DE102015207291A1 - Plasticizer composition containing furan derivatives and 1,2-cyclohexanedicarboxylic acid ester - Google Patents

Abstract

The present invention relates to a plasticizer composition containing at least one furan derivative and at least one 1,2-cyclohexanedicarboxylic acid ester, molding compositions containing a thermoplastic polymer or an elastomer and such a plasticizer composition, and the use of these plasticizer compositions and molding compositions.

Description

BACKGROUND OF THE INVENTION

The present invention relates to a plasticizer composition containing at least one furan derivative and at least one 1,2-cyclohexanedicarboxylic acid ester, molding compositions containing a thermoplastic polymer or an elastomer and such a plasticizer composition, and the use of these plasticizer compositions and molding compositions.

STATE OF THE ART

To achieve desired processing or application properties, so-called plasticizers are added to a large number of plastics in order to make them softer, more flexible and / or more elastic. In general, the use of plasticizers serves to shift the thermoplastic range of plastics to lower temperatures in order to obtain the desired elastic properties in the range of lower processing and operating temperatures.

Polyvinyl chloride (PVC) is one of the most widely produced plastics in terms of quantity. Due to its versatile applicability, it is found today in a variety of products of daily life. PVC is therefore given a very important economic importance. PVC is originally a hard and brittle plastic up to approx. 80 ° C, which is used as rigid PVC (PVC-U) by adding heat stabilizers and other additives. Only by the addition of suitable plasticizers can soft PVC (PVC-P) be obtained, which can be used for many applications for which rigid PVC is unsuitable.

Other important thermoplastic polymers in which plasticizers are usually used are, for. As polyvinyl butyral (PVB), homo- and copolymers of styrene, polyacrylates, polysulfides or thermoplastic polyurethanes (PU).

Whether a substance is suitable for use as a plasticizer for a particular polymer depends largely on the properties of the polymer to be plasticized. As a rule, plasticizers are desirable which have a high compatibility with the polymer to be plasticized, give it good thermoplastic properties and have only a slight tendency to evaporate and / or exude (high permanence).

There are many different compounds available on the market for softening PVC and other plastics. Due to their good compatibility with the PVC and their advantageous performance properties have been used in the past often phthalic acid with alcohols of different chemical structure as a plasticizer, such as. Diethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP). Short chain phthalates such as dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), benzyl butyl phthalate (BBP) or diisoheptyl phthalate (DIHP) are also used as fast fusers, e.g. B. in the production of so-called plastisols. In addition to the short-chain phthalates, dibenzoic acid esters such as dipropylene glycol dibenzoates can also be used for the same purpose. Another class of plasticizers with good gelling properties, such as the phenyl and Cresylester of alkyl sulfonic acids, which are available under the brand name mesamoll ^® are.

Plastisols are initially a suspension of fine-powdered plastics in liquid plasticizers. The rate of dissolution of the polymer in the plasticizer at ambient temperature is very low. Only when heated to higher temperatures, the polymer dissolves noticeably in the plasticizer. The individual isolated plastic aggregates swell and fuse to a three-dimensional highly viscous gel. This process is referred to as gelling and takes place at a certain minimum temperature, referred to as the gelling or dissolving temperature. The gelation step is not reversible.

Since plastisols are in liquid form, they are very often used for coating various materials, such. As textiles, glass fleeces, etc., used. The coating is very often composed of several layers.

In practice, when plastisol products are processed, it is therefore often the case that a layer of plastisol is applied and, immediately afterward, the plastic, in particular PVC, with the Plasticizer is gelled above the dissolution temperature, ie a solid layer consisting of a mixture of gelled, partially gelled and non-gelled plastic particles is formed. The next layer is then applied to this gelled layer and, after application of the last layer, the entire structure is completely processed by heating to higher temperatures to form the completely gelled plastic product.

In addition to plastisols, dry powdery mixtures of plasticizers and plastics can also be produced. Such dry blends, especially based on PVC, can then at elevated temperatures, for. B. by extrusion, further processed into granules or processed by conventional molding processes, such as injection molding, extrusion or calendering, the fully gelled plastic product.

Due to increasing technical and economic demands on the processing of thermoplastic polymers and elastomers, plasticizers are also desired which have good gelling properties.

In particular, in the production and processing of PVC plastisols, for example for the production of PVC coatings, it is desirable, inter alia, to have available a plasticizer with a low gelling temperature as a fast fuser ("fast fuser"). In addition, a high storage stability of the plastisol is desired, d. H. the ungelled plastisol should have no or only a slight increase in viscosity with time at ambient temperature. If possible, these properties should be achieved by adding a suitable plasticizer with rapid gelation properties, which should eliminate the need for further viscosity-reducing additives and / or solvents.

However, fast gelators usually often have a compatibility with the additierten polymers to be improved and a permanence that is also worthy of improvement. To set the desired plasticizer properties is therefore also known to use mixtures of plasticizers, for. At least one plasticizer which confers good thermoplastic properties but less well gels, in combination with at least one fast gelator.

Furthermore, there is a need to replace at least some of the phthalate plasticizers mentioned above, as they are suspected to be harmful to health. This is especially true for sensitive applications such as children's toys, food packaging or medical items.

Various alternative plasticizers with different properties for various plastics and especially for PVC are known in the prior art.

A plasticizer class known from the prior art which can be used as an alternative to phthalates is based on cyclohexanepolycarboxylic acids as described in US Pat WO 99/32427 are described. In contrast to their unhydrogenated aromatic analogues, these compounds are toxicologically harmless and can also be used in sensitive applications. The corresponding lower alkyl esters generally have fast gelling properties.

The WO 00/78704 describes selected dialkylcyclohexane-1,3- and 1,4-dicarboxylic acid esters for use as plasticizers in synthetic materials.

The US Pat. No. 7,973,194 B1 teaches the use of dibenzylcyclohexane-1,4-dicarboxylate, benzylbutylcyclohexane-1,4-dicarboxylate and dibutylcyclohexane-1,4-dicarboxylate as fast-gelling plasticizers for PVC.

Another plasticizer class are the esters of 2,5-furandicarboxylic acid (FDCS).

The WO 2012/113608 describes C ₅ dialkyl esters of 2,5-furandicarboxylic acid and their use as plasticizers. These short-chain esters are especially suitable for the production of plastisols.

The WO 2012/113609 describes C ₇ dialkyl esters of 2,5-furandicarboxylic acid and their use as plasticizers.

The WO 2011/023490 describes C ₉ dialkyl esters of 2,5-furandicarboxylic acid and their use as plasticizers.

The WO 2011/023491 describes C ₁₀ dialkyl esters of 2,5-furandicarboxylic acid and their use as plasticizers.

RD Sanderson et al. (J. Appl. Pol. Sci., 1994, Vol. 53, 1785-1793) describe the synthesis of esters of 2,5-furandicarboxylic acid and their use as plasticisers for plastics, in particular polyvinyl chloride (PVC), polyvinyl butyral (PVB), polylactic acid (PLA), polyhydroxybutyric acid (PHB) or polyalkyl methacrylate (PA-MA). Specifically, the di (2-ethylhexyl), di (2-octyl), dihexyl and dibutyl esters of 2,5-furandicarboxylic acid are described and their softening properties are characterized by dynamic mechanical thermal analyzes.

The WO 2012/026861 describes tetraesters of pentaerythritol with monocarboxylic acids and a composition containing a tetraester of pentaerythritol and di- (2-ethylhexyl) -2,5-furandicarboxylate as a plasticizer for PVC.

The present invention has for its object to provide a toxicologically acceptable plasticizer composition for thermoplastic polymers and elastomers available, on the one hand good thermoplastic properties and on the other hand good gelling properties, d. H. a low gelling temperature, gives. The plasticizer composition should thereby be particularly suitable for the provision of plastisols. The plasticizer composition is said to have a high compatibility with the polymer to be plasticized, and therefore do not tend to swell at all or only to a slight extent during use, whereby the elastic properties of the plasticized plastics produced using these plasticizers are retained over longer periods of time.

• a) wenigstens eine Verbindung der allgemeinen Formel (I),
  
  worin X für *-(C=O)-O-, *-(CH₂)_n-O- oder *-(CH₂)_n-O-(C=O)- steht, wobei * den Verknüpfungspunkt mit dem Furanring darstellt und n den Wert 0, 1 oder 2 aufweist; und R¹ und R² unabhängig voneinander für einen unverzweigten oder verzweigten C₈-Alkylrest stehen,
• b) wenigstens eine Verbindung der allgemeinen Formel (II),
  
  worin R³ und R⁴ unabhängig voneinander ausgewählt sind unter verzweigten und unverzweigten C₇-C₁₂-Alkylresten.

This object is surprisingly achieved by a plasticizer composition containing

• a) at least one compound of the general formula (I),
  
  where X is * - (C = O) -O-, * - (CH ₂ ) _n -O- or * - (CH ₂ ) _n -O- (C = O) -, where * is the point of attachment to the furan ring and n is 0, 1 or 2; and R ¹ and R ² independently of one another represent an unbranched or branched C ₈ -alkyl radical,
• b) at least one compound of the general formula (II),
  
  wherein R ³ and R ^{4 are} independently selected from branched and unbranched C ₇ -C ₁₂ alkyl radicals.

Another object of the invention are molding compositions containing at least one thermoplastic polymer or elastomer and a plasticizer composition as defined above and below.

Another object of the invention is the use of a plasticizer composition, as defined above and hereinafter, as a plasticizer for thermoplastic polymers, in particular polyvinyl chloride (PVC), and elastomers.

Another object of the invention is the use of a plasticizer composition, as defined above and hereinafter, as a plasticizer in plastisols.

Another object of the invention is the use of these molding compositions for the production of moldings and films.

DESCRIPTION OF THE INVENTION

• – Die erfindungsgemäßen Weichmacher-Zusammensetzungen zeichnen sich durch eine hohe Verträglichkeit mit den weichzumachenden Polymeren, insbesondere PVC, aus.
• – Die erfindungsgemäßen Weichmacher-Zusammensetzungen neigen gar nicht oder nur in geringem Umfang zum Ausschwitzen während des Gebrauchs der Endprodukte. Dadurch bleiben die elastischen Eigenschaften der unter Verwendung dieser Weichmacher-Zusammensetzungen hergestellten weichgemachten Kunststoffe auch über längere Zeiträume erhalten.
• – Die erfindungsgemäßen Weichmacher-Zusammensetzungen eignen sich in vorteilhafter Weise zur Erzielung einer Vielzahl unterschiedlichster und komplexer Verarbeitungs- und Anwendungseigenschaften von Kunststoffen.
• – Die erfindungsgemäße Weichmacher-Zusammensetzung eignet sich in vorteilhafter Weise zur Herstellung von Plastisolen.
• – Die in der erfindungsgemäßen Weichmacher-Zusammensetzung enthaltenen Verbindungen (I) eignen sich aufgrund ihrer äußerst niedrigen Lösetemperaturen nach DIN 53408 sehr gut als Schnellgelierer. Um die zum Gelieren eines thermoplastischen Polymers erforderliche Temperatur zu verringern und/oder dessen Geliergeschwindigkeit zu erhöhen, reichen bereits geringe Mengen der Verbindungen (I) in der erfindungsgemäßen Weichmacher-Zusammensetzung aus.
• – Die erfindungsgemäßen Weichmacher-Zusammensetzungen eignen sich für die Verwendung zur Herstellung von Formkörpern und Folien für sensible Anwendungsbereiche, wie Medizinprodukte, Lebensmittelverpackungen, Produkte für den Innenraumbereich, beispielsweise von Wohnungen und Fahrzeugen, Spielzeuge, Kinderpflegeartikel, etc.
• – Zur Herstellung der in den erfindungsgemäßen Weichmacher-Zusammensetzungen enthaltenen Verbindungen (I) können leicht zugängliche Edukte verwendet werden. Ein besonderer ökonomischer und ökologischer Vorteil liegt in der Möglichkeit, zur Herstellung der erfindungsgemäß eingesetzten Verbindungen (I) sowohl in großen Mengen zur Verfügung stehender petrochemischer Rohstoffe als auch nachwachsender Rohstoffe nutzen zu können. So sind beispielsweise die Ausgangsstoffe der Furankerne aus natürlich vorkommenden Kohlenhydraten, wie Cellulose und Stärke, erhältlich, wohingegen die zur Einführung der Seitenketten einsetzbaren Alkohole aus großtechnischen Verfahren zur Verfügung stehen. So kann einerseits der Bedarf an „nachhaltigen“ Produkten gedeckt werden, anderseits ist aber auch eine wirtschaftliche Herstellung möglich.
• – Die Verfahren zur Herstellung der erfindungsgemäß eingesetzten Verbindungen (I) sind einfach und effizient, wodurch diese problemlos in großtechnischem Maßstab bereitgestellt werden können.

The plasticizer compositions according to the invention have the following advantages:

• The plasticizer compositions according to the invention are distinguished by high compatibility with the polymers to be plasticized, in particular PVC.
• - The plasticizer compositions according to the invention are not at all or only to a small extent to sweat during use of the final products. As a result, the elastic properties of the plasticized plastics produced using these softener compositions are retained over extended periods of time.
• The plasticizer compositions according to the invention are advantageously suitable for achieving a large number of different and complex processing and application properties of plastics.
• The plasticizer composition according to the invention is advantageously suitable for the production of plastisols.
• - The compounds (I) contained in the plasticizer composition according to the invention are suitable because of their extremely low dissolution temperatures DIN 53408 very good as a fast gelator. In order to reduce the temperature required for gelling a thermoplastic polymer and / or to increase its gelling speed, even small amounts of the compounds (I) in the plasticizer composition according to the invention are sufficient.
• The plasticizer compositions according to the invention are suitable for use in the production of moldings and films for sensitive applications, such as medical devices, food packaging, products for the interior sector, for example of apartments and vehicles, toys, childcare articles, etc.
• - For the preparation of the compounds (I) contained in the plasticizer compositions according to the invention easily accessible starting materials can be used. A particular economic and ecological advantage lies in the possibility of being able to use both the petrochemical raw materials available as well as renewable raw materials for the preparation of the compounds (I) used according to the invention. For example, the starting materials of the furan cores are available from naturally occurring carbohydrates, such as cellulose and starch, whereas the alcohols which can be used to introduce the side chains are available from industrial processes. So on the one hand, the need for "sustainable" products can be covered, on the other hand, however, an economical production is possible.
• The processes for the preparation of the compounds (I) used according to the invention are simple and efficient, as a result of which they can be provided on a large scale without any problems.

As mentioned above, it has surprisingly been found that the compounds of the general formula (I) present in the plasticizer composition according to the invention have very low dissolution temperatures and also excellent gelling properties. So are their Lösetemperaturen after DIN 53408 significantly below the dissolution temperatures of the corresponding dialkyl esters of phthalic acid and have at least equally fast gelatinizing properties.

It has been found that the compounds (I), especially in combination with 1,2-cyclohexanedicarboxylic acid esters of the general formula (II), are suitable for improving the gelling behavior of thermoplastic polymers and elastomers. In this case, even small amounts of the compounds (I) in the plasticizer composition according to the invention are sufficient to reduce the temperature required for gelling and / or to increase the gelling speed.

In the context of the present invention, a fast gelator is understood as meaning a plasticizer which recycles a dissolving temperature DIN 53408 of less than 120 ° C. Such rapid gels are used in particular for the production of plastisols.

The term "C ₈ alkyl" includes straight and branched C ₈ alkyl groups. Preferably, C ₈ alkyl is selected from n-octyl, iso-octyl or 2-ethylhexyl. C ₈ alkyl is particularly preferably 2-ethylhexyl.

The term "C ₇ -C ₁₂ alkyl" includes straight and branched C ₇ -C ₁₂ alkyl groups. Preferably, C ₇ -C ₁₂ alkyl is selected from n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, 1-ethyl-2-methylpropyl, n-octyl, isooctyl, 2 Ethylhexyl, n-nonyl, isononyl, 2-propylhexyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl and the like. C ₇ -C ₁₂ -alkyl is particularly preferably n-octyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2-propylheptyl, n-undecyl or isoundecyl.

The groups X in the compounds of the general formula (I) preferably have the same meaning.

In a first preferred embodiment, in the compounds of the general formula (I) the groups X are both * - (C = O) -O-.

In a further preferred embodiment, in the compounds of general formula (I), the groups X are both * - (CH ₂ ) -O- (C = O) -.

In a further preferred embodiment, in the compounds of the general formula (I), the groups X are both * - (CH ₂ ) _n -O-, where n is 0, 1 or 2. More preferably, n is 1.

In the compounds of the general formula (I), the radicals R ¹ and R ² are preferably, independently of one another, an unbranched or branched C ₈ -alkyl radical selected from n-octyl, isooctyl or 2-ethylhexyl.

Particularly preferably, in the compounds of the general formula (I), the radicals R ¹ and R ² independently of one another are n-octyl or 2-ethylhexyl.

In a further particularly preferred embodiment, in the compounds of general formula (I), the radicals R ¹ and R ^{2 have the} same meaning.

In a very particularly preferred embodiment, in the compounds of the general formula (I), the radicals R ¹ and R ^{2 are} 2-ethylhexyl.

Preferred compounds of the general formula (I) are selected from
Di- (n-octyl) -2,5-furandicarboxylate,
Di-n-octyl ether of 2,5-di (hydroxymethyl) furan,
2,5-di (hydroxymethyl) furan-di-n-octanoate,
Di- (isooctyl) -2,5-furandicarboxylate,
Diisooctyl ether of 2,5-di (hydroxymethyl) furan,
2,5-di (hydroxymethyl) furan-di-isooctanoat,
Di- (2-ethylhexyl) -2,5-furandicarboxylate,
Di-2-ethylhexyl ether of 2,5-di (hydroxymethyl) furan,
2,5-di (hydroxymethyl) furan-di-2-ethylhexanoate and mixtures of two or more than two of the aforementioned compounds.

A particularly preferred compound of the general formula (I) is di- (2-ethylhexyl) -2,5-furandicarboxylate.

In a further preferred embodiment, in the compounds of the general formula (II), the radicals R ³ and R ^{4 have the} same meaning.

In the compounds of the general formula (II), the radicals R ³ and R ⁴ are preferably both 2-ethylhexyl, both isononyl or both are 2-propylheptyl.

A particularly preferred compound of the general formula (II) is di- (isononyl) -1,2-cyclohexanedicarboxylate.

By adjusting the proportions of the compounds (I) and (II) in the plasticizer composition according to the invention, the plasticizer properties can be matched to the corresponding intended use. For use in special fields of application, it may be helpful to add to the softener compositions according to the invention further plasticizers other than the compounds (I) and (II). For this reason, the plasticizer composition of the present invention may optionally contain at least one other plasticizer other than the compounds (I) and (II).

The additional plasticizer other than compounds (I) and (II) is selected from phthalic acid alkyl esters, phthalic acid alkylaralkyl esters, 1,2-cyclohexanedicarboxylic acid esters other than compounds (II), terephthalates, trimellitic acid triesters, alkyl benzoates, glycol dibenzoates, hydroxybenzoic esters, saturated mono- and dicarboxylic acids, esters of unsaturated dicarboxylic acids, amides and esters of aromatic sulfonic acids, alkylsulfonic acid esters, glycerol esters, isosorbide esters, phosphoric acid esters, citric acid triesters, alkylpyrrolidone derivatives, 2,5-furandicarboxylic acid esters other than Compound (I), 2,5-tetrahydrofurandicarboxylic acid esters, epoxidized vegetable oils and epoxidized fatty acid monoalkyl esters , Polyesters of aliphatic and / or aromatic polycarboxylic acids with at least dihydric alcohols.

Suitable dialkyl phthalates, which can be mixed in an advantageous manner with the compounds (I) and (II), independently of one another have 4 to 13 C atoms, preferably 8 to 13 C atoms, in the alkyl chains. A suitable alkyl phthalate alkylaralkyl ester is, for example, benzyl butyl phthalate. Suitable 1,2-cyclohexanedicarboxylic acid esters other than the compounds (II) each independently have 3 to 6 C atoms, preferably 4 to 6 C atoms, in the alkyl chains. Suitable terephthalic acid dialkyl esters preferably each independently have 4 to 13 C atoms, in particular 7 to 11 C atoms, in the alkyl chains. Suitable dialkyl terephthalates are, for example, di (n-butyl) terephthalates, di (2-ethylhexyl) terephthalates, di (isononyl) terephthalates or di (2-propylheptyl) terephthalates. Suitable trimellitic acid trialkyl esters preferably each independently have 4 to 13 C atoms, in particular 7 to 11 C atoms, in the alkyl chains. Suitable alkyl benzoates preferably each independently have 7 to 13 C atoms, in particular 9 to 13 C atoms, in the alkyl chains. Suitable benzoic acid alkyl esters are, for example, isononyl benzoate, isodecyl benzoate or 2-propylheptyl benzoate. Suitable dibenzoic acid esters of glycols are diethylene glycol dibenzoate and dibutylene glycol dibenzoate. Suitable esters of saturated mono- and dicarboxylic acids are, for example, esters of acetic acid, butyric acid, valeric acid, succinic acid or lactic acid and the mono- and dialkyl esters of glutaric acid, adipic acid, sebacic acid, malic acid or tartaric acid. Suitable adipic acid dialkyl esters preferably each independently have 4 to 13 C atoms, in particular 6 to 10 C atoms, in the alkyl chains. Suitable esters of unsaturated dicarboxylic acids are, for example, esters of maleic acid and of fumaric acid. Suitable alkylsulfonic acid esters preferably have an alkyl radical having 8 to 22 carbon atoms. These include, for example, phenyl or cresyl esters of pentadecylsulfonic acid. Suitable isosorbide esters are isosorbide diesters, which are preferably esterified with C ₈ -C ₁₃ -carboxylic acids. Suitable phosphoric acid esters are tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecyldiphenyl phosphate, bis (2-ethylhexyl) phenyl phosphate and 2-ethylhexyldiphenyl phosphate. In the citric acid triesters, the OH group can be present in free or carboxylated form, preferably acetylated. The alkyl radicals of the acetylated citric acid triesters preferably have, independently of one another, 4 to 8 C atoms, in particular 6 to 8 C atoms. Suitable alkylpyrrolidone derivatives having alkyl radicals of 4 to 18 carbon atoms. Suitable 2,5-furandicarboxylic acid dialkyl esters other than the compounds (I) each independently have 4 to 7 C atoms, preferably 4 to 5 C atoms, in the alkyl chains. Suitable 2,5-tetrahydrofurandicarboxylic acid dialkyl esters each independently have 7 to 13 C atoms, preferably 8 to 12 C atoms, in the alkyl chains. A suitable epoxidized vegetable oil is, for example, epoxidized soybean oil, available, for example, from Galata-Chemicals, Lampertheim, Germany. Epoxidized fatty acid monoalkyl esters, for example available under the trade name reFlex ^™ from PolyOne, USA, are also suitable. The polyesters of aliphatic and aromatic polycarboxylic acids are preferably polyesters of adipic acid with polyhydric alcohols, in particular dialkylene glycol polyadipates having 2 to 6 carbon atoms in the alkylene radical.

In all the cases mentioned above, the alkyl radicals may each be linear or branched and in each case identical or different. Reference is made to the general statements made at the outset on suitable and preferred alkyl radicals.

The content of the at least one further plasticizer other than compounds (I) and (II) in the plasticizer composition according to the invention is usually from 0 to 50% by weight. %, preferably 0 to 40 wt .-%, particularly preferably 0 to 30 wt .-% and in particular 0 to 25 wt .-%, based on the total amount of the at least one further plasticizer and the compounds (I) and (II) in the plasticizer composition.

In a preferred embodiment, the plasticizer composition according to the invention contains no other plasticizer other than the compounds (I) and (II).

The content of compounds of the general formula (I) in the plasticizer composition according to the invention is preferably from 1 to 65% by weight, more preferably from 1 to 50% by weight, very preferably from 15 to 50% by weight and in particular from 25 to 50% by weight, based on the total amount of the compounds (I) and (II) in the plasticizer composition.

In a specific embodiment of the invention, the content of compounds of the general formula (I) in the plasticizer composition according to the invention is from 25 to 65% by weight and especially from 35 to 60% by weight, based on the total amount of the compounds (I) and (II) in the softener composition. By using plasticizer compositions according to the invention, which contain the compounds I in these proportions by weight, as plasticizers in polymers, especially in PVC, particularly low Shore A values can be achieved, wherein the process volatility and / or the film volatility still in a very good Area lie.

The content of the compounds of the general formula (II) in the plasticizer composition according to the invention is usually from 10 to 99% by weight, preferably from 35 to 99% by weight, more preferably from 50 to 99% by weight, very particularly preferably from 50 to 85 wt .-% and in particular 50 to 75 wt .-%, based on the total amount of the compounds (I) and (II) in the plasticizer composition.

In a specific embodiment of the invention, the content of the compounds of the general formula (II) in the plasticizer composition according to the invention is from 35 to 75% by weight and more particularly from 40 to 65% by weight, based on the total amount of the compounds (I) and (II) in the softener composition.

In the plasticizer composition according to the invention, the weight ratio between compounds of the general formula (I) and compounds of the general formula (II) is preferably in the range from 1: 100 to 2: 1, particularly preferably in the range from 1: 100 to 1: 1, very particularly preferably in the range from 1: 6 to 1: 1 and in particular in the range from 1: 3 to 1: 1.

In the plasticizer composition of the present invention, the weight ratio between compounds of general formula (I) and compounds of general formula (II) is especially in the range of 1: 3 to 2: 1, and more particularly in the range of 1: 2 to 3: 2 , By using plasticizer compositions according to the invention which contain the compounds I and compounds II in these specific weight ratios as plasticizers in polymers, in particular in PVC, particularly low Shore A values can be achieved, the process volatility and / or film volatility still being achieved in a very good area.

molding compounds

Another object of the present invention relates to a molding composition containing at least one polymer and a plasticizer composition as defined above.

In a preferred embodiment, the polymer contained in the molding composition is a thermoplastic polymer.

• – Homo- oder Copolymere, die in einpolymerisierter Form wenigstens ein Monomer enthalten, das ausgewählt ist unter C₂-C₁₀ Monoolefinen, wie beispielsweise Ethylen oder Propylen, 1,3-Butadien, 2-Chlor-1,3-Butadien, Vinylalkohol und dessen C₂-C₁₀-Alkylestern, Vinylchlorid, Vinylidenchlorid, Vinylidenfluorid, Tetrafluorethylen, Glycidylacrylat, Glycidylmethacrylat, Acrylaten und Methacrylaten mit Alkoholkomponenten von verzweigten und unverzweigten C₁-C₁₀-Alkoholen, Vinylaromaten wie beispielsweise Styrol, (Meth)acrylnitril, α,β-ethylenisch ungesättigten Mono- und Dicarbonsäuren, und Maleinsäureanhydrid;
• – Homo- und Copolymere von Vinylacetalen;
• – Polyvinylestern;
• – Polycarbonaten (PC);
• – Polyestern, wie Polyalkylenterephthalaten, Polyhydroxyalkanoaten (PHA), Polybutylensuccinaten (PBS), Polybutylensuccinatadipaten (PBSA);
• – Polyethern;
• – Polyetherketonen;
• – thermoplastischen Polyurethanen (TPU);
• – Polysulfiden;
• – Polysulfonen;

und Mischungen davon.Suitable thermoplastic polymers are all thermoplastically processable polymers. In particular, these thermoplastic polymers are selected from:

• Homopolymers or copolymers containing in copolymerized form at least one monomer selected from C ₂ -C ₁₀ monoolefins, such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and its C ₂ -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 C ₁ -C ₁₀ -alcohols, vinylaromatics such as styrene, (meth) acrylonitrile, α, β-ethylenically unsaturated mono- and dicarboxylic acids, and maleic anhydride;
• - Homo- and copolymers of vinyl acetals;
• - polyvinyl esters;
• - polycarbonates (PC);
• Polyesters, such as polyalkylene terephthalates, polyhydroxyalkanoates (PHA), polybutylene succinates (PBS), polybutylene succinate adipates (PBSA);
• - polyethers;
• - polyether ketones;
• - thermoplastic polyurethanes (TPU);
• - polysulfides;
• - polysulfones;

and mixtures thereof.

Examples include polyacrylates having identical or different alcohol radicals from the group of C ₄ -C ₈ -alcohols, especially of 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), ethylcellulose (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.

Depending on which thermoplastic polymer or thermoplastic polymer mixture is contained in the molding composition, different amounts of plasticizer are used. As a rule, the total plasticizer content in the molding composition is 0.5 to 300 phr (parts per hundred resin = parts by weight per hundred parts by weight polymer), preferably 0.5 to 130 phr, particularly preferably 1 to 100 phr.

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

Polyvinyl chloride is obtained by homopolymerization of vinyl chloride. The polyvinyl chloride (PVC) used in the present invention can be prepared by, for example, suspension polymerization, microsuspension polymerization, emulsion polymerization or bulk polymerization. The production of PVC by polymerization of vinyl chloride and the preparation and composition of plasticized PVC are described, for example, in US Pat "Becker / Braun, Plastics Handbook, Volume 2/1: Polyvinyl chloride", 2nd edition, Carl Hanser Verlag, Munich ,

The K value, which characterizes the molecular weight of the PVC and after DIN 53726 is determined, is for the plasticized PVC according to the invention usually between 57 and 90, preferably between 61 and 85, in particular between 64 and 80.

In the context of the invention, the content of PVC of the mixtures is from 20 to 95% by weight, preferably from 40 to 90% by weight and in particular from 45 to 85% by weight.

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.

Another object of the present invention relates to molding compositions containing at least one elastomer and at least one plasticizer composition as defined above.

The elastomer contained in the molding compositions according to the invention is preferably at least one natural rubber (NR), or at least one synthetic rubber, or mixtures thereof. Preferred synthetic rubbers are For example, polyisoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile-butadiene rubber (NBR) or chloroprene rubber (CR).

Preference is given to rubbers or rubber mixtures which can be vulcanized with sulfur.

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.

In the context of the invention, the molding compositions containing at least one elastomer may contain, in addition to the above ingredients, other suitable additives. For example, reinforcing fillers such as carbon black or silica, other fillers, a methylene donor such as hexamethylenetetramine (HMT), a methylene acceptor such as cardanol (cashew nut) modified phenolic resins, a vulcanizing or crosslinking agent, a vulcanizing or crosslinking accelerator, activators , various types of oil, anti-aging agents and other various additives blended into, for example, tire and other rubber compounds.

If the polymer in the molding compounds according to the invention is rubbers, the content of the plasticizer composition according to the invention, as defined above, in the molding compound is 1 to 60 phr, preferably 1 to 40 phr, particularly preferably 2 to 30 phr.

Additives molding compound

In the context of the invention, the molding compositions 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.

In the following, some suitable additives are described in more detail. However, the examples listed do not represent a restriction of the molding compositions according to the invention, but are merely illustrative. All data on the content are in% by weight based on the total molding composition.

Suitable stabilizers are all customary PVC stabilizers in solid and liquid form, for example customary Ca / Zn, Ba / Zn, Pb or Sn stabilizers and also acid-binding phyllosilicates, such as hydrotalcite.

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

Lubricants reduce the adhesion between the plastics to be processed and metal surfaces and are intended to counteract frictional forces during mixing, plasticizing and deformation.

As a lubricant, the molding compositions of the invention may contain all the usual for the processing of plastics lubricant. For example, hydrocarbons such as oils, paraffins and PE waxes, fatty alcohols containing 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.

The molding compositions according to the invention may have a content of lubricant of from 0.01 to 10%, preferably from 0.05 to 5%, particularly preferably from 0.1 to 3% and in particular from 0.2 to 2%.

In particular, fillers have a positive influence on the compressive, tensile and flexural strength as well as the hardness and heat resistance of plasticized PVC.

In the context of the invention, the molding compositions may also fillers, such as carbon black and other organic fillers, such as natural calcium carbonates, such as chalk, limestone and marble, synthetic calcium carbonates, dolomite, silicates, silica, sand, diatomaceous earth, aluminum silicates, such as kaolin, mica and feldspar contain. The fillers used are preferably calcium carbonates, chalk, dolomite, kaolin, silicates, talc or carbon black.

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

The molding compositions according to the invention may also contain pigments in order to adapt the product obtained to different possible uses.

In the context of the present invention, both inorganic pigments and organic pigments can be used. As the inorganic pigments, for example, cobalt pigments such as CoO / Al ₂ O ₃ and chromium pigments such as Cr ₂ O ₃ may be used. Suitable organic pigments are, for example, monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments and dioxazine pigments.

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

In order to reduce the flammability and reduce the smoke during combustion, the molding compositions according to the invention may also contain flame retardants.

For example, antimony trioxide, phosphate esters, chloroparaffin, aluminum hydroxide and boron compounds can be used as flame retardants.

The molding compositions according to the invention can have a content of flame inhibitors of from 0.01 to 10%, preferably from 0.1 to 8%, particularly preferably from 0.2 to 5% and in particular from 0.5 to 2%.

In order to protect articles produced from the molding compositions according to the invention from damage in the surface region by the influence of light, the molding compositions may also comprise light stabilizers, e.g. UV absorber, included.

As light stabilizers, for example hydroxybenzophenones, hydroxyphenylbenzotriazoles, cyanoacrylates or so-called hindered aminine light stabilizers (HALS), such as the derivatives of 2,2,6,6-tetramethylpiperidine, can be used in the context of the present invention.

The molding compositions according to the invention may have a content of light stabilizers, for. As UV absorber, from 0.01 to 7%, preferably 0.1 to 5%, more preferably from 0.2 to 4% and in particular from 0.5 to 3%.

worin R¹ und R² die zuvor genannten Bedeutungen aufweisen, sind erhältlich durch ein Verfahren bei dem man

• a) gegebenenfalls 2,5-Furandicarbonsäure oder ein Anhydrid oder Säurehalogenid davon mit einem C₁-C₃-Alkanol in Gegenwart eines Katalysators unter Erhalt eines Di-(C₁-C₃-Alkyl)-2,5-furandicarboxylats umsetzt,
• b) 2,5-Furandicarbonsäure oder ein Anhydrid oder Säurehalogenid davon oder das in Schritt a) erhaltene Di-(C₁-C₃-Alkyl)-2,5-furandicarboxylat mit wenigstens einem Alkohol R¹-OH und, falls R¹ und R² unterschiedliche Bedeutung haben, zusätzlich mit wenigstens einem Alkohol R²-OH in Gegenwart wenigstens eines Katalysators unter Erhalt einer Verbindung der Formel (I.1) umsetzt.

Preparation of the compounds of the general formula (I) The following describes the preparation of the compounds of the general formula (I) which are contained in the plasticizer compositions according to the invention. Preparation of the diesters of 2,5-furandicarboxylic acid Compounds of the general formula (I.1),

wherein R ¹ and R ^{2 have} the meanings given above, are obtainable by a method in which

• a) optionally reacting 2,5-furandicarboxylic acid or an anhydride or acid halide thereof with a C ₁ -C ₃ -alkanol in the presence of a catalyst to give a di- (C ₁ -C ₃ -alkyl) -2,5-furandicarboxylate,
• b) 2,5-furandicarboxylic acid or an anhydride or acid halide thereof or the di (C ₁ -C ₃ alkyl) -2,5-furandicarboxylate obtained in step a) with at least one alcohol R ¹ -OH and, if R ¹ and R ^{2 have} different meanings, additionally with at least one alcohol R ² -OH in the presence of at least one catalyst to obtain a compound of formula (I.1) is reacted.

With regard to suitable and preferred embodiments of the radicals R ¹ and R ² , reference is made to the previous information in its entirety.

Suitable for use in step a) C ₁ -C ₃ alkanols are, for. As methanol, ethanol, n-propanol or mixtures thereof.

In step b) of the process, the 2,5-furandicarboxylic acid or the di- (C ₁ -C ₃ -alkyl) -2,5-furandicarboxylate obtained in step a) is esterified or transesterified with at least one alcohol R ¹ -OH and, if R ¹ and R ^{2 have} different meanings, additionally with at least one alcohol R ² -OH to the compounds of formula (I.1) subjected.

esterification

The conversion of the 2,5-furandicarboxylic acid (FDCS) into the corresponding di- (C ₁ -C ₃ -alkyl) -2,5-furandicarboxylates and / or ester compounds of the general formulas (I.1) can be carried out by customary methods known to the person skilled in the art respectively. This includes the reaction of at least one alcohol component selected from C ₁ -C ₃ -alkanols or the alcohols R ¹ -OH or R ² -OH, with FDCS or a suitable derivative thereof. Suitable derivatives are, for. As the acid halides and acid anhydrides. A preferred acid halide is the acid chloride. As esterification catalysts customary catalysts can be used, for. For example, mineral acids such as sulfuric acid and phosphoric acid; organic sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid; amphoteric catalysts, especially titanium, tin (IV) - or zirconium compounds, such as tetraalkoxytitans, z. As tetrabutoxytitanium, and tin (IV) oxide. The resulting in the reaction water can be removed by conventional means, for. B. by distillation, are removed. The WO 02/38531 describes a process for the preparation of esters of multibasic carboxylic acids in which a) in a reaction zone a mixture consisting essentially of the acid component or an anhydride thereof and the alcohol component is boiled in the presence of an esterification catalyst, b) the vapors containing alcohol and water are rectified c) separating the alcohol-rich fraction into the reaction zone and discharging the water-rich fraction from the process into an alcohol-rich fraction and a water-rich fraction; That in the WO 02/38531 described method and the catalysts disclosed therein are also suitable for the esterification.

The esterification catalyst is used in an effective amount, which is usually in the range of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the sum of acid component (or anhydride) and alcohol component.

Further suitable processes for the preparation of the compounds of the general formula (I.1) by means of esterification are described, for example, in US Pat US 6,310,235 . US 5,324,853 . DE-A 2612355 or DE-A 1945359 described. These documents are referred to in their entirety.

In general, the esterification of FDCS preferably takes place in the presence of the above-described alcohol components, by means of an organic acid or mineral acid, in particular concentrated sulfuric acid. In this case, the alcohol component is advantageously used at least in twice the stoichiometric amount, based on the amount of FDCS or a suitable derivative thereof in the reaction mixture.

The esterification can usually be carried out at ambient pressure or reduced or elevated pressure. Preferably, the esterification is carried out at ambient or reduced pressure.

The esterification may 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 which 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.

The esterification is usually carried out in a temperature range of 50 to 250 ° C.

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.

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

The esterification can take place in the absence or in the presence of an inert gas. An inert gas is generally understood to mean a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed.

transesterification:

The transesterification of the di- (C ₁ -C ₃ -alkyl) -2,5-furandicarboxylate to the corresponding ester compounds I.1 according to process step b) can be carried out by conventional methods known in the art. This includes the reaction of the di- (C ₁ -C ₃ ) -alkyl esters with at least one C ₈ -alkanol in the presence of a suitable transesterification catalyst.

Suitable transesterification catalysts are the customary catalysts customarily used for transesterification reactions, which are usually also used in esterification reactions. These include z. For example, mineral acids such as sulfuric acid and phosphoric acid; organic sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid; or special metal catalysts from the group of tin (IV) catalysts, for example dialkyltin dicarboxylates such as dibutyltin diacetate, trialkyltin alkoxides, monoalkyltin compounds such as monobutyltin dioxide, tin salts such as tin acetate or tin oxides; from the group of titanium catalysts, monomeric and polymeric titanates and titanium chelates such as tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate, triethanolamine titanate; from the group of zirconium catalysts, zirconates and zirconium chelates such as tetrapropyl zirconate, tetrabutyl zirconate, triethanolamine zirconate; and lithium catalysts such as lithium salts, lithium alkoxides; or aluminum (III), chromium (III), iron (III), cobalt (II), nickel (II) and zinc (II) acetylacetonate.

The amount of transesterification catalyst used is 0.05 to 5 wt .-%, preferably 0.1 to 1 wt .-%. The reaction mixture is preferably heated to the boiling point of the reaction mixture, so that the reaction temperature is between 20 ° C and 200 ° C, depending on the reactants.

The transesterification can be carried out at ambient pressure or reduced or elevated pressure. The transesterification is preferably carried out at a pressure of 0.001 to 200 bar, more preferably 0.01 to 5 bar. The lower-boiling alcohol split off during the transesterification is preferably distilled off continuously in order to shift the equilibrium of the transesterification reaction. The distillation column required for this purpose is usually in direct communication with the transesterification reactor, preferably it is installed directly on this. In the case of using a plurality of transesterification reactors connected in series, each of these reactors may be equipped with a distillation column or, preferably from the last boilers of the transesterification reactor cascade, the evaporated alcohol mixture may be fed via one or more manifolds to a distillation column. The recovered in this distillation higher boiling alcohol is preferably recycled back to the transesterification.

In the case of using an amphoteric catalyst whose separation generally succeeds by hydrolysis and subsequent separation of the metal oxide formed, for. B. by filtration. Preferably, after the reaction, the catalyst is hydrolyzed by washing with water and the precipitated metal oxide is filtered off. If desired, the filtrate may be subjected to further workup to isolate and / or purify the product. Preferably, the product is separated by distillation.

The transesterification of the di- (C ₁ -C ₃ -alkyl) -2,5-furandicarboxylates is preferably carried out in the presence of the alcohol component and in the presence of at least one titanium (IV) -alcoholate. Preferred titanium (IV) alcoholates are tetrapropoxy titanium, tetrabutoxy titanium or mixtures thereof. The alcohol component is preferably used at least in twice the stoichiometric amount, based on the di (C ₁ -C ₃ -alkyl) ester used.

The transesterification may be carried out in the absence or in the presence of an added organic solvent. The transesterification is preferred in the presence of an inert organic Solvent carried out. Suitable organic solvents are those mentioned above for the esterification. These include especially toluene and THF.

The temperature in the transesterification is preferably in a range of 50 to 200 ° C.

The transesterification can be carried out in the absence or in the presence of an inert gas. An inert gas is generally understood to mean a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed. Preferably, the transesterification is carried out without adding an inert gas.

• a) Umsetzung von 2,5-Furandicarbonsäure mit Methanol in Gegenwart von konzentrierter Schwefelsäure unter Erhalt des 2,5-Furandicarbonsäuredimethylesters,
• b) Umsetzung des in Schritt a) erhaltenen 2,5-Furandicarbonsäuredimethylesters mit wenigstens einem Alkohol R¹-OH in Gegenwart wenigstens eines Titan(IV)-Alkoholats zu den Verbindungen der allgemeinen Formel (I.1).

Herstellung der C₈-Diether- bzw. C₈-Diesterderivate der Formel (I.2) bzw. (I.3) Verbindungen der allgemeinen Formel (I.2) oder (I.3),

worin R¹ und R² eine der zuvor genannten Bedeutungen und n den Wert 1 oder 2 aufweist, sind erhältlich durch ein Verfahren, bei dem man entweder

• a) 2,5-Di-(hydroxymethyl)furan (n = 1) oder 2,5-Di-(hydroxyethyl)furan (n = 2) mit wenigstens einem Alkylierungsreagenz R¹-Z und, falls R¹ und R² unterschiedliche Bedeutung haben, zusätzlich mit wenigstens einem Alkylierungsreagenz R²-Z, wobei Z für eine Abgangsgruppe steht, in Gegenwart einer Base zu Verbindungen der Formel (I.2) umsetzt,

oder

• b) 2,5-Di-(hydroxymethyl)furan (n = 1) oder 2,5-Di-(hydroxyethyl)furan (n = 2) mit wenigstens einem Säurehalogenid R¹-(C=O)X und, falls R¹ und R² unterschiedliche Bedeutung haben, zusätzlich mit wenigstens einem Säurehalogenid R²- (C=O)X, wobei X für Br oder Cl steht, in Gegenwart wenigstens eines tertiären Amins in Verbindungen der Formel (I.3) umgesetzt.

A particularly suitable embodiment of the method comprises:

• a) reaction of 2,5-furandicarboxylic acid with methanol in the presence of concentrated sulfuric acid to give 2,5-furandicarboxylic acid dimethyl ester,
• b) reacting the 2,5-furandicarboxylic acid dimethyl ester obtained in step a) with at least one alcohol R ¹ -OH in the presence of at least one titanium (IV) alcoholate to give the compounds of the general formula (I.1).

Preparation of the C ₈ -Diether- or C ₈ -diester derivatives of the formula (I.2) or (I.3) compounds of the general formula (I.2) or (I.3),

wherein R ¹ and R ^{2 have} one of the meanings mentioned above and n is 1 or 2, are obtainable by a process in which either

• a) 2,5-di- (hydroxymethyl) furan (n = 1) or 2,5-di- (hydroxyethyl) furan (n = 2) with at least one alkylating reagent R ¹ -Z and, if R ¹ and R ^{2 are} different In addition to having at least one alkylating reagent R ² -Z, where Z is a leaving group, in the presence of a base to give compounds of the formula (I.2),

or

• b) 2,5-di (hydroxymethyl) furan (n = 1) or 2,5-di- (hydroxyethyl) furan (n = 2) with at least one acid halide R ¹ - (C = O) X and, if R ¹ and R ^{2 have} different meanings, additionally reacted with at least one acid halide R ² - (C = O) X, wherein X is Br or Cl, in the presence of at least one tertiary amine in compounds of formula (I.3).

In general, the alkylation is carried out in the presence of an organic solvent which is inert under the reaction conditions. Suitable solvents are those mentioned above in the esterification. Preferred solvents are aromatic hydrocarbons, such as toluene.

The leaving group Z preferably represents a radical which is selected from Br, Cl, the tosyl, mesyl or triflyl group.

Particularly preferably, the leaving group Z is Br.

The alkylating reagents R ¹ -Z or R ² -Z are commercially available or can be prepared from the corresponding alcohols by means of suitable reactions or procedures familiar to the person skilled in the art. For example, the alkyl bromides R ¹ -Br or R ² -Br preferably used for this process can be prepared in a known manner on a large scale using hydrogen bromide (HBr) from the corresponding alcohols R ¹ -OH or R ² -OH.

Suitable bases are mineral and / or strong organic bases. These include z. As inorganic bases or base formers, such as hydroxides, hydrides, amides, oxides and carbonates of the alkali and alkaline earth metals. These include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , LiH, NaH, sodium amide (NaNH ₂ ), lithium diisopropylamide (LDA), Na ₂ O, K ₂ CO ₃ , Na ₂ CO ₃ and Cs ₂ CO ₃ ; and organometallic compounds such as n-BuLi or tert-BuLi. Preference is given to NaOH, KOH, K ₂ CO ₃ and Na ₂ CO ₃ .

The base is preferably used in an at least twice the stoichiometric excess, based on the 2,5-di- (hydroxymethyl) furan or 2,5-di- (hydroxyethyl) furan used. More preferably, at least four times the stoichiometric excess of base is used.

The alkylation may be carried out in the absence or in the presence of an organic solvent. In general, the reaction is in the presence of an inert organic solvent such as pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dibutyl ether, THF, dioxane and mixtures thereof , carried out.

The alkylation can be carried out usually at ambient pressure, reduced pressure or elevated pressure. Preferably, the alkylation is carried out at ambient pressure.

The alkylation is preferably carried out in a temperature range from 30 to 200.degree. C., preferably from 50 to 150.degree.

The alkylation can be carried out in the absence or in the presence of an inert gas. Preferably, no inert gas is used in the alkylation.

In a particular suitable embodiment of the alkylation is 2,5-di (hydroxymethyl) furan, or 2,5-di (hydroxyethyl) furan in the presence of at least four-fold excess of base in an inert organic solvent and at least one alkyl bromide R ¹ -Br or R ² -Br converted into the diether compounds of the general formula (I.2). With regard to the radicals R ¹ and R ² , reference is made to the previous statements. The alkali is preferably used as the base, in particular KOH.

For the preparation of the ester compounds of general formula (I.3) is preferably 2,5-di- (hydroxymethyl) furan or 2,5-di (hydroxyethyl) furan with at least one acid halide R ¹ - (C = O) X and if R ¹ and R ^{2 have} different meanings, with at least one acid halide R ² - (C = O) X, where X is Br or Cl, in the presence of at least one tertiary amine, to the compounds of the formula (I.3) implemented.

In addition to this process, other common esterification methods are available to the person skilled in the art, as described above in the case of the esterification of FDCS.

• – aus der Gruppe der Trialkylamine: Trimethylamin, Triethylamin, Tri-n-propylamin, Diethylisopropylamin, Diisopropylethylamin und dergleichen;
• – aus der Gruppe der N-Cycloalkyl-N,N-dialkylamine: Dimethylcyclohexylamin und Diethylcyclohexylamin;
• – aus der Gruppe der N,N-Dialkylaniline: Dimethylanilin und Diethylanilin;
• – aus der Gruppe der Pyridin- und Chinolinbasen: Pyridin, α-, β- und γ-Picolin, Chinolin und 4-(Dimethylamino)pyridin (DMAP).

For the preparation of the ester compounds of the general formula (I.3), it is customary to use all types of tertiary amines which are familiar to the person skilled in the art. Examples of suitable tertiary amines are:

• From the group of trialkylamines: trimethylamine, triethylamine, tri-n-propylamine, diethylisopropylamine, diisopropylethylamine and the like;
• From the group of N-cycloalkyl-N, N-dialkylamines: dimethylcyclohexylamine and diethylcyclohexylamine;
• From the group of N, N-dialkylanilines: dimethylaniline and diethylaniline;
• - From the group of pyridine and quinoline bases: pyridine, α-, β- and γ-picoline, quinoline and 4- (dimethylamino) pyridine (DMAP).

Preferred tertiary amines are trialkylamines and pyridine bases, in particular triethylamine and 4- (dimethylamino) pyridine (DMAP) and mixtures thereof.

The esterification can be carried out at ambient pressure, at reduced or elevated pressure. Preferably, the esterification is carried out at ambient pressure.

The esterification may be carried out in the absence or in the presence of an organic solvent. Preferably, the esterification is carried out in the presence of an inert organic solvent as defined above.

The esterification is usually carried out in a temperature range of 50 to 200 ° C.

The esterification can take place in the absence or in the presence of an inert gas.

In a preferred embodiment of the process for preparing the compounds I.3, 2,5-di- (hydroxymethyl) furan with an acid chloride R ¹ - (C = O) Cl in the presence of triethylamine and / or DMAP and an inert organic solvent Implemented compounds of formula (I.3).

For the preparation of the compounds of general formula (I) C ₈ alkanols are used as starting materials.

Preferred C ₈ -alkanols may be straight-chain or branched or consist of mixtures of straight-chain and branched C ₈ -alkanols. These include n-octanol, iso-octanol and 2-ethylhexanol and mixtures thereof. Preference is given to n-octanol and 2-ethylhexanol. Particularly preferred is 2-ethylhexanol.

The furan-2,5-dicarboxylic acid (FDCS, CAS No. 3238-40-2) used for the preparation of the compounds of general formula (I) can either be obtained commercially or prepared by synthesis routes known from the literature. Thus, possibilities for synthesis can be found in the publication published by Lewkowski et al. entitled "Synthesis, Chemistry and Application of 5-hydroxymethylfurfural and its derivatives" (Lewkowski et al., ARKIVOC 2001 (i), pp. 17-54, ISSN 1424-6376) , Common to most of these syntheses is an acid-catalyzed reaction of carbohydrates, especially glucose, fructose, preferably fructose, to form 5-hydroxymethylfurfural (5-HMF), which can be separated from the reaction mixture by process engineering operations, such as two-phase operation. Corresponding results were, for example, from Leshkov et al. in Science 2006, Vol. 312, pages 1933-1937 and from Zhang et al. in Angewandte Chemie 2008, Vol. 120, pages 9485-9488 described. In a further step, the 5-HMF can then be oxidized to FDCS, such as from Christensen in ChemSusChem 2007, Vol. 1, pages 75-78 cited.

2,5-bis (hydroxymethyl) furan (CAS No. 1883-75-6) can also be either purchased or synthesized commercially. The syntheses described are based on 5-HMF, which can be reduced in two steps via 2,5-bis (hydroxymethyl) furan (2,5-BHF) ( Lewkowski et al., ARKIVOC 2001 (i), pages 17-54, ISSN 1424-6376 ).

2,5-bis (hydroxyethyl) furan can be obtained by reduction of the 2,5-furandiacetic acid methyl ester. 2,5-Furandiacetic acid methyl ester can be synthesized via suitable reactions known to those skilled in the art from 2,5-bis (hydroxymethyl) furan (2,5-BHF), for example analogously to that of US Pat Rau et al. in Liebigs Ann. Chem., Vol. 1984 (8, 1984), pages 1504-1512, ISSN 0947-3440 , described methods. 2,5-BHF is prepared from 2,5-bis (chloromethyl) furan by reaction with thionyl chloride, which is converted into 2,5-bis (cyanomethyl) furan by the action of KCN in benzene in the presence of [18] crown-6 becomes. The 2,5-bis (cyanomethyl) furan can then be saponified to 2,5-furandiacetic acid and esterified with methanol to dimethyl ester or be converted by alcoholysis with methanol directly into the 2,5-Furandiessigsäuremethylester (Pinner reaction). The 2,5-furandiacetic acid methyl ester can then be reduced to 2,5-bis (hydroxyethyl) furan.

The representation of 2,5-Furandiessigsäuremethylesters can also analogously to that of Kern et al. in Liebigs Ann. Chem., Vol. 1985 (6, 1985), pages 1168-1174, ISSN 0947-3440 , described methods.

Compounds of the general formula (II)

The compounds of general formula (II) can either be obtained commercially or prepared by methods known in the art.

In general, the 1,2-cyclohexanedicarboxylic acid esters are usually obtained by nuclear hydrogenation of the corresponding phthalic acid esters. The nuclear hydrogenation can after the in the WO 99/32427 described method. A particularly suitable nuclear hydrogenation process describes, for example, the WO 2011082991 A2 ,

Further, 1,2-cyclohexanedicarboxylic acid esters can be obtained by esterification of 1,2-cyclohexanedicarboxylic acid or suitable derivatives thereof with the corresponding alcohols. The esterification can be carried out by conventional methods known in the art.

The process for preparing the compounds of general formula (II) has in common that starting from phthalic acid, 1,2-cyclohexanedicarboxylic acid or suitable derivatives thereof, an esterification or a transesterification is carried out, wherein the corresponding C ₇ -C ₁₂ alkanols are used as starting materials. These alcohols are usually not pure substances, but mixtures of isomers whose composition and degree of purity depends on the particular method with which they are presented.

Preferred C ₇ -C ₁₂ -alkanols which are used for the preparation of the compounds (II) contained in the plasticizer composition according to the invention may be straight-chain or branched or consist of mixtures of straight-chain and branched C ₇ -C ₁₂ -alkanols. These include n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol, 2-propylheptanol, n-undecanol, isoundecanol, n-dodecanol or isododecanol. Particularly preferred C ₇ -C ₁₂ alkanols are 2-ethylhexanol, isononanol and 2-propylheptanol, in particular isononanol.

heptanol

The heptanols used for the preparation of the compounds of general formula (II) may be straight-chain or branched or consist of mixtures of straight-chain and branched heptanols. Preference is given to mixtures of branched heptanols, also referred to as isoheptanol, which are obtained by the rhodium- or, preferably, cobalt-catalyzed hydroformylation of dimerpropene, obtainable by, for example, B. after the Dimersol ^® process, and subsequent hydrogenation of the obtained isoheptanals are prepared to an isoheptanol mixture. According to its production, the isoheptanol mixture thus obtained consists of several isomers. Substantially straight-chain heptanols can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-hexene and subsequent hydrogenation of the resulting n-heptanal to n-heptanol. The hydroformylation of 1-hexene or dimerpropene can be carried out according to methods known per se. In the hydroformylation with rhodium catalysts homogeneously dissolved in the reaction medium, both uncomplexed rhodium carbonyls which are in situ under the conditions of the hydroformylation reaction in the hydroformylation reaction mixture under the action of synthesis gas z. B. from rhodium salts, as well as complex rhodium carbonyl compounds, in particular complexes with organic phosphines, such as triphenylphosphine, or organophosphites, preferably chelating biphosphites, such as. In US-A 5288918 described, be used as a catalyst. In the cobalt-catalyzed hydroformylation of these olefins generally homogeneously in the reaction mixture soluble cobalt carbonyl compounds are used, which form under the conditions of the hydroformylation under the action of synthesis gas in situ from cobalt salts. If the cobalt-catalyzed hydroformylation is carried out in the presence of trialkyl or triarylphosphines, the desired heptanols are formed directly as the hydroformylation product, so that no further hydrogenation of the aldehyde function is required any more.

For cobalt-catalyzed hydroformylation of 1-hexene or hexene isomer mixtures, for example, in Falbe, New Syntheses with Carbon Monoxide, Springer, Berlin, 1980 at pages 162-168 , explained industrially established processes, such as the Ruhrchemie process, the BASF process, the Kuhlmann process or the Shell process. While the Ruhrchemie, BASF and Kuhlmann processes work with non-ligand-modified cobalt carbonyl compounds as catalysts and thereby obtain hexanal mixtures, the Shell process ( DE-A 1593368 ) Phosphine or phosphite ligand-modified cobalt carbonyl compounds as catalyst, which lead directly to the hexanol mixtures due to their additional high hydrogenation activity. Advantageous embodiments for carrying out the hydroformylation with non-ligand-modified cobalt carbonyl complexes are disclosed in US Pat DE-A 2139630 . DE-A 2244373 . DE-A 2404855 and WO 01014297 described in detail.

For the rhodium-catalyzed hydroformylation of the 1-hexene or hexene isomer mixtures, the industrially established rhodium-low-pressure hydroformylation process with triphenylphosphine ligand-modified rhodium carbonyl compounds can be used, as is the subject of US-A 4148830 is. For the rhodium-catalyzed hydroformylation of long-chain olefins, such as the hexane isomer mixtures obtained by the abovementioned processes, it is advantageous to use non-ligand-modified rhodium carbonyl compounds as the catalyst, wherein, in contrast to the low-pressure process, a higher pressure of from 80 to 400 bar must be set. The implementation of such rhodium high-pressure hydroformylation is in z. B. EP-A 695734 . EP-B 880494 and EP-B 1047655 described.

The isoheptanal mixtures obtained after hydroformylation of the hexene-isomer mixtures are catalytically hydrogenated in conventional manner to give isoheptanol mixtures. For this purpose, preference is given to using heterogeneous catalysts which, as the catalytically active component, comprise metals and / or metal oxides of VI. to VIII. and the I. subgroup of the Periodic Table of the Elements, in particular chromium, molybdenum, Manganese, rhenium, iron, cobalt, nickel and / or copper, optionally deposited on a support material such as Al ₂ O ₃ , SiO ₂ and / or TiO ₂ included. Such catalysts are z. In DE-A 3228881 . DE-A 2628987 and DE-A 2445303 described. The hydrogenation of the isoheptanals is particularly advantageously carried out with an excess of hydrogen of 1.5 to 20% above the hydrogen amount required stoichiometrically for the hydrogenation of the isoheptanals, at temperatures of 50 to 200 ° C. and under a hydrogen pressure of 25 to 350 bar, and to avoid them of side reactions to the hydrogenation feed according to DE-A 2628987 a small amount of water, advantageously in the form of an aqueous solution of an alkali metal hydroxide or carbonate according to the teaching of WO 01087809 added.

octanol

2-ethylhexanol, which was the plasticizer alcohol produced in the largest amounts for many years, can be obtained via the aldol condensation of n-butyraldehyde to 2-ethylhexenal and its subsequent hydrogenation to 2-ethylhexanol (cf. Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, Vol. A 10, pp. 137-140, VCH Verlagsgesellschaft GmbH, Weinheim 1987 ).

Substantially straight-chain octanols can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-heptene and subsequent hydrogenation of the resulting n-octanal to n-octanol. The 1-heptene required for this can be obtained from the Fischer-Tropsch synthesis of hydrocarbons.

The alcohol isooctanol, in contrast to 2-ethylhexanol or n-octanol, due to its method of preparation, is not a uniform chemical compound, but an isomer mixture of differently branched C ₈ -alcohols, for example from 2,3-dimethyl- 1-hexanol, 3,5-dimethyl-1-hexanol, 4,5-dimethyl-1-hexanol, 3-methyl-1-heptanol and 5-methyl-1-heptanol, which may vary depending on the conditions and methods of preparation used in may be present in different ratios in Isooctanol. Isooctanol is usually prepared by the codimerization of propene with butenes, preferably n-butenes, and subsequent hydroformylation of the resulting mixture of heptene isomers. The octanal isomer mixture obtained in the hydroformylation can then be hydrogenated in a conventional manner to the isooctanol.

The codimerization of propylene with butenes to isomeric heptenes may be advantageous (with the aid of the ^® process homogeneously Dimersol Chauvin et al; Chem. Ind .; May 1974, pp. 375-378 ) in which the catalyst used is a soluble nickel-phosphine complex in the presence of an ethylaluminum chloride compound, for example ethylaluminum dichloride. As phosphine ligands for the nickel complex catalyst may, for. As tributylphosphine, tri-isopropylphosphine, tricyclohexylphosphine and / or Tribenzylphosphin be used. The reaction takes place at temperatures of 0 to 80 ° C, wherein advantageously a pressure is set at which the olefins are present dissolved in the liquid reaction mixture ( cornils; Hermann: Applied Homogeneous Catalysis with Organometallic Compounds; 2nd Edition; Vol. 1; Pp. 254-259, Wiley-VCH, Weinheim 2002 ).

Alternatively to the operated homogeneously dissolved in the reaction medium nickel catalysts Dimersol ^® process, the co-dimerization of propylene with butenes can be carried out with deposited on a support, NiO heterogeneous catalysts, wherein similar heptene-isomer distributions are obtained as with the homogeneously catalyzed processes. Such catalysts are, for example, in the so-called Octol ^® method ( Hydrocarbon Processing, February 1986, pp. 31-33 ), a well-suited specific nickel heterogeneous catalyst for Olefindimerisierung or codimerization is z. In WO 9514647 disclosed.

Instead of nickel-based catalysts, Brønsted-acidic heterogeneous catalysts can also be used for the codimerization of propene with butenes, with higher branched heptenes generally being obtained than in the nickel-catalyzed processes. Examples of catalysts suitable for this purpose are solid phosphoric acid catalysts z. B. impregnated with phosphoric acid diatomaceous earth or diatomaceous earth, as used by the PolyGas ^® method for Olefindi- or oligomerization ( Chitnis et al; Hydrocarbon Engineering 10, No. 6 - June 2005 ). For the co-dimerization of propene and butenes to heptenes very suitable Bronsted acidic catalysts are zeolites, which uses the enhanced on the basis of Polygas ^® process EMOGAS ^® process.

The 1-heptene and the heptene isomer mixtures are prepared by the known processes described above in connection with the preparation of n-heptanal and heptanal isomer mixtures Rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation, in n-octanal or octanal isomer mixtures. These are then z. B. hydrogenated by means of one of the above-mentioned in connection with the n-heptanol and isoheptanol preparation catalysts to the corresponding octanols.

nonanol

Substantially straight chained nonanol can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-octene and subsequent hydrogenation of the n-nonanal thus obtained. The starting olefin 1-octene can, for example, an ethylene oligomerization by means of a homogeneously in the reaction medium - 1,4-butanediol - soluble nickel complex catalyst with z. B. diphenylphosphinoacetic acid or 2-Diphenylphosphinobenzoesäure be obtained as ligands. This process is also known under the name Shell Higher Olefins Process or SHOP process (s. Weisermel, Arpe: Industrial Organic Chemistry; 5th edition; P. 96; Wiley-VCH, Weinheim 1998 ).

In the case of isononanol, which is used for the synthesis of the diisononyl ester of the general formula (II) contained in the plasticizer composition according to the invention, it is not a uniform chemical compound but a mixture of differently branched isomeric C ₉ -alcohols, which, depending on the nature of their preparation, in particular the starting materials used, may have different degrees of branching. In general, the isononanols are prepared by dimerization of butenes to mixtures of isooctene, subsequent hydroformylation of the isooctene mixtures and hydrogenation of the resulting isononanal mixtures to form isononanol mixtures, as described in US Pat Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A1, pp. 291-292, VCH Verlagsgesellschaft GmbH, Weinheim 1995 , explained.

As starting material for the preparation of the isononanols, both isobutene, cis- and trans-2-butene and 1-butene or mixtures of these butene isomers can be used. In the predominantly by means of liquid, z. As sulfuric or phosphoric acid, or solid, z. B. on kieselguhr, SiO ₂ or Al ₂ O ₃ as a carrier material applied phosphoric acid or zeolites or Brønsted acids catalyzed dimerization of pure isobutene, predominantly the highly branched 2,4,4-trimethylpentene, also referred to as diisobutylene obtained after Hydroformylation and hydrogenation of aldehyde highly branched isononanols provides.

Preference is given to isononanols having a lower degree of branching. Such low branched isononanol mixtures are from the linear butenes 1-butene, cis- and / or trans-2-butene, which may optionally contain even lower amounts of isobutene, via the above-described way of butene dimerization, hydroformylation of isooctene and hydrogenation of obtained Isononanal mixtures prepared. A preferred raw material is the so-called raffinate II, from the C _{4 cut of} a cracker, for example a steam cracker, after elimination of allenes, acetylenes and dienes, in particular 1,3-butadiene, by its partial hydrogenation to linear butenes or its separation by extractive distillation, for example by means of N-methylpyrrolidone, and subsequent Brønsted acid catalyzed removal of the isobutene contained therein by its reaction with methanol or isobutanol by industrially established methods to form the fuel additive methyl tert-butyl ether (MTBE) or to obtain pure Isobutene serving isobutyl tert-butyl ether.

Raffinate II contains, in addition to 1-butene and cis- and trans-2-butene, n- and iso-butane and residual amounts of up to 5% by weight of isobutene.

The dimerization of the linear butenes or of the butene mixture contained in the raffinate II can be carried out by means of the common, industrially practiced processes, as described above in connection with the production of Isoheptengemischen, for example by means of heterogeneous Brønsted-acid catalysts, as in PolyGas ^® - or EMOGAS ^® methods can be used, by means of the Dimersol ^® method using homogeneously dissolved in the reaction medium nickel complex catalysts or by heterogeneous, nickel (II) oxide-containing catalysts by the Octol ^® method or the method according to WO 9514647 be performed. The resulting isooctene mixtures are converted into isononanal mixtures by the known processes described above in connection with the preparation of heptanal isomer mixtures by means of rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation. These are then z. B. hydrogenated by means of one of the above-mentioned in connection with the isoheptanol preparation catalysts to the suitable Isononanolgemischen.

The isononanol isomer mixtures thus prepared can be characterized by their isoindex, which can be calculated from the degree of branching of the individual isomeric isononanol components in the isononanol mixture multiplied by their percentage in the isononanol mixture. To wear z. B. n-nonanol with the value 0, methyl octanols (a branching) with the value 1 and dimethylheptanols (two branches) with the value 2 to the iso index of a Isononanolgemisches at. The higher the linearity, the lower the isoindex of the respective isononanol mixture. Accordingly, the isoindex of an isononanol mixture can be determined by gas chromatographic separation of the isononanol mixture into its individual isomers and concomitant quantification of their percentage in the isononanol mixture, determined by standard methods of gas chromatographic analysis. In order to increase the volatility and improve the gas chromatographic separation of the isomeric nonanols, these are expediently trimethylsilylated prior to the gas chromatographic analysis by standard methods, for example by reaction with N-methyl-N-trimethylsilyltrifluoroacetamide. In order to achieve the best possible separation of the individual components in the gas chromatographic analysis, capillary columns with polydimethylsiloxane are preferably used as the stationary phase. Such capillary columns are commercially available, and it only takes a few routine experiments by the skilled person to select from the wide range of trade a suitable for this separation task suitable product.

The diisononyl esters of the general formula (II) used in the plasticizer composition according to the invention are generally associated with isononanols having an iso index of from 0.8 to 2, preferably from 1.0 to 1.8, and more preferably from 1.1 to 1.5 esterified, which can be prepared by the above-mentioned methods.

By way of example only possible compositions of isononanol mixtures are given below, as they can be used for the preparation of the compounds of the general formula (II) used according to the invention, wherein it should be noted that the proportions of the individual isomers in the isononanol mixture depend on the composition of the starting material, For example, raffinate II, whose composition may vary due to production of butenes and may vary from variations in the production conditions used, for example, the age of the catalysts used and the temperature and pressure conditions to be matched thereto.

• – 1,73 bis 3,73 Gew.-%, bevorzugt 1,93 bis 3,53 Gew.-%, besonders bevorzugt 2,23 bis 3,23 Gew.-% 3-Ethyl-6-methyl-hexanol;
• – 0,38 bis 1,38 Gew.-%, bevorzugt 0,48 bis 1,28 Gew.-%, besonders bevorzugt 0,58 bis 1,18 Gew.-% 2,6-Dimethylheptanol;
• – 2,78 bis 4,78 Gew.-%, bevorzugt 2,98 bis 4,58 Gew.-%, besonders bevorzugt 3,28 bis 4,28 Gew.-% 3,5-Dimethylheptanol;
• – 6,30 bis 16,30 Gew.-%, bevorzugt 7,30 bis 15,30 Gew.-%, besonders bevorzugt 8,30 bis 14,30 Gew.-% 3,6-Dimethylheptanol;
• – 5,74 bis 11,74 Gew.-%, bevorzugt 6,24 bis 11,24 Gew.-%, besonders bevorzugt 6,74 bis 10,74 Gew.-% 4,6-Dimethylheptanol;
• – 1,64 bis 3,64 Gew.-%, bevorzugt 1,84 bis 3,44 Gew.-%, besonders bevorzugt 2,14 bis 3,14 Gew.-% 3,4,5-Trimethylhexanol;
• – 1,47 bis 5,47 Gew.-%, bevorzugt 1,97 bis 4,97 Gew.-%, besonders bevorzugt 2,47 bis 4,47 Gew.-% 3,4,5-Trimethylhexanol, 3-Methyl-4-ethylhexanol und 3-Ethyl-4-methylhexanol;
• – 4,00 bis 10,00 Gew.-%, bevorzugt 4,50 bis 9,50 Gew.-%, besonders bevorzugt 5,00 bis 9,00 Gew.-% 3,4-Dimethylheptanol;
• – 0,99 bis 2,99 Gew.-%, bevorzugt 1,19 bis 2,79 Gew.-%, besonders bevorzugt 1,49 bis 2,49 Gew.-% 4-Ethyl-5-methylhexanol und 3-Ethylheptanol;
• – 2,45 bis 8,45 Gew.-%, bevorzugt 2,95 bis 7,95 Gew.-%, besonders bevorzugt 3,45 bis 7,45 Gew.-% 4,5-Dimethylheptanol und 3-Methyloctanol;
• – 1,21 bis 5,21 Gew.-%, bevorzugt 1,71 bis 4,71 Gew.-%, besonders bevorzugt 2,21 bis 4,21 Gew.-% 4,5-Dimethylheptanol;
• – 1,55 bis 5,55 Gew.-%, bevorzugt 2,05 bis 5,05 Gew.-%, besonders bevorzugt 2,55 bis 4,55 Gew.-% 5,6-Dimethylheptanol;
• – 1,63 bis 3,63 Gew.-%, bevorzugt 1,83 bis 3,43 Gew.-%, besonders bevorzugt 2,13 bis 3,13 Gew.-% 4-Methyloctanol;
• – 0,98 bis 2,98 Gew.-%, bevorzugt 1,18 bis 2,78 Gew.-%, besonders bevorzugt 1,48 bis 2,48 Gew.-% 5-Methyloctanol;
• – 0,70 bis 2,70 Gew.-%, bevorzugt 0,90 bis 2,50 Gew.-%, besonders bevorzugt 1,20 bis 2,20 Gew.-% 3,6,6-Trimethylhexanol;
• – 1,96 bis 3,96 Gew.-%, bevorzugt 2,16 bis 3,76 Gew.-%, besonders bevorzugt 2,46 bis 3,46 Gew.-% 7-Methyloctanol;
• – 1,24 bis 3,24 Gew.-%, bevorzugt 1,44 bis 3,04 Gew.-%, besonders bevorzugt 1,74 bis 2,74 Gew.-% 6-Methyloctanol;
• – 0,1 bis 3 Gew.-%, bevorzugt 0,2 bis 2 Gew.-%, besonders bevorzugt 0,3 bis 1 Gew.-% n-Nonanol;
• – 25 bis 35 Gew.-%, bevorzugt 28 bis 33 Gew.-%, besonders bevorzugt 29 bis 32 Gew.-% sonstige Alkohole mit 9 und 10 Kohlenstoffatomen; mit der Maßgabe, dass die Gesamtsumme der genannten Komponenten 100 Gew.-% ergibt.

For example, an isononanol mixture prepared by cobalt-catalyzed hydroformylation followed by hydrogenation from a product using raffinate II as the raw material by means of the catalyst and process of WO 9514647 produced Isooctengemisches was prepared, have the following composition:

• From 1.73 to 3.73% by weight, preferably from 1.93 to 3.53% by weight, particularly preferably from 2.23 to 3.23% by weight, of 3-ethyl-6-methylhexanol;
• From 0.38 to 1.38% by weight, preferably from 0.48 to 1.28% by weight, particularly preferably from 0.58 to 1.18% by weight, of 2,6-dimethylheptanol;
• From 2.78 to 4.78% by weight, preferably from 2.98 to 4.58% by weight, particularly preferably from 3.28 to 4.28% by weight, of 3,5-dimethylheptanol;
• From 6.30 to 16.30% by weight, preferably from 7.30 to 15.30% by weight, particularly preferably from 8.30 to 14.30% by weight of 3,6-dimethylheptanol;
• From 5.74 to 11.74% by weight, preferably from 6.24 to 11.24% by weight, particularly preferably from 6.74 to 10.74% by weight, of 4,6-dimethylheptanol;
• From 1.64 to 3.64% by weight, preferably from 1.84 to 3.44% by weight, more preferably from 2.14 to 3.14% by weight, of 3,4,5-trimethylhexanol;
• From 1.47 to 5.47% by weight, preferably from 1.97 to 4.97% by weight, particularly preferably from 2.47 to 4.47% by weight, of 3,4,5-trimethylhexanol, 3-methyl 4-ethylhexanol and 3-ethyl-4-methylhexanol;
• From 4.00 to 10.00% by weight, preferably from 4.50 to 9.50% by weight, particularly preferably from 5.00 to 9.00% by weight, of 3,4-dimethylheptanol;
• From 0.99 to 2.99% by weight, preferably from 1.19 to 2.79% by weight, particularly preferably from 1.49 to 2.49% by weight of 4-ethyl-5-methylhexanol and 3-ethylheptanol ;
• 2.45 to 8.45% by weight, preferably 2.95 to 7.95% by weight, more preferably 3.45 to 7.45% by weight, of 4,5-dimethylheptanol and 3-methyloctanol;
• From 1.21 to 5.21% by weight, preferably from 1.71 to 4.71% by weight, particularly preferably from 2.21 to 4.21% by weight, of 4,5-dimethylheptanol;
• From 1.55 to 5.55% by weight, preferably from 2.05 to 5.05% by weight, particularly preferably from 2.55 to 4.55% by weight, of 5,6-dimethylheptanol;
• From 1.63 to 3.63% by weight, preferably from 1.83 to 3.43% by weight, particularly preferably from 2.13 to 3.13% by weight, of 4-methyloctanol;
• From 0.98 to 2.98% by weight, preferably from 1.18 to 2.78% by weight, particularly preferably from 1.48 to 2.48% by weight of 5-methyl-octanol;
• From 0.70 to 2.70% by weight, preferably from 0.90 to 2.50% by weight, particularly preferably from 1.20 to 2.20% by weight, of 3,6,6-trimethylhexanol;
• From 1.96 to 3.96% by weight, preferably from 2.16 to 3.76% by weight, particularly preferably from 2.46 to 3.46% by weight, of 7-methyloctanol;
• From 1.24 to 3.24% by weight, preferably from 1.44 to 3.04% by weight, particularly preferably from 1.74 to 2.74% by weight, of 6-methyloctanol;
• From 0.1 to 3% by weight, preferably from 0.2 to 2% by weight, particularly preferably from 0.3 to 1% by weight, of n-nonanol;
• - 25 to 35 wt .-%, preferably 28 to 33 wt .-%, particularly preferably 29 to 32 wt .-% of other alcohols having 9 and 10 carbon atoms; with the proviso that the total of said components gives 100% by weight.

• – 6,0 bis 16,0 Gew.-%, bevorzugt 7,0 bis 15,0 Gew.-%, besonders bevorzugt 8,0 bis 14,0 Gew.-% n-Nonanol;
• – 12,8 bis 28,8 Gew.-%, bevorzugt 14,8 bis 26,8 Gew.-%, besonders bevorzugt 15,8 bis 25,8 Gew.-% 6-Methyloctanol;
• – 12,5 bis 28,8 Gew.-%, bevorzugt 14,5 bis 26,5 Gew.-%, besonders bevorzugt 15,5 bis 25,5 Gew.-% 4-Methyloctanol;
• – 3,3 bis 7,3 Gew.-%, bevorzugt 3,8 bis 6,8 Gew.-%, besonders bevorzugt 4,3 bis 6,3 Gew.-% 2-Methyloctanol;
• – 5,7 bis 11,7 Gew.-%, bevorzugt 6,3 bis 11,3 Gew.-%, besonders bevorzugt 6,7 bis 10,7 Gew.-% 3-Ethylheptanol;
• – 1,9 bis 3,9 Gew.-%, bevorzugt 2,1 bis 3,7 Gew.-%, besonders bevorzugt 2,4 bis 3,4 Gew.-% 2-Ethylheptanol;
• – 1,7 bis 3,7 Gew.-%, bevorzugt 1,9 bis 3,5 Gew.-%, besonders bevorzugt 2,2 bis 3,2 Gew.-% 2-Propylhexanol;
• – 3,2 bis 9,2 Gew.-%, bevorzugt 3,7 bis 8,7 Gew.-%, besonders bevorzugt 4,2 bis 8,2 Gew.-% 3,5-Dimethylheptanol;
• – 6,0 bis 16,0 Gew.-%, bevorzugt 7,0 bis 15,0 Gew.-%, besonders bevorzugt 8,0 bis 14,0 Gew.-% 2,5-Dimethylheptanol;
• – 1,8 bis 3,8 Gew.-%, bevorzugt 2,0 bis 3,6 Gew.-%, besonders bevorzugt 2,3 bis 3,3 Gew.-% 2,3-Dimethylheptanol;
• – 0,6 bis 2,6 Gew.-%, bevorzugt 0,8 bis 2,4 Gew.-%, besonders bevorzugt 1,1 bis 2,1 Gew.-% 3-Ethyl-4-methylhexanol;
• – 2,0 bis 4,0 Gew.-%, bevorzugt 2,2 bis 3,8 Gew.-%, besonders bevorzugt 2,5 bis 3,5 Gew.-% 2-Ethyl-4-methylhexanol;
• – 0,5 bis 6,5 Gew.-%, bevorzugt 1,5 bis 6 Gew.-%, besonders bevorzugt 1,5 bis 5,5 Gew.-% sonstige Alkohole mit 9 Kohlenstoffatomen; mit der Maßgabe, dass sich die Gesamtsumme der genannten Komponenten 100 Gew.-% ergibt.

According to the above embodiments, a isononanol, the Butengemisches Isooctengemisches generated as a raw material by means of the Polygas ^® or EMOGAS ^® process was prepared by cobalt-catalyzed hydroformylation and subsequent hydrogenation using an ethylene-containing, in the range of the following compositions, depending on the raw material composition and variations in the reaction conditions used vary:

• From 6.0 to 16.0% by weight, preferably from 7.0 to 15.0% by weight, particularly preferably from 8.0 to 14.0% by weight of n-nonanol;
• From 12.8 to 28.8% by weight, preferably from 14.8 to 26.8% by weight, more preferably from 15.8 to 25.8% by weight, of 6-methyl-octanol;
• From 12.5 to 28.8% by weight, preferably from 14.5 to 26.5% by weight, particularly preferably from 15.5 to 25.5% by weight, of 4-methyloctanol;
• From 3.3 to 7.3% by weight, preferably from 3.8 to 6.8% by weight, particularly preferably from 4.3 to 6.3% by weight, of 2-methyl-octanol;
• From 5.7 to 11.7% by weight, preferably from 6.3 to 11.3% by weight, particularly preferably from 6.7 to 10.7% by weight of 3-ethylheptanol;
• From 1.9 to 3.9% by weight, preferably from 2.1 to 3.7% by weight, particularly preferably from 2.4 to 3.4% by weight, of 2-ethylheptanol;
• From 1.7 to 3.7% by weight, preferably from 1.9 to 3.5% by weight, particularly preferably from 2.2 to 3.2% by weight, of 2-propylhexanol;
• From 3.2 to 9.2% by weight, preferably from 3.7 to 8.7% by weight, particularly preferably from 4.2 to 8.2% by weight, of 3,5-dimethylheptanol;
• From 6.0 to 16.0% by weight, preferably from 7.0 to 15.0% by weight, particularly preferably from 8.0 to 14.0% by weight of 2,5-dimethylheptanol;
• From 1.8 to 3.8% by weight, preferably from 2.0 to 3.6% by weight, more preferably from 2.3 to 3.3% by weight, of 2,3-dimethylheptanol;
• From 0.6 to 2.6% by weight, preferably from 0.8 to 2.4% by weight, particularly preferably from 1.1 to 2.1% by weight, of 3-ethyl-4-methylhexanol;
• From 2.0 to 4.0% by weight, preferably from 2.2 to 3.8% by weight, particularly preferably from 2.5 to 3.5% by weight, of 2-ethyl-4-methylhexanol;
• From 0.5 to 6.5% by weight, preferably from 1.5 to 6% by weight, particularly preferably from 1.5 to 5.5% by weight, of other alcohols having 9 carbon atoms; with the proviso that the total sum of said components is 100% by weight.

decanol

Isodecanol, which is used to synthesize the diisodecyl esters of general formula (II) contained in the plasticizer composition according to the invention, is not a uniform chemical compound but a complex mixture of differently branched isomeric decanols.

These are generally prepared by the nickel or Bronsted acid-catalyzed trimerization of propylene, for example, according to the above-described Polygas ^® - or the EMOGAS ^® methods, subsequent hydroformylation of the thus obtained isononene isomer mixture using homogeneous rhodium or cobalt catalysts, preferably by means of cobalt carbonyl catalysts and hydrogenation of the resulting isodecanal isomer mixture, for. Example by means of the above-mentioned in connection with the production of C ₇ -C ₉ alcohols mentioned catalysts and processes ( Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, Vol. A1, p. 293, VCH Verlagsgesellschaft GmbH, Weinheim 1985 ), produced. The isodecanol produced in this way is generally highly branched.

In the case of 2-propylheptanol, which is used for the synthesis of the di (2-propylheptyl) ester of the general formula (II) contained in the plasticizer composition according to the invention, it may be pure 2-propylheptanol or propylheptanol isomer mixtures, as described in US Pat Generally, in the industrial production of 2-propylheptanol are formed and commonly also referred to as 2-propylheptanol.

Pure 2-propylheptanol can be prepared by aldol condensation of n-valeraldehyde and subsequent hydrogenation of the resulting 2-propylheptenal, for example according to US-A 2921089 , to be obtained. In general, commercially available 2-propylheptanol contains, in addition to the main component 2-propylheptanol, one or more of the 2-propylheptanol isomers, such as 2-propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-isopropylheptanol, 2-isopropyl 4-methylhexanol, 2-isopropyl-5-methylhexanol and / or 2-propyl-4,4-dimethylpentanol. The presence of other isomers of 2-propylheptanol, for example 2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methyl-heptanol and / or 2-ethyl-2,5-dimethylhexanol in 2-propylheptanol, is possible due to the low rates of formation of the aldehyde precursors of these isomers in the course of aldol condensation these, if any, contained only in trace amounts in 2-propylheptanol and play for the plasticizer properties of the compounds prepared from such 2-propyheptanol isomer mixtures practically no role.

As starting material for the preparation of 2-propylheptanol, a variety of hydrocarbon sources can be used, for example 1-butene, 2-butene, raffinate I - an alkane / alkene mixture obtained from the C _{4 cut of} a cracker after separation of allenes, acetylenes and dienes, which in addition to 1- and 2-butene still contains significant amounts of isobutene - or raffinate II, which is obtained from raffinate I by separation of isobutene and contains as olefin components except 1- and 2-butene only small amounts of isobutene. Of course, mixtures of raffinate I and raffinate II can be used as a raw material for 2-propylheptanol production. These olefins or olefin mixtures can be hydroformylated according to conventional methods with cobalt or rhodium catalysts, wherein from 1-butene a mixture of n- and iso-valeraldehyde - the name iso-valeraldehyde refers to the compound 2-methylbutanal - is formed, whose n / iso ratio may vary within relatively wide limits depending on the catalyst and hydroformylation conditions used. For example, using a triphenylphosphine-modified rhodium homogeneous catalyst (Rh / TPP) of 1-butene, n- and iso-valeraldehyde are formed in an n / iso ratio of generally 10: 1 to 20: 1, whereas when using with phosphite ligands, for example according to US-A 5288918 or WO 05028407 , or with phosphoamidite ligands, for example according to WO 0283695 , modified rhodium hydroformylation almost exclusively n-valeraldehyde is formed. While the Rh / TPP catalyst system converts 2-butene very slowly in the hydroformylation, so that most of the 2-butene can be recovered from the hydroformylation mixture, the hydroformylation of the 2-butene with the mentioned phosphite ligand or Phosphoramidite ligand-modified rhodium catalysts, wherein predominantly n-valeraldehyde is formed. On the other hand, isobutene contained in the olefinic raw material is hydroformylated, albeit at a different rate, from virtually all catalyst systems to 3-methylbutanal and depending on the catalyst to a lesser extent to pivalaldehyde.

The C ₅ aldehydes obtained, depending on the starting materials and catalysts used, ie n-valeraldehyde, optionally in admixture with iso-valeraldehyde, 3-methylbutanal and / or pivalaldehyde, can, if desired, be separated completely or partly by distillation into the individual components before the aldol condensation, so that Here, too, there is a possibility to influence and control the isomer composition of the C ₁₀ -alcohol component of the ester mixtures used according to the invention. Likewise, it is possible to add the C ₅ aldehyde mixture as formed in the hydroformylation to the aldol condensation without prior separation of individual isomers. In the aldol condensation, using a basic catalyst, such as an aqueous solution of sodium or potassium hydroxide, for example, according to the in EP-A 366089 . US-A 4426524 or US-A 5434313 When n-valeraldehyde is used as the only condensation product, 2-propylheptenal is formed, whereas if a mixture of isomeric C ₅ -aldehydes is used, a mixture of isomers of the products of the homoaldol condensation of the same aldehyde molecules and of the crossed aldol condensation of different valeraldehyde isomers is formed. Of course, the aldol condensation can be controlled by the targeted implementation of individual isomers so that predominantly or completely a single Aldolkondensationsisomer is formed. The aldol condensation products in question can then, usually after prior, preferably distillative separation from the reaction mixture and, if desired distillative purification, hydrogenated with conventional hydrogenation catalysts, for example those mentioned above for the hydrogenation of aldehydes, to the corresponding alcohols or alcohol mixtures.

As already mentioned, the compounds of the general formula (II) present in the plasticizer composition according to the invention can be esterified with pure 2-propylheptanol. In general, however, mixtures of 2-propylheptanol with the stated propylheptanol isomers are used for preparing these esters, in which the content of 2-propylheptanol is at least 50% by weight, preferably 60 to 98% by weight and particularly preferably 80 to 95 Wt .-%, in particular 85 to 95 wt .-% is.

Suitable mixtures of 2-propylheptanol with the propylheptanol isomers include, for example, those of 60 to 98 wt .-% of 2-propylheptanol, 1 to 15 wt .-% of 2-propyl-4-methyl-hexanol and 0.01 to 20 wt. -% 2-propyl-5-methyl-hexanol and 0.01 to 24 wt .-% 2-isopropylheptanol, wherein the sum of the proportions of the individual components does not exceed 100 wt .-%. Preferably, the proportions of the individual components add up to 100 wt .-%.

Further suitable mixtures of 2-propylheptanol with the propylheptanol isomers include, for example, those from 75 to 95% by weight of 2-propylheptanol, 2 to 15% by weight of 2-propyl-4-methylhexanol, 1 to 20% by weight. % 2-propyl-5-methylhexanol, 0.1 to 4% by weight of 2-isopropylheptanol, 0.1 to 2% by weight of 2-isopropyl-4-methylhexanol and 0.1 to 2% by weight 2-isopropyl-5-methyl-hexanol, wherein the sum of the proportions of the individual constituents does not exceed 100 wt .-%. Preferably, the proportions of the individual components add up to 100 wt .-%.

Preferred mixtures of 2-propylheptanol with the propylheptanol isomers include those containing 85 to 95% by weight of 2-propylheptanol, 5 to 12% by weight of 2-propyl-4-methylhexanol and 0.1 to 2% by weight. % 2-propyl-5-methylhexanol and 0.01 to 1 wt .-% 2-isopropylheptanol, wherein the sum of the proportions of the individual components does not exceed 100 wt .-%. Preferably, the proportions of the individual components add up to 100 wt .-%.

When using said 2-propylheptanol isomer mixtures instead of pure 2-propylheptanol for the preparation of the compounds of general formula (II), the isomeric composition of the alkyl ester groups or alkyl ether groups corresponds practically to the composition of the propylheptanol isomer mixtures used for the esterification.

undecanol

The undecanols which are used for the preparation of the compounds of the general formula (II) present in the plasticizer composition according to the invention can be straight-chain or branched or can be composed of mixtures of straight-chain and branched undecanols. Preference is given to using mixtures of branched undecanols, also referred to as isoundecanol, as the alcohol component.

Substantially straight-chain undecanol can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-decene and subsequent hydrogenation of the resulting n-undecanal. The starting olefin 1-decene is prepared via the SHOP process previously mentioned in the preparation of 1-octene.

For the preparation of branched isoundecanol, the 1-decene obtained in the SHOP process can undergo skeletal isomerization, e.g. Example by means of acidic zeolitic molecular sieves, as in WO 9823566 be described, which form mixtures of isomeric decenes, their rhodium or preferably cobalt-catalyzed hydroformylation and subsequent hydrogenation of the resulting isoundecanal mixtures to the isoundecanol used for the preparation of the compounds (II) used in the invention leads. The hydroformylation of 1-decene or isodecene mixtures by means of rhodium or cobalt catalysis can be carried out as previously described in connection with the synthesis of C ₇ - to C ₁₀ -alcohols. The same applies to the hydrogenation of n-undecanal or isoundecanal mixtures to n-undecanol or isoundecanol.

After purification by distillation of the effluent of the hydrogenation, the C ₇ - to C ₁₁ -alkyl alcohols or mixtures thereof thus obtained, as described above, can be used to prepare the diester compounds of the general formula (II) used according to the invention.

dodecanol

^® process be won or Epal - essentially straight-chain dodecanol can advantageously over the Alfol ^®. These processes involve the oxidation and hydrolysis of straight-chain trialkylaluminum compounds which, starting from triethylaluminum, are built up stepwise over several ethylation reactions using Ziegler-Natta catalysts. From the resulting mixtures of substantially straight-chain alkyl alcohols of different chain length, the desired n-dodecanol can be obtained after the C ₁₂ -alkyl alcohol fraction has been removed by distillation.

Alternatively, n-dodecanol can also be prepared by hydrogenation of natural fatty acid methyl esters, for example from coconut oil.

Branched isododecanol can analogously to the known processes for the codimerization and / or oligomerization of olefins, such as in the WO 0063151 described, with subsequent hydroformylation and hydrogenation of isoundecene mixtures, such as in the DE-A 4339713 described, can be obtained. After purification by distillation of the discharge of the hydrogenation, the thus obtained isododecanols or mixtures thereof, as described above, for the preparation of the diester compounds of the general formula (II) used in the invention can be used.

Plastisol applications

As already explained, the plasticizer composition according to the invention is particularly suitable for the production of plastisols because of its good gelling properties.

Another object of the invention therefore relates to the use of a plasticizer composition as defined above as a plasticizer in a plastisol.

Plastisols can be made from a variety of plastics. The plastisols according to the invention are, in a preferred embodiment, a PVC plastisol.

The proportion of plasticizer composition according to the invention in the PVC plastisols is usually from 5 to 300 phr, preferably from 50 to 200 phr.

Plastisols are usually brought into the form of the final product at ambient temperature by various methods, such as brushing, screen printing, casting, such as the shell casting or spin casting, dipping, spraying, and the like. Subsequently, the gelation is carried out by heating, after cooling a homogeneous, more or less flexible product is obtained.

PVC plastisols are particularly suitable for the production of PVC films, for the production of seamless hollow bodies, gloves and for use in the textile sector, such. B. for textile coatings.

Specifically, the PVC plastisols based on the inventive softening composition are suitable for the production of artificial leather, e.g. of artificial leather for motor vehicle construction; Underbody protection for motor vehicles; Seam sealing; Carpet backings; heavy coatings; conveyor belts; Dip coatings and dipped articles; Toys, such as dolls, balls or toy animals; anatomical models for training; flooring; Wall coverings; (coated) textiles, such as latex clothing, protective clothing or rainwear, such as rain jackets; Tarpaulins, such as truck tarpaulins, tarpaulins or roofing membranes; tents; Coil coatings; Sealants for closures; Respiratory masks and gloves.

Applications molding compound

The molding composition according to the invention is preferably used for the production of moldings and films. These include in particular housings of electrical appliances, such as kitchen appliances and computer cases; tools; cameras; Pipelines; Electric wire; 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; Foam for upholstery and mattresses; seals; Composite films, such as laminated safety glass films, in particular for vehicle and window panes; records; Packaging containers; Adhesive tape or coatings.

In addition, the molding composition according to the invention is additionally suitable for the production of moldings and films which come into direct contact with humans or foodstuffs. These are predominantly medical devices, hygiene products, food packaging, indoor products, toys and child care articles, sports and leisure products, clothing or fibers for fabrics and the like.

The medical products which can be produced from the molding composition according to the invention are, for example, hoses for enteral nutrition and hemodialysis, respiratory hoses, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves or respiratory masks.

In the food packaging that can be produced from the molding composition according to the invention, it is, for example, cling films, food hoses, drinking water hoses, containers for storing or freezing of food, lid seals, caps, bottle caps or artificial wine corks.

The products for the interior area which can be produced from the molding composition according to the invention are, for example, floor coverings which can be constructed homogeneously or from several layers consisting of at least one foamed layer, such as, for example, floor coverings, sports floors or Luxury Vinyl Tiles (LVT), imitation leather, wall coverings or foamed or unfoamed wallpapers in buildings or around carcasses or console covers in vehicles.

The toys and child care articles that can be made from the molding composition according to the invention are, for example, dolls, inflatable toys such as balls, toy figures, toy animals, anatomical models for training, play dough, buoyancy aids, stroller covers, changing mattresses, hot water bottles, teething rings or vials.

The sports and leisure products which can be produced from the molding composition according to the invention are, for example, gymnastic balls, exercise mats, seat cushions, massage balls and rollers, shoes or shoe soles, balls, air mattresses or drinking bottles.

The clothing that can be made from the molding compositions according to the invention are, for example, rubber boots.

Non-PVC applications

In addition, the present invention includes the use of the plasticizer composition according to the invention as auxiliaries and / or in auxiliaries selected from: calendering auxiliaries; rheological; surface-active compositions such as flow, film-forming aids, defoamers, foam inhibitors, wetting agents, coalescing agents and emulsifiers; Lubricants, such as lubricating oils, greases and lubricating pastes; Quenchers for chemical reactions; desensitizing agents; pharmaceutical products; Plasticizers in adhesives or sealants; Impact modifiers and adjusters.

The invention will be explained in more detail with reference to the examples and figures described below. The examples and figures should not be understood as limiting the invention.

In the following examples and figures, the following abbreviations are used: Hexamoll ^® DINCH ^® stands for Diisononylcyclohexan-1,2-dicarboxylate,
Palatinol ^® N is diisononyl phthalate,
Vestinol ^® INB stands for isononyl benzoate,
Jayflex ^® MB10 is Isodecylbenzoat,
phr is parts by weight per 100 parts by weight of polymer.

DESCRIPTION OF THE FIGURES

Fig. 1:

1 shows the gelling behavior of PVC plastisols with a total content of inventive plasticizer composition of 100 phr. Shown is the complex viscosity η * [Pa · s] of the plastisols as a function of the temperature [° C]. Thereby softening compositions were used containing the plasticizer commercially available Hexamoll ^® DINCH ^® and the Schnellgelierer 2,5-furan dicarboxylic acid-2-ethylhexyl esters in different ratios. Additives is ätzlich shown as comparison, the gelling of PVC plastisols, which contain only the plasticizer Palatinol ^® N or Hexamoll ^® DINCH ^® commercially available.

Fig. 2:

2 shows the gelling of PVC plastisols containing plasticizers as specific mixtures of Hexamoll ^® DINCH ^® with the Schnellgelierer 2,5-furan dicarboxylic acid-2-ethylhexyl ester and the commercially available Schnellgelierern dibutyl phthalate, Vestinol ^® INB or Jayflex ^® MB 10th Shown is the complex viscosity η * [Pa · s] of the plastisols as a function of the temperature [° C]. The proportion of the plasticizer in Schnellgelierers mixtures is that the gelation temperature of Palatinol ^® N is achieved so selected. In addition, as a comparison, the gelling of PVC plastisols is shown, which contain only the plasticizer Hexamoll DINCH ^{® ® ®} or Palatinol N commercially available. The total plasticizer content of the plastisols is 100 phr.

3:

3 shows the process volatility of PVC plastisols containing 60 phr of the plasticizer composition of the invention and various mixtures of Hexamoll ^® DINCH ^® with the commercially available rapid gelators dibutyl phthalate, Vestinol ^® INB or Jayflex ^® MB 10. Shown is the weight loss of the plastisols in% after a gelling time of 2 minutes at 190 ° C. In addition, the Prozessflüchtigkeit of PVC plastisols is shown, which contain only the plasticizer Hexamoll DINCH ^{® ® ®} or Palatinol N commercially available.

4:

4 shows the film volatility of PVC films, which were prepared from plastisols containing 60 phr of the plasticizer composition used in the invention and various mixtures of Hexamoll ^® DINCH ^® with the commercially available rapid gelators dibutyl phthalate, Vestinol ^® INB or Jayflex ^® MB 10. Shown is the weight loss of the PVC films in% after a residence time of 24 h in a drying oven at 130 ° C. In addition, the film volatility of PVC films is shown, which were prepared from plastisols containing only the commercially available plasticizers Hexamoll ^® DINCH ^® or Palatinol ^® N.

Fig. 5:

5 shows the Shore A hardness of PVC films, which were made of PVC plastisols containing 60 phr of the plasticizer composition according to the invention as well as various mixtures of Hexamoll ^® DINCH ^® with the commercially available Schnellgelierern dibutyl phthalate, Vestinol ^® INB or Jayflex ^® MB 10th In addition, the Shore A hardness of films is shown, containing the plasticizer Hexamoll DINCH ^{® ® ®} or Palatinol N commercially available, were prepared from PVC plastisols exclusively. The Shore A hardness measurement was carried out after DIN ISO 868 , with readings taken every 15 seconds.

Fig. 6:

6 shows the values for the 100% modulus (elastic modulus) in MPa from PVC films, consisting of plastisols containing 60 phr of the inventively used softening composition as well as various mixtures of Hexamoll ^® DINCH ^® with the commercially available Schnellgelierern dibutyl phthalate, Vestinol ^® INB or Jayflex ^® MB were 10 made. In addition, the values for the 100% modulus (elastic modulus) of PVC films are shown, containing the plasticizer Hexamoll DINCH ^{® ® ®} or Palatinol N commercially available, were prepared from PVC plastisols exclusively.

EXAMPLES

In the examples, u. A. uses the following starting materials: feedstock Manufacturer Homopolymer emulsion PVC, brand name SolVin ^® 367 NC SolVin SA, Brussels, Belgium Homopolymer emulsion PVC, brand name Vinnolit ^® P 70 Vinnolit GmbH, Ismaning, Germany Diisononylcyclohexan-1,2-dicarboxylate, trade name DINCH ^{® ®} Hexamoll BASF SE, Ludwigshafen, Germany Isononyl, brand name Vestinol® ^® INB Evonik, Marl, Germany Isodecylbenzoat, brand name Jayflex ^® MB 10 Exxonmobil Chemical Belgium, Antwerp, Belgium Diisononylphthalat, brand name Palatinol® ^® N BASF SE, Ludwigshafen, Germany Ba-Zn stabilizer, brand name ^Reagens® SLX / 781 Reagens SpA, Bologna, Italy

I) Preparation Examples of Compounds (I) Used According to the Invention:

example 1

Synthesis of di- (2-ethylhexyl) -2,5-furandicarboxylate by direct esterification

In a 2 L round bottom flask equipped with a Dean-Stark water separator and a pressure equalizing dropping funnel, 782 g (6.00 moles, 4.0 equivalents) of 2-ethylhexanol in 500 g of toluene were charged. The mixture was heated to reflux with stirring and 234 g (1.50 mol, 1.0 equiv.) Of 2,5-furandicarboxylic acid followed by 11.5 g (0.12 mol, 8 mol%) 99.9% Sulfuric acid was added in 3 to 4 portions whenever the reaction slowed down. The course of the reaction was monitored by the amount of water deposited in the Dean-Stark apparatus. After complete conversion, a sample was taken from the reaction mixture and analyzed by GC. The reaction mixture was cooled to room temperature, transferred to a separatory funnel and washed twice with saturated NaHCO ₃ solution. The organic phase was washed with brine, dried with anhydrous Na ₂ SO ₄ and the solvent removed under reduced pressure. The crude product was purified by fractional distillation. The desired di- (2-ethylhexyl) -2,5-furandicarboxylat could be obtained in a yield of 80% and a purity of 98.9%. The identity and purity of the final product was determined by NMR and GC-MS analysis (GC separation column: Agilent J & W DB-5, 30 m × 0.32 mm × 1.0 μm or Ohio Valley OV-1701 60 m × 0.32 mm × 0.25 μm).

II) Technical Tests:

II.a) Determination of the Dissolution Temperature According to DIN 53408:

To characterize the gelling behavior of the compounds (I) used in accordance with the invention in PVC, the dissolution temperature was after DIN 53408 certainly. To DIN 53408 For example, a drop of a slurry of 1 g of PVC in 19 g of plasticizer is observed under a translucent light microscope equipped with a heatable microscope stage. The temperature is increased from 60 ° C linearly by 2 ° C per minute. The dissolution temperature is the temperature at which the PVC particles become invisible, ie their contours and contrasts are no longer recognizable. The lower the dissolution temperature, the better the gelling behavior of the substance in question for PVC.

In the following table, the dissolution temperature of the plasticizer is di (2-ethylhexyl) -2,5-furandicarboxylate and, as a comparison, the dissolution temperatures of the commercially available standard plasticizers di (2-ethylhexyl) phthalate (dioctyl phthalate, BOC Sciences, NY, US), Diisononylphthalat (Palatinol® ^® DINP, BASF Corp., Florham Park, US) and Diisononylcyclohexan-1,2-dicarboxylate (Hexamoll ^® DINCH ^®, BASF SE, Ludwigshafen, Germany) listed. Expl substance Dissolution temperature after DIN 53408 [° C] 1 Di (2-ethylhexyl) -2,5-furandicarboxylate 118 V1 Di (2-ethylhexyl) phthalate (dioctyl phthalate, BOC Sciences, NY, US) 126 V2 Diisononylphthalat (Palatinol® ^® DINP, BASF Corp., Florham Park, US) 131 V3 Diisononylcyclohexan-1,2-dicarboxylate (Hexamoll ^® DINCH ^®, BASF SE, Ludwigshafen, Germany) 151

As can be seen from the table, di (2-ethylhexyl) -2,5-furandicarboxylate shows the lowest dissolution temperature. With a value of 118 ° C this is surprisingly in the range of fast-gelling plasticizers, d. H. below 120 ° C.

II.b) Determination of the gelling behavior of PVC plastisols containing the plasticizer composition according to the invention:

To investigate the gelling of PVC plastisols based on the softener compositions according to the invention, were PVC plastisols, the plasticizer blends of commercially available Hexamoll ^® DINCH ^® with the gellant 2,5-furan dicarboxylic acid-di-2-ethylhexyl esters in different proportions contain (Hexamoll ^® DINCH ^® to 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester 50/50, 70/30 and 80/20) prepared according to the following formulation: feedstock Share [phr] PVC (mixture of 70 parts by weight of homopolymer emulsion PVC, brand name Solvin ^® 367 NC and 30 parts by weight of homopolymer emulsion PVC, brand name Vinnolit P ^® 70) 100 Plasticizer composition of the invention 100 Ba-Zn stabilizer, type ^Reagens® SLX / 781 2

Moreover plastisols were produced as comparison, which exclusively contain plasticizers Hexamoll ^® DINCH ^® or Palatinol® ^® N commercially available.

The plastisols were prepared by weighing the two types of PVC together in a PE (polyethylene) cup. The liquid components were weighed into a second PE beaker. With the aid of a dissolver (Jahnke & Kunkel, IKA-Werk, type RE-166 A, 60-6000 1 / min, dissolver disc diameter = 40 mm), the PVC was stirred into the liquid components at 400 rpm. After a plastisol had been formed, the speed was increased to 2500 1 / min and homogenized for 150 s. The plastisol was transferred from the PE cup to a steel bowl and exposed to a pressure of 10 mbar in a desiccator. This is intended to remove the air contained in the plastisol. Depending on the air content, the plastisol inflates more or less strongly. At this stage shaking the desiccator destroys the surface of the plastisol and causes it to collapse. From this point on the plastisol is left for 15 minutes in the desiccator at a pressure of 10 mbar. Then the vacuum pump is switched off, the desiccator is vented and the plastisol is transferred back to the PE cup. The plastisol is now ready for rheological measurements. The beginning of the measurement was 30 min after homogenization for all plastisols.

In order to gel a liquid PVC plastisol and to convert it from the state of homogeneous PVC particles dispersed in plasticizer into a homogeneous, solid soft PVC matrix, the energy required for this must be supplied in the form of heat. In a processing process, the parameters temperature and dwell time are available for this purpose. The faster the gelation proceeds (indication here is the dissolving temperature, ie the lower it is, the faster the material gels), the lower the temperature (with the same residence time) or the residence time (at the same temperature) can be selected.

The investigation of the gelling behavior of a plastisol takes place with a rheometer MCR101 from Anton Paar. The viscosity of the paste is measured under heating at constant, low shear (oscillation). The following parameters were used for the oscillation experiments: Measuring system: Parallel plates, 50 mm diameter Amplitude γ: 1 % Frequency: 1 Hz Slit width: 1 mm Outlet temperature: 20 ° C Temperature profile: 20 ° C-200 ° C Heating rate: 10 ° C / min Number of measuring points: 201 Measurement duration of the individual measuring points: 0.09 min

The measurement was carried out in two steps. The first step is only the tempering of the sample. At 20 ° C, the plastisol is sheared gently for 2 min at constant amplitude (γ = 1%). In the second step, the temperature program starts. During measurement, the memory module and the loss modulus are recorded. From these two quantities the complex viscosity η * is calculated. The temperature at which the maximum of the complex viscosity is reached is referred to as the gelling temperature of the plastisol.

Like in the 1 can be seen very well, the PVC plastisols gel with the plasticizer composition according to the invention in comparison to the PVC plastisol, which contains only the commercially available plasticizer Hexamoll ^® DINCH ^® , at significantly lower temperatures. At a composition of 50% Hexamoll ^® DINCH ^® and 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester a gelling temperature of 150 ° C is reached, corresponding to the gelling temperature of the plasticizer commercially available Palatinol ^® N and for many Plastisol applications is sufficient. By further increasing the proportion of the gelling aid 2,5-furandicarboxylic acid di-2-ethylhexyl ester in the plasticizer compositions used according to the invention, the gelling temperature of the plastisols can be further significantly reduced.

II.c) Determination of the gelling behavior of PVC plastisols based on the plasticizer composition according to the invention in comparison with PVC plastisols which contain conventional fast gels:

In order to compare the gelling behavior of PVC plastisols containing the plasticizer compositions according to the invention with PVC plastisols containing plasticizer compositions from conventional rapid gels, the procedure described in II.b) was followed. The mixing ratio with the commercially available plasticizer Diisononylcyclohexan-1,2-dicarboxylate (DINCH ^® Hexamoll ^®) was initially for the conventional Schnellgelierer isononyl benzoate (INB Vestinol ^®) and Isodecylbenzoat (Jayflex ^® MB 10) determines that a setting temperature of 150 ° C causes corresponding to the gelling temperature of the plasticizer commercially available Palatinol ^® N and which is sufficient for many plastisol applications.

For Vestinol ^® INB this mixing ratio is 55% and 45% Vestinol ^® INB Hexamoll ^® DINCH ^® and Jayflex ^® MB 10 MB 67% Jayflex ^® 10 and 33% Hexamoll ^® DINCH ^®.

In 2 are the gelling curves of the PVC plastisols with softener compositions from the commercially available Schnellgelierern Vestinol ^® INB and Jayflex ^® MB compared to the gelling curves of the PVC plastisols containing softener compositions according to the invention, assembled. The gelling curves of the PVC plastisol also included as a comparison, which exclusively contain plasticizers Hexamoll ^® DINCH ^® or Palatinol® ^® N commercially available. From the 2 It can be seen very clearly that in the plasticizer compositions according to the invention a proportion of the 50% strength double-agent 2,5-furandicarboxylic acid di-2-ethylhexyl ester according to the invention is sufficient to achieve a gelling temperature of 150 ° C., which corresponds to the gelling temperature of commercially available plasticizer Palatinol® ^® N is and is sufficient for many plastisol applications. However, are in the softening compositions containing the conventional Schnellgelierer Vestinol ^® INB or Jayflex ^® MB 10, higher levels of 55% Vestinol ^® INB and 67% Jayflex ^® MB 10 are required to achieve a gelling temperature of the plastisols of 150 ° C. Accordingly, the Schnellgelierer inventively used 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester has better than the conventional gelling Schnellgelierer Vestinol ^® INB and Jayflex ^® MB 10th

II.d) Determination of the process volatility of the plasticizer compositions according to the invention in comparison with plasticizer compositions with conventional fast gels

Process volatility refers to the weight loss of plasticizer during the processing of plastisols. Plastisols were made with a softener composition of 50% of the Schnellgelierers as described under II.c) of 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% of the plasticizer commercially available Hexamoll ^® DINCH ^® and with the softener compositions 55% of the commercially available Gelierhilfsmittels Vestinol ^® INB and 45% of the plasticizer commercially available Hexamoll ^® DINCH ^® and 67% of the commercially available Schnellgelierers Jayflex ^® MB 10 and 33% of the plasticizer commercially available Hexamoll ^® DINCH ^®. The following recipe was used. feedstock Share (phr) PVC (mixture of 70 parts by weight of homopolymer emulsion PVC, brand name Solvin ^® 367 NC and 30 parts by weight of homopolymer emulsion PVC, brand name Vinnolit P ^® 70) 100 Plasticizer composition 60 Ba-Zn stabilizer, type ^Reagens® SLX / 781 2

Moreover plastisols were produced as comparison, which exclusively contain plasticizers Hexamoll ^® DINCH ^® or Palatinol® ^® N commercially available.

Production of a prefilm

In order to be able to determine the application properties of the plastisols, the liquid plastisol must be converted into a processible solid film. For this, the plastisol is pre-gelled at low temperature.

• • Abluft: Klappe ganz offen
• • Frischluft: offen
• • Umluft: maximale Position
• • Oberluft/Unterluft: Oberluft Stellung 1

Gelation of the plastisols took place in a Mathis oven. The following settings were used on the Mathisofen:
Settings at Mathisofen:

• • Exhaust air: flap completely open
• • Fresh air: open
• • Recirculation: maximum position
• • Upper / lower air: upper air position 1

manufacturing procedure:

A new relay paper was clamped in the fixture at the Mathisofen. The oven is preheated to 140 ° C and the gel time is set to 25 s. For the gap adjustment, the gap between the paper and the squeegee with the thickness template is set to 0.1 mm. The thickness gauge is set to 0.1 mm. Then the gap is set to a value of 0.7 mm on the dial gauge.

The plastisol is applied to the paper and smoothed with a squeegee. Then the jig is moved into the oven via the start button. After 25 s, the clamping device moves out of the oven again. The plastisol is gelled and the resulting film can just be peeled in one piece from the paper. The thickness of this film is about 0.5 mm.

Determination of process volatility

To determine the process volatility, 3 square specimens (49.times.49 mm) are punched out with a Shore hardness punching iron from the prefilm, weighed and then at 190.degree. C. for 2 minutes Mathisofen gels. After cooling, these specimens are weighed back and the weight loss in% is calculated. The specimens were always positioned exactly in the same position of the relay paper.

How out 3 very well seen, the Prozessflüchtigkeit the present softening composition consisting of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll ^® DINCH ^® is significantly lower than the Prozessflüchtigkeit the softening compositions of 55% Vestinol ^® INB and 45% Hexamoll DINCH ^{® ® ®} MB and 67% Jayflex 10 and 33% Hexamoll ^® DINCH ^®. The Prozessflüchtigkeit the composition of the invention is also significantly lower than the volatility of a mixture of 20% di-n-butyl phthalate and 80% Hexamoll ^® DINCH ^®. In the processing of the plastisols based on the plasticizer compositions used according to the invention, significantly less plasticizer is lost.

The Prozessflüchtigkeit the present softening composition consisting of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll ^® DINCH ^® is, however, slightly higher than the pure plasticizer Hexamoll ^® DINCH ^® or Palatinol ^® N.

II.e) Determination of the film volatility of films of plastisols containing the plasticizer compositions according to the invention in comparison to films made of plastisols containing plasticizer compositions with conventional fast gels

Foil volatility is a measure of the volatility of a plasticizer in the final plasticized PVC article. For the examination of the plastisols were Folienflüchtigkeit containing plasticizer composition according to the invention consisting of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll ^® DINCH ^® and plastisols with softening compositions of 55% of the commercially available Vestinol ^® INB and 45% Hexamoll ^® DINCH ^®, 67% Jayflex MB ^® 10 and 33% Hexamoll ^® DINCH ^® and 20% di-n-butyl phthalate and 80% Hexamoll ^® DINCH ^® prepared as described under II.d). Moreover plastisols were produced as comparison, which exclusively contain plasticizers Hexamoll ^® DINCH ^® or Palatinol® N commercially available. For the tests, however, not only was a preliminary film produced, but the plastisol was gelled directly at 190 ° C. for 2 minutes in the Mathis oven. On the approximately 0.5 mm thick films thus obtained, the film volatility test was carried out.

Testing the film volatility for 24 h at 130 ° C:

To determine the film volatility, four individual sheets (150 × 100 mm) are cut out, perforated and weighed from the plastisols gelled at 190 ° C. for 2 minutes. The films are hung on a rotating star in a Heraeus Type 5042 E drying oven set at 130 ° C. In the cabinet, the air is changed 18 times an hour. This corresponds to 800 l / h of fresh air. After 24 hours in the cabinet, the slides are removed and weighed back. The percent weight loss indicates the film volatility of the softener compositions.

How out 4 very well seen, the Folienflüchtigkeit the present softening composition consisting of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll ^® DINCH ^® is considerably lower, ie to the 5- to 7-fold lower than the Folienflüchtigkeit the plasticizer composing Requirements of 55% and 45% Vestinol ^® INB Hexamoll DINCH ^{® ® ®} and 67% Jayflex 10 MB and 33% Hexamoll ^® DINCH ^®. The Folienflüchtigkeit the composition of the invention is also significantly lower than the volatility of a mixture of 20% di-n-butyl phthalate and 80% Hexamoll ^® DINCH ^®. In the case of PVC films containing the plasticizer compositions according to the invention, therefore, substantially less plasticizer escapes in the finished plasticized PVC article.

The Folienflüchtigkeit the present softening composition consisting of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll ^® DINCH ^® is, however, slightly higher than the pure plasticizer Hexamoll ^® DINCH ^® or Palatinol ^® N.

II.f) Determination of Shore A hardness of films made from plastisols containing the plasticizer composition of the invention compared to films made from plastisols containing plasticizer compositions with conventional fast gels

Shore A hardness is a measure of the elasticity of plasticized PVC articles. The lower the Shore hardness, the higher the elasticity of PVC articles. For the determination of the Shore A hardness, 49 × 49 mm pieces of film were punched out of the prefilms and described in the same way as described under II.d) Volatility test each in three-pack 2 min at 190 ° C gelled. In total, 27 pieces of film were gelled. These 27 pieces were superimposed in the press frame and pressed at 195 ° C to a 10 mm thick Shore logs.

• • Methode: DIN EN ISO 868 , Okt. 2003,
• • Titel: Bestimmung der Eindruckhärte mit einem Durometer (Shore-Härte),
• • Gerät: Fa. Hildebrand- Digital Durometer Modell DD-3,
• • Probekörper:
• • Maße: 49mm × 49mm × 10mm (Länge × Breite × Dicke),
• • Herstellung: gepresst aus ca. 27, 0,5mm dicken Gelierfolien,
• • Presstemperatur: 195 °C = 5 °C über der Herstellung der Gelierfolien.
• • Lagerzeit vor Messung: 7d im Klimaraum bei 23 °C und 50 % rel. Feuchte,
• • Messzeit: 15 s (Dauer der Nadel auf dem Probekörper bis zum Ablesen des Wertes),
• • es werden 10 Einzelwerte gemessen und daraus der Mittelwert berechnet.

Description of Shore hardness measurement:

• • Method: DIN EN ISO 868 , Oct. 2003,
• • Title: Determination of indentation hardness with a durometer (Shore hardness),
• • Device: Fa. Hildebrand- Digital Durometer Model DD-3,
• • test specimen:
• • Dimensions: 49mm × 49mm × 10mm (length × width × thickness),
• • Production: pressed from approx. 27, 0.5mm thick gelling foils,
• • Pressing temperature: 195 ° C = 5 ° C above the production of the gelling foils.
• • Storage time before measurement: 7d in the climatic room at 23 ° C and 50% rel. humidity,
• • Measuring time: 15 s (duration of the needle on the sample until reading the value),
• • 10 individual values are measured and from this the mean value is calculated.

How out 5 well seen that the Shore A hardness of the film of the plastisol with the plasticizer composition of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll ^® DINCH ^® is significantly lower than the Shore A hardness of the films of the plastisols with the softening compositions of 55% and 45% Vestinol ^® INB Hexamoll® DINCH ^® and 67% Jayflex ^® MB and 33% Hexamoll ^® DINCH ^®. The inventive use of softening compositions containing 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and Hexamoll ^® DINCH ^®, thus resulting in a higher elasticity of the PVC article.

The Shore A hardness of the film of the plastisol with the plasticizer composition of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll ^® DINCH ^® is also significantly lower than the Shore A hardness beyond the film of the plastisol with the pure plasticizer Hexamoll ^® DINCH ^® and surprisingly equivalent or even slightly lower than the Shore A hardness of the film from the plastisol with the pure plasticizer Palatinol ^® N.

II.g) Determination of the mechanical values of films of plastisols containing plasticizer compositions used according to the invention, in comparison to films of plastisols containing plasticizer compositions of commercially available gelling aids:

The mechanical properties of plasticized PVC articles are characterized, for example, by means of the 100% modulus (elastic modulus). The lower the value of the 100% modulus (modulus of elasticity), the more efficient is usually the effect of the plasticizer. For the examination of the 100% modulus (elastic modulus) were plastisols with a softening composition consisting of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll ^® DINCH ^® and plastisols with the softening compositions of 55% Vestinol ^® INB and 45% Hexamoll ^® DINCH ^®, 67% Jayflex ^® MB and 33% Hexamoll® DINCH ^® and 20% di-n-butyl phthalate and 80% Hexamoll ^® DINCH ^®, prepared as described under II.d). Moreover plastisols were produced as comparison, which exclusively contain plasticizers Hexamoll ^® DINCH ^® or Palatinol® ^® N commercially available. For the tests, however, not only was a preliminary film produced, but the plastisol was gelled directly at 190 ° C. for 2 minutes in the Mathis oven. The mechanical properties were tested on the approx. 0.5 mm thick films thus obtained.

• • Maschine: Zwicki Typ TMZ 2.5/TH1S,
• • Methode: Prüfung nach DIN EN ISO 527 Teil 1 und Teil 3 ,
• • Probekörper: Folienstreifen Typ 2 nach DIN EN ISO 527 Teil 3 , 150 mm lang, 15 mm breit, ausgestanzt,
• • Anzahl Probekörper pro Prüfung werden 10 Proben gerissen,
• • Klima: Normklima 23 °C (+–1 °C), 50 % relative Luftfeuchtigkeit,
• • Lagerzeit der Probekörper vor der Messung: 7 Tage im Normklima,
• • Klemmen: Glatt-Konvex mit 6 bar Klemmendruck,
• • Einspannlänge: 100 mm,
• • Messlänge (= Einspannlänge): 100 mm,
• • Prüfgeschwindigkeit: 100 mm/min.

The 100% module was after DIN EN ISO 527, part 1 and following 3 , certainly. More specifically, the procedure is as follows.

• • machine: Zwicki type TMZ 2.5 / TH1S,
• • Method: check after DIN EN ISO 527 Part 1 and Part 3 .
• • Test specimen: foil strip type 2 after DIN EN ISO 527 Part 3 , 150 mm long, 15 mm wide, punched out,
• • Number of specimens per test are torn 10 samples,
• • Climate: standard climate 23 ° C (+ -1 ° C), 50% relative humidity,
• • Storage time of the specimens before the measurement: 7 days in standard atmosphere,
• • clamps: smooth convex with 6 bar clamping pressure,
• • clamping length: 100 mm,
• • measuring length (= clamping length): 100 mm,
• • Test speed: 100 mm / min.

How out 6 very well seen, the value for the 100% modulus (elastic modulus) of the film made of the plastisol with the plasticizer composition of 50% 2,5-furan dicarboxylic acid-di-2-ethylhexyl ester and 50% Hexamoll DINCH ^{® ®} significantly lower than the values for the films, prepared from the plastisols with the softener compositions of 55% Vestinol ^® INB and 45% Hexamoll ^® DINCH ^® and 67% Jayflex ^® MB 10 and 33% Hexamoll ^® DINCH ^® and in something lower than the values for the films prepared from the plastisol containing the plasticizer composition of 20% di-n-butyl phthalate and 80% Hexamoll ^® DINCH ^® or solely the pure plasticizers Hexamoll ^® DINCH ^®.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (27)

Plasticizer composition comprising a) at least one compound of the general formula (I),

where X is * - (C = O) -O-, * - (CH ₂ ) _n -O- or * - (CH ₂ ) _n -O- (C = O) -, where * is the point of attachment to the furan ring and n is 0, 1 or 2; and R ¹ and R ² independently of one another are an unbranched or branched C ₈ -alkyl radical, b) at least one compound of the general formula (II),

wherein R ³ and R ^{4 are} independently selected from branched and unbranched C ₇ -C ₁₂ alkyl radicals. Plasticizer composition according to claim 1, wherein in the compounds of general formula (I) R ¹ and R ² independently of one another represent an unbranched or branched C ₈ -alkyl radical selected from n-octyl, iso-octyl or 2-ethylhexyl. Plasticizer composition according to any one of the preceding claims, wherein in the compounds of general formula (I) R ¹ and R ^{2 are} both 2-ethylhexyl. Plasticizer composition according to any one of the preceding claims, wherein in the compounds of general formula (I) the group X is both * - (C = O) -O-. Plasticizer composition according to one of the preceding claims, wherein in the compounds of general formula (II) R ³ and R ^{4 are} both 2-ethylhexyl, both isononyl or both are 2-propylheptyl. Plasticizer composition according to one of the preceding claims, wherein the plasticizer composition optionally contains a further plasticizer other than the compounds (I) and (II) selected from phthalic acid dialkyl esters, phthalic acid alkylaralkyl esters, 1,2-cyclohexanedicarboxylic acid esters other than compounds (II) , Terephthalic acid dialkyl esters, trimellitic acid trialkyls, alkyl benzoates, dibenzoic acid esters of glycols, hydroxybenzoic acid esters, esters of saturated mono- and dicarboxylic acids, esters of unsaturated dicarboxylic acids, amides and esters of aromatic sulfonic acids, alkylsulfonic esters, glycerol esters, isosorbide esters, phosphoric acid esters, citric acid triesters, alkylpyrrolidone derivatives, of compounds (I) various 2,5-furandicarboxylic acid esters, 2,5-tetrahydrofurandicarboxylic acid esters, epoxidized vegetable oils and epoxidized fatty acid monoalkyl esters, polyesters of aliphatic and / o the aromatic polycarboxylic acids with at least dihydric alcohols. A plasticizer composition according to any one of claims 1 to 6, wherein the content of compounds of the general formula (I) in the plasticizer composition is 1 to 65% by weight. A plasticizer composition according to any one of claims 1 to 6, wherein the content of compounds of the general formula (I) in the plasticizer composition is 1 to 50% by weight. A plasticizer composition according to any one of claims 1 to 6, wherein the content of compounds of the general formula (I) in the plasticizer composition is 25 to 65% by weight. A plasticizer composition according to any one of claims 1 to 6, wherein the content of compounds of the general formula (II) in the plasticizer composition is 10 to 99% by weight. A plasticizer composition according to any one of claims 1 to 6, wherein the content of compounds of the general formula (II) in the plasticizer composition is 35 to 75% by weight. A plasticizer composition according to any one of claims 1 to 11, wherein the weight ratio between compounds of general formula (I) and compounds of general formula (II) ranges from 1: 100 to 2: 1. A plasticizer composition according to any one of claims 1 to 11 wherein the weight ratio between compounds of general formula (I) and compounds of general formula (II) ranges from 1: 100 to 1: 1. A plasticizer composition according to any one of claims 1 to 11, wherein the weight ratio between compounds of general formula (I) and compounds of general formula (II) ranges from 1: 3 to 2: 1. A molding composition containing at least one polymer and a plasticizer composition as defined in any one of claims 1 to 14. Molding composition according to Claim 15, in which the polymer is a thermoplastic polymer selected from the group consisting of - homopolymers or copolymers which contain, in copolymerized form, at least one monomer selected from C ₂ -C ₁₀ -monoolefins, Butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and its C ₂ -C ₁₀ -alkyl esters, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of C ₁ -C ₁₀ -alcohols, vinylaromatics, ( Meth) acrylonitrile, maleic anhydride and α, β-ethylenically unsaturated mono- and dicarboxylic acids, - homo- and copolymers of vinyl acetals, - polyvinyl esters, - polycarbonates, - polyesters, - polyethers, - polyether ketones, - thermoplastic polyurethanes, - polysulfides, - polysulfones, - Polyethersulfonen, - Cellulosealkylestern, and mixtures thereof. Molding composition according to claim 16, 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. A molding composition according to any one of claims 16 or 17, wherein the thermoplastic polymer is polyvinyl chloride (PVC). A molding composition according to claim 18, wherein the content of the plasticizer composition in the molding composition is 1.0 to 300 phr. A molding composition according to any one of claims 16 or 17, comprising at least one thermoplastic polymer other than polyvinyl chloride, the content of the plasticizer composition in the molding composition being from 0.5 to 300 phr. Molding composition according to claim 15, wherein the polymer is an elastomer, preferably selected from natural rubbers, synthetic rubbers and mixtures thereof. A molding composition according to claim 21, wherein the content of the plasticizer composition in the molding composition is 1.0 to 60 phr. Use of a plasticizer composition as defined in any one of claims 1 to 14 as a plasticizer for thermoplastic polymers and elastomers. Use of a plasticizer composition as defined in any one of claims 1 to 14 as a plasticizer in a plastisol. Use of a molding composition as defined in any of claims 15 to 22 for the production of moldings and films, such as housings of electrical appliances, computer housings, tools, pipelines, cables, hoses, wire sheathings, window profiles, components for vehicle construction, tires, Furniture, foam for upholstery and mattresses, tarpaulins, gaskets, composite films, vinyl records, imitation leather, packaging containers, adhesive tape or coatings. Use of a molding composition as defined in any one of claims 15 to 22 for the manufacture of moldings and films which come into direct contact with humans or foodstuffs. Use as defined in claim 26, wherein the moldings and films which come into direct contact with humans or food include medical devices, hygiene products, food packaging, indoor products, toys and childcare articles, sports and leisure products, clothing or fibers for tissue acts.

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