Mixture of diesters of dianhydrohexitol derivatives with carboxylic acids of empirical formula c₈h₁₇cooh, methods of producing said diesters and use of said mixtures

FIELD: chemistry.

SUBSTANCE: invention relates to a mixture of diesters of formula I with R¹-R⁸=H or an alkyl group with 1-6 carbon atoms, wherein residues R¹-R⁸ may be identical or different, which is characterised by that the mixture contains at least two different diesters I differing in the structure of at least one of the carboxylic acid radicals C₈H₁₇COO present, plasticiser properties; the invention also relates to use of said mixtures in paints, inks or coatings, in plastisols, adhesives or adhesive components, in sealants, as plasticisers in plastic or plastic components, as solvents, as lubricant components and as auxiliary materials in metal processing, and a method of producing diesters of isosorbide derivatives of formula I. The invention also describes compositions with PVC or plastisol containing the disclosed mixtures.

EFFECT: described are mixtures which can be used as plasticisers in plastic or plastic components, as solvents, as lubricant components and as auxiliary materials in metal processing.

The present invention relates to a complex mixture of diesters derived diaminohexane with carboxylic acids total formula C₈H₁₇COOH, in particular esters of isosorbide of these carboxylic acids. Also the present invention relates to a method of producing these esters or mixtures and their application.

Polyvinyl chloride (PVC) is one of the most important in the economy of the polymers. Versatile used as unplasticized PVC and plasticized PVC.

To obtain a plasticized PVC to PVC type plasticizers, and in most cases, using esters of phthalic acid, such as di-2-ethylhexylphthalate (DEHP), diisononylphthalate (DINP) and diisodecylphthalate (DIDP). Along with this, as plasticizers for such synthetic materials such as polyvinyl chloride (PVC), polyvinylbutyral (PVB) and the polyolefin is also used, for example, alicyclic esters of polycarboxylic acids as esters of cyclohexane-1,2-dicarboxylic acid, since they are considered safer for health than the corresponding esters of phthalic acid. In addition, these esters can be used as components of lubricating oils or as an aid in the metal.

The above-mentioned aromatic or aliphatic the Kie esters of polycarboxylic acids are based entirely on fossil raw materials with limited availability. Therefore, to conserve fossil resources necessary esters of polycarboxylic acids which are at least partially based on reproducible raw materials.

From patent WO 99/45060 known application of isosorbide derivatives, in particular esters of isosorbide as plasticizers, for example, polyvinyl chloride (PVC). To obtain esters isosorbide undergoes reaction with the corresponding carboxylic acids. Residues of carboxylic acids can contain from 3 to 12 carbon atoms, and as a possible residues of carboxylic acids are named butanol, hexanol, 2-ethylhexanol, octanol and decanol. In the examples describes how to get isosorbide-dictyota, isosorbide-debutante, isosorbide-directoraat and isosorbide bis(2-ethylhexanoate).

In WO 01/83488 describes how to obtain esters of isosorbide, which digitalcity, monoaminergic or glycidol subjected to reaction with the corresponding carboxylic acid, which mainly has 3-20 carbon atoms, in the presence of a macroporous acid ion-exchange resin. When this molar ratio ((di), anhydrous)gliricola to carboxylic acid is from 2 to 5. The description indicated that the reaction can be carried out with acids with branched or unbranched chain. For example, as a possible acids called the propanoic acid, hexanoic acid, octanoic acid, novanova or cekanova acid. In the examples isosorbide reacts octanoic acid or 2-ethylhexanoate acid.

Proceeding from the prior art, the present invention is to obtain an alternative esters of isosorbide suitable as plasticizers, particularly for the PVC plasticization.

When using both commercially available Romanovyh acids, pelargoniums acid (n-nonanol acid and 3,5,5-trimethylhexanoic acid, to obtain the corresponding derivative diaminohexane it was found that the thus obtained esters only conditionally can be used as plasticizers for PVC.

However, unexpectedly it was found that esters diaminohexane, in particular esters of isosorbide, carboxylic acids with 9 hydrocarbons that contain a mixture of at least two Romanovyh acids with different structure and are predominantly one a certain degree of branching, is particularly well suitable as plasticizers, in particular as plasticizers for PVC.

Therefore, the object of the present invention is a mixture containing a complex diesters of the formula I derived diaminohexane with carboxylic acids total formula C₈H₁₇COOH

with R¹-R⁸=H or alkyl group with 1-6 carbon atoms, and the remainders R¹-R⁸may be the same or differentiating, characterized in that the mixture contains at least two different complex diapir I, which differ in the structure, at least one of the available residues of carboxylic acid C₈H₁₇COO.

The object of the present invention is also a method of obtaining complex diesters of the formula I, characterized in that hexavalent alcohol of the formula II

where the residues R¹-R⁸have the meanings indicated in formula I, and/or anhydrous or dianhydro-derived alcohol of formula II is subjected to reaction with a mixture having at least two different carboxylic acids total formula C₈H₁₇COOH.

In addition, the subject of the present invention is the use of mixtures according to the invention in paints, inks or varnishes, plastisols, adhesives or components of adhesives, sealing compounds, as plasticizers in plastics or plastics components, as solvents, as components of lubricants and as auxiliary materials for Metalworking, as well as composition with PVC or plastisol containing PVC and from 5 to 250 mass parts, see the si according to the invention on 100 mass parts of the PVC.

The advantage of the mixtures according to the invention lies in the fact that they are partly based on reproducible raw materials, and therefore are guaranteed their availability in the future. As shown by research first dialkanolamine esters of isosorbide are generally favorable Toxicological properties (van Haveren et al., ACS Symposium series 2006, Vol.921, p.99-115). Further, if the acid residue no Quaternary carbon atoms, or has only a small amount, we can hope for a good capability to biological decomposition.

Compared to mixtures containing the compounds of formula I, based on the carboxylic acid isomer, and in which residues of carboxylic acids have a degree of branching less than 0.7, the mixture according to the invention differ, as a rule, the best Miscibility with PVC. For example, isosorbide ether n-nonanol acid (pelargoniums acid) solid at room temperature, which complicates or precludes its use in the application of plastisols. Compared to mixtures containing the compounds of formula I which have a degree of branching residues of carboxylic acids greater than 2.0, the mixture according to the invention differ considerably better properties at low temperatures (elasticity of plastics at low temperatures) and lower viscosity of the plastisols.

If within the present invention it is about isononanoic acid or sonnoli, this always refers to the isomer or mixture of isomers of nonanalog acid or nonanol. Isononanoate acid or isononanol may have isomers both branched and unbranched chain.

The mixture according to the invention of complex diesters derived diaminohexane with carboxylic acids total formula I

with R¹-R⁸=H or alkyl group with 1-6 carbon atoms, and the remainders R¹-R⁸may be the same or different, are distinguished by the fact that the mixture contains at least two different complex diapir I, which differ in the structure, at least one of the available residues and/or the two residues of carboxylic acid C₈H₁₇COO. When this mixture may have a difficult diesters, where one or both of the remainder of the carboxylic acids are unbranched, with monorities and/or multiply branched chain.

Mainly a mixture according to the invention are prepared in such a manner that carboxylic acids obtained by saponification of complex mixtures of diesters, had at least two carboxylic acid total formula with different structural formula, and none of the members of the mixture of carboxylic acids and not eat share of more than 95 mol.%, preferably, not more than 90 mol.%.

Can be advantageous, if the carboxylic acid total formula C₈H₁₇COOH, obtained by saponification included in the mixture according to the invention of complex diesters of the formula I, have less than 10 mol.%, preferably less than 5 mol.%, even more preferably less than 1 mol.% and most preferably from 0.0001 to 1 mol.% 3,5,5-trimethylhexanoic acid or other trisemester Romanovyh acids with Quaternary carbon atoms.

Preferably the mixture of carboxylic acids total formula C₈H₁₇COOH, obtained by saponification according to the invention of complex mixtures of diesters of the formula I, have less than 1 mol.%, preferably less than 0.001 mol.% acids, which have a Quaternary carbon atom, and preferably their complete absence. This gives the advantage that the corresponding acids or esters are more biodegradable and thus contribute to a better environmental balance.

In addition, it may be advantageous if the carboxylic acid total formula C₈H₁₇COOH, obtained by saponification included in the mixture according to the invention of complex diesters of the formula I, have 1-85%, especially 1-50%, preferably 2-20% n-nonanol acid.

Saponification complex diesters of the formula I can be carried out by conventional methods by exchange reaction with alkaline environments (see, n is the sample, Ullmann''s Enzyklopädie der Technischen Chemie, 5th Ed. A 10, S.254-260, 1986). The proportion of carboxylic acids in the mixture, in particular the share of 3,5,5-trimethylhexanoic acid, can be determined in the usual way, for example by the methods gasochromatic analysis (GC), preferably after derivation in methyl or silyl ether.

Especially preferred residues of carboxylic acids total formula C₈H₁₇COO complex diesters contained in the mixture, are the remains with a degree of branching of from 0.7 to 2.0, mostly from 0.9 to 1.9, preferably from 1.0 to 1.8, and particularly preferably from 1.2 to 1.7. At the same time balances carboxylic acids are those which are based on a mixture of two or more isomers of carboxylic acids total formula C₈H₁₇COOH.

The average degree of branching can be determined by methods of nuclear magnetic resonance (NMR), if esters of isosorbide carboxylic acids total formula C₈H₁₇COOH in the ring are unsubstituted complex diesters. According to this invention the determination of the degree of branching is done using¹H-NMR spectroscopy in solution of complex diesters in deuterium chloroform (CDCl₃). To remove the spectrum, for example, 20 mg of the substance can be dissolved in 0.6 ml CDCl₃(containing 1 wt.% TMS) and poured in a NMR tube with a diameter of 5 mm As investigated the matter, and CDCl₃can be first dried over molecular sieve to eliminate the error of the measurement results due to the possible presence of water. This method of determining the degree of branching has the advantage over other methods for the characterization of residues of alcohols, as described, for example, in WO 03/029339 because of the admixture of water, essentially no influence on the measurement results and their evaluation. Since the signal band of 2.3 ppm in partially α-branched isononanoic acids near-CH₂-COOR denotes the group-CH-COOR-as a comparison of selected signal group esterified groups core isosorbide between the 5.3 and 5.5 ppm. Studies by NMR spectroscopy can be performed with any standard NMR instrument. For these NMR spectroscopic studies were used device type Avance 500 (Bruker). Spectra were filmed with the following parameters: temperature 303 K, the delay dl=5 seconds, passage 32, the pulse is 30° and the spectral width of 1000 Hz, using a 5 mm BBO-trial head (observation in a wide band). Other standard NMR devices with the same operating parameters were obtained comparable results.

Received¹H-NMR spectra of complex mixtures of diesters of isosorbide show resonance signals in the range from 0.5 ppm to at least the bottom of the trench in the region of from 0.9 to 1.1 ppm, which is ratwani signals of the hydrogen atoms of the methyl group (metal groups) carboxylic acids. Signals at chemical shifts between 3.5 to 5.5 ppm may correspond to the signals of the main part of the isosorbide, and this may partly be the imposition of separate signals 8 protons(1+1):1:1:(1+1+1):1. Quantitative expression is carried out by determining the area under the respective resonance signals, i.e. the area bounded by the main signal line, the Standard NMR devices have device for summing the square of the signal. In the present NMR-spectroscopic studies, the summation was carried out using the program "xwinnmr version 3.5. Then we took the ratio of the aggregate value of the signals in the range of from 0.5 to at least the bottom of the trench in the region of from 0.9 to 1.1 ppm (=I(CH₃)) and signals in the range of from 5.0 to 5.3 ppm (=I(core)), divided by the number of protons. Since each methyl group has three hydrogen atoms, and each molecule contains two₉acid residue, the intensity of the signal group SN₃must be divisible by 6; since each molecule has 2 esterified group core isosorbide, this signal should be divided by 2 to get the number of metal bands in each remnant of isononanol. Since linear primary novanova acid having only one terminal methyl group has no branches and, respectively, the degree is the effect should be equal to 0, of this amount, subtract 1.

Thus, the degree of divergence of V can be calculated from the measured intensity ratio according to the following formula:

where V = average degree of branching, i.e. the number of branches in C₉acid residue;

I(CH₃) = the integral over the surface between 0.5 and 1.0 ppm, which corresponds to the hydrogen atoms of a metal of groups;

I(core) = the integral over the surface between 5.0 and 5.3 ppm esterified core group of isosorbide.

In an alternative method of determining the degree of branching is used for the esterification of carboxylic acids are converted to methyl ether, and then, by analogy with the above described method is determined by the intensity of the signal related to the methyl groups of the alkyl residue, and the intensity of the signal methoxy ether group (I (och₃)), and taken their relationship. The advantage of this method is that it can be applied even in the presence of the ring substituted complex diesters. The degree of branching in this way is determined by the following formula:

For complex diesters of the formula I, in particular complex diesters isosorbide, had maybe a wide range of applications, they must be liquid at room temperature and less viscous. The complex EF the ditch phthalic acid viscosity decreases with increasing linearity used danilovogo alcohol (C ₉-alcohol) or a mixture with nonlawyer alcohol (mixture with₉-alcohol). The lowest viscosity is di-n-nonliteral and therefore the most easily processed. Unexpectedly, it was found that for complex diesters of the formula I, in particular for complex isosorbide diesters, the situation is completely different. If isosorbide tarifitsiruetsya with pelargoniums acid (n-novanova acid), the resulting plasticizer is a solid at room temperature (MP according to our measurements using a differential scanning calorimeter DSC at 27°C, "Onset") and cannot therefore be used for most applications plastisol without additional costs for his treatment. Further, complex fluids commercially available 3,5,5-trimethylhexanoic acid has only a very limited fluidity at room temperature (melting temperature of 21.7°C, "Onset" in the measurement instrument DSC). On the contrary, according to the invention a complex diesters of the formula I, in particular of complex fluids isosorbide based, at least two different carboxylic acids total formula C₈H₁₇COOH, have good fluidity and demonstrate, as shown in the examples, good processing characteristics. The most suitable are such complex diesters of the formula I, in particular complex diefy the s isosorbide, on the basis of a mixture of carboxylic acids total formula C₈H₁₇COOH, derived from dimers of 1-or 2-butene.

According to the invention a complex mixture of diesters of the formula I can be prepared in various ways:

a) a mixture according to the invention may contain extremely difficult diesters, which all have the same bicyclic substructure of formula I, and the individual isomers of complex diesters differ only residues of carboxylic acids with different structures. Thus, this mixture consists exclusively of isomers of complex diesters, which all have the same skeleton derived diaminohexane. Isomerism is that there are at least two different balance With₉-carboxylic acids. If there are only two different balance With₉-carboxylic acid, the mixture has a maximum of 4, in the case of complex isosorbide diesters maximum of 3 different isomer complex diesters;

b) the mixture according to the invention may contain, for example, at least two isomers of complex diesters with different bicyclic the substructures of the formula I, which differ in the configuration. This mixture may consist of isomers of complex diesters which have two or more skeletons derived diaminohexane with a different configuration. In turn, there are at least two ladies who, for example by transferring them balance With ₉-carboxylic acids;

c) the mixture according to the invention may contain, for example, at least two complex diapir with different molar masses. This mixture may consist of complex diesters which have two or more skeletons derived diaminohexane with different molar masses (due to the substitution of the skeleton). In turn, there are at least two balance With₉-carboxylic acids with different structure,

d) the mixture according to the invention can be as complex diesters of different molar masses, and the isomers of complex diesters with different configuration of the bicyclic substructure.

It may be advantageous to complex diesters of the formula I contained in the mixture according to the invention, the residues R¹-R⁸meant N.

Particularly preferred mixture according to the invention differs in that its constituent complex diesters of the formula I are extremely complex diesters of the formula Ia

in which the chiral carbon atoms can have the R configuration or s depending on the relative position of the acid groups for complex diesters of the formula I can talk about complex diesters Samanid, izodia or isosorbide. Particularly preferred complex diesters of the formula I in the mixture are the only complex on the ethers of isosorbide.

The mixture according to the invention may consist either solely of complex diesters of the formula I, or in addition to them to have at least one polymer and/or at least one plasticizer, without complex fluids formula I. Plasticizers can be selected, for example, from the group consisting of trialkylsilyl, pilirani of trialkylsilanes, esters of glycerin, glycosidases, alkylbenzoates, dialkylamino, trialmicrosoft, dialkyldimethyl, diallylphthalate or dialkylamino esters 1,2-, 1,3 - or 1,4-cyclohexanedicarboxylic acids, and alkyl residues have from 4 to 13, mainly 5, 6, 7, 8, 9, 10, 11, 12 or 13 carbon atoms. Plasticizers may also be esters diaminohexane, preferably esters of isosorbide or other carboxylic acids, such as n - or ISO-butyric acid, valerianic acid or 2-ethylhexanoic acid Polymers, which can be included in the composition of the mixture according to the invention are, for example, polyvinyl chloride (PVC), polyvinylbutyral (PVB) and polyalkylacrylate (PAM). Particularly preferred polymer is polyvinyl chloride (PVC).

In the preferred mixtures contain a complex diesters of the formula I and polymers, the mass ratio of polymer/polymer and complex diafora/diesters of the formula I, the composition of AET mainly from 30 to 1 to 1 to 2.5, and preferably from 20 to 1 to 1 to 2.

In the preferred mixtures contain a complex diesters of the formula I and plasticizers without complex diesters of the formula I, the molar ratio of plasticizers, in particular of alkylbenzoates, dialkylamino, trialkylsilyl, acylated trialkylsilanes of trialmicrosoft, glycosidases, dialkyldimethyl, diallylphthalate, dialkanolamine esters of isosorbide and/or dialkylamino esters 1,2-, 1,3 - or 1,4 - cyclohexanedicarboxylic acids, complex W/the diesters of formula I is predominantly from 1 to 10 to 10 to 1, preferably from 1 to 6 to 6 to 1.

The mixture according to the invention with complex fluids of formula I or complex diesters of the formula I can be obtained in various ways. Mainly a mixture of complex fluids of formula I or complex diesters of the formula I get the following ways :

The methods according to the invention produce complex diesters of the formula I

with R¹-R⁸=H or alkyl group with 1-6 carbon atoms, and the remainders R¹-R⁸may be the same or different, are distinguished by the fact that hexavalent alcohol of the formula II

in which the residues R¹-R⁸have the meanings indicated in formula I, and/or anhydrous or dia is hydro-derived alcohol of formula II is subjected to the reaction with the mixture, having at least two different carboxylic acids total formula C₈H₁₇COOH.

Mainly uses a mixture of carboxylic acids having at least two carboxylic acid total formula C₈H₁₇COOH with different structural formulas, and none of the members of the mixture of carboxylic acids does not have a share of more than 95 mol.%, preferably, at least 90 mol.%.

Preferably, in the methods according to the invention a mixture of isomeric carboxylic acids total formula C₈H₁₇COOH contain less than 10 mol.%, mostly less than 5 mol.%, preferably less than 1 mol.% and, in particular, from 0 to 0.5 mol.%, preferably less than 0.1 mol.%, in particular, from 0.0001 to 0.1 mol.%, and particularly preferably less than 0.05 mol.%, in particular from 0.01 to 0.05 mol.% 3,5,5-trimethylhexanoic acid or other trisemester carboxylic acids with a total formula C₈H₁₇COOH, in particular acids with Quaternary carbon atoms. The distribution of isomers of carboxylic acids in the mixtures can be determined by standard methods known in the art of measurement, for example, using NMR spectroscopy, gasochromatic (GC) or gasochromatic/mass spectroscopy (GC/MS), preferably after silloway or methyl ester.

In the methods according to the invention particularly preferred is sustained fashion the application of a mixture of isomeric carboxylic acids total formula C ₈H₁₇COOH, in which the degree of branching is from 0.7 to 2.0, mostly from 1.0 to 1.9, preferably from 1.1 to 1.8, and most preferably a value of from 1.1 to 1.7. For example, n-novanova acid has a degree of branching of 0, the degree of branching 3,5,5-trimethylhexanoic acid equal to 3. The degree of branching of the mixture is obtained from the sum of the degrees of branching of the individual components multiplied by the corresponding mass or molar fraction of the individual components and divided by the number of all components.

In the simplest case, the degree of branching can be found by directly determining the number of individual components. If such a determination is impossible, the degree of branching for a mixture of isomeric Romanovyh acids can be determined, for example, by using¹H-NMR, by analogy with the method described above.

Getting nonanalog acid

In principle, you can apply all the technical mixture of carboxylic acids total formula C₈H₁₇COOH, which have at least two different isomeric structures. Mainly used as a mixture of isomeric carboxylic acids total formula C₈H₁₇COOH, in which the percentages of the different isomers, the average degree of branching and/or content 3,3,5-trimethylhexanoic acids lie within the above parameters.

₈H₁₇COOH (hereinafter called isomeric nonanoyl acids) can be obtained, for example, hydroformylation of octenol, which can also be obtained in various ways, and subsequent oxidation.

As a starting substance to obtain octene in the General case can be used With technical₄-a number that contains all of isomeric With₄-olefins and, in addition, saturated butanes and, in some cases, impurities in the form of a₃- and₅-olefins and acetylenic compounds. By oligomerization included in₄-a number of olefins get mainly isomeric mixture of octanol, as well as higher oligomers, as a mixture of C₁₂and C₁₆-olefins. This mixture of octanol, if necessary, after the separation by distillation C₁₂- and₁₆-olefins can be hydroformylation into the corresponding aldehydes and then oxidized to carboxylic acids. The composition, i.e. the isomer distribution of technical mixtures Romanovyh acids, depends on the source of the substance and methods of oligomerization, oxidation and hydroformylation.

As oktanovyh mixtures can be used in a mixture, for example, received the so-called multigate way in which oligomerization With₃-/C₄-mixtures is performed on a solid acidic catalyst, preimushestvenno is, on the solid catalyst of phosphoric acid (SPA). This method is described, inter alia, in US patents 6284938, US 6080903, US 6072093, US 6025533, US 5990367, US 5895830, US 5856604, US 5847252 and US 5081086. If gereformeerde mixture of olefins, obtained exclusively in this way, then, as a rule, the result is still the proportion of octanal and dikanarov, so it may be different average chain length of 9 carbon atoms. After oxidation is obtained a mixture of isomeric Romanovyh acids, which can also still be isomers of octane or decanoas acid. But it has no effect on the determination of the degree of branching V as described above.

In addition, success can also be used octene obtained from the oligomerization of ethylene.

Particularly preferred mixtures of isomeric Romanovyh acids used in the methods according to the invention are mixtures obtained by hydroformylation isomeric octanol with subsequent oxidation of the resulting aldehyde and, in some cases, the resulting alcohols, and a mixture of isomeric octenol is obtained by attaching a hydrocarbon mixture having a butene, the share of which in the isobutylene is mostly less than 20 wt.%, preferably less than 10 wt.%, preferably less than 5 wt.%, more preferably less than 3 wt.%, especially preferably less than 1 m is from.%, and regarding butene-mostly between 0.01 and 1 wt.% and more preferably from 0.05 to 0.5 wt.%, with the oligomerization catalyst, particularly a catalyst containing Nickel oxide. Getting isomeric octenol by oligomerization essentially linear butenes on the Nickel catalyst carrier is known, for example, as OCTOL process, described, for example, in EP 0395857 or EP 1029839. In embodiments, OCTOL process is used, for example, catalysts with Ti or Zr. Such alternatives and, in particular, the catalysts described, for example, in EP 1171413. As already mentioned above, thus obtained octene can be separated by distillation from the higher olefins, i.e. C₁₂-C₁₆-With₂₀- etc. olefins.

Hydroformylation

Octene obtained, for example, as described above, or a mixture of isomeric octenol are hydroformylating. Hydroformylation can be carried out in the presence of modified or unmodified cobalt or rhodium catalysts. Mainly hydroformylation is carried out in the presence of unmodified compounds of cobalt. Appropriate ways of hydroformylation known, for example, from the patents EP 0850905 and EP 1172349. These methods receive, as a rule, a mixture of nonanalog may not yet converted octanol and corresponding obtained by hydrogenation of mixtures of isomeric nonanols and octanol.

Gidratirovana can be performed also in the presence of rhodium catalysts. Such methods hydrophilinae well-known, for example, they are described in EP 0213639, EP 1201675, WO 03/16320, WO 03/16321, WO 2005/090276 and works cited therein. Special methods hydroformylation, suitable for use in the methods according to the invention mixtures of isomeric Romanovyh acids described, for example, in WO 2004/020380 or DE 10327435. Shown in these studies, the methods hydrophilinae performed in the presence of cyclic esters of carbonic acid.

Can also be advantageous separation of the mixture of isomeric octanol into fractions before performing hydroformylation, as described in EP 1172349. This method allows to obtain a fraction of octanol, which are particularly well suited for obtaining mixtures Romanovyh acids used in the methods according to the invention. By mixing fractions of suitable relatively simple method can be obtained a mixture of isomeric octanol, suitable for the production of mixtures of isomeric Romanovyh acids for use in the methods according to the invention. It is possible and even preferable to divide into fractions obtained after hydroformylating the reaction mixture, in order to concentrate nonanalogue fraction intended for oxidation, In particular, if scheduled for xidirov the Oia mixture of nonanalog contains an even higher proportion of nonanalog, it is recommended to purify the mixture by distillation. Hydroformylation oktanovyh mixtures can be performed in one or in several stages and after each stage can not be separated reacts octene.

Oxidation

Oxidation With₉-aldehydes or one or more isomeric C₉-aldehydes present in the mixture, to the corresponding carboxylic acids can be well-known manufacturer way. As the oxidizing agent can be used, for example, oxygen, air or other oxygen-containing gases. The oxidation can be carried out without a catalyst or in the presence of a catalyst. In the latter case it may be best used as a catalyst compounds of transition metals, particularly cobalt. Oxidation of aldehydes can be carried out at normal or at elevated pressure (1-30 bar, preferably 1.1 to 5 bar). The reaction temperature lies in the region from 30°C to 150°C, preferably between 40 and 90°C., particularly preferably between 50 and 80°C. the reaction Time depends on the conditions of oxidation and can vary from several minutes to several hours.

Carboxylic acid or carboxylic acid can be obtained from the oxidation mixture by distillation under normal or reduced pressure. If necessary, a mixture of carboxylic acids m which may be separated into fractions with different carboxylic acids.

The same method can be obtained fraction of carboxylic acids that are most suitable for the production of esters diaminohexane according to the invention, in particular complex isosorbide diesters of formula I. By such fractionation and subsequent mixing fractions with each other or even with other mixtures of carboxylic acids is a great opportunity to build such mixtures of carboxylic acids, which have the above-mentioned preferred share certain components. This simple method can be obtained a complex mixture of diesters of the formula I having the desired characteristics.

In the methods according to the invention as a mixture of isomeric Romanovyh acids can also be used a mixture obtained by mixing Romanovyh acids without isomerism and/or fractions of several isomeric Romanovyh acids. At least two from pure isomers nonmovie acid are commercially available, namely n-novanova acid (pelargonia acid and 3,5,5-trimethylhexanoic acid (CAS No. 3302-10-1). On sale are also mixtures or fractions Romanovyh acids, which do not have characteristics, preferred methods according to the invention. Mean mixture mnohorozmernych Romanovyh acids with a high proportion (93-95%) 3,5,5-trimethylhexanoic acid (CAS No. 26896-18-4, company Celanese). Simple efficient when blended the eat clean from such isomers Romanovyh acids with other nonanoyl acids without showing isomerism or with mixtures Romanovyh acids can be produced mixture Romanovyh acids, when the esterification form a complex diesters of the formula I with the desired properties. In particular, such a simple mixing can be obtained mixture Romanovyh acids having the desired proportion of 3,5,5-trimethylhexanoic acid and other components.

Alcohol educt

As the alcohol component used in the methods according to the invention, taken either alcohol of the formula II or dianhydro or monoamide-derivative of this alcohol. Mainly as a alcohol of the formula II used alcohol, which remains R¹-R⁸mean N or dianhydro-, or monoamide-derivative of this alcohol. Especially preferred from this group are hexitol, sorbitol, mannitol and iditol preferred sorbitol. Can also be used mixtures of the above compounds.

Preferably as dianhydro-derived alcohol of the formula II is used isosorbide or its isomer Samanid or isoide formula IIa

which can be obtained using the dual dehydration (intramolecular esterification) of the alcohol of formula II, in which all residues R¹-R⁸mean N (sorbitol and mannitol or iditol), or from the corresponding monoamide-derived (sorbitan and mannitan or Editon) formula IIb

Persons who NGOs preferred is the use of isosorbide as dianhydro-derived alcohol of formula II.

In particular, sorbitol, commercially available in quantities of several hundred thousand tons per year, for a sufficient capacities isosorbide reported by several manufacturers, so that the supply of the starting substances is guaranteed, at least in the medium term.

Complex diesters of the formula I according to the invention can formally be obtained in various ways, which will be described in detail below.

First, complex diesters of the formula I can be obtained from dianhydro-derived alcohol by esterification with mixing at least two isomeric Romanovyh acids. Etherification diaminohexane, in particular isosorbide, various aliphatic carboxylic acids is described in the literature. In General dangerosity converted to carboxylic acid in the presence of a catalyst in an appropriate complex fluids diaminohexane. Mostly the reaction is carried out with an excess of carboxylic acids (i.e. more than two molar equivalents), preferably with a molar excess of from 10 to 100%, preferably from 20 to 50%. Separation from the reaction mixture the water formed during the esterification may be carried out in various ways. For example, water can Athanasia flow of inert gas passed through the reaction mixture, or removed using vacuum. In addition to the, water can be separated by azeotropic distillation or by using any separating agent as toluene, benzene, xylene or cyclohexane, or itself carboxylic acid serves as a separating agent, and removed mass is replaced completely or partially carboxylic acid. A review of the literature describing these methods can be found in WO 2006/103338. In addition to describing techniques there is also a method of obtaining complex diesters diaminohexane.

Secondly, obtaining complex diesters of the formula I according to the invention can be performed by a sequence of reactions on the basis of hexitol formula II, consisting of two intramolecular dehydration to dianhydro-derivative with subsequent or simultaneous etherification, or on the basis of monohydro-derived hexitol formula II, consisting of a single intramolecular dehydration to dianhydro-derivative with subsequent or simultaneous etherification. Two separate reactions (esterification and one or two dehydration) may be conducted separately or as a so-called eintopf-reaction. The description can be found, for example, in WO 01/83488.

Dehydration (intramolecular etherification)

If you use monoamino-derived alcohol of the formula II, it formally in previous or simultaneity is temporal held intramolecular dehydration is translated in dianhydro-derived. If you are using hexavalent alcohol of the formula II, formally he previously or simultaneously held intramolecular dehydration is translated in dianhydro-derived or monoamide-derived, the latter at the next intramolecular dehydration can also be converted in dianhydro-derived.

Dehydration (removal of water) alcohol of formula II or the corresponding anhydrous-derived conversion in dianhydro is derived according to the formula IIc

with R¹-R⁸whose values are defined in formula I, can be performed in the method according to the invention a separate process prior to etherification. The obtained reaction mixture, the substance of which is dianhydro and monoamide-derived hexitol together with by-products, and then either immediately subjected to esterification or first processed, in this case, for example, separates the catalyst for dehydration and by cleaning, for example, distillation, crystallization, washing, bleaching, etc. can be increased purity of the mixture for the next stage of purification desired diaminohexane.

Dehydration (intramolecular etherification) in this form of execution of the method according to the invention is mainly in temp is the temperature from 100 to 200°C. preferably from 110 to 180°C., if the same should degidratirutego sorbitol or monoamide-derivative, particularly preferred temperature is from 120 to 150°C. at normal pressure or low vacuum. Dehydration in this form of execution is preferably carried out in the presence of a catalyst. If the mixture after dehydration immediately subjected to the esterification, it is particularly preferred catalyst, identical to that used in the esterification catalyst. As described in WO 01/83488, for this purpose the most suitable macroporous acid ion exchanger.

However, in many cases, the reasons kinetics can be advantageous to a mixture of isomeric Romanovyh acid was added to the reaction mixture only when the alcohol of formula II has already reacted to obtain, basically, dianhydro-derived, and only a small number of monoamide-derived (<10%, according to gas chromatographic analysis). Otherwise, is the second removal of water from monoamineoxidase in becoming dangerosity in contrast to the esterification of monoamide-derived, which leads to less output at diethanolamine esters diaminohexane. The appropriate point in which to add the carboxylic acid can be easily determined by preliminary research. These moments, the others, depend on the type and amount of catalyst and the temperature.

When dehydration can be beneficial, if generated in the process water is removed by passing the gas, particularly an inert gas through the reaction mixture. As the inert gas can be used, for example, nitrogen.

But you can also remove generated during the dehydration of water from the reaction mixture by distillation. It is preferable to perform this distillation under reduced pressure.

In a preferred form of execution of the method according to the invention when using an alcohol of formula II or monoamide-derived alcohol, in particular sorbitol, or sorbitan, dehydration and esterification are carried out in one process. In this case, the mixture of isomeric Romanovyh acids may be added to the reaction mixture before the beginning of the process. When selecting catalysts for the sequence of dehydration and esterification should pay attention to the fact that they had a high selectivity for complex diesters of dianhydride-derived, because otherwise may be formed in probably the biggest (unwanted) fractions of a complex of mono-, di-, tri - or terrafire monoamide-derived alcohol of formula II. Particularly suitable catalysts are, as a rule, a strong acid Bronsted as sulfuric acid, or the already mentioned is acroporidae acidic ion-exchange resin. Pure Lewis acid, such as tetrabutyltin, for a stage of dehydration is not suitable.

Etherification

The etherification can be carried out in a known manner, for example by reaction of alcohols of the formula II or their monoamide or dianhydro-derivative with the appropriate mixture of isomeric Romanovyh acids. The reaction can be carried out without a catalyst or in the presence of a catalyst. Mainly etherification is carried out in the presence of a catalyst. In the method according to the invention, in principle, can be applied to all known methods of esterification. Mainly the process of esterification is performed in such a way that the resulting reaction water is removed by azeotropic distillation with carboxylic acid, and the number of resected by azeotropic distillation of the liquid from the reaction fully or partially compensated by a mixture of isomeric Romanovyh acids. In the future this amount of liquid means remote from the reaction by azeotropic distillation volume of fluid, consisting mainly from the reaction of water and isomeric Romanovyh acids. Preferred complete replacement remote fluid. This can be done, for example, regular feed mixture Romanovyh acids in the reactor.

For technical reasons, the full replacement remote fluid may not be realistic is avana or can be realized only with great difficulty. In such cases, a remote amount of liquid is compensated only partially, for example only added a mixture of isomeric Romanovyh acids, but not remote, the reaction water, in any case be reimbursed for not more than 90%, preferably 95-98%. You might also need to supply the liquid in the reactor more than distilled liquid, i.e. in addition to the remote acid is replaced by reacting water and in addition to acid. In this form of execution of the esterifying acid is replaced by 110-100%, preferably 105-100% remote fluid.

This form of execution of esterification has the advantage that, compared with traditional methods increases the reaction rate. This reduces cycle time and improves spatial-temporal indicator output of the finished product.

Etherification is commonly performed in the reactor in which the reaction mixture can intensively mixed using a stirrer or the circulation pump. Liquid and catalyst may be introduced into the reactor simultaneously or sequentially. If the applied substance is solid at the temperature of its filling, it is advisable to enter the liquid components. Solids can be in the form of powders, granules, crystals or melt. To reduce the process time, it is recommended to begin with beneath the roar during the filling. The catalyst can be introduced in pure form or in the form of a solution, preferably dissolved in one of the filling substances, in the beginning of the process or only after reaching the reaction temperature.

Designed to convert a mixture of isomeric Romanovyh acid, which also acts as a separating agent, can be used in stoichiometric excess. The preferred excess of 5 to 50%, particularly preferred excess of 10-30%.

Regarding the implementation of esterification (assuming dianhydro-derived) or of the sequence of dehydration and esterification (assuming hexavalent alcohol of formula II or its monoamide-derived) can be referenced patent EP 1278752 (WO 01/83488). Particularly advantageous application of the methods for the synthesis of esters.

Etherification, on the basis of the net dianhydro-derived, is mainly performed on macroporous acid ion-exchange resin as a catalyst for esterification. The reaction temperature when the esterification is limited, usually thermal stability of the resin. Depending on the temperature of stitching such resins can be used at a maximum temperature of 100 to 190°C, the relevant information is provided by the manufacturer.

In the methods according to the invention from the group of acidic ion exchange what's resins are preferably used resin with sulfo. Suitable ion exchange resins can be, for example, those obtained by sulfonation of the phenol/aldehyde condensate or cooligomers aromatic vinyl compounds. Examples of aromatic vinyl compounds to obtain cooligomers are the following: styrene, vinyltoluene, vinylnaphthalene, vinylethylene, methylsterol, vinylcarbazole, finalcial and divinylbenzene. In particular, as a preliminary step to obtain ion-exchange resins with sulfo apply cooligomers, which are formed in the exchange reaction of styrene with divinylbenzene.

The properties of these resins, in particular specific surface area, porosity, stability, swelling or shrinkage and exchange capacity, can vary in the process of getting.

In the methods according to the invention the ion exchange resin can be used in the protonated form. Strongly acidic macroporous resin type styrene-divinylbenzene available commercially under the following names: Amberlyst 15, Amberlyst 35, Amberlyst 70.

The pore volume is preferably used ion-exchange resins is mainly from 0.3 to 0.9 ml/g, preferably from 0.5 to 0.9 ml/g, the grain Size is preferably used resin is mainly from 0.3 mm to 1.5 mm, preferably from 0.5 mm to 1.25 mm, the Distribution of grains sizes can be selected narrow or wide. Especially the site ctically ion-exchange resin with the same grain size. Capacity preferably used ion-exchange resins relative to the supplied form is mainly from 0.7 to 2.0 EQ./l, in particular from 1.1 to 2.0 EQ./l, or predominantly from 0.5 to 5.5 mol/kg, in particular from 0.8 to 5.5 mol/kg (data capacity in mol/kg refer to the ion-exchange resin, dried, for example at 105°C to constant weight in a hot nitrogen form).

In addition to ion exchange resins to produce complex diesters of diaminohexane can apply also many other catalysts. Such esterification catalysts can be such acids, such as sulfuric acid, methanesulfonate or p-toluensulfonate, or metal-containing catalysts. Exemplary representatives of the most preferably used metal catalysts are esters of Titanic acid, as tetraisopropyldisiloxane or tetraethylorthosilicate, as well as esters of zirconium, as tetrabutyltin. Metal catalysts in contrast to catalysts based on proton acids are high-temperature catalysts, the total activity of which is often achieved only at temperatures above 180°C.

The concentration of the catalysts depends on their type. When used preferably titanium compounds it ranges from 0.005 to 1.0 wt.% regarding the reaction sm is si, in particular from 0.01 to 0.3 wt.%.

The reaction temperature when using titanium catalysts are in the range from 160°C to 260°C. the Optimum temperature will vary depending on the substances, reaction time and concentration of catalyst. For each case they can easily be determined by experiment. Higher temperatures increase the reaction rate and promote side reactions such as the formation of colored by-products. To remove the reaction water required to mixture of isomeric Romanovyh acids it was possible to drive away from the reaction mixture. The desired temperature or the desired temperature range can be adjusted by the pressure in the reactor. In the case of the exchange reaction of isosorbide with a mixture of isomeric Romanovyh acids using tetramethylsilane as the catalyst temperature range seems to be best from 180 to 260°C., preferably from 210 to 250°C.

Returned in response to the amount of liquid partially or completely consists of isomeric Romanovyh acids obtained by processing the azeotropic distillate. Processing may also be performed to a later time, and the remote amount of liquid partially or completely replaced with fresh isomeric nonanoyl acids, i.e. available in the collection of isomeric nonanoyl acids. In other the forms of execution of esterification distilled liquid is converted into isomeric nonmovie acid.

After completion of the reaction, the reaction mixture consisting mainly of normal esters (target product) and excess carboxylic acid, contains in addition to the catalyst and/or formed products thereof a small number of complex monoamino diaminohexane. In addition, there may be more by-products formed in parallel or sequentially occurring reactions, in particular, mono-, di-, tri - and Tetra esters of monoamide-derived hexavalent alcohol of formula II. Typically, a mixture of original products range in color from yellow to light brown and for their technological applicability in need of cleaning, which is associated with certain costs. This process can be simplified by using the systems of the catalysts described, for example, in WO 06/103338.

For processing such initial mixture of esters is removed much of the excess carboxylic acid through distillation under vacuum or by steam distillation at temperatures from 120 to 225°C. After that, connect the standard processes for neutralization, purification and filtration of the raw product, which occur at different times and with different intensity depending on the color saturation and the fraction of insoluble by-products.

Neutralization of acidic substances as carbon to the slots, or, under certain conditions, the acidic catalysts may be carried out by adding alkalizing compounds of alkali and alkaline earth metals. These compounds can be used in the form of their carbonates, hydrogencarbonates or hydroxides. Neutralizing agents can be used in solid form or in the form of a solution, particularly an aqueous solution. The neutralization is preferably performed after the distillation of the principal amount of excess carboxylic acid.

In most cases, neutralized the original product, we recommend one or more times to rinse with water or saline solution, to separate insoluble side components.

Clarification of the original product can be performed, first, by adsorption on solids with large surface as activated carbon and polymeric adsorption resins, for example, on the basis of styrene and divinylbenzene. Alternative proposed bleaching with hydrogen peroxide or ozone. Which option to choose for clarification, it is possible to determine empirically. In some cases, can combine two or more of these methods.

After purification the product is dried in vacuum at an elevated temperature and then filtered.

Additional details of suitable methods of etherification is, which can be used in the method according to the invention as a stage of esterification can be found, for example, in patents EP 1186593 and EP 1300388.

The mixture according to the invention, which contain a complex diesters of the formula I or consist of them can be used in paints, inks, varnishes, plastisols, adhesives or its components, sealing compositions, in plastics or plastics components as plasticizers, can be used as solvents, components of lubricating oils, coolant or flushing of drilling fluids and their components, or as a supporting tool during the machining. While the preferred plastisols are, in particular, PVC or PMK-plastisol. The preferred plastics are, in particular, polyvinyl chloride (PVC), polyvinylbutyral (PVB), Homo - and copolymers based on ethylene, propylene, butadiene, vinyl acetate, acetylcellulose, glycidylmethacrylate, glycidylmethacrylate, methacrylates, acrylates, acrylate with is bound to the oxygen atom of the ether group of alkyl residues of alcohols with unbranched or branched chain with 1 to 10 carbon atoms, based on styrene, Acrylonitrile, Homo - or copolymers of cyclic olefins.

Representatives of the above groups can be named, for example, the following plastics: acrylate with the same or different alkyl residues with 4-8 carbon atoms, bound to the oxygen atom of the ester group, in particular n-botilinum, n-hexylene, n-aktiline and 2-ethylhexyl balance, polymethacrylate, polymethylmethacrylate, copolymers of methacrylate and butyl acrylate, copolymers of methyl methacrylate and butyl methacrylate or polyalkylacrylate (PAMC), copolymers of ethylene and vinyl acetate, chlorinated polyethylene, nitrile rubber, copolymers of Acrylonitrile, butadiene and styrene, copolymers of ethylene and propylene, copolymers of ethylene, propylene and diene, copolymers of styrene and Acrylonitrile, rubber based on Acrylonitrile and butadiene, elastomers based on styrene and butadiene, copolymers of methyl methacrylate, styrene and butadiene, cellulose acetate, PVB and PVC. Of them the most preferred is PVC.

In addition, the mixtures according to the invention can be used for modification of mixtures of plastics, for example a mixture of a polyolefin with a polyamide.

The composition of plastics, in particular PVC or PAMC that contain mixtures according to the invention, a complex diesters of the formula I or consist of them, can be included in the following products, such as housings for electrical appliances, for example kitchen devices, computer casings, housings and parts for phones and TVs, pipelines, apparatus, cables, wires facing, insulation tapes, interior trim parts, prod the automotive industry and furniture production, plastisols, flooring, medical devices, food packaging, gaskets, films, composite films, vinyl, artificial leather, toys, containers, adhesive tape, cladding layers, coatings, flocking and printing fibers for fabrics, fabrics by impregnation. In addition, the composition of plastics, in particular PVC, which contain a mixture according to the invention, esters of the formula I or consist of them can be used, for example, to obtain the following products: pipes, hoses, cables, wires facing, insulation tapes, automotive product and furniture production, plastisols, profiles, flooring, medical devices (for example, blood bags, harnesses, ampoules for injections etc), toys, food packaging, gaskets, films, composite films, plates, artificial leather, Wallpaper, containers, adhesive films, coatings, coatings or fibers for fabrics, shoes, corrosion protection of the undercarriage, sealing joints, simulating masses or balls.

PVC-plastisol composition or that contain a mixture according to the invention, a complex diesters of the formula I or consist of them consist primarily of from 5 to 250 by mass, preferably from 10 to 200 mass percent and more preferably about is 20 to 100 mass fractions of the mixtures according to the invention relative to 100 mass fractions of PVC.

Example 1. The synthesis of isononanoic acid

a) Receiving With₉-aldehydes-based debathena

To obtain₉-aldehydes (icononly) by hydroformylation C₈-olefins as eductor used a mixture of C₈-olefins (debute), obtained from the Octol process of the firm OXENO Olefinchemie GmbH. The following describes the chosen experimental method.

In the high pressure autoclave with a capacity of 5 l with agitator and an electric heating 2000 g debathena been hydroformylation in the presence of a cobalt catalyst at 175°C and pressure of the synthesis gas 280 bar for 3 hours. To obtain catalyst 640 g of an aqueous solution of cobalt acetate with 1.0 wt.% cobalt 6 hours were treated synthesis gas at a temperature of 170°C and a pressure of 28 MPa. After cooling and pressure reduction educated CARBONYLS of cobalt by extraction with 2000 g of di-n-butene was transferred to the organic phase, which is then separated from the aqueous phase. The concentration of catalyst in dibucaine were 0.02 wt.% regarding dibucaine and was considered metal cobalt. After that hydroformylating the mixture at 80°C was released from cobalt by treatment with 1000 g of a 5% acetic acid in the presence of air, which is supplied to the mixture through a porous glass filter with a flow rate of 30 l/h for 30 minutes. Then osvobojdenie is from cobalt hydroformylation the mixture was separated from the aqueous phase.

The process was repeated four times under the same reaction conditions. Exempt from cobalt hydroformylation mixture was purified. Received 9450 g of the mixture. Received the original product according to gas chromatographic analysis (GC analysis) had the following composition in wt.%: 19,8%₈-hydrocarbons, and 57.6%₉-aldehydes, and 18.3% With₉-alcohols, 2.7% With₉-alcoholtramadol and 1.6% of sediment.

Received the original product by periodic distillation was freed from unreacted C₈-hydrocarbons (low-boiling components). GC analysis gave the following composition of the bottom fraction in wt.%: 73,2%₉-aldehydes, 21,5%₉-spirits of 3.1% With₉-alcoholtramadol and 2.0% high-boiling components and 0.2% C₈-hydrocarbons.

Waste fraction containing₉-aldehydes, was subsequently used to obtain a₉-carboxylic acids.

b) Receiving From₉acids by oxidation With₉-aldehydes

Getting₉acids by liquid phase oxidation With₉-aldehydes was carried out in a heated reactor mixing with a double jacket with a capacity of 6 liters as educt used the product hydroformylation from example 1A with 73 wt.% With₉-aldehydes.

For the initial reaction mixture in the reactor was increased to 3500 g of liquid educt. As the reaction gas using the eh is a mixture of nitrogen with oxygen, which through a porous glass filter evenly distributed in the liquid in the lower part of the reactor.

To the reactor was dotirovala a constant flow of nitrogen of 30 Nl/h, and depending on the consumption reaction was fed a stream of oxygen-regulated by continuously measuring the oxygen content in the exhaust gas. In the gas space of the reactor in the upper part of dotirovala a constant stream of nitrogen at 330 Nl/h of the Maximum oxygen content in the exhaust gas was allowed no more than 6%vol. Oxidation With₉-aldehydes was carried out at the reaction temperature of 55°C and a pressure of 0.12 MPa. The result of oxidation was determined by regular sampling and GC analysis.

When the selected reaction conditions after 20 hours of the experiment was the original product whose composition is given in table 1 in the second column.

Then the resulting oxidation product was processed by periodic distillation. Distillation has been used laboratory Packed column (Sulzer DX Packung) with a boiling cube capacity of 5 L. the Composition of the product before distillation and thereafter are shown in table 1.

As shown in table 1, the resulting mixture With₉-carboxylic acids with high purity are described below for the exchange reaction.

Example 2. The esterification of isononanoic acid from example 1 using isosorbide (according to the invention)

In the flask with several necks with a capacity of 2 l with a stirrer, water separator, a dropping funnel, internal thermometer and immersed tube 365 g (2.5 mol) of isosorbide (company Cerestar) 1027 g (6.5 mol) of isononanoic acid from example 1 and of 0.91 g tetrabutyl-orthotitanate (0.25 wt.% on isosorbide, DuPont, Tyzor TnBT) was heated to 230°C with stirring and the flow of nitrogen through the immersion tube (6 l/h). Weak vacuum at this temperature provides the output of the whole reaction liquid through the separator. The control over the course of reactions was carried out using GC-analysis. After 8 hours the reaction was terminated, and the separator was changed to distillation nozzle through which the distilled excess isononanoate acid at a temperature of from 200 to 230°C. While gradually reducing the pressure to approximately 3 GPa. The mixture is then cooled to 80°C and was kind of balanced out 10%sodium hydroxide (50 ml). The original broadcast was three times washed in a separating funnel with 5%NaCl solution (300 ml) with the appropriate Department and discard the aqueous phase. Then to the mixture was added 1 wt.% activated charcoal within one hour the mixture was dried in a flask with stirrer at 125°C and a pressure of 5 GPa and after cooling to 100°C was filtered. Because of the intense staining of the product mixture again was Svetlanas at 90°C with 2 wt.% H₂About₂(35%hydrogen peroxide Merck), and then again was kind of balanced out (40 ml 10%NaOH), then two more times was filtered, dried and filtered. Because the color was still unsatisfactory, then twice repeated sequence of H₂O₂-clarification, neutralizes and, washing, drying and filtering, as described above. Thus obtained product had an index of staining Gazin ARNA 62. Purity, some GC-analysis, was about 99% (ether). The degree of branching of the side chains according to NMR data was equal to 1.3.

Example 3. The esterification of 2-ethylhexanoic acid with isosorbide (comparative example)

In the flask with several necks with a capacity of 2 l with a stirrer, water separator, a dropping funnel, internal thermometer and immersion 292 g (2 mol) of isosorbide (company Cerestar) 730 g (5 mol) of 2-ethylhexanoic acid (firm European Oxo) and 1.45 g of tetrabutyl-orthotitanate (0.5 wt.% regarding the isosorbide, the firm DuPont Tyzor TnBT) was heated to 240°C with stirring and the flow of nitrogen through the immersion tube (6 l/h). Weak vacuum at this temperature, provided that all of the reaction liquid through the separator. Tracking the course of reactions was carried out using GC-analysis. After 8 hours the reaction was terminated, and the separator was changed to distillation nozzle, through which at a temperature of 180°C, it was possible to drive off excess 2-ethylhexanol acid at a pressure of at least 5 GPa. Then the precipitate OSVETLENIE solution of H₂O₂(2.5 wt.%, 35%hydrogen peroxide Merck) at a temperature of 80-90°C, after which, respectively, in example 2 was kind of balanced out by the NaOH solution, was filtered and dried. For Otsego lighten the mixture is again mixed with the same amount of H ₂O₂were dried at 120°C, and then twice washed with 5%NaCl, were again dried at 120°C. at this temperature for 2 hours was mixed with 2% activated charcoal and then filtered. Thus obtained isosorbide-2-ethylhexanoate ester had a purity of about 99% (GC analysis) and the index of staining Gazin 50, the latter value is obtained by following the standard DIN EN ISO 6271, using measuring index color LICO 400 company Hach-Lange.

Example 4. Etherification 3,5,5-trimethylhexanoic acid with isosorbide (comparative example)

By analogy with the synthesis on the basis of isononanoic acid, described in example 1, produces di-3,5,5-trimethylhexanoyl ether of isosorbide. As the original product was used a commercially available 3,5,5-trimethylhexanoic acid ("isononanoate acid" by European Oxo).

Thus obtained ester isosorbide-di-3,5,5-trimethylhexanoate after performing various cleaning operations (see examples 2 and 3) may have a purity of 98.2% and the index of the color in Haveno 68 (method, see example 3). The melting point of the ester, as measured by DSC (onset of melting), 21.7°C. further, it will be referred to as the ether C.

Example 5. Etherification pelargonii acid (n-novanova acid) isosorbide (comparative example)

In the flask with several mountains is askamy capacity of 4 l with agitator, a water separator, a dropping funnel, internal thermometer and immersion 876 g (6 mol) of isosorbide (company Cerestar) 2370 g (15 mol) pelargonii acid (FLUKA) and 2,19 g tetrabutyl-orthotitanate (0.25 wt.% regarding the isosorbide, the firm DuPont Tyzor TnBT) was heated to 220°C with stirring and the flow of nitrogen through the immersion tube (6 l/h). Weak vacuum at this temperature provides the output of the whole reaction liquid through the separator. Tracking the course of reactions was carried out using GC-analysis. After approximately 8.5 hours the reaction was terminated, and the separator was changed to distillation nozzle, through which at a temperature of 180°C and the gradual reduction of pressure up to 2 GPa, you could drive away a significant part of the excess pelargonii acid. Followed by steam distillation at 180°C and drying in the presence of activated charcoal (1 wt.%). The mixture is then by analogy with example 2 was kind of balanced out, were washed twice with 5%NaCl solution (250 ml) and after the last distillation of steam at 140°C in vacuum dried and filtered. For further clarification, the mixture was primatives with 2% H₂O₂at a temperature of from 80 to 120°C., then again was kind of balanced out, were washed twice and after the last steam distillation at 140°C were dried after addition of 1% activated charcoal and filter is stayed. The obtained ether isosorbide di pelargonate (IsDnN) had an index of coloring on Haveno ARNA 38 (method see example 3) and a purity of 99%determined by GC.

Upon cooling to room temperature the ether hardening, melting point determination using DSC (differential scanning calorimeter) gave a value of 27°C. the fact that the ether (the ether D) at room temperature is a solid, virtually eliminates its use as the sole plasticizer for plastisols, because it is very difficult to achieve by adding auxiliary means necessary pasty consistency for processing (promazyvanija, dipping, comminution, centrifugation). Therefore, the ether was not used in further research.

Example 6. Production of esters of isosorbide-based mixtures of pelargoniums acid and 3,5,5-trimethylhexanoic acid

The fact that the melting temperature obtained in examples 4 and 5 esters are in the field of ambient temperature, makes them unsuitable for processing plastisols. Reducing the tendency to crystallization can be achieved by mixing both acid and subsequent esterification. For this purpose were prepared according to table 2, the mixture pelargonii acid and 3,5,5-trimethylhexanoic acid and was subjected to tarifica the AI as described above. In the table except the molar fraction of acids in the reaction mixture are also obtained GC-analysis of data on the content of esters of isosorbide and their melting point, and the parameters of esters of examples 4 and 5.

The melting temperature was determined by DSC from the increase of the signal of the beginning of melting (so-called "beginning"). If there are multiple melting points (different phases, for example, ether F) were selected maximum melting point, since below this temperature begins the first crystallization. In addition, all the esters have also the temperature of vitrification, which indicates a more or less high proportion of amorphous components.

Esters in which one of the acids has a share of 95 mol.% and more, because of the high melting at room temperature cannot be used for plastisols or applied only with disproportionate costs of their treatment. Ester F, in contrast, can easily be processed at room temperature.

Example 7. Getting plastisols

Used sample components for various plastisols are listed in the following table.

Temperature before adding plasticizers were maintained at 25°C. First in a polyethylene Cup was otvalivalas liquid components, and then added the powder components. The mixture was mixed BP is know spatula until complete wetting of the powder. Then a mixing glass was placed in the clamping device for solvent mixers. Before immersion mixer and the mixture was set speed of 1800 revolutions per minute. After switching on the stirrer and the mixture was mixed so long as the temperature reading on the digital display of the temperature sensor was not set equal to 30,0°C. This showed that it had been the homogenization of the plastisol when definitely applied energy. Then immediately installed the temperature of the plastisol 25,0°C.

Example 8. The measurement curves gelation

Study of the process of gelation plastisols were performed in oscillating viscometer brand Bohlin CVO (measuring system RR), which was governed by shear stress.

Were set the following options:

Mode: Temperature-gradient

Initial temperature: 25°C

Final temperature: 180°C

The heating rate/cooling 2°C/min

The temperature after the measurement: 25°C

Generation frequency: 2 Hz

Time delay: 1

Standby time: 15

Continuous generation: on

Automatic voltage supply shift: on

The initial shear stress: 0.3 PA

Given deformation: 0,002

Slit width: 0.5mm

Implementation measure

On the lower plate measuring system with a spatula were put one CA the La measured composition of the plastisol without air bubbles. This drew attention to the fact that when the connection of the measuring system a small amount of plastisol evenly flowed from the measuring system (not more than 6 mm in diameter). Then superimposed protective cover, which is designed for thermal insulation, and began measuring.

Figure 1 shows the so-called comprehensive plastisol viscosity depending on temperature. According to the invention plastisol 2 (IsDIN) is represented by a solid line indicated by the circles, plastisol 1 (Vestinol 9) represented by the dashed line with diamonds, and comparative example IsDEH as a plasticizer represented by the dotted line with triangles. The beginning of the process of gelation can be identified by a sharp increase in complex viscosity. The earlier increase in the viscosity, the better the gelling capacity of the system.

Result. The plastisol gelation with complex ether IsDIN according to the invention is comparable to the ability of DINP on the basis of the corresponding phthalate and only slightly slower than in the case of IsDEH.

Example 9. The measurement of viscosity plastisols

The viscosity measurements obtained in example 7 plastisols were performed in accordance with DIN 53019 using the Physica rheometer DSR 4000 (firm Paar-Physica), running supplied to the device program U 200. Plastisol again mixed with a spatula in spare capacity, and the measurement was performed in the measuring system Z3 (DIN 25 mm) according to maintenance instructions. The measurement was carried out in an automatic mode under the control of the above programs at 25°C. was Adjusted following:

- before shift 100^-1for a time period of 60 s, which was not filmed testimony;

- reduction of the trailing edge, starting at 200^-1to 0.1 s^-1divided into logarithmic sequence 30 steps, each step with the duration of the measuring points 5 C.

The measured data is automatically processed by the program after the measurement. The viscosity was measured depending on the shear rate. The measurements were performed after 2 hours, 4 hours, 24 hours and 28 days. In the intervals between measurements paste was stored at 25°C.

The following table shows the viscosity values obtained after the specified retention periods for the shear rate 100 s^-1.

The viscosity of the plastisol 2 according to the invention is comparable with the viscosity of the plastisol from the comparative example IsDEH as a plasticizer. The plastisol according to the invention shows better stability during storage.

Example 10. Obtaining films

To obtain samples for testing was first made film with a thickness of 1 mm for each formulation of table 3. For that extra glossy adhesive paper company Sappi, Italy) pre-cut into rectangles 30×44 cm and they fit in the clamping R. the MKI nematocera device for LTSV furnace Matisse. Then the clamping frame was placed on the guides, the temperature of the furnace Matisse (type LTF) was set equal to 200°C., and after reaching this temperature, the frame was heated for 15 seconds. Then Rachel was placed in the clamping device and the gap squeegee previously so regulated that the film thickness after complete gelation was equal to 1 mm (+/- 0.05 mm). On the front edge of the paper was applied a strip of glue to cover the excess paste. Then the rod was applied paste was smeared by pulling the guide frame with the squeegee over fixed with a release paper (with a speed of 6 m/min). Then the rod was withdrawn and was filmed strips of glue with extra pasta. In the end fell melting the platen and the clamping frame digilas in the oven. After gelation (2 minutes at 200°C) the frame is moved from the furnace and after cooling, the film was separated from the paper.

Example 11. The measurement of the volatility of the films according to DIN 53407

From the prepared films of example 10 with a thickness of about 1 mm was cut out circular plates with a diameter of 50 mm and after storage for 24 hours at normal climate (23°C/50% relative humidity) were weighed. Then round washers according to DIN 53407 (method A, direct contact with activated carbon, grain size 2.5 mm) were heated for 24 hours in a heating Cabinet at 80°C. Then washers removed from the heating Cabinet, within 24 hours, cooled in normal microclimate and again weighed, then placed in a heat chamber. After storage for 7 days the test was completed. Table 5 shows the results.

Result. The volatility of the films prepared from the esters according to the invention, comparable to the volatility of the films prepared from DINP on the basis of the corresponding phthalate, and significantly less than that of the comparative product IsDEH and brand IsD355TMH.

Example 12. Measurement of transition temperature of the films in the glassy state

Of the films prepared in example 10, was cut out strips of a length of 60 mm, 80 mm wide and 1 mm thick, and in torsion pendulum type MYRENNE III ATM according to DIN EN ISO 6721 (part 2) at temperatures from -100°C to +100°C and a frequency of 1^-1was determined stiffness G` and loss modulus G`.

The maximum G` you can determine the transition temperature in the glassy state T_G. It is a measure of the elasticity at low temperatures.

The junction temperature of the test samples in the glassy state are shown in table 6.

The temperature of transition to the glassy state of the films prepared from diethanolamine esters according to the invention is significantly lower than films prepared from IsDEH (comparative example), but worse than those of DINP on the basis of the corresponding phthalate.

Conclusion

Thus, it can be ascertained that diethanolamine esters of isosorbide (IsDIN) show good quality plasticizer and in the technological aspect surpass esters of isosorbide obtained from 2-ethylhexanoic acid (IsDEH, example 3), 3,5,-trimethylhexanoic acid (IsD355TMH, example 4) and pelargoniums acid (IsDnN, example 5).

1. A mixture having the properties of the plasticizer containing complex diesters derived diaminohexane with carboxylic acids total formula C₈H₁₇COOH formula I

where R¹-R⁸- H or an alkyl group with 1-6 carbon atoms, and the remainders R¹-R⁸may be the same or different, characterized in that the mixture contains at least two different complex diapir I, which differ in structure, at least one of the available residues of carboxylic acid C₈H₁₇COO.

2. The mixture according to claim 1, characterized in that obtained by saponification contained in a mixture complex mixture of diesters of carboxylic acids has at least two carboxylic acid total formula C₈H₁₇COOH with different structural formula, and none of the members of the mixture of carboxylic acids does not have a share of more than 95 mol.% in a mixture of carboxylic acids.

3. The mixture according to claim 1, characterized in that obtained by saponification contained in a complex mixture of diesters of carboxylic acids total formula C₈H₁₇COOH contain less than 10 mol.% 3,5,5-trimethylhexanoic acid.

4. The mixture according to claim 1, characterized in that the residues of carboxylic acids C₈H₁₇COO contained in a complex mixture of diesters have a degree of branching of from 0.7 to 2.0.

5. The mixture according to claim 1, characterized in that the residues of carboxylic acids C₈H₁₇COO contained in a complex mixture of diesters have a degree of branching of from 1.2 to 1.9.

6. The mixture according to claim 1, characterized in that the residues R¹-R⁸who appoints the hydrogen.

7. The mixture according to claim 1, characterized in that the complex mixture of diesters have at least two different bicyclic substructure of formula I, which differ in their configuration.

8. The mixture according to claim 1, characterized in that the complex mixture of diesters have at least two complex diapir with different molar masses.

9. The mixture according to claim 1, characterized in that the mixture can be as complex diesters of different molar masses, and the isomers of complex diesters with different configuration of the bicyclic substructure.

10. The mixture according to claim 1, characterized in that the mixture has only complicated the diesters with the same the bicyclic substructure of formula I, and the individual isomers of complex diesters differ only in variously structured residues of carboxylic acids.

11. The mixture according to claim 1, characterized in that the complex diesters of the formula I are, in the main, complex diesters of the formula Ia

and chiral carbon atoms of the bicyclic skeleton independently of one another can have the R configuration or s

12. The mixture according to claim 10, characterized in that the complex diesters are mostly complex isosorbide diesters.

13. The mixture according to claims 1 to 12, characterized in that it further comprises at least one polymer and/or at least one additional plasticizer, non-complex the m W of formula I.

14. The mixture according to item 13, wherein the mass ratio of the polymer and complex diesters of the formula I is from 30 to 1 to 1 to 2.5.

15. The mixture according to item 13, wherein the molar ratio of plasticizer and complex diesters of the formula I is from 1 to 10 to 10 to 1.

16. The mixture according to item 13, wherein the polymer is PVC.

17. A method of manufacturing complex diesters of the formula I

where R¹-R⁸Is h or an alkyl group with 1-6 carbon atoms, and the remainders R¹-R⁸may be the same or different, wherein the hexavalent alcohol of the formula II

in which the remains of the remains of R¹-R⁸have the meanings indicated in formula I, and/or anhydrous or dianhydro-derived alcohol of formula II is subjected to reaction with a mixture having at least two different carboxylic acids total formula C₈H₁₇COOH.

18. The method according to 17, characterized in that it is a mixture of isomeric carboxylic acids total formula C₈H₁₇COOH, which has an average degree of branching of from 0.7 to 2.0.

19. The method according to 17, characterized in that the application of the alcohol of formula II or monoamide-derived alcohol is dehydration in a separate process prior to esterification.

20. The method according to 17, is great for the decomposing those that the use of alcohol of the formula II or monoamide-derived alcohol dehydration and esterification are carried out in one process.

21. The method according to 17, characterized in that the dehydration is performed at a temperature of from 100 to 180°C., if necessary in the presence of a catalyst, identical to the catalyst used in the process of esterification.

22. The method according to 17, characterized in that the esterification is performed in acidic ion-exchange resin.

23. The method according to 17, characterized in that formed when performing the way water is removed from the reaction mixture by passing through the reaction mixture with an inert gas.

24. The method according to 17, characterized in that formed when performing the way water is removed from the reaction mixture by distillation.

25. The method according to one of PP-24, characterized in that the esterification is carried out at a temperature of from 120 to 260°C or at a temperature of from 130 to 180°C, if made as a separate stage of dehydration.

26. The use of mixtures according to one of claims 1 to 16 in paints, inks or varnishes, plastisols, adhesives or components of adhesives, sealing compounds, as plasticizers in synthetic materials or their components, as solvents, components, lubricants and as auxiliary materials for matloob is abode.

27. Use p, characterized in that the synthetic material is PVC.

28. Use p, wherein the plastisol is a PVC plastisol.

29. Composition with PVC containing PVC and 5-250 mass fractions of the mixture according to one of claims 1 to 16 per 100 mass fractions of PVC.

30. Plastisol containing PVC and 5-250 mass fractions of the mixture according to one of claims 1 to 16 per 100 mass fractions of PVC.