after gelation was 1 mm (+ / - 0.05 mm). The adhesive tape was installed on the leading edge of the paper to capture excess plastisol. The plastisol was then applied in front of the coating knife and spread on the clamped release paper (at a speed of 3 m / min) by pulling out the guide frame with the coating knife. The coating knife was then removed, and the adhesive tape with excess plastisol was removed. The clamping frame was then moved into the furnace. After gelation has occurred (2 minutes at 200° C.), the rack is removed from the oven again and, after cooling, the film is removed from the paper.

[0156] Example 15: Mass loss of thin films

[0157] Each of the 6 dumbbell-shaped specimens (type S2 according to DIN 53504) of the formulation from Example 14 was conditioned overnight in a standard climate (23° C., 50% relative humidity) and then weighed. Subsequently, the dumbbell-shaped specimens were stored at 80° C., suspended above a tray (28×20×6 cm) filled with activated carbon in a convection-operated heating cabinet with a minimum gap of 20 mm. After 7 or 14 days, the dumbbell-shaped specimens were removed, stored overnight in a desiccator and then weighed. The mass loss was determined by subtraction for each single dumbbell-shaped specimen. The average value of the mass loss percentage for each of the six independent measurements of the formulation is listed in Table 8.

[0158] Table 8: Mass loss of films in air (80°C)

[0159]

[0160] * Inventiveness

[0161] The mass loss of films comprising the triesters according to the invention is lower than the mass loss of films comprising the corresponding cyclohexane-1,2,4-tricarboxylic acid trialkyl esters.

[0162] Example 16: Glass transition temperature of thin films

[0163] The glass transition temperature was determined by DMTA measurements using an MCR 302 rheometer purchased from Anton Paar according to DIN 65583. Under constant dynamic mechanical conditions (1 Hz, deformation of 0.3%), the viscoelasticity of the film with temperature changes (temperature change from -100 to +50°C) was recorded, and the storage modulus, loss modulus and loss factor were determined. In this case, the maximum value of the loss modulus was interpreted as the glass transition temperature. The table below shows the average value of duplicate determinations in each case.

[0164] Table 9: Glass transition temperature T of the films g (℃)

[0165]

[0166] * Inventiveness

[0167] As is evident from the lower glass transition temperature, the low-temperature flexibility of the esters according to the invention is significantly improved compared to the comparative compounds.

[0168] Example 17: Production of dry blend, rolled sheet and pressed sheet

[0169] The test specimens required for the following examples were produced by dry blending (dry blending production), calendering (rolling) and pressing the following formulations:

[0170] Table 10: Dry blend formulations

[0171]

[0172] phr: (phr = parts per hundred parts of resin)

[0173] Tri(2-ethylhexyl) trimellitate: Eastman Chemical Company, purity >99%

[0174] Tri(isononyl) trimellitate: UPC Technology, Taiwan, China, purity>98%

[0175] For example, cable and wire insulation, hoses or floor and roof waterproofing membranes can be produced using dry mixtures, known as dry blends, after thermoplastic processing (eg calendering or extrusion).

[0176] The dry blend was produced in a Brabender planetary mixer.

[0177] The following parameters were set in a Brabender planetary mixer using the "Winmix" software:

[0178] Speed ​​Program: Activated

[0179] Brief description: speed 50rpm; holding time: 9 minutes;

[0180] (Speed) growth time: 1 minute;

[0181] Speed ​​100rpm; Holding time: 20 minutes

[0182] Temperature: 88℃

[0183] Measuring range: 2Nm

[0184] Damping: 3

[0185] After an equilibrium period of one hour, the temperature in the mixing vessel is 88° C. Once the planetary mixer has been internally calibrated, the solid ingredients (PVC, stabilizer) that have previously been weighed in four times the amount (four times the amount in grams in phr based on Table 10) in a PE beaker on an analytical balance are fed to the mixing vessel via the solids funnel and the filling stub present in the Brabender mixing vessel. The program is started and the powder mixture is stirred and balanced in the mixing vessel for 9 minutes, and then the liquid ingredients that have also been weighed in four times the amount in a PE beaker on the balance are fed via the liquids funnel and the filling stub present in the Brabender mixing vessel. The mixture is stirred in the planetary mixer for a further 20 minutes. At the end of the program, the final dry mixture (dry blend) is removed.

[0186] These dry blends are used to produce rolled sheets. The rolled sheets are produced on a Collin W150 AP calender. The Collin calender has an automatic sample feeder and its temperature is controlled with the aid of an additional oil thermostat. Control is achieved with the aid of the Collin software.

[0187] A five-stage process is used to produce rolled sheets:

[0188]

[0189] When the roller temperature is reached, the roller gap is calibrated. To start the measurement, the roller gap is set to 0.2 mm. 160 g of each dry blend are weighed and introduced into the roller gap with the rollers stationary. The program is started.

[0190] Pressed plaques were produced with a Collin laboratory press. Prefabricated rolled plaques (see above) were used to produce the pressed plaques. The side edges of the rolled plaques were removed with the aid of a cutter and the rolled plaques were then cut into pieces with dimensions of approximately 14.5×14.5 cm. For pressed plaques with a thickness of 1 mm, 2 rolled plaques were placed one above the other in each case in a stainless steel pressing frame with dimensions of 15×15 cm.

[0191] A three-stage process is used to produce pressed board:

[0192]

[0193] Example 18: Glass transition temperature of pressed sheets

[0194] The glass transition temperature was determined by DMTA measurements using an MCR 302 rheometer from Anton Paar according to DIN 65583. Under constant dynamic mechanical conditions (1 Hz, deformation of 0.3%), the viscoelasticity of the film was recorded as a function of temperature (temperature change from -100 to +50° C.), and the storage modulus, loss modulus and loss factor were determined. In this case, the maximum value of the loss modulus was interpreted as the glass transition temperature. The table below shows the average value of duplicate determinations in each case.

[0195] Table 11: Glass transition temperature T of pressed plates g (℃)

[0196]

[0197] * Inventiveness

[0198] As is evident from the low glass transition temperature, the low temperature flexibility of the esters according to the invention is higher than that of the comparative compounds. The good low temperature flexibility is particularly suitable for outdoor applications.

[0199] Example 19: Mass loss of pressed board

[0200] Six test pieces (each in the form of a tensile specimen of type S2 according to the formulation) were punched out of the pressed plate of Example 17, conditioned in a desiccator overnight and then weighed. Subsequently, the test specimens were stored at 135°C and suspended above a tray (28×20×6 cm) filled with activated carbon in a convection-operated heating cabinet with a minimum gap of 20 mm. After 14 days, the test specimens were removed, stored overnight under standard climate and then weighed. The difference in mass determined for each test specimen is the mass loss. The percentage average of each of the three independent measurements according to the formulation is listed in Table 12.

[0201] Table 12: Mass loss of pressed boards in air (after storage at 135°C for 14 days), expressed in mass %

[0202] * Inventiveness

[0203] The mass loss of the pressed boards comprising the triesters according to the invention is lower than the mass loss of the films comprising the corresponding cyclohexane-1,2,4-tricarboxylic acid trialkyl esters or the corresponding trimellitic acid trialkyl esters.

Claims

1. Trisesters of cyclohexanetripropionic acid, which are triesters of cyclohexane-1,2,4-tripropionic acid, wherein the three alcohol moieties of the three ester groups each contain 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms and, apart from the oxygen of the ester function, do not contain any other heteroatoms and do not contain multiple bonds.

2. The triester of cyclohexanetripropionic acid according to claim 1, characterized in that All alcohol moieties present in one molecule have the same empirical formula and at the same time the same or different structural formulas.

3. A mixture of at least two triesters of cyclohexanetripropionic acid according to any one of claims 1 to 2.

4. The mixture according to claim 3, characterized in that The at least two cyclohexanetripropionate triesters differ in their empirical formula and / or their structural formula.

5. The triester of cyclohexanetripropionic acid according to any one of claims 1 to 2 or the mixture according to claim 3 or 4, characterized in that It is selected from the group consisting of: Tri(n-butyl)cyclohexane-1,2,4-triproinate, tri(methylpropyl)cyclohexane-1,2,4-triproinate, tri(n-pentyl)cyclohexane-1,2,4-triproinate, tri(isopentyl)cyclohexane-1,2,4-triproinate, tri(2-methylbutyl)cyclohexane-1,2,4-triproinate, tri(3-methylbutyl)cyclohexane-1,2,4-triproinate, tri(n-hexyl)cyclohexane-1,2,4-triproinate, tri(isohexyl)cyclohexane-1,2,4-triproinate, tri(n-heptyl)cyclohexane-1,2,4-triproinate , tri(isoheptyl)cyclohexane-1,2,4-triproinate, tri(n-octyl)cyclohexane-1,2,4-triproinate, tri(isooctyl)cyclohexane-1,2,4-triproinate, tri(2-ethylhexyl)cyclohexane-1,2,4-triproinate, tri(n-nonyl)cyclohexane-1,2,4-triproinate, tri(isononyl)cyclohexane-1,2,4-triproinate, tri(n-decyl)cyclohexane-1,2,4-triproinate, tri(isodecyl)cyclohexane-1,2,4-triproinate, tri(2-propylheptyl)cyclohexane-1,2,4-triproinate.

6. A plasticizer for polymers, comprising the triester of cyclohexanetripropionic acid according to any one of claims 1 to 2 and 5 or the mixture according to any one of claims 3 to 5 and optionally at least one other compound which plasticizes the polymer.

7. A composition comprising the triester of cyclohexanetripropionic acid according to any one of claims 1 to 2 and 5 or the mixture according to any one of claims 3 to 5 or the plasticizer according to claim 6 and one or more polymers.

8. The composition according to claim 7, characterized in that At least one polymer is selected from the group consisting of polyvinyl chloride, polyalkyl methacrylate (PAMA), polyvinyl butyral (PVB), polyurethane, polysulfide, polylactic acid (PLA), polyhydroxybutyral (PHB), nitrocellulose, copolymers of vinyl chloride and vinyl acetate or butyl acrylate.

9. The composition according to any one of claims 7 or 8, characterized in that The composition is a component of an adhesive, a sealing compound, a coating composition, a varnish, a paint, a plastisol, a dry mix, a foam, a synthetic leather, a floor covering, a roofing membrane, an underbody protection, a textile coating, a cable, a wire insulation, a hose, an extruded article, a film, an article in an automotive interior, wallpaper, ink, a toy, a photographic plate, a food packaging or a medical article.

10. Use of the triester of cyclohexanetripropionic acid according to any one of claims 1 to 2 and 5 or the mixture according to any one of claims 3 to 5 as a plasticizer for polymers.

11. The use according to claim 10, characterized in that Cyclohexane tripropionate triesters whose alcohol moieties each contain 7 to 12 carbon atoms are used as compounds for plasticizing polymers in high-temperature applications.

12. The use according to claim 10, characterized in that Cyclohexane tripropionate triesters whose alcohol moieties each contain 2 to 9 carbon atoms are used in plastisol applications as compounds for plasticizing polymers.

13. A method for preparing a triester of cyclohexanetripropionic acid according to any one of claims 1 to 2 and 5, by the following method: - Cyclohydrogenation of the corresponding benzene tripropropionate triester, - transesterification of a trialkyl ester of cyclohexanetripropionic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, wherein the alcohol of the alcohol part of the trialkyl ester to be introduced in the transesterification has a higher boiling point than the alcohol of the alcohol part to be replaced, - esterification of cyclohexanetripropropionic acid with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, or - Alkoxycarbonylation of trivinylcyclohexane with at least one alcohol containing 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms.

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