EP3041829A1 - Dérivés de tétrahydrofurane et leur utilisation comme plastifiants - Google Patents

Dérivés de tétrahydrofurane et leur utilisation comme plastifiants

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Publication number
EP3041829A1
EP3041829A1 EP14758566.5A EP14758566A EP3041829A1 EP 3041829 A1 EP3041829 A1 EP 3041829A1 EP 14758566 A EP14758566 A EP 14758566A EP 3041829 A1 EP3041829 A1 EP 3041829A1
Authority
EP
European Patent Office
Prior art keywords
plasticizer
compounds
acid
general formula
esters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14758566.5A
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German (de)
English (en)
Inventor
Jochen Wagner
Boris Breitscheidel
Martin Alexander BOHN
Benoit BLANK
Alois Kindler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Application filed by BASF SE filed Critical BASF SE
Priority to EP14758566.5A priority Critical patent/EP3041829A1/fr
Publication of EP3041829A1 publication Critical patent/EP3041829A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C307/04—Diamides of sulfuric acids
    • C07C307/08—Diamides of sulfuric acids having nitrogen atoms of the sulfamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/18—Plasticising macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to tetrahydrofuran derivatives, a plasticizer composition containing these tetrahydrofuran derivatives, molding compositions containing a thermoplastic polymer and such a tetrahydrofuran derivative, a process for producing these tetrahydrofuran derivatives and their use.
  • plasticizers are added to a large number of plastics in order to make them softer, more flexible and / or more elastic.
  • the use of plasticizers serves to shift the thermoplastic range of plastics to lower temperatures in order to obtain the desired elastic properties in the range of lower processing and operating temperatures.
  • PVC Polyvinyl chloride
  • PVC-U rigid PVC
  • PVC-P soft PVC
  • thermoplastic polymers in which plasticizers are usually used are, for.
  • PVB polyvinyl butyral
  • PU thermoplastic polyurethanes
  • phthalic diesters with alcohols of different chemical structure have been used in the past as plasticizers, such as.
  • DEHP diethylhexyl phthalate
  • DIDP diisononyl phthalate
  • DIDP diisodecyl phthalate
  • Short-chain phthalates such as dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), benzyl butyl phthalate (BBP) or diisoheptyl phthalate (DIHP), are also used as gelling aids ("fast fuser"), for example in the production of so-called plastisols
  • Short-chain phthalates may also be used for the same purpose as dibenzoic acid esters such as dipropylene glycol dibenzoates
  • Another class of plasticizers with good gelling properties are phenyl esters of alkylsulfonic acids, which are available for example as mixtures under the name Mesamoll® TP-LXS 51067 on the market.
  • plastisols for example for the production of PVC films or PVC coatings, it is desirable to have available a plasticizer with the lowest possible gelling temperature and low viscosity.
  • a high storage stability of the plasticizer-plastic mixtures is desired, d. H. that in their non-gelled form, they should show no or only a slight increase in viscosity with time at ambient temperature. If possible, these properties should be achieved by adding a suitable plasticizer with good gelling properties, whereby the use of further viscosity-reducing additives and / or of solvents should be unnecessary.
  • plasticizers for. At least one plasticizer which gives good thermoplastic properties but poorly gelled in combination with at least one plasticizer having good gelling properties.
  • a plasticizer class known from the prior art which can be used as an alternative to phthalates is based on cyclohexanepolycarboxylic acids, as described in WO 99/32427. In contrast to their unhydrogenated aromatic analogues, these compounds are toxicologically harmless and can also be used in sensitive applications.
  • This plasticizer class includes, among others, the diisononyl esters of 1,2-cyclohexanedicarboxylic acid, which are available, for example, from BASF SE as a mixture of isomers under the trade name Hexamoll® DINCH® (CAS No. in Europe and Asia: 166412-78-8; CAS No.
  • WO 00/78704 describes selected dialkylcyclohexane-1, 3 and 1, 4-dicarboxylic acid esters for use as plasticizers in synthetic materials.
  • No. 7,973,194 B1 teaches the use of dibenzylcyclohexane-1,4-dicarboxylate, benzylbutylcyclohexane-1,4-dicarboxylate and dibutylcyclohexane-1,4-dicarboxylate as fast-gelling plasticizers for PVC.
  • Some diether derivatives of 2,5-di (hydroxymethyl) tetrahydrofuran are already known in the art.
  • WO 2009/141 166 describes a fuel composition consisting of ring-hydrogenated alkylfurfuryl ethers of the general formula: FT-TF-CH -OR, in which TF is a 2,5-disubstituted tetrahydrofuran ring, R is a hydrocarbyl group having 1 to 20 C atoms, R represents a methyl group, a hydroxymethyl group and the product of an aldol condensation, or an alkoxymethyl group of the general formula: - CH 2 -O-R ', where R' represents a hydrocarbyl group of 1 to 20 carbon atoms
  • FT-TF-CH -OR in which TF is a 2,5-disubstituted tetrahydrofuran ring, R is a hydrocarbyl group having 1 to 20 C atoms, R represents a methyl group, a hydroxymethyl group and the product of an aldol condensation, or an alkoxymethyl group of the general formula:
  • plasticizers are the esters of 2,5-furandicarboxylic acid (FDCA).
  • WO 2012/1 13608 describes C 5 dialkyl esters of 2,5-furandicarboxylic acid and their use as plasticizers. These short-chain esters are also suitable for the production of plastisols.
  • WO 2012/1 13609 describes C 7 dialkyl esters of 2,5-furandicarboxylic acid and their use as plasticizers.
  • WO 201 1/023490 describes C 9 dialkyl esters of 2,5-furandicarboxylic acid and their use as plasticizers.
  • WO 201 1/023491 describes Cio-dialkyl esters of 2,5-furandicarboxylic acid and their use as plasticizers.
  • 3,259,636 describes a process for the preparation of esters of cis-2,5-tetrahydrofurandicarboxylic acid which comprises, in a one-pot reaction, hydrogen, 2,5-furandicarboxylic acid and an alcohol in the presence of a noble metal catalyst implements. Specifically, the preparation of the methyl, propyl and phenoxyethyl diesters of cis-2,5-tetrahydrofurandicarboxylic acid is described. It is further disclosed that the esters of alcohols having 6 or more carbon atoms are useful as plasticizers in resin compositions.
  • Plastisols are initially a suspension of fine-powdered plastics in liquid plasticizers.
  • the rate of dissolution of the polymer in the plasticizer at ambient temperature is very low. Only when heated to higher temperatures, the polymer dissolves noticeably in the plasticizer.
  • the individual isolated plastic aggregates swell and fuse to a three-dimensional highly viscous gel. This process is referred to as gelling and takes place at a certain minimum temperature, referred to as the gelling or dissolving temperature.
  • the gelation step is not reversible.
  • plastisols are in liquid form, they are very often used for coating various materials, such. As textiles, glass fleeces, etc. used. The coating is very often composed of several layers.
  • the processing of plastisol products is therefore often carried out in such a way that a layer of plastisol is applied and directly afterwards the plastic, in particular PVC, is gelled with the plasticizer above the dissolution temperature, ie a solid layer consisting of a mixture gelled, partially gelled and ungelled plastic particles.
  • the next layer is then applied to this gelled layer and, after application of the last layer, the entire structure is completely processed by heating to higher temperatures to form the completely gelled plastic product.
  • plasticizers and plastics can also be produced. Such dry blends, especially based on PVC, can then be used at elevated temperatures z. B. further processed by extrusion into a granulate or processed by conventional molding processes, such as injection molding, extrusion or calendering, the fully gelled plastic product. It is an object of the present invention to provide novel compounds which can be advantageously used as or in plasticizers for thermoplastic polymers and elastomers. They should be toxicologically safe and can be prepared from readily available educts, which are preferably at least partially derived from renewable raw materials. They should have good softening properties and thus the production of products with good mechanical properties, such.
  • connection should furthermore have good gelling properties and / or have a low viscosity in the non-gelled state and are therefore suitable in particular for the production of flexible PVC and PVC plastisols. Accordingly, the new compounds should be able to replace the currently prevailing standard plasticizer on a petrochemical basis, at least on an equal basis.
  • R 1 and R 2 are independently selected from unbranched and branched C 7 -C 12 -alkyl radicals.
  • a further subject of the invention are softener compositions comprising at least one compound of the general formula (I) as defined above and hereinafter and at least one plasticizer other than the compounds of the formula (I).
  • Another object of the invention are processes for the preparation of compounds of the general formula (I).
  • Another object of the invention is the use of compounds of general formula (I) as or in plasticizers for polymers, in particular for polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • Another object of the invention are molding compositions containing at least one thermoplastic polymer, and at least one compound of general formula (I), as defined above and hereinafter.
  • Another object of the invention are molding compositions containing at least one elastomer, and at least one compound of general formula (I), as defined above and hereinafter.
  • Another object of the invention is the use of these molding compositions for the production of moldings and films.
  • the compounds (I) according to the invention are very suitable for use as plasticizers or as components of a plasticizer composition for thermoplastic polymers, in particular for PVC.
  • the polymers plasticized with the compounds (I) according to the invention have good mechanical properties, such as, for example, a low Shore hardness or a high tensile strength.
  • the compounds (I) according to the invention have very good gelling properties due to their low dissolving temperatures according to DIN 53408. They are thus suitable for reducing the temperature required for gelling a thermoplastic polymer and / or for increasing the gelling speed.
  • the compounds of the general formula (I) according to the invention are distinguished by very good compatibility with a large number of different plasticizers. They are particularly suitable in combination with conventional plasticizers to improve the gelling behavior.
  • the compounds (I) according to the invention are advantageously suitable for the preparation of plastisols.
  • the compounds (I) according to the invention are suitable for use in the production of moldings and films for sensitive applications, such as
  • a special economic and ecological Advantage of the present invention is the ability to use both in large quantities available petrochemical raw materials, as well as renewable raw materials in the preparation of compounds of the invention (I).
  • the starting materials of the furan cores are available from naturally occurring carbohydrates, such as cellulose and starch, whereas the alcohols which can be used to introduce the side chains are available from industrial processes. So on the one hand, the need for "sustainable" products can be covered, on the other hand, however, an economical production is possible.
  • the processes for preparing the compounds (I) of the present invention are simple and efficient, whereby they can be easily provided on an industrial scale.
  • the compounds of the general formula (I) in particular the C7-C12 dialkyl esters of tetrahydrofuranic dicarboxylic acid, are very suitable for plasticizing thermoplastic polymers and make it possible to produce products with good mechanical properties.
  • these compounds have low dissolution temperatures and excellent gelling properties in the production of plasticized PVC and plastisols, especially PVC plastisols.
  • the compounds of the general formula (1.1) according to the invention may be pure cis isomers or pure trans isomers or cis / trans isomer mixtures. Both the pure isomers and the isomer mixtures of any composition are equally suitable as plasticizers.
  • the term "C 1 -C 3 -alkyl” encompasses straight-chain or branched C 1 -C 3 -alkyl groups. These include methyl, ethyl, propyl or isopropyl. Most preferably, this is methyl.
  • C7-C12-alkyl includes straight-chain and branched C7-C12-alkyl groups.
  • C 7 -C 12 alkyl is selected from n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, 1-ethyl-2-methylpropyl, n-octyl, isooctyl, 2 Ethylhexyl, n-nonyl, isononyl, 2-propylhexyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl and the like.
  • C 7 -C 12 -alkyl is particularly preferably n-octyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2-propylheptyl, n-undecyl or isoundecyl.
  • the groups X in the compounds of the general formula (I) preferably have the same meaning.
  • the groups X are both * - (CH 2) n -O-, where n is 0, 1 or 2. More preferably, n is 2.
  • radicals R 1 and R 2 are preferably, independently of one another, an unbranched or branched C 7 -C 12 -alkyl radical.
  • radicals R 1 and R 2 independently of one another are isononyl, 2-propylheptyl or 2-ethylhexyl.
  • radicals R 1 and R 2 have the same meaning.
  • Preferred compounds of the general formula (I) are selected from
  • a particularly preferred compound of the general formula (I) is di (2-propylheptyl) -2,5-tetrahydrofurandicarboxylate.
  • Another particularly preferred compound of general formula (I) is di- (isononyl) -2,5-tetrahydrofurandicarboxylate.
  • Another particularly preferred compound of the general formula (I) is di- (2-ethylhexyl) -2,5-tetrahydrofurandicarboxylate.
  • Another object of the invention is a process for the preparation of compounds of general formula (1.1),
  • R 1 and R 2 are independently selected from branched and unbranched C7-Ci2-alkyl radicals, which optionally 2,5-furandicarboxylic acid or an anhydride or acid halide thereof with a Ci-C3-alkanol in the presence of a catalyst to obtain a di ( C 1 -C 3 -alkyl) -2,5-furandicarboxylate,
  • step b1 the compound (1.1a) obtained in step b1) is hydrogenated with hydrogen in the presence of at least one hydrogenation catalyst to obtain the compound of the general formula (1.1),
  • step b2) the compound (1.1b) obtained in step b2) with at least one alcohol R 1 -OH and, if R 1 and R 2 have different meanings, additionally with at least one alcohol R 2 -OH in the presence of a catalyst to give a compound of formula (1.1).
  • the process according to the invention makes it possible to prepare the 2,5-tetrahydrofuran dicarboxylic acid esters of the general formula (1.1) in two different ways (referred to below as variant 1 and variant 2).
  • Ci-C3 alkanols are z.
  • methanol ethanol, n-propanol or mixtures thereof.
  • the 2,5-furandicarboxylic acid or di- (C 1 -C 3 -alkyl) -2,5-furandicarboxylate obtained in step a) is esterified or transesterified with at least one alcohol R 1 -OH and if R 1 and R 2 have different meanings, additionally subjected to at least one alcohol R 2 -OH to the compounds of formula (1.1 a), which are then hydrogenated to compounds of general formula (1.1) (step c1)).
  • the 2,5-furandicarboxylic acid or the 2,5-di- (C 1 -C 3 -alkyl) furandicarboxylate obtained in step a) is first obtained to give 2,5-tetrahydrofurandicarboxylic acid or a compound of the general formula ( 1.1 b) hydrogenated (step b2)) and the product of the hydrogenation then with at least one alcohol R 1 -OH and, if R 1 and R 2 have different meanings, additionally with at least one alcohol R 2 -OH to the compounds of the general formula (1.1) implemented (step c2)).
  • the conversion of the 2,5-furandicarboxylic acid (FDCS) or 2,5-tetrahydrofuranic dicarboxylic acid into the corresponding ester compounds of the general formulas (1.1), (1.1a) and (1.1b) can be carried out by customary methods known to the person skilled in the art. This includes the reaction of at least one alcohol component selected from C 1 -C 3 -alkanols or the alcohols R 1 -OH or R 2 -OH, with FDCS or a suitable derivative thereof. Suitable derivatives are, for.
  • a preferred acid halide is the acid chloride.
  • esterification catalysts customary catalysts can be used, for.
  • mineral acids such as sulfuric acid and phosphoric acid
  • organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid
  • amphoteric catalysts especially titanium, tin (IV) - or zirconium compounds, such as tetraalkoxytitans, z.
  • tetrabutoxytitanium, and tin (IV) oxide are removed.
  • WO 02/038531 describes a process for the preparation of esters in which a) in a reaction zone a mixture consisting essentially of the acid component or an anhydride thereof and the alcohol component is boiled in the presence of an esterification catalyst, b) the alcohol and water-containing vapors separated by distillation into an alcohol-rich fraction and a water-rich fraction, c) the alcohol-rich fraction in the reaction zone leads back and discharges the water-rich fraction from the process.
  • esterification catalysts the aforementioned catalysts are used.
  • the esterification catalyst is used in an effective amount, which is usually in the range of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the sum of acid component (or anhydride) and alcohol component.
  • an effective amount which is usually in the range of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the sum of acid component (or anhydride) and alcohol component.
  • 2,5-tetrahydrofurandicarboxylic acid in the presence of the abovementioned alcohol components, by means of an organic acid or mineral acid, in particular centered sulfuric acid.
  • the alcohol component is advantageously used at least in twice the stoichiometric amount based on the FDCS or the 2,5-tetrahydrofurandicarboxylic acid or a derivative.
  • the esterification can usually be carried out at ambient pressure or reduced or elevated pressure. Preferably, the esterification is carried out at ambient or reduced pressure.
  • the esterification may be carried out in the absence of an added solvent or in the presence of an organic solvent.
  • esterification is carried out in the presence of a solvent, it is preferably an organic solvent which is inert under the reaction conditions.
  • organic solvent which is inert under the reaction conditions.
  • organic solvent include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic
  • the solvent is preferably selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dibutyl ether, THF, dioxane and mixtures thereof.
  • the esterification is usually carried out in a temperature range of 50 to 250 ° C.
  • esterification catalyst is selected from organic acids or mineral acids
  • the esterification is usually carried out in a temperature range from 50 to 160.degree.
  • esterification catalyst is selected from amphoteric catalysts
  • the esterification is usually carried out in a temperature range of 100 to 250 ° C.
  • the esterification can take place in the absence or in the presence of an inert gas.
  • An inert gas is generally understood to mean a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed during the reaction.
  • the esterification takes place without the addition of an inert gas.
  • Transesterification The transesterification of the di- (C 1 -C 3 -alkyl) -2,5-furandicarboxylates or of the di (C 1 -C 3 -alkyl) -2,5-tetrahydrofurandicarboxylates described in steps b1) and c2) to the corresponding Ester compounds 1.1 a or 1.1 can according to the usual expert take place known methods. This includes the reaction of the di- (C 1 -C 3) -alkyl esters with at least one C 7 - to C 12 -alkanol or mixtures thereof in the presence of a suitable transesterification catalyst.
  • Suitable transesterification catalysts are the customary catalysts usually used for transesterification reactions, which are usually also used in esterification reactions. These include z.
  • mineral acids such as sulfuric acid and phosphoric acid
  • organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid
  • special metal catalysts from the group of tin (IV) catalysts for example dialkyltin dicarboxylates such as dibutyltin diacetate, trialkyltin alkoxides, monoalkyltin compounds such as monobutyltin dioxide, tin salts such as tin acetate or tin oxides; from the group of titanium catalysts, monomeric and polymeric titanates and titanium chelates such as tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate, triethanolamine titanate; from the group of zirconium
  • the amount of transesterification catalyst used is from 0.001 to 10% by weight, preferably from 0.05 to 5% by weight.
  • the reaction mixture is preferably heated to the boiling point of the reaction mixture, so that the reaction temperature is between 20 ° C and 200 ° C, depending on the reactants.
  • the transesterification can be carried out at ambient pressure or reduced or elevated pressure.
  • the transesterification is preferably carried out at a pressure of 0.001 to 200 bar, more preferably 0.01 to 5 bar.
  • the lower-boiling alcohol split off during the transesterification is preferably distilled off continuously in order to shift the equilibrium of the transesterification reaction.
  • the distillation column required for this purpose is generally in direct contact with the transesterification reactor, preferably it is installed directly on it. In case of using several in
  • each of these reactors can be equipped with a distillation column or it can, preferably from the last boilers of the transesterification reactor cascade the evaporated alcohol mixture via one or more manifolds to a distillation column are supplied.
  • the recovered in this distillation higher boiling alcohol is preferably recycled back to the transesterification.
  • the separation generally succeeds by hydrolysis and subsequent separation of the metal oxide formed, eg. B. by filtration.
  • the catalyst is hydrolyzed by washing with water and the precipitated metal oxide is filtered off.
  • the product is separated by distillation.
  • steps 1 b) and 2c) the transesterification of the di- (C 1 -C 3 -alkyl) -2,5-furandicarboxylates or di- (C 1 -C 3 -alkyl) -2,5-
  • Tetrahydrofurandicarboxylate in the presence of the alcohol component and in the presence of at least one titanium (IV) alcoholate.
  • Preferred titanium (IV) alcoholates are tet rapropoxytitanium, tetrabutoxytitanium or mixtures thereof.
  • the alcohol component is preferably used at least in twice the stoichiometric amount, based on the di (C 1 -C 3 -alkyl) esters used.
  • the transesterification may be carried out in the absence or in the presence of an added organic solvent.
  • the transesterification is carried out in the presence of an inert organic solvent.
  • Suitable organic solvents are those mentioned above for the esterification. These include, in particular, toluene and THF.
  • the temperature in the transesterification is preferably in a range of 50 to 200 ° C.
  • the transesterification can be carried out in the absence or in the presence of an inert gas.
  • An inert gas is generally understood to mean a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed during the reaction.
  • the transesterification is preferably carried out without adding an inert gas.
  • Subgroup of the Periodic Table of the Elements for example platinum, rhodium, palladium, cobalt, nickel or ruthenium, preferably ruthenium, either alone or together with at least one metal of the I or VII subgroup of the periodic table, such as copper or rhenium deposited on a mesoporous aluminum oxide support material with bimodal pore distribution.
  • WO 02/100536 is also suitable.
  • Further suitable processes are described in the following documents: EP-A 1266882 - Use of a nickel / magnesium oxide on kieselguhr catalyst, WO 03/029181 - Use of a nickel / zinc on silicon dioxide catalyst, WO 03/029168 - Use of a palladium / ZnO Alumina catalyst and a ruthenium / ZnO on a-AI2O3 Kat.alysat.ors or
  • WO 04/09526 Use of a ruthenium on titanium dioxide catalyst.
  • Other suitable catalysts are also Raney catalysts, preferably Raney nickel.
  • Zirconia dioxide (ZrO 2), sulfated zirconia, tungsten carbide (WC), titanium dioxide (TIO 2), sulfated carbon, activated carbon, aluminum phosphate, aluminosilicates or phosphated aluminum oxide, as well as combinations thereof, are also suitable in addition to the already mentioned support materials.
  • the hydrogenation can be carried out in analogy to the known hydrogenation for the hydrogenation of organic compounds which have hydrogenatable groups.
  • the organic compound as a liquid phase or gas phase, preferably as a liquid phase, brought into contact with the catalyst in the presence of hydrogen.
  • the liquid phase can z. B. via a catalyst fluidized bed (fluidized bed mode) or a fixed catalyst bed (fixed bed mode) are passed.
  • the hydrogenation is preferably carried out in a fixed bed reactor.
  • the hydrogenation can be configured both continuously and discontinuously, wherein the continuous process embodiment is preferred.
  • a conventional reaction apparatus for. B. a stirred reactor can be used.
  • the hydrogenation according to the invention is preferably carried out continuously in fixed-bed reactors in the upflow mode or trickle-bed mode.
  • the hydrogen can be passed both in cocurrent with the solution of the educt to be hydrogenated and in countercurrent over the catalyst.
  • Suitable apparatus for carrying out a hydrogenation on the catalyst fluidized bed and fixed catalyst bed are known in the art, for. See, for example, Ullmann's Enzyklopadie der Technischen Chemie, 4th Edition, Vol. 13, p. 135 ff., And P.N. Rylander, "Hydrogenation and Dehydrogenation” in Ullmann's Encyclopaedia of Industrial Chemistry, 5th ed. On CD-ROM.
  • the hydrogenation is usually carried out under elevated hydrogen pressure. Preference is given to a hydrogen pressure in the range from 2 to 500 bar, more preferably from 10 to 300 bar.
  • the hydrogenation is preferably carried out in the presence of an organic solvent which is inert under the hydrogenation conditions.
  • Suitable solvents are those previously in the Esterification defined.
  • an ether such as THF, a dialkylene glycol or a mono- or diether thereof such as glyme is used.
  • the hydrogenation is carried out at a temperature in a range from 20 to 350.degree. C., more preferably from 50 to 300.degree.
  • the amount of hydrogen used for the hydrogenation generally corresponds to 1 to 15 times the amount of the stoichiometric amount of hydrogen theoretically required for complete hydrogenation of the furan nucleus.
  • the hydrogenation of the furan core with platinum, rhodium, palladium, cobalt, nickel or ruthenium, in particular platinum and palladium is deposited on alumina, zirconia, sulfated zirconia, zinc oxide or silicon dioxide, in particular zirconium dioxide, in the presence of an inert solvent under 150 to 300 bar hydrogen pressure at a temperature of 150 to 250 ° C.
  • cis or trans isomer of the 2,5-tetrahydrofuran-dicarboxylic acid ester it is possible to form the cis or trans isomer of the 2,5-tetrahydrofuran-dicarboxylic acid ester, depending on the chosen hydrogenation condition, such as catalyst composition or hydrogenation temperature.
  • essentially isomerically pure cis or trans-2,5-tetrahydrofuran dicarboxylic acid esters can be generated, but also mixtures with different cis or trans isomeric proportions.
  • Substantially isomerically pure is understood to mean a content of at least 95% by weight of a particular isomer, based on the total weight of the 2,5-tetrahydrofurandicarboxylic acid ester.
  • the compounds of the general formula (1.1) according to the invention can be present both as pure cis isomers or as pure trans isomers or as cis / trans isomer mixtures. Both the pure isomers and the isomer mixtures of any composition are suitable as plasticizers to the same extent.
  • FDCS or the esters of 2,5-furandicarboxylic acid from steps a) and b1) is dissolved in an inert solvent and in the presence of a heterogeneous Pd / Pt catalyst at 50 to 300 bar hydrogen pressure and fully hydrogenated at 100 to 250 ° C.
  • the hydrogenation is preferably carried out continuously in the fixed bed mode, wherein the hydrogen is passed in countercurrent over the catalyst.
  • THF is preferably used as the solvent.
  • a Pd / Pt catalyst is preferably used on ZrÜ2.
  • the preferred reaction temperature of this embodiment is in the range of 100 to 200 ° C.
  • a particularly preferred embodiment of the process according to the invention comprises: a) reaction of 2,5-furandicarboxylic acid with methanol in the presence of concentrated sulfuric acid to give 2,5-furandicarboxylic acid dimethyl ester,
  • step 2c) Reaction of the obtained in step 2b) 2,5-Tetrahydrofurandicarbonklare- dimethyl ester with at least one alcohol R 1 -OH in the presence of at least one titanium (IV) alcoholate to the compounds of general formula (1.1).
  • Another object of the invention is a process for the preparation of compounds of general formula (I.2) or (I.3),
  • the alkylation is carried out in the presence of an organic solvent which is inert under the reaction conditions.
  • Suitable solvents are those mentioned above in the esterification.
  • Preferred solvents are aromatic hydrocarbons, such as toluene.
  • the leaving group Z preferably represents a radical which is selected from Br, Cl, the tosyl, mesyl or triflyl group. Particularly preferably, the leaving group Z is Br.
  • the alkylating reagents R 1 -Z or R 2 -Z are commercially available or can be prepared from the corresponding alcohols by means of suitable reactions or procedures familiar to the person skilled in the art.
  • the alkyl bromides R 1 -Br or R 2 -Br preferably used for this process can be prepared in a known manner on a large scale using hydrogen bromide (HBr) from the corresponding alcohols R 1 -OH or R 2 -OH.
  • Suitable bases in the process according to the invention are mineral and / or strong organic bases. These include z.
  • inorganic bases or base formers such as hydroxides, hydrides, amides, oxides and carbonates of the alkali and alkaline earth metals. These include LiOH, NaOH, KOH, Mg (OH) 2 , Ca (OH) 2 , LiH, NaH, sodium amide (NaNH 2), lithium diisopropylamide (LDA), Na 2 O, K 2 CO 3, Na 2 CO 3, and CS 2 CO 3; and organometallic compounds such as n-BuLi or tert-BuLi. Preference is given to NaOH, KOH, K 2 CO 3 and Na 2 C0 3 .
  • the base is preferably used in a least twice the stoichiometric excess based on the 2,5-di- (hydroxymethyl) tetrahydrofuran or 2,5-di- (hydroxyethyl) tetrahydrofuran. More preferably, at least four times the stoichiometric excess of base is used.
  • the alkylation may be carried out in the absence or in the presence of an organic solvent.
  • an organic solvent such as pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dibutyl ether, THF, dioxane and Mixtures thereof, carried out.
  • the alkylation can be carried out usually at ambient pressure, reduced pressure or elevated pressure. Preferably, the alkylation is carried out at ambient pressure.
  • the alkylation is preferably carried out in a temperature range from 30 to 200.degree. C., preferably from 50 to 150.degree.
  • the alkylation can be carried out in the absence or in the presence of an inert gas. Preferably, no inert gas is used in the alkylation.
  • the alkylation is 2,5-di (hydroxymethyl) - tetrahydrofuran or 2,5-di- (hydroxyethyl) tetrahydrofuran in the presence of at least four-fold excess of base in an inert organic solvent and at least one alkyl bromide R 1 -Br or R 2 -Br converted into the diether compounds of the general formula (I.2).
  • R 1 and R 2 reference is made to the previous statements.
  • the alkali is preferably used as the base, in particular KOH.
  • ester compounds of the general formula (I.3) it is customary to use all types of tertiary amines which are familiar to the person skilled in the art.
  • suitable tertiary amines are:
  • trialkylamines trimethylamine, triethylamine, tri-n-propylamine, diethylisopropylamine, diisopropylethylamine and the like;
  • N-cycloalkyl-N, N-dialkylamines dimethylcyclohexylamine and
  • pyridine and quinoline bases from the group of pyridine and quinoline bases: pyridine, ⁇ -, ⁇ - and ⁇ -picoline, quinoline and 4- (dimethylamino) pyridine (DMAP).
  • DMAP dimethylamino pyridine
  • Preferred tertiary amines are trialkylamines and pyridine bases, in particular triethylamine and 4- (dimethylamino) pyridine (DMAP), and mixtures thereof.
  • the esterification can be carried out at ambient pressure, at reduced or elevated pressure. Preferably, the esterification is carried out at ambient pressure.
  • the esterification may be carried out in the absence or in the presence of an organic solvent.
  • the esterification is carried out in the presence of an inert organic solvent as defined above.
  • the esterification is usually carried out in a temperature range of 50 to 200 ° C.
  • the esterification can take place in the absence or in the presence of an inert gas.
  • Preferred C 7 -C 12 -alkanols may be straight-chain or branched or consist of mixtures of straight-chain and branched C 7 -C 12 -alkanols. These include n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol, 2-propylheptanol, n-undecanol, isoundecanol, n-dodecanol or isododecanol.
  • C 7 -C 12 -alkanols are n-octanol, 2-ethylhexanol, n-nonanol, isononanol and 2-propylheptanol, in particular isononanol and
  • Heptanols required for the preparation of the compounds of the general formula (I) according to the invention can be straight-chain or branched or consist of mixtures of straight-chain and branched heptanols. Preference is given to mixtures of branched heptanols, also referred to as isoheptanol, which are obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of dimer derivatives, obtainable, for example, by B. after the Dimersol® process, and subsequent hydrogenation of the obtained isoheptanals to an isoheptanol mixture produced.
  • the isoheptanol mixture obtained in this way consists of several isomers.
  • Substantially straight-chain heptanols can be obtained by the rhodium or preferably cobalt-catalyzed hydroformylation of 1-hexene and subsequent hydrogenation of the resulting n-heptanal to n-heptanol.
  • the hydroformylation of 1-hexene or dimerpropene can be carried out by processes known per se.
  • both uncomplexed rhodium carbonyls which react in situ under the conditions of the hydroformylation reaction in the hydroformylation reaction mixture under the action of synthesis gas can be used.
  • organic phosphines such as triphenylphosphine
  • organophosphites preferably chelating biphosphites, such as.
  • cobalt carbonyl compounds which are generally homogeneously soluble in the reaction mixture are generally used which form under the conditions of the hydroformylation reaction under the action of synthesis gas in situ from cobalt salts. If the cobalt-catalyzed hydroformylation is carried out in the presence of trialkyl- or triarylphosphines, the desired heptanols are formed directly as the hydroformylation product, so that no further hydrogenation of the aldehyde function is required any more.
  • rhodium-catalyzed hydroformylation of long-chain olefins such as the hexane isomer mixtures obtained by the abovementioned processes
  • the implementation of such rhodium high-pressure hydroformylation is in z.
  • EP-A 695734, EP-B 880494 and EP-B 1047655 described.
  • the isoheptanal mixtures obtained after hydroformylation of the hexene-isomer mixtures are catalytically hydrogenated in conventional manner to give isoheptanol mixtures.
  • heterogeneous catalysts which, as the catalytically active component, comprise metals and / or metal oxides of VI. to VIII.
  • the I. subgroup of the Periodic Table of the Elements in particular chromium, molybdenum, manganese, rhenium, iron, cobalt, nickel and / or copper, optionally deposited on a support material such as Al2O3, S1O2 and / or ⁇ 2 included.
  • Such catalysts are z. B.
  • 2-ethylhexanol which was the plasticizer alcohol produced in the largest amounts for many years, can be obtained via the aldol condensation of n-butyraldehyde to 2-ethylhexenal and its subsequent hydrogenation to 2-ethylhexanol (see Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, Bd. A 10, pp. 137-140, VCH Verlagsgesellschaft GmbH, Weinheim 1987).
  • Substantially straight-chain octanols can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-heptane and subsequent hydrogenation of the n-octanal obtained to give n-octanol. The needed
  • 1 -Hepten can be obtained from the Fischer-Tropsch synthesis of hydrocarbons.
  • the alcohol isooctanol in contrast to 2-ethylhexanol or n-octanol, due to its method of preparation, is not a uniform chemical compound but an isomeric mixture of differently branched Cs-alcohols, for example 2,3-dimethyl-1 - hexanol, 3,5-dimethyl-1-hexanol, 4,5-dimethyl-1-hexanol, 3-methyl-1-heptanol and 5-methyl-1-heptanol, which vary according to the manufacturing conditions and processes used - Can be present in ratios of isooctanol.
  • Isooctanol is usually prepared by the codimerization of propene with butenes, preferably n-butenes, and subsequent hydroformylation of the resulting mixture of heptene isomers. provides.
  • the octanal isomer mixture obtained in the hydroformylation can then be hydrogenated in a conventional manner to the isooctanol.
  • the codimerization of propene with butenes to isomeric heptenes can advantageously be carried out with the aid of the homogeneously catalyzed Dimersol® process (Chauvin et al., Chem. Ind., May 1974, pp. 375-378), in which a soluble nickel-phosphine catalyst is used as the catalyst.
  • a soluble nickel-phosphine catalyst is used as the catalyst.
  • Complex in the presence of an ethylaluminum chlorine compound, for example ethylaluminum dichloride serves.
  • phosphine ligands for the nickel complex catalyst can, for.
  • Tribenzylphosphine As tributylphosphine, tri-isopropyl-phosphine, tricyclohexylphosphine and / or Tribenzylphosphin be used.
  • the reaction takes place at temperatures of 0 to 80 ° C., advantageously setting a pressure at which the olefins are dissolved in the liquid reaction mixture (Cornils, Hermann: Applied Homogeneous Catalysis with Organometallic Compounds, 2nd Edition, Vol 254-259, Wiley-VCH, Weinheim 2002).
  • the codimerization of propene with butenes can also be carried out with heterogeneous NiO catalysts deposited on a support, similar heptene isomer distributions being obtained as in the case of the highly catalyzed process.
  • heterogeneous NiO catalysts are used for example in the so-called Octol® process (Hydrocarbon Processing, February 1986, pp 31-33), a well-suited specific nickel heterogeneous catalyst for Olefindimeri- tion or codimerization z.
  • Octol® process Hydrocarbon Processing, February 1986, pp 31-33
  • a well-suited specific nickel heterogeneous catalyst for Olefindimeri- tion or codimerization z As disclosed in WO 9514647.
  • catalysts based on nickel it is also possible to use brominated-acid heterogeneous catalysts for the codimerization of propene with butenes, as a rule higher-branched heptenes than in the nickel-catalyzed process are obtained.
  • catalysts suitable for this purpose are solid phosphoric acid catalysts z.
  • diatomaceous earth impregnated with phosphoric acid or diatomaceous earth as used by the PolyGas® process for Olefindi- or oligomerization (Chitnis et al; Hydrocarbon Engineering ⁇ 0, No. 6 - June 2005).
  • Br ⁇ nsted-acidic catalysts are zeolites, which uses the advanced based on the PolyGas® process EMOGAS® process.
  • the 1-heptene and the heptene isomer mixtures are prepared by the known processes described above in connection with the preparation of n-heptanal and heptanal isomer mixtures by means of rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation, in n-octanal or Octanal isomer mixtures transferred. These are then z. B. hydrogenated by means of one of the above-mentioned in connection with the n-heptanol and isoheptanol preparation catalysts to the corresponding octanols. nonanol
  • Substantially straight chained nonanol can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-octene and subsequent hydrogenation of the n-nonanal thus obtained.
  • the starting olefin 1 -Octen can, for example, an ethylene oligomerization by means of a homogeneously in the reaction medium - 1, 4-butanediol - soluble nickel complex catalyst with z.
  • diphenylphosphinoacetic acid or 2-diphenylphosphinobenzoic acid can be obtained as ligands.
  • This process is also known by the name Shell Higher Olefins Process or SHOP process (see Weisermel, Arpe: Industrielle Organische Chemie, 5th Edition, p 96, Wiley-VCH, Weinheim 1998).
  • the alcohol component isononanol required for the synthesis of the diisononyl esters or diisononyl ethers according to the invention is not a uniform chemical compound but a mixture of differently branched, isomeric C 12 -alcohols which differ depending on the nature of their preparation, in particular also of the starting materials used May have branching degrees.
  • the isononanols are prepared by dimerization of butenes to isooctene mixtures, subsequent hydroformylation of the isooctene mixtures and hydrogenation of the resulting isononal mixtures to form isononanal mixtures, as described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A1, pp.
  • isononanols having a lower degree of branching are prepared from the linear butenes 1-butene, cis- and / or trans-2-butene, which may optionally contain even lower amounts of isobutene, via the above-described route of butene dimerization, hydroformylation of the isooctene and hydrogenation of the obtained isononanal mixtures produced.
  • a preferred raw material is the so-called raffinate II from the C 4 cut of a cracker, for example a steam cracker, which after elimination of allenes, acetylenes and dienes, in particular 1, 3-butadiene, by its partial hydrogenation to linear butenes or its Separation by extractive distillation, while For example, by means of N-methylpyrrolidone, and subsequent Br ⁇ nsted acid-catalyzed removal of the isobutene contained therein by its reaction with methanol or isobutanol by industrially established method to form the fuel additive methyl tert-butyl ether (MTBE) or to obtain pure isobutene isobutyl tert-butyl ether.
  • MTBE methyl tert-butyl ether
  • Raffinate II in addition to 1-butene and cis- and trans-2-butene still n- and iso-butane and residual amounts of up to 5 wt .-% of isobutene.
  • the dimerization of the linear butenes or of the butene mixture contained in the raffinate II can be carried out by means of the customary industrially practiced processes, as described above in connection with the production of isoheptene mixtures, for example by means of heterogeneous, brominated-acid catalysts such as those used in polygas ® or EMOGAS® method can be used by means of the Dimersol® method using homogeneously dissolved in the reaction medium nickel complex catalysts or by means of heterogeneous, nickel (II) oxide-containing catalysts according to the Octol® process or the method according to WO 9514647 are performed.
  • the resulting isooctene mixtures are converted into isononanal mixtures by the known methods described above in connection with the preparation of heptanal isomer mixtures by means of rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation. These are then z. B. by means of one of the catalysts mentioned above in connection with the isoheptanol production hydrogenated to the suitable Isononanolgemi- rule.
  • the isononanol isomer mixtures thus prepared can be characterized by their isoindex, which can be calculated from the degree of branching of the individual, isomeric isononanol components in the isononanol mixture multiplied by their percentage in the isononanol mixture.
  • isoindex can be calculated from the degree of branching of the individual, isomeric isononanol components in the isononanol mixture multiplied by their percentage in the isononanol mixture.
  • the isoindex of an isononanol mixture can be determined by gas chromatographic separation of the isononanol mixture into its individual isomers and concomitant quantification of their percentage in the isononanol mixture, determined by standard methods of gas chromatographic analysis.
  • these are conveniently trimethylsilylated prior to gas chromatographic analysis by standard methods, for example by reaction with N-methyl-N-trimethylsilyltrifluoroacetamide.
  • capillary columns with Polydimethylsiloxane used as a stationary phase.
  • Such capillary columns are commercially available and it only takes a few routine experiments of the skilled person to select from the wide range of trade a suitable for this separation task suitable product.
  • the diisononyl esters or diisononyl ethers of the general formula (I) according to the invention are generally esterified with isononanols having an iso-index of from 0.8 to 2, preferably from 1, 0 to 1, 8 and more preferably from 1, 1 to 1, 5 or etherified, which can be prepared by the above-mentioned methods.
  • compositions of isononanol mixtures are given below, such as those used to prepare the compounds according to the invention 2,5-tetrahydrofurandicarboxylic acid diisononyl ester, 2,5-di (hydroxymethyl) -tetrahydrofurandiisononanoate and diisononyl ether of 2,5-di (hydroxymethyl) -tetra- hydrofuran, it being noted that the proportions of the isomers in the isononanol mixture listed in detail depending on the composition of the starting material, such as raffinate II, the composition of which may vary production Butenen, and of variations in the applied production conditions, such as age of the catalysts used and the temperature and pressure conditions to be matched.
  • an isononanol mixture which has been prepared by cobalt-catalyzed hydroformylation and subsequent hydrogenation from an isooctene mixture produced using raffinate II as raw material by means of the catalyst and process according to WO 9514647 can have the following composition:
  • From 6.30 to 16.30% by weight preferably from 7.30 to 15.30% by weight, particularly preferably from 8.30 to 14.30% by weight of 3,6-dimethylheptanol;
  • 0.98 to 2.98 wt.% Preferably 1.18 to 2.78 wt.%, Particularly preferably 1.48 to 2.48 wt.% 5-methyl-octanol;
  • n-nonanol 0.1 to 3 wt .-%, preferably 0.2 to 2 wt .-%, particularly preferably 0.3 to 1 wt .-% of n-nonanol;
  • an isononanol mixture prepared by cobalt-catalyzed hydroformylation followed by hydrogenation using an ethylene-containing butene mixture as raw material by the polygas® or EMOGAS® process isooctene mixture may be used in the range of the following compositions Raw material composition and variations of the applied reaction conditions vary:
  • the alcohol component isodecanol required for the preparation of the compounds of the general formula (I) according to the invention is not a uniform chemical compound but a complex mixture of differently branched, isomeric decanols. These are generally prepared by the nickel- or brominated-acid-catalyzed trimerization of propylene, for example by the above-described PolyGas® or the EMOGAS® process, subsequent hydroformylation of the resulting isonone isomer mixture by means of homogeneous rhodium or cobalt carbonyl Catalysts, preferably by means of cobalt carbonyl catalysts and hydrogenation of the resulting isodecanal isomer mixture z.
  • the 2-propylheptanol required for the preparation of the di (2-propylheptyl) ester or di (2-propylheptyl) ether according to the invention may be pure 2-propylheptanol or propylheptanol isomer mixtures, such as are generally formed in the industrial production of 2-propylheptanol and commonly also referred to as 2-propylheptanol.
  • Pure 2-propylheptanol can be obtained by aldol condensation of n-valeraldehyde and subsequent hydrogenation of the resulting 2-propylheptenal, for example according to US Pat. No. 2,921,089.
  • 2-propylheptanol contains, in addition to the main component 2-propylheptanol, one or more of the 2-propylheptanol isomers, such as 2-propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-isopropylheptanol, 2-isopropyl- 4-methylhexanol,
  • hydrocarbon sources for example 1-butene, 2-butene, raffinate I - an alkane / alkene mixture obtained from the C 4 cut of a cracker after separation of allenes, acetylenes and dienes, which in addition to 1- and 2-butene still contains significant amounts of isobutene - or raffinate II, which is obtained from raffinate I by separation of isobutene and contains only small amounts of isobutene as olefin components except 1- and 2-butene.
  • 1-butene, 2-butene, raffinate I - an alkane / alkene mixture obtained from the C 4 cut of a cracker after separation of allenes, acetylenes and dienes, which in addition to 1- and 2-butene still contains significant amounts of isobutene - or raffinate II, which is obtained from raffinate I by separation of isobutene and contains only small amounts of isobutene as olefin components except
  • mixtures of raffinate I and raffinate II can be used as a raw material for 2-propylheptanol production.
  • These olefins or olefin mixtures can be hydroformylated according to conventional methods with cobalt or rhodium catalysts, from 1-butene, a mixture of n- and iso-valeraldehyde - the name iso-valeraldehyde called the compound 2-methylbutanal - is formed, whose n / iso ratio may vary within relatively wide limits depending on the catalyst and hydroformylation conditions used.
  • n- and iso-valeraldehyde are formed in an n / iso ratio of generally 10: 1 to 20: 1, whereas when using With phosphite ligands, for example according to US Pat. No. 5,288,918 or WO 05028407, or of rhodium hydroformylation catalysts modified with phosphoamidite ligands, for example according to WO 0283695, almost exclusively n-valeraldehyde is formed.
  • Rh / TPP triphenylphosphine-modified rhodium homogeneous catalyst
  • Rh / TPP catalyst system reacts 2-butene only very slowly in the hydroformylation, so that most of the 2-butene can be recovered from the hydroformylation mixture
  • the hydroformylation of the 2-butene can be achieved with the phosphite ligands mentioned above. or phosphoramidite ligand-modified rhodium catalysts, wherein predominantly n-valeraldehyde is formed.
  • isobutene contained in the olefinic raw material is hydroformylated, albeit at a different rate, from virtually all catalyst systems to 3-methylbutanal and depending on the catalyst to a lesser extent to pivalaldehyde.
  • n-valeraldehyde in admixture with isovaleraldehyde, 3-methylbutanal and / or pivalaldehyde, can be separated completely or partially by distillation into the individual components before the aldol condensation, so that there is also a possibility of the isomeric composition of the do-alcohol component to influence and control the ester and ether mixtures according to the invention.
  • aldol condensation which can be carried out by means of a basic catalyst, such as an aqueous solution of sodium or potassium hydroxide, for example according to the method described in EP-A 366089, US-A 4426524 or US-A 5434313, arises when using a basic catalyst, such as an aqueous solution of sodium or potassium hydroxide, for example according to the method described in EP-A 366089, US-A 4426524 or US-A 5434313, arises when using a basic catalyst, such as an aqueous solution of sodium or potassium hydroxide, for example according to the method described in EP-A 366089, US-A 4426524 or US-A 5434313, arises when using a basic catalyst, such as an aqueous solution of sodium or potassium hydroxide, for example according to the method described in EP-A 366089, US-A 4426524 or US-A 5434313, arises when using a basic catalyst, such as an aqueous solution of sodium or potassium
  • n-Valeraldehyd as the only condensation product 2-propylheptenal, whereas when using a mixture of isomeric Cs-aldehydes an isomeric mixture of the products of Homoaldolkondensation same aldehyde molecules and the crossed aldol condensation different valeraldehyde isomers is formed.
  • the aldol condensation can be controlled by the targeted implementation of individual isomers so that predominantly or completely a single Aldolkondensations- isomer is formed.
  • the aldol condensation products in question can then be hydrogenated, usually after previous, preferably distillative removal from the reaction mixture and, if desired, purification by distillation, with conventional hydrogenation catalysts, for example those mentioned above for the hydrogenation of aldehydes, to the corresponding alcohols or alcohol mixtures.
  • the compounds can be di (2-propylheptyl) 2,5-tetrahydrofurandicarboxylates, 2,5-di (hydroxymethyl) tetrahydrofuran-di (2-propyl) heptanoate and di (2-propyl) heptyl ether of 2,5-di (hydroxymethyl) tetrahydrofuran be esterified or etherified with pure 2-propylheptanol.
  • mixtures of 2-propylheptanol with said propylheptanol isomers are used for preparing these esters or ethers, in which the content of 2-propylheptanol at least 50 wt .-%, preferably 60 to 98 wt .-% and particularly preferably 80 to 95 wt .-%, in particular 85 to 95 wt .-% is.
  • Suitable mixtures of 2-propylheptanol with the propylheptanol isomers include for example those from 60 to 98 wt .-% of 2-propylheptanol, 1 to 15 wt .-% 2-Propyl-4-methyl-hexanol and 0.01 to 20 wt .-% of 2-propyl-5-methyl-hexanol and 0.01 to 24 wt .-% 2-isopropylheptanol, wherein the sum of the proportions of the individual constituents 100 wt .-% does not exceed.
  • the proportions of the individual components add up to 100 wt .-%.
  • 2-propylheptanol with the propylheptanol isomers include, for example, those from 75 to 95% by weight of 2-propylheptanol, 2 to 15% by weight of 2-propyl-4-methylhexanol, 1 to 20% by weight.
  • the proportions of the individual components add up to 100 wt .-%.
  • Preferred mixtures of 2-propylheptanol with the propylheptanol isomers include those containing from 85 to 95% by weight of 2-propylheptanol, from 5 to 12% by weight of 2-propyl-4-methylhexanol and from 0.1 to 2% by weight % Of 2-propyl-5-methylhexanol and 0.01 to 1% by weight of 2-isopropylheptanol, the sum of the proportions of the individual constituents not exceeding 100% by weight.
  • the proportions of the individual components add up to 100 wt .-%.
  • the isomeric composition of the alkyl ester groups or alkyl ether groups corresponds in practice to the composition of Esterification used propylheptanol isomer mixtures.
  • the undecanols required for the preparation of the compounds of the general formula (I) according to the invention can be straight-chain or branched or can be composed of mixtures of straight-chain and branched undecanols. Preference is given to using mixtures of branched undecanols, also referred to as isoundecanol, as the alcohol component of the diundecyl esters or diundecyl ethers according to the invention.
  • Substantially straight-chain undecanol can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-decene and subsequent hydrogenation of the resulting n-undecanal.
  • the starting olefin 1-decene is prepared by the SHOP process mentioned above in the preparation of 1-octene.
  • the 1-decene obtained in the SHOP process can undergo skeletal isomerization, for Example by means of acidic zeolitic molecular sieves, as described in WO 9823566, are subjected to, mixtures of isomeric decenes form, their rhodium or preferably cobalt-catalyzed hydroformylation tion and subsequent hydrogenation of the resulting isoundecanal mixtures to that for the preparation of the compounds of the invention used Isoundecanols leads.
  • hydroformylation of 1-decene or isodecene mixtures by means of rhodium or cobalt catalysis can be carried out as previously described in connection with the synthesis of C7 to C10 alcohols.
  • the C7 to Cn-alkyl alcohols or mixtures thereof thus obtained can be used for the preparation of the diester or diether derivatives according to the general formula (I).
  • Substantially straight-chain dodecanol can advantageously be obtained via the Alfol® or Epal® process. These processes involve the oxidation and hydrolysis of straight-chain trialkylaluminum compounds which, starting from triethylaluminum, are built up stepwise over several ethylation reactions using Ziegler-Natta catalysts. From the resulting mixtures of substantially straight-chain alkyl alcohols of different chain length, the desired n-dodecanol can be obtained after the removal by distillation of the C 12 -alkyl alcohol fraction.
  • n-dodecanol can also be prepared by hydrogenation of natural fatty acid methyl esters, for example from coconut oil.
  • Branched isododecanol can be obtained analogously to the previously described processes for the codimerization and / or oligomerization of olefins with subsequent hydroformylation and hydrogenation of the isoundecene mixtures. After purification by distillation of the hydrogenation, the resulting isododecanols or mixtures thereof, as described above, can be used to prepare the diesters. Diether derivatives according to the general formula (I) can be used.
  • furan-2,5-dicarboxylic acid required as starting material for the preferred processes for the preparation of compounds of the general formula (I) can either be obtained commercially or prepared by synthesis routes known from the literature.
  • possibilities for synthesis can be found in the publication published by Lewkowski et al. entitled “Synthesis, Chemistry and Application of 5-hydroxymethylfurfural and its derivatives “(Lewkowski et al., ARKIVOC 2001 (i), pages 17-54, ISSN 1424-6376).
  • 2,5-bis (hydroxymethyl) tetrahydrofuran may also be either purchased or synthesized commercially.
  • the syntheses described proceed from 5-HMF, which can be reduced in two steps via 2,5-bis (hydroxymethyl) furan (2,5-BHF) or directly to 2,5-di (hydroxymethyl) tetrahydrofuran (Lewkowski et al. , ARKIVOC 2001 (i), pages 17-54, ISSN 1424-6376).
  • 2,5-bis (hydroxyethyl) tetrahydrofuran can be obtained by reduction of the 2,5-furandiessigklare- methyl ester.
  • 2,5-Furandiacetic acid methyl ester can be synthesized by suitable reactions known to those skilled in the art from 2,5-bis (hydroxymethyl) furan (2,5-BHF), for example analogously to that of Rau et al. in Liebigs Ann. Chem., Vol. 1984 (8, 1984), pages 1504-1512, ISSN 0947-3440.
  • 2,5-BHF is prepared from 2,5-bis (chloromethyl) furan by reaction with thionyl chloride, which is converted into benzene by the action of KCN in the presence of [18] crown-6 to 2,5-bis (cyanomethyl) furan becomes.
  • the 2,5-bis (cyanomethyl) furan can then be saponified to 2,5-furandiacetic acid and esterified with methanol to dimethyl ester or be converted by alcoholysis with methanol directly into the 2,5-furan-susig acid methyl ester (Pinner reaction) ,
  • the 2,5-furan-diacetic acid methyl ester can then be hydrogenated first to methyl tetrahydro-2,5-furan diacetic acid (analogously to steps b2) or c1)) or directly to 2,5-bis (hydroxyethyl ) tetrahydrofuran be reduced.
  • the compounds of the general formula (I) according to the invention are distinguished by very good compatibility with a large number of different plasticizers. They are particularly suitable in combination with other plasticizers, which have even better gelling properties, to improve the gelling behavior. Thus, they enable the reduction of the temperature required for gelling a thermoplastic polymer and / or the increase of the gelling rate of plasticizer compositions. For special or complex application requirements, such as high cold elasticity, high extraction or migration resistance, or very low plasticizer volatility, it may be advantageous to use plasticizer compositions for softening thermoplastic polymers. This is especially true for soft PVC applications.
  • the invention also relates to plasticizer compositions containing at least one compound of the general formula (I) and at least one plasticizer other than the compounds (I).
  • suitable and preferred compounds of general formula (I) for the preparation of plasticizer compositions reference is made in its entirety to the above-described suitable and preferred compounds of general formula (I).
  • the plasticizer compositions according to the invention preferably comprise at least one compound of the general formula (I) in which R 1 and R 2, independently of one another, are an unbranched or branched C 7 -C 12 -alkyl, in particular isononyl, 2-propylheptyl or 2-ethylhexyl.
  • a compound of general formula (I) which is especially suitable for the preparation of plasticizer compositions is di- (2-propylheptyl) -2,5-tetrahydrofurandicarboxylate. That of the compounds of general formula (I) different additional
  • Plasticizer is preferably selected from phthalic acid dialkyl esters, phthalic acid alkylaralkyl esters, terephthalic acid dialkyl esters, trimellitic acid trialkyls, alkyl dialkyl esters, benzoic acid esters, dibenzoic acid esters of glycols, hydroxybenzoic acid esters, esters of saturated mono- and dicarboxylic acids, esters of unsaturated dicarboxylic acids, amides and esters of aromatic sulfonic acids , Alkylsulfonklaestern, glycerol esters, isosorbide esters, phosphoric esters, citric acid triesters, alkylpyrrolidone derivatives, 2,5-Furandicarbonklareestern of compounds (I) different 2,5-Tetrahydrofurandicarbonklastern, epoxidized vegetable oils based on triglycerides and saturated or unsaturated fatty acids, polyesters of aliphatic and aromatic Polycarbox
  • Preferred dialkyl phthalates independently of one another have 4 to 13 C atoms, preferably 8 to 13 C atoms, in the alkyl chains.
  • a preferred phthalic acid alkyl-alkyl ester is, for example, benzyl butyl phthalate.
  • the terephthalic acid dialkyl esters preferably each independently have 4 to 13 C atoms, in particular 7 to 1 C atoms, in the alkyl chains.
  • Preferred dialkyl terephthalates are for example di (n-butyl) terephthalates, di (2-ethylhexyl) terephthalate, di (isononyl) terephthalates or di (2-propylheptyl) - terephthal Aciddialkylester.
  • the trimellitic acid trialkyl esters preferably each independently have 4 to 13 C atoms, in particular 7 to 1 C atoms, in the alkyl chains.
  • the esters of saturated mono- and dicarboxylic acids are preferably esters of acetic acid, butyric acid, valeric acid, succinic acid, adipic acid, sebacic acid, lactic acid, malic acid or tartaric acid.
  • the adipic acid dialkyl esters preferably each independently have 4 to 13 C atoms, in particular 6 to 10 C atoms, in the alkyl chains.
  • the esters of unsaturated dicarboxylic acids are preferably esters of maleic acid and fumaric acid.
  • the benzoic acid alkyl esters preferably each independently have 7 to 13 C atoms, in particular 9 to 13 C atoms, in the alkyl chains. Examples of preferred benzoic acid alkyl esters are isononyl benzoate, isodecyl benzoate or 2-propylheptyl benzoate.
  • Preferred dibenzoic acid esters of glycols are diethyl englycoldibenzoate and dibutylene glycol dibenzoate.
  • Preferred alkylsulfonic acid esters preferably have an alkyl radical having 8 to 22 C atoms. These include, for example, the phenyl or cresyl esters of pentadecylsulfonic acid.
  • Preferred isosorbide diesters are isosorbide diesters, which are preferably esterified independently of one another in each case with Cs to C 13 -carboxylic acids.
  • Preferred phosphoric acid esters are tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecyldiphenyl phosphate, 2-ethylhexyldiphenyl phosphate and bis (2-ethylhexyl) phenyl phosphate.
  • the OH group may be present in free or carboxylated form, preferably acetylated.
  • the alkyl radicals of the citric acid triesters preferably have, independently of one another, 4 to 8 C atoms, in particular 6 to 8 C atoms.
  • alkylpyrrolidone derivatives having alkyl radicals of 4 to 18 carbon atoms.
  • Preferred 2,5-furan dicarboxylic acid dialkyl esters each independently have 4 to 13 C atoms, preferably 8 to 13 C atoms, in the alkyl chains.
  • the epoxidized vegetable oils are, for example, preferably epoxidized fatty acids from epoxidized soybean oil, available under the trade name reFlex TM from PolyOne, USA, the trade name Proviplast TM PLS Green 5 and Proviplast TM PLS Green 8 from Proviron, Belgium, and the trade name Drapex Alpha TM from Galata, USA.
  • the polyesters of aliphatic and aromatic polycarboxylic acids are preferably polyesters of adipic acid with polyhydric alcohols, in particular dialkylene glycol polyadipates having 2 to 6 carbon atoms in the alkylene radical.
  • the alkyl radicals may each be linear or branched and in each case identical or different. Reference is made to the general statements made at the outset on suitable and preferred alkyl radicals.
  • the plasticizer compositions according to the invention comprise at least one of the compounds (I) various plasticizer selected from adipic acid dialkyl esters having 4 to 9 C atoms in the side chain.
  • the inventive plasticizer compositions contain at least one Cs to Cn dialkyl ester of 2,5-furandicarboxylic acid. Particularly preferred are the C7 to do-dialkyl esters of 2,5-furandicarboxylic acid.
  • Suitable and preferred dialkyl esters of 2,5-furandicarboxylic acid are described in WO 2012/1 13608 (C 5 dialkyl esters), WO 2012/1 13609 (C 7 dialkyl esters),
  • WO 201 1/023490 C 9 dialkyl esters
  • WO 201 1/023491 Cio dialkyl esters
  • the dihexyl, di (2-ethylhexyl) and di (2-octyl) esters of 2,5-furandicarboxylic acid and their preparation are described by RD Sanderson et al. in J. Appl. Pole. Sci., 1994, Vol. 53, 1785-1793. The disclosure of these documents is hereby incorporated by reference in its entirety.
  • dialkyl esters of 2,5-furandicarboxylic acid are the isomeric nonyl esters of 2,5-furandicarboxylic acid disclosed in WO 201 1/023490.
  • the isomeric nonyl radicals are preferably derived from a mixture of isomeric nonanols, as described in WO 201 1/023490, page 6, line 32 to page 10, line 15.
  • the plasticizer compositions according to the invention contain at least one plasticizer other than the compounds (I), preferably selected from C 4 - to
  • Another object of the present invention relates to a molding composition containing at least one thermoplastic polymer and at least one compound of general formula (I).
  • thermoplastic polymers are all thermoplastically processable polymers.
  • these thermoplastic polymers are selected from:
  • Homo- and copolymers containing in copolymerized form at least one monomer selected from C2-C10 monoolefins, such as Ethylene or propylene, 1, 3-butadiene, 2-chloro-1, 3-butadiene, vinyl alcohol and its C2-Cio-alkyl esters, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates with alcohol components of branched and unbranched C 1 -C 10 -alcohols, vinylaromatics such as, for example, polystyrene, (meth) acrylonitrile, ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, and maleic anhydride;
  • C2-C10 monoolefins such as Ethylene or propylene, 1, 3-butadiene, 2-
  • PC Polycarbonates
  • Polyesters such as polyalkylene terephthalates, polyhydroxyalkanoates (PHA), polybutylene succinates (PBS), polybutylene succinate adipates (PBSA);
  • thermoplastic polyurethanes TPU
  • polysulfones and mixtures thereof. Mention may be made, for example, of polyacrylates having identical or different alcohol radicals from the group of C 4 -C 8 -alcohols, especially butanol, hexanol, octanol and 2-ethylhexanol, polymethyl methacrylate (PMMA), methyl methacrylate-butyl acrylate copolymers, acrylonitrile-butadiene-styrene Copolymers (ABS), ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EPDM), polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-styrene-acrylate (ASA), styrene-butadiene Methyl methacrylate copolymers (SBMMA), styrene-maleic anhydride copolymers, styren
  • the at least one thermoplastic polymer contained in the molding composition according to the invention is preferably polyvinyl chloride (PVC), polyvinyl butyral (PVB), homo- and copolymers of vinyl acetate, homo- and copolymers of styrene, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides.
  • PVC polyvinyl chloride
  • PVB polyvinyl butyral
  • homo- and copolymers of vinyl acetate homo- and copolymers of styrene
  • polyacrylates homo- and copolymers of styrene
  • TPU thermoplastic polyurethanes
  • Another object of the present invention relates to molding compositions comprising at least one elastomer and at least one compound of general formula (I).
  • the elastomer contained in the molding compositions according to the invention preferably comprises at least one natural rubber (NR), at least one synthetic rubber or mixtures thereof.
  • Preferred synthetically produced rubbers are, for example, polyisoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile-butadiene rubber (NBR) or chloroprene rubber (CR).
  • the content (% by weight) of elastomer in the molding compositions is 20 to 99%, preferably 45 to 95%, particularly preferably 50 to 90% and in particular 55 to 85%.
  • At least one plasticizer other than the compounds (I) may be present in the molding composition according to the invention.
  • Suitable plasticizers other than the compounds (I) are those as already defined above.
  • the molding compositions containing at least one elastomer may contain, in addition to the above ingredients, other suitable additives.
  • reinforcing fillers such as carbon black or silica, further fillers, a methylene donor such as hexamethylenetetramine (HMT), a methylene acceptor such as cardanol (cashew nut) modified phenolic resins, a vulcanizing or crosslinking agent, a vulcanizing or crosslinking accelerator , Activators, various types of oil, anti-aging agents and other various additives, which are mixed, for example, in tire and other rubber compounds may be included.
  • the at least one thermoplastic polymer contained in the molding composition according to the invention is polyvinyl chloride (PVC).
  • Polyvinyl chloride is obtained by homopolymerization of vinyl chloride.
  • the polyvinyl chloride (PVC) used in the invention can be prepared, for example, by suspension polymerization, microsuspension polymerization, emulsion polymerization or bulk polymerization.
  • the production of PVC by polymerization of vinyl chloride and the preparation and composition of plasticized PVC are described, for example, in "Becker / Braun, Kunststoff-Handbuch, Volume 2/1: Polyvinyl chloride", 2nd edition, Carl Hanser Verlag, Kunststoff.
  • the K value which characterizes the molar mass of the PVC and is determined according to DIN 53726, is for the PVC softened according to the invention usually between 57 and 90, preferably between 61 and 85, in particular between 64 and 75.
  • the content is PVC of the mixtures at 20 to 99% by weight, preferably at 45 to 95 wt .-%, particularly preferably at 50 to 90 wt .-% and in particular at 55 to 85 wt .-%.
  • At least one plasticizer other than the compounds (I) may be present in the molding composition according to the invention.
  • the proportion of the at least one plasticizer other than compounds (I) in the molding composition according to the invention is from 10 to 90% by weight, preferably from 20 to 85% by weight and more preferably from 50 to 80% by weight, based on the total amount of plasticizer contained in the molding composition.
  • Suitable plasticizers other than the compounds (I) are those as already defined above.
  • the at least one additional plasticizer present in the molding composition according to the invention is particularly preferably selected from dialkyl adipates having 4 to 9 C atoms in the side chain and 2,5-furandicarboxylic acid esters having 4 to 10 C atoms in the side chain, where the ester groups are either the same or may have a different number of carbon atoms.
  • thermoplastic polymer or thermoplastic polymer mixture Depending on which thermoplastic polymer or thermoplastic polymer mixture is contained in the molding composition, different amounts of plasticizer are used.
  • thermoplastic polymer in the molding compositions according to the invention is polyvinyl chloride and if only at least one of the (C 7 -C 12) dialkyl esters of tetrahydrofurandicarboxylic acid according to the invention is used as the plasticizer, the total plasticizer content in the molding compound is 5 to 300 phr, preferably 10 to 100 phr and more preferably 30 to 70 phr.
  • thermoplastic polymer in the molding compositions according to the invention is polyvinyl chloride
  • plasticizer mixtures comprising at least one compound of the general formula (I) and at least one of the compounds fertilizer (I) various plasticizers used
  • the total plasticizer content in the molding composition is 1 to 400 phr, preferably 5 to 130 phr, more preferably 10 to 100 phr and in particular 15 to 85 phr.
  • the polymer in the molding compounds according to the invention is rubbers
  • the total plasticizer content in the molding compound is 1 to 60 phr, preferably 1 to 40 phr, particularly preferably 2 to 30 phr.
  • the molding compositions containing at least one thermoplastic polymer may contain other suitable additives.
  • suitable additives for example, stabilizers, lubricants, fillers, pigments, flame retardants, light stabilizers, blowing agents, polymeric processing aids, impact modifiers, optical brighteners, antistatic agents or biostabilizers may be included.
  • Suitable stabilizers are all customary PVC stabilizers in solid and liquid form, for example customary Ca / Zn, Ba / Zn, Pb or Sn stabilizers and also acid-binding phyllosilicates such as hydrotalcite.
  • the molding compositions according to the invention may have a content of stabilizers of from 0.05 to 7%, preferably from 0.1 to 5%, particularly preferably from 0.2 to 4% and in particular from 0.5 to 3%.
  • Lubricants should act between the PVC pastilles and counteract frictional forces during mixing, plasticizing and shaping.
  • the molding compositions of the invention may contain all the usual for the processing of plastics lubricant.
  • plastics lubricant for example, hydrocarbons, such as oils, paraffins and PE waxes, fatty alcohols having 6 to 20 carbon atoms, ketones, carboxylic acids, such as fatty acids and montanic acid, oxidized PE wax, metal salts of carboxylic acids, carboxylic acid amides and carboxylic acid esters, for example, with the alcohols ethanol, fatty alcohols, glycerol, ethanediol, pentaerythritol and long-chain carboxylic acids as the acid component.
  • the molding compositions according to the invention may have a content of lubricant of from 0.01 to 10%, preferably from 0.05 to 5%, particularly preferably from 0.1 to 3% and in particular from 0.2 to 2%.
  • fillers have a positive influence on the compressive, tensile and flexural strength as well as the hardness and heat resistance of plasticized PVC.
  • the molding compositions may also fillers such as carbon black and other organic fillers such as natural calcium carbonates, for example chalk, limestone and marble, synthetic calcium carbonates, dolomite, silicates, silica, sand, diatomaceous earth, aluminum silicates such as kaolin, mica and Feldspar included. Preference is given to using as fillers, calcium carbonates, chalk, dolomite, kaolin, silicates, talc or carbon black.
  • the molding compositions according to the invention may have a content of fillers of from 0.01 to 80%, preferably from 0.1 to 60%, particularly preferably from 0.5 to 50% and in particular from 1 to 40%.
  • the molding compositions according to the invention may also contain pigments in order to adapt the obtained product to different possible uses.
  • inorganic pigments for example, cadmium pigments such as CdS, cobalt pigments such as C0O / Al2O3, and chromium pigments such as Cr203 can be used.
  • Suitable organic pigments are, for example, monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, dioxazine pigments and aniline pigments.
  • the molding compositions according to the invention may have a content of pigments of from 0.01 to 10%, preferably from 0.05 to 5%, particularly preferably from 0.1 to 3% and in particular from 0.5 to 2%.
  • the molding compositions according to the invention may also contain flame retardants.
  • antimony trioxide, phosphate ester, chloroparaffin, aluminum hydroxide, boron compounds, molybdenum trioxide, ferrocene, calcium carbonate or magnesium carbonate can be used as flame retardants.
  • the molding compositions according to the invention can have a content of flame inhibitors of from 0.01 to 10%, preferably from 0.1 to 8%, particularly preferably from 0.2 to 5% and in particular from 0.5 to 2%.
  • the molding compositions may also contain light stabilizers.
  • hydroxybenzophenones or hydroxyphenylbenzotriazoles can be used.
  • the molding compositions according to the invention may have a content of light stabilizers of from 0.01 to 7%, preferably from 0.1 to 5%, particularly preferably from 0.2 to 4% and in particular from 0.5 to 3%.
  • the compounds according to the invention are advantageously suitable for the preparation of plastisols because of their good gelling properties.
  • Piastisols can be made from a variety of plastics.
  • the plastisols according to the invention are, in a preferred embodiment, a PVC plastisol.
  • the plastisols according to the invention may contain, in addition to at least one plastic and at least one tetrahydrofuran derivative of the general formula (I), optionally at least one plasticizer other than the compounds (I).
  • the proportion of the additional at least one plasticizer other than the compounds (I) in the plastisol is from 10 to 90% by weight, preferably from 20 to 85% by weight and more preferably from 50 to 80% by weight, based on the total amount of plasticizer contained in the plastisol.
  • plasticizer In the case of PVC plastisols which contain exclusively at least one (C 7 -C 12) dialkyl ester of tetrahydrofurandicarboxylic acid according to the invention as plasticizer, the total amount of plasticizer is usually from 5 to 300 phr, preferably from 10 to 100 phr.
  • the total amount of plasticizer is usually from 5 to 400 phr, preferably from 50 to 200 phr.
  • Plastisols are usually made into the form of the final product at ambient temperature by various methods, such as brushing, casting, such as the shell casting or spin casting, dipping, spraying, and the like. Subsequently, the gelation is carried out by heating, after cooling a homogeneous, more or less flexible product is obtained.
  • PVC plastisols are particularly suitable for the production of PVC films, for the production of seamless hollow bodies, gloves and for use in the textile sector, such. B. for textile coatings.
  • the molding composition according to the invention is preferably used for the production of molded articles and films.
  • These include in particular housings of electrical appliances, such as kitchen appliances and computer cases; tools; cameras; Pipelines; Electric wire; Hoses, such as plastic hoses, water and irrigation hoses, industrial rubber hoses or chemical hoses; Wire sheathing; Window profiles; Components for vehicle construction, such as, for example, body components, vibration dampers for engines; Tires; Furniture, such as chairs, tables or shelves; Foam for upholstery and mattresses; Tarpaulins, such as truck tarpaulins or tarpaulins; seals; Composite films, such as films for laminated safety glass, in particular for vehicle and window panes; records; Leatherette; Packaging containers; Adhesive tape or coatings.
  • the molding composition according to the invention is additionally suitable for the production of moldings and films which come into direct contact with humans or foodstuffs.
  • These are mainly medical devices, hygiene products, food packaging, indoor products, toys and childcare articles, sports and leisure products, clothing and fibers for fabrics and the like.
  • the medical products which can be produced from the molding composition according to the invention are, for example, hoses for enteral nutrition and hemodialysis, respiratory hoses, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves or respiratory masks.
  • the food packaging which can be produced from the molding composition according to the invention comprises, for example, cling films, food hoses, drinking water hoses, containers for storage or for freezing. food, cover gaskets, caps, bottle caps or artificial wine corks.
  • the products for the interior area which can be produced from the molding composition according to the invention are, for example, floor coverings which can be constructed homogeneously or from several layers consisting of at least one foamed layer, such as, for example, floor coverings, sports floors or luxury Vinyl Tiles (LVT), imitation leather, wall coverings or foamed or unfoamed wallpapers in buildings or around vehicle trims or console covers.
  • floor coverings which can be constructed homogeneously or from several layers consisting of at least one foamed layer, such as, for example, floor coverings, sports floors or luxury Vinyl Tiles (LVT), imitation leather, wall coverings or foamed or unfoamed wallpapers in buildings or around vehicle trims or console covers.
  • LVT Luxury Vinyl Tiles
  • the toys and child care articles which can be produced from the molding composition according to the invention are, for example, dolls, inflatable toys such as balls, game figures, plasticine, swimming aids, stroller covers, changing mattresses, hot water bottles, teething rings or vials.
  • the sports and leisure products which can be produced from the molding composition according to the invention are, for example, exercise balls, exercise mats, seat cushions, massage balls and rollers, shoes or shoe soles, balls, air mattresses or drinking bottles.
  • the clothing that can be produced from the molding compositions according to the invention are, for example, latex clothing, protective clothing, rain jackets or rubber boots.
  • the present invention includes the use of the compounds of the invention as and / or in adjuvants selected from: calendering auxiliaries; rheological; Surface-active compositions such as flow, film-forming aids, defoamers, foam inhibitors, wetting agents, coalescing agents and emulsifiers; Lubricants, such as lubricating oils, greases and lubricating pastes; Quenchers for chemical reactions; desensitizing agents; pharmaceutical products; Plasticizers in adhesives; Impact modifiers and adjusters.
  • adjuvants selected from: calendering auxiliaries; rheological; Surface-active compositions such as flow, film-forming aids, defoamers, foam inhibitors, wetting agents, coalescing agents and emulsifiers; Lubricants, such as lubricating oils, greases and lubricating pastes; Quenchers for chemical reactions; desensitizing agents; pharmaceutical products; Plasticizers in adhesives; Impact modifiers and adjusters.
  • FIG. 1 is a diagrammatic representation of FIG. 1:
  • FIG. 1 shows in the form of a bar chart the Shore A hardness of soft PVC specimens which cross-hatches the plasticizers 2,5-THFDCS-di (2-propylheptyl) ester and, as a comparison, the commercially available plasticizer Hexamoll® DINCH® (black) in different quantities.
  • the Shore hardness A is plotted against the plasticizer content of the soft PVC specimens (stated in phr). The measured values were always determined after a time of 15 seconds.
  • FIG. 2 shows in the form of a bar chart the Shore A hardness of soft PVC specimens which cross-hatches the plasticizers 2,5-THFDCS-di (2-propylheptyl) ester and, as a comparison, the commercially available plasticizer Hexamoll® DINCH® (black) in different quantities.
  • the Shore hardness A is plotted against the plasticizer content of the soft PVC specimens (stated in phr). The measured values were always determined after a time of 15
  • FIG. 2 shows in the form of a bar chart the Shore hardness D of soft PVC specimens containing the softener 2, 5-THFDCS-di (2-propylheptyl) ester according to the invention (hatched in white) and, as comparison, the commercially available plasticizer Hexamoll® DINCH ® (black) in 50 or 70 phr.
  • the Shore hardness D is plotted against the plasticizer content of the soft PVC specimens (stated in phr). The measured values were always determined after a time of 15 seconds.
  • FIG. 3 shows in the form of a bar chart the Shore hardness D of soft PVC specimens containing the softener 2, 5-THFDCS-di (2-propylheptyl) ester according to the invention (hatched in white) and, as comparison, the commercially available plasticizer Hexamoll® DINCH ® (black) in 50 or 70 phr.
  • the Shore hardness D is plotted against the plasticizer content of the soft PVC specimens (
  • FIG. 3 shows in the form of a bar chart the 100% modulus of soft PVC specimens comprising the plasticizer 2, 5-THFDCS-di (2-propylheptyl) ester according to the invention (hatched in white) and, as comparison, the commercially available plasticizer Hexamoll® DINCH ® (black) in 50 or 70 phr.
  • the 100% modulus is plotted against the plasticizer content of the soft PVC specimens (stated in phr).
  • FIG. 4 shows, in the form of a bar chart, the cold break temperature of flexible PVC films containing the plasticizer 2, 5-THFDCS-di (2-propylheptyl) ester according to the invention and, for comparison, the commercially available plasticizer Hexamoll® DINCH®.
  • the cold break temperature in ° C is plotted for soft PVC films with a plasticizer content of 50 and 70 phr, respectively.
  • FIG. 5 is a diagrammatic representation of FIG. 5
  • FIG. 5 shows in the form of a bar chart the glass transition temperature (T g ) of flexible PVC films containing the plasticizer 2,5-THFDCS-di (2-propylheptyl) according to the invention and, for comparison, the commercially available plasticizer Hexamoll® DINCH®.
  • the glass transition temperature (T g ) in ° C is plotted for plasticized PVC films with a plasticizer content of 50 and 70 phr, respectively.
  • FIG. 6 shows in the form of a bar chart the glass transition temperature (T g ) of flexible PVC films containing the plasticizer 2,5-THFDCS-di (2-propylheptyl) according to the invention and, for comparison, the commercially available plasticizer Hexamoll® DINCH®.
  • T g glass transition temperature in ° C
  • FIG. 6 shows, in the form of a bar graph, the tear resistance of flexible PVC films comprising the plasticizer 2, 5-THFDCS-di (2-propylheptyl) ester according to the invention and, for comparison, the commercially available plasticizer Hexamoll®
  • the tensile strength in MPa is plotted for soft PVC films with a plasticizer content of 50 and 70 phr, respectively.
  • Figure 7 shows in the form of a bar graph, the elongation at break of flexible PVC films containing the plasticizer 2, 5-THFDCS di (2-propylheptyl) - ester according to the invention and as a comparison the commercially available plasticizer Hexamoll®
  • FIG. 8 is a diagrammatic representation of FIG. 8
  • FIG. 8 shows the gelling behavior of PVC plastisols containing the plasticizer 2,5-THFDCS-di (2-propylheptyl) according to the invention and, for comparison, the commercially available plasticizer Hexamoll® DINCH®. Shown is the viscosity of the plastisols as a function of temperature.
  • reaction mixture was cooled to room temperature, filtered, and the titanium (IV) alkoxide was hydrolyzed by the addition of 100 mL of water.
  • the biphasic mixture was transferred to a separatory funnel, the aqueous phase removed and the organic phase washed once with brine. Subsequently, the solvent and other volatile components under reduced Removed pressure by distillation.
  • the crude product was purified by fractional distillation to afford di (2-propylheptyl) -2,5-tetrahydrofurandicarboxylate as a clear, colorless liquid in 58% yield and 98.5% purity.
  • the identity and purity of the final product was determined by NMR and GC-MS analysis (GC separation column: Agilent J & W DB-5, 30 mx 0.32 mm x 1, 0 ⁇ ).
  • the reaction mixture was cooled to room temperature, transferred to a separatory funnel and washed twice with saturated NaHCO 3 solution.
  • the organic phase was washed with brine, dried with anhydrous Na 2 SO 4 and the solvent removed under reduced pressure.
  • the crude product was purified by fractional distillation.
  • the desired di- (2-propylheptyl) -2,5-furandicarboxylat could be obtained in a yield of 58% and a purity of 97.8%.
  • the final hydrogen pressure was increased to 200 bar and the autoclave was heated to 180.degree. The course of the reaction was followed by GC analysis. After complete conversion (usually after 40 to 60 hours), the autoclave was vented and the contents filtered off to remove the solid catalyst. The solvent present in the filtrate was then removed by distillation under reduced pressure, the remaining crude product diluted in 300 ml_ MTBE and transferred to a separating funnel. The organic phase was washed twice with saturated NaHCO 3 solution and once with saturated brine. Subsequently, the solvent and other volatile components were removed by distillation under reduced pressure.
  • di- (2-ethylhexyl) -2,5-tetrahydrofurandicarboxylate was carried out analogously to Example 2 (steps b1 and c1). After purification by distillation, di- (2-ethylhexyl) -2,5-tetrahydrofurandicarboxylate was obtained as a colorless to slightly brown liquid in a yield of 31% and a purity of 99.5%. The identity and purity of the final product was determined by NMR and GC-MS analysis (GC separation column: Agilent J & W DB-5, 30 m x 0.32 mm x 1, 0 ⁇ ).
  • reaction mixture was stirred for one hour at room temperature and for 4 hours at 60 ° C. The mixture was then cooled to room temperature and stirred overnight. The course of the reaction was monitored by GC analysis. After completion of the reaction, the reaction mixture was transferred to a separatory funnel and washed with 100 ml of water. The aqueous phase was extracted three times with 150 ml of ethyl acetate. The combined organic phases were washed with saturated brine and over
  • the ingredients were mixed with a hand blender at room temperature. The mixture was then plasticized on a steam-heated laboratory blender from Collin (type "150") and processed into a rolled coat. The speeds were 15 rpm (front roller) and 12 rpm (rear roller) with a rolling time of 5 minutes. This gave a rolled skin with a thickness of 0.55 mm. The cooled rolled skin was then pressed under a pressure of 220 bar in 400 seconds on a press of the type "400P" from Colin to a soft PVC film with the thickness of 0.50 mm.
  • V2 2,5-FDCS-di (2-propylheptyl) ester 70 170 180
  • the dissolution temperatures of the plasticizers according to the invention are di (n-octyl) -2,5-tetrahydrofurandicarboxylate, di (2-ethylhexyl) -2,5-tetrahydrofuran-dicarboxylate and di (2-propylheptyl) -2,5-tetrahydrofurandicarboxylate and as a comparison of Hexamoll® DINCH® (V1) and the corresponding diester of furandicarboxylic acid (V2 to V4) or phthalic acid (V5 to V7).
  • the plasticizers according to the invention show lower dissolution temperatures than Hexamoll® DINCH® (V1). In addition, their dissolution temperatures are also lowered compared to the corresponding diesters of furandicarboxylic acid (V2 to V4) or the corresponding diesters of phthalic acid (V5 to V7).
  • Example 1 di (2-propylheptyl) -2,5-tetrahydrofurandicarboxylate (Example 1) are given in the table below in comparison with the plasticizer Hexamoll® DINCH® (Comparative Example C1) used on the market.
  • Plasticizer Di (2-propylheptyl) - Hexamoll®
  • the 2,5-THFDCS dibutyl ester according to the invention has a slightly better softening effect than the commercially available plasticizer Hexamoll® DINCH®. lll.d) Determination of the 100% modulus:
  • the 100% modulus in addition to the Shore hardness, is another property that enhances the softening effect of plasticizers, i. H. the plasticizer efficiency, characterized.
  • the 100% modulus was determined in accordance with DIN EN ISO 527 Parts 1 and 3 with a test device from Zwick Type TMZ 2.5 / TH1 S.
  • the test specimens with the dimensions 150 mm ⁇ 10 mm ⁇ 0.5 mm (length ⁇ width x thickness) correspond to Type 2 according to DIN EN ISO 527 Part 3 and are punched out of the rolling / press foils by means of a punching iron.
  • the specimens are conditioned for 7 days. The conditioning and the tensile tests are carried out at 23 ° C +/- 1, 0 ° C and 50% +/- 5% relative humidity according to DIN EN ISO 291.
  • the values plotted in FIG. 3 in each case represent mean values from the test of 10 individual tests Specimens represent.
  • the 2,5-THFDCS-di (2-propylheptyl) ester according to the invention has a better softening effect than the commercially available plasticizer Hexamoll® DINCH®.
  • lll.e Determination of cold flexibility: To determine the cold flexibility PVC films were used, which contained the respective plasticizer to be tested in different concentrations. Two methods were used. On the one hand the determination of the cold break temperature based on the outdated standard DIN 53372, on the other hand the glass transition temperature T g of the films was determined by DMA (dynamic mechanical analysis) according to ISO 6721 -7 from the maximum of the loss modulus "G" Results of the two test methods are shown in FIGS. 4 and 5.
  • the PVC films containing the 2,5-THFDCS-di (2-propylheptyl) ester according to the invention contain a somewhat increased cold break temperature compared to PVC films with Hexamoll® DINCH®. The same applies to the glass transition temperature.
  • the tear strength and the elongation at break were determined according to DIN EN ISO 527 Parts 1 and 3 with a test device from Zwick Type TMZ 2.5 / TH1 S.
  • the specimens used with the dimensions 150 mm x 10 mm x 0.5 mm (length x Width x thickness) correspond to Type 2 according to DIN EN ISO 527 Part 3 and were conditioned for 7 days before the test.
  • the conditioning and tensile tests are carried out at 23 ° C +/- 1, 0 ° C and 50% +/- 5% relative humidity according to DIN EN ISO 291.
  • the values plotted in FIGS. 6 and 7 each represent average values from the testing of 10 individual test specimens.
  • PVC plastisols were prepared using the plasticizers 2,5-THFDCS- di (2-propylheptyl) ester and the commercially available Hexamoll® DINCH® according to the following recipe:
  • Reagent SLX 781 8 > 2 commercially available PVC from Solvin GmbH & Co. KG, produced by suspension polymerization (K value according to ISO 1628-2: 73)
  • the necessary energy must be supplied in the form of heat.
  • the parameters temperature and dwell time are available for this purpose.
  • the faster the gelation proceeds (indication here is the dissolving temperature, ie the lower it is, the faster the material gels), the lower the temperature (with the same residence time) or the residence time (at the same temperature) can be selected.
  • the investigation of the gelling behavior of a plastisol is carried out by internal method with a rheometer MCR101 Anton Paar. Here, the viscosity of the paste is measured under heating at constant shear (rotation). The measurement is carried out with a plate / plate system (PP50) starting at 30 ° C at a shear rate of 10 1 / s and a heating rate of 5 ° C / minute.
  • the viscosity of a plastisol initially decreases with increasing temperature and reaches a minimum. Subsequently, the viscosity increases again.
  • the temperature at the minimum of the curve and the steepness of the increase after the minimum indicate the gelling behavior, i. H. the lower the temperature at the minimum and the steeper the subsequent increase, the better or faster the gelation takes place.

Abstract

La présente invention concerne des dérivés de tétrahydrofurane, une composition de plastifiants qui contient ces dérivés de tétrahydrofurane, des matières à mouler qui contiennent un polymère thermoplastique et un dérivé de tétrahydrofurane de ce type, un procédé de préparation de ces dérivés de tétrahydrofurane et leur utilisation.
EP14758566.5A 2013-09-04 2014-09-03 Dérivés de tétrahydrofurane et leur utilisation comme plastifiants Withdrawn EP3041829A1 (fr)

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EP13182979 2013-09-04
PCT/EP2014/068687 WO2015032794A1 (fr) 2013-09-04 2014-09-03 Dérivés de tétrahydrofurane et leur utilisation comme plastifiants
EP14758566.5A EP3041829A1 (fr) 2013-09-04 2014-09-03 Dérivés de tétrahydrofurane et leur utilisation comme plastifiants

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CN (1) CN105517997A (fr)
CA (1) CA2923059A1 (fr)
MX (1) MX2016002835A (fr)
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EP3107517B1 (fr) * 2014-02-20 2019-02-20 Fresenius Kabi Deutschland GmbH Contenants médicaux et constituants de système à ramollissants autres qu'en dehp servant à contenir des produits de globules rouges, du plasma et des plaquettes
KR20170067813A (ko) * 2014-10-07 2017-06-16 바스프 에스이 2,5-디(히드록시메틸)테트라히드로푸란의 장쇄 모노 및 디-에스테르, 그 용도 및 제조
EP3325457B1 (fr) 2015-07-22 2020-01-01 Basf Se Procédé de préparation d'acide furanne-2,5-dicarboxylique
WO2017091437A1 (fr) * 2015-11-24 2017-06-01 Archer Daniels Midland Company Catalyseurs d'organotine dans des procédés d'estérification d'acide furane -2,5-dicarboxylique (fdca)
CN106079723B (zh) * 2016-06-24 2018-08-31 浙江大学宁波理工学院 阻燃改性苎麻织物/苯并噁嗪树脂层压板及其制备方法
WO2018060241A1 (fr) * 2016-09-29 2018-04-05 Sulzer Chemtech Ag Procédé de préparation d'un polymère de polyester et polymère de polyester pouvant être obtenu par ce procédé
US10392489B2 (en) * 2017-07-31 2019-08-27 Inteplast Group Corporation Method of making a low density cellular PVC boards with sealed edges
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MX2020012575A (es) 2018-05-23 2021-01-29 Basf Se Un lubricante que comprende dialcanoatos de 2,5-(bishidroximetil)t etrahidrofurano.
CN111349492B (zh) * 2020-02-28 2021-05-25 浙江糖能科技有限公司 2,5-四氢呋喃二甲醇脂肪酸二酯在柴油添加剂的应用
CN113842902B (zh) * 2020-06-28 2023-10-10 中国石油化工股份有限公司 一种氧化催化材料及其制备方法
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RU2016112345A (ru) 2017-10-09
CA2923059A1 (fr) 2015-03-12
MX2016002835A (es) 2016-06-17
KR20160048943A (ko) 2016-05-04

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