WO2024256670A1 - Composition de plastifiant - Google Patents

Composition de plastifiant Download PDF

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Publication number
WO2024256670A1
WO2024256670A1 PCT/EP2024/066631 EP2024066631W WO2024256670A1 WO 2024256670 A1 WO2024256670 A1 WO 2024256670A1 EP 2024066631 W EP2024066631 W EP 2024066631W WO 2024256670 A1 WO2024256670 A1 WO 2024256670A1
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WIPO (PCT)
Prior art keywords
esters
plasticizer
acid
mixtures
plastisol
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German (de)
English (en)
Inventor
Axel Grimm
Sina Witzel
Herbert Morgenstern
Matthias Pfeiffer
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BASF SE
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BASF SE
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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

Definitions

  • the present invention relates to a plasticizer composition containing certain dicarboxylic acid diesters and diesters selected from 1,2-cyclohexanedicarboxylic acid esters and terephthalic acid esters, their use as plasticizers for polymers, and a molding compound or a plastisol containing the plasticizer composition.
  • Plasticizers are incorporated into polymers or elastomers to increase their flexibility or processability. Plasticizers are most commonly used in the manufacture of "plasticized” or flexible polyvinyl chloride (PVC) products. Plasticizers can be characterized by their chemical structure. The most important chemical class of plasticizers are the esters of aliphatic or aromatic polycarboxylic acids. Among the most commonly used aliphatic dicarboxylic acids is, for example, adipic acid, which is used as a plasticizer for polymers, e.g. for thermoplastics, after esterification with alcohol components to form adipic acid esters (adipates).
  • adipic acid which is used as a plasticizer for polymers, e.g. for thermoplastics, after esterification with alcohol components to form adipic acid esters (adipates).
  • the plasticizers have a high compatibility with the plasticized plastic, i.e. that they do not leak out of the plasticized plastic or only leak out relatively slowly, and/or are largely harmless from a toxicological point of view.
  • plasticizers are also commonly used in other plastics.
  • Such other plastics can be, for example, polyvinyl butyral (PVB), homo- or copolymers of styrene, polyacrylates, polysulfides, polylactic acid (PLA) or thermoplastic polyurethanes (TPU).
  • PVB polyvinyl butyral
  • PLA polylactic acid
  • TPU thermoplastic polyurethanes
  • the prior art discloses various plasticizers for plastics, for example for PVC.
  • a plasticizer with a low gelling temperature available as a fast geller it is desirable, among other things, to have a plasticizer with a low gelling temperature available as a fast geller.
  • a high storage stability of the plastisol is also desired, i.e. the non-gelled plastisol should show no or only a slight increase in viscosity over time at ambient temperature.
  • rapid gelling agents often have a compatibility with the polymers they contain that needs to be improved. They also usually exhibit high volatility both during processing and during use of the end products. In addition, the addition of rapid gelling agents often has a detrimental effect on the mechanical properties of the end products.
  • plasticizers e.g. at least one plasticizer which imparts good thermoplastic properties but gels less well, in combination with at least one rapid gelling agent.
  • these properties are not achieved with just any combination of a plasticizer with a rapid gelling agent.
  • EP 1 354 867 B1 discloses mixtures of isononyl benzoates in combination with alkyl phthalates and/or dialkyl adipic esters and/or alkyl cyclohexanedicarboxylates, which can be used as plasticizers for PVC.
  • Moshkin in: Voprosy Ispol'zovan. Pentozansoderzhashchego Syr'ya, Trudy Vsesoyuz. Soveshchaniya, Riga 1958, 225-254 describes the synthesis of 4-oxopimelic acid ester from furfuryl alcohol. The use of di-2-ethylhexyl ester in PVC is described.
  • the known plasticizers are subject to constant need for optimization, e.g. with regard to their volatility, cold fracture temperature, compatibility and/or toxicological safety.
  • the present invention was therefore based on the object of providing plasticizers for plastics, for example for PVC, which give the plastics plasticized with them good mechanical properties.
  • the plasticizer composition should also have good gelling properties and a high level of compatibility with the plastics to be plasticized, show low volatility during use of the end products and be toxicologically harmless.
  • a plasticizer composition containing a) at least one compound of the general formula (I) where R1 and R2 are independently selected from Cs-Cs-cycloalkyl which is unsubstituted or carries one or more Ci-Cio-alkyl substituents, and n1 and n2 independently represent 1, 2 or 3; and b) at least one compound of the general formula (II) where R 3 and R 4 are independently selected from branched or unbranched C4-Ci2-alkyl, and Y is selected from (Ya) and (Yb)
  • phr parts per hundred resin
  • a mixture is any mixture of two or more components, for example a mixture can contain two to five or more components. A mixture can also contain any number of components.
  • n1 and n2 are 1.
  • the compounds of the general formula (I) are diesters of 4-oxoheptanedioic acid.
  • R1 and R2 are independently selected from Cs-Cs-cycloalkyl which is unsubstituted or carries one or more Ci-Cw-alkyl substituents.
  • Substituted Cs-Cs-cycloalkyl can, depending on the ring size, carry one or more Ci-Cw-alkyl substituents, e.g. 1, 2, 3, 4, 5 or 6 Ci-Cw-alkyl substituents, preferably 1 or 2 Ci-Cw-alkyl substituents.
  • Ci-Cw-alkyl substituents are each independently selected from straight-chain and branched Ci-Cio-alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the structural isomers thereof.
  • Ri and R2 are independently selected from cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2,5-dimethylcyclopentyl, cyclohexyl,
  • R1 and R2 are independently selected from cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Ri and R2 in a compound of general formula (I) are generally independent of each other, Ri and R2 are preferably the same.
  • a compound of general formula (I) can be:
  • the plasticizer composition may also contain a mixture of compounds of general formula (I), for example a mixture of compounds of general formula (I) selected from 1.1, 1.2, I.3, and I.4.
  • the plasticizer composition according to the invention comprises, in addition to a compound of the general formula (I) or a mixture of compounds of the general formula (I), at least one compound of the general formula (II) where R 3 and R 4 are independently selected from branched or unbranched C4-Ci2-alkyl, and Y is selected from (Ya) and (Yb) where # indicates attachment points, that is, the positions to which -COOR 3 and -COOR 4 are attached.
  • C4-Ci2-alkyl in compounds of the general formula (II) includes unbranched or branched alkyl groups having 4 to 12 carbon atoms. These include, for example, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, 1-ethyl-2-methylpropyl, n-octyl, isooc
  • R 3 and R 4 in compounds of the general formula (II) are independently selected from branched or unbranched C 7 -C 12 -alkyl, such as 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, issoundecyl, n-dodecyl, isododecyl, and the structural isomers thereof.
  • R 3 and R 4 in compounds of the general formula (II) are independently selected from branched or unbranched C s -C n -alkyl, such as n-octyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2-propylheptyl, n-undecyl, isundecyl, and the structural isomers thereof.
  • R3 and R4 in a compound of general formula (II) are generally independent of each other, R3 and R4 are preferably the same.
  • R3 and R4 both represent 2-ethylhexyl or both represent isononyl.
  • the plasticizer composition may also contain a mixture of compounds of the general formula (II).
  • iso-alkyl refers to both a branched alkyl radical as well as a mixture of a branched alkyl radical with at least one constitutionally isomeric alkyl radical with an identical carbon number.
  • R 3 and R 4 can be selected independently of one another from branched and unbranched C 2 -C 12 -alkyl.
  • R 3 and R 4 are identical.
  • R 3 and R 4 are identical and both represent isononyl.
  • a particularly preferred compound of the general formula (II. a) is di-(isononyl)-1,2-cyclohexanedicarboxylate.
  • R 3 and R 4 can preferably be selected independently of one another from branched and unbranched C 2 -C 12 -alkyl, preferably from 2-ethylhexyl, isononyl and 2-propylheptyl.
  • R 5 and R 4 are identical.
  • R 3 and R 4 are identical and both represent 2-ethylhexyl.
  • a particularly preferred compound of the general formula (II.b) is di-(2-ethylhexyl) terephthalate.
  • the plasticizer composition contains the at least one compound of the general formula (I) in an amount of 5 to 60 wt.%, preferably 7 to 40 wt.%, more preferably 9 to 30 wt.%, based on the total mass of the compounds of the general formula (I) and (II).
  • plasticizer composition as a plasticizer for polymers
  • the plasticizer composition is used as a plasticizer for polymers, preferably for thermoplastics and elastomers, more preferably in a molding compound or a plastisol.
  • the plasticizer properties can be tailored to the corresponding intended use. For use in special areas of application, it may be helpful to add at least one additional plasticizer other than the compounds (I) and (II) to the plasticizer composition according to the invention. For this reason, the plasticizer composition according to the invention may optionally contain at least one additional plasticizer other than the compounds (I) and (II).
  • the additional plasticizer can be selected from:
  • Phthalic acid dialkyl esters e.g. with 9 to 13 C atoms in the alkyl chains
  • Dibenzoic acid esters e.g. dibenzoic acid esters of glycols
  • Citric acid diesters and citric acid triesters e.g. acylated citric acid triesters
  • a dialkyl phthalate can have 9 to 13 C atoms in the alkyl chains.
  • the alkyl chains can independently have a different number of C atoms.
  • a dialkyl phthalate can, for example, be di-isononyl phthalate.
  • a trimellitic acid trialkyl ester can have 4 to 13 C atoms in the alkyl chains.
  • the alkyl chains of the trimellitic acid trialkyl ester can independently have a different number of C atoms.
  • An alkyl benzoate can have 9 to 13 C atoms in the alkyl chain.
  • An alkyl benzoate can be, for example, isodecyl benzoate or 2-propylheptyl benzoate.
  • a dibenzoic acid ester can be, for example, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, or dibutylene glycol dibenzoate.
  • a saturated monocarboxylic acid ester can be, for example, an ester of acetic acid, an ester of butyric acid, an ester of valeric acid, or an ester of lactic acid.
  • a saturated monocarboxylic acid ester can also be an ester of a monocarboxylic acid with a polyhydric alcohol.
  • valeric acid can be esterified with pentaerythritol.
  • An unsaturated monocarboxylic acid ester can, for example, be an ester of acrylic acid.
  • An unsaturated dicarboxylic acid diester can, for example, be an ester of maleic acid.
  • An alkylsulfonic acid ester can have 8 to 22 C atoms in the alkyl chain.
  • An alkylsulfonic acid ester can, for example, be a phenyl or cresyl ester of pentadecylsulfonic acid.
  • An isosorbide ester is usually an isosorbide diester esterified with Cs to C carboxylic acids.
  • An isosorbide diester can have different or identical Cs to C alkyl chains.
  • a phosphoric acid ester can be tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecy idiphenyl phosphate, or bis-2(2-ethyl hexyl)phenyl phosphate, 2-ethyl hexyldiphenyl phosphate.
  • the OH group can be present in free or carboxylated form, for example acetylated form.
  • the alkyl chains of the citric acid triester or the acetylated citric acid triester independently comprise 4 to 8 C atoms.
  • An alkylpyrrolidone derivative can have 4 to 18 C atoms in the alkyl chain.
  • a 2,5-furandicarboxylic acid dialkyl ester can have 5 to 13 C atoms in the alkyl chains.
  • the alkyl chains of the 2,5-furandicarboxylic acid dialkyl ester can independently have a different number of C atoms.
  • a 2,5-tetrahydrofurandicarboxylic acid dialkyl ester can have 5 to 13 C atoms in the alkyl chains.
  • the alkyl chains of the 2,5-tetrahydrofurandicarboxylic acid dialkyl ester can independently have a different number of C atoms.
  • a cyclohexane-1,2-dicarboxylic acid dialkyl ester usually has 4 to 13 C atoms in the alkyl chains.
  • the alkyl chains of the cyclohexane-1,2-dicarboxylic acid dialkyl ester can independently have a different number of C atoms.
  • a cyclohexane-1,2-dicarboxylic acid dialkyl ester can contain di-(2-ethylhexyl)-1,2- cyclohexanoic acid dicarboxylate, di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate or di-(2-propylheptyl)-1,2-dicarboxylic acid dicarboxylate.
  • a cyclohexane-1,3-dicarboxylic acid dialkyl ester can have 4 to 13 C atoms in the alkyl chains.
  • the alkyl chains of the cyclohexane-1,3-dicarboxylic acid dialkyl ester can independently have a different number of C atoms.
  • a cyclohexane-1,4-dicarboxylic acid dialkyl ester can have 4 to 13 C atoms in the alkyl chains.
  • the alkyl chains of the cyclohexane-1,4-dicarboxylic acid dialkyl ester can independently of one another have a different number of C atoms.
  • a cyclohexane-1,4-dicarboxylic acid dialkyl ester can, for example, be di-(2-ethylhexyl)-cyclohexane-1,4-dicarboxylate, di-(isononyl)-1,4-cyclohexanoic acid dicarboxylate or di-(2-propylhepty l)-1,4-dicarboxylic acid dicarboxylate.
  • a polyester with aromatic or aliphatic polycarboxylic acids can be a polyester based on adipic acid with polyhydric alcohols, such as dialkylene glycol polyadipates with 2 to 6 C atoms in the alkylene unit. Examples can be polyester adipates, polyglycol adipates and polyester phthalates.
  • plasticizer composition (hereinafter also referred to as "plasticizer”) is expediently used as a plasticizer for a polymer or a mixture of polymers.
  • a polymer is a plastic.
  • a polymer can be a thermoplastic or an elastomer.
  • thermoplastic can usually be processed thermoplastically.
  • An elastomer can be, for example, a rubber.
  • a rubber can be a natural rubber or a synthetic rubber.
  • Synthetic rubber can be, for example, polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber, and mixtures thereof.
  • the plasticizer can therefore be used as a plasticizer for a thermoplastic or a mixture of thermoplastics.
  • the plasticizer can also be used as a plasticizer for an elastomer or a mixture of elastomers.
  • the plasticizer can also be used as a plasticizer for a mixture containing at least one elastomer and at least one thermoplastic.
  • the plasticizer is used as a plasticizer for polyvinyl chloride, a polyvinyl chloride copolymer, a mixture of polymers containing polyvinyl chloride, or a plastisol preferably containing polyvinyl chloride.
  • thermoplastic can be, for example:
  • - TP.1 a homo- or copolymer which contains, in polymerized form, at least one monomer selected from C2 to Cw monoolefins, for example ethylene, propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohols or their C2 to Cw alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates or methacrylates with alcohol components of branched or unbranched Ci to Cw alcohols, vinyl aromatics such as styrene, (meth)acrylonitrile, ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acids and maleic anhydride.
  • C2 to Cw monoolefins for example ethylene, propylene, 1,3-butadiene, 2-chloro
  • - TP.14 a polyacrylate with identical or different alcohol residues from the group of C4 to Cs-
  • Alcohols such as butanol, hexanol, octanol, 2-ethylhexanol
  • - TP.26 a polyoxymethylene - TP.27: a polyvinyl alcohol
  • polyvinyl chloride is obtained by homopolymerization of vinyl chloride.
  • Polyvinyl chloride can be produced, for example, by suspension polymerization, such as microsuspension polymerization, or bulk polymerization.
  • suspension polymerization such as microsuspension polymerization, or bulk polymerization.
  • the production of polyvinyl chloride by polymerization of vinyl chloride as well as the production and composition of plasticized polyvinyl chloride are described, for example, in "Becker/Braun, Kunststoff-Handbuch, Band 2/1 : Polyvinyl chloride", 2nd edition, Carl Hanser Verlag, Kunststoff.
  • the K value characterizing the molar mass of the polyvinyl chloride is determined according to DIN-EN 1628-2 (Nov 1999) and for the polyvinyl chloride plasticized with the plasticizer is usually in the range of 57 to 90, preferably 61 to 85, particularly preferably 64 to 80.
  • the plasticizer in question is advantageously characterized by a high level of compatibility with the plastic to be plasticized.
  • the plasticizer in question can have a positive effect on the gelling behavior of the plasticized plastics.
  • the plasticizer in question can be characterized by low volatility, both during processing and during use of the end products.
  • the plasticizer can also have a beneficial effect on the mechanical properties of the plastics plasticized with it.
  • a measure of good gelling properties can be a low dissolving temperature/gelling temperature.
  • the compatibility (permanence) of plasticizers in plasticized plastics characterizes the extent to which plasticizers tend to exude during use of the plasticized plastics and thus impair the performance properties of the plastics.
  • Low volatility during processing can, for example, be reflected by low process volatility.
  • low volatility during use of the final product can be reflected by low film volatility.
  • Another object of the present invention is a molding compound or a plastisol, wherein the molding compound or the plastisol contains the plasticizer composition as described above and at least one polymer.
  • the plasticizer can therefore be used as a plasticizer in a molding compound or a plastisol.
  • molding compound refers to unformed or preformed materials that are processed into semi-finished or finished parts by means of mechanical force and elevated temperatures through non-cutting shaping.
  • a plastisol is a suspension of finely powdered polymer in liquid plasticizer, whereby the dissolution rate of the polymer in the liquid plasticizer is very low at room temperature.
  • a largely homogeneous phase forms between the polymer and the plasticizer.
  • the individual isolated plastic aggregates swell and combine (gel) to form a three-dimensional, highly viscous gel. This process is usually referred to as gelling and takes place above a certain minimum temperature. This minimum temperature is generally referred to as the gelling or dissolving temperature.
  • the heat required for this can be introduced using the parameters temperature and/or residence time.
  • An indication of the speed of gelling is the dissolution temperature, i.e. the lower this is, the faster the plastisol gels.
  • the molding compound or plastisol may also contain a mixture of polymers.
  • the polymer is selected from a thermoplastic, an elastomer, and mixtures thereof.
  • the molding compound or plastisol containing the plasticizer usually contains at least one thermoplastic.
  • the molding compound or plastisol can also contain a mixture of thermoplastics.
  • thermoplastic is selected from:
  • - homo- or copolymers which contain at least one monomer in polymerized form, selected from C2-Cio-monoolefins such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohols and their C2-Cio-alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of Ci-Cw-alcohols, vinyl aromatics such as styrene, acrylonitrile, methacrylonitrile, ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acids and maleic anhydride,
  • C2-Cio-monolefins such as ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butad
  • the molding compound or plastisol can, for example, have the composition shown in Table 1.
  • thermoplastic properties of the molding compound is generally a routine task for the person skilled in the art.
  • the amount of plasticizer in the molding compound is generally 0.5 to 300 phr. It may be preferred that the amount of plasticizer in the molding compound is 1.0 to 130 phr. It may be more preferred that the amount of plasticizer in the molding compound is 2.0 to 100 phr.
  • the amount of plasticizer contained in the molding compound can be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95 phr.
  • the amount of plasticizer in the molding compound is typically 5 to 300 phr. It may be preferred that the amount of plasticizer in the molding compound is 15 to 200 phr. It may be more preferred that the amount of plasticizer in the molding compound is 30 to 150 phr.
  • the amount of plasticizer included in the molding compound may be, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, or 145 phr.
  • the molding compound contains 20 to 90% by weight, preferably 40 to 90% by weight, more preferably 45 to 85% by weight of polyvinyl chloride.
  • the molding compound can contain 50, 55, 60, 65, 70, 75 or 80% by weight of polyvinyl chloride.
  • the plasticizer may need to be included in the plastisol to achieve the desired plastisol properties.
  • the adjustment of the desired plastisol properties is generally a matter of routine practice for the skilled person.
  • the proportion of plasticizer in the plastisol is usually 30 to 400 phr, preferably 50 to 200 phr.
  • the content of plasticizer in a plastisol containing polyvinyl chloride is usually at least 10 phr, preferably at least 15 phr and more preferably at least 20 phr.
  • the molding compound containing at least one thermoplastic and the plasticizer or the plastisol containing at least one thermoplastic and the plasticizer may additionally contain at least contain an additive.
  • the additive can be selected from stabilizers, lubricants, fillers, colorants, flame retardants, light stabilizers, blowing agents, polymer processing agents, impact modifiers, optical brighteners, antistatic agents, biostabilizers, and mixtures thereof.
  • the additives described below do not represent a limitation of the molding compound or plastisol, but merely serve to explain the molding compound or plastisol.
  • Stabilizers can be the usual polyvinyl chloride stabilizers in solid and liquid form, such as Ca/Zn, Ba/Zn, Pb, Sn stabilizers, acid-binding layered silicates, carbonates such as hydrotalcite or mixtures thereof.
  • the molding compound or plastisol may have a stabilizer content of 0.05 to 7 wt.%, preferably 0.1 to 5 wt.%, more preferably 0.5 to 3 wt.%, based on the total weight of the molding compound or plastisol.
  • Lubricants are generally used to reduce the adhesion between the molding compound or plastisol and surfaces and are intended, for example, to reduce the frictional forces during mixing, plasticizing or deforming.
  • Common lubricants used in plastics processing can be used as lubricants in the molding compound or in the plastisol.
  • Common lubricants in plastics processing include hydrocarbons such as oils, paraffins, PE waxes or mixtures thereof, fatty alcohols with 6 to 20 carbon atoms, ketones, carboxylic acids such as fatty acids, montanic acids or mixtures thereof, oxidized PE waxes, metal salts of carboxylic acids, carboxylic acid amides, carboxylic acid esters which result from the esterification of alcohols such as ethanol, fatty alcohols, glycerin, ethanediol or pentaerythritol with long-chain carboxylic acids.
  • the molding compound or plastisol may have a lubricant content of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, more preferably 0.2 to 2 wt.%, based on the total weight of the molding compound or plastisol.
  • Fillers are generally used to positively influence the compressive, tensile and/or flexural strength, the hardness and/or the heat resistance of the molding compound or plastisol.
  • carbon black and/or inorganic fillers can be contained in the molding compound or in the plastisol as fillers.
  • Inorganic fillers can be selected from natural calcium carbonates such as chalk, limestone, marble, synthetic calcium carbonates, dolomite, silicates, silicic acids, sand, diatomaceous earths, aluminum silicates such as kaolin, mica, feldspar, or mixtures of two or more of the aforementioned fillers.
  • the molding compound or plastisol can have a filler content of 0.01 to 80 wt.%, preferably 0.01 to 60 wt.%, more preferably 1 to 40 wt.%, based on the total weight of the molding compound or plastisol.
  • the molding compound or plastisol can have a filler content of 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 27, 30, 33, 36 or 39 wt.%.
  • Colorants can be used to adapt the molding compound or plastisol to different applications.
  • Colorants can be pigments or dyes, for example.
  • Pigments that can be contained in the molding compound or in the plastisol include, for example, inorganic and/or organic pigments.
  • Inorganic pigments can be cobalt pigments such as COO/AI2O3 and/or chromium pigments such as Cr2Ü3.
  • Organic pigments can be monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments and/or dioxazine pigments.
  • the molding compound or plastisol may have a colorant content of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, more preferably 0.1 to 3 wt.%, based on the total weight of the molding compound or plastisol.
  • Flame inhibitors can be used to reduce the flammability of the molding compound or plastisol and to reduce the formation of smoke during combustion.
  • Flame retardants that may be contained in the molding compound or plastisol may be, for example, antimony trioxide, chlorinated paraffin, phosphate esters, aluminum hydroxide and/or boron compounds.
  • the molding compound or plastisol may have a flame inhibitor content of 0.01 to 10 wt.%, preferably 0.2 to 5 wt.%, more preferably 0.5 to 2 wt.%, based on the total weight of the molding compound or plastisol.
  • Light stabilizers such as UV absorbers, can be used to protect the molding compound or plastisol from damage caused by the influence of light.
  • Light stabilizers can be, for example, hydroxybenzophenones, hydroxyphenylbenzotriazoles, cyanoacrylates, hindered amine light stabilizers such as derivatives of 2,2,6,6-tetramethylpiperidine or mixtures of the aforementioned compounds.
  • the molding compound or plastisol may have a light stabilizer content of 0.01 to 7 wt.%, preferably 0.02 to 4 wt.%, more preferably 0.05 to 3 wt.%, based on the total weight of the molding compound or plastisol.
  • Additives Molding compound with elastomers may have a light stabilizer content of 0.01 to 7 wt.%, preferably 0.02 to 4 wt.%, more preferably 0.05 to 3 wt.%, based on the total weight of the molding compound or plastisol.
  • the molding compound can contain the plasticizer and at least one elastomer.
  • the molding compound can also contain the plasticizer and a mixture of elastomers.
  • an elastomer can be, for example, a rubber.
  • a rubber can be a natural rubber or a synthetic rubber.
  • Synthetic rubber can be, for example, polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber, and mixtures thereof.
  • the molding compound contains at least natural rubber and/or at least one synthetic rubber, whereby the rubber or rubber mixture contained therein can be vulcanized with sulfur.
  • the molding compound usually contains at least one elastomer in a proportion of 20 to 95% by weight based on the total weight of the molding compound. It may be preferred that the molding compound contains at least one elastomer in a proportion of 45 to 90% by weight. It may also be preferred that the molding compound contains at least one elastomer in a proportion of 50 to 85% by weight.
  • the molding compound can contain, for example, 55, 60, 65, 70, 75 or 80% by weight of at least one elastomer.
  • the amount of plasticizer in the molding compound is generally 1 to 60 phr. It may be preferred that the amount of plasticizer in the molding compound is 2 to 40 phr and more preferably 3 to 30 phr. The amount of plasticizer contained in the molding compound may be, for example, 5, 10, 15, 20 or 25 phr.
  • the molding compound can also contain a mixture of at least one thermoplastic and at least one elastomer.
  • the molding compound can contain a mixture of polyvinyl chloride and at least one elastomer.
  • the elastomer content is generally 1 to 50% by weight based on the total weight of the molding compound. It may be preferred that the elastomer content is 3 to 40% by weight based on the total weight of the molding compound. It may be more preferred that the elastomer content is 5 to 30% by weight based on the total weight of the molding compound.
  • the molding compound may contain, for example, 10, 15, 20 or 25% by weight of elastomer.
  • the required amount of plasticizer in the molding compound to achieve the desired Properties vary greatly. It is the routine work of the skilled person to use appropriate amounts of the plasticizer in order to achieve the desired properties.
  • the amount of plasticizer in the molding compound containing polyvinyl chloride and at least one elastomer is 0.5 to 300 phr. It may be preferred that the amount of plasticizer in the molding compound containing polyvinyl chloride and at least one elastomer is 1 to 150 phr, and more preferably 2 to 120 phr.
  • the amount of plasticizer contained in the molding compound may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110 or 115 phr.
  • the molding compound containing at least one elastomer and the plasticizer can expediently additionally contain at least one additive.
  • the additive can be selected from carbon black, silicon dioxide, phenolic resins, vulcanizing or crosslinking agents, vulcanizing or crosslinking accelerators, activators, various oils, anti-aging agents or mixtures of the additives mentioned.
  • additives may be substances that the expert would mix into tires or other rubber compounds based on his or her expertise in order to achieve a certain effect.
  • the molding compound can be used, for example, for the production of molded articles, gloves, films, wallpapers, or heterogeneous flooring, or for textile coating.
  • Shaped bodies can be, for example, containers, apparatus or foamed devices.
  • Containers can be, for example, housings of electrical appliances, such as kitchen appliances or computer cases, pipes, hoses, such as water or irrigation hoses, industrial rubber hoses, chemical hoses, sheaths for wire or cables, sheaths for tools, bicycle, scooter or wheelbarrow handles, metal coatings or packaging containers.
  • electrical appliances such as kitchen appliances or computer cases
  • pipes such as water or irrigation hoses, industrial rubber hoses, chemical hoses, sheaths for wire or cables, sheaths for tools, bicycle, scooter or wheelbarrow handles, metal coatings or packaging containers.
  • Devices can be, for example, tools, furniture such as chairs, shelves, tables, records, profiles such as window profiles, floor profiles for outdoor use, or profiles for conveyor belts, components for vehicle construction such as body components, underbody protection, or vibration dampers, or erasers.
  • Foamed devices can be, for example, upholstery, mattresses, foams or insulation materials.
  • Films can be, for example, tarpaulins such as truck tarpaulins, roof tarpaulins, geomembrane tarpaulins, stadium roofs or tent tarpaulins, seals, composite films such as films for laminated safety glass, self-adhesive films, laminating films, These can be shrink films, outdoor floor coverings, adhesive tape films, coatings, swimming pond liners, ornamental pond liners, tablecloths or artificial leather.
  • tarpaulins such as truck tarpaulins, roof tarpaulins, geomembrane tarpaulins, stadium roofs or tent tarpaulins, seals, composite films such as films for laminated safety glass, self-adhesive films, laminating films, These can be shrink films, outdoor floor coverings, adhesive tape films, coatings, swimming pond liners, ornamental pond liners, tablecloths or artificial leather.
  • the molding compound can be used to produce molded articles or films that come into direct contact with humans or food.
  • Moulded bodies or films that come into direct contact with people or food can be, for example, medical products, hygiene products, food packaging, interior products, baby and children's products, child care articles, sports or leisure products, clothing, fibres or fabrics.
  • Medical devices that can be manufactured using the molding compound can be, for example, tubes for enteral nutrition or hemodialysis, ventilation tubes, drainage tubes, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves or breathing masks.
  • Food packaging that can be produced using the molding compound can be, for example, cling film, food tubes, drinking water tubes, containers for storing or freezing food, lid seals, closure caps, crown corks or artificial wine corks.
  • Products for the interior that can be manufactured using the molding compound can be, for example, floor coverings, which can be homogeneous or composed of several layers consisting of at least one foamed layer, such as floor coverings, mudguard mats, sports floors, luxury vinyl tiles (LVT), artificial leather, wall coverings, foamed or non-foamed wallpapers in buildings, paneling or console covers in vehicles.
  • floor coverings which can be homogeneous or composed of several layers consisting of at least one foamed layer, such as floor coverings, mudguard mats, sports floors, luxury vinyl tiles (LVT), artificial leather, wall coverings, foamed or non-foamed wallpapers in buildings, paneling or console covers in vehicles.
  • Baby and children's products that can be manufactured using the molding compound can be, for example, toys such as dolls, toy figures or clay, inflatable toys such as balls or rings, anti-slip socks, swimming aids, stroller covers, changing mats, hot water bottles, teething rings or bottles.
  • Sports or leisure products that can be manufactured using the molding compound can be, for example, exercise balls, exercise mats, seat cushions, massage balls or rollers, shoes, shoe soles, balls, air mattresses, safety glasses, gloves or drinking bottles.
  • Clothing that can be manufactured using the molding compound can include, for example, latex clothing, protective clothing, rain jackets or rubber boots. Use of plastisols
  • Plastisols are usually formed into the shape of the finished product at ambient temperature by various processes such as spreading, casting, such as the shell casting or rotational casting process, dipping, printing, such as screen printing, spraying and the like. Gelling then takes place by heating, and after cooling a homogeneous, more or less flexible product is obtained.
  • the plastisol can be used for the production of films, wallpapers, seamless hollow bodies, gloves, heterogeneous flooring or for applications in the textile sector, such as textile coatings.
  • Films can be, for example, truck tarpaulins, roof tarpaulins, covers in general, such as boat covers, stroller covers or stadium roofs, tent tarpaulins, geomembranes, tablecloths, coatings, swimming pond liners, artificial leather or ornamental pond liners.
  • Gloves can be, for example, gardening gloves, medical gloves, chemical gloves, protective gloves or disposable gloves.
  • the plastisol can be used to manufacture, for example, seals, lid seals, panels or console covers in vehicles, dolls, toy figures or clay, inflatable toys such as balls or rings, anti-slip socks, swimming aids, changing mats, exercise balls, exercise mats, seat cushions, vibrators, massage balls or rollers, latex clothing, protective clothing, rain jackets or rubber boots.
  • inflatable toys such as balls or rings, anti-slip socks, swimming aids, changing mats, exercise balls, exercise mats, seat cushions, vibrators, massage balls or rollers, latex clothing, protective clothing, rain jackets or rubber boots.
  • the plastisol usually contains polyvinyl chloride.
  • the present disclosure also relates to the use of the plasticizer as a calendering aid or rheology aid.
  • the present disclosure also relates to the use of the plasticizer in surface-active compositions such as flow or film-binding aids, defoamers, antifoam agents, wetting agents, coalescing agents or emulsifiers.
  • the plasticizer can also be used in lubricants such as lubricating oils, lubricating greases or lubricating pastes.
  • the plasticizer can also be used as a quenching agent for chemical reactions, phlegmatizing agent, in pharmaceutical products, in adhesives, in sealants, in inks such as printing inks, in impact modifiers or setting agents. Products containing the plasticizer
  • the subject matter of the disclosure is molded bodies or films that contain the plasticizer. Reference is made to the information on molded bodies or films provided when using molding compounds to produce molded bodies or films. The examples of molded bodies or films given therein are to be used to interpret the terms molded body or film in this section.
  • Suitable derivatives are, for example, acid halides and acid anhydrides.
  • An acid halide can be, for example, an acid chloride.
  • the reaction can take place in the presence of an esterification catalyst.
  • the usual catalysts can be used as esterification catalysts, e.g. mineral acids such as sulfuric acid or phosphoric acid; organic sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid; amphoteric catalysts, in particular titanium, tin(IV) or zirconium compounds such as tetraalkoxytitanium, e.g. tetrabutoxytitanium, or tin(IV) oxide.
  • the water formed during the reaction can be removed by conventional measures, e.g. distillation.
  • WO 02/038531 describes a process for producing 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 heated to boiling in the presence of an esterification catalyst, b) the vapors containing alcohol and water are separated by rectification into an alcohol-rich fraction and a water-rich fraction, c) the alcohol-rich fraction is returned to the reaction zone and the water-rich fraction is discharged from the process.
  • the previously mentioned catalysts are used as esterification catalysts.
  • the esterification catalyst is used in an effective amount which is usually in the range of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the sum of the acid component (or anhydride) and the alcohol component.
  • esterification of the corresponding dicarboxylic acid e.g. 4-oxoheptanedioic acid
  • the esterification of the corresponding dicarboxylic acid can be carried out in the presence of the above-described alcohol components Ri-GH and/or R2-OH by means of an organic acid or mineral acid, in particular concentrated sulfuric acid. It can be advantageous for the alcohol component to be used in at least twice the stoichiometric amount, based on the dicarboxylic acid.
  • the esterification can be carried out at ambient pressure or reduced or elevated pressure. It may be preferred that the esterification is carried out at ambient pressure or reduced pressure.
  • the esterification can be carried out in the absence of an added solvent or in the presence of a solvent.
  • a solvent that is inert under the reaction conditions.
  • An inert solvent is generally understood to mean a solvent that does not react with the reactants, reagents, solvents or the resulting products involved in the reaction under the given reaction conditions.
  • the inert solvent can preferably form an azeotrope with water. These include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons or ethers.
  • the solvent is selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, dibutyl ethers, THF, dioxane and mixtures thereof.
  • 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 of 50 to 160 °C.
  • 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 be a gas which, under the given reaction conditions, does not react with the reactants, reagents, solvents or the resulting products involved in the reaction. It may be preferable for the esterification to take place without the addition of an inert gas.
  • the alcohol and the acid are combined in a molar ratio of 2:1 in a stirred flask together with the esterification catalyst aluminum trimethylsulfonate in a molar ratio of 400:1, based on the acid, without inert gas.
  • the reaction mixture is heated to boiling, preferably from 100 to 140 °C.
  • the water formed during the reaction is distilled off azeotropically together with the alcohol and then separated.
  • the alcohol is returned to the reaction mixture.
  • the dicarboxylic acid and aliphatic alcohols used to prepare the compounds of general formula (I) can either be purchased commercially or prepared according to synthesis routes known from the literature.
  • the preparation of the compounds of the general formula (I) can also be carried out by transesterification. Transesterification processes and specific process measures are either known to the person skilled in the art or are apparent to him from his general specialist knowledge.
  • the starting materials used are generally compounds of the general formula (I) in which R 1 and R 2 independently of one another are Ci to C 2 -alkyl.
  • carboxylic acid dialkyl esters for example 4-oxoheptanedioic acid dimethyl ester or 4-oxoheptanedioic acid diethyl ester or 4-oxoheptanedioic acid ethyl methyl ester or mixtures thereof.
  • transesterification catalysts are the usual catalysts that are usually used for transesterification reactions and are also usually used in esterification reactions. These include, for example, mineral acids such as sulfuric acid or phosphoric acid; organic sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid; or special metal catalysts from the group of tin (IV) catalysts, for example dialkyltin dicarboxylates such as dibutyltin diacetate, trialkyltin alkoxides, monoalkyltin compounds such as monobutyltin dioxide, tin salts such as tin acetate or tin oxides; from the group of titanium catalysts, monomeric or polymeric titanates or titanium chelates such as tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate, triethanolamine titanate; from the group of zirconium catalysts
  • the amount of transesterification catalyst used can generally be 0.001 to 10% by weight, preferably 0.05 to 5% by weight.
  • the reaction mixture is generally heated to the boiling point of the reaction mixture, so that the reaction temperature is in a temperature range of 20 to 200 °C, depending on the reactants.
  • the transesterification can be carried out at ambient pressure or reduced or increased pressure. It may be preferred that the transesterification is 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 can be distilled off continuously in order to shift the equilibrium of the transesterification reaction.
  • the distillation column required for this is usually directly connected to the transesterification reactor.
  • the distillation column can be installed directly on the transesterification reactor. If several transesterification reactors are used in series, each of these reactors can be equipped with a distillation column or the evaporated alcohol mixture can be fed to a distillation column via one or more collecting lines, preferably from the last boilers in the transesterification reactor cascade.
  • the higher boiling alcohol recovered during this distillation is preferably fed back into the transesterification.
  • an amphoteric catalyst its separation is generally achieved by hydrolysis and subsequent separation of the metal oxide formed, e.g. by filtration. It may be preferred that after the reaction the catalyst is hydrolyzed by washing with water and the precipitated metal oxide is filtered off. The filtrate can be subjected to further processing to isolate and/or purify the product. It may be preferred that the product is separated by distillation.
  • the transesterification of the di-(Ci-C2)-alkyl esters of corresponding dicarboxylic acids, for example 4-oxoheptanedioic acid dimethyl ester, with at least one alcohol component selected from the alcohols R1-GH and R2-OH can preferably be carried out in the presence of at least one titanium (IV) alkoxide.
  • Preferred titanium (IV) alkoxides are tetrapropoxytitanium, tetrabutoxytitanium or mixtures thereof. It may be preferred that the alcohol component is used in at least twice the stoichiometric amount, based on the di-(Ci-C2-alkyl) esters used.
  • the transesterification can be carried out in the absence or in the presence of an added solvent. It may be preferred that the transesterification is carried out in the presence of an inert solvent. Suitable solvents are those previously mentioned for the esterification. These include in particular toluene and THF.
  • the temperature during transesterification is usually in the range of 20 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 be a gas which, under the given reaction conditions, does not react with the reactants, reagents, solvents or the resulting products involved in the reaction. It may be preferable for the transesterification to be carried out without adding an inert gas.
  • the aliphatic dicarboxylic acids and cycloaliphatic alcohols used to prepare the compounds of general formula (I) can either be purchased commercially or prepared according to synthesis routes known from the literature.
  • Cyclohexanol can basically be obtained by hydrogenation of phenol in the gas phase or by a catalyzed oxidation of cyclohexane with the aid of transition metal catalysts in the liquid phase using atmospheric oxygen. Cyclohexanol can be obtained more selectively and in higher yields by using boric acid in the liquid phase and oxidizing it with the aid of atmospheric oxygen.
  • This latter process proceeds via the intermediate stage of a peroxoboric acid ester of cyclohexanol.
  • a process starting from benzene has also been realized on an industrial scale.
  • benzene is hydrogenated step by step and cyclohexene is separated from the secondary components, such as unreacted benzene and cyclohexane.
  • cyclohexene is then converted to cyclohexanol very selectively and in high yields (up to 95% across all steps).
  • the compounds of the general formulas (II), (II. a) and (II. b) can either be purchased commercially or prepared by processes known in the art.
  • the diesters can be obtained by esterification or transesterification of the diacids or suitable derivatives thereof with the corresponding alcohols.
  • Customary processes are known to the person skilled in the art.
  • the esterification can be carried out by customary processes known to the person skilled in the art.
  • the 1,2-cyclohexanedicarboxylic acid esters are usually obtained by core hydrogenation of the corresponding phthalic acid esters.
  • the core hydrogenation can be carried out according to the process described in WO 99/32427.
  • a particularly suitable core hydrogenation process is also described, for example, in WO 2011/082991 A2.
  • 1,2-cyclohexanedicarboxylic acid esters can be prepared in a reaction sequence of Diels-Alder reaction and subsequent hydrogenation and esterification or subsequent esterification and hydrogenation. Suitable processes are known to the person skilled in the art, for example from WO 02/066412. Furthermore, 1,2-cyclohexanedicarboxylic acid esters can be obtained by esterification of 1,2-cyclohexanedicarboxylic acid or suitable derivatives thereof with the corresponding alcohols. The esterification can be carried out by conventional methods known to the person skilled in the art.
  • Preferred C4-Ci2-alkanols which are used to prepare the compounds (II. a) contained in the plasticizer composition according to the invention can be straight-chain or branched or consist of mixtures of straight-chain and branched C4-Ci2-alkanols. These include n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol, 2-propylheptanol, n-undecanol, isoundecanol, n-dodecanol or isododecanol. Particular preference is given to Cz-Ci2-alkanols, in particular 2-ethylhexanol, isononanol and 2-propylheptanol, in particular isononanol.
  • a suitable commercially available plasticizer of formula (II. a) is, for example, di-(1,2-isononyl-cyclohexanoate), which is sold under the brand name Hexamoll® DINCH by BASF SE, Ludwigshafen, Germany.
  • the terephthalic acid dialkyl esters are obtained by esterification of terephthalic acid or suitable derivatives thereof with the corresponding alcohols.
  • the esterification can be carried out by customary methods known to the person skilled in the art, as described, for example, in WO 2009/095126.
  • the processes for preparing the compounds of formula (II. b) have in common that an esterification or transesterification is carried out starting from terephthalic acid or suitable derivatives thereof, with the corresponding C4-Ci2-alkanols being used as starting materials.
  • These alcohols are generally not pure substances, but rather mixtures of isomers, the composition and degree of purity of which depend on the particular process used to prepare them.
  • C7-C12-alkanols are preferably used as starting materials.
  • Preferred C4-Ci2-alkanols used to prepare the compounds (II. b) contained in the plasticizer composition according to the invention can be straight-chain or branched or consist of mixtures of straight-chain and branched C4-Ci2-alkanols.
  • Particular preference is given to Cz-Ci2-alkanols, in particular 2-ethylhexanol, isononanol and 2-propylheptanol, especially 2-ethylhexanol.
  • a suitable commercially available plasticizer of formula (II. b) is, for example, di-(2-ethylhexyl) terephthalate (DOTP), which is sold under the brand name Eastman 168TM by Eastman Chemical B.V., Capelle aan den Ijssel, Netherlands, and under the brand name Palatinol® DOTP by BASF Corp., Florham Park, NJ, USA.
  • DBP di-(2-ethylhexyl) terephthalate
  • isoalcohol is to be understood as a mixture of structural isomers, unless otherwise stated.
  • the heptanols used to prepare the compounds of the general formula (II) can be straight-chain or branched or consist of mixtures of straight-chain and branched heptanols. Preference is given to using mixtures of branched heptanols, also referred to as isoheptanol, which are prepared by the rhodium- or preferably cobalt-catalyzed hydroformylation of dimerpropene, obtainable e.g. by the Dimersol® process, and subsequent hydrogenation of the isoheptanals obtained to give an isoheptanol mixture. Depending on its preparation, the isoheptanol mixture obtained in this way consists of several isomers.
  • Essentially 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 give n-heptanol.
  • the hydroformylation of 1-hexene or dimer propene can be carried out by processes known per se: In the hydroformylation with rhodium catalysts dissolved homogeneously in the reaction medium, both uncomplexed rhodium carbonyls, which are formed in situ under the conditions of the hydroformylation reaction in the hydroformylation reaction mixture under the action of synthesis gas, for example from rhodium salts, and complex rhodium carbonyl compounds, in particular complexes with organic phosphines, such as triphenylphosphine, or organophosphites, preferably chelating biphosphites, as described, for example, in US-A 5288918, can be used as catalysts.
  • cobalt carbonyl compounds which are homogeneously soluble in the reaction mixture and which are formed in situ from cobalt salts under the conditions of the hydroformylation reaction under the action of synthesis gas. 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.
  • Non-ligand-modified rhodium carbonyl compounds can advantageously serve as catalysts for the rhodium-catalyzed hydroformylation of long-chain olefins, such as the hexene isomer mixtures obtained by the abovementioned processes, whereby, in contrast to the low-pressure process, a higher pressure of 80 to 400 bar must be set.
  • rhodium high-pressure hydroformylation processes is described in, for example, EP-A 695734, EP-B 880494 and EP-B 1047655.
  • the isoheptanal mixtures obtained after hydroformylation of the hexene isomer mixtures are catalytically hydrogenated in a conventional manner to give isoheptanol mixtures.
  • Heterogeneous catalysts are preferably used for this purpose which contain metals and/or metal oxides of subgroups VI to VIII and I 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, SIÜ2 and/or TO2, as the catalytically active component.
  • Such catalysts are described, for example, in DE-A 3228881, DE-A 2628987 and DE-A 2445303.
  • the hydrogenation of the isoheptanals is particularly advantageously carried out with an excess of hydrogen of 1.5 to 20% over the amount of hydrogen stoichiometrically required for the hydrogenation of the isoheptanals, at temperatures of 50 to 200 °C and at a hydrogen pressure of 25 to 350 bar and, in order to avoid side reactions, a small amount of water, advantageously in the form of an aqueous solution of an alkali metal hydroxide or carbonate in accordance with the teaching of WO 01087809, is added to the hydrogenation feed according to DE-A 2628987.
  • 2-Ethylhexanol which for many years was the plasticizer alcohol produced in the largest quantities, can be obtained via the aldol condensation of n-butyraldehyde to 2-ethylhexenal and its subsequent hydrogenation to 2- Ethylhexanol can be obtained (see Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, Vol. A 10, pp. 137 - 140, VCH Verlagsgesellschaft GmbH, Weinheim 1987).
  • octanols can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-heptene and subsequent hydrogenation of the resulting n-octanal to n-octanol.
  • the 1-heptene required for this can be obtained from the Fischer-Tropsch synthesis of hydrocarbons.
  • the alcohol isooctanol is not a uniform chemical compound due to the way it is produced, but rather an isomer 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 can be present in isooctanol in different proportions depending on the production conditions and processes used.
  • Isooctanol is usually produced by codimerizing propene with butenes, preferably n-butenes, and then hydroformylating the resulting mixture of heptene isomers.
  • the octanal isomer mixture obtained in the hydroformylation can then be hydrogenated to isooctanol in a conventional manner.
  • the codimerization of propene with butenes to form isomeric heptenes can advantageously be carried out using the homogeneously catalyzed Dimersol® process (Chauvin et al; Chem. Ind.; May 1974, pp. 375 - 378), in which a soluble nickel-phosphine complex in the presence of an ethylaluminum chloride compound, for example ethylaluminum dichloride, serves as the catalyst.
  • Phosphine ligands for the nickel complex catalyst can be, for example, tributylphosphine, triisopropylphosphine, tricyclohexylphosphine and/or tribenzylphosphine.
  • the reaction takes place at temperatures of 0 to 80 °C, whereby a pressure is advantageously set at which the olefins are dissolved in the liquid reaction mixture (Cornils; Hermann: Applied Homogeneous Catalysis with Organometallic Compounds; 2nd edition; Vol. 1; pp. 254 - 259, Wiley-VCH, Weinheim 2002).
  • the codimerization of propene with butenes can also be carried out using heterogeneous NiO catalysts deposited on a support, whereby similar heptene isomer distributions are obtained as in the homogeneously catalyzed process.
  • heterogeneous NiO catalysts deposited on a support, whereby similar heptene isomer distributions are obtained as in the homogeneously catalyzed process.
  • Such 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 olefin dimerization or codimerization is disclosed, for example, in WO 9514647.
  • Bronsted-azide heterogeneous catalysts can also be used for the codimerization of propene with butenes, whereby higher branched heptenes are generally obtained than in the nickel-catalyzed processes.
  • suitable catalysts for this purpose are solid phosphoric acid catalysts, e.g. kieselguhr or diatomaceous earth impregnated with phosphoric acid, as used by PolyGasO processes can be used for olefin di- or oligomerization (Chitnis et al; Hydrocarbon Engineering 10, No. 6 - June 2005).
  • Bronsted-azide catalysts that are very suitable for the codimerization of propene and butenes to heptenes are zeolites, which are used in the EMOGASO process, which has been further developed on the basis of the PolyGasO process.
  • the 1-heptene and the heptene isomer mixtures are converted into n-octanal or octanal isomer mixtures by means of rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation, according to the known processes explained above in connection with the preparation of n-heptanal and heptanal isomer mixtures. These are then hydrogenated to the corresponding octanols, for example by means of one of the catalysts mentioned above in connection with the preparation of n-heptanol and isoheptanol.
  • Essentially straight-chain nonanol can be obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-octene and subsequent hydrogenation of the resulting n-nonanal.
  • the starting olefin 1-octene can be obtained, for example, via ethylene oligomerization using a nickel complex catalyst that is homogeneously soluble in the reaction medium - 1,4-butanediol - with, for example, diphenylphosphinoacetic acid or 2-diphenylphosphinobenzoic acid as ligands.
  • This process is also known as the Shell Higher Olefins Process or SHOP process (see Weisermel, Arpe: Industrial Organic Chemistry; 5th edition; p. 96; Wiley-VCH, Weinheim 1998).
  • Isononanol which is used to synthesize the diisononyl esters of the general formula (II) contained in the plasticizer composition according to the invention, is not a uniform chemical compound, but a mixture of differently branched isomeric Cg alcohols, which can have different degrees of branching depending on the method of their preparation, in particular the starting materials used.
  • the isononanols are prepared by dimerizing butenes to form isooctene mixtures, subsequent hydroformylation of the isooctene mixtures and hydrogenation of the resulting isononanal mixtures to form isononanol mixtures, as explained in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A1, pp. 291 - 292, VCH Verlagsgesellschaft GmbH, Weinheim 1995.
  • Isobutene, cis- and trans-2-butene as well as 1-butene or mixtures of these butene isomers can be used as starting materials for the production of isononanols.
  • dimerization of pure isobutene which is mainly catalyzed by liquid, e.g. sulfuric or phosphoric acid, or solid, e.g.
  • the highly branched 2,4,4-trimethylpentene also known as diisobutylene
  • diisobutylene the highly branched 2,4,4-trimethylpentene, also known as diisobutylene, is predominantly obtained, which, after hydroformylation and hydrogenation of the aldehyde, yields highly branched isononanols. Isononanols with a lower degree of branching are preferred.
  • Such slightly branched isononanol mixtures are prepared from the linear butenes 1-butene, cis- and/or trans-2-butene, which may optionally contain even smaller amounts of isobutene, via the route described above of butene dimerization, hydroformylation of the isooctene and hydrogenation of the resulting isononanal mixtures.
  • a preferred raw material is the so-called raffinate II, which is obtained from the C4 cut of a cracker, for example a steam cracker, after elimination of allenes, acetylenes and dienes, in particular 1,3-butadiene, by its partial hydrogenation to linear butenes or its separation by extractive distillation, for example by means of N-methylpyrrolidone, and subsequent Bronsted acid-catalyzed removal of the isobutene contained therein by its reaction with methanol or isobutanol according to industrially established processes to form the fuel additive methyl tert-butyl ether (MTBE) or the isobutyl tert-butyl ether used to obtain pure isobutene.
  • MTBE methyl tert-butyl ether
  • isobutyl tert-butyl ether used to obtain pure isobutene.
  • raffinate II In addition to 1-butene and cis- and trans-2-butene, raffinate II also contains 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 common, industrially practiced processes as explained above in connection with the production of isoheptene mixtures, for example by means of heterogeneous, Bronsted-acidic catalysts as used in the PolyGas® or EMOGAS® process, by means of the Dimersol® process using nickel complex catalysts homogeneously dissolved in the reaction medium or by means of heterogeneous, nickel(II) oxide-containing catalysts according to the Octol® process or the process according to WO 9514647.
  • the isooctene mixtures obtained are converted into isononanal mixtures by means of rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation, according to the known processes explained above in connection with the production of heptanal isomer mixtures. These are then hydrogenated to the suitable isononanol mixtures, for example using one of the catalysts mentioned above in connection with isoheptanol production.
  • the isononanol isomer mixtures produced in this way 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.
  • n-nonanol contributes a value of 0, methyloctanols (one branch) a value of 1 and dimethylheptanols (two branches) a value of 2 to the isoindex of an isononanol mixture.
  • the isoindex of an isononanol mixture can be determined by gas chromatographic separation of the isononanol mixture into its individual isomers and the associated quantification of their percentage in the isononanol mixture, determined using standard methods of gas chromatographic analysis.
  • these are expediently trimethylsilylated before the gas chromatographic analysis using standard methods, for example by reaction with N-methyl-N-trimethylsilyltrifluoroacetamide.
  • capillary columns with polydimethylsiloxane as the stationary phase are preferably used. Such capillary columns are commercially available and only a few routine tests are required by the expert to select a product that is optimally suited to this separation task from the wide range available on the market.
  • the diisononyl esters of the general formula (II) used in the plasticizer composition according to the invention are generally esterified with isononanols having an isoindex of from 0.8 to 2, preferably from 1.0 to 1.8 and particularly preferably from 1.1 to 1.5, which can be prepared by the processes mentioned above.
  • compositions of isononanol mixtures are given below purely by way of example, as can be used to prepare the compounds of the general formula (II) used according to the invention, it being noted that the proportions of the isomers listed in detail in the isononanol mixture can vary depending on the composition of the starting material, for example raffinate II, the composition of butenes of which can vary depending on production, and on fluctuations in the production conditions used, for example the age of the catalysts used and the temperature and pressure conditions to be adapted thereto.
  • an isononanol mixture 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:
  • 0.38 to 1.38 wt.% preferably 0.48 to 1.28 wt.%, particularly preferably 0.58 to 1.18 wt.% 2,6-dimethylheptanol;
  • 1.47 to 5.47 wt.% preferably 1.97 to 4.97 wt.%, particularly preferably 2.47 to 4.47 wt.% 3,4,5-trimethylhexanol, 3-methyl-4-ethylhexanol and 3-ethyl-4-methylhexanol; 4.00 to 10.00 wt.%, preferably 4.50 to 9.50 wt.%, particularly preferably 5.00 to 9.00 wt.% 3,4-dimethylheptanol;
  • 0.70 to 2.70 wt.% preferably 0.90 to 2.50 wt.%, particularly preferably 1.20 to 2.20 wt.% 3,6,6-trimethylhexanol;
  • 0.1 to 3% by weight preferably 0.2 to 2% by weight, particularly preferably 0.3 to 1% by weight of n-nonanol; 25 to 35% by weight, preferably 28 to 33% by weight, particularly preferably 29 to 32% by weight of other alcohols having 9 and 10 carbon atoms; with the proviso that the total sum of the components mentioned is 100% by weight.
  • an isononanol mixture produced by cobalt-catalyzed hydroformylation and subsequent hydrogenation using an ethylene-containing butene mixture as raw material of an isooctene mixture produced by the PolyGas® or EMOGAS® process can vary in the range of the following compositions, depending on the raw material composition and variations in the reaction conditions used:
  • Isodecanol is generally not a single chemical compound, but a complex mixture of differently branched isomeric decanols.
  • 2-Propylheptanol can be pure 2-propylheptanol or propylheptanol isomer mixtures, as they are generally formed during the industrial production of 2-propylheptanol and are also commonly referred to as 2-propylheptanol. Pure 2-propylheptanol can be obtained, for example, by aldol condensation of n-valeraldehyde and subsequent hydrogenation of the 2-propylheptenal formed thereby, for example according to US-A 2921089.
  • 2-propylheptanol contains, in addition to the main component 2-propylheptanol, one or more of the 2-propylheptanol isomers 2-propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-isopropyl-heptanol, 2-isopropyl-4-methylhexanol, 2-isopropyl-5-methylhexanol and/or 2-propyl-4,4-dimethylpentanol.
  • hydrocarbon sources can be used as starting material for the production of 2-propylheptanol, for example 1-butene, 2-butene, raffinate I (an alkane/alkene mixture obtained from the C4 cut of a cracker after separation of allenes, acetylenes and dienes, which contains considerable amounts of isobutene in addition to 1- and 2-butene) or raffinate II, which is obtained from raffinate I by separation of isobutene and contains only small amounts of isobutene as olefin components apart from 1- and 2-butene.
  • raffinate I and raffinate II can of course also be used as raw materials for 2-propylheptanol production.
  • olefins or olefin mixtures can be hydroformylated using conventional methods with cobalt or rhodium catalysts, whereby a mixture of n- and iso-valeraldehyde (the term iso-valeraldehyde refers to the compound 2-methylbutanal) is formed from 1-butene, the n/iso ratio of which can vary within relatively wide limits depending on the catalyst used and the hydroformylation conditions.
  • n- and iso-valeraldehyde are formed from 1-butene in an n/iso ratio of generally 10:1 to 20:1, whereas when using rhodium hydroformylation catalysts modified with phosphite ligands, for example according to US-A 5288918 or WO 05028407, or with phosphoamidite ligands, for example according to WO 0283695, almost exclusively n-valeraldehyde is formed.
  • Rh/TPP catalyst system converts 2-butene only very slowly during hydroformylation, so that most of the 2-butene can be recovered from the hydroformylation mixture
  • the hydroformylation of 2-butene is successful with the aforementioned phosphite ligand or phosphoramidite ligand-modified rhodium catalysts, with predominantly n-valeraldehyde being formed.
  • isobutene contained in the olefinic raw material is hydroformylated by practically all catalyst systems to 3-methylbutanal and, depending on the catalyst, to a lesser extent to pivalaldehyde.
  • the Cs-aldehydes obtained depending on the starting materials and catalysts used ie n-valeraldehyde optionally in a mixture with iso-valeraldehyde, 3-methylbutanal and/or pivalaldehyde, can, if desired, be completely or partially separated into the individual components by distillation before the aldol condensation. so that here too there is a possibility of influencing and controlling the isomer composition of the Cw-alcohol component of the ester mixtures according to the disclosure. It is also possible to feed the Cs-aldehyde mixture, as it is formed in the hydroformylation, to the aldol condensation without the prior separation of individual isomers.
  • aldol condensation which can be carried out using a basic catalyst such as an aqueous solution of sodium or potassium hydroxide, for example according to the processes described in EP-A 366089, US-A 4426524 or US-A 5434313
  • a basic catalyst such as an aqueous solution of sodium or potassium hydroxide
  • the only condensation product formed when n-valeraldehyde is used is 2-propylheptenal
  • an isomer mixture is formed from the products of the homoaldol condensation of the same aldehyde molecules and the crossed aldol condensation of different valeraldehyde isomers.
  • the aldol condensation can be controlled by the targeted conversion of individual isomers so that a single aldol condensation isomer is formed predominantly or completely.
  • the aldol condensation products in question can then be hydrogenated to the corresponding alcohols or alcohol mixtures using conventional hydrogenation catalysts, for example those mentioned above for the hydrogenation of aldehydes, usually after prior separation, usually by distillation, from the reaction mixture and, if desired, purification by distillation.
  • the compounds of the general formula (II) contained in the plasticizer composition can be esterified with pure 2-propylheptanol.
  • mixtures of 2-propylheptanol with the propylheptanol isomers mentioned are used to produce these esters, in which the content of 2-propylheptanol is at least 50% by weight. It may be preferred that the content of 2-propylheptanol is 60 to 98% by weight and more preferably 80 to 95% by weight and particularly preferably 85 to 95% by weight.
  • Suitable mixtures of 2-propylheptanol with the propylheptanol isomers include, for example, those of 60 to 98% by weight of 2-propylheptanol, 1 to 15% by weight of 2-propyl-4-methylhexanol and 0.01 to 20% by weight of 2-propyl-5-methylhexanol and 0.01 to 24% by weight of 2-isopropylheptanol, where the sum of the proportions of the individual components does not exceed 100% by weight. It may be preferred that the proportions of the individual components add up to 100% by weight.
  • suitable mixtures of 2-propylheptanol with the propylheptanol isomers include, for example, those of 75 to 95% by weight of 2-propylheptanol, 2 to 15% by weight of 2-propyl-4-methylhexanol, 1 to 20% by weight of 2-propyl-5-methylhexanol, 0.1 to 4% by weight of 2-isopropylheptanol, 0.1 to 2% by weight of 2-isopropyl-4-methylhexanol and 0.1 to 2% by weight of 2-isopropyl-5-methylhexanol, where the sum of the proportions of the individual components does not exceed 100% by weight. It may be preferred that the proportions of the individual components add up to 100% by weight.
  • mixtures of 2-propylheptanol with the propylheptanol isomers are those containing 85 to 95% by weight of 2-propylheptanol, 5 to 12% by weight of 2-propyl-4-methylhexanol and 0.1 to 2% by weight of 2-propyl-5- methylhexanol and 0.01 to 1 wt.% 2-isopropylheptanol, the sum of the proportions of the individual components not exceeding 100 wt.%. It may be preferred that the proportions of the individual components add up to 100 wt.%.
  • the isomer composition of the alkyl ester groups or alkyl ether groups practically corresponds to the composition of the propylheptanol isomer mixtures used for the esterification.
  • the undecanols may be branched or composed of mixtures of straight-chain and branched undecanols. It may be preferred that mixtures of branched undecanols, also referred to as isoundecanol, are used as the alcohol component.
  • Essentially straight-chain undecanol can be obtained, for example, 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, for example, via the SHOP process mentioned above for the preparation of 1-octene.
  • the 1-decene obtained in the SHOP process can be subjected to skeletal isomerization, e.g. using acidic zeolitic molecular sieves, as described in WO 9823566, to form mixtures of isomeric decenes, the rhodium- or preferably cobalt-catalyzed hydroformylation of which and subsequent hydrogenation of the isoundecanal mixtures obtained also leads to the production of the isoundecanols used in the disclosed compounds of the general formula (I).
  • hydroformylation of 1-decene or isoundecane mixtures using rhodium or cobalt catalysis can be carried out as described above in connection with the synthesis of C2 to Cw alcohols.
  • the C2 to Cn-alkyl alcohols thus obtained or mixtures thereof can be used, as described above, to prepare the diester compounds of the general formula (I) according to the disclosure.
  • the dodecanols can be branched or composed of mixtures of straight-chain and branched dodecanols.
  • Essentially straight-chain dodecanol can be obtained, for example, via the Alfol® or Epal® process. These processes involve the oxidation and hydrolysis of straight-chain trialkylaluminum compounds, which are built up step by step from triethylaluminum via several ethylation reactions using Ziegler-Natta catalysts.
  • the desired n-dodecanol can be obtained from the resulting mixtures of largely straight-chain alkyl alcohols of different chain lengths after the C12 alkyl alcohol fraction has been removed by distillation.
  • n-dodecanol can also be produced by hydrogenation of natural fatty acid methyl esters, for example from coconut oil.
  • Branched isododecanol can be obtained analogously to the known processes for the codimerization and/or oligomerization of olefins, as described for example in WO 0063151, with subsequent hydroformylation and hydrogenation of the isoundecene mixtures, as described for example in DE-A 4339713. After distillative purification of the hydrogenation output, the isododecanols thus obtained or mixtures thereof can be used, as described above, to prepare the diester compounds of the general formula (I) according to the disclosure.
  • Fig. 1 shows the gelling behaviour of various plastisols with plasticisers according to the disclosure.
  • Fig. 2 shows the gelling behaviour of various plastisols with plasticisers according to the disclosure.
  • a split/splitless with Topaz Split Precision Liner Whool from Restek was used as the injector.
  • the temperature program was: Start: 60 °C, dwell time 1: 5 min, temperature ramp 1: 8 °C/min, final temperature 1: 240 °C, dwell time 2: 0 min, temperature ramp 2: 30 °C/min, final temperature 2: 300 °C, dwell time 3: 10 min, Total running time: 59.5 min. Detection was performed using FID with 300 mL/min air, 30 mL/min hydrogen and 30 mL/min make-up gas (nitrogen) at 320 °C.
  • a 1.6 L reactor vessel was filled with diethyl 4-oxopimelate (296 g, 1.28 mol, 1.0 eq., BLDpharm), cyclohexanol (384 g, 3.83 mol, 3.0 eq., BASF) and Tyzor TPT-20B (0.34 g, 0.05 wt. %, Dorf Ketal).
  • the reaction mixture was heated to 157-192 °C under a nitrogen stream. After 16 hours of reaction time, no more ethanol was produced. The excess cyclohexanol was then distilled off (max. 185 °C,
  • Table 3 below shows the properties of the compound as described above together with comparative examples not according to the invention.
  • 4-oxoheptanedioic acid di-cyclohexyl ester shows a significantly lower dissolution temperature for PVC compared to the plasticizers isononyl benzoate (Vestinol INB), isodecyl benzoate (Jayflex MB10), diisononyl phthalate (Palatinol® N), di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH) and di-(2-ethylhexyl)-terephthalate (Palatinol DOTP).
  • plastisols were also produced which, in addition to PVC, only contained the plasticizers di-(2-ethylhexyl) terephthalate (Palatinol DOTP), diisononyl phthalate (Palatinol® N) or di-(isononyl)-1,2-cyclohexanoic acid dicarboxylate (Hexamoll DINCH), or plastisols with 73 wt.% of the plasticizer di-(2-ethylhexyl) terephthalate (Palatinol DOTP) with 27 wt.% of the gelling agent isononyl benzoate (Vestinol® INB), a plastisol with 64 wt.% of the plasticizer di-(2-ethylhexyl) terephthalate (Palatinol DOTP) with 36 wt.% of the gelling agent isodecyl benzoate (Jayflex® MB 10),
  • the viscosity measurements were carried out using a heated oscillation and rotation rheometer MCR 302 from Anton Paar in an oscillation test.
  • a composition of just 91% by weight of di-(2-ethylhexyl) terephthalate (Palatinol DOTP) and 9% by weight of 4-oxoheptanedioic acid di-cyclohexyl ester (compound I.2) achieves a gelling temperature of 150 °C, which corresponds to the gelling temperature of the plasticizer Palatinol® N and is sufficient for many plastisol applications.
  • the gelling temperature of the plastisols can be further reduced.
  • the gelling temperature of 150 °C is also reached, which corresponds to the gelling temperature of the diisononyl phthalate.
  • the plastisols of formulations I*, II*, III*, V and VI were prepared as described under II. b). Films with a thickness of 0.5 mm were produced from the plastisols thus obtained by gelling the plastisols in a Mathis oven.
  • a new relay paper was clamped into the clamping device on the Mathis oven.
  • the oven was preheated to 190 °C and the gelling time was set to 120 s.
  • the gap between the paper and the doctor blade was set to 0.1 mm using the thickness template.
  • the thickness gauge was set to 0.1 mm.
  • the gap was then set to a value of 0.7 mm on the gauge.
  • the plastisol was applied to the paper and smoothed out with a squeegee.
  • the clamping device was then moved into the oven using the start button. After 120 seconds, the clamping device was moved out of the oven again.
  • the plastisol had gelled and the resulting film with a thickness of 0.5 mm could be peeled off.
  • Films of formulation IV* were prepared as follows: 150 g PVC (homopolymer suspension PVC, brand name Inovyn® 271 PC); 90 g plasticizer composition and 3 g Ba/Zn stabilizer, brand name Baerostab® UBZ 760 XLP RF were mixed with a hand mixer at room temperature. The mixture was then plasticized on an oil-heated laboratory mixing roller mill (Collin, automatic roller mill type W250M, diameter: 252 mm, width: 450 mm) and processed into a rolled sheet. The temperature of both rollers was 180 °C each; the speeds were 15 revolutions/min. (front roller) and 12 revolutions/min. (rear roller); the rolling time was 5 minutes.
  • PVC homopolymer suspension PVC, brand name Inovyn® 271 PC
  • 90 g plasticizer composition and 3 g Ba/Zn stabilizer, brand name Baerostab® UBZ 760 XLP RF were mixed with a hand mixer at room temperature. The mixture was then plasticized
  • the roller gap was set to 0.5 mm. This gave a rolled sheet with a thickness of 0.53 mm.
  • the cooled rolled sheet was then pressed at a temperature of 190 °C and a pressure of 150 bar within 180 s on a press of the type "Laboratory Plate Press 400 P" from Collin to form a soft PVC film with a thickness of 0.50 mm. While maintaining the pressing pressure, the pressed film was cooled to approx. 40 °C within 10 minutes.
  • test specimens are pressed at 185 °C and 200 bar for a total of 15 minutes.
  • the cooled test specimens are then conditioned for 7 days in a climate chamber at 23 °C and approx. 50% humidity before measurement.
  • a Durometer HDD-2 from Hildebrand is used to measure the Shore A hardness. 10 readings are taken on a test specimen after a penetration time of 15 s.
  • test specimens measuring 75 x 110 x 0.5 mm were cut out of the pressed foils produced under II. d) or the foils produced under II. c). The foils were punched on the wide side, labeled and weighed. The test specimens produced in this way were then placed on a metal frame made of stainless material in a glass basin. To avoid mutual influence, only test specimens with the same composition may be stored in a glass basin. The glass basins are filled with demineralized water to a level of around 3 cm. Care must be taken to ensure that the test specimens are a further 2 cm above the water surface and do not touch the water. The glass vessels, which are then hermetically sealed, are then placed in a heating cabinet with interior temperature control.
  • the test is carried out at 70 °C and 100% relative humidity for a total of 28 days. Two samples were taken at intervals of 1, 3, 7, 14 and 28 days and conditioned in air for 1 hour while hanging freely. The films were then cleaned in a fume hood with methanol. The films were then dried in a drying cabinet (natural convection) while hanging freely for 16 hours at 80 °C. After removal from the drying cabinet, the films were conditioned in the laboratory while hanging freely for 1 hour and then weighed. The test result given in each case was the arithmetic mean of the weight changes compared to the samples before they were placed in the heating cabinet.
  • the determination of the residual HCl stability is carried out according to DIN EN 60811-405 (VDE 0473-811-405): A metal block thermostat from Liebisch Labortechnik is used as the test device at a test temperature of 200 °C. A triplicate determination is always carried out. Approx. 50 mg of the films produced under II. c) or II. d) are weighed, cut to a length of 3 cm and positioned in the lower part of the glass tube. A strip of indicator paper (litmus paper) approx. 10 mm long is positioned at the upper end of the glass tube so that approx. 2 mm protrudes. The glass tubes prepared in this way are placed in the metal block and the time until a color change towards red occurs is noted. The arithmetic mean is calculated from the three measured values of the three samples.
  • the test is carried out in accordance with the draft of DIN 53372 from 1981.
  • the dimensions and number of test specimens are in accordance with the requirements of the DIN standard (length of 60 mm, width of 15 mm, thickness exactly 0.50 mm).
  • the test specimens must be stored at room temperature for at least 4 days before the test.
  • test specimens Six identical test specimens are tested in a row at the same time.
  • the freezer is set to an expected starting temperature and the sample carrier (bomb) with the test specimens is inserted. To condition the test specimens, they are heated for 1 hour per test temperature. For evaluation purposes, only those test loops that have broken completely into two or more pieces are considered defective.
  • To determine the cold fracture temperature at least one row of 6 test specimens must be assessed as completely broken and one row of 6 as completely intact.
  • the temperature interval of the tests to be carried out is 5 °C in each case.
  • the cold fracture temperature is calculated according to the formula in the draft of DIN standard 53372 (1981).
  • the properties of the plasticizer compositions according to the invention are comparable to the properties of the already known plasticizers not according to the invention.

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Abstract

L'invention concerne une composition de plastifiant, contenant a) au moins un composé de formule générale (I), dans laquelle R1 et R2 indépendamment l'un de l'autre sont choisis parmi un cycloalkyle en C5-C8, qui est non substitué ou porte un ou plusieurs substituants alkyle en C1-C10, et n1 et n2 représentent indépendamment l'un de l'autre 1, 2 ou 3 ; et b) au moins un composé de formule générale (II), dans laquelle R3 et R4 indépendamment l'un de l'autre sont choisis parmi un alkyle en C4-C12, et Y est choisi parmi (Y.a) et (Y.b), où # indique des points de fixation, présente de bonnes propriétés de gélification et est hautement compatible avec les matières plastiques à plastifier, confère de bonnes propriétés mécaniques aux matières plastiques plastifiées avec celles-ci, a peu de volatilité pendant l'utilisation des produits finaux et est toxicologiquement acceptable.
PCT/EP2024/066631 2023-06-15 2024-06-14 Composition de plastifiant Pending WO2024256670A1 (fr)

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WO2011082991A2 (fr) 2009-12-15 2011-07-14 Basf Se Catalyseur et procédé d'hydrogénation de composés aromatiques
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EP1354867B1 (fr) 2002-04-18 2015-04-01 Evonik Degussa GmbH Esters isononyliques d'acide benzoique et leur utilisation
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