Plasticizer based on sebacic acid

Abstract

The invention relates to a polyester plasticizer of formula (I), wherein R1 and R2 represent alkyl groups with 8 or 9 carbon atoms, G represent a -(CH2)8- group, A is an alkylene group and m is a number from 1 to 10, to a process for the production thereof, to molding compounds that contain a polymer and a plasticizer of this type, and to moldings and films produced from these molding compounds.

Description

[0001] Plasticizer based on sebacic acid

[0002] Description

[0003] The present invention relates to plasticizers based on sebacic acid, molding compositions containing a thermoplastic polymer or an elastomer and such a plasticizer, and the use of these plasticizers and molding compositions.

[0004] To achieve desired processing or application properties, so-called plasticizers are added to a variety of plastics to make them softer, more flexible, and / or more stretchable. Plasticizers shift the usable thermoplastic range of plastics toward lower temperatures, so that they exhibit the desired elastic properties even at relatively low processing and application temperatures.

[0005] One of the most important plastics to which plasticizers are added on a large scale is polyvinyl chloride (PVC). PVC is one of the most important plastics in terms of quantity. Due to its versatility, it is found in a wide variety of everyday products. PVC is therefore of great economic importance. PVC itself is a hard and brittle plastic up to around 80°C, which is used as rigid PVC (PVC-U) with the addition of heat stabilizers and other additives. Only with the addition of suitable plasticizers can one obtain flexible PVC (PVC-P), which can be used for many applications for which rigid PVC is unsuitable. Other important thermoplastic polymers in which plasticizers are commonly used include polyvinyl butyral (PVB), homo- and copolymers of styrene, polyacrylates, polysulfides, thermoplastic polyurethanes (PU) and polyesters such as polylactide (PLA).

[0006] A wide variety of different plasticizers are known for PVC and other plastics. In addition to phthalic acid diesters such as diethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP), terephthalic acid diesters such as di-2-ethylhexyl terephthalate, and their analogues with a hydrogenated aromatic ring, i.e. the corresponding 1,2- or 1,4-cyclohexanedicarboxylic acid esters, polyester plasticizers, various benzoates, aromatic sulfonic acid esters, citrates, and phosphates are also known. Whether a substance is suitable for use as a plasticizer for a particular polymer also depends on the properties of the polymer to be plasticized, so the plasticizer and polymer must be matched to one another. The most important thing for a plasticizer is its suitability for shifting the thermoplastic range of a polymer to lower temperatures—in other words, lowering the glass transition temperature of the polymer.This property is usually assessed as the "cold fracture temperature," i.e., the temperature below which molded polymer bodies break upon impact. On the other hand, the plasticizer must not render the polymer unusably soft, and the hardness—usually assessed as Shore A hardness—of the plasticized polymer must not be too low. Furthermore, the chemical resistance of the plasticizer in the polymer is important, often assessed as resistance to the effects of hydrochloric acid ("HCl residual stability"). Important mechanical properties of the polymer that are influenced by the plasticizer are elongation at break. D (also called “tear strength”), breaking stress n b (also called “elongation at break”) and the stress value at 100% elongation.

[0007] The viscosity of the plasticizer should not be too high to facilitate the preparation of the molding compound from polymer and plasticizer, and the gelling behavior of a mixture of polymer and plasticizer during the preparation of the plasticized polymer should not be adversely affected.

[0008] Also important for a plasticizer is high permanence in the polymer to be plasticized, i.e., a low tendency to evaporate (i.e., low volatility) and exude (i.e., high compatibility). Where the polymer is in contact with other materials, such as in composites or food packaging, a low tendency to migrate into other solids (i.e., high migration resistance) or liquids (i.e., high extraction resistance) that are in contact with the polymer is also desirable as a further aspect of permanence. All of these properties are not necessarily concurrent, so the choice of a plasticizer is often a compromise between the characteristics of these properties depending on the intended application of the polymer.

[0009] Soft PVC with plasticizers with low volatility and very low cold fracture temperature is used primarily in automobiles. Typically, the plasticizers are phthalic acid esters with C9 to C 13 -alkanols. For example, a mixed ester of linear C9 and C n Alcohols with phthalic acid (commercially available from BASF Corp. as Palatinol® 911) result in a volatility of 0.6% weight loss (130°C / 24 h) and a cold fracture temperature of -45°C. Some phthalate plasticizers are no longer available on the market due to toxicological disadvantages, while others raise concerns, particularly when used in applications such as food packaging, children's toys, or medical devices. Therefore, alternatives to phthalates are being sought.

[0010] Low cold fracture temperatures can also be achieved with adipic acid diesters. For example, with di-2-ethylhexyl adipate, a cold fracture temperature of below -50°C is achievable, but only with undesirably high volatility (over 5% weight loss at 130°C / 24 h). Low to very low volatilities are more likely to be achieved with polyester plasticizers, but typically only at unsatisfactory cold fracture temperatures. For example, a polyadipate made from neopentyl glycol, 1,4-butanediol with isononanol as endcapping (commercial Palamoll® 656 from BASF SE) leads to a volatility of 0.5% weight loss (130°C / 24 h), but to a cold fracture temperature of -21°C.

[0011] Polyester plasticizers and their production are well known. Polyester plasticizers have polyester chains that are usually end-capped with either an acid or an alcohol. Alcohol-terminated polyester plasticizers have the following general formula: and those with acid termination the following general formula: where R lrR2, R3, and R4 are typically alkyl radicals, G and A are alkylene radicals, and m is the number of complete repeating units in the polyester chain. The radicals Rj and R2, as well as R3 and R4, are usually identical in common polyester plasticizers, but in principle they can also be different from one another. Likewise, G and A can be the same or different from one another. These polyesters are usually produced by catalytic esterification of at least one dicarboxylic acid HOOC-G-COOH with at least one diol HO-A-OH, in the case of alcohol-end-capped polyesters in the presence of at least one monoalcohol Rj-OH (when Rj = R2) and in the case of acid-end-capped polyesters in the presence of at least one monoacid R3-COOH (when R3 = R4), in each case with removal of the water formed during esterification.The composition and properties of the polyester can be determined by the choice of dicarboxylic acid, diol, and end group, as well as the degree of polymerization (i.e., ultimately, the selected stoichiometry of the starting materials). During synthesis, a low OH number, i.e., a low number of free -OH groups, is desirable, as otherwise incompatibilities with the PVC may occur, particularly under humid conditions. As is always the case with polyesters due to their manufacturing processes, they are a mixture of longer and shorter chain components. Therefore, m is commonly used to denote the number-average degree of polymerization, which is determined by gel permeation chromatography analysis of the polyester. Therefore, a polyester with a specific value of m always contains portions of molecules that have fewer or more complete repeat units of the polyester within the molecule. Typically, the portions decrease the more this value deviates from the overall number average.

[0012] The most commonly used dicarboxylic acid is adipic acid, which is readily available from petrochemicals. However, there is also increasing demand for plasticizers that are entirely or partially derived from non-fossil raw materials.

[0013] A general and fundamental overview of the effects, production, and evaluation of plasticizers for PVC is provided by L. Meier in Section 6.7, "Plasticizers for PVC," in: Kunststoff-Handbuch, GW Becker, D. Braun (eds.), Volume 2 / 1: "Polyvinyl Chloride," Carl Hanser Verlag, Munich 1986. A corresponding overview of non-phthalate plasticizers, such as polyester plasticizers, is provided by WD Arendt and M. Joshi in Chapter 8, "Specialty Plasticizers," in: Handbook of Vinyl Formulating, F. Grossmann (ed.), John Wiley, New York 2008.

[0014] EP 4116373 A1 (WO 2021 / 176901) describes the synthesis and application of various polymer plasticizers based on sebacic acid with diols and usually acid-terminated with long-chain fatty acids. These plasticizers are said to be characterized by excellent migration behavior and improved temperature stability (volatility), and good cold flexibility is also mentioned. The OH numbers mentioned are relatively high, so poor compatibility with PVC is to be expected. Likewise, JP 08-120143 teaches certain polyester plasticizers and acrylate polymers in PVC that are said to exhibit good migration resistance and flexibility. One example is a polymer consisting of sebacic acid, 1,4-butanediol, and 1,3-butanediol with 2-ethylhexanol as the terminal group. A disadvantage here is its very high viscosity.

[0015] EP 4177310 A1 (WO2022 / 004320) discloses polyester plasticizers in which the proportion of low-molecular-weight components with a molecular weight below 600 g / mol is reduced to the range of 0.5–3 wt.% by thin-film distillation. It is plausible that this reduces a potential negative influence of low-molecular-weight components on the properties of the plasticizer and the plasticized polymer, thus improving the property profile of the plasticizer and polymer. Similarly, US 2023 / 0265276 A1 (WO 2022 / 050027) teaches polymer plasticizers based on adipic or sebacic acid with 3-methyl-1,5-pentanediol and 2-ethylhexanol as the final product, which are also obtained by thin-film distillation. However, large-scale and economical production of plasticizers is not feasible in this complex, expensive and time-consuming way.

[0016] JP 2002 / 121361 A describes polyester plasticizers based on sebacic acid and diols with benzoic acid as terminal groups, which offer advantages in injection molding of the PVC plasticized with them, particularly reduced sagging. CN 104926648 A lists a number of polyester plasticizers, including those with sebacic acid as the diacid. WO 2023 / 32862 A1 also teaches polyester plasticizers that may contain sebacic acid as the diacid and also contain 12-hydroxystearic acid. The plasticizers are said to exhibit good extraction resistance, low-temperature resistance, and low volatility. The high proportion of hydroxy groups in PVC leads to incompatibility, so that reliable saturation of all free OH groups with acid functions must be ensured during production, which is complex and therefore disadvantageous. JP 07 / 126466 teaches polyesters with a content of more than 60% 1,4-butanediol.According to CN 111533889 A, polyesters with high migration stability are achieved when terephthalic acid is also used as a polymer building block. SU 427029 describes a polymer plasticizer based on a mixture of sebacic acid and adipic acid with polyethylene glycol as the diol, which is said to exhibit high compatibility.

[0017] Against this background, there is still a need for additional or optimized plasticizers, especially plasticizers that exhibit low volatility values ​​in the plasticized polymer and lead to low cold fracture temperatures of the plasticized polymer. Other properties of the plasticized polymer, such as chemical resistance and mechanical properties such as hardness, elongation at break, breaking stress, and modulus at 100% elongation, should not be impaired. High permanence, particularly high compatibility, is also desired. Furthermore, it is desirable that the components of the plasticizer be at least partially economically obtainable from raw materials other than fossil fuels, and it is also desirable that the plasticizer be producible without complex process steps. The object of this invention is achieved by a polyester plasticizer of the formula (I): where Rj and R2 are alkyl radicals having 8 or 9 carbon atoms, G is a -(CH2)8- group, A is an alkylene radical and m is a number from 1 to 10.

[0018] R1 and R2 are alkyl radicals with 8 or 9 carbon atoms. The alkyl radicals can be linear or branched. These include n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, and 2-propylhexyl. Preferred alkyl radicals with 8 carbon atoms are n-octyl and 2-ethylhexyl, and preferred alkyl radicals with 9 carbon atoms are isononyl.

[0019] Isononyl residues (in other words, the isononanol used to prepare the polyesters of the invention) are typically isomer mixtures, such as those obtained in the conventional synthesis of isononanol, starting with the dimerization of the 1- and 2-butenes contained in a mixture obtained from the C4 stream of a steam cracker, as it exists after removal of butynes, butadiene, and isobutene ("raffinate II"), to isooctene, followed by hydroformylation and hydrogenation to isononanol. The exact isomer composition of such an isononanol depends on the proportions of 1- and 2-butenes in the raffinate II and the other production conditions. A measure of the proportion of more highly branched C9 residues in isononanol is the degree of branching, i.e. the ratio of methyl groups to CH2-O group in the isononanol minus 1. Accordingly, n-nonanol, for example, has a degree of branching of 0 and 3,5,5-trimethylhexanol a degree of branching of 3.The degree of branching can be conveniently measured by n-NMR spectroscopy on a sample of isononanol in CDCl3 by relating the area of ​​the signals attributable to the methyl groups in the chemical shift range from 0 to 1 ppm relative to tetramethylsilane to the area of ​​the signals attributable to the CH2-O group in the range from 3.6 to 4.4 ppm, multiplied by a factor of 2 / 3 to compensate for the different number of hydrogen atoms in the CH3 and CH2O groups. The value 1 is subtracted from the result, since n-nonanol has a degree of branching of 0 but also contains a methyl group. Preferably, the degree of branching of the isononanol used according to the invention, i.e. the isononyl group in a compound of formula (I), is from 1.0 to 2.0, more preferably from 1.1 to 1.9, particularly preferably from 1.1 to 1.5 and most preferably from 1.1 to 1.4.

[0020] Rj and R2 may be different from each other, but preferably Rj and R2 are identical.

[0021] A is a branched or unbranched alkylene radical, in particular a C2-C 12 -alkylene radical. The term "C x -C y-Alkylene" means a divalent hydrocarbon radical having x to y carbon atoms. The divalent hydrocarbon radicals can be unbranched or branched. Examples are 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 2-methyl-1,3-propylene, 1,1-dimethyl-1,2-ethylene, 1,4-pentylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 2,3-dimethyl-1,4-butylene, 1,7-heptylene, 2-methyl-1,6-hexylene, 3-Methyl-1,6-hexylene, 2-Ethyl-1,5-pentylene, 3-Ethyl-1,5-pentylene, 2,3-Dimethyl-1,5-pentylene, 2,4-Dimethyl-1,5-pentylene, 1,8-Octylene, 2-Methyl-1,7-heptylene, 3-methyl-l,7-heptylene, 4-methyl-l,7-heptylene, 2-ethyl-l,6-hexylene, 3-ethyl-l,6-hexylene, 2,3-dimethyl-l,6-hexylene, 2,4-dimethyl-l,6-hexylene, 1,9-nonylene, 2-Methyl-1,8-Octylene, 3-Methyl-1,8-Octylene, 4-Methyl- 1,8-octylene, 2-ethyl-1,7-heptylene, 3-ethyl-l,7-heptylene, 1,10-decylene, 2-methyl-l,9-nonylene, 3-methyl-l,9-nonylene, 4-methyl-1,9-nonylene, 5-methyl-1,9-nonylene, 1,11-undecylene, 2-methyl-1,10-decylene, 3-methyl-1,10-decylene, 4-methyl-1,10-decylene, 5-methyl-1,10-decylene, 1,12-dodecylene and the like. Preferably, "C2-C, 12-Alkylene" are branched or unbranched C2-C8 alkylene groups, particularly preferably branched or unbranched C2-C5 alkylene groups. Very particular preference is given to 1,2-radicals, in particular 1,2-propylene and 1,2-pentylene. In other words, the particularly preferred alkylene radicals A in the polyester according to the invention are those in which both ester bonds to A are located on directly adjacent carbon atoms, or in still other words, the corresponding diols HO-A-OH are preferably vicinal diols. The very particular preferred diols in the polyester are 1,2-propanediol (propylene glycol) and 1,2-pentanediol (pentylene glycol). A mixture of diols can also be used to produce the polyester, and accordingly, different alkylene radicals A can be present in the polyester according to the invention, but preferably only one diol is used and accordingly the alkylene radicals A in the polyester according to the invention are preferably all identical.G is a -(CH2)8- group. The dicarboxylic acid of the polyester according to the invention is therefore sebacic acid (decane-1,10-dioic acid, also 1,8-octanedicarboxylic acid). Apart from sebacic acid, the polyester according to the invention contains no other intentionally added dicarboxylic acid. In other words, the sebacic acid used to produce the polyesters according to the invention contains no other dicarboxylic acids, with the exception of unavoidable impurities from the production or extraction of the sebacic acid, so that the polyester produced with this sebacic acid also contains no other such dicarboxylic acids, with the exception of unavoidable impurities. m is the number of complete repeat units of the polyester, i.e., the number of complete dicarboxylic acid / diol pairings. The parameter m is often also referred to as the "degree of polymerization." m is preferably a number from 1 to 5, more preferably a number from 2 to 4, and most preferably 3.As always in polyesters, these are a mixture of longer- and shorter-chain components. Therefore, m is, as is customary in the art, the number-average value of the degree of polymerization, which is determined by gel permeation chromatography analysis of the polyester. A polyester according to the invention with a specific value of m therefore always contains fractions of molecules that have fewer or more complete repeating units of the polyester within the molecule. Typically, the fractions become smaller the more this value deviates from the overall number average.

[0022] In a preferred embodiment of the polyesters according to the invention, R1 and R2 are each an n-octyl radical, in a further preferred embodiment each is a 2-ethylhexyl radical, and in a further preferred embodiment each is an isononyl radical. In a preferred embodiment, A is a branched 1,2-alkylene radical, for example a 1,2-propylene radical, or a 1,2-pentylene radical. Particularly preferred are therefore the compounds of formula (I) with the combinations of Rj = R2 = n-octyl and A = 1,2-propylene, of Rj = R2 = n-octyl and A = 1,2-pentylene, of Rj = R2 = 2-ethylhexyl and A = 1,2-propylene and of Rj = R2 = 2-ethylhexyl and A = 1,2-pentylene as well as of Rj = R2 = isononyl and A = 1,2-propylene and of Rj = R2 = isononyl and A = 1,2-pentylene. In all these cases, m is preferably 3 and the degree of branching of the isononyl radicals is from 1.0 to 2.0, preferably from 1.1 to 1.9, particularly preferably from 1.1 to 1.5 and most preferably from 1.1 to 1.4.

[0023] The polyester compounds of the general formula (I) prove to be plasticizers for plastics, in particular for PVC (polyvinyl chloride), with an optimized combination of cold fracture strength and volatility with overall unimpaired other properties of plasticizer and plasticized polymer.

[0024] The present invention further provides a process for producing the polyesters of the formula (I) according to the invention. These polyester plasticizers according to the invention are prepared in a technically known manner, as described, for example, in WO 02 / 038531, but by esterifying sebacic acid with at least one diol of the formula HO-A-OH in the presence of monohydric alcohols Rj-OH and optionally R2-OH as terminal groups, and of an esterification catalyst. The chain length m or the average molecular weight of the polyester plasticizers is adjusted by appropriately selecting the stoichiometric amounts of sebacic acid, the at least one diol HO-A-OH, and the mono-ol(s) Rj-OH and R2-OH.

[0025] The usual catalysts used for esterification are mineral acids such as sulfuric acid and phosphoric acid; organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid; amphoteric catalysts, in particular titanium, tin(IV) or zirconium compounds such as tetraalkoxytitanium, e.g. tetrabutoxytitanium, and tin(IV) oxide.

[0026] The esterification catalyst is used in an effective amount which is usually in the range of 0.001 to 10 wt.%, preferably 0.005 to 2 wt.%, for example 0.01 wt.% or 0.05 wt.%, based on the sum of acid and alcohol components.

[0027] Further suitable processes for preparing the compounds of general formula (I) by esterification are described, for example, in US 6,310,235, US 5,324,853, DE-A 2612355 or DE-A 1945359. Reference is made to these documents.

[0028] The esterification can be carried out at ambient pressure or at reduced or elevated pressure. Esterification is preferably carried out at ambient pressure or reduced pressure.

[0029] The esterification can be carried out in the absence of an added solvent or in the presence of an organic solvent. If the esterification is carried out in the presence of a solvent, it is preferably an organic solvent that is inert under the reaction conditions. These include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons, or ethers. The solvent is preferably selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dibutyl ether, THF, dioxane, and mixtures thereof.

[0030] Esterification is usually carried out in a temperature range of 50 to 250 ° C.

[0031] If the esterification catalyst is selected from organic acids or mineral acids, the esterification is usually carried out in a temperature range of 50 to 160 °C.

[0032] If the esterification catalyst is selected from amphoteric catalysts, the esterification is usually carried out in a temperature range of 100 to 250 °C.

[0033] Esterification can occur in the absence or presence of an inert gas. An inert gas is generally defined as a gas that, under the given reaction conditions, does not react with the reactants, reagents, solvents, or the resulting products.

[0034] For example, sebacic acid, diol and monool as well as isopropyl butyl titanate as esterification catalyst are placed in a reaction vessel, initially heated to 100 °C to 140 °C while passing nitrogen through it, and homogenized by stirring. The reaction mixture is then heated to 160 °C to 240 °C at atmospheric pressure. Esterification with elimination of water begins at approximately 150 °C. The water of reaction formed is separated off by distillation via a column. Alcohol components occurring at the top of the column are separated off and recycled until no more water can be distilled off under atmospheric pressure. The reaction mixture is then stirred at 200 °C to 245 °C at atmospheric pressure to remove residual water and excess alcohols while passing through an increased stream of nitrogen until no more distillate is formed.The reaction mixture is then stirred by reducing the pressure in the vessel to 10 mbar and increasing the nitrogen flow until no further distillate is produced. It is also possible to produce the polyesters according to the invention using other processes generally known for polyester production, for example, by transesterification.

[0035] The starting materials used to prepare the compounds of general formula (I) are known and commercially available. An advantage of the compounds according to the invention and their preparation is that sebacic acid can be obtained from castor oil and thus from renewable raw materials.

[0036] The invention also relates to the use of the polyesters of formula (I) according to the invention as plasticizers for plastics, in particular as plasticizers for PVC homopolymers or copolymers. In addition to their use as plasticizers for plastics, compounds of general formula (I) are suitable as plasticizers in plastisols, in particular in plastisols containing PVC homopolymers or copolymers.

[0037] In principle, other known plasticizers can be used in a plastic or plastisol in addition to the plasticizer according to the invention to optimize the properties of the plastic or plastisol. Preferably, no additional plasticizer is used.

[0038] molding compounds

[0039] The invention also provides a molding composition comprising the plasticizer of the formula (I) according to the invention and at least one polymer. The molding composition according to the invention may also contain a mixture of polymers. The molding composition containing the plasticizer composition according to the invention usually contains at least one thermoplastic. The molding composition according to the invention may also contain a mixture of thermoplastics. In a preferred embodiment, the polymer contained in the molding composition is a thermoplastic polymer.

[0040] All thermoplastically processable polymers are suitable as thermoplastic polymers. In particular, these thermoplastic polymers are selected from: homopolymers or copolymers which, in polymerized form, contain at least one monomer selected from C2-C 10Monoolefins, such as ethylene or propylene, 1,3-butadiene, 2-chloro-l,3-butadiene, vinyl alcohol and its C2-C 10 -alkyl esters, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates with alcohol components of branched and unbranched C1-C10 alcohols, vinyl aromatics such as styrene, (meth)acrylonitrile, 2,3-ethylenically unsaturated mono- and dicarboxylic acids, and maleic anhydride;

[0041] Homo- and copolymers of vinyl acetals;

[0042] polyvinyl esters;

[0043] Polycarbonates (PC);

[0044] Polyesters such as polyalkylene terephthalates, polyhydroxyalkanoates (PHA), polybutylene succinates (PBS), polybutylene succinate adipates (PBSA), polylactide (PLA);

[0045] polyethers;

[0046] polyether ketones; thermoplastic polyurethanes (TPU);

[0047] polysulfides;

[0048] Polysulfones; and mixtures thereof.

[0049] Examples include polyacrylates with identical or different alcohol residues from the group of C4-C8 alcohols, particularly butanol, hexanol, octanol and 2-ethylhexanol, polymethyl methacrylate (PMMA), methyl methacrylate-butyl acrylate copolymers, acrylonitrile-butadiene-styrene copolymers (ABS), ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EPDM), polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-styrene-acrylate (ASA), styrene-butadiene-methyl methacrylate copolymers (SBMMA), styrene-maleic anhydride copolymers, styrene-methacrylic acid copolymers (SMA), polyoxymethylene (POM), polyvinyl alcohol (PVAL), polyvinyl acetate (PVA), polyvinyl butyral (PVB), polycaprolactone (PCL), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polylactic acid (PLA), ethyl cellulose (EC), cellulose acetate (CA), cellulose propionate (CP) or cellulose acetate / butyrate (CAB).The at least one thermoplastic polymer contained in the molding composition according to the invention is preferably polyvinyl chloride (PVC), polyvinyl butyral (PVB), homo- and copolymers of vinyl acetate, homo- and copolymers of styrene, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides.

[0050] Depending on which thermoplastic polymer or thermoplastic polymer blend is contained in the molding compound, different amounts of plasticizer are used. The total plasticizer content in the molding compound is generally 0.5 to 300 phr (parts per hundred resin = parts by weight per hundred parts by weight of polymer), preferably 0.5 to 130 phr, and particularly preferably 1 to 100 phr.

[0051] In particular, the at least one thermoplastic polymer contained in the molding composition according to the invention is polyvinyl chloride (PVC).

[0052] Polyvinyl chloride is obtained by homopolymerization of vinyl chloride. The polyvinyl chloride (PVC) used in the invention can be produced, for example, by suspension polymerization, microsuspension polymerization, emulsion polymerization, or bulk polymerization. The production of PVC by polymerization of vinyl chloride as well as the production and composition of plasticized PVC are described, for example, in "Becker / Braun, Kunststoff-Handbuch, Volume 2 / 1: Polyvinyl Chloride," 2nd edition, Carl Hanser Verlag, Munich.

[0053] The K value, which characterizes the molar mass of the PVC and is determined according to DIN 53726, is usually between 57 and 90, preferably between 61 and 85, in particular between 64 and 80, for the PVC plasticized according to the invention.

[0054] In the context of the invention, the PVC content of the mixtures is 20 to 95 wt.%, preferably 40 to 90 wt.% and in particular 45 to 85 wt.%.

[0055] If the thermoplastic polymer in the molding compositions according to the invention is polyvinyl chloride, the total plasticizer content in the molding composition is 1 to 300 phr, preferably 5 to 150 phr, particularly preferably 10 to 130 phr, and in particular 15 to 120 phr. The present invention further relates to molding compositions comprising at least one elastomer and at least one plasticizer composition as defined above.

[0056] The elastomer present in the molding compositions according to the invention is preferably at least one natural rubber (NR), or at least one synthetically produced rubber, or mixtures thereof. Preferred synthetically produced rubbers include, for example, polyisoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile-butadiene rubber (NBR), or chloroprene rubber (CR).

[0057] Preferred are rubbers or rubber mixtures that can be vulcanized with sulfur.

[0058] In the context of the invention, the content of elastomer in the molding compositions according to the invention is from 20 to 95% by weight, preferably from 45 to 90% by weight and in particular from 50 to 85% by weight.

[0059] Within the scope of the invention, the molding compounds containing at least one elastomer may contain other suitable additives in addition to the above components. For example, reinforcing fillers, such as carbon black or silicon dioxide, further fillers, a methylene donor, such as hexamethylenetetramine (HMT), a methylene acceptor, such as phenolic resins modified with cardanol (from cashew nuts), a vulcanizing or crosslinking agent, a vulcanizing or crosslinking accelerator, activators, various types of oil, anti-aging agents, and other various additives, which are, for example, blended into tire and other rubber compounds.

[0060] If the polymer in the molding compositions according to the invention is rubber, the content of the plasticizer composition according to the invention, as defined above, in the molding composition is 1 to 60 phr, preferably 1 to 40 phr, particularly preferably 2 to 30 phr.

[0061] Molding compound additives: Within the scope of the invention, the molding compounds containing at least one thermoplastic polymer may contain other suitable additives. For example, stabilizers, lubricants, fillers, pigments, flame retardants, light stabilizers, blowing agents, polymeric processing aids, impact modifiers, optical brighteners, antistatic agents, or biostabilizers may be included.

[0062] Some suitable additives are described in more detail below. However, the examples listed do not represent a limitation of the inventive molding compounds, but serve merely as illustrations. All content data are given in wt. % based on the total molding compound.

[0063] All common PVC stabilizers in solid and liquid form can be used as stabilizers, for example common Ca / Zn, Ba / Zn or Sn stabilizers as well as acid-binding layered silicates such as hydrotalcite.

[0064] The molding compositions according to the invention may have a stabilizer content of 0.05 to 7%, preferably 0.1 to 5%, particularly preferably 0.2 to 4% and in particular 0.5 to 3%.

[0065] Lubricants reduce the adhesion between the plastics to be processed and metal surfaces and should counteract frictional forces during mixing, plasticizing and forming.

[0066] The molding compositions of the invention can contain any of the lubricants customary for processing plastics as lubricants. Examples of suitable lubricants include hydrocarbons such as oils, paraffins, and PE waxes; fatty alcohols with 6 to 20 carbon atoms; ketones; carboxylic acids such as fatty acids and montanic acid; oxidized PE wax; metal salts of carboxylic acids; carboxylic acid amides; and carboxylic acid esters, for example, with the alcohols ethanol, fatty alcohols, glycerol, ethanediol, pentaerythritol, and long-chain carboxylic acids as the acid component.

[0067] The molding compositions according to the invention can contain a lubricant content of 0.01 to 10%, preferably 0.05 to 5%, particularly preferably 0.1 to 3%, and especially 0.2 to 2%. Fillers primarily positively influence the compressive, tensile, and flexural strength, as well as the hardness and heat resistance of plasticized PVC.

[0068] Within the scope of the invention, the molding compounds may also contain fillers, such as carbon black and other inorganic fillers, such as natural calcium carbonates, for example, chalk, limestone, and marble; synthetic calcium carbonates, dolomite, silicates, silicic acid, sand, diatomaceous earth, and aluminum silicates such as kaolin, mica, and feldspar. Calcium carbonates, chalk, dolomite, kaolin, silicates, talc, or carbon black are preferably used as fillers.

[0069] The molding compositions according to the invention may have a filler content of 0.01 to 80%, preferably 0.1 to 60%, particularly preferably 0.5 to 50% and in particular 1 to 40%.

[0070] The molding compositions according to the invention may also contain pigments in order to adapt the resulting product to different applications.

[0071] Both inorganic and organic pigments can be used within the scope of the present invention. Examples of inorganic pigments that can be used include cobalt pigments, such as CoO / Al2O3, and chromium pigments, such as Cr2O3. Examples of organic pigments that can be used include monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, and dioxazine pigments.

[0072] The molding compositions according to the invention may have a pigment content of 0.01 to 10%, preferably 0.05 to 5%, particularly preferably 0.1 to 3% and in particular 0.5 to 2%.

[0073] To reduce flammability and smoke development during combustion, the molding compounds of the invention may also contain flame inhibitors. Examples of flame inhibitors that can be used include antimony trioxide, phosphate esters, chlorinated paraffin, aluminum hydroxide, and boron compounds.

[0074] The molding compositions according to the invention may have a flame inhibitor content of 0.01 to 10%, preferably 0.1 to 8%, particularly preferably 0.2 to 5% and in particular 0.5 to 2%.

[0075] In order to protect articles produced from the molding compositions according to the invention from damage in the surface area due to the influence of light, the molding compositions can also contain light stabilizers, e.g. UV absorbers.

[0076] Light stabilizers which can be used in the context of the present invention are, for example, hydroxybenzophenones, hydroxyphenylbenzotriazoles, cyanoacrylates or so-called "hindered aminine light stabilizers" (HALS), such as the derivatives of 2,2,6,6-tetram methyl piperidine.

[0077] The molding compositions according to the invention may contain light stabilizers, e.g. UV absorbers, of 0.01 to 7%, preferably 0.1 to 5%, particularly preferably 0.2 to 4% and in particular 0.5 to 3%.

[0078] Applications molding compound

[0079] The molding compound according to the invention is preferably used for the production of molded articles and films. These include, in particular, housings for electrical appliances, such as kitchen appliances and computer housings; tools; apparatus; pipelines; cables; hoses, such as plastic hoses, water and irrigation hoses, industrial rubber hoses, or chemical hoses; wire sheathing; window profiles; components for vehicle construction, such as body components, vibration dampers for engines; tires; furniture, such as chairs, tables, or shelves;

[0080] Foam for upholstery and mattresses; tarpaulins, such as truck tarpaulins, tent tarpaulins, or roofing membranes; seals; composite films, such as films for laminated safety glass, especially for vehicle and window panes; records; artificial leather; packaging containers; adhesive tape films or coatings. The molding compound of the invention is also suitable for the production of molded articles and films that come into direct contact with humans or foodstuffs. These primarily include medical devices, hygiene products, food packaging, products for interior use, toys and childcare items, sports and leisure products, clothing, or fibers for fabrics, and the like.

[0081] The medical products that can be produced from the molding compound according to the invention include, for example, tubes for enteral nutrition and hemodialysis, ventilation tubes, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves or breathing masks.

[0082] The food packaging that can be produced from the molding compound according to the invention includes, for example, cling film, food tubes, drinking water tubes, containers for storing or freezing food, lid seals, closure caps, crown corks or artificial wine corks.

[0083] The products for the interior area that can be produced from the molding composition according to the invention are, for example, floor coverings that can be homogeneous or composed of several layers consisting of at least one foamed layer, such as floor coverings, sports floors or luxury vinyl tiles (LVT), artificial leather, wall coverings or foamed or non-foamed wallpapers in buildings or paneling or console covers in vehicles.

[0084] The toys and childcare articles that can be produced from the molding compound according to the invention include, for example, dolls, inflatable toys such as balls, toy figures, toy animals, anatomical models for training, modeling clay, swimming aids, stroller covers, changing mats, hot water bottles, teething rings or bottles.

[0085] Examples of sports and leisure products that can be produced from the molding composition according to the invention include exercise balls, exercise mats, seat cushions, massage balls and rollers, shoes or shoe soles, balls, air mattresses, or drinking bottles. Clothing that can be produced from the molding compositions according to the invention includes, for example, (coated) textiles, such as latex clothing, protective clothing, or rainwear, such as rain jackets or rubber boots.

[0086] N ich tP VC- An anwendungen

[0087] In addition, the present invention includes the use of the plasticizer composition according to the invention as an assistant or / and in assistants selected from: calendering assistants; rheology assistants; surface-active compositions such as flow and film-forming assistants, defoamers, antifoams, wetting agents, coalescing agents and emulsifiers; lubricants such as lubricating oils, lubricating greases and lubricating pastes; quenchers for chemical reactions; phlegmatizing agents; pharmaceutical products; plasticizers in adhesives or sealants; impact modifiers and extenders.

[0088] In the simplest case, the molding compound according to the invention is a plastisol, i.e. a suspension of finely powdered polymer in liquid plasticizer. In general, the dissolution rate of the polymer in the liquid plasticizer is very low at room temperature. When the suspension of finely powdered polymer in liquid plasticizer is heated, a largely homogeneous phase forms between polymer and plasticizer. The individual isolated plastic aggregates swell and combine (gel) to form a three-dimensional, highly viscous gel. This process is generally referred to as gelling and takes place above a certain minimum temperature. The introduction of the heat required for this can be controlled by selecting the parameters temperature and / or residence time. The faster the gelling process takes place (indicated here by the dissolution temperature, i.e.the lower this is, the faster the plastisol gels), the lower the temperature (at the same residence time) or the residence time (at the same temperature) can be selected.

[0089] The above-mentioned products are manufactured in the usual and known manner from the molding compound by shaping and gelling, typically by heating in a mold (in the simplest case a layer of molding compound) until gelling is complete.

[0090] Plastisols can be formed into the finished product shape at ambient temperature using various known processes, such as coating, casting (such as tray casting or rotational casting), dipping, printing (such as screen printing), injection molding, and the like. Gelation then occurs through heating, resulting in a homogeneous, more or less flexible product upon cooling.

[0091] Examples

[0092] The following materials were used in the examples:

[0093] I. Preparation of compounds l.la to I.21, l.23a to I.24 and II.1

[0094] A 1.6 L reactor vessel equipped with a triple cross-beam stirrer, a column, and a water separator on the column was filled with the starting materials listed in Table 1. The reaction mixture was heated to reflux (TI) under a nitrogen flow of 0.5–1 L / h, and the resulting reaction water was removed from the reaction mixture. The reaction temperature (TI) and the nitrogen flow were adjusted so that water was removed from the reaction mixture without removing too much organic matter, while still allowing the reaction to proceed under reflux. The organic matter that was distilled off was separated from the water and returned to the reaction mixture. The reaction mixture was heated to reflux until no more water was removed.

[0095] In the next step, the catalyst Tyzor® TPT-20B (0.07 wt%) was added, and the reaction was continued for two hours with a nitrogen flow of 10 L / h under distillation (T2). The remaining alcohol was then distilled off under a further nitrogen flow and reduced pressure (up to 10 mbar) (T3), yielding the product as a residue.

[0096] Preparation of compound 1.22 (comparative experiment from EP 4116373, Example 7)

[0097] The starting materials sebacic acid, 1,3-butanediol, and 1,6-hexanediol listed in Table 1, Compound 1.22, were initially charged to a 1.6 L reactor vessel. The mixture was initially impermeable. After heating for 12 minutes (bath: 117 °C, bottom: 56 °C), it could be stirred gently. Reflux at 167 °C (bath: 208 °C, stirrer 320 rpm). The reaction mixture distilled from 175 °C under nitrogen (1 L / h). The distillate was cloudy and drained from the water separator in a slightly oily state. The heating was continued up to 220 °C (bath: 221 °C, distillation time 2 h 10 min until the target temperature was reached). 85 mL of distillate were separated. Then the 2-ethylhexanol with the dissolved catalyst was added over a period of 5 minutes. The remaining reaction water (another 7 mL) was then removed at 220°C for another 4 hours and 40 minutes. Reaction ended.

[0098] The remaining low-boiling components were removed under nitrogen (> 5 L / h) and at up to 15 mbar. Distillate weight at the end of the reaction: 98 g.

[0099] Product weight: 565g

[0100] Table 1: Materials, quantities and temperatures for examples 1.1a to 1.21, 1.23a to 1.24 and II.1

[0101]

[0102]

[0103]

[0104]

[0105] belle 2: Properties of the compounds prepared

[0106] compare the two pie

[0107] belle 2 (continued)

[0108] rgl ei ch s beis pie

[0109] belle 2 (continued)

[0110] compare the two pie

[0111] II. General description of the measurement methods for plasticizers

[0112] II. a) Dissolution temperature:

[0113] To determine the dissolution temperature of the disclosed plasticizer compositions, approximately 10 grams of a mixture are prepared according to the following recipe. The mixture is stirred with a pipette, and then approximately 30 drops of the homogeneous mixture are immediately added to the plate-on-plate measuring system:

[0114] The viscosity measurements are carried out using a heated oscillation and rotation rheometer MCR 302 from Anton Paar in a rotation test.

[0115] Measuring system: plate / plate d=50 mm

[0116] Shear rate D: 10 (1 / s)

[0117] Gap width: 0.25 mm

[0118] Starting temperature: 30° C

[0119] Temperature profile: 30 - 180 ° C

[0120] Temperature increase: 5 ° C / min

[0121] Value recording: every 3 seconds

[0122] The measurement is performed in two ramps. The first ramp, lasting 120 s at D=10 (1 / s) and 30°C, serves only to temper the sample. The second ramp, at D=10 (1 / s) and a continuous temperature increase of 5°C min, is the actual measurement. The measurement is aborted manually after the viscosity maximum has been exceeded. The temperature at which the viscosity maximum is reached is determined as the result of the measurement. These measurements are performed four times in total, and the arithmetic mean of all four measurements is used as the final result.

[0123] II. b) Molar mass of plasticizers by GPC: Sample preparation:

[0124] Approximately 20 mg of the sample to be analyzed is dissolved in 10 ml of the eluent (THF) overnight. All sample solutions are filtered through a Macherey-Nagel PTFE (0.2 μm) filter before injection. The sealed sample vials are placed in an autosampler.

[0125] Experimental conditions:

[0126] An Agilent 1200 HPLC system, consisting of an isocratic pump, vacuum degasser, autosampler, and a column oven (35°C), was used to measure the GPC data. A Differential Refractive Index (DRI) and an Ultra Violet (UVW) detector were used as detectors. Data collection and processing of the conventional SEC data were performed using WinGPC Unichrom, build 9666, software from PSS (Polymer Standard Services). A combination of three PLgel MIXED-E columns (7.5 x 300 mm, 3µ) from Agilent was connected in series. THF was used as the eluent at a flow rate of 1 mL / min. 100µL of each sample solution was injected. Narrowly distributed polystyrene standards from Polymer Standard Services with a molecular weight between M = 266 and M = 50,400 g / mol were used for calibration. Molar masses outside this range are extrapolated. The lowest possible integration limit is set at 23.9 ml (M=256 g / mol).(Lower molecular weights cannot be determined due to possible polymer additives or solvent contamination.)

[0127] II. c) Stoichiometry of the individual components of the plasticizers using the 1H-NMR method:

[0128] The stoichiometry of the individual components in the plasticizer (“incorporation ratio”) is determined by means of X H-NMR spectroscopy. The spectra were measured on a Bruker Avance III 400 spectrometer, with a measurement frequency of 400.33 MHz for J H. The spectrometer is equipped with an inverse 5 mm broadband probe head with z-gradient. For the measurement, the sample is dissolved in approximately 700 pL of deuterated chloroform (CDCl3, Eurisotop GmbH) and transferred into a 5 mm NMR sample tube. Tetramethylsilane (TMS, Eurisotop GmbH) is added as an internal standard for referencing the chemical shift. The ID JH NMR spectra were recorded at room temperature using a zg30 pulse program (direct excitation with a 30° pulse) and 64k data points. 64 transients were summed per spectrum, and the relaxation delay (Dl) was set to 5 seconds. Bruker's TopSpin software version 4.0.9 was used for processing. 32k data points and an exponential window function with a line broadening of 0.3 Hz were used. Automatic baseline correction with a polynomial of 5 was performed for each spectrum. Phase correction and integration were performed manually by the user.

[0129] The composition is determined using the NMRQuant program. The integral values ​​are set in a relative ratio, taking into account the protons that generate the signal, and normalized to 100%.

[0130] III. Production of soft PVC films with the plasticizers according to the invention

[0131] Using the plasticizers according to the invention, soft PVC films were produced as test specimens according to the following recipe:

[0132] For this purpose, 150 g of PVC (homopolymer suspension PVC, brand name Inovyn® 271 PC), 90 g of plasticizer, and 3 g of Ba / Zn stabilizer, brand name Baerostab® UBZ 760 XLP RF, were mixed with a hand mixer at room temperature. The mixture was then plasticized on an oil-heated laboratory mixing mill (Collin, automatic mill type W250M, diameter: 252 mm, width: 450 mm) and processed into a rolled sheet. The temperature of both rolls was 180 °C each; the speeds were 15 rpm (front roll) and 12 rpm (rear roll); the rolling time was 5 minutes. The roll gap was set to 0.5 mm. This produced a rolled sheet with a thickness of 0.53 mm. The cooled rolled sheet was then pressed at a temperature of 190 °C and a pressure of 150 bar within 180 s on a press (laboratory plate press 400 P, Collin) to form a soft PVC film with a thickness of 0.50 mm.While maintaining the pressing pressure, the press film was cooled to approximately 40°C within 10 minutes.

[0133] IV. General description of the measurement methods for soft PVC test specimens

[0134] IV. a) Shore A hardness

[0135] The measurement is carried out in accordance with DIN EN ISO 868, Oct. 2003. A total of 22 pieces measuring 49 x 49 mm are punched out of the films produced as described above under III. using a suitable punch. These are placed in a press frame (dimensions 400 x 400 mm; thickness 10 mm) without any air bubbles, which contains a total of 16 cavities for the production of Shore A test specimens. Each cavity has internal dimensions of 50 x 50 mm. After loading the frame, the films are pressed between two highly polished, chrome-plated brass press plates measuring 400 x 400 mm on a Collin 400 P laboratory plate press at 185 °C and 200 bar for a total of 15 minutes to a thickness of 2 mm and then cooled. The test specimens thus produced are then conditioned for 7 days in a climate chamber at 23 ° C and approximately 50 % humidity before measurement.

[0136] A Hildebrand HDD-2 durometer is used to measure Shore A hardness. Ten readings are taken on a test specimen after 15 seconds of penetration time.

[0137] IV. b) Film volatility

[0138] To determine the film volatility of the plasticizers, four pieces of film (150 x 100 mm) are cut from the pressed films obtained as described under III., perforated, and weighed. The films are suspended on a rotating star-shaped wire holder in a Heraeus Type 5042 E drying oven set to 130°C. The oven is supplied with 800 l / h of fresh air, corresponding to 18 air changes per hour. The air inlet is in the floor with a metal sintered plate, which ensures a laminar air flow from bottom to top. An opening is located in the ceiling of the drying oven through which the air can then escape. After 24 hours, the films are removed and weighed again. The weight loss in percent indicates the film volatility of the plasticizers.

[0139] IV. c) Compatibility of plasticizers

[0140] To determine compatibility, 10 test specimens (film pieces) measuring 75 x 110 x 0.5 mm are cut from the pressed films produced as described in III. These film pieces are punched on the wide side, labeled and weighed. The test specimens produced in this way are then hung on a metal frame made of stainless material and placed in a glass basin. To avoid mutual influences, only test specimens with the same composition may be stored in a glass basin. The glass basins are filled with demineralized water to a level of approximately 3 cm. Care must be taken that the test specimens are a further 2 cm above the water surface and do not touch the water. The glass vessels are then hermetically sealed and placed in an oven with internal temperature control. The test is carried out under conditions of 70°C and 100% rel.Humidity in the test vessels for a total of 28 days. After 1, 3, 7, 14 and 28 days, two test specimens are removed and hung freely in the air for 1 hour. These films are then cleaned in the fume hood with a cloth soaked in methanol. The films are then dried freely in a drying cabinet (natural convection) at 80 °C for 16 hours. After removal from the drying cabinet, the films are left to cool freely in the air for 1 hour and are then weighed. The test result given in each case was the arithmetic mean of the weight changes for the samples before they were placed in the heating cabinet.

[0141] In addition to the gravimetric evaluation, a visual and tactile assessment of the films is performed. The following assessment table is used: 0 dry touch, the film is smooth and dry (best compatibility)

[0142] 1 Dull grip: The film is still dry, a small amount of plasticizer remains on the surface, resulting in a dull grip. Fingerprints are visible.

[0143] 2 sticky feel, plasticizer has noticeably leaked out onto the surface, fingerprints are easily and clearly visible.

[0144] 3 Weak, dry coating; visible to the naked eye.

[0145] 4 weak, liquid or greasy coating.

[0146] 5 strong, dry surface.

[0147] 6 heavy, greasy coating.

[0148] IV. d) HCI residual stability

[0149] The determination of residual HCl stability is carried out according to DIN EN 60811-405 (VDE 0473-811-405) (December 2012). A metal block thermostat from Liebisch Labortechnik is used as the test device at a test temperature of 200 °C. A triplicate determination is always performed. Approximately 50 mg of the rolled foil is weighed, cut to a length of 3 cm, and placed in the lower part of the glass tube. A strip of indicator paper (litmus paper) approximately 10 mm long is placed at the upper end of the glass tube, leaving approximately 2 mm protruding. The prepared glass tubes are placed in the metal block, and the time until a color change to red occurs is recorded. The arithmetic mean is calculated from the three measured values ​​of the three samples.

[0150] IV. e) Cold fracture temperature

[0151] The cold fracture temperature test is performed on test specimens obtained from the pressed films produced as described under III. The test is based on the draft of DIN 53372 from 1981, to which reference is made for further details. The dimensions and number of test specimens are in accordance with the specifications of this draft of the DIN standard (length 60 mm, width 15 mm, thickness exactly 0.50 mm). The test specimens must be stored at room temperature for at least 4 days before testing.

[0152] In contrast to the aforementioned draft of DIN 53372, the hammers here do not fall vertically onto the test specimen loops. Instead, the hammers are mounted on a shaft and, after the impact weights are triggered, fall in a circular arc from the same height (= distance from the test specimen) onto the test loops. Six identical test specimens are tested simultaneously in a row.

[0153] The freezer is set to an expected starting temperature, and the sample carrier ("bomb") containing the test specimens is inserted. To condition the test specimens, they are held at a temperature of 1 hour per test temperature. For evaluation, only those test loops that have completely broken into two or more pieces are considered defective. To determine the cold fracture temperature, at least one row of six test specimens must be considered completely broken, and one row of six must be considered completely unbroken. The temperature interval for each test is 5 °C. The cold fracture temperature is calculated according to the formula in the draft of DIN standard 53372 (1981).

[0154] IV. f) Tensile test properties

[0155] This test is used to determine the parameters elongation at break s D , breaking stress n band stress value at 100% elongation. For this purpose, Type 2 test specimens according to DIN EN ISO 527-3 are measured on the Zwick / Z 2.5 tensile testing machine. The test specimens are 150 mm long, 15 mm wide, and approximately 0.50 mm thick. The test specimens are punched out of the pressed films produced as described in III. using a punch. Before testing, the test specimens are conditioned for 7 days in a climate chamber under standard conditions. It is important to ensure that exactly 7 days elapse between the production of the pressed films and the tensile test. Conditioning takes place at 23 °C + / - 1.0 °C and 50% + / - 5 RH according to DIN EN ISO 291.

[0156] The tensile tests are carried out according to DIN EN ISO 527, Parts 1 + 3.

[0157] Each measurement consists of testing 10 individual specimens.

[0158] The measuring length of 100 mm is determined by the free clamping length of the specimen between the clamping jaws. The test speed is 100 mm / min.

[0159] Within the measuring length, the average thickness is determined from 5 individual values.

[0160] The strain and the 100% modulus are measured by changing the crosshead travel. V. Results

[0161] The values ​​measured on the films produced as described in Section III (with the plasticizers produced as described in Section I) are summarized in Table 3.

[0162] Table 3: Properties of the test specimens

[0163] Comparison example

[0164] Table 3 (continued)

[0165] Comparison example

[0166] Table 3 (continued)

[0167] Compare this to pie

[0168] The examples show that the plasticizers according to the invention lead to an optimized combination of good cold fracture properties with low volatility, without exhibiting noticeable disadvantages in other typical properties of polyester plasticizers or polymers plasticized therewith.

Claims

Patent claims:

1. Polyester plasticizers of formula (I): where Rj and R2 are alkyl radicals having 8 or 9 carbon atoms, G is a -(CH2)8- group, A is an alkylene radical and m is a number from 1 to 10.

2. Polyester plasticizer according to claim 1, characterized in that Rj and R2n are octyl, 2-ethylhexyl, or isononyl.

3. Polyester plasticizer according to one of claims 1 or 2, characterized in that Rj and R2 are identical.

4. Polyester plasticizer according to one of claims 1 to 3, characterized in that A is a C2-C 12 -alkylene radical.

5. Polyester plasticizer according to one of claims 1 to 4, characterized in that the two ester bonds at A are located on directly adjacent carbon atoms.

6. Polyester plasticizer according to one of claims 1 to 5, characterized in that A is either exclusively 1,2-propylene or exclusively 1,2-pentylene.

7. Polyester plasticizer according to one of claims 1 to 6, characterized in that m is a number from 2 to 4.

8. Polyester plasticizer according to one of claims 1 to 7, characterized in that m is 3.

9. A molding composition comprising at least one polymer and a plasticizer as defined in claims 1 to 8.

10. Moulding composition according to claim 9, wherein the polymer is a thermoplastic polymer selected from Homo- or copolymers containing at least one polymerized monomer selected from C2-C 10 -monoolefins, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and its C2-C 10-alkyl esters, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of Cj-Cjo alcohols, vinyl aromatics, (meth)acrylonitrile, maleic anhydride and 2,3-ethylenically unsaturated mono- and dicarboxylic acids, Homo- and copolymers of vinyl acetals, polyvinyl esters, polycarbonates, Polyesters, polyethers, Polyetherketones, thermoplastic polyurethanes, polysulfides, polysulfones, polyethersulfones, Cellulose alkyl esters, and mixtures thereof.

11. Molding compound according to claim 10, wherein the thermoplastic polymer is selected from polyvinyl chloride (PVC), polyvinyl butyral (PVB), homo- and copolymers of vinyl acetate, homo- and copolymers of styrene, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides.

12. A molding composition according to claim 11, wherein the thermoplastic polymer is polyvinyl chloride (PVC).

13. Molding composition according to one of claims 9 to 12, wherein the content of the plasticizer in the molding composition is 1.0 to 300 phr.

14. Molding composition according to claim 9, wherein the polymer is an elastomer, preferably selected from natural rubbers, synthetic rubbers and mixtures thereof.

15. A molding composition according to claim 14, wherein the content of the plasticizer in the molding composition is 1.0 to 60 phr.

16. Use of a plasticizer as defined in any one of claims 1 to 8 as a plasticizer for thermoplastic polymers and elastomers.

17. Use of a molding composition as defined in any one of claims 9 to 15 for producing molded articles and films.

18. A process for the preparation of a plasticizer as defined in any one of claims 1 to 8 by catalytic esterification of a mixture of sebacic acid, at least one diol HO-A-OH and at least one mono-ol (when R1=R2) or two mono-ols Rj and R2, wherein the stoichiometry of the starting materials is selected so that the desired degree of polymerization m is established stoichiometrically.

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