plasticizer composition, uses of a plasticizer composition, polymeric composition and molding or fil

专利摘要:
PLASTIFYING OR PLASTIFYING COMPOSITION, PLASTIFYING COMPOSITION, PROCESSES FOR PREPARING A PENTILE ESTER, USES OF A PLASTIFYING, POLYMERIC COMPOSITION AND MOLDING OR FILM. The invention relates to the use of pentyl esters of furandicarboxylic acid as a softener.
公开号:BR112013020342B1
申请号:R112013020342-0
申请日:2012-01-27
公开日:2021-02-02
发明作者:Hinnerk Gordon Becker；Michael Grass
申请人:Evonik Operations Gmbh；
IPC主号:

专利说明:

[001] The present invention relates to pentyl esters of furandicarboxylic acid.
[002] The invention also provides for the use of these pentyl esters as or in plasticizers and in compositions, especially those comprising polymers, especially PVC, and a preparation process for these pentyl esters. The invention further provides polymeric compositions comprising such pentyl esters and moldings or films produced therefrom or the use of such compositions.
[003] Polyvinyl chloride (PVC) is one of the most economically important polymers and is used in various applications both in the form of rigid PVC and in the form of flexible PVC. Important areas of use are, for example, cable coverings, floor coverings, wallpapers and plastic window frames. To increase elasticity and better processability, plasticizers are added to PVC. Such conventional plasticizers include, for example, phthalic esters such as di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP). Due to their toxicological properties, efforts are made in many cases to replace phthalic esters with other plasticizers. Alternative plasticizers that have been described recently are therefore, for example, cyclohexanedicarboxylic esters such as diisononyl cyclohexanedicarboxylate (DINCH).
[004] In addition, the state of the art has also described terephthalic acid esters as alternative plasticizers.
[005] With respect to the raw material base, the distinguishing feature of the present invention lies in the optional use of renewable raw materials to produce the furandicarboxylic esters according to the invention. In the context of the present invention, renewable raw materials, in contrast to petrochemical raw materials based on fossil resources, for example mineral oil or anthracite, are designed to mean those raw materials that form or are produced based on biomass. The terms "biomass", "biobased" or "based on" and "produced from renewable raw materials" encompass all materials of biological origin that originate from the so-called "short-term carbon cycle", and therefore, they are not part of geological formations or fossil strata. Renewable raw materials are identified and quantified according to the ASTM method D6866. A characteristic feature of renewable raw materials is the proportion of the 14C carbon isotope there when contrasted with petrochemical raw materials.
[006] It is known that with the increase in the alkyl chain length of the esters, there will be an increase in their incompatibility with polymers, specifically with PVC. This can have the consequence, for example, of PVC-based compositions that contain such molecules, for example as plasticizers, exhibit atypical and unviable viscosity profiles which complicates processing. In the production of films, it is often found that they have an increasingly non-transparent appearance and that discoloration of the film occurs, which is reflected, for example, in an accentuated undesired yellow tone in most applications. A lower compatibility of plasticizers and PVC also reduces the permanence of the plasticizer which means that these plasticizers escape relatively quickly from the semi-finished or finished PVC product, which leads to product fragility and therefore a significant reduction in the function and value of the product corresponding. The behavior of the plasticizer is also called "exudation" or "sweating".
[007] Secondly, esters with short alkyl chains are generally known to have relatively high volatility first, but also, especially where esters with high gelling capacity are referred to, lead when processed in pasted PVC pastes to low pastes. storage stability, the shear viscosity of these often depends a lot on the shear rate, which again leads to restricted processability.
[008] In the production of PVC plastisols, special care must be taken so that a minimum viscosity is maintained in the course of processing in order to obtain homogeneous distribution of the plasticizer in PVC. In addition, high storage stability of Plastisol PVC and low dependence on the shear viscosity of the paste in relation to the shear rate are also desirable. Unloaded films produced from PVC Plastisols must be transparent and have a minimum yellowish tone. The plasticizer must also have a high permanence.
[009] In the state of the art, several alternative plasticizers have become known for use in PVC. Patent document EP 1 808 457 A1 describes the use of dialkyl terephthalates, which are characterized by the fact that the alkyl radicals have a longer length of at least 4 carbon atoms and have a total number of carbon atoms per alkyl radical of 5. It is also indicated that terephthalic esters with 4 or 5 carbon atoms in the longest carbon chain of alcohol have good suitability as quick-gel plasticizers for PVC.
[010] In addition, the use of C5-alkyl esters of citric acid as plasticizers with good gelling properties is also known from patent document EP 1864964B1.
[011] Many of the furandicarboxylic acid esters are crystalline spolides at room temperature at room temperature which, being solid, can only be used with difficulty for the production of liquid compositions, especially of plastisols (polymeric). In this way, the production of polymer pastes or plastisols on an industrial scale can only be achieved with liquid plasticizers. Solid plasticizers must be dissolved beforehand in appropriate solvents, which makes the process inconvenient and costly, and in many applications causes problems with the material properties as a result of evaporation of the solvents used during processing.
[012] The technical object of the invention is therefore to provide compounds that can be used as or in plasticizers and that can also be processed into plastisols, which have good gelling properties, exhibit, low dependence on plastisol viscosity on the plastisol viscosity rate of shear in plastisols, and have little yellowing and high transparency when processed form films. It is an additional object to dissolve solution for such technical purpose in connection with a substance or compound that can be produced at least partially from renewable raw materials.
[013] This technical object is obtained through pentyl esters of furandicarboxylic acid.
[014] These pentyl esters are preferably dipentyl esters.
[015] More particularly, the technical object is obtained through pentyl esters of furandicarboxylic acid, which have at least one of the following properties: - density at 20 ° C is up to 1.06 g / cm3; - intrinsic viscosity at 25 ° C is up to 60 mPa * s; - when analyzed with a differential calorimeter, there is no sign of melting at temperatures> 25 ° C.
[016] In another embodiment, the pentyl ester has at least two of the above properties.
[017] A specific economic advantage and simultaneously favorable to the environment of the present invention resides in the simultaneous use of renewable and petrochemical raw materials for the production of furandicarboxylic esters according to the invention, which first allows for a particularly cheap production and great applicability but it also enables particularly "sustainable" products.
[018] It has been found that, surprisingly, such pentyl esters, unlike the corresponding homologous butyl and hexyl esters, are not solid and have good processability as liquids at room temperature. The corresponding homologous di-n-butyl furandicarboxylates and di-n-hexyl furandicarboxylates are solid at room temperature and have melting points in the range of 30-40 ° C. They therefore cannot be used on an industrial scale for the production of polymeric pastes or plastisols.
[019] Di-n-butyl furanedicarboxylate and di-n-hexyl furanedicarboxylate are known from studies by Sanderson et al (RD Sanderson, DFSchneider, I. Schreuder; J.Appl.Polym.Sci .; 53 (1991); 1785 -1793). These are crystalline solids with melting points of approximately 42 ° C (di-n-butyl furanedicarboxylate) and approximately 32 ° C (di-n-hexyl furanedicarboxylate), which cannot be used conveniently for numerous applications, for example the production of polymeric pastes.
[020] Dipentyl esters of furandicarboxylic acid have not been described so far; more particularly, there are no suggestions for the use of dipentyl furandicarboxylic acid esters in polymeric compositions and / or as plasticizers.
[021] It has been found that, surprisingly, the inventive pentyl esters can be produced in liquid form without solidification, and can be used advantageously as a component in polymeric formulations, for example as plasticizers in PVC-based formulations.
[022] The inventive pentyl esters have also been found to have excellent gelling properties when they are processed with PVC. These gelling properties are currently better than the gelling properties of the corresponding dialkyl terephthalates.
[023] PVC pastes based on the inventive pentyl esters show only a low dependence on the viscosity of the paste in relation to the shear rate. They are processable within a wide range of shear rates and with a wide variety of different processing methods.
[024] Due to the favorable gelling characteristics, the corresponding PVC pastes can be processed more quickly or at lower temperatures.
[025] It has also been found that transparent PVC films comprising the plasticizer according to the invention have a very high transparency, which in some cases is superior to that of films that were produced with dibutyl terephthalate as a plasticizer.
[026] In a preferred embodiment, the pentyl ester is a dipentyl furan-2,5-dicarboxylate. This can also be present in the form of at least two isomeric dipentyl furan-2,5-dicarboxylates.
[027] In a preferred embodiment, isomeric dipentyl furan-2,5-dicarboxylates esters are also used, the latter comprising pentyl groups selected from: n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl groups, 3- methylbutyl, 3-methylbut-2-yl, 2-methylbut-2-yl.
[028] It is particularly preferred to use mixtures of n-pentanol and 2-methylbutanol in a mass ratio of 99.9 to 70% pentanol and 0.1 to 30% 2-methylbutanol.
[029] The alkyl radicals of the furandicarboxylic esters are preferably more than 60% of n-pentyl radicals. Preferably, the alkyl radicals of the dialkyl terephthalates are 70 to 99.9% n-pentyl radicals and 30 to 0.1% methylbutyl radicals, especially 2-methylbutyl radicals, more preferably 85 to 98% n-pentyl radicals and 15 to 2% methylbutyl radicals, especially 2-methylbutyl radicals, and most preferably 90 to 96% n-pentyl radicals and 10 to 4% methylbutyl radicals, especially 2-methylbutyl radicals. Preferably, the methylbutyl radicals are more than 50%, preferably more than 75% and more preferably more than 95% 2-methylbutyl radicals. The percentage distribution of the C5-alkyl radicals can be determined in a simple way by hydrolyzing the esters, removing the alcohol obtained and analyzing the alcohol by gas chromatography (GC). For example, separation by gas chromatography can be carried out on a polydimethylsiloxane column (for example DB 5) as the stationary phase with a length of 60 m, an internal diameter of 0.25 mm and a film thickness of 0.25 μm.
[030] In an especially preferred embodiment, the pentyl ester according to the invention is a di-n-pentyl ester. This has the advantage that it is a compound with a distinct molecular structure that can be produced in an easy way from the industrially available raw material n-pentanol.
[031] In another particularly preferred embodiment, at least one of the two pentyl ester groups according to the invention is a 2-methylbutyl or 3-methylbutyl group. This has the advantage that the pentyl esters have a very high storage stability both intrinsically and in polymeric compositions.
[032] In another preferred embodiment, the pentyl esters according to the invention are isomeric pentanol ester mixtures. This has the advantage that it is possible to produce mixtures with a tendency to very low crystallization, which leads to good properties at low temperature in polymeric compositions.
[033] The pentyl esters according to the invention can preferably be prepared using primary alcohols or mixtures of alcohol as obtainable, for example, by hydroformylation of an alkene with subsequent hydrogenation. Pentanole precursors are preferably technical hydrocarbon mixtures that contain one or more olefin (s) with 4 carbon atoms. The most important source of C4-olefins is the C4 cut of gasoline cracked from steam crackers. This is used to produce, after extraction / extraction distillation of butadiene or selective hydrogenation of it to produce a mixture of n-butene, a hydrocarbon mixture (raffinate I or C-crack) that comprises isobutene, 1-butene and the two 2 - butenes. Another raw material for C4-olefins is the C4 cut of FCC plants that can be prepared as described above. C4-Olefins produced by Fischer-Tropsch synthesis, after selective hydrogenation of the butadiene present here to produce n-butenes, also a suitable raw material. In addition, mixtures of olefin are obtained by hydrogenation of C4 hydrocarbons or by metathesis reactions or other technical olefin streams may be suitable raw materials. In addition for raffinate I, precursors suitable for pentanols are also raffinate II and / or raffinate III, a current that is obtained by removing much of the 1-butene from raffinate II, which is called crude butane, which is obtained in raffinate II oligomerization and which, in addition to alkanes, comprises 2-butene as virtually the exclusive olefin. The advantage of using raffinate II, raffinate III or crude butane as a precursor to pentanols is that these precursors contain virtually no isobutene, if any, and the pentanols present therefore contain only small amounts (less than 0.5% by weight in relation to pentanols), if it contains, 3-methylbutanol.
[034] Due to the often very high separation complexity of the starting mixtures, it may be advantageous not to separate the olefins present in the technical mixture for use as a starting mixture, but for direct use of the mixtures.
[035] The compositions according to the invention, in addition to additional plasticizers with the exception of pentyl esters of furandicarboxylic acid, may preferably be present.
[036] Such additional plasticizers are, for example, selected from the following relationship: dialkyl phthalates, preferably having 4 to 13 carbon atoms in the alkyl chain; trialkyl trimellites, preferably with 4 to 9 carbon atoms in the side chain; dialkyl adipates, preferably with 4 to 9 carbon atoms in the side chain; dialkyl terephthalates, preferably each having 4 to 13 carbon atoms, especially 4 to 9 carbon atoms, in the side chain; alkyl 1,2-cyclohexanediesters, alkyl 1,3-cyclohexanediesters and alkyl 1,4-cyclohexanediesters, with alkyl 1,2-cyclohexanediesters being preferred, preferably with 4 to 10 carbon atoms in the side chain respectively; dibenzoic esters of glycols; alkyl sulfonic esters of phenol with preferably an alkyl radical containing 8 to 22 carbon atoms; glyceryl esters; isosorbide esters, especially isosorbide diesters; epoxidized vegetable oils; esters of unsaturated or saturated fatty acid eu can also be partially or totally epoxidized; citric triesters with a free or carboxylated OH group and, for example, alkyl radicals of 4 to 8 carbon atoms, alkylpyrrolidone derivatives with alkyl radicals of 4 to 18 carbon atoms and alkyl benzoates, preferably with 7 to 13 carbon atoms in the alkyl chain. In all cases, the alkyl radicals can be linear or branched, the same or different.
[037] More preferably, in the mixtures according to the invention, no ortho-phthalate is used as an additional plasticizer.
[038] In a preferred embodiment, at least one of the additional plasticizers used in the composition according to the invention is a trialkyl trimellitate. This trialkyl trimellitate preferably has ester side chains with 4 to 9 carbon atoms, where the ester groups can have the same number or a different number of carbon atoms. More preferably, at least one of the ester groups present is a group with up to 8 carbon atoms per ester group, especially preferably a group with up to 7 carbon atoms and most preferably a group with up to 6 carbon atoms. The combination of the pentyl esters according to the invention with trialkyl trimellites, when used in PVC plastisols, produces especially products that have a low proportion of volatile constituents and good thermal stability.
[039] In another particular embodiment, at least one of the additional plasticizers used in the composition according to the invention is a dialkyl adipate. This dialkyl adipate preferably has ester side chains with 4 to 9 carbon atoms, where the ester groups in this case can also have the same number or a different number of carbon atoms. More preferably, at least one of the ester groups present is a group with up to 8 carbon atoms per ester group, especially preferably a group with up to 7 carbon atoms. More particularly, at least one of the dialkyl adipates used is dioctyl adipate. The combination of dipentyl furandicarboxylates according to the invention with dialkyl adipates, when used in PVC plastisols, especially produces products that have a low viscosity of plastisol and, in the processed state, good properties at low temperature (for example a glass transition temperature very low).
[040] In another particular embodiment, at least one of the additional plasticizers used in the composition according to the invention is a dialkyl terephthalate. This dialkyl terephthalate preferably has ester side chains with 4 to 13 carbon atoms, where the ester groups can again have the same number or a different number of carbon atoms. More preferably, at least one of the ester groups present is a group with up to 10 carbon atoms per ester group, especially preferably a group with up to 9 carbon atoms and most preferably a group with up to 8 carbon atoms. More particularly, at least one of the dialkyl terephthalates used is di (isononyl) terephthalate, di (2-ethylhexyl) terephthalate, di-n-heptyl terephthalate, diisohepty terephthalate, di-n-butyl terephthalate, di (3-methylbutyl) terephthalate or di-n-pentyl terephthalate. The combination of dipentyl furandicarboxylates according to the invention with dialkyl terephthalates, when used in PVC plastisols, especially produces products which (according to the length of the ester chain of the dialkyl terephthalates used) have excellent thermal stability and good properties at low temperature at the same time low level of volatile constituents.
[041] In another particular embodiment, at least one of the additional plasticizers used in the composition according to the invention is a dialkyl ester of cyclohexanedicarboxylic acid, more preferably a dialkyl ester of 1,2-cyclohexanedicarboxylic acid. Preferably, this dialkyl cyclohexanedicarboxylate has ester side chains with 4 to 10 carbon atoms, where the ester groups can again have the same number or a different number of carbon atoms. More preferably, at least one of the ester groups present is a group with up to 9 carbon atoms per ester group, especially preferably a group with up to 8 carbon atoms and most preferably a group with up to 7 carbon atoms. More particularly, at least one of the dialkyl cyclohexanedicarboxylates used is di-iso-nonyl 1,2-cyclohexanoate, di-2-ethylhexyl 1,2-cyclohexanoate, di-n-pentyl 1,2-cyclohexanoate, di-n-heptyl 1 , 2-cyclohexanoate, diisopropyl 1,2-cyclohexanoate, di-n-butyl 1,2-cyclohexanoate, di-n-butyl 1,4-cyclohexanoate, di-n-butyl 1,3-cyclohexanoate or di (3-methylbutyl) 1,2-cyclohexanoate. The combination of dipentyl furandicarboxylates according to the invention with dialkyl esters of cyclohexanedicarboxylic acid, when used in PVC plastisols, especially produces products that have the particular characteristics of very high hydrolysis stability and very low plastisol viscosity with good gelling properties at the same time .
[042] In another particular embodiment, at least one of the additional plasticizers used in the composition according to the invention is a glyceryl ester, more preferably a glyceryl triester. Ester groups can be aliphatic or aromatic in structure. This glyceryl ester preferably has ester side chains with 1 to 24 carbon atoms, where the ester groups can again have the same number or a different number of carbon atoms. More preferably, one of the ester groups is hydroxystearic acid where the hydroxyl functionality is preferably also esterified, more preferably by an acetyl group. Additionally more preferably, at least one of the ester groups present is a group with up to 9 carbon atoms per ester group, especially preferably a group with up to 8 carbon atoms and most preferably a group with up to 7 carbon atoms. More particularly, at least one of the glyceryl esters used is a glyceryl triacetate. The combination of the dipentyl furandicarboxylates according to the invention with glyceryl esters produces especially particularly sustainable products that can be produced largely on the basis of renewable raw materials.
[043] In another particular embodiment, at least one of the additional plasticizers used in the composition according to the invention is a citric triester with a free or carboxylated OH group. Ester groups can also be aliphatic or aromatic in structure. The citric triester is especially preferably a trialkyl citrate with a carboxylated OH group. This trialkyl citrate preferably has ester side chains with 1 to 9 carbon atoms, where the ester groups can again have the same number or a different number of carbon atoms. More preferably, at least one of the ester groups present is a group with up to 9 carbon atoms per ester group, especially preferably a group with up to 8 carbon atoms and most preferably a group with up to 7 carbon atoms. More particularly, at least one of the citrus esters used is acetyl tributyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n-pentyl citrate or acetyl tri-isoheptyl citrate. The combination of the dipentyl furandicarboxylates according to the invention with citrus triesters with a free or carboxylated OH group produces plastisols which have a particularly good gelation capacity at low temperatures.
[044] In a preferred embodiment, the mass ratio of additional plasticizers used and pentyl esters of furandicarboxylic acid is between 1:20 and 20: 1, preferably between 1:10 and 20: 1, more preferably between 1: 5 and 20: 1 and especially preferably between 1: 1 and 15: 1.
[045] The pentyl esters according to the invention or the plasticizers produced from them can be present in all possible forms of presentation, for example as a liquid, especially as a pumpable liquid (pumpable at room temperature), with a paste , protective composition, plastisol, powder or solid. Especially preferably, they are present in liquid form and especially preferably in the form of a pumpable liquid (pumpable at room temperature).
[046] In addition to the pentyl ester itself, a process for preparing it is also claimed.
[047] Process for the preparation of a pentyl ester described above, comprising the process steps: a) putting in contact with furandicarboxylic acid and / or at least one furandicarboxylic acid derivative, especially dimethyl furanedicarboxylate or furanedicarbonyl chloride, with one or more aliphatic alcohols with 5 carbon atoms, and optionally one or more esterification catalysts and / or other substances; b) heating the described reaction mixture to a temperature of> 50 ° C and esterification or transesterification during the removal of at least one low molecular weight substance from the reaction mixture, the removal in process step b) being preferably thermally accomplished.
[048] In an alternative preparation process, a pentyl ester described above, this process comprises process steps of: a) contacting 5-hydroxymethylfurfural and / or at least one furan derivative with one or more aliphatic alcohols with 5 carbon atoms and at least one catalyst and at least one oxygen-containing component; b) adjusting the described reaction mixture to a temperature of> 0 ° C and performing an oxidative esterification, the term "oxidative esterification" being understood as (any) combination of oxidation and esterification in preferably a process step, especially preferably in a reaction space.
[049] The latter process in this case is preferred.
[050] Pentyl esters can be prepared by direct esterification of furandicarboxylic acid or by transesterification, for example from the methyl esters of furandicarboxylic acid.
[051] To prepare the pentyl esters according to the invention by means of esterification, whether furandicarboxylic acid or a reactive derivative, for example the corresponding dichloride, is reacted with one or more aliphatic alcohols with 5 carbon atoms. The esterification preferably takes place from furandicarboxylic acid and one or more aliphatic alcohols with 5 carbon atoms with the help of a catalyst.
[052] The esterification of furandicarboxylic acid with one or more aliphatic alcohols with 5 carbon atoms to form the corresponding pentyl esters can be carried out autocatalytically or catalytically, for example with Br0nsted or Lewis acids. No matter what type of catalysis is selected, the result is always a temperature-dependent balance between acid and alcohol raw materials and ester and water products. To change the balance in favor of the ester, it is possible to use a entraining agent with the help of which the reaction water is removed from the mixture. As the alcohols used for esterification have a lower boiling point than furandicarboxylic acid, the reactive derivatives of these and esters of these, they are often used as a entraining agent that, after removing water, can be recycled from back to the process.
[053] The alcohol used to form the pentyl ester or isomeric pentanol mixture that serves as a entraining agent simultaneously when a entraining agent is used in an excess of preferably 5 to 50% by weight, especially 10 to 30% by weight. mass, of the amount needed to form ester.
[054] The esterification catalysts used can be acids, for example Br0nsted acids, for example sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, or metals or compounds thereof (generally Lewis acids). Suitable examples are tin, titanium, zirconium which are used in the form of finely divided metals or appropriately in the form of salts thereof (for example halides), soluble or insoluble organic oxides or compounds. Unlike protic acids, metal catalysts are high temperature catalysts that often reach their full activity only at temperatures above 180 ° C. However, it should be noted that in this context furandicarboxylic acid tends to eliminate CO2 (decarboxylation) at temperatures above 190 ° C to form the monocarboxylic acid that can no longer be converted into the target product.
[055] However, metal catalysts are preferably used as compared to protic catalysts they form a lower level of by-products, for example olefins from the alcohol used. Illustrative representatives of metal catalysts are tin powder, tin (II) oxide, tin (II) oxalate, titanic esters such as tetrapentyl orthotitanate, tetraisopropyl orthotitanate or tetrabutyl orthotitanate, and zirconium esters such as zirconium tetentate zirconate or tetrabutyl zirconate.
[056] The catalyst concentration depends on the type of catalyst. In the case of the titanium compounds used preferably, the concentration is 0.005 to 2.0 mass% based on the reaction mixture, especially 0.01 to 0.5 mass%, most preferably 0.01 to 0.1 mass%.
[057] The reaction temperatures in the case of the use of titanium catalysts are especially between 160 ° C and 270 ° C, preferably 160 ° C to 200 ° C. Ideal temperatures depend on raw materials, reaction progress and catalyst concentration. They can be easily determined by tests for each individual case. Higher temperatures increase the reaction rates and promote side reactions, for example elimination of water from alcohols or formation of colored by-products. It is favorable for the removal of the reaction water that the alcohol can be removed by distilling the reaction mixture. The desired temperature or the desired temperature range can be established by the pressure in the reaction vessel. In the case of low boiling alcohols the reaction is therefore carried out under high pressure and in the case of higher boiling alcohols under reduced pressure. For example, the reaction of furandicarboxylic acid with a mixture of isomeric pentanols is carried out within a temperature range of 160 ° C to 190 ° C within the pressure range of 0.1 MPa to 0.001 MPa.
[058] The amount of liquid to be recycled for the reaction can consist partially or entirely of alcohol that can be obtained by preparing the distillate. It is also possible to carry out the preparation at a later time and replace the amount of liquid removed completely or partially with fresh alcohol, i.e., alcohol available in a reservoir container.
[059] Crude ester mixtures which comprise, in addition to the pentyl ester (s), alcohol, catalyst or conversion products and possibly by-products are prepared by processes known per se. The preparation comprises the following steps: removal of excess alcohol and any low temperature boilers, neutralization of the acids present, optionally steam distillation, conversion of the catalyst into a readily filterable residue, removal of solids and optionally drying. Depending on the preparation process used, the sequence of these steps may be different.
[060] Optionally, the reaction product can be removed by distillation of the reaction mixture, optionally after neutralization of the mixture.
[061] Alternatively, the pentyl esters according to the invention can be obtained by transesterification of a furan-2,5-dicarboxylic diester with one or more aliphatic alcohols having 5 carbon atoms. The reagents used are preferably furan-2,5-dicarboxylic diesters whose alkyl radicals attached to the oxygen atom of the ester group have 1-4 carbon atoms. These radicals can be aliphatic, straight chain or branched and alicyclic or aromatic. One or more methylene groups of these alkyl radicals can be replaced by oxygen. It is appropriate that the parent alcohols of the reagent ester have a lower boiling point than the pentanol (ies) used. A preferred raw material is furan-2,5-dicarboxylate.
[062] The use of furan-2,5-dicarboxylic diester for the preparation of the pentyl ester according to the invention is particularly advantageous since furan-2,5-dicarboxylic diesters in general have a higher thermal stability than furan acid -2,5-dicarboxylic and more particularly can also be purified without decomposition by thermal separation processes (for example distillation).
[063] Transesterification can be carried out catalytically, for example with Br0nsted acids or Lewis or bases. No matter which catalyst is used, the result is always a temperature-dependent balance between raw materials (dialkyl ester and pentanol or mixture of pentanol) and products (dipentyl ester or mixture of dipentyl ester and released alcohol). To change the balance in favor of the dipentyl ester or the dipentyl ester mixture, the alcohol formed from the reagent ester is removed by distillation of the reaction mixture.
[064] It is also appropriate to use excess pentanol mixture.
[065] The transesterification catalysts used can be acids, for example sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, or metals or compounds thereof. Suitable examples are tin, titanium, zirconium which are used in the form of finely divided metals or suitably in the form of salts thereof (for example halides), oxides or soluble and insoluble organic compounds. Unlike protic acids, metal catalysts are high temperature catalysts that reach their full activity at temperatures above 180 ° C. However, they are used preferably, as they form a lower level of by-products compared to protic catalysts, for example olefins of the alcohol used. Illustrative representatives of metal catalysts are tin powder, tin (II) acid, tin (II) oxalate, titanic esters such as tetraisopropyl orthotitanate, tetrabutyl orthotitanate or tetrapentyl orthotitanate, and zirconium esters such as tetrabutyl zirconate or tetrapentyl zirconate.
[066] In addition, it is possible to use basic catalysts, for example oxides, hydroxides, hydrogen carbonates, carbonates or alkoxides of alkali metals or alkaline earth metals. Of this group, the use of alkoxides, for example sodium methoxide, is preferred. Alkoxides can also be prepared in situ from an alkali metal and a pentanol or an isomeric pentanol mixture.
[067] The concentration of catalyst depends on the type of catalyst. It is typically between 0.005 to 2.0% by mass based on the reaction mixture.
[068] The reaction temperatures for transesterification are typically between 50 ° C and 220 ° C. They must be at least high enough so that the alcohol formed from the reagent ester can be removed by distilling the reaction mixture at the prescribed pressure, usually standard pressure.
[069] Transesterification mixtures can be prepared in the same way as described for esterification mixtures.
[070] In addition to direct esterification and transesterification, the dipentyl furandicarboxylates according to the invention can also be prepared by means of the so-called oxidative esterification. This has a particular advantage that the intermediate of furandicarboxylic acid or furandicarboxylic ester does not need to be separated, but instead it can be prepared directly with the intermediate (semi-stable), for example 5-hydroxymethylfurfural or other furan derivatives. An additional factor is that in general low temperatures (i.e., lesser tendency to form by-products) and relatively short reaction times are possible.
[071] To allow the oxidation reaction, an oxygen-containing component needs to be present in the reaction mixture. Particularly advantageously suitable for this purpose are oxygen, air and / or peroxides, especially hydrogen peroxide.
[072] Oxidative esterification is most preferably carried out in the presence of a catalyst that significantly reduces the reaction time. The catalyst can be a homogeneous or heterogeneous catalyst. The catalyst - the active catalyst surface in the case of heterogeneous catalysts - most preferably has Lewi acidity. The catalyst is preferably a noble metal catalyst, in the case of a heterogeneous catalyst a noble metal catalyst with a nanoscale surface, especially a gold catalyst with a nanoscale surface. In the case of heterogeneous catalysts, the use of an inorganic catalyst support is particularly advantageous, with macroporous or microporous supports being preferred, especially those with porous surfaces with a nanoscale structure.
[073] In addition to the pentyl ester itself, its use as a polymer plasticizer is also claimed. The polymer is preferably PVC.
[074] The pentylester according to the invention can be used particularly advantageously in adhesives, sealing compounds, varnishes, paints, plastisols, synthetic leather, floor coverings, underbody protection, fabric coverings, wallpaper or paints.
[075] In addition, polymeric compositions comprising a plasticizer described above are claimed.
[076] The plasticizers according to the invention can be used in compositions comprising polymers. These polymers are specially selected from the group consisting of: polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylates, especially polymethyl methacrylate (PMMA), polyalkyl methacrylate (PAMA), fluoropolymers, especially polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetals, especially polyvinyl butyral (PVB), polystyrene polymers, especially polystyrene (PS), expandable polystyrene (EPS), acrylonitrile copolymers styrene-acrylate (ASA), styrene acrylonitrile (SAN) copolymers, acrylonitrile-butadiene-styrene copolymers (ABS), styrene-maleic anhydride (SMA) copolymers, styrene-methacrylic acid copolymers, polyolefins and / or copolymers and / or polyolefins , especially polyethylene (PE) or polypropylene (PP), thermoplastic polyolefins (TPO), polyethylene-vinyl acetate (EVA) copolymers, polycarbonates, tereph polyethylene talate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPU), polysulfites (PSu), biopolymers, especially polylactic acid (PLA) ), polyhydroxybutyral (PHB), polyhydroxyvaleric acid (PHV), polyesters, starch, cellulose and cellulose derivatives, especially nitro cellulose (NC), ethyl cellulose (EC), cellulose acetate (CA), cellulose acetate / butyrate (CAB ), rubber or silicones, and mixtures or copolymers of the mentioned polymers or monomer units thereof. The polymeric compositions according to the invention preferably comprise PVC or homo- or copolymers based on ethylene, propyl o, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, methyl acrylates, ethyl acrylates, butyl acrylates or methacrylates with alkyl radicals, attached to the oxygen atom of the ester group, of branched or unbranched alcohols with one to ten carbon atoms, styrene, acrylonitrile or cyclic olefins.
[077] More preferably, the polymeric compositions according to the invention comprise as the PVC type, suspension, volume / mass, microsuspension or PVC emulsion.
[078] Based on 100 parts by weight of polymer, the polymeric compositions according to the invention preferably comprise from 5 to 200, more preferably from 10 to 150, parts by weight of plasticizer.
[079] The polymeric compositions according to the invention may comprise, in addition to the mentioned constituents, additives that are specially selected from the group consisting of fillers, pigments, thermal stabilizers, co-stabilizers, UV stabilizers, antioxidants, viscosity regulators, flame retardants and lubricants.
[080] Thermal stabilizers neutralize, inter alia, hydrochloric acid eliminated during and / or after PVC processing and prevent thermal degradation of the polymer. Useful thermal stabilizers include all conventional PVC stabilizers in solid and liquid form, for example based on Ca / Zn, Ba / Zn, Pb, Sn or organic compounds (OBS), as well as acid bonding sheet silicates such as hydrotalcite . The mixtures according to the invention have a content of 0.5 to 10, preferably 1 to 5 and more preferably 1.5 to 4 parts by weight of thermal stabilizer per 100 parts by weight of polymer.
[081] The so-called co-stabilizers (i.e., substances that prolong, improve and / or supplement the effect of thermal stabilizers) used can, for example, be derived from vegetable oil, for example epoxidized soybean oil or epoxidized linseed oil.
[082] The pigments used in the context of the present invention can be inorganic or organic pigments. The pigment content is between 0.01 to 10% by weight, preferably 0.05 to 5% by weight and more preferably 0.1 to 3% by weight per 100 parts by weight of polymer. Examples of inorganic pigments are TiO2, CdS, CoO / Al2O3, Cr2O3. Known organic pigments are, for example, azo paints, phthalocyanine pigments, dioxazine pigments and aniline pigments.
[083] The polymeric compositions according to the invention can comprise all charges corresponding to the state of the art. Examples of such fillers are mineral and / or synthetic and / or natural, organic and / or inorganic materials, for example calcium oxide, magnesium oxide, calcium carbonate, barium sulfate, silicone dioxide, sheet silicate, black carbon bitumen, wood (eg pulverized, such as granules, microgranules, fibers etc.), paper, natural and / or synthetic fibers. More preferably, at least one of the fillers used is a calcium carbonate or a magnesium calcium carbonate.
[084] The viscosity reducing reagents used can be aliphatic or aromatic hydrocarbons, but also alcohols and / or derivatives of carboxylic acid, for example 2,2,4-trimethyl-1,3-pentanediol diisobutyrate. Viscosity reducing reagents are added to the compositions according to the invention especially in proportions of 0.5 to 50, preferably 1 to 30 and more preferably 2 to 10 parts by weight per 100 parts by weight of polymer.
[085] The invention also provides moldings or films comprising the polymeric composition according to the invention.
[086] These moldings or films are preferably a floor covering, a wall covering, a hose, a profile, a roof covering, a fence covering, a cable or a wire covering, awning, a billboard, synthetic leather , packaging film, a medical article, a toy, a gasket, a piece of furniture.
[087] The pentyl esters according to the invention, when used as plasticizers, have numerous advantages over the known plasticizers of the prior art. For example, these compounds are surprisingly, in contrast to the homologous di-n-butyl furandicarboxylates and di-n-hexyl furandicarboxylates, both of which are in the form of crystalline solids with melting points well above room temperature, liquids with good processability (including good dosage).
[088] The production of liquid compositions, especially polymeric compositions such as polymeric pastes and plastisols, on an industrial scale can be better implemented with liquid plasticizers since the use of solvents in this case is only necessary in the largely reduced form, if effectively necessary. Solvents in general also lead to "dilution" of the plasticizer effect and, therefore, must be removed again during production. Since this can be accomplished quantitatively in the rarest cases, volatile (organic) components called "VOCs" are present in semi-finished or cabled products and are again prohibitive for the use of such products especially in the interior compartment and in vehicles engines. An additional factor is the risk of crystallization of solid plasticizers in the semi-finished or finished product, which leads to a severe deterioration in material properties that extends as much as to material failure. The existing alternative solution for the use of solvents, of using solid plasticizers in the molten state (i.e. under high temperature), cannot be implemented industrially in many cases. There is also a risk of thermal damage to other formulation constituents.
[089] The crystallinity of the esters according to the invention and the position and type of melting point signals (peaks) and glass transition signals (stages) in the DSC thermogram depends on the degree of branching of the ester chains and the composition of the esters , and are adjustable via the alcohols used to prepare the esters. In the analysis of the pentyl esters according to the invention (GCs analysis purity at least 98% per area) in a differential calorimeter (DSC) after cooling to -150 ° C, no melting point occurs under temperatures above 25 ° C in the first heating, preferably no melting point at temperatures above 22 ° C, more preferably, no melting point at temperatures above 18 ° C and especially preferably no melting point at temperatures above 16 ° C.
[090] In a particular embodiment, in the DSC analysis described, a glass transition temperature at <0 ° C is detected, preferably at <-10 ° C, more preferably at <-20 ° C and especially preferably at < -30 ° C.
[091] The shear viscosity (intrinsic viscosity) of the esters according to the invention also depends on the degree of branching of the ester chains and the composition of the esters, and is adjustable through the alcohols used to prepare the esters. The shear viscosity, determined at 20 ° C, of the liquid pentyl esters according to the invention (purity according to GC analysis at least 98% per area) depends on the degree of branching of the ester chains and the composition of the esters. It is especially up to 60 mPa * s, preferably up to 55 mPa * s, more preferably up to 50 mPa * s and especially preferably below 46 mPa * s.
[092] The density of esters according to the invention also depends on the degree of branching of the ester chains and the composition of the esters, and is adjustable through the alcohols used to prepare the esters. The density determined at 20 ° C of the esters according to the invention (purity by GC analysis min. 99% per area) is especially up to 1.06 g / cm3, preferably up to 1.05 g / cm3, more preferably up to 1.03 g / cm3 and especially preferably up to 1.01 g / cm3.
[093] Another advantage is that the pentyl esters according to the invention have an extraordinary polymer gelling capacity, especially for PVC, and surprisingly also have a much lower dissolution temperature for PVC than, for example, di-n -butyl furanedicarboxylate. PVC pastes based on furandicarboxylic esters according to the invention also have a much lower gelation temperature than, for example, dibutyl terephthalate pastes known for industrial use, even though the esters according to the invention have side chains ester longer than dibutyl terephthalate. They can be processed more quickly and at lower temperatures.
[094] PVC plastisols / PVC pastes comprising the pentyl esters according to the invention in a proportion of at least 10 m% with respect to the plasticizers used in total (depending on the type and quantity of additionally used plasticizers and solvents), in the gelation test carried out by means of oscillation rheometry with dynamic temperature control (constant heating rate), especially a paste viscosity of> 1000 Pa * s under temperatures up to 100 ° C, preferably up to 95 ° C, more preferably up to 90 ° C, especially preferably up to 85 ° C and most especially preferably up to 82 ° C.
[095] The temperature at which the maximum viscosity is reached in the gelation test described above is especially up to 130 ° C, preferably up to 120 ° C, more preferably up to 118 ° C, especially preferably up to 115 ° C and very especially preferably up to 112 ° C.
[096] It should be noted that PVC pastes based on a pentyl ester according to the invention have less dependence on the viscosity of the paste with respect to the shear rate than comparable pastes. Thus, these polymeric compositions are useful within a wide shear rate and with a wide variety of different processing methods.
[097] Transparent PVC-free films comprising a pentyl ester according to the invention as a plasticizer have also been found to have very low opacity and therefore high transparency. In some cases, it is much less than in films that are produced based on standard plasticizers or in which dibutyl terephthalate is used as a plasticizer.
[098] More particularly, in the case of production of transparent films (film thickness 0.9-1.1 mm) from PVC plastisols / PVC pastes comprising a pentyl ester according to the invention in a proportion of at least 10 m% with respect to plasticizers used in general, opacity values of up to 15 are obtained, preferably up to 14, more preferably up to 13, especially preferably up to 12 and most especially preferably up to 11. The yellowing index (YD index 1925) of the transparent films described above is especially up to 18, preferably up to 16, more preferably up to 15 and most especially preferably up to 14.
[099] The following examples are designed to illustrate the invention, without restricting the range of applications of which appear in the description and the claims. EXAMPLES EXAMPLE 1 PREPARATION OF FURAN-2,5-DICARBONILLA DICHORIDE (II)
[100] The esters according to the invention were prepared in a two-stage synthesis proceeding from furan-2,5-dicarboxylic acid through dichloride. A 250 ml three-mouthed flask with reflux condenser and drip funnel was initially charged under argon with 72.1 g (462 mmol) of furan-2,5-dicarboxylic acid. In a period of 10 minutes, 165 g (1.39 mol) of thionyl chloride with a few drops of N, N-dimethylformamide were added. The suspension was heated under reflux temperature and the gas that formed was derived through washing flasks containing aqueous KOH solution. The mixture was then heated under reflux for 4 hs until the gas evolution was stopped and the solid completely dissolved. The product was isolated after removal of excess thionyl chloride by distillation purification (T = 110 ° C, p = 0.0012 MPa). This resulted in 79.4 g of dichloride as a colorless crystalline solid (89% yield) with a melting point of 79.5-80.0 ° C. Furan-2,5-dicarbonyl dichloride was stored under protective gas (argon) in the dark at room temperature until further use. PREPARATION OF FURAN-2,5-DICARBOXYL ESTERS FROM FURAN-2,5-DICARBONILLA DICHORIDE (II)
[101] Under argon, a three-necked flask with reflux condenser and drip funnel was initially charged with the dichloride which was melted by heating. 2.4 equivalents of n-pentanol were slowly added in drops to the liquid, which resulted in an exothermic reaction with gas evolution. The formed gas was passed through washing flasks containing an aqueous KOH solution. After complete addition, the mixture was stirred at a temperature of 80-100 ° C for 16 hs.
[102] The excess alcohol was removed under reduced pressure in the presence of boiling granules and the crude product was purified by distillation. This produced dipentyl furan-2,5-dicarboxylate, which was used for the other tests. CHARACTERIZATION OF DIPENTIL FURAN-2,5-DICARBOXILATE 1.1 DETERMINATION OF ESTER PURITY THROUGH GAS CHROMATOGRAPHY (GC) ANALYSIS
[103] The determination of the purity of the esters prepared by GC is carried out with an Agilent Technologies "6890N" GC machine using a DB-5 column (length: 20 m, internal diameter: 0.25 mm, film thickness 0.25 μm) from J&W Scientific and a flame ionization detector under the following conditions: - Initial oven temperature: 150 ° C Final oven temperature: 350 ° C (1) heating rate 150-300 ° C: 10 K / min . (2) Isothermal: 10 min. under 300 ° C (3) heating rate 300-350 ° C: 25 K / min. - Total processing time: 27 min. - Injection block inlet temperature: 300 ° C split ratio: 200: 1 - Split flow rate: 512.2 ml / min. - Total flow rate: 517.7 ml / min. - Carrier gas: helium - Injection volume: 3 microliters - Detector temperature: 350 ° C - Flue gas: hydrogen - Hydrogen flow rate: 40 ml / min. - Air flow rate: 440 ml / min. - Make-up gas: helium - Make-up gas flow rate: 45 ml / min.
[104] The gas chromatograms obtained are manually analyzed for comparative substances present; purity is recorded in percent of area. Due to the high final content of the target substance of> 98%, the estimated error resulting from the lack of calibration for the test substance is low.
[105] The measurement resulted in a purity of the ester prepared in example 1 of 98.9% per area. 1.2 DETERMINATION OF PREPARED ESTER DENSITY
[106] The density of the prepared esters was determined by means of an oscillating U-tube according to DIN 51757 - method 4.
[107] The measurement resulted in a density of 1.0468 g / cm3. 1.3 DETERMINATION OF THE APHA COLOR NUMBER OF THE PREPARED ESTER
[108] The color number of the esters prepared was determined according to DIN EN ISO 6271-2.
[109] The measurement resulted in the APHA color number of 41. 1.4 DETERMINATION OF THE PREPARED ESTER ACIDITY INDEX
[110] The acidity index of the esters prepared was determined according to DIN EN ISO 2114.
[111] The determination provided an acid number of 0.16 mg KOH / g. 1.5 DETERMINATION OF PREPARED ESTER WATER CONTENT
[112] The water content of the prepared esters was determined according to DIN 51777 Part 1 (direct method).
[113] The determination provided a water content of 0.042%. 1.6 DETERMINATION OF THE INTRINSIC VISCOSITY OF THE PREPARED ESTER
[114] The intrinsic viscosity (shear viscosity) of the prepared ester was determined using a Physica MCR 101 (from Anton-Paar) with a Z3 measuring system (DIN 25 mm) in rotary mode using the following method:
[115] Ester and measurement system were first balanced at a temperature of 20 ° C, then the following actions were performed: 1. Preliminary shear at 100 s-1 for a period of 60 s, in the course of which measurements were not recorded (leveling any thixotropic effects that occur and for better temperature distribution). 2. An upward frequency ramp that starts at 500 s-1 and ends at 10 s-1, divided into a logarithmic series of 20 steps each with a 5 s measurement point duration (Newtonian behavior check).
[116] The ester showed Newtonian flow behavior.
[117] The measurement resulted in a shear viscosity (at 42 s-1) of 44 mPa * s. 1.7 DETERMINATION OF GLASS TRANSITION TEMPERATURE AND ESTER MELTING POINT PREPARED THROUGH DSC
[118] The glass transition temperature and melting point were determined by means of differential calorimetry (DSC) according to DIN 51007 (temperature range -150 ° C to +200 ° C) from the first curve heating at a heating rate of 10 K / min. The turning point of the hot flow curve is analyzed as the glass transition temperature.
[119] The measurement provided a glass transition temperature of -34 ° C and a melting point of +12 ° C, the sample was stored in liquid form at room temperature for 7 days previously. EXAMPLE 2 DISSOLUTION TEMPERATURE OF PLASTICIZERS
[120] The dissolution temperature indicates the temperature at which a PVC powder dispersed in an excess of continuously heated plasticizer (96 g of plasticizer to 4 g of polymer) is dissolved, and allows conclusions about the gelation characteristics. Di-n-butyl furan-2,5-dicarboxylate (DNBFDC) and di-n-hexyl furan-2,5-dicarboxylate (DNHFDC) were prepared using n-butanol and n-hexanol respectively, analogously to example 1. The di-n-butyl furan-2,5-dicarboxylate and di-n-hexyl furan-2,5-dicarboxylate solids were first melted at 50 ° C, and the di-n-pentyl furan-2,5-dicarboxylate according to the invention (DNPFDC) was heated to 50 ° C, before the PVC powder was dispersed in liquid and the temperature increased. TEST PROCEDURE
[121] 96 g of the appropriate plasticizer and 4 g of Lacovyl PB 1704 H PVC (from Arkema) were weighed in a 150 ml beaker. A magnetic stir bar and an internal thermometer attached to a clamp holder (range: 0 ° C-250 ° C, display accuracy: 0.5 ° C) were added to the mixture. A wire or tape is used to attach a strip of paper that bears the message “dissolving temperature” in the font “Times New Roman”, size 12, on the back side of the beaker so that the message can be seen through the beaker . Then, the electric plate of a heatable laboratory stirrer unit (MR-Hei-Standard) is adjusted to 200 ° C and the speed to 600 rpm. Upon reaching an internal liquid temperature of 140 ° C, the target temperature increased again to 250 ° C. The dissolution temperature was reached when the message was well readable through the liquid.
[122] For DNBFDC, DNPFDC and DNHFDC, the following values were determined in table 1 (double determination):
according to the invention
[123] Totally surprisingly, the dissolution temperature of the DNPFDC according to the invention is well below that of the homologous DNBFDC. As the tests show below, DNPFDC has a much better gelling capacity. EXAMPLE 3 USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PVC PLASTISOL FOR THE PRODUCTION OF FINAL FINISH FILMS FOR FLOOR COVERINGS: PRODUCTION OF PLASTISOLS
[124] The advantageous properties that can be acquired with the plasticizers according to the invention will now be illustrated using plastisols / pastes as used, for example, to produce a transparent top layer (so-called "topcoat") in coatings multilayer structure floor tiles. Starting weights used, in grams, of the components for the different pastes can be found in table 2 below. Examples 3 and 6 are according to the invention; the other examples 1, 2, 4, 5, 7 and 8 are comparative examples.
= according to the invention
[125] The substances used are described below: - Vestolit B 7021 - Ultra: microsuspension PVC (homopolymer) with a K value (determined according to DIN EN ISO 1628-2) of 70; from Vestolit GmbH. - Vestinol® 9: diisononil (ortho) phthalate (DINP), plasticizer; from Evonik Oxeno GmbH. - DNBFDC: di-n-butyl furan-2,5-dicarboxylate (prepared with n-butanol analogously to example 1) - DNPFDC: dipentyl furanodicarboxylate according to the invention, according to Ex. 1 - DNHFDC: di -n-hexyl furan-2,5-dicarboxylate (prepared with n-hexanol analogously to example 1) - Eastman DBT: dibutyl terephthalate, plasticizer with rapid gelation, from Eastman Chemicals - Drapex 39: epoxidized soybean oil; co-stabilizer with plasticizer action; from Galata Chemicals. - Mark CZ 149: Ca / Zn stabilizer, from Galata Chemicals
[126] The liquid constituents were weighed in a PE beaker before the solid constituents. The mixture was stirred with a spatula so that no further wet powder was present. The mixing beaker was then attached to the fixing device of a dissolving stirrer. A mixing disc used to homogenize the sample. This was done by increasing the speed from 330 rpm to 2000 rpm and stirring until the temperature of the temperature sensor's digital display reaches 30.0 ° C. This ensured that the homogenization of the paste had been achieved with a defined energy input. Then, the slurry was equilibrated immediately to 25.0 ° C.
[127] Formulations 2 and 4 were feasible only by heating the furandicarboxylates present in solid form. After preparation, however, the pastes solidified to such a degree that further processing was not possible.
[128] Paste 6 shows the mode of action of a di-n-pentyl furanodicarboxylate according to the invention in mixtures with another plasticizer. EXAMPLE 4 USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PVC PLASTISOL FOR PRODUCTION OF FINAL FINISH FILMS FOR FLOOR COATINGS: PASTE VISCOSITY MEASUREMENT
[129] The measurement of the pastes produced in example 3 was done with a Physica MCR 101 rheometer (from Anton Paar), as follows.
[130] The paste was stored after production at 25 ° C for 24 hours, was homogenized again with a spatula and analyzed in the Z3 measuring system (diameter 25 mm) according to the operating instructions. The measurement was performed isothermally at 25 ° C. The following actions have been taken.
[131] Preliminary shear of 100 s-1 for a period of 60 s, during which measurements were not recorded (leveling thixotropic effects).
[132] An isothermal downhill ramp that starts at a shear rate of 200 s-1 down to 0.1 s-1, divided into a logarithmic series with 30 steps of 5 s measurement point duration. The measurement results are shown in table 3. TABLE 3: RESULTS OF VISCOSITY MEASUREMENTS (SHEAR RATE PROFILES)
nda .: not determinable; strongly solidified paste; measurement impossible. * = according to the invention
[133] Compared to pastes comprising only one plasticizer (pastes 1, 2, 3, 4, 8), the paste according to the invention has by far the smallest range of variation of the paste viscosity. This result is surprising when comparing dipentyl furanedicarboxylate according to the invention and structurally similar dibutyl terephthalate. A mixture of the standard plasticizer Vestinol 9 with the dipentyl furanodicarboxylate according to the invention (paste 6) produces a quite significant reduction in the variation range compared to a paste comprising Vestinol 9 only as a plasticizer (paste 1). The general increase in the viscosity level of the pastes according to the invention can be easily combined by the person skilled in the art in relation to the circumstances present in the specific method of processing, for example, by the addition of viscosity additives or solvents. EXAMPLE 5 USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PVC PLASTISOL FOR PRODUCTION OF FINAL FINISH FILMS FOR FLOOR COATINGS: DETERMINATION OF GELIFICATION CHARACTERISTICS (GELIFICATION RATE)
[134] The study of the gelation characteristics of plastisols was carried out on Physica MCR 101 in oscillation mode with a plate-to-plate measurement system (PP25), which was operated under shear stress control. An additional temperature control hood was attached to the system in order to obtain homogeneous heat distribution.
[135] Measurement parameters: - Mode: Temperature gradient (temperature ramp) - Initial temperature: 25 ° C - Final temperature: 180 ° C - Heating / cooling rate: 5 K / min - Oscillation frequency: ramp 4 -0.1 Hz (logarithmic) - Omega angular frequency: 10 1 / s - Number of measuring points: 63 - Measuring point duration: 0.5 min - Automatic interim distance readjustment F: 0 N - Constant measuring point duration - Distance between edges 0.5 mm MEASUREMENT PROCEDURE
[136] A drop of the plastisol formulation to be analyzed, free of air bubbles, was applied to the lower measuring system plate. It was ensured that after the measurement system was closed, some plastisol could evenly exude out of the measurement system (up to approx. 6 mm in general). Then, the temperature control hood was positioned over the sample and the measurement was started.
[137] The "complex viscosity" of plastisol was determined as a function of temperature. Beginning of the gelation process was verified by a very large sudden increase in the complex viscosity. The sooner this viscosity starts, the better the gelling capacity of the system.
[138] By interpolating each plastisol, the measurement curves obtained were used to determine the temperatures at which a complete viscosity of 1000 Pa * s or 10,000 Pa * s had been reached. In addition, using the tangent method, the maximum plastisol viscosity achieved in the present test configuration was determined by dropping a perpendicular, from which the maximum plastisol viscosity occurs. The results are shown in Table 4.

nda .: not determinable; strongly solidified paste; measurement impossible. * = according to the invention
[139] Compared to pastes that comprise only one plasticizer substance (pastes 1, 2, 3, 4, 8), the paste according to the invention has the fastest gelation (ie, in this case also gelation at the lowest temperatures ). In comparison with the standard plasticizer Vestinol® 9, the di-n-pentyl furan-2,5-dicarboxylate (DNPFDC) according to the invention was considered to be a "fast gelling", ie a compound that has the ability to gel in much lower temperatures than standard plasticizers. The DNPFDC paste currently gels a little more quickly than the paste comprising Eastman DBT, a substance with a similar structure and shorter ester chains. This is all the more surprising due to the fact that the gelation capacity in the case of aromatic dicarboxylic esters (eg orthophthalates, terephthalates, etc.) in general increases with the reduction of the chain length. By mixing the dipentyl furanodicarboxylate according to the invention with the standard Vestinol 9 plasticizer, a significant acceleration (compared to pure Vestinol® 9) of the gelation process (especially with respect to the temperature at which maximum viscosity is achieved) is allowed.
[140] Naturally, the gelling process of paste 3 according to the invention leads to a much higher viscosity than in the case of all other pastes. The use of the dipentyl furanodicarboxylate according to the invention thus leads, in the fully gelled state, to extraordinary material properties (especially resistance) in the molding produced / semi-finished or finished product. EXAMPLE 6: USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PVC PLASTISOL FOR THE PRODUCTION OF FINAL FINISH FILMS FOR FLOOR COATINGS: DETERMINATION OF SHORE A MOLDING HARDNESS (PLASTICER EFFICIENCY)
[141] Shore hardness is a measure of the softness of a specimen. The more a standardized needle enters the specimen with a specific measurement duration, the lower the measured value. The plasticizer with maximum efficiency provides the lowest Shore hardness value for the same amount of plasticizer. Since the formulations / recipes in practice are often adjusted or optimized in the sense of a specific Shore hardness, it is therefore possible in the case of very efficient plasticizers to save a specific percentage in the formulation, which means, for example, a reduction in costs for the processor.
[142] To determine Shore hardness, the plastisols produced according to example 3 are poured into round casting molds with a diameter of 42 mm (starting weight: 20.0 g). Then the plastisols were gelled in the molds in a forced air drying cabin at 200 ° C for 30 minutes, removed after cooling and, before measurement, stored in a drying cabin (25 ° C) for at least 24 hours. The thickness of the discs was approximately 12 mm. The results of the hardness determination were compiled in Table 5.
nda. = not determinable; strongly solidified paste; no producable molding. * = according to the invention
[143] Compared to pastes comprising only one plasticizer (pastes 1, 2, 3, 4, 8), the molding produced from paste 3 according to the invention has minimal Shore A hardness and is therefore "the softer ". This also means that the efficiency of dipentyl furanedicarboxylate according to the invention with respect to PVC plasticization in the pulp is surprisingly the highest, and is currently higher than that of dibutyl terephthalate (pulp 8). It is fantastic that - similar to the gelling capacity - the plasticizing action in the case of aromatic dicarboxylic esters (eg orthophthalates, terephthalates, etc.) in general increases with the reduction of the chain length. EXAMPLE 7: USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PVC PLASTISOL FOR THE PRODUCTION OF FINAL FINISH FILMS FOR FLOOR COATINGS: DETERMINATION OF TRANSPARENCY AND YELLOW INDEX OF TRANSPARENT FINAL FINISH FILMS
[144] The films were produced after a plastisol maturity of 24 hours (at 25 ° C). For film production, a 1.40 mm roll opening was established in the scraper cylinder of a Mathis Labcoater (manufacturer: W. Mathis AG). This opening was monitored by a slide gauge and readjusted when necessary. The produced pastes were scraped on a high-gloss paper (Ultracast Patent; from Sappi Ltd.) fixed flat on a structure by means of the scraper cylinder from Mathis Labcoater. The plastisol applied by scraping was then fully gelled at 200 ° C in the Mathis oven for 2 minutes. After cooling, the film thickness was determined to an accuracy of 0.01 mm with the help of a thickness gauge (KXL047; from Mitutoyo). The film thickness of the cylinder opening specified in all cases was between 0.95 and 1.05 mm. The thickness measurement was performed at three different points on the film.
[145] Transparency is an important criterion for assessing the quality of final PVC finishes in the floor covering sector, since an ideal overall appearance can be achieved only with high transparency (= low opacity). The transparency of a final PVC finishing film is also considered to be a measure of the compatibility of the formulation constituents used for the production of film, more particularly being a measure to access the compatibility of PVC matrix and plasticizer. High transparency (= low opacity) generally means good compatibility. Opacity was determined with a "Spectro Guide" instrument from Byk Gardner. As a reference for opacity measurements, a white tile and a black tile were used. The measurements were made at 3 different points in the samples and analyzed automatically (average value).
[146] The yellowing index is another important quality criterion. Yellowing in the final finish can lead to considerable visual damage to a floor finish and therefore only very low yellowing rates can in general be tolerated in a final PVC finish. Yellowing can be caused primarily by formulation constituents (and also by-products and degradation products thereof), and secondly by degradation (for example thermooxidative) during the production process and / or during the use of the final finish or coating of floor.
[147] The yellowing index (YD 1925 index) is a measure of the yellowing of a specimen. The color was analyzed with a "Spectro Guide" instrument from Byk-Gardner. As a reference for color measurements, a white reference tile was used. The following parameters were established: - Illuminant: C / 2 ° - Number of measurements: 3 - Display: CIE L * a * b * - Measured index: YD1925
[148] Measurements were made at 3 different points on the specimens. The values for the 3 measurements were proportionally calculated. Table 6 shows the results. TABLE 6: OPACITY AND YELLOW INDEXES OF TRANSPARENT FINAL FINISH FILMS
* = according to the invention
[149] Examples 2 and 4 could not be determined as the plastisols were too hard (i.e. unsuitable) for producing finished films. In comparison with the individual substances (1, 3 and 8), the final finishing film produced from the DNPFDC paste (3) according to the invention exhibits very high transparency (low opacity), especially when compared to the one produced on the basis Eastman DBT. This is fantastic because - similar to the gelling capacity - compatibility with the PVC matrix (crucial for transparency) in general increases with the reduction of the chain length in the case of aromatic dicarboxylic esters (eg orthophthalates, terephthalates, etc.) , as the nanopolar percentage decreases at the same time. What is particularly noteworthy is the small difference from the standard DINP (1) plasticizer, which indicates excellent compatibility of the DNPFDC according to the invention with the PVC matrix. The slightly increased yellowing in the case of the final finishing film produced from the DNPFDC according to the invention can be attributed to the renewable raw materials (sugars and carbohydrate derivatives) used to produce the product according to the invention and can be reduced by simple way for those versed in the technique through another improvement of the production process or selection of an ideal (additional) stabilizer. EXAMPLE 8: USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PVC PLASTISOL FOR THE PRODUCTION OF POLYMERIC FOAMS FOR FLOOR COATINGS: PRODUCTION OF PLASTISOLS
[150] In the following example mixtures of the dipentyl furandicarboxylates according to the invention with other plasticizers are shown in formulations as used, for example, for the production of multilayer floor coverings. Folders with the composition as specified in table 7 below were produced. The pastes were produced in a manner analogous to the procedure described in example 3. TABLE 7: PASTE FORMULATIONS (ALL INDICATIONS IN MASS PARTS)
= plasticizer according to the invention
[151] The substances used are explained in detail below: - Vinnolit MP 6852: microsuspension PVC (homopolymer) with K value (according to DIN EN ISO 1628-2) of 68; from Vinnolit GmbH & Co KG. - Vestinol® 9: diisononil (ortho) phthalate (DINP), plasticizer; from Evonik Oxeno GmbH. - Unifoam AZ Ultra 7043: azodicarbonamide; thermally activated blowing agent; from Hebron S.A. - Zinc oxide: ZnO; decomposition catalyst for thermal blowing agent; intrinsic decomposition temperatures of the blowing agent; it also acts simultaneously as a stabilizer; "Zinkoxid aktiv®"; from Lanxess AG. The zinc oxide was previously mixed with a sufficient portion / amount of the specific plasticizer used and then added. - DINFDC: diisononyl furanedicarboxylate, laboratory product; preparation analogous to example 1, except using isononyl alcohol (from Evonik Oxeno GmbH) - DINT: diisononyl terephthalate; laboratory product; prepared according to WO 2009/095126 A1 of isononyl alcohol (from Evonik Oxeno GmbH) - Hexamoll ® DINCH: diisononyl cyclohexanecarboxylate; from BASF SE - DNPFDC: di-n-pentyl furan-2,5-dicarboxylate according to Example 1. EXAMPLE 9: USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PVC PLASTISOL FOR THE PRODUCTION OF POLYMERIC FOAMS FOR FLOOR COATINGS: DETERMINATION OF PASTE VISCOSITY
[152] The paste viscosity was determined as described in example 4; the results are shown in table 8.

* = according to the invention
[153] The results show that especially mixtures with plasticizers such as terephthalate according to the DINT standard and with DINCH lead to low paste viscosities and excellent processing properties. These are much better than the comparative product Vestinol® 9; especially by mixing with DINCH, it is possible to establish a very low paste viscosity which is also suitable for high speed processing methods (for example, in the case of scraping application). In a particularly advantageous manner, these mixtures combine good processability, absence of phthalates and particularly high suitability (with respect to the raw material base of the dipentyl furandicarboxylates according to the invention). EXAMPLE 10: USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PVC PLASTISOL FOR THE PRODUCTION OF POLYMERIC FOAMS FOR FLOOR COATINGS: DETERMINATION OF GELIFICATION PROPERTIES (GELIFICATION RATE)
[154] The gelling properties were determined as described in example 5, except using the plastisols produced according to Example 8. The results are shown in table 9

= according to the invention
[155] Compared to the standard Vestinol® 9 plasticizer, all mixtures of the furandicarboxylic esters according to the invention exhibit a distinct improvement in gelling characteristics with gelling under much lower temperatures in some cases. As the ester concentration in accordance with the invention decreases, the gelation rate increases, the maximum obtainable viscosity decreases considerably and the gelation temperature significantly decreases. By mixing DINCH (very slowly gelling) (paste 5) with the ester according to the invention, gelling characteristics very similar to those of the standard Vestinol® 9 plasticizer are established. By adding the furandicarboxylic ester according to the invention, the processability is thus greatly improved; more particularly, it is possible to process such pastes more quickly or at lower temperatures. EXAMPLE 11: USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A PLASTISOL PVC FOR THE PRODUCTION OF POLYMERIC FOAMS FOR FLOOR COATINGS: DETERMINATION OF FOAMING CHARACTERISTICS
[156] The defoaming characteristics were determined to an accuracy of 0.01 mm with the help of a quick thickness gauge suitable for measurements on soft PVC (KXL047, from Mitutoyo). For film production, an opening of cylinders of 1 mm was established in the scraper cylinder of a Mathis Labcoater (model: LTE-TS; manufacturer: W. Mathis AG). This opening was monitored with a slide gauge and readjusted when necessary. The pastes were scraped on silicone paper (Warran Release Paper; from Sappi Ltd.) fixed flat on a structure of the scraper cylinder of Mathis Labcoater. In order to calculate the percentage of defoaming, a non-foamed and partially gelled film was first produced at 200 ° C / residence time of 30 seconds. The film thickness (starting thickness) of this film at the specified cylinder aperture was in all cases between 0.74 and 0.77 mm. The thickness measurement was performed at three different points on the film. Then, the foamed films (foams) were also produced with an oven permanence time (60s, 90s, 120s and 150s) using, or more specifically, the Mathis Labcoater. After cooling the foams, the thicknesses were also measured at three different points. The thickness average and the starting thickness were necessary for the expansion calculation. (Example: (foam thickness - starting thickness) / starting thickness * 100% = expansion). The results are shown in table 10. TABLE 10: EXPANSION CHARACTERISTICS OF FOAM FILMS

[157] Foaming of pastes comprising furandicarboxylic ester according to the invention takes place much more quickly than with the standard Vestinol ® 9 plasticizer and leads to higher foam weights. This applies to mixing with DINCH and terephthalate according to the DINT standard. EXAMPLE 12: USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A MIXTURE WITH ADDITIONAL PLASTICORS FOR THE PRODUCTION OF TARPAULINS: PRODUCTION OF PLASTISOLS
[158] The advantages of pastes according to the invention are illustrated here using PVC pastes which comprise fillers and pigments and are suitable for the production of tarpaulins (for example as a base finish for flow impregnation). In the appropriate application, the present formulation can be combined with the specific requirements in a simple way, for example by the addition of adhesion promoters and / or flame retardants. The pastes were produced analogously to example 3, but with an altered formulation. The starting weights of the components used for the different pastes can be found in table 11 below. All indications are in bulk.
* = according to the invention
[159] The materials and substances used, which have not been explained in the previous examples, are presented in detail below: - Vestolit P 1430 K70: PVC microsuspension from Vestolit GmbH - DNPFDC: dipentyl furanodicarboxylate according to the invention, according to Ex. 1 - Calcilit 6G: load; calcium carbonate - Kronos 2220: Kronos rutile pigment - Brand BZ 561: Galata Chemicals Ba / Zn stabilizer EXAMPLE 13 USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A MIXTURE WITH ADDITIONAL PLASTICIZERS FOR THE PRODUCTION OF TARPAULINES: DETERMINATION PLANTS
[160] The paste viscosity was determined as described in example 4; the results are shown in table 12. TABLE 12: VISCOSITY MEASUREMENT RESULTS (SHEAR RATE PROFILES)
* = according to the invention
[161] In mixtures with terephthalate according to the DINT standard and DINCH, much lower plastisol viscosities are obtained in some cases than with the standard Vestinol® 9 plasticizer; thus, it is possible to process these plastisols much more quickly in spreading processes than, for example, plastisols based purely on Vestinol® 9. EXAMPLE 14 Use of DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A MIXTURE WITH ADDITIONAL PLASTICIZERS FOR THE PRODUCTION OF TARPAULINS: DETERMINATION OF GELIFICATION CHARACTERISTICS
[162] The gelling characteristics were determined as described in example 5, but using the plastisols produced according to example 12. The results are shown in table 13. TABLE 13: GELIFICATION TEST RESULTS
maximum [° C] 136 126 88 85 132 134 = according to the invention
[163] In all cases, gelation is much faster than in the case of the standard Vestinol® 9 plasticizer. With the increase in the percentage of dipentyl furanedicarboxylate according to the invention, especially in combination with diisononyl furanedicarboxylate (samples 2-4), there is a very rapid acceleration of the gelation process, as is particularly evident from the temperature at which the maximum viscosity is obtained . In combination with terephthalate according to the DINT standard and DINCH, gelling properties are obtained, which are even better than those of the standard Vestinol® 9 plasticizer. EXAMPLE 15: USE OF DIPENTIL FURANDICARBOXILATES ACCORDING TO THE INVENTION IN A MIXTURE WITH ADDITIONAL PLASTICANTS FOR THE PRODUCTION OF TARPAULINS: DETERMINING THE EFFICIENCY OF PLASTICANT (SHORE A)
[164] Moldings were produced and Shore hardness was measured analogously to the procedure described in example 6. The results are shown in table 14. TABLE 14: PLASTISOL FORMULATIONS
= according to the invention
[165] All mixtures reach Shore A values below the values for standard Vestinol 9 plasticizer. The plasticizing action of all samples comprising the pentyl esters according to the invention is therefore greater than that of the standard plasticizer. The plasticizer action also increases with the concentration of the pentyl esters according to the invention. In mixtures with terephthalate according to the DINT standard and with DINCH, lower Shore A values are also obtained with Vestinol® 9. It is correspondingly possible for the person skilled in the art to reduce the total amount of plasticizer using the pentyl esters according to with the invention.

权利要求:
Claims (13)
[0001]
1. PLASTIFYING COMPOSITION, containing pentyl ester of furandicarboxylic acid, characterized by comprising at least two isomeric dipentyl furan-2,5-dicarboxylates and dipentyl furan-2,5-dicarboxylates having at least one of the following properties: - their density at 20 ° C is up to 1.06 g / cm3 - its intrinsic viscosity at 25 ° C is up to 60 mPa * s - when analyzed with a differential calorimeter, there is no fusion signal at temperatures> 25 ° C.
[0002]
2. PLASTIFYING COMPOSITION, according to claim 1, characterized in that the isomeric dipentyl furan-2,5-dicarboxylates comprise isomeric pentyl groups.
[0003]
PLASTIFYING COMPOSITION according to any one of claims 1 to 2, characterized in that none of the isomeric dipentyl furan-2,5-dicarboxylates has a ratio of more than 99.9% by weight in the ester mixture.
[0004]
4. PLASTIFYING COMPOSITION according to any one of claims 2 to 3, characterized in that the isomeric pentyl groups are selected from the group of n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 3- methylbut-2-yl, 2-methylbut-2-yl.
[0005]
5. PLASTIFYING COMPOSITION, according to any one of claims 1 to 4, characterized in that it comprises an additional plasticizer selected from the group of alkyl benzoates, dialkyl adipates, glyceryl esters, trialkyl citrates, trialkyl acylated citrates, trialkyl melitates, glycol dibenzoates , dialkyl terephthalates, dialkyl phthalates, dialcanoyl esters of isosorbitol, dialkyl esters of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid.
[0006]
6. USE OF A PLASTIFYING COMPOSITION, as defined in any one of claims 1 to 5, characterized as being a plasticizer for polymers.
[0007]
7. USE OF A PLASTIFYING COMPOSITION, as defined in claim 1, characterized by being adhesives, sealing compounds, coating materials, varnishes, paints, plastisols, pastes, synthetic leather, floor coverings, underbody protection protection), fabric coverings, wallpaper and paints.
[0008]
8. POLYMERIC COMPOSITION, characterized by comprising a plasticizer composition, as defined in claim 1.
[0009]
9. COMPOSITION according to claim 8, characterized in that it comprises at least one polymer selected from polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylates, especially polymethyl methacrylate (PMMA), polyalkyl methacrylate (PAMA ), fluoropolymers, especially polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetals, especially polyvinyl butyral (PVB), polystyrene polymers, especially polystyrene (polystyrene) ), expandable polystyrene (EPS), acrylonitrile-styrene-acrylate (ASA), styrene acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), styrene-methacrylic acid copolymer (SMA), styrene-methacrylic acid copolymer, polyolefins , especially polyethylene (PE) or polypropylene (PP), thermoplastic polyolefins (TPO), polyethylene-vinyl acetate (EVA), polycarbonates, polyethylene terephthalate (PET), polybutylene terephthalate (PB T), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPU), polysulfites (PSu), biopolymers, especially polylactic acid (PLA), polyhydroxybutyric acid (PHB), acid polyhydroxyvaleric (PHV), polyesters, starch, cellulose and cellulose derivatives, especially nitrocellulose (NC), ethyl cellulose (EC), cellulose acetate (CA), cellulose acetate / butyrate (CAB), rubber or silicones, and mixtures or copolymers of the mentioned polymers or monomer units thereof.
[0010]
COMPOSITION according to any one of claims 8 to 9, characterized in that the plasticizer is present in an amount of 5 to 200 parts by weight per 100 parts by weight of polymer.
[0011]
11. COMPOSITION according to any one of claims 8 to 10, characterized in that at least one of the polymers present is a vinyl chloride copolymer with one or more monomers selected from the group consisting of vinylidene chloride, vinyl acetate , vinyl propionate, vinyl butyrate, vinyl benzoate, methyl acrylate, ethyl acrylate and butyl acrylate.
[0012]
12. MOLDING OR FILM, characterized in that they comprise a polymeric composition, as defined in any one of claims 8 to 11.
[0013]
13. MOLDING OR FILM according to claim 12, characterized in that the film or molding is a floor covering, a wall covering, a hose, a profile, a roof covering, a sealing coating, a cable or coating threads, an awning, a billboard, synthetic leather, packaging film, a medical article, a toy, a joint, a piece of furniture.

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同族专利:

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公开号 | 公开日

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CN103380120B|2017-03-08|

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EP2678322A1|2014-01-01|

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US9133321B2|2015-09-15|

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JP2014507438A|2014-03-27|

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JP5984849B2|2016-09-06|

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WO2012113608A1|2012-08-30|

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BR112013020342A2|2016-07-12|

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LT2678322T|2017-10-25|

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KR101943122B1|2019-01-28|

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CN103380120A|2013-10-30|

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KR20140003574A|2014-01-09|

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DE102011004676A1|2012-08-30|

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ES2639043T3|2017-10-25|

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HUE034715T2|2018-02-28|

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EP2678322B1|2017-07-19|

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PL2678322T3|2017-12-29|

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US20130331491A1|2013-12-12|

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法律状态:
2017-08-15| B25C| Requirement related to requested transfer of rights|Owner name: EVONIK OXENO GMBH (DE) |

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2017-12-05| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA GMBH (DE) |

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2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-22| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |

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2020-08-25| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-02-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/01/2012, 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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DE102011004676A|DE102011004676A1|2011-02-24|2011-02-24|Pentyl ester of furandicarboxylic acid|

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DE102011004676.3|2011-02-24|

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PCT/EP2012/051315|WO2012113608A1|2011-02-24|2012-01-27|Pentyl esters of furandicarboxylic acid as softeners|

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