mixtures of nonyl esters, process for preparing mixtures of nonyl esters, compositions and use of no

专利摘要:
NONILA ESTER MIXTURES, PROCESS FOR THE PREPARATION OF NONILA ESTER MIXTURES, COMPOSITIONS AND USE OF NONILA ESTERS AND COMPOSITION USES.The present invention relates to the mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I), methods for said production of mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I), compositions containing mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I), uses of mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I) as plasticizers, and uses of the previously mentioned compositions containing a mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I).
公开号:BR112012004223A2
申请号:R112012004223-8
申请日:2010-08-17
公开日:2020-08-18
发明作者:Michael Grass；Hinnerk Gordon Becker
申请人:Evonik Oxeno Gmbh；
IPC主号:

专利说明:

'1 “NONILA ESTER MIXTURES, PROCESS FOR THE PREPARATION OF NONILA ESTER MIXTURES, COMPOSITIONS AND USE OF NONILA ESTERS AND COMPOSITION USES”
FIELD OF THE INVENTION The present invention relates to a mixture of esters of 2,5-furanedicarboxylic acid (FDCA) with C% isomeric alcohols, more particularly mixtures of linear and branched nonanols. The present invention also relates to a process for the preparation of such esters and mixtures and the use of them as plasticizers for polymers, such as polyvinyl chloride, for example.
BACKGROUND OF THE INVENTION Polyvinyl chloride (PVC) is among the most economically important polymers. It finds diverse applications in non-plasticized PVC and plasticized PVC.
To produce a plasticized PVC, PVC is mixed with plasticizers, for which, in the vast majority of cases, phthalic acid esters are used, more particularly, di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP). As a result of existing legal regulations, and possible future regulations regarding the restricted use of phthalates, there is a need to find new esters suitable as plasticizers for PVC and other polymers, where, preferably, the same alcohols as before can be used . Due to the limited availability of fossil raw materials, in particular, such esters should have good market opportunities in the future, where at least the acid component is based on natural sources, such as sugars, fats or oils.
In the publication “Top Value Added Chemicals from Biomass”, by T. Werpy and G. Petersen (U.S. Dept. Of Energy (DOE); 08/2004), 2,5-
* 2 furanodicarboxylic (FDCA) is considered one of the most promising sugar-based platform chemicals.
Due to its structural similarity to terephthalic acid, the last few years have been accompanied by the publication of numerous articles on the use of 2,5-furanedicarboxylic acid or various derivatives, mainly in polymers.
The main application in most cases has been the partial or complete replacement of terephthalic acid or its derivatives in polymers.
A very comprehensive review of FDCA, its applications and its possibilities for synthesis is found in the publication on the Internet by Jaroslaw Lewkowski, ARKIVOC 2001 (1), pages 17-54, ISSN 1424-6376, with the title “Synthesis, Chemistry and Applications of 5-hydroxymethylfurfural and its derivatives ". Common to most of these syntheses is an acid-catalyzed reaction of carbohydrates, especially glucose or fructose, preferably fructose, to provide B5-hydroxymethylfurfural (S-HMF), which can be isolated from reaction medium by processing operations, such as a two-phase regime, for example.
The corresponding results were described, for example, by Roman-Leshkov et al., In Science 2006, 312, pages 1933 to 1937, and by Zhang in Angewandte Chemie 2008, 120, pages 9485 to 9488. In another step, the 5- HMF can then be oxidized to FDCA, - as quoted by Christensen in ChemSusChem 2007, 1, pp. 75-78, for example.
In addition, the preparation of some FDCA esters by direct synthesis from muscic acid is also described (Tagouchi in Chemistry Letter vol. 37, No. 1 (2008)) and the corresponding alcohols.
The use of 2,5-furanedicarboxylic acid esters as plasticizers for plastics, in particular PVC, PVB, PLA, PHB or PAMA, has not been frequently described so far.
The most extensive review in this context is found in the publication of R.D.
Sanderson et al., In Journal of
Wi 3 Appl. Pol. Sci. 1994, vol. 53, p. 1785-1793. The corresponding esters based on n-butanol, n-hexanol, 2-octanol and 2-ethylexanol are explicitly described. Investigations on the interaction of esters with PVC show that they could be used as plasticizers for PVC. However, these conclusions were drawn only from measures of DMTA. Performance investigations, which are important and most significant to the processor, have not been carried out. There is also no reference, for example, to the fact that the FDCA 2-ethylhexyl ester tends to crystallize at relatively low temperatures, as can be demonstrated by DSC measurements (maximum melting point at 12º C starting at - 2.7º OC). Therefore, for many processors, this ester will have only limited utility, since at low temperatures there is no guarantee of pumping capacity. An additional factor is the classification of 2-ethylexanol as a - dangerous substance, which imposes limits on its usefulness, especially in sectors that come into contact with the skin and / or in contact with food. Starting from the state of the art, therefore, the object was to provide esters based on 2,5-furanedicarboxylic acid that can be used as plasticizers for plastics, such as PVC, PVB, —PLA, oPHB or PAMA, for example, with which the problem mentioned above does not occur or occurs only in a markedly attenuated manner, and which have the technical potential to replace the current standard petrochemical plasticizers.
DESCRIPTION OF THE INVENTION It has been found that mixtures of isomeric nonyl esters of 2,5-furanedicarboxylic acid (Formula |) can be used as plasticizers for plastics, more particularly in PVC, PVB, PLA, PHB and PAMA, in which they exhibit advantageous properties in relation to the FDCA esters known in the literature. Furthermore, in relation to esters
. 4 corresponding to phthalic acid, these esters also exhibit performance advantages. | ]
A to AA o o Formula | The present invention provides mixtures of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of formula | Further provided by the present invention are compositions comprising the mixtures of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of Formula | With regard to the raw material base, the particular feature of the present invention is the optional use of renewable raw materials for the preparation of furanodicarboxylic esters from | present invention. Renewable raw materials are understood in the sense of the present invention, in contrast to petrochemical raw materials that are based on fossil resources, such as oil or coal, for example, as the raw materials that form or are produced based on biomass. The terms “biomass”, “biological basis” or “based on and / or produced from renewable raw materials” cover all materials of biological origin, which comes from the so-called “short-term carbon cycle” and therefore , are not part of geological formations or fossil strata. The identification and quantification of renewable raw materials is carried out according to ASTM Method D68686. A characteristic of renewable raw materials, among others, is their fraction of the carbon isotope * C, in contrast to petrochemical raw materials. A certain economic and environmental advantage of the present invention lies in the simultaneous use of materials
W 5. renewable and petrochemical raw materials for the preparation of the furanodicarboxylic esters of the present invention, this not only allows for particularly cheap production and wide applicability, but also leads to particularly sustainable products.
The present invention also provides for the use of these mixtures in paints, dyes or varnishes, in plastisols, adhesives or adhesive components, in sealants, as plasticizers in plastics or plastic components, as solvents, as a lubricating oil component and as an auxiliary in metal processing, and also provides a composition of PVC or a plastisol comprising PVC and from 5 to 250 parts by weight of the mixture of the present invention per 100 parts by weight of PVC.
| The present invention also provides a process for preparing mixtures of isomeric nonyl esters of 2,5- | 15 furanodicarboxylic acid, characterized by the fact that 2,5- | furanodicarboxylic acid is esterified with a mixture of isomeric non-metals, referred to below as isononanol, optionally in the presence of a | catalyst, or dimethyl 2,5-furanedicarboxylate is transesterified with isononanol, with methanol release, optionally using a catalyst, to check the mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid. For the preparation of a mixture of isomeric nonyl esters, it is additionally possible to start from musclic acid, as well, which, in the presence of isomeric nonanols and, preferably, with acid catalysis, is simultaneously - in a single step reaction - cyclized and reacted to provide the corresponding furanodicarboxylic ester.
In relation to the state's furanodicarboxylic esters
In the prior art, but also in relation to the present standard di (lisononyl) phthalate (DINP) plasticizer, the FDCA isomeric nonyl ester mixtures of the present invention exhibit significantly better properties | in the context of their use as plasticizers in plastics, especially PVC.
In relation to esters of the prior art FDCA based on 2-ethylexanol, the diisononyl esters of the present invention have a lower volatility of the film and, also, in plastisols, a smaller increase in viscosity over time and, therefore, a better aging stability. In addition, the isononanol ester mixture based on the present invention, in contrast to the di-2-ethylhexyl ester, shows no tendency to crystallize in the -20 ° C range, but instead presents a glass transition point only about -80º. Interestingly, in terms of properties that are central to the user, the diisononyl esters of the present invention also exhibit properties that are better than those of the corresponding phthalate (diisononyl phthalate, DINP), such as, for example, faster gelation and better plasticizing effect. For the processor, this means either a lower processing temperature or, for a given processing temperature, a higher production rate per unit time, in combination with the present effect in which less plasticizer is required for the same degree of plasticity / flexibility as is the case with the corresponding phthalate.
The composition of the 2,5-furanedicarboxylic acid isomeric nonyl ester mixtures of the present invention is preferably such that the mixture comprises at least two different esters which differ in the constitution of the C9isomeric radicals, with none of the C9 radicals present in the mixture with a fraction greater than 90 mol%.
The mixture of the present invention can consist exclusively of
'TOO Esc MOS SANA EYÊ) AA CAÊP * AO9Ôê O O VU RSRS So Rms UR OO' 7 of the esters mixtures of Formula | or it can also comprise at least one polymer and / or at least one plasticizer that is not a diester of Formula | Plasticizers can be selected, for example, from citric acid trialkyl esters, citric acid acyl trialkyl esters, glycerol esters, glycol dibenzoates, alkyl benzoates, dialkyl adipates, trialkyl trimellitates, dialkyl terephthalates, or dialkyl phthalates dialkyl esters of 1,2-, 1,3-, or 1,4-cyclohexanedicarboxylic acids, the alkyl radicals containing 4 to 13, preferably 5, 6, 7, 8, 9, 10, 11 or 13 carbon atoms. Plasticizers can also be esters of dianhydroxytol, | Preferably, isosorbide diesters of carboxylic acids, such as acid | n- or isobutyric, valeric acid or 2-ethylhexanoic acid or isononanoic acid, for example.
Polymers that may be present in the mixture of the present invention are, for example, polyvinyl chloride (PVC), polyvinyl butyral (PVB), polylactic acid (PLA), polyhydroxybutyral (PHB) and polyalkyl methacrylates (PAMA). With particular preference, the polymer is polyvinyl chloride (PVC). In preferred mixtures comprising the diesters of Formula | and polymers, the ratio of mass of polymer / polymers to diester / diesters of Formula | it is preferably 30: 1 to 1: 2.5 and more preferably 20: 1 to 1: 2. In preferred mixtures comprising the diesters of Formula | and plasticizers that are not a diester of Formula |, the molar ratio of plasticizers, more particularly of alkyl benzoates, dialkyl adipates, glycerol esters, citric acid trialkyl esters, trialkyl esters - citric acid acylates, trialkyl trimellitates, glycol dibenzoates , dialkyl terephthalates, dialkyl phthalates, dialkoyl esters of isosorbide and / or dialkyl esters of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acids, for the diester / diesters of Formula | is preferably from 1:15 to 15: 1, most preferably,
8 from 1: 6 to 6: 1.
The diester mixtures of Formula | of the present invention, and the Formula | diesters themselves, can be prepared in various ways. Preferably, diester mixtures of Formula | and / or the diesters of —Formula are prepared by the process described below.
The process of the present invention for the preparation of isomeric nonyl esters of 2,5-furanedicarboxylic acid is distinguished by the fact that 2,5-furanedicarboxylic acid or a relatively short chain dialkyl ester of this compound, especially the dimethyl ester , is reacted with a mixture of isomeric nonanols, with a catalyst being used optionally. In addition, the 2,5-furanedicarbonyl dichloride that can be obtained by reacting the FDCA with chlorinating agents, such as thionyl chloride, for example, can be used as a starting material for the preparation of diisononyl esters. Suitable conditions for the FDCA reaction to supply the diisononyl ester through the dichloride as an intermediate are found in the examples.
It is preferred to use a mixture of isomeric nonanols comprising at least two nonanols of empirical formula CaH; CH7OH with different constitutional formulas, with none of the nonyl alcohols present in the mixture containing a fraction, preferably greater than 90 mol%.
Preferably, mixtures of isomeric nonanols of empirical formula CaH, sOH, more particularly of formula CgH,;; CH; OH, which are used in the process of the present invention contain less than 10 mol%, preferably less than 5% in mol, more preferably less than 1 mol%, and more preferably from 0 to 0.5 mol%, preferably less than 0.1 mol%, more preferably 0.0001 to 0.1 mol%, and more preferably less than 0.05 mol%, more preferably 0.01 to 0.05 mol%, to 3,5,5-trimethylexanol or other nonyl alcohols
'9 tri-substituted having the empirical formula CgH,; CH2OH, especially those with quaternary C atoms. The presence of these alcohols impairs the performance properties and reduces the rate of biodegradation of the molecule. It may also be advantageous if isononanols with an empirical formula | 5 - CaHi5OH, more particularly of formula CgH,;; CHzOH, which are used for the preparation of diesters of Formula | present in the mixture of the present invention, contain from 1% to 85%, preferably from 1% to 50%, of | most preferably, from 2% to 20%, of n-nonanol.
| The isomer distributions of isomeric alcohols in the mixtures can be determined using the usual measurement methods! known to those skilled in the art, such as NMR spectroscopy, | GC or GC / MS spectroscopy, preferably following conversion to silyl or methyl esters.
SYNTHESIS OF NONYL ISOMERIC ALCOHOLS In principle, all technical mixtures of nonanols having the empirical formula CaH, sOH, more particularly those having the formula CeH; CH2OH, which have at least two different types of constitutional isomers, can be used. It is preferred to use mixtures of isomeric nonanols with the formula CaH; CH7OH which, in terms of the fraction of the different isomers and / or the amount of C9 alcohols with quaternary C atoms, are within the ranges indicated above.
l Mixtures of isomeric nonanols with the empirical formula CaH9OH, more particularly, formula C; H,; CH2OH (referred to below as isononanols), which are used in the process of the present invention, can be - prepared, for example, by hydroformylation of octenes which, in turn, can be produced in a variety of ways, and subsequent hydrogenation.
As raw material for the preparation of octenes it is possible
. 10 use technical C4 streams that initially contain all isomeric C4 olefins, as well as saturated butanes and possibly impurities such as C3 and C5 olefins and acetylenic compounds. The oligomerization of the olefins present in C4 streams produces predominantly isomeric mixtures of octene, together with higher oligomers, such as mixtures of C12 and C16 olefins. These mixtures of octene, possibly after removal by distillation of C12 and Cie olefins, can be hydroformylated to the corresponding aldehydes and subsequently hydrogenated in alcohol. The composition, that is, the distribution of the isomer, of the mixtures of nonane! technical is dependent on the starting material and substantially dependent on oligomerization and | hydroformylation processes.
Mixtures of octene, which can be used include, for example, those obtained by the process known as the Polygas process, in which C3 / C mixtures are oligomerized on a solid acid catalyst, preferably a solid phosphoric acid catalyst ( SPA process). This process is described in documents, including US 6,284,938, US 6,080,903, US 6,072,093, US 6,025,533, US 5,990,367, US 5,895,830, US 5,856,604, US
5,847,252, US 5,081,086. If the olefin mixtures obtained exclusively in this way are hydroformylated, the product usually also includes decane octanaise fractions, so the average chain length at present can deviate by 9 carbon atoms. After hydrogenation, therefore, a mixture is obtained, which contains isomeric nonanols and which may also contain isomeric octanols or decanols. In addition, ethylene oligomerization octenes can also be used to advantage.
The particularly preferred mixtures of isomeric nonanols that can be used in the process of the present invention are those that are viable by hydroformylation of the isomeric octenes and, subsequently,
. 11 hydrogenation of the resulting aldehydes, with the mixture of isomeric octenes being obtained by contacting a hydrocarbon mixture comprising butenes, with an isobutene fraction, preferably less than 20% by weight, more preferably less than 10 % by mass, more preferably still less than 5% by mass, more preferably still less than 3% by mass, more preferably still less than 1% by mass, most preferably still between 0.01% and 1% by mass, and more preferably between 0.05% and 0.5% by mass, based on butenes, with an oligomerization catalyst, preferably a catalyst containing oxide nickel. The preparation of isomeric octenes by oligomerization of substantially linear butenes on nickel-supported catalysts is known, for example, in the form of an OCTOL process, which is described in EP 0.395.857 or EP 1.029.839, for example . In variants of the OTOL process, catalysts containing Ti or Zr, for example, are used. Such alternative variants and particularly the catalysts are described in EP 1,171,413, for example. As already described above, the resulting octenes can be separated from the upper olefins - that is, from the C15, C16, Cxo olefins, etc. - by distillation, for example.
Octenes or mixtures of isomeric octenes prepared as described above, for example, are subsequently pursued for hydroformylation. Hydroformylation can occur in the presence of modified or unmodified cobalt or rhodium catalysts. Hydroformylation preferably occurs in the presence of cobalt compounds - unmodified. Suitable hydroformylation processes are known from EP 0.850.905 and EP 1,172,349, for example. In general, a mixture is obtained in this way and consists of substantially isomeric non-channels, optionally octenes that have not yet reacted,
'12 and also the corresponding mixtures of isomeric nonanols and octanes formed by hydrogenation (following the reaction). | Hydroformylation can also occur in the presence of rhodium catalysts. Hydroformylation processes of this type are common knowledge, for example, from EP documents
0.213.639, EP 1,201.675, WO 03/16320, WO 03/16321, WO 2005/090276, and the documents cited herein. Special processes for hydroformylation, which are also suitable for the preparation of mixtures of isomeric nonanols which can be used in the process of the present invention, are described in WO 2004/020380 or DE 10.327.435, for example. The processes described herein are carried out in the presence of cyclic carbonic esters. It may also be advantageous to fractionate the isomeric octene mixture to begin with, as described in EP 1,172,349, before proceeding to hydroformylation. In this way it is possible to obtain fractions of octene which are especially suitable for the preparation of mixtures of isomeric nonanols which can be used in the process of the present invention. From the fractions it is then possible, in a relatively simple way, when mixing appropriate fractions, to obtain a mixture of isomeric octenes which is suitable for the preparation of | isomeric nonanols for use in the process of the present invention. | Hydroformylation of octene mixtures can be carried out in one or more stages, optionally with removal of unreacted octenes after each stage. The reaction mixture obtained from hydroformylation can | 25 optionally - and preferably it is - fractionated, thus concentrating the fraction of nonanal destined for hydrogenation. In general, however, the hydroformylation product will be released directly from the catalyst and then fed into the hydrogenation. In general, hydrogenation occurs above
13 of the heterogeneous catalysts, at high temperatures and pressures, in a liquid phase or conventional gas phase regime, as described in WO 2009/027135, for example. Suitable isononanol mixtures for the purposes of the present invention are also specified in EP 1,171,413, for example. FURANODICARBOXYLIC ACID 2,5-furanedicarboxylic acid (FDCA, CAS: 3238-40-2), a white solid that has a melting point above (>) 300º C, is not available, so far, on an industrial scale, but it can be prepared according to the literature or purchased commercially. Conversion to dichloride, which may be desired or preferred is described in detail in the examples.
STERIFICATION For the preparation of the esters of the present invention, furanedicarboxylic acid or a reactive derivative, such as the corresponding dichloride, for example (see examples), is reacted with a mixture of isomeric nonanols. The esterification takes place, preferably, from furanodicarboxylic acid and isononanol, with the aid of a catalyst. The esterification of furanodicarboxylic acid with an isononanol mixture to provide the corresponding esters can be carried out autocatalytically or catalytically, with Brônsted or Lewis acids, for example. Regardless of the type of catalysis selected, there is always a temperature-dependent balance developed between the reagents (acid and alcohol) and the products (ester and water). In order to shift the balance in favor of the ester, an anterior azeotrope can be used to help remove the reaction water from the batch. Since the alcohol mixtures used for the esterification boil at a lower temperature than furanodicarboxylic acid, its reactive derivatives, and its esters, and
'14 exhibit a miscibility gap with water, they are often | used as a previous azeotrope and can be recycled into the process after removing the water.
The alcohol used to form the ester or isomeric mixture of | Nonanol, which simultaneously serves as the anterior azeotrope, is used in excess, preferably from 5% to 50% by weight, more preferably from 10% to 30% by weight of the amount necessary to form the ester.
As esterification catalysts, it is possible to use acids, such as sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, for example, or metals or compounds thereof.
Suitable examples include tin, titanium, zirconium, which are used as finely divided metals or usefully in the form of their salts, oxides or soluble organic compounds.
In contrast to protic acids, metal catalysts are high temperature catalysts, which often reach their full activity only at temperatures above 180º C.
Here, however, it should be borne in mind that furanodicarboxylic acid tends to supply CO; in | temperatures above 190º C, and then monocarboxylic acid is formed from then on, and can no longer react to supply the target product.
However, metal catalysts are preferably used, since compared to proton catalysis, they form less by-products from the alcohol used, such as olefins, for example.
Exemplary representatives of metal catalysts are tin powder, tin oxide (11), tin oxalate (II), titanic esters, such as tetraisopropyl orthotitanate or tetrabutyl orthotitanate, and zirconium esters, such as tetrabutyl zirconate .
The concentration of catalyst is dependent on the type of catalyst.
In the case of the titanium compounds preferably used, the concentration is from 0.005% to 2.0% by weight, based on the mixture of
| 15 reaction, more preferably from 0.01% to 0.5%, by mass, more preferably still from 0.01% to 0.1% by mass.
The reaction temperatures when using titanium catalysts are between 160º C and 270º C, preferably between 160 and 200º C.
Optimal temperatures are dependent on the reagents, the progress of the reaction and the concentration of catalyst.
They can be easily determined by experiments for each individual case.
Higher temperatures increase reaction rates and promote secondary reactions, such as the elimination of water from alcohols or the formation of colored by-products, for example.
A beneficial fact regarding the removal of water from the reaction is that the alcohol can be removed by distillation from the reaction mixture.
At the desired temperature or the desired temperature range can be caused by pressure in the reaction vessel.
Therefore, in the case of low boiling alcohols, the reaction is carried out at a superatmospheric pressure, and at reduced pressure in the case of higher boiling alcohols.
In the case of the reaction of FDCA with a mixture of isomeric nonanols, for example, the operation occurs in a temperature range of 160º C to 190º C in the pressure range of 0.1 MPa to 0.001 MPa.
The amount of liquid to be recycled for the reaction can consist of all or part of the alcohol obtained when working the azeotropic distillate.
It is also possible to perform the purification at a later time and replace some or all of the amount of liquid removed with alcohol! fresh, that is, from an alcohol prepared in a reservoir vessel.
Mixtures of crude ester, which in addition to the ester or esters include alcohol, the catalyst or its subsequent products and, optionally, by-products, are purified by conventional methods.
This purification includes the following steps: removal of excess alcohol and, when present, low boiling point products; neutralization of acids
: 16 present; optionally a steam distillation; converting the catalyst to a residue that is easily filterable; removal of solids; and, optionally, drying. The sequence of these steps may differ according to the purification procedure employed. The mixture of the diisononyl esters can optionally be: separated from the reaction mixture by distillation, optionally after neutralization of the batch.
TRANSESTERIFICATION The diisononyl esters of the present invention can alternatively be obtained by transesterification of a 2,5-furanedicarboxylic diester with an isononanol mixture. The reagents used are 2,5-furanedicarboxylic diesters whose alkyl radicals attached to the O atom of the ester group contain 1 to 8 C atoms. These radicals can be aliphatic, straight chain or branched, alicyclic or aromatic. One or more methylene groups on these alkyl radicals can be replaced by oxygen. It is advantageous for alcohols, on which the ester reagent is based, to boil at a temperature below the isononane mixture used. A preferred reagent is dimethyl 2,5-furanedicarboxylate. Transesterification is carried out catalytically, using Brônsted or Lewis acids or using bases, for example. Regardless of which catalyst is used, there is always a temperature-dependent balance developed between the reagents (dialkyl ester and isononanol mixture) and products (mixture of diisononyl ester and released alcohol). In order to shift the balance in favor of the mixture of esters - diisononil, alcohol! The resulting ester reagent is removed from the reaction mixture by distillation. At present, it is also useful to use the excess isononanol mixture. As transesterification catalysts it is possible to use acids,
| 7 17 such as sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, for example, or metals or compounds thereof. Suitable examples include tin, titanium, zirconium, which are used as finely divided metals or usefully in the form of their salts, oxides or soluble organic compounds. In contrast to protic acids, metal catalysts are «high temperature catalysts that reach their full activity only at temperatures above 180º C. However, these are preferably used once. that, compared to proton catalysis, they form less by-products from the alcohol used, such as olefins, for example. Exemplary representatives of metal catalysts are tin powder, tin (II) oxide, tin (II) oxalate, titanic esters, such as tetraisopropyl orthotitanate or tetrabutyl orthotitanate, and zirconium esters, such as tetrabutyl zirconate .
In addition, it is possible to use basic catalysts, such as oxides, hydroxides, hydrogen carbonates, carbonates or alkoxides of alkali metals or alkaline earth metals, for example. From this group it is preferable to use alkoxides, such as sodium methoxide, for example. Alkoxides can also be prepared in situ from an alkali metal and a nonanol and / or an isononanol mixture.
The concentration of catalyst is dependent on the type of catalyst. This is typically between 0.005% and 2.0% by weight, based on the reaction mixture.
Reaction temperatures for transesterification are typically between 100 and 220º C. They must be at least high enough to allow the alcohol formed from the ester reagent to be removed by distillation at the defined pressure, usually at atmospheric pressure, from of the reaction mixture.
Transesterification mixtures can be purified
'18 in exactly the same way as described for esterification mixtures.
Use The isomeric non-ester esters of 2,5-furanedicarboxylic acid of the present invention can be used as plasticizers, especially in compositions of plastics, adhesives, sealants, varnishes, paints, plastisols, synthetic leathers, floor covering, carcass protection , coated fabrics, wallpapers or paints. The plasticizers of the present invention can be used with preference in profiles, joints, food packaging, films, toys, medical articles, tiles, synthetic leathers, floor covering, carcass protection, coated fabrics, wallpapers, cable lining and yarns, and more preferably, in food packaging, toys, medical articles, such as in bags and tube material for infusions, dialysis and drains, for example, wallpapers, floor coverings and coated fabrics.
Can be obtained using mixtures of nonyl esters | isomers of 2,5-furanedicarboxylic acid of the present invention, in particular the compositions of the present invention which comprise the mixture of isomeric non-esters of 2,5-furanedicarboxylic acid.
The compositions of this type may comprise the mixture of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of the present invention alone or in mixtures with other plasticizers. When the compositions of the present invention comprise the mixture of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of the present invention in admixture with other plasticizers, the other plasticizers can preferably be selected from the group of dialkyl phthalates, preferably , with 4 to 13 C atoms in the alkyl chain; trialkyl trimellites, preferably with 4 to 10 C atoms in the side chain; dialkyl adipates
. 19 and, preferably, dialkyl terephthalates, each preferably having 4 to 13 C atoms in the side chain; 1,2-cyclohexanedicarboxylic alkyl esters, 1,3-cyclohexanedicarboxylic alkyl esters, and 1,4-cyclohexanedicarboxylic alkyl esters, preferably 1,2-cyclohexanedicarboxylic alkyl esters, each preferably with an alkyl = alkyl radical containing 4 to 13 carbon atoms in the side chain; dibenzoic esters of glycols; alkyl sulfonic esters of phenol and preferably an alkyl radical containing 8 to 22 C atoms; polymer plasticizers, glycerol esters, isosorbide esters, and alkyl benzoates, preferably containing 7 to 13 C atoms in the alkyl chain.
In all cases, the alkyl radicals can be linear or branched, and also identical or different.
With particular preference, the composition, in addition to the mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid, comprises, in particular, an alkyl benzoate with alkyl = alkyl containing from 7 to 13 carbon atoms, preferably isononyl benzoate, nonyl benzoate, isodecyl benzoate, propyl heptyl benzoate or decyl benzoate.
The fraction of mixtures of isomeric nonyl esters of 2,5-furanedicarboxylic acid of the present invention in admixture with other plasticizers is preferably from 15% to 90% by weight, more preferably from 20% to 80% by weight , and | 20 greater preference, still, from 30% to 70% by mass, with the mass fractions of all plasticizers presenting a sum to provide 100% in | mass, The indicated compositions comprising mixtures of isomeric nonyl esters of 2,5-furanedicarboxylic acid and other —plasticizers can be used as a plasticizer composition in compositions of plastics, adhesives, sealants, varnishes, paints, plastisols or dyes .
Examples of plastic products produced from the plasticizer compositions of the present invention can include the following:
'20 profiles, joints, food packaging, films, toys, medical articles, tiles, synthetic leathers, floor covering, carcass protection, coated fabrics, wallpapers, cable and wire coating.
The favorites of this group are the packaging of food, toys, articles
| 5 doctors, wallpapers, coated fabrics and floor covering.
The compositions of the present invention that comprise a mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid can comprise a polymer selected from polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylates, preferably methacrylate —Polymethyl (PMMA), polyalkyl methacrylate (PAMA), fluoropolymers, preferably polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinylacetals, greater | preferably polyvinylbutyral (PVB), polystyrene polymers, preferably polystyrene (PS), expandable polystyrene (EPS), acrylonitrile-styrene-acrylate (ASA), styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), | styrene-maleic anhydride copolymer (SMA), styrene-methacrylic acid copolymer, polyolefins, preferably polyethylene (PE) or polypropylene (PP), thermoplastic polyolefins (TPO), polyethylene-vinyl acetate (EVA), polycarbonates, terephthalate polyethylene (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPU), polysulphides (PSU), biopolymers, preferably the polylactic acid (PLA), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polyesters, starch, cellulose and cellulose derivatives, preferably nitrocellulose (NC), ethyl cellulose (EC), cellulose acetate (CA), acetate / cellulose butyrate (CAB), rubber or silicones, as well as mixtures or copolymers of the indicated polymers or their monomer units, The compositions of the present invention preferably comprise PVC or homopolymers or copolymers based on ethylene,
| | - 21 propylene, butadiene, vinyl acetate, glycidyl acrylate, l glycidyl methacrylate, methacrylates, acrylates, acrylates or methacrylates containing radicals | alkyl, attached to the oxygen atom of the ester group, from branched or non-branched alcohols containing from one to ten carbon atoms, styrene, acrylonitrile or cyclic olefins.
The type of PVC in the composition of the present invention is preferably suspended PVC, bulky PVC, PVC microsuspension or PVC emulsion. Based on 100 parts by weight of polymer, the compositions of the present invention preferably comprise from 5 to 200, most preferably from 10 to 150 parts by weight of plasticizer.
In addition to the indicated constituents, the compositions of the present invention may comprise additional constituents, more particularly, for example, other plasticizers, fillers, pigments, stabilizers, co-stabilizers, such as epoxidized soybean oil, for example, and also lubricating agents, fluid agents, kickers, antioxidants or biocides.
The compositions of the present invention preferably take the form of a liquid, more preferably a pumpable liquid, a paste, protective compound, plastisol, powder, solid or solid.
The aforementioned compositions comprising said polymers can be used as adhesives, sealants, varnishes, paints, plastisols, synthetic leathers, floor coverings, carcass protection, fabric coverings, wallpapers or dyes or for their production.
When the indicated compositions comprise plastics, these - can be processed into profiles, joints, one part or multiple parts closing devices, food packaging, films, toys, medical items, particularly bag and tube material, as used for infusions, dialysis, and drains, for example, tiles, synthetic leathers,
'22 of floors, carcass protection, coated fabrics, wallpapers, cable and wire coating. The compositions of the present invention are preferably used for the production of food packaging, toys, medical articles, wallpapers, and floor covering. The following examples are intended to illustrate the present invention without restricting its scope, which is evident from the description and the claims. Even without further observations, it is assumed that the person skilled in the art is capable of using the present invention in the broadest conceivable scope.
EXAMPLES The esters of the present invention were prepared in a two-phase synthesis from furan-2,5-dicarboxylic acid by means of dichloride. EXAMPLE 1 SYNTHESIS PROCESS FOR -2,5-FURANODICARBONILLA DICHORIDE (II) A 250 mL three-necked flask with reflux condenser and drip funnel was charged under argon with 72.1 g (462 mmol) of 2,5-furanedicarboxylic acid. Over a 10 minute period, 165 g (1.89 mol) of thionyl chloride, to which a few drops of N, N-dimethylformamide were added, were added. The suspension was heated to reflux temperature and the resulting gas was removed using washing bottles containing aqueous KOH solution. The suspension was then heated for 4 hours under reflux until the evolution of the gas was complete and the dissolution of the solid was complete. After removing excess thionyl chloride, the product was isolated by distillation purification (T = 110º C, p = 0.0012 MPa). This provided 79.4 g of dichloride as a colorless crystalline solid (89% yield) with a melting point of 79.5 to 80.0 ° C. |
S 23 Í 2,5-Furanedicarbonyl dichloride was stored under inert gas (argon) in the dark, at room temperature, before being used later. | EXAMPLE 2 SYNTHESIS OF 2,5-FURANODICARBOXYL ESTERS Under an argon atmosphere, a three-necked flask with reflux condenser and decanting funnel was charged with the dichloride, which was melted by heating.
2.4 equivalents of alcohol were added! drop by drop slowly in the liquid, and an exothermic reaction occurred with evolution of gas.
The produced gas was passed through washing bottles containing aqueous KOH solution.
After complete addition, the mixture was stirred at a temperature of 80 to 100 ° C for 16 hours.
The excess alcohol was removed under reduced pressure in the presence of boiling, and the crude product was purified by distillation. : For the synthesis of the comparative example, commercially available 2-ethylexanol was used. To prepare the ester mixture of the present invention, the Depositor's isononanol, CAS No. 27458-94-2, commercially available under the product name of Isononanol INA, was used.
The isononane! used has a density (DIN 51757) at 20º Cde08348g / cm , a refractive index (DIN 51423/2) at 20º C of 1.4362, and a shear viscosity (DIN 53015) at 20º C 13.2 mPass, | and also a solidification point below (<) -75º C, and had the following composition as determined by gas chromatography analysis: 7.5 mol% of n-nonanol; 19.8 mol% of 6-methyloctanol; 20.0 mol% of 4- — methyloctanol; 3.8 mol% of 2-methyloctanol; 8.3 mol% of 3-ethylptanol; 2.1 mol% of 2-ethylptanol; 1.8 mol% of 2-propylexane! 1; 15.0 mol% of 4,5-dimethylptanol; 10.1 mol% of 2,5-dimethylptanol; 2.5 mol% of 2,3-dimethylptanol; 4.1 mol% of 3-ethyl-4-methylexanol; 2.9 mol% of 2-ethyl-4-
. 24 methylexanol; 2.1 mol% of other unidentified compounds with 9 carbon atoms; the total sum of the specified components was 100 mol%. Table 1 below records the results of the two syntheses. TABLE 1 Boiling point | Yield of Bis (2-ethylxy) 2,5-furanedicarboxylate ester 137 to 138º C 11 (Comparative Example) (p = 0.0002.MPa) Bis (isononyl) 2.5-furanedicarboxylate 155a 185º C 98% (1) ( inventive) (p = 0.0004-MPa) Conversions of 2,5-furanedicarbonyl dichloride (2) for | Corresponding esters are therefore practically quantitative. | EXAMPLE 3
DETERMINATION OF BEHAVIOR AT LOW TEMPERATURE OF THE ESTERS THROUGH DIFFERENTIAL SCANNING CALORIMETRY (DSC) INSTRUMENT: METTLER TOLEDO DSC820 Analysis conditions: Temperature range: -100 to 250º C Heating rate: 10 K / minute Initial mass: about 10 - 11 mg Crucible: standard aluminum crucible with holes in the cap Gas flow: N, Result: Considering that the 2-EH ester | l (Comparative Example) shows a melting signal above 0º C, that is, it is present in solid form already above the freezing point, the isononyl ester | of the present invention was subjected to vitrified solidification at about -80º C. In the DSC thermogram, there are no signs of apparent melting, but instead, only a glass transition point of around 80º C. Therefore, it can be assumed that
'25 the ester | of the present invention does not become solid, even at low temperatures, but instead remains fluid and pumpable. EXAMPLE 4
PREPARATION OF PLASTISOLS The advantageous properties attainable with the esters of the present invention must be shown below in plastisols and semi-finished products capable of being obtained from them. The initial masses used for the components for the various plastisols are shown in Table 2 below. TABLE 2 FORMULAS [ALL VALUES IN PHR (= MASS PARTS PER 100 PIECES IN PVC MASS)] Plastiso formula! 3 mta e GmbH) | 2.5-furanodicarboxtate from Disononta 1cinventvo) | so | = f 2,5-Furanodicarboxylate of Di-2-ethylexyl 11 (example * i | comparative) DINP (VESTINOL 9 from Evonik Oxeno GmbH, |] js comparative example) Ca / zn stabilizer (Mark CZ 149, from Chemitura) Os liquid constituents were weighed before the solid components in a suitable PE beaker. Using a spatula, the mixture was stirred by hand so as not to leave any powder not wet. The mixture beaker was then trapped inside the fixing device of a dissolving stirrer. THE
MM DD | The sample was homogenized using a mixing disc. | The rotation speed of 330 rpm was increased to 2,000 rpm, and stirring was continued until the temperature in the digital display of the thermal sensor reached 30.0º C. This ensured that the homogenization of the -plastisol with a defined energy input. Then, the plastisol was immediately conditioned at a temperature of 25.0º C. EXAMPLE 5
MEASUREMENT OF PLASTISOL VISCOSITY The viscosities of the plastisols prepared in Example 4 were measured using a Physica MCR 101 rheometer (from Paar-Physica), controlled by the associated Rheoplus software, as follows.
The plastisol was stirred again with a spatula in the stock container, and was subjected to measurement in the measurement system 23 (DIN | 25 mm), in accordance with the operating instructions. The measurement ran automatically at 25º C using the software mentioned above. The following procedures were activated: A preliminary shear of 100 s * for a period of 60 s, | during which unmeasured values were recorded (stabilization refers to | thixotropic effects).
A decreasing isothermal ramp, from a shear speed of 200 s * to 0.1 s', divided into a logarithmic series with 30 steps, each with a 5 s duration point measurement. The measurement data was processed automatically after the measurement by the software. The parameter produced was viscosity as a function of the shear rate. In order to capture changes in plastisol viscosity during plastisol storage (also: “plastisol aging”), measurements were taken in each case after 2 hours, 24 hours, and 7 days. Between these time points, plastisols were
RS AAA "=“ ““ OOSooÉEOA AOS ss RR RR RSRS RS RR RR RR RR URI OTA UE pp ONLY,: '27 | | stored at 25º C.
The table below shows the corresponding viscosity values obtained after the storage times indicated in each case, for a shear rate of 100 s as an example.
TABLE 3 PLASTISOL VISCOSITIES AT A 100 s ”SHEAR RATE Plastisol | Used plasticizer | Viscosity | Viscosity | Viscosity | Percentage after 2h in | after 24h | after 7 days | of Pa.s increase in Pa.s in Pa.s: 1 2.5-10.3 10.6 11.6 13 Disononyl furanodicarboxylate 1 | | (inventive) 2 2.5 - 9.0 94 1111 23 | Di-2-ethylhexyl furanedicarboxylate | | (comparative example) | 3 DINP (example | 5.9 6.14 6.5 comparative) Isononyl esters | of the present invention exhibit much smaller increases in plastisol viscosity over time compared to the 2-ethylhexyl Il esters. The viscosity level of the PVC plastisol of the present invention, which is higher compared to the standard DINP plasticizer of the present formulation, can be reduced, as the skilled person knows, in (optimized) formulations and / or other compositions by appropriate measures, such as, for example, an increase in the total amount of plasticizer, the addition of additional plasticizers with a
Lower intrinsic viscosity, the addition of rheological additives (eg dispersion additives or other surfactants) and / or the addition of (co) solvents. EXAMPLE 6
MEASUREMENT OF THE GELIFICATION RATE The gelation behavior of the plastisols was investigated in the MCR Physica 101 in oscillation mode, using a measurement plate / plate system (PP25), which was operated under the control of the shear rate. An additional temperature-conditioned hood was fitted to the instrument in order to achieve a homogeneous heat distribution and a uniform sample temperature. The set of parameters were as follows: Mode: temperature gradient Start temperature: 25º C Final temperature: 180º C Heating / cooling rate: 5º C / minute Oscillation frequency: 4 to 0.1 Hz ramp, logarithmic Omega frequency circular: 10 1 / s Number of measuring points: 63 | Duration of the measuring point: 0.5 minutes | Automatic adjustment of the interval: ON Duration constant measurement point Width of the interval: 0.5 mm Measurement procedure: A drop of the customized plastisol formula was applied with the spatula, without any air bubbles, on the bottom plate of the | measure. In the course of this operation it was recalled that, after the | | |
29 measurement is brought together, some plastisols may evenly swell out of the measurement system (no more than about 6 mm in all). Then, the temperature conditioning hood was positioned over the sample, and the measurement was started. The determined parameter was the complex viscosity of plastisol as a function of temperature. Because a defined temperature is reached over a period of time (determined by the heating rate of 5º C / min), not only the gelation temperature, but also an indication of the gelation rate of the measurement system is obtained. The beginning of the gelation process was evident from a sudden increase in the complex viscosity. The sooner this increase in viscosity appears, the better the gelling capacity of the system.
For comparison, the interpolation of the curves for each | plastisol was used to determine the temperature at which a complex l15 viscosity of 1000 Pa.s was reached.
l In this procedure, the values obtained are established in Table 4: TABLE 4
GELIFICATION BEHAVIOR Example plastisols 4 1 (Inventive) [2 (Comparative example) | Comparative) Temperature at viscosity | 85º C 80,5º C 88,5º C of 1000 Pa.s It is clear that the furanodicarboxylic esters gel earlier (that is, at lower temperatures) than the corresponding phthalates. EXAMPLE 7 MEASUREMENT OF SHORE MOLDED HARDNESS
. 30 Shore hardness is a measure of the plasticity of a specimen. The more a standardized needle can penetrate the sample within a defined measurement time, the lower the measurement value. The plasticizer with the highest efficiency provides the lowest Shore hardness value for a given amount of plasticizer. Conversely, in the case of highly efficient plasticizers, it is possible to make a certain saving in the proportion in the formula, and in many cases, this translates into lower costs for the processor. For the determination of Shore hardnesses, plastisols prepared in accordance with Example 4 were poured into circular casting molds with a diameter of 42 mm. The plastisols in the molds were then gelled in a forced air drying oven at 200º C for 30 minutes, demolded after cooling, and stored at 25º C for at least 24 hours before measurement. The thickness of the castings was about 12 mm. The measurements were carried out in accordance with the DIN 53 505 standard using a Zwick-Roell Shore A measuring instrument, the measurement value to be read after 3 seconds in each case. In each specimen, three different measurements were taken at different points (not in the marginal zone), and the mean was recorded in each case. Table 5 lists the measurement values obtained. TABLES
SHORE HARDNESSES À 1 (inventive) 2 (Example Comparative example 4) | comparative) Dweza shore - | 78 | 7 | so The listed examples demonstrate that the furanodicarboxylic acid diisononyl ester | of the present invention has the decisive advantage over the closest prior art, (2-ethylexyl) -bis-furan-2,5-
. 31 dicarboxylate Il, of non-crystallized. Compared to the corresponding phthalate DINP, there are improvements, in some cases, significantly less, in the plasticization effect and in the gelation rate. EXAMPLE 8 Ss USE OF THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN THE FORMULATION OF PVC FINISH (PLASTISOL), ALONG WITH DIISONONILE TEREFTALATE (DINT) - PREPARATION OF FINISHING FINISHES
PLASTISOLS | Plastisols were prepared according to Example 4, but with a modified formula. The initial masses used for the 1 components of the various plastisols are shown in the table below (Table 6). TABLE 6
FORMULAS [All figures in phr (= parts by mass per 100 parts by mass of PVC)] | ————— Formulatedpastsor - ==> | 14 12 | Micro-suspension of PVC K70 (VESTOLIT B7021 Ultra, from Vestolit) 2,5-furanodicarboxylate of diisononyl; preparation by Example 2 (inventive) (ortho) Diisononyl phthalate [DINP] (VESTINOL 9 from | Evonik Oxeno GmbH, comparative example) Diisononyl terephthalate (laboratory product, | 40 35 preparation by document DE 102.008.006.400 A1 / Example 1 )
'32 | Fermusdopastsor - === [1 [2 | Calcium / zinc stabilizer (Mark CZ 149, from 2 Chemtura / Galata) EXAMPLE 9
DETERMINATION OF THE PLASTISOL VISCOSITY OF THE FINISHING PLASTISOLS (EXAMPLE 8) THAT UNDERSTANDS THE FURANODICARBOXYL ESTERS OF
PRESENT INVENTION AND DIISONONILLA TEREFTALATE AFTER A 24 H STORAGE PERIOD (AT 25ºC) The viscosities of the plastisols prepared in Example 8 were measured using a Physica MCR 101 rheometer (from Paar-Physica), according to the procedure described in Example 5, The results are shown in the table below (Table 7) by way of example for shear rates of 100 / s, 10 / s, 1 / s and 0.1 / s. TABLE 7 SHEARING VISCOSITY OF PLASTISOLS IN EXAMPLE 8, AFTER 24 H OF STORAGE AT 25º C | Plastisol formula (from Examples) === | n +> Ts »| Shear viscosity at a rate of er) shear = 100 / s [Pa.s] Shear viscosity at a rate of 3.1 shear = 10 / s [Pa.s] shear = 1 / s [Pa.s] Viscosity shear at a rate of / 3.1 3.4 3.7 shear = 0.1 / s [Pa.s] ** = Comparative example * = Inventive
'33 | In a range of low shear rates, the plastisols comprising the furanodicarboxylic esters of the present invention are in terms of their shear viscosity at or below the level of the plastisol DINP analog. At higher shear rates, the shear viscosities of the plastisols of the present invention are only slightly above the shear viscosity of the plastisol analog DINP. By mixing the diisononyl terephthalate with the furanodicarboxylic esters of the present invention, it is therefore possible to prepare plastisols that have similar processing properties to those of | 10 — DINP plastisols, but at the same time do not contain orthophthalates, which are based on renewable raw materials. EXAMPLE 10
USE OF THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN THERMALLY EXPANDABLE PLASTISOLS (COATING), ALONG WITH QUICK GELIFICANTS - PLASTISOL PREPARATION Plastisols were prepared as in Example 4, but with a modified formula. The initial masses used in the components for the various plastisols are shown in the table below (Table 8). TABLE 8 | 20 THERMALLY EXPANDABLE PLASTISOL FORMULAS [All figures in phr (= parts by mass per 100 parts by mass of PVC)] | Plasticizer form - ==> [4% [2 [a [e 5 [e | | vinotmesesa = === >>> 100 [100 1100 [ro j1oo [100 | | vesinoro so [ans | [eiator in O es | Mesamant O es
. 34 | Ptastisor formulation - ==> | ja 1x [a [5 Te | | uanmen eta gÇ
EESTI oiee grs ias ans ans [576 o7 ** = Comparative Example * Inventive The compounds and substances used are explained below: | Vinnolit MP 6852: Microsuspensions of PVC (homopolymer) | with a K value (according to DIN EN ISO 1628-2) of 68, by Vinnolit GmbH & Co KG. Vestinol 9: (ortho) diisononyl phthalate [DINP], plasticizer; from Evonik Oxeno GmbH. Citrofol BIl: acetyl tributyl citrate, plasticizer with rapid coagulation, from Jungbunzlauer AG. Mesamol |: phenol alkyl sulfonic ester; plasticizer with rapid coagulation; from Lanxess AG. Jayflex MB10: isodecyl benzoate; fast coagulation plasticizer from ExxonMobil Chemicals. Eastman DBT: dibutyl terephthalate; fast coagulation plasticizer, from Eastman Chemical Co. DINFDC: diisononyl 2,5-furanedicarboxylate of the present invention; preparation as in Example 2. Unifoam AZ Ultra 7043: Azodicarbonamide; thermally activated blowing agent, from Hebron S.A. ZnO: zinc oxide; decomposition catalyst for the thermal blowing agent; reduces the inherent decomposition temperature of the blowing agent; active zinc oxide; from Lanxess AG.
35 EXAMPLE 11 DETERMINATION OF THE VISCOSITY OF THERMALLY EXPANDABLE PLASTISOLS (FROM EXAMPLE 10) UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION AND (ORTHO) DIISONONILLA PHTHALATE AND / OR GELIFANTS IN A LONGER THROUGH 24 HOUR PERIOD (AVAILABLE IN TIME) AT THE FASTEST TIME.
The viscosities of the plastisols prepared in Example 10 were measured using a Physica MCR 101 rheometer (from Paar-Physica), in accordance with the procedure described in Example 5. The results are shown in the table below (Table 9) by way of example for shear rates of 100 / s, 10 / s, 1 / s, and 0.1 / s.
TABLE 9 SHEAR VISCOSITY OF THE PLASTISOLS OF EXAMPLE 8, AFTER 24 H OF STORAGE AT 25º C Formula of plastisol (as in rejelepepjs | Example 10) shear rate = 100 / s [Pa.s] Shear viscosity with | 4.5 | 7.8 | 8.5 | 10.2 | 4.7 | 9.2 shear speed = 10 / s [Pa.s] Shear viscosity with | 5.2 | 8.5 10.7 | 5.7 [11.7 shear rate = 1 / s [Pa.s] Shear viscosity at 15.2 | 15.7 shear rate = 0.1 / s [Pa.s]
** = Comparative examples * = Inventive
By choosing the quick gelling agent, it is possible to adjust the |
. 36 plastisol viscosity! in a deliberate way, with the combination of diisononyl furanodicarboxylate of the present invention and alkyl benzoate, in the present case (Formula 5 plastisol) leading to a rheological behavior similar to that found when using the universal plasticizer (ortho) diisononyl phthalate. In other words, the plastisols of the present invention are provided, which can be used in similar processing conditions (for example, application rates) as the current standard DINP plasticizer, but do not (have to) contain orthophthalates and are based on least partly in renewable raw materials. EXAMPLE 12 PRODUCTION OF FOAM SHEETS AND DETERMINATION OF THE BEHAVIOR OF
EXPANSION AND FOAM FORMATION OF THERMALLY EXPANDABLE PLASTISOLS (FROM EXAMPLE 10) THAT UNDERSTAND THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION AND (ORTHO) DIISONONILE PHALATE AND / OR FAST GELIFYERS using a determined foam thickness of 200º C (suitable for plasticized PVC measurements) to an accuracy of 0.01 mm. For sheet production, a 1 mm blade opening was defined on the blade roll of a Labcoaters Mathis (manufacturer: W. Mathis AG). This opening of the slide was checked with a calibrator and adjusted, if necessary. The plastisols prepared in Example 10 were coated using the rolling blade of Labcoater Mathis on a release paper (GUARANTEES Paper Release; from Sappi Ltd) stretched flat on a board. In order to be able to calculate the percentage of foaming, an incipiently gelled and foamless sheet was first produced. The thickness of this sheet with the indicated blade opening was 0.74 mm. The thickness was measured at three different points on the sheet. Subsequently, again with / in Labcoater Mathis, the foam |
'37 sheets (foams) were produced with four different residence times in the oven (60, 90, 120s and 150s). After the foams had cooled, the thickness was also measured at three different points. The average thickness values, and the original thickness of 0.74 mm, were necessary for the “expansion calculation (example: (foam thickness - original thickness) / original thickness * 100% = expansion). The results are shown in the table below (Table 10). TABLE 10
EXPANSION FEES OF POLYMER FOAMS PREPARED FROM THERMAL EXPANDABLE PLASTISOLS (FROM EXAMPLE 10) WITH DIFFERENT RESIDENCE TIMES IN THE OVEN AT LABCOATER MATHIS AT 200º C [Domus done take 1 1 19 le e e | Expansion after -> 119 to [Je | Expansion after 12th sima -> jasa [ara [amm [so1 [ava [sos | | ** = Comparative example * = Inventive The plastisol formulas of the present invention that comprise diisononyl furanodicarboxylates expand much faster than with the diisononyl phthalate plasticizer used alone in the comparative example (Formula 1 plastisol). Through the deliberate use of specific fast gelling agents, such as certain citric acid esters, for example (Formula 3 plastisol), PVC plastisols can be prepared which, on the one hand, can be subjected to heat pretreatment (for example, example, preliminary gelling in the case of a multilayered construction), without exhibiting measurable expansion at this initial point, but on the other hand, they expand later even more quickly. Through the selection of different
% 38 combination plasticizers, it is also possible to prepare PVC plastisols which (such as Formulas 4 and 5 plastisol, for example) exhibit strong expansion right from the start, and allow significantly less total processing time compared to the current standard DINP plasticizer . PVC plastisols | consequently, they are provided with a wide spectrum of different processing possibilities. EXAMPLE 13
DETERMINATION OF PLASTISOL GELIFICATION BEHAVIOR | THERMICALLY EXPANDABLE (FROM EXAMPLE 10) THAT UNDERSTANDS THE ESTERS - FURANODICARBOXYLIC OF THE PRESENT INVENTION AND (ORTHOUS) DIISONONILLA PHYTALATE AND / OR FAST GELIFICANTS The gelation behavior of the thermally 'expandable plastisols prepared in Example 10 was investigated in the MCR 101 oscillation using a plate / measurement plate system (PP25) which was operated under shear rate control, according to the procedure described in example 6. The parameter determined was the complex viscosity of the plastisol as a function of temperature, with a constant heating rate (ie, the gelation curve). The start of the gelation process results from a sudden increase in the complex viscosity. The sooner this increase in viscosity appears, the faster the corresponding plastisol will gel. By interpolating each plastisol, the measurement curves obtained were used to determine the temperatures at which a complex viscosity of 1000 Pa.s and 10,000 Pa.s was reached. In addition, a tangent method was used to determine the maximum plastisol viscosity achieved in the present experimental system, and the temperature from which the maximum plastisol viscosity occurs was determined by dropping a perpendicular. The results are shown in the table below (Table 11).
'39 TABLE 11 KEY DATA, DETERMINED FROM THE GELIFICATION CURVES (VISCOSITY CURVES), THE GELIFICATION BEHAVIOR OF THE THERMALLY EXPANDABLE PLASTISOLS PREPARED IN EXAMPLE 10 mamae | ") example 10) Obtaining viscosity 78 78 T7 74 of the plastis to 1,000 Pa.s in [PC] Obtaining a plastisol | 84 82 82 77 viscosity of 10,000 | Pa.s in [ºC] | plastisol [Pa.s] 'Temperature in obtaining | 92 88 88 88 of the maximum viscosity of plastisol [ºC] ** Comparative example * = Inventive By choosing the quick gelling agent, it is not only possible, but expected, to adjust the gelling rate and also the gelling temperature, but also, to a Surprisingly high degree, the maximum viscosity of the fully gelled plastisol (maximum plastisol viscosity), and therefore the physical properties of the PVC foam produced through thermal expansion.
Therefore, thermally expandable PVC plastisols are supplied, which on the one hand gels substantially faster than plastisols produced using the current DINP plasticizer alone, but on the other hand can also be
. 40 processed into foams with significantly higher viscosity, and greater strength and / or elasticity. EXAMPLE 14 USE OF THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN CONNECTION WITH OTHER DRY MIXTURES - PLASTICANTS
DRY MIXTURES The advantageous properties obtained with the esters of the present invention will be demonstrated below by way of example for dry mixtures, known as dry mixtures, and for semi-finished products that can be obtained from these mixtures. The prepared formulas are shown in the table below (Table 12). TABLE 12
DRY MIXTURES FORMULAS [All figures in phr (= parts of mass per 100 parts of PVC mass) | Misturaseca | 1% 2 | 32 4 | 5 [6 | eds Ri Pl | in | ars FA By hs Porver g
NA Potrsarto A grs] BRA ER E and na ans o 3 o4
'41 ** = Comparative example * = Inventive The compounds and substances used are explained below: Solvin S 271 PC: PVC suspension with a K value (determined to DIN EN ISO 1628-2) of 71, from SolVin, S.A.
Vestinol 9: (ortho) diisononyl phthalate [DINP], plasticizer; from Evonik Oxeno GmbH.
DEHT: di (2-ethylhexyl) terephthalate; “Eastman 168"; plasticizer, Eastman Chemical.
DINT: diisononyl terephthalate (laboratory product, prepared - according to document DE 102008006400 A1 / Example 1). DINCH: Di (isononyl) cyclohexanedicarboxylate; DINCH hexamoll; plasticizer; BASF AG. | GSS: otadecanoic acid 12- (acetyloxy) -2,3-bis (acetyloxy) propyl ester; glycerol triester produced from castor oil; “Soft Grindsted 'n Safe”; plasticizer; from Danisco A / S.
Polysorb ID 37: Di (octanoic acid) ester isosorbide; plasticizer; from Roquette Freres.
DINFDC: diisononyl 2,5-furanedicarboxylate of the present invention; preparation as in Example 2. Drapex 39: epoxylated soybean oil; Costabilizer &Coplasticizer; from Chemtura / Galata.
Mark BZ 561: barium / zinc stabilizer, from Chemtura / Galata.
Calcium stearate: Calcium salt of stearic acid; lubricant.
The dry mixes were produced in a Brabender planetary mixer.
A thermostat heated the mixing bowl of the planetary mixer to a constant temperature of 90º C.
Through the | “Winmix” software, the following parameters were defined on the Brabender planetary mixer:
| : 42 Rotation speed program: Active Profile: Rotation speed of 50 rpm, dwell time: 9 min, increase time: 1 min Rotation speed at 100 rpm; waiting time: 20 min Kneader temperature: 88º C Measuring range: 2 NM Attenuation: 3 The temperature in the mixing vessel was 88º C. After the planetary mixer performed the self-calibration, the solid constituents were supplied to the mixing vessel . The program was started and the powder mixture was stirred in the mixing vessel for 10 minutes and brought to a controlled temperature before the liquid constituents were added. The mixture was stirred in the planetary mixer for another 20 minutes. After the end of the program, the completed dry mixture (powder) was discharged. The transferred torque / time diagram was evaluated by the Brabender software. After the addition of the liquid constituents, a distinct increase is evident in the curve. Only when the curve falls significantly again, the incorporation of the plasticizer is completed. The time difference between these two points is the plasticizer incorporation time (dry mix time). The maximum torque is automatically evaluated by the program. The incorporation of the plasticizer and the maximum torque determined in the production of dry mixtures are shown in Table 13. TABLE 13
TIME REQUIRED FOR THE INCORPORATION OF THE LIQUID COMPONENTS OF THE FORMULA BY THE PRE-HEATED PVC (INCORPORATION OF THE PLASTIFIER) AND THE MAXIMUM TOUCH DETERMINED DURING THE DRY MIXTURE PRODUCTION | Example 14 dry mix - [15 [2 [3/2 [5/6 | 7]
'43 mrs seca do suenei a - Imizis ereleir ** = Comparative example * = Inventive The processing speed of the mixtures of the present invention is higher, in some cases much less, than for the comparative formula with the standard DINP plasticizer; the maximum torque is comparable in all cases. Therefore, dry mixtures are provided which, compared to the current standard DINP plasticizer, allow a significantly higher processing rate for a similar applied force. EXAMPLE 15
PRODUCTION OF MILLED SHEETS AND PRESS MOLDED PLATES FROM | 10 DRY MIXTURES (FROM EXAMPLE 14) UNDERSTANDING THE ESTERS OF | FURANODICARBOXYLIC OF THE PRESENT INVENTION IN CONNECTION WITH OTHERS PLASTIFIERS
MILLED SHEET PRODUCTION The milled sheets were produced in a Collin AP W150 calender. 'The parameters established in the calender were as follows: Roll temperature: 165º C Roll gap: 0.5 mm Rolling time: 5 minutes | 20 Five-phase program for the production of the milled sheet When the roll temperature has been reached, the roll slot has been calibrated. At the beginning of the measurement, the roll slot was adjusted to 0.2 mm. 160 grams of a dry mixture (from Example 14) were weighed in each case and placed in the roll slot, with the rollers stationary. The program has started. The rollers started with a rotation speed of 5 rpm and a friction of 20%. After about 1 minute, plasticization was in great
'44 starts at the end, and the roll slot has been enlarged to 0.5 mm. Triple homogenization was performed by means of an automatic volume unit in the calender. After 5 minutes, the milled sheet was removed from the roll and cooled.
PRODUCTION OF PRESS MOLDED PLATES The molded press plates were produced in a Collin laboratory press. The prefabricated milled sheets (see above) were used to produce the press-molded plates. The lateral margins of the milled sheets were removed by means of a shearing machine, after which the milled sheet was cut into sections measuring approximately 14.5 x 14.5 cm. For the 1 mm thick molded plates, two sections of milled sheets were placed in 15 x 15 cm of stainless steel pressing frame. The parameters established in the laboratory press were as follows: Three-phase program: Phase 1: Both plates at 165º; plate pressure in the press: 5 bar, phase time: 60 seconds. Phase 2: Both plates at 165º; plate pressure in the press: 200 bar; phase time: 120 seconds. Phase 3: Both plates at 40º; plate pressure in the press: 200 bar, phase time: 270 seconds. The exudate from the excess press was removed after the molded plates on the press were produced. EXAMPLE 16 DETERMINATION OF THE PLASTIFICATION EFFECT AND PLASTIFICATION EFFICIENCY ON PRESS MOLDED PLATES PRODUCED FROM DRY MIXTURES UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN CONNECTION WITH OTHER PLASTICORS, BY DETERMINING SHORE HARDNESS
'45 (SHORE A AND D) Shore hardness is a measure of the plasticity of a specimen. The more a standardized needle can penetrate the sample within a defined measurement time, the lower the measurement value. For a given amount of plasticizer, the plasticizer with the highest efficiency produces the lowest value for Shore hardness. Since, in practice, formulations / formulas are often defined or optimized for a defined Shore hardness, accordingly, it is possible in the case of very efficient plasticizers to save on the formula of a given fraction, which implies a reduction in costs for processor, Hardness measurements were performed in accordance with DIN 53 505 using a Shore A and Shore D Zwick-Roell measuring instrument, the measurement value to be read after 3 seconds in each case. In each specimen (produced as in Example 15), measurements were taken at three different points, and an average was formed. The results of | determination of hardness are summarized in table 14. | TABLE 14 | SHORE A AND SHORE D HARDNESSES OF PRESS MOLDED PLATES PRODUCED (ACCORDING TO EXAMPLE 15) FROM DRY MIXTURES (FROM EXAMPLE 14) UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION
IN conjunction with other plasticizers | Dry mix from Example 14 | 1st | 2 | 3 [4 [5 [6/7 Shore A her le nie is Shore D 27 ** = Comparative example * = Inventive The mixture of different standard plasticizers with esters | Furanodicarboxylic acid of the present invention in dry mixtures produces a
. 46 plasticizer efficiency that is similar to or better than that of DINP (plasticizer standard). In addition, dry mixtures are provided which, compared to DINP currently in use as a universal plasticizer, exhibit significantly better efficiency and, therefore, can lead to, in particular, reduced formula costs. EXAMPLE 17 DETERMINATION OF WATER ABSORPTION AND LEACHING BEHAVIOR IN MOLDED PRESS PLATES (SEMI-FINISHED PRODUCTS) PRODUCED FROM FROM DRY MIXTURES UNDERSTANDING ESTERS FURANODICARBOXYLIC OF THE PRESENT INVENTION IN CONNECTION WITH OTHERS
PLASTIFIERS Water absorption and leaching behavior are two main criteria for assessing the quality of semi-finished products produced based on dry PVC mixtures. If a semi-finished PVC product absorbs water to a substantial extent, this results, on the one hand, in a change in its physical properties, and on the other hand, in a change in its visual appearance (for example, cloudy). A high level of water absorption, accordingly, is generally undesirable. The leaching behavior is an additional criterion of the permanence of the components of the formulation under conditions of use (for example, on floors or tiles). This applies particularly to stabilizers, plasticizers and / or their ingredients, since a reduction in the concentration of these constituents in the formula of the semi-finished product can not only impair the physical properties, but also drastically reduce the life span of the semi-finished products.
PRODUCTION OF TEST SPECIMENS For each sample / dry mixture, 3 circles (each 10 cm ) Were cut with the aid of a circular cutter from the plates molded in
'47 press (produced as in Example 15). The circles were punctured. Before storing the water, the circles were stored in a desiccator equipped with drying agent (KC drying beads) at 25º C for 24 hours. The original weight (starting mass) was determined on an analytical balance to the nearest 0.1 mg. The circles were then stored in a shaking bath filled with completely demineralized water, at a temperature of 30º C, below the water surface, with suitable sample supports, for 24 hours, and were moved continuously. After storage, the circles were removed from the water bath, dried and weighed (weight after 24 h). The heavy circles were placed back in the water bath and after 7 days, weighed again in the dry state (weight after 7 days). After the second weighing, the cycles were again stored in a desiccator equipped with a | drying (drying KC beads) at 25º C for 24 hours, and then weighing again (final mass = weight after drying). The changes in weight were calculated as percentages and are shown in Table 15. TABLE 15 WATER ABSORPTION AND LEAKAGE BEHAVIOR DETERMINED IN
TEST SPECIMENS PRODUCED FROM PRESS MOLDED PLATES - (COMONO EXAMPLE 15) PRODUCED FROM DRY MIXTURES (FROM EXAMPLE 14) UNDERSTANDING THE FURANODICARBOXYLIC ESTERS OF THIS INVENTION
IN conjunction with other plasticizers Dry mix of [| Example 14 1 day [% ma] Change in weight after | +0.33 | +0.34 | +0.34 | +0.38 | +0.41 7 days [% ma]
. 48 Dry mix of 7 Example 14 Change in weight after | -0.16 | -0.14 | -0.17 | -0.43 | -0.16 | -0.35 | -1.16 drying [% ma] ** = Comparative example * = Inventive The test specimens comprising furanodicarboxylic esters are similar in terms of water storage behavior in the test specimen containing only the standard plasticizer DINP. Water absorption is extremely low, which is a special advantage for calendered floor coverings, but also for roofing sheets. Mass loss through leaching is also within narrow limits, with the exception of the mixture of isosorbide ester Polysorb ID 37 and diisononyl furanedicarboxylate. Thus, dry mixes and semi-finished products with a production capacity from them are supplied, which are distinguished by low water absorption and low leaching characteristics, and are therefore ideal also for use in contact areas. with continuous or frequent water. EXAMPLE 18 DETERMINATION OF TENSION / STRETCH PROPERTIES IN PRESS MOLDED PLATES (SEMI-FINISHED PRODUCTS) PRODUCED FROM DRY MIXTURES UNDERSTANDING THE FURANODICARBOXYL ESTERS OF
PRESENT INVENTION IN CONNECTION WITH OTHER PLASTIFIERS Tensile strength and elongation at break are physical properties that play an important role, especially for semi-finished products under mechanical load. This mechanical load can occur both during the production process of the semi-finished product and during its use. Preferably (particularly in the tile sector) it is given in most
'49 cases for materials that exhibit high tensile strength with moderate elongation. For the tensile tests, standard “S-2” test bars were perforated from the press molded sheets produced as in Example 15. The tensile tests were carried out in accordance with DIN 53504 on a “Z tensile tester 1445 "from Zwick. The set of test parameters were as follows: Test conditions: 23º C, RH 50% Initial force: 0.5 N Initial force speed: 5 mm / minute Test speed: 100 mm / minute For to determine the tensile strength and elongation at break, 5 measurements were taken per sample, the mean values of measurement were inserted in the table below (Table 16). TABLE 16 TENSION PROPERTIES DETERMINED ACCORDING TO DIN 53504 IN TEST SAMPLES S2 PRODUCED FROM PRESS MOLDED PLATES (as in EXAMPLE 15) PRODUCED FROM DRY MIXTURES (FROM EXAMPLE 14) UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION
IN conjunction with other plasticizers | Dry mix from Example 14 | 1st | 2nd | 3 [4 | 5 | 6 | 7) ** = Comparative example * = Inventive By using the mixtures of the present invention it is possible to achieve a considerable increase in tensile strength compared to pure DINP (plasticizer standard). There are no restrictions at present on flexibility
", 50 of the material, instead, the elongation at break is in fact somewhat increased. Therefore, dry mixtures and semi-finished products with production capacity from them are supplied, which are distinguished by a high resistance to traction together with high flexibility and high dimensional stability, which are therefore also suitable for use under high mechanical load (for shoring, among other uses).
USE OF THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN PROTECTION COMPOUNDS (EXAMPLE, BOTTOM OF THE PROTECTIVE BODY / UBP) - PREPARATION OF UBP PLASTISOLS) The advantageous properties attainable with the esters of the present invention will be shown below in the plastisols ). Plastisols were prepared as in Example 4, but with a modified formula. The initial masses used for the components of the various plastisols can be seen from the table below (Table 17). TABLE 17 FORMULAS OF UBP PROTECTION COMPOUNDS (PLASTISOLS) | 20 [All figures in phr (= parts by mass per 100 parts by mass of PVC)) rlz PVC emulsion with K value of 70 (7031 VESTOLIT E, | 100 100 from Vestolit) | Furon-2,5-diisonon dicarboxtate (invertive) - [130] | DINP (VESTINOL 9 from Evonik Oxeno GmbH, comparative example 130)
* 51 | Fómuadopiastsor - =] 1 | 2nd) Coated calcium carbonate (Socal 312, from Solvay Chemicals) White lime DIN EN 459-1 / CL-Q-fine lime (Precal 30 S, by Schãfer-Krusemark) ** = Comparative example * = Inventive! EXAMPLE 20
DETERMINATION OF PLASTISOL VISCOSITY OF UBP PLASTISOLS | UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION, | 5 AFTER A 2 H STORAGE TIME (AT 25º C) Protective compounds, especially those used in the vehicle body protection area, are required to meet different viscosity requirements according to the current shear rate. Therefore, during application, which is generally carried out at high spray shear rates, the protective compounds must flow very easily and exhibit, on the treated surface, a homogeneous spray pattern and good leveling. After application (that is, in the absence, to a large extent, of any shear force), in contrast, they must have a high viscosity and to exhibit little post-application flow.
The viscosities of the plastisols prepared in Example 19 were measured using a Physica MCR 101 rheometer (from Paar-Physica), in accordance with the procedure described in Example 5, after the pastes had been conditioned in temperature for a time of 2 hours at 25º C The results are shown in the table below (Table 18) by means of
* 52 »1 example for shear rates of 100 / s, 10 / s, 1 / s, and 0.1 / s. TABLE 18 SHEARING VISCOSITY OF PLASTISOLS IN EXAMPLE 19, AFTER 2 HOURS OF STORAGE AT 25º C | Plastic formula of Example 46 - = | + | 2 »| Shear viscosity at a shear rate = 100 / s [Pa.s] Shear viscosity at a rate of 50 54.5 shear = 10 / s [Pa.s] Shear viscosity at a shear rate = 1 / s [Pa.s) Shear viscosity at a shear rate = 0.1 / s [Pa.s] ** = Comparative example * = Inventive Compared to DINP (plasticizer standard, Formula 2 plastisol), UBP / plastisol UBP based on the furanodicarboxylic ester mixture of the present invention (Formula 1 plastisol) also has a low shear viscosity with high shear rates, while at low shear rates it is well above the shear viscosity of the DINP paste. Therefore, in the application with the same processing properties, there is a clear advantage in terms of the drip resistance of the formulation. Thus, UBP plastisols are provided that combine excellent spraying and leveling with very low post-application flow properties. EXAMPLE 21 DETERMINATION OF THE GELIFICATION RATE OF PLASTISOLS UBP UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION
* 53 and | Gelling of UBP protective compounds must be possible, | within the thermal curing processes that exist in the automotive industry.
On the one hand, an important factor is an extremely rapid solidification of the protective compound, in order to prevent further dripping, while, on the other hand, another important factor is a complete or almost complete gelation within an extremely short time, the in order to achieve maximum protection effect.
The gelation behavior of the UBP plastisols prepared in Example 19 was investigated in Physica MCR 101 in oscillation mode using a measurement plate / plate system (PP25) which was operated under the control of the shear rate, according to the procedure described in Example 6. The parameter determined was the complex viscosity of plastisol! as a function of temperature, with a constant heating rate (ie, the gelation curve). The start of the gelation process results from a sudden increase in the complex viscosity.
The sooner this increase in viscosity appears, the faster the corresponding plastisol will gel.
By interpolation for each plastisol, the measurement curves obtained were used to determine the temperatures at which the viscosity of a complex of 1,000 Pa.s and 10,000 Pa.s was reached.
In addition, a tangent method was used to determine the maximum plastisol viscosity achieved in the present experimental system, and the temperature at which the maximum plastisol viscosity occurs was determined by dropping a perpendicular.
The results are shown - table below (Table 19). TABLE 19 KEY DATA, DETERMINED FROM THE GELIFICATION CURVES (VISCOSITY CURVES), THE GELIFICATION BEHAVIOR OF THE UBP PLASTISOLS
PREPARED IN EXAMPLE 19 | - Example 19 plastisol formula | + | 2 »Obtaining a plastisol viscosity! 1,000 Pa.s in PC] Pa.s in [ºC] Temperature in obtaining the maximum viscosity of the plastisol! [ºC] ** = Comparative example * = Inventive The UBP protective compound comprising the furanodicarboxylic esters "of the present invention exhibits a gelation - substantially faster than the comparable DINP protective compound; consequently, substantially faster processing or, alternatively, the use of lower processing temperatures (= energy and cost savings) is possible. The substantially higher final viscosity of the UBP protective compound of the present invention also points to an improved effect of protecting the compound against stone scratches, for example. Therefore, UBP plastisols are provided, which compared to UBP plastisols based on the present standard DINP plasticizer, have significantly better processing and physical properties. EXAMPLE 22 EFFECT OF ADHESION OF UBP PROTECTIVE COMPOUNDS UNDERSTANDING FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION ON THE PANELS OF
STANDARD METAL Crucial to the ongoing protective effect of protective compounds
UBP are, among other properties, the adhesion properties of UBP protection compounds totally gelled on automotive body panels. For the adhesion test, specially coated “Cathogard” panels (BASF Coatings Es GmbH) were used. A measuring blade was' used to coat the metal panels with the UBP plastisols of Example
19. The UBP plastisols were used after a storage time of 2 hours at 25º C. For the coating, the metal panels were labeled with adhesive tape, in order to produce four areas with a size of about 7x3cm The plastisols were first distributed along the four areas using a spatula. With the metering blade, the plastisols were then coated without problems. Excess plastisol and adhesive tape have been removed. The coated panels were gelled in a drying oven at a temperature of 130º C for 25 minutes.
The adhesion test was performed after three different time conditions (2 hours / 24 hours / 168 hours). For the test, the areas were divided with a razor blade for a number of small areas. Then, using a special purpose spatula, an attempt was made to separate the first area. The adhesion / detachment behavior was assessed (see Table 20). Between tests, the fully gelled panels were stored in a temperature conditioning cabinet at 25º C.
TABLE 20 ASSESSMENT SYSTEM FOR THE MEMBERSHIP TEST! DETACHMENT ON THE
TOTALLY GELIFIED PLASTISOLS UBP 3 Satisfactory adhesion
»56» [adessodenceme - ==> le = UU | semadesãornadeuada - | The results of the adhesion / detachment test on fully gelated UBP plastisols are collected in the table below (Table 21). TABLE 21 5 MEMBERSHIP PROPERTIES! DETACHING OF THE UBP PLASTISOLS FULLY GELIFIED, PREPARED ACCORDING TO EXAMPLE 19 | ——— Plastisol plated Example 19 - | q | 2 ») Adhesion after 2 hours of storage of the fully gelled sample Adhesion after 24 hours of storage of the fully gelled sample Adhesion after 168 hours of storage of the fully gelled sample ** = Comparative example * = Inventive The protective compound comprising the furanodicarboxylic esters of The present invention therefore has the same adhesion properties as the DINP analogue protective compound.
Thus, the UBP protection compounds that are provided, which in addition to very good processing and physical properties also have good adhesion to car panels and therefore have a good protective effect.

权利要求:
Claims (15)
[1]
1. MIXTURES OF NONILE ESTERS OF 2,5-furanedicarboxylic acid, characterized by the fact that they are of Formula |
A AAA Oo o O
[2]
2. MIXTURE, according to claim 1, characterized in that the mixture comprises at least two different esters, which differ in the constitution of the isomeric C9 radicals, with none of the C9 radicals present in the mixture with a fraction greater than 90 mol%.
[3]
3. PROCESS FOR THE PREPARATION OF NONYL ESTER MIXTURES isomeric from the 2,5-furanedicarboxylic acid of Formula |, characterized by the fact that: (a) 2,5-furanedicarboxylic acid is brought into contact with a mixture of C9 alcohols isomeric, with water release; (b) the mixture of isomeric C9 alcohols is used in a molar excess of up to 50%; (c) the reaction in (a) occurs using a catalyst selected from the groups of Bronsted acids and / or Lewis acids.
[4]
4. PROCESS FOR THE PREPARATION OF NONYL ESTER MIXTURES isomeric from the 2,5-furanedicarboxylic acid of Formula |, characterized by the fact that: (a) 2,5-furanedicarboxylic acid is converted into the corresponding -2,5 chloride -furanedicarbonyl which (b) following isolation and purification, is subsequently brought into contact with a mixture of isomeric C9 alcohols, with release
" 2
Hydrogen chloride tee.
[5]
5. PROCESS FOR THE PREPARATION OF NONYL ESTER MIXTURES isomeric from the 2,5-furanedicarboxylic acid of formula |, characterized by the fact that: (a) the dimethyl -2,5-furanedicarboxylate is placed in contact with a mixture of isomeric C9 alcohols, with methanol release; (b) the reaction in (a) occurs using a catalyst selected from the groups of Bransted acids and / or Lewis acids.
[6]
6. COMPOSITION, characterized by the fact that it comprises mixtures of isomeric nonyl esters of 2,5-furanodicarboxylic acid of Formula | and also plasticizers selected from the group of alkyl benzoates, dialkyl adipates, glycerol esters, citric acid trialkyl esters, citric acid acylated trialkyl esters, trialkyl trimellitates, glycol dibenzoates, dialkyl terephthalates, dialkyl phthalates dialcanoyl esters of isosorbide and / or dialkyl esters of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acids.
[7]
7. COMPOSITION, according to claim 6, characterized by the fact that the ratio between the isomeric nonyl esters of the 2,5-furanedicarboxylic acid of Formula | and the plasticizers are located at an interval of 1:15 to 15:01.
[8]
8. COMPOSITION, according to claim 7, characterized by the fact that it comprises a polymer selected from polyvinyl chloride, polyvinyl butyral, polylactic acid, polyhydroxy butyral and / or polyalkyl methacrylate.
[9]
9. COMPOSITION, characterized by the fact that it comprises mixtures of isomeric nonyl esters of 2,5-furanodicarboxylic acid of Formula | and a polymer selected from polyvinyl chloride, polyvinyl butyral, polylactic acid, polyhydroxy butyral and / or polyalkyl methacrylate.
”3 s
[10]
10. COMPOSITION, according to claim 9, characterized in that the ratio between polymer and isomeric nonyl esters of 2,5-furanedicarboxylic acid of Formula | be in a range of 30: 1 to 1: 2.5.
[11]
11. USE OF NONILA ESTERS isomeric from 2,5-furanedicarboxylic acid of Formula |, as defined in one of claims 1 and 2, characterized by the fact that they are as plasticizers.
[12]
12. USE OF THE COMPOSITION, as defined in one of claims 6 to 9, characterized by the fact that it is in the preparation of paints, dyes, adhesives or adhesive components, varnishes, plastisols, sealants as plasticizers, more particularly in plastics or plastic components.
[13]
13. USE OF THE COMPOSITION, as defined in one of claims 6 to 9, characterized by the fact that it is as a solvent in the preparation of paints, dyes, adhesives or adhesive components, varnishes, plastisols, sealants.
[14]
14. USE OF THE COMPOSITION, as defined in one of claims 6 to 9, characterized by the fact that it is as a component of lubricating oil.
| 20
[15]
15. USE OF THE COMPOSITION, as defined in one of claims 6 to 9, characterized by the fact that it is an auxiliary in metal processing.
- 1 2 Abstract “NONILA ESTER MIXTURES, PROCESS FOR THE PREPARATION OF NONILA ESTER MIXTURES, COMPOSITIONS AND USE OF NONILA ESTERS AND COMPOSITION USES” The present invention relates to the mixture of isomeric nonyl esters of acid 2, 5-furanedicarboxylic acid of formula (1), methods for said production of mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (1), compositions containing mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (1), uses of the mixture mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (1) as plasticizers, and uses of the aforementioned compositions containing mixture of isomeric nonyl esters | 2,5-furanodicarboxylic acid of formula (1). | | |

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法律状态:
2020-09-08| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-09-08| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA GMBH (DE) |

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2020-10-06| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |

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2020-10-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2021-01-19| B09A| Decision: intention to grant|

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2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 02/03/2021, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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DE102009028975A|DE102009028975A1|2009-08-28|2009-08-28|Ester derivatives of 2,5-furandicarboxylic acid and their use as plasticizers|

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DE102009028975.5|2009-08-28|

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PCT/EP2010/061941|WO2011023590A1|2009-08-28|2010-08-17|2,5-furan dicarboxylate derivatives, and use thereof as plasticizers|

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