WO2019185409A1 - Composition de pvc, contenant au moins un plastifiant, qui présente au moins un groupe ester d'acide carboxylique, et au moins un composé carbodiimide - Google Patents

Composition de pvc, contenant au moins un plastifiant, qui présente au moins un groupe ester d'acide carboxylique, et au moins un composé carbodiimide Download PDF

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Publication number
WO2019185409A1
WO2019185409A1 PCT/EP2019/056910 EP2019056910W WO2019185409A1 WO 2019185409 A1 WO2019185409 A1 WO 2019185409A1 EP 2019056910 W EP2019056910 W EP 2019056910W WO 2019185409 A1 WO2019185409 A1 WO 2019185409A1
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compounds
general formula
composition
branched
weight
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PCT/EP2019/056910
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German (de)
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Axel Grimm
Herbert Morgenstern
Matthias Pfeiffer
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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
    • C08K5/11—Esters; Ether-esters of acyclic 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
    • C08K5/10—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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • a PVC composition comprising at least one plasticizer having at least one carboxylic acid ester group and at least one carbodiimide compound
  • the present invention relates to a composition containing
  • a plasticizer component comprising at least one plasticizer having at least one carboxylic acid ester group
  • polymer (s) selected from polyvinyl chloride homo- and copolymers.
  • the invention further relates to molding compositions and plastisols consisting of or containing a composition as defined herein.
  • the invention further relates to the use of a composition, a molding material or a plastisol as defined herein.
  • 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 low processing and operating temperatures.
  • Polyvinyl chloride is one of the most widely produced plastics in terms of quantity. Due to its versatile applicability, it is found today in a variety of products of daily life. PVC is therefore given a very important economic importance.
  • PVC is originally a hard and brittle plastic up to approx. 80 ° C, which is used as rigid PVC (PVC-U) by adding heat stabilizers and other additives. Only by the addition of suitable plasticizers can soft PVC (PVC-P) be obtained, which can be used for many applications for which rigid PVC is unsuitable.
  • thermoplastic polymers in which plasticizers are commonly used are, for.
  • PVB polyvinyl butyral
  • TPU thermoplastic polyurethanes
  • plasticizers which have high compatibility with the polymer to be plasticized, give it good thermoplastic properties and have only a slight tendency to evaporate and / or exude (high permanence). Furthermore, a low sensitivity to hydrolysis is desired.
  • Polyester plasticizers for example based on aliphatic C 2 -C 8 -dicarboxylic acids and C 2 -C 12 -dialcohols and C 1 -C 12 -monoalcohols;
  • Phthalic diesters for example with C 1 -C 12 monoalcohols
  • Terephthalic diesters for example with C 1 -C 12 monoalcohols
  • aliphatic non-cyclic dicarboxylic acid diesters for example based on C 2 -C 10 -
  • Cyclohexandicarbonklarediester for example with C 1 -C 12 monoalcohols.
  • plasticizers or plasticizer compositions are sensitive to hydrolysis and, on contact with water and / or atmospheric moisture, lead to the formation of polar hydrolysis products which have a high incompatibility with the PVC and thus to result in a partial loss of the elastic properties of the plasticized plastics produced using these plasticizers.
  • the composition should have a high compatibility of the components used and thus tend not or only to a small extent during use to exudation.
  • the composition should have a reduced susceptibility to hydrolysis.
  • the elastic properties of the plasticized plastics produced using this composition should also be retained over longer periods of time.
  • a plasticizer component comprising at least one plasticizer having at least one carboxylic acid ester group
  • polymer component containing one or more polymer (s) selected from polyvinyl chloride homo- and copolymers.
  • Another object of the invention are molding compositions and plastisols, consisting of or containing a composition as defined herein.
  • Another object of the invention is the use of a composition as defined herein, in a molding material and / or in a plastisol.
  • Another object of the invention is the use of a composition as defined herein, for the production of moldings and films.
  • a plasticizer component comprising at least one plasticizer which is selected from
  • X is independently of one another an unbranched or branched C 2 -C 8 -alkylene group or a straight-chain or branched C 2 -C 8 -alkenylene group having at least one double bond,
  • Y is an unbranched or branched C 2 -C 12 -alkylene group or a straight-chain or branched C 2 -C 12 -alkenylene group having at least one double bond, a is an integer from 1 to 100, and
  • R 1 independently of one another represents an unbranched or branched C 4 -C 12 -alkyl group
  • compositions according to the invention are distinguished by high compatibility with the polymers to be plasticized.
  • compositions of the invention are characterized by a low sensitivity to hydrolysis.
  • the plasticizers used in the compositions according to the invention have little or no tendency to exude during use of the end products. As a result, the elastic properties of the plasticized plastics produced using these compositions are retained even over long periods of time.
  • compositions according to the invention are advantageously suitable for achieving a multiplicity of very different and complex processing and application properties of plastics.
  • C n -C m - which is used as a prefix for compounds, groups and radicals, specifies the number of possible C atoms in the particular compound, group or radical, the expressions “ n “and” m “are each independently an integer.
  • C 1 -C n -alkyl is, for example, a linear or branched alkyl radical having 1 to n C atoms.
  • C 2 -C 4 -alkylene is a divalent, unbranched or branched hydrocarbon radical having 2, 3 and / or 4 C atoms.
  • C 1 -C 12 -alkyl refers to unbranched or branched alkyl groups having 1 to 12 carbon atoms. These include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2 -Dimethylpropyl, 1,1-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-propyl
  • C 1 -C 12 -alkyl also includes in its definition the terms “C 1 -C 8 -alkyl", “C 1 -C 5 -alkyl", “C 4 -C 12 -alkyl", “C” 7 C 12 alkyl "and the like.
  • C 2 -C 12 -alkylene refers to divalent hydrocarbon radicals having 2 to 12 carbon atoms.
  • the divalent hydrocarbon radicals can be unbranched or branched. These include, for example, 1, 2-ethylene,
  • C 2 -C 12 -alkylene also includes in its definition the terms “C 2 -C 8 -alkenylene”, “C 2 -C 6 -alkylene”, “C 2 -C 5 -alkylene”, “C 3 -C5 alkylene "and the like.
  • C 2 -C 12 -alkenylene refers to bivalent hydrocarbon radicals having 2 to 12 carbon atoms, which may be unbranched or branched, wherein the main chain at least one double bond, for example 1, 2 or 3 double bonds, has.
  • ethenylene propenylene, 1-methylethenylene, 1-butenylene, 2-butenylene, 1-methylpropenylene, 2-methylpropenylene, 1-pentenylene, 2-pentenylene, 1-methyl-1-butenylene, 1-methyl 2-butenylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1-methyl-1-pentenylene, 1-methyl-2-pentenylene, 1-methyl-3-pentenylene, 1, 4-dimethyl-1 -butenylene, 1,4-dimethyl-2-butenylene, 1-heptenylene, 2-heptenylene, 3-heptenylene, 1-octenylene, 2-octenylene, 3-octenylene, nonenylene, decenylene, undecenylene, dodecenylene and the like ,
  • C 2 -C 12 alkenylene also includes in its definition the terms “C 2 -C 8 alkenylene”, “C 2 -C 6 alkenylene”, “C 2 -C 5 alkenylene” and the like ,
  • the double bonds in the alkenylene groups may independently exist in the E or Z configuration or as a mixture of both configurations.
  • the alkenylene groups have at least one double bond, for example 1, 2 or 3 double bonds. Unless stated otherwise, the alkenylene groups usually preferably have a double bond. For alkenyl groups applies accordingly.
  • substantially in the context of the present invention means at least 20 wt .-% of the respective component, based on the total amount of the reference. Essentially, preferably at least 50% by weight, more preferably at least
  • the measurement standards and standard sizes refer to the respective DIN, ISO, IUPAC standard or literature at the time of the filing date.
  • the plasticizer component (A) contains at least one plasticizer having at least one carboxylic acid ester group.
  • This plasticizer is usually selected from plasticizers known to those skilled in the art, for example
  • Polyester plasticizers for example based on aliphatic C 2 -C 8 -dicarboxylic acids and C 2 -C 12 -dialcohols and C 1 -C 12 -monoalcohols;
  • Phthalic diesters for example with C 1 -C 12 monoalcohols
  • Terephthalic diesters for example with C 1 -C 12 monoalcohols
  • aliphatic non-cyclic dicarboxylic acid diesters for example based on C 2 -C 10 -D 1 -carboxylic acids with C 1 -C 12 monoalcohols;
  • Cyclohexanedicarboxylic acid diesters for example with C 1 -C 12 monoalcohols
  • aliphatic non-cyclic tricarboxylic acid esters for example based on C 3 -C 10 -tricarboxylic acids with C 1 -C 12 monoalcohols;
  • aliphatic non-cyclic tetracarboxylic esters for example based on C 4 -C 10 -tetracarboxylic acids with C 1 -C 12 monoalcohols.
  • the at least one plasticizer is selected from:
  • the at least one plasticizer is selected from among
  • the plasticizer component preferably contains at least 10% by weight, based on the total amount of the plasticizers, of at least one compound selected from compounds of the general formulas (Al), (A.II.), (A.III), (A.IV ), (AV), (A.VI), (A.VII) and mixtures thereof, preferably selected from compounds of general formulas (Al), (A.IV), (AV), (A.VI), (A .VII) and mixtures thereof, in particular selected from compounds of the general formulas (Al), (A.IV), (AV) and mixtures thereof.
  • the plasticizer component particularly preferably contains at least 30% by weight, more preferably at least 50% by weight, more preferably at least 70% by weight, more preferably at least 90% by weight, based on the total amount of Plasticizer, at least one of the corresponding plasticizer compounds or a mixture thereof.
  • the at least one plasticizer is selected from among
  • the proportion of these compounds in the plasticizer component is at least 10% by weight, preferably at least 30% by weight, more preferably at least 50% by weight, more preferably at least 70 Wt .-%, more preferably at least 90 wt .-%, based on the total amount of the plasticizer.
  • the plasticizer component contains at least 10 wt .-%, based on the total amount of the plasticizer, of at least one compound of the general formula (A.l).
  • the plasticizer component particularly preferably contains at least 30% by weight, more preferably at least 50% by weight, more preferably at least 70% by weight, more preferably at least 90% by weight, based on the total amount of Plasticizer, at least one compound of the general formula (Al).
  • the at least one plasticizer is preferably selected from compounds (A1) of the general formula (A.I.),
  • X is independently of one another an unbranched or branched C 2 -C 8 -alkylene group or a straight-chain or branched C 2 -C 8 -alkenylene group having at least one double bond,
  • Y is an unbranched or branched C 2 -C 12 -alkylene group or a straight-chain or branched C 2 -C 12 -alkenylene group having at least one double bond, a is an integer from 1 to 100, and
  • R 1 independently of one another represents an unbranched or branched C 4 -C 12 -alkyl group
  • X in the general formula (A1) preferably independently of one another represents an unbranched or branched C 2 -C 8 -alkylene group, particularly preferably an unbranched or branched C 2 -C 6 -alkylene group.
  • X in the general formula (A1) is, independently of one another, an unbranched C 2 -C 5 -alkylene group, especially 1, 3-propylene and 1, 4-butylene.
  • Y in the general formula (A1) preferably represents an unbranched or branched C 2 -C 12 -alkylene group, more preferably an unbranched or branched C 2 -C 8 -alkylene group.
  • Y in the general formula (Al) is a branched or unbranched C 2 -C 5 -alkylene group and especially 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-buty - len, 1, 4-butylene and 2,2-dimethyl-1, 3-propylene.
  • the compounds of the general formula (A.I) contain more than one group Y, these may be identical or have different meanings.
  • the groups Y are the same.
  • at least two groups Y are different from one another.
  • the compounds of the general formula (A.I) contain more than one group Y, where at least two groups Y are different from one another.
  • a in the compounds of the general formula (A.I) is an integer from 1 to 70, particularly preferably an integer from 2 to 50, in particular an integer from 5 to 40.
  • the radicals R 1 in the general formula (A1) are preferably, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methyl butyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 1- Methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, 2-propylhexyl, n-decyl, isodecyl or 2-propylheptyl, n- Octy
  • the radicals R 1 in the general formula (A1) are preferably, independently of one another, an unbranched or branched C 4 -C 12 -alkyl group, with both radicals R 1 preferably being identical.
  • the radicals R 1 in the general formula (I) are n-octyl, isooctyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2-propylheptyl, 2-propylhexyl, n-undecyl or isoundecyl, where preferably both radicals R 1 are the same.
  • the radicals R 1 are both n-octyl, both are isononyl or both are 2-propylheptyl.
  • the compounds of the general formula (A1) are, because of their polymeric character, not mixtures which are uniform but mixtures of different compounds.
  • the compounds (Al) have different chain lengths, ie they are characterized by an average molecular weight.
  • both radicals R 1 and the groups X and Y contained in the repeating units can be different from one another.
  • the radicals R 1 can be mixtures of isomers.
  • the compounds of the general formula (A.I) generally have a weight average molecular weight in the range from 500 to 15,000 g / mol, preferably in the range from 2,000 to
  • the weight-average molecular weight is generally determined by gel permeation chromatography (GPC) in tetrahydrofuran against polystyrene standard.
  • THF tetrahydrofuran
  • the compounds of the general formula (A1) generally have a density at 20 ° C. according to DIN 51757 in the range from 1, 00 to 1, 30 g / cm 3 , preferably in the range from 1, 01 to 1, 25 g / cm 3 , more preferably in the range of 1, 02 to 1, 20 g / cm 3 .
  • the compounds of the general formula (A1) generally have a viscosity at 20 ° C. according to DIN EN ISO 3219 in the range from 1000 to 20 000 mPa * s, preferably in the range from 1200 to 15000 mPa * s, particularly preferably in the range from 1500 to 14000 mPa * s.
  • a sample of the polymer softening agent concerned is applied to the stator of the rotor-stator unit, consisting of a conical plate measuring unit with 25 mm diameter, of a suitable rheometer. The dynamic viscosity is then determined by a rotation measurement at 20 ° C and
  • the compounds of the general formula (A1) generally have a refractive index nD20 according to DIN 51423 in the range from 1.450 to 1.485, preferably in the range of 1.460 and 1.480, particularly preferably in the range of 1.462 to 1 , 472nd
  • the at least one plasticizer is selected, for example, from compounds (A2) of the general formula (A.II),
  • R 21 and R 22 are independently selected from branched and unbranched C 4 -C 12-AI ky I radicals n.
  • R 21 and R 22 independently of one another are preferably branched and unbranched C 9 -C 12 -alkyl radicals.
  • the radicals R 21 and R 22 independently of one another are n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, 2-propyl-4-methylhexyl, 2 -Propyl-5-methylhexyl, 2-isopropylheptyl, 2-isopropyl-4-methylhexyl, 2-isopropyl-5-methylhexyl, 2-propyl-4,4-dimethylpentyl, n-undecyl, isoundecyl, n-dodecyl or isododecyl, in particular n-nonyl, isononyl, 2-propylheptyl, 2-propyl-4-methylhexyl, in particular n-nonyl, isonon
  • R 21 and R 22 independently of one another are branched and unbranched C 9 -alkyl radicals, for example n-nonyl, isononyl or 2-propylheptyl and other C 9 -alkyl derivatives.
  • R 21 and R 22 are independently selected from n-nonyl, isononyl and 2-propylheptyl.
  • radicals R 21 and R 22 in the compounds of the general formula (A.II) are identical.
  • R 21 and R 22 are both n-nonyl, isononyl or 2-propylheptyl.
  • Especially preferred compounds of the general formula (A.II) are diisononyl phthalate and di (2-propylheptyl) phthalate.
  • the at least one plasticizer is selected, for example, from compounds (A3) of the general formula (A.III)
  • R 31 and R 32 are independently selected from branched and unbranched C 4 -C 9 alkyl radicals.
  • the radicals R 31 and R 32 independently of one another are C 7 -C 9 -alkyl, in particular n-heptyl, n-octyl, n-nonyl, isononyl, 2-ethylhexyl ,
  • radicals R 31 and R 32 in the compounds of the general formula (A.III) are identical.
  • the radicals R 31 and R 32 are both C 7 -C 9 -alkyl.
  • the radicals R 31 and R 32 are both 2-ethylhexyl or both isononyl.
  • a particularly preferred compound of the general formula (A.III) is di (2-ethylhexyl) terephthalate.
  • the at least one plasticizer is selected, for example, from compounds (A4) of the compounds of the general formula (A.IV)
  • R 41 is an unbranched or branched C 2 -C 8 -alkylene group or a straight-chain or branched C 2 -C 8 -alkenylene group containing at least one double bond
  • R 42 and R 43 are independently selected from branched and unbranched C 4 - C 12 -AI kyl radicals.
  • the group R 41 is non-cyclic, preferably linear.
  • the groups R 41 are preferably an unbranched C 2 -C 8 -alkylene group or an unbranched C 2 -C 8 -alkenylene group, particularly preferably an unbranched C 2 -C 6 -alkylene group or an unbranched C 2 -C 6 -alkenylene group having one double bond.
  • R 41 in the compounds of the general formula (A.IV) is an unbranched C 2 -C 5 -alkylene group, especially for 1, 3-propylene or 1, 4
  • the radicals R 42 and R 43 independently of one another are C 7 -C 12 -alkyl, for example n-heptyl, isoheptyl, n-octyl, n-nonyl, isononyl, 2 Ethylhexyl, isodecyl, 2-propylheptyl, n-undecyl or isoundecyl.
  • the radicals R 42 and R 43 in the compounds of the general formula (A.IV) independently of one another are C 8 -C 10 -alkyl.
  • radicals R 42 and R 43 are both 2-ethylhexyl, both are isononyl or both are 2-propylheptyl.
  • Especially preferred compounds of the general formula (A.IV) are di- (2-ethylhexyl) adipate, di- (isononyl) adipate and di- (2-propylheptyl) adipate.
  • the at least one plasticizer is selected, for example, from compounds (A5) of the general formula (A.V)
  • R 51 and R 52 are independently selected from branched and unbranched C 4 -C 12 -alkyl radicals.
  • the compounds of general formula (A.V) may exist as cis or trans isomer. Likewise, an isomeric mixture of cis- and trans-compounds may be present.
  • the radicals R 51 and R 52 independently of one another are n-octyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2-propylheptyl, n-undecyl or isoundecyl.
  • radicals R 51 and R 52 in the compounds of the general formula (AV) are identical.
  • radicals R 51 and R 52 are both 2-ethylhexyl, both isononyl or both are 2-propylheptyl.
  • a particularly preferred compound of the general formula (A.V) is di- (isononyl) -1,2-cyclohexanedicarboxylate.
  • the at least one plasticizer is, for example, selected from compounds (A6) of the general formula (A.VI)
  • R 61 , R 62 and R 63 are independently selected from branched and unbranched C 1 -C 12 -alkyl radicals and
  • the radicals R 61 , R 62 and R 63 independently of one another are C 3 -C 5 -alkyl, in particular C 4 -alkyl.
  • the radicals R 61 , R 62 and R 63 are the same.
  • a particularly preferred compound of the general formula (A.VI) is acetyltributyl citrate.
  • the at least one plasticizer is selected, for example, from compounds (A7) of the general formula (A.VII)
  • R 71 , R 72 , R 73 and R 74 are independently selected from branched and unbranched C 1 -C 12 -alkyl radicals.
  • the radicals R 71 , R 72 , R 73 and R 74 independently of one another are C 3 -C 5 -alkyl, in particular C 4 -alkyl.
  • the radicals R 71 , R 72 , R 73 and R 74 are the same.
  • carbodiimide compounds thus have at least one carbodiimide group of the general formula (B.a)
  • C B1 and C B2 each independently represent an sp 3 -hybridized carbon atom which can carry any radicals.
  • the synthesis of the carbodiimide compounds of the general formula (B.II) can be carried out, for example, from 4,4'-diisocyanatodicyclohexylmethane (H12MDI) and cyclohexyl isocyanate.
  • H12MDI 4,4'-diisocyanatodicyclohexylmethane
  • cyclohexyl isocyanate The synthesis of 4,4'-diisocyanatodicyclohexylmethane is described, for example, in Six, C. and Richter, F, Isocyanates, Organic. Ullmann's Encyclopedia of Industrial Chemistry 2003 (DOI:
  • the at least one carbodiimide compound is preferably selected from compounds of the formula (B.l)
  • R 101 are independently selected from compounds of the formulas (B.la), (B.lb), (B.lc), (B.ld),
  • R 104 and R 105 are independently selected from hydrogen and C 1 -C 4 -alkyl
  • R 106 and R 107 are independently selected from C 1 -C 20 -alkyl and C 1 -C 20 -alkoxy, x1 for a whole Number from 0 to 4,
  • y1 is an integer from 0 to 4,
  • z1 is an integer from 0 to 4,
  • R 102 and R 103 are independently selected from C 1 -C 20 alkyl, C 3 C 20 cycloalkyl, polyalkylene glycols of the general formula - (OC q H 2q) P -O-R ', wherein R' is hydrogen or C C 1 -C 4 -alkyl, p is an integer from 2 to 100 and q independently of one another represents an integer from 1 to 5,
  • n is an integer from 1 to 100.
  • the groups R 101 are preferably independently of one another (B.la), (B.lb) or (B.lc), particularly preferably (B.lb).
  • all groups R 101 are the same. Particularly preferred are then all groups R 101 for (B.lb). Specifically, in this embodiment, x1 is 0.
  • R 104 and R represents hydrogen or C 1 -C 4 alkyl, preferably hydrogen, methyl or ethyl. In a preferred embodiment, R 104 and R 105 are both methyl.
  • R 106 and R 107 are preferably, independently of one another, C 1 -C 10 -alkyl or C 1 -C 10 -alkoxy, preferably C 1 -C 4 -alkyl or C 1 - C 4 - alkoxy, wherein in each case the alkyl radicals are preferred.
  • R 106 and R 107 are the same.
  • x1 in the groups (B.la), (B.lb) or (B.lc) is O.
  • x1 and y1 in the groups (B.ld) are 0.
  • R 102 and / or R 103 are a polyalkylene glycol, then preferably polyethylene glycol, polyethylene glycol monomethyl ether or polyethylene glycol monoethyl ether.
  • R 102 and R 103 are preferably independently of one another C 1 -C 20 -alkyl, C 3 -C 20 -cycloalkyl or polyalkylene glycol of the general formula - (OC q H 2q ) P- O R ', wherein R' is hydrogen or C 1 -C 4 alkyl, p is an integer from 2 to 100 and q is independently an integer from 1 to 5.
  • R 102 and R 103 are independently C 1 -C 10 alkyl, C 3 -C 10 -cycloalkyl or polyvinyl lyalkylenglykol the general formula - (OC q H 2q) -O-R ', wherein R' Is hydrogen or C 1 -C 4 -alkyl, p is an integer from 2 to 100 and q is independently 2 or 3. In a preferred embodiment, R 102 and R 103 are the same.
  • R 102 and R 103 independently of one another are C 1 -C 10 -alkyl, or C 3 -C 10 -cycloalkyl, in particular C 1 -C 4 -alkyl or C 6 -cycloalkyl.
  • R 102 and R 103 are independently polyalkylene glycols of the general formula - (OC q H 2q ) -O-R 'where R' is hydrogen or C 1 -C 4 alkyl and p is an integer Number from 2 to 100 and where q stands independently of each other for 2 or 3.
  • x1 is preferably 0, 1, 2 or 3, preferably 0 or 1, more preferably 0.
  • y1 is 0, 1, 2 or 3, preferably 0 or 1, more preferably 0.
  • z1 is preferably 0, 1, 2 or 3, preferably 1.
  • n is an integer from 2 to 100, preferably from 2 to 50, more preferably from 5 to 20.
  • Particularly preferred compounds of the formula (B1) are compounds of the formula (B1) in which R 101 is the compounds of the formula (B.lb), x1 is 0, R 104 and R 105 are methyl, and wherein R 102 , R 103 and n are as defined above.
  • carbodiimide compounds based on 1, 3-bis (1-isocyanato-1 - methylethyl) benzene are, for example, commercially available under the brand name Elastostab® from BASF SE, Ludwigshafen, Germany.
  • carbodiimide compounds which have at least one structural unit (B.1.1).
  • carbodiimide compounds which are selected from compounds of the formula (B.I.2).
  • R 1022 and R 1032 for polyalkylene glycol of the general formula - (OC 2 H 4 ) P -OR ', where R' is methyl or ethyl, and p is an integer from 2 to 100, and wherein
  • p is an integer from 2 to 50 and I for 4.
  • the at least one carbodiimide compound is preferably selected from compounds of the formula (B.II)
  • R 201 are independently selected from compounds of the formulas (B.IIa), (B1b), (B.llc), (B.lld),
  • R 214 , R 215 , R 224 , R 225 , R 234 , R 235 , R 244 and R 245 are independently selected from a covalent bond and C 1 -C 20 -alkylene
  • R 216 , R 226 , R 236 , R 246 and R 247 are selected from C 1 -C 20 -alkyl and C 1 -C 20 -alkoxy
  • x2 is an integer from 0 to 4,
  • y2 is an integer from 0 to 4,
  • z2 is an integer from 0 to 4,
  • R 202 and R 203 are independently selected from C 1 -C 20 alkyl, C 3 C 20 cycloalkyl, polyalkylene glycol of the general formula -R "- (OC q H2q) P -O-R ', wherein R" is C C 1 -C 4 -alkylene, R 'is hydrogen or C 1 -C 4 -alkyl, p is an integer from 2 to 100 and q independently of one another is an integer from 1 to 5,
  • n is an integer from 0 to 100
  • R 201 in a first embodiment is independently (B.IId).
  • R 201 in a second embodiment independently of one another is (B.IIa), (B.IIb) or (B.IIc), preferably (B.IIc).
  • all R 201 are the same.
  • R 216 , R 226 , R 236 , R 246 and R 247 independently of one another are C 1 -C 10 -alkyl or C 1 -C 10 -alkoxy, preferably C 1 C 4 alkyl or C 1 -C 4 alkoxy, wherein in each case the alkyl radicals are preferred.
  • all R 216 , R 226 , R 236 , R 246 and R 247 are the same.
  • R 214 , R 215 , R 224 , R 225 , R 234 , R 23 5 ⁇ R 24 4 and R 24 5 are independently selected for a covalent bond or for C 1 -C 10 alkylene.
  • R 214 , R 224 , R 234 , and R 244 are covalent bonds, more preferably R 214 , R 215 , R 224 , R 225 , R 234 , R 235 , R 244, and R 245 a covalent bond.
  • R 214 , R 224 , R 234 , and R 244 are C 1 -C 10 alkylene, more preferably R 214 , R 215 , R 224 , R 225 , R 234 , R 235 , R 244 and R 245 is C 1 -C 10 -alkylene, with each C 1 -C 4 -alkylene being preferred.
  • R 202 and R 203 are preferably independently of one another C 1 -C 20 -alkyl, C 3 -C 20 -cycloalkyl or polyalkylene glycol of the general formula -R "- (OC q H2q ) P -O-R ', where R "is C 1 -C 4 -alkylene, R' is hydrogen or C 1 -C 4 -alkyl, p is an integer from 2 to 100 and q is independent each other is an integer from 1 to 5.
  • R 202 and R 203 are the same.
  • R 202 and R 203 are independently C 1 -C 10 alkyl, C 3 -C 10 -cycloalkyl o- polyalkylene glycol of the general formula -R "- (0C q H2 q), -0-R 'wherein R' is C 1 -C 4 -alkylene, R 'is hydrogen or C 1 -C 4 -alkyl, p is an integer from 2 to 100 and q is independently 2 or 3, preferably C 3 -C 10 -cycloalkyl ,
  • R 202 and R 203 independently of one another are C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl, in particular C 1 -C 4 -alkyl or C 6 -cycloalkyl.
  • R 202 and R 203 are identical and are, for example, both C 1 -C 10 -alkyl or C 3 -C 10 -cycloalkyl, in particular C 3 -C 10 -cycloalkyl, particularly preferably C 6 -cycloalkyl.
  • x.sup.2 is preferably 0, 1, 2 or 3, preferably 0 or 1, more preferably 0.
  • y2 is 0, 1, 2 or 3, preferably 0 or 1, more preferably 0.
  • z 2 is preferably 0, 1, 2 or 3, preferably 1.
  • n is preferably an integer from 1 to 100, preferably from 2 to 50, more preferably from 5 to 20. In a specific embodiment, m is 9, 10 or 1 1, in particular for 10.
  • Particularly preferred compounds of the formula (B.II) are compounds of the formula (B.II) in which R 201 is the compounds of the formula (B.IId), x 2 is 0, y 2 is 0, z 2 is 1 R 244 and R 245 represent a covalent bond, and wherein R 202 , R 203 and m are as defined above.
  • carbodiimide compounds based on 4,4'-bis (diisocyanato) - dicyclohexylmethane are particularly preferred. These are, for example, commercially available under the trade name Carbodilite® from Nisshinbo Chemical Inc., Tokyo, Japan.
  • carbodiimide compounds which have at least one structural unit (B.II.1).
  • carbodiimide compounds which are selected from compounds of the formula (B.II.2)
  • i is a number from 5 to 20, preferably 10.
  • Production methods for the compounds mentioned are known to the person skilled in the art, for example from the abovementioned literature. Furthermore, some compounds are commercially available, for example, in the manufacturers and suppliers mentioned in the examples.
  • composition according to the invention contains a polymer component (C) containing one or more polymer (s) selected from polyvinyl chloride (PVC) homopolymers and copolymers.
  • a polymer component (C) containing one or more polymer (s) selected from polyvinyl chloride (PVC) homopolymers and copolymers.
  • the composition contains one or more polymer (s) selected from PVC homopolymers and copolymers, with the proviso that the composition is 50 to 100% by weight, more preferably 80 to 100% by weight, more preferably 90 to 100 Wt .-%, based on the total amount of the polymer component of the composition, contains at least one polymer which is selected from PVC homo- and copolymers.
  • the polymer component of the composition consists essentially of one or more polymer (s) selected from PVC homopolymers and copolymers.
  • At least 20% by weight, based on the total amount of polymer in the polymer component, consists of PVC homopolymers and copolymers. Essentially, preferably at least 50 wt .-%, more preferably at least 80 wt .-%, more preferably at least 90 wt .-%, more preferably at least 95 wt .-% and more preferably at least 98 wt .-%, based on the total amount of polymer in the polymer component.
  • Polyvinyl chloride (PVC) Homopolymers are obtained by homopolymerization of vinyl chloride.
  • the PVC used according to the invention can be prepared, for example, by suspension polymerization, microsuspension polymerization, emulsion polymerization or bulk polymerization.
  • the preparation of PVC homopolymers 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.
  • Polyvinyl chloride (PVC) copolymers are composed of vinyl chloride and other comonomers different therefrom.
  • the proportion of vinyl chloride is generally at least 20% by weight, preferably at least 50% by weight and particularly preferably at least 80% by weight, based on the total weight of the monomers.
  • the PVC copolymers can be prepared similarly to the PVC homopolymers.
  • Suitable comonomers are monomers having a C-C double bond, for example ethylene or propylene, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and their C 2 -C 10 -alkyl esters, vinylidene chloride, Vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, Glycidyl methacrylate, acrylates and methacrylates with alcohol components of branched and unbranched C 1 -C 10 alcohols, vinyl aromatics such as styrene, acrylonitrile, methacrylonitrile, a, b-ethylenically unsaturated mono- and dicarboxylic acids, and maleic anhydride.
  • ethylene or propylene 1,3-butadiene, 2-chloro-1,3-butadiene
  • vinyl alcohol and their C 2 -C 10 -alkyl esters vinylidene chloride
  • a common further monomer is, for example, vinyl acetate.
  • a common PVC copolymer is, for example, polyvinyl chloride acetate (PVCA), a copolymer of vinyl chloride and vinyl acetate.
  • the polymer component may optionally contain other polymers. These are preferably selected from thermoplastic polymers and elastomers and mixtures thereof.
  • thermoplastic polymers are selected under
  • Homopolymers or copolymers which, in copolymerized form, contain at least one monomer which is selected from monomers having a C-C double bond,
  • PC Polycarbonates
  • thermoplastic polyurethanes TPU
  • Suitable monomers having a C-C double bond are, for example, ethylene, propylene,
  • Homopolymers or copolymers which contain in copolymerized form at least one monomer which is selected from monomers having a C-C double bond are, for example, polyethylene (PE), polypropylene (PP), polybutadiene, polyvinyl alcohol (PVAL), polyvinyl acetate (PVA).
  • Polyvinyl chloride (PVC) homopolymers and copolymers polyacrylates having identical or different alcohol radicals from the group of C 4 -C 8 -alcohols, polystyrene (PS), polyacrylonitrile, and copolymers thereof, as well as Polymethyl methacrylate (PMMA), methyl methacrylate-butyl acrylate copolymers, acrylonitrile-butadiene-styrene copolymers (ABS), ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EPDM), styrene-acrylonitrile copolymers (SAN ), Acrylonitrile-styrene-acrylate (ASA), styrene-butadiene-methyl methacrylate copolymers (SBMMA), styrene-maleic anhydride copolymers, styrene-methacrylic acid copolymers (SMA).
  • PVC
  • Homopolymers and copolymers of vinyl acetals are, for example, polyvinylformal (PVFO), polyvinyl acetaldehyde and polyvinyl butyral (PVB).
  • PVFO polyvinylformal
  • PVB polyvinyl butyral
  • PC Polycarbonates
  • Polyesters are, for example, polyalkylene terephthalates, polyhydroxyalkanoates (PHA), polybutylene succinates (PBS), polybutylene succinate adipates (PBSA), polycaprolactone (PCL), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV) and polylactic acid (PLA).
  • PHA polyhydroxyalkanoates
  • PBS polybutylene succinates
  • PBSA polybutylene succinate adipates
  • PCL polycaprolactone
  • PHB polyhydroxybutyric acid
  • PV polyhydroxyvaleric acid
  • PLA polylactic acid
  • Polyethers are, for example, polyoxymethylene (POM), polyphenylene ether, polyethylene glycol and polypropylene glycol.
  • Polyether ketones are, for example, polyaryl ether ketones.
  • Cellulose alkyl esters are, for example, ethylcellulose (EC), cellulose acetate (CA), cellulose propionate (CP) or cellulose acetate / butyrate (CAB).
  • EC ethylcellulose
  • CA cellulose acetate
  • CP cellulose propionate
  • CAB cellulose acetate / butyrate
  • the elastomers are preferably selected from natural rubber (NR) or synthetically produced rubber or mixtures thereof.
  • Preferred synthetically produced rubbers are, for example
  • SBR Styrene-butadiene rubber
  • BR butadiene rubber
  • NBR Nitrile butadiene rubber
  • Chloroprene rubber (CR).
  • rubbers or rubber mixtures which can be vulcanized with sulfur.
  • composition preferably contains
  • plasticizer component (A) comprising at least one plasticizer which has at least one carboxylic acid ester group
  • the compositions consist essentially of PVC homo- and copolymers.
  • At least 20% by weight, based on the total amount of polymer in the composition consists of PVC homopolymers and copolymers. Essentially, preferably at least 50% by weight, more preferably at least 80% by weight, more preferably at least 90% by weight, more preferably at least 95% by weight, and even more preferably at least 98% by weight. %, based on the total amount of polymer in the composition.
  • the content of PVC homo- and copolymers in the composition in the range of 20 to 95 wt .-%, preferably 30 to 90 wt .-% and more preferably 40 to 85 wt. -%, based on the total amount of the composition.
  • composition according to the invention contains essentially no carbodiimide compound which has a carbodiimide group of the general formula (B.x)
  • C Bx1 stands for an sp 2 -hybridized carbon atom which can carry any radicals
  • C Bx2 stands for an sp 2 -hybridized carbon atom which can carry any radicals.
  • Typical carbodiimide compounds having a carbodiimide group of the general formula (Bx) are carbodiimide compounds based on 1,3,5-triisopropyl-phenylene-2,4- diisocyanate, on 1, 3,5-triisopropyl-phenylene-2,4-diisocyanate, and / or on 1, 3,5-triisopropyl-phenylene-2,4-diisocyanate. Such compounds are commercially available as indicated in the examples.
  • compositions may contain 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.
  • At least one plasticizer selected from compounds of the general formula (A.I.), (A.IV.), (A.V.), (A.VI.) and (A.VII),
  • At least one or more polymer (s) selected from PVC homopolymers and copolymers with the proviso that the composition contains from 50 to 100% by weight, based on the total amount of the polymer component of the composition, of at least one polymer, which is selected from PVC homo- and copolymers.
  • At least one plasticizer selected from compounds of the general formula (A.I.), (A.IV.), (A.V.), (A.VI.) and (A.VII),
  • At least one or more polymer (s) selected from PVC homopolymers and copolymers with the proviso that the composition contains from 50 to 100% by weight, based on the total amount of the polymer component of the composition, of at least one polymer, which is selected from PVC homo- and copolymers.
  • At least one plasticizer selected from compounds of general formula (A.l) and
  • At least one plasticizer selected from compounds of general formula (A.l) and
  • At least one or more polymer (s) selected from PVC homopolymers and copolymers with the proviso that the composition contains from 50 to 100% by weight, based on the total amount of the polymer component of the composition, of at least one polymer, which is selected from PVC homo- and copolymers.
  • At least one plasticizer selected from compounds of general formula (A.l) and
  • At least one plasticizer selected from compounds of the general formulas (A.II.), (Al.sub.11) (A.IV.), (AV), (A.VI) and (A.VII), preferably selected from compounds of the general formulas (A.IV), (AV), (A.VI) and (A.VII).
  • the polymer component consists essentially of PVC homopolymers and copolymers.
  • the composition consists essentially of PVC homo- and copolymers.
  • Another object of the invention are molding compositions consisting of or containing a composition as defined herein.
  • the molding compositions may additionally contain at least one further polymer.
  • the further polymer may be a thermoplastic polymer or an elastomer or a mixture thereof.
  • the polymer contained in the molding composition is a thermoplastic polymer.
  • the molding compositions consist essentially of PVC homo- and copolymers. These are commonly referred to as PVC molding compounds.
  • a special embodiment are molding compositions which contain PVC homopolymers and copolymers as the sole polymer component.
  • the K value which characterizes the molar mass of the PVC and is determined according to DIN EN ISO 1628-2 (November 1999), is for the PVC softened according to the invention usually between 57 and 90, preferably between 61 and 85, in particular between 64 and 80th
  • the polymer contained in the molding composition is an elastomer.
  • Preferred elastomers are those mentioned herein.
  • the content of elastomer in the molding compositions according to the invention is from 20 to 95% by weight, preferably from 45 to 90% by weight, and in particular from 50 to 85% by weight. %, based on the total weight of the composition.
  • the molding compositions containing at least one elastomer may contain, in addition to the above constituents, other suitable additives.
  • suitable additives 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, antidegradants and other various additives that are mixed in, for example, tire and other rubber compounds.
  • HMT hexamethylenetetramine
  • a methylene acceptor such as cardanol (cashew nut) modified phenolic resins
  • a vulcanizing or crosslinking agent such as hexamethylenetetramine (HMT)
  • cardanol (cashew nut) modified phenolic resins such as hexamethylenetetramine (cashe
  • the total content of the plasticizer components (A) in the molding composition is from 1 to 60 phr, preferably from 1 to 40 phr, particularly preferably from 2 to 30 phr.
  • the molding compositions 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 reduce the adhesion between the plastics and metal surfaces to be processed and serve to counteract frictional forces during mixing, plasticizing and deformation.
  • the molding compositions of the invention may contain all the usual for the processing of plastics lubricant.
  • hydrocarbons such as oils, paraffins and polyethylene waxes (PE waxes) are suitable.
  • fatty alcohols having 10 to 20 carbon atoms fatty acids having 10 to 20 carbon atoms, montanic acid, oxidized polyethylene wax, metal salts of fatty acids having 10 to 20 carbon atoms, fatty acid esters having 10 to 20 carbon atoms.
  • 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 include fillers, such as carbon black and other inorganic 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.
  • fillers such as carbon black and other inorganic 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.
  • fillers such as carbon black and other inorganic 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.
  • calcium carbonates
  • 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 product obtained to different possible uses.
  • inorganic pigments for example, cobalt pigments, for example CoO / Al 2 O 3 , and chromium pigments, for example Cr 2 O 3 , can be used.
  • Suitable organic pigments are, for example, monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, dioxazine pigments and diketopyrrolopyrrole 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 inhibitors.
  • antimony trioxide, phosphate esters, chloroparaffin, aluminum hydroxide or boron compounds can be used as flame inhibitors.
  • 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 such as, for example, UV absorbers.
  • HALS hindered amine light stabilizers
  • the molding compositions according to the invention may have a content of light stabilizers, for example UV absorbers, of from 0.01 to 7%, preferably from 0.1 to 5%, more preferably from 0.2 to 4% and in particular from 0.5 to 3%.
  • light stabilizers for example UV absorbers
  • Another object of the invention are plastisols consisting of or containing a composition as defined herein.
  • Plastisols in the context of this invention are a suspension of finely powdered polymers in the composition according to the invention.
  • Suitable polymers are the aforementioned polymers, especially thermoplastic polymers.
  • Suitable and preferred polymers are hereby fully referenced to the compounds mentioned under molding compositions.
  • the plastisols are usually present in liquid form and gel irreversibly.
  • the plastisols consist essentially of PVC homo- and copolymers. These are commonly referred to as PVC plastisols.
  • a special embodiment are plastisols containing PVC as the sole polymer component.
  • the total content of the plasticizer component (A) in the plastisols is from 5 to 300 phr, preferably from 30 to 200 phr.
  • Plastisols are usually made into the form of the finished product at ambient temperature by various methods, such as brushing, screen printing, casting, such as shell casting or rotary 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.
  • compositions, molding compositions and plastisols according to the invention are preferably used for the production of moldings and films.
  • compositions, molding compositions and plastisols according to the invention are used, for example, for shaped articles, such as tool sheathing, bicycle, scooter or wheelbarrow handles, hoses, water hoses, irrigation hoses, industrial hoses made of elastomers, chemical hoses, wire sheaths or ka furniture, vehicle profiles, bodywork components, underbody protection, vibration dampers, erasers, foamed or unfoamed wallpapers, metal coatings and others.
  • shaped articles such as tool sheathing, bicycle, scooter or wheelbarrow handles, hoses, water hoses, irrigation hoses, industrial hoses made of elastomers, chemical hoses, wire sheaths or ka furniture, vehicle profiles, bodywork components, underbody protection, vibration dampers, erasers, foamed or unfoamed wallpapers, metal coatings and others.
  • compositions, molding compositions and plastisols according to the invention are used, for example, for films, such as, for example, tarpaulins, tarpaulins, roof tarpaulins, Geomembranes, stadium roofs, tarpaulins, gaskets, self-adhesive foils, laminating foils, shrink foils, outdoor floor coverings, tablecloths, adhesive foils, coatings, swimming pool foils, decorative foils, imitation leather and others.
  • films such as, for example, tarpaulins, tarpaulins, roof tarpaulins, Geomembranes, stadium roofs, tarpaulins, gaskets, self-adhesive foils, laminating foils, shrink foils, outdoor floor coverings, tablecloths, adhesive foils, coatings, swimming pool foils, decorative foils, imitation leather and others.
  • compositions, molding compositions and plastisols according to the invention are used, for example, for housings of electrical appliances, housings of kitchen appliances, computer housings, tools, apparatuses, pipelines, cables, hoses, plastic hoses, water hoses, irrigation hoses, industrial hoses made of elastomers, chemical hoses, wire sheathings , Window profiles, components for vehicle construction, body parts, automotive interior fittings, vibration dampers for engines, tires, furniture, chairs, tables, shelves, foam for upholstery and mattresses, tarpaulins, tarpaulins, tarpaulins, roof tarpaulins, roofing membranes, Gaskets, laminated films, laminated safety glass films, automotive and window films, artificial leather, packaging containers, foamed or unfoamed wallpapers, adhesive tape, coatings and others.
  • compositions, molding compositions and plastisols according to the invention are used, for example, for products for the interior sector, such as 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 and cladding or console covers in vehicles and others.
  • 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 and cladding or console covers in vehicles and others.
  • 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 and cladding or console covers in vehicles and others.
  • compositions, molding compositions and plastisols according to the invention are used, for example, for products for outdoor use, such as, for example, tools, apparatuses, pipelines, cables, hoses, plastic hoses, water hoses, irrigation hoses, industrial hoses, chemical hoses, wire sheathings, window profiles, Components for vehicle construction, tires, furniture, garden furniture, foam for upholstery and mattresses, tarpaulins, tarpaulins, tarpaulins, gaskets, laminated films, films for laminated safety glass, films for vehicle and window panes, artificial leather, packaging containers, adhesive tape, coatings and other.
  • products for outdoor use such as, for example, tools, apparatuses, pipelines, cables, hoses, plastic hoses, water hoses, irrigation hoses, industrial hoses, chemical hoses, wire sheathings, window profiles, Components for vehicle construction, tires, furniture, garden furniture, foam for upholstery and mattresses, tarpaulins,
  • compositions, molding compositions and plastisols according to the invention are used, for example, for sports and leisure products such as exercise balls, exercise mats, seat cushions, vibrators, massage balls and rollers, shoes, soles, balls, air mats, safety glasses, gloves and drinking bottles.
  • compositions, molding compositions and plastisols according to the invention are used, for example, for clothing such as, for example, latex clothing, protective clothing, raincoats and rubber boots.
  • compositions, molding compositions and plastisols according to the invention are suitable for the production of seamless hollow bodies, gloves and for use in the textile sector and for textile coatings.
  • the compositions according to the invention, molding compositions and plastisols, in particular PVC plastisols are suitable for the production of artificial leather, underbody protection for motor vehicles, seam seals, carpet back coatings, heavy coatings, conveyor belts, dip coatings and articles produced by dipping, toys, anatomical models for training, flooring, wall coverings, coated textiles, tarpaulins, tents, coil coatings, roofing membranes, sealing compounds for closures, respiratory masks and gloves.
  • the artificial leather is, for example, artificial leather for motor vehicle construction or handbags.
  • the toy is, for example, dolls, balls or toy animals.
  • the textiles are, for example, latex clothing, protective clothing or rainwear such as rain jackets.
  • auxiliaries selected from: calendering auxiliaries, rheological aids, surface-active compositions, lubricants, quenchers for chemical reactions, phlegmatizers, pharmaceutical products, plasticizers in adhesives fen or sealants, impact modifiers and adjusters.
  • the surface-active compositions are, for example, flow binders, film image aids, defoamers, defoamers, wetting agents, coalescing agents and emulsifiers.
  • the lubricants are, for example, lubricating oils, lubricating greases and lubricating pastes.
  • compositions, molding compositions and plastisols according to the invention are preferably used for improving the weathering resistance and / or for improving the hydrolysis resistance.
  • the compounds of general formula (A1) are prepared in a manner known per se technically, for example as described in WO 02/038531, by esterification of aliphatic dicarboxylic acids with diols in the presence of monohydric alcohols as end groups and an esterification catalyst.
  • the chain length or the average molecular weight of the compounds of the general formula (A1) is controlled via the addition ratio of the dicarboxylic acids and the dialcohols.
  • the dicarboxylic acids which are used for the preparation of the compounds of the general formula (A1) are preferably unbranched or branched C 2 -C 6 -alkyl dicarboxylic acids, more preferably unbranched C 2 -C 5 -alkyldicarboxylic acids.
  • the dicarboxylic acids are glutaric acid and / or adipic acid, especially adipic acid.
  • the diols which are used for the preparation of the compounds of the general formula (A1) are preferably unbranched or branched C 2 -C 8 -alkyldiols, more preferably unbranched and branched C 2 -C 6 -alkyldiols, for example 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 3 Pentanediol, 2-methyl-1,3-pentanediol, 2,2-dimethyl-1, 3-pentanediol, 1, 4-pentanediol,
  • diols are 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 2-dimethyl-1, 3-pentanediol or mixtures of these diols. Further preferred diols are the compounds listed herein.
  • the monohydric alcohols which are used as chain terminators in the preparation of the compounds of the general formula (Al) are preferably unbranched or branched C 7 -C 12 -alkanols, more preferably n-octanol, isooctanol , 2-ethylhexanol, n-nonanol, isononanol, 2-propylhexanol, n-decanol, isodecanol, 2-propylheptanol or mixtures of these alcohols and in particular n-octanol, isononanol, 2-propylheptanol or mixtures of these alcohols.
  • Further preferred monohydric alcohols are the compounds listed herein.
  • Adipic acid 1, 2-propanediol and n-octanol or
  • Adipic acid 1, 2-propanediol, 2, 2-dimethyl-1, 3-pentanediol and isononanol or
  • Adipic acid 1, 4-butanediol, 2, 2-dimethyl-1, 3-pentanediol and isononanol.
  • esterification catalysts usually customary catalysts are 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 is usually in the range of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the sum of acid component and alcohol component.
  • 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.
  • a solvent it is preferably an organic solvent which is inert under the reaction conditions.
  • organic solvent which is inert under the reaction conditions.
  • the solvent is preferably selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, 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 of 50 to 160 ° C.
  • the esterification catalyst is selected from amphoteric catalysts, the esterification is usually carried out in a temperature range of 100 to 250.degree.
  • 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 resulting products involved in the reaction.
  • adipic acid, 1,4-butanediol, neopentyl glycol, isononanol and isopropyl butyl titanate are initially charged as esterification catalyst in a reaction vessel, first heated to 100 ° C. to 140 ° C. and homogenized by stirring. The reaction mixture is then heated at atmospheric pressure to 160 ° C to 190 ° C. The esterification with dehydration starts at about 150 ° C. The formed reaction water is separated by distillation via a column. Over distilled alcohol components are separated and recycled.
  • reaction mixture is further heated to 200 ° C to 250 ° C, a vacuum of 150 mbar to 300 mbar applied and removed by passing nitrogen further reaction water from the reaction mixture.
  • the reaction mixture is stirred under vacuum and passed through nitrogen at 200 ° C to 250 ° C until the acid number of the reaction mixture has reached a value of ⁇ 15 mg KOH / g.
  • reaction mixture is then pumped to final esterification in a second vessel and stirred at 200 ° C to 250 ° C, a vacuum of 10 mbar to 150 mbar and removal of residual water and excess isononanol by passing an increased nitrogen flow until the acid number of the reaction mixture has reached a value of ⁇ 1.0 mg KOH / g. Thereafter, the reaction product is still filtered at 100 ° C to 140 ° C.
  • the aliphatic dicarboxylic acids, diols and monohydric alcohols used for the preparation of the compounds of the general formula (A.I) can either be obtained commercially or prepared by synthesis routes known from the literature.
  • the compounds of general formula (A.II) can either be obtained commercially or prepared by methods known in the art.
  • the preparation of the dialkyl phthalates is carried out by esterification of phthalic acid or suitable derivatives thereof with the corresponding alcohols by customary methods known to the person skilled in the art, as described, for example, in WO 2010076192 or WO 2010076194.
  • a suitable derivative is, for example, phthalic anhydride.
  • the preparation of the ester compounds of the general formula (A.II) can also be carried out by esterification of esters other than the esters of the general formula (II) with the corresponding C 10 -C 12 -alcohols according to customary methods
  • Suitable transesterification catalysts are the customary catalysts customarily 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-di-carboxylates 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
  • the amount of transesterification catalyst used is 0.05 to 5 wt .-%, preferably 0.10 to 1 wt .-%.
  • 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.
  • each of these reactors may be equipped with a distillation column, or it may be fed, preferably from the last boilers of the transesterification reactor cascade, the evaporated alcohol mixture via one or more manifolds of a distillation column.
  • the higher-boiling alcohol recovered in this distillation is preferably returned 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. If desired, the filtrate may be subjected to further workup to isolate and / or purify the product.
  • the product is separated by distillation.
  • the transesterification of the di- (C 1 -C 4 ) -alkyl esters, in particular the dimethyl or diethyl esters, of phthalic acid with at least one alcohol R 2 -OH or R 3 -OH or mixtures thereof is preferably carried out in the presence of at least one titanium (IV ) alcoholate.
  • Preferred titanium (IV) alcoholates are tetrapropoxytitanium, tetrabutoxytitanium or mixtures thereof.
  • the alcohol component is preferably used in at least twice the stoichiometric amount, based on the di (C 1 -C 4 -alkyl) esters used.
  • the transesterification can be carried out in the absence or in the presence of an added organic solvent.
  • the transesterification is preferred in the presence of an inert carried out organic solvent.
  • Suitable organic solvents are those mentioned above for the esterification. These include especially 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 resulting products involved in the reaction.
  • the transesterification is carried out without adding an inert gas.
  • the process for preparing the compounds of the general formula (A.II) has in common that, starting from phthalic acid, phthalic anhydride or other suitable derivatives thereof, an esterification or transesterification is carried out, the corresponding C 9 -C 12 -alkanols being used as starting materials be used.
  • Preferred C 9 -C 12 -alkanols which are used for the preparation of the compounds (A.II) contained in the plasticizer composition may be straight-chain or branched or consist of mixtures of straight-chain and branched C 9 -C 12 -alkanols , These include n-nonanol, isononalol, n-decanol, isodecanol, 2-propylheptanol, 2-propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-isopropylheptanol, 2-isopropyl-4-methylhexanol, 2-isopropyl-5-methylhexanol, 2-propyl-4,4-dimethylpentanol, n-undecanol, isoundecanol, n-dodecanol or isododecanol.
  • C 10 -C 12 -alkanols are 2-propylheptanol, 2-propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-isopropylheptanol, 2-isopropyl-4-methylhexanol, 2-isopropyl- 5-methylhexanol and 2-propyl-4,4-dimethylpentanol.
  • 2-propylheptanol is particularly preferred.
  • Further preferred alkanols are the compounds listed herein.
  • the abovementioned alkanols which are used for preparing the compounds (I) and / or (II) contained in the plasticizer composition may be pure substances or isomer mixtures. Frequently, the abovementioned alkanols which are used to prepare the compounds (I) and / or (II) contained in the plasticizer composition are isomer mixtures, their composition and degree of purity of the respective process depends, with which these are represented.
  • the compounds of general formula (A.III) can either be obtained commercially or prepared by methods known in the art.
  • dialkyl terephthalates are obtained by esterification of terephthalic acid or suitable derivatives thereof with the corresponding alcohols.
  • the esterification can be carried out by conventional methods known in the art, as described for example in WO 2009/095126.
  • the process for preparing the compounds of the general formula (A. III) has in common that, starting from terephthalic acid or suitable derivatives thereof, an esterification or a transesterification is carried out, wherein the corresponding C 4 -C 12 alkanols are used as starting materials .
  • These alcohols are generally not pure substances but mixtures of isomers whose composition and degree of purity depend on the particular process with which they are prepared. Preference is given to using C 7 -C 12 -alkanols as starting materials.
  • Preferred C 7 -C 12 -alkanols which are used for the preparation of the compounds (A.III) contained in the plasticizer composition according to the invention may be straight-chain or branched or of mixtures of straight-chain and branched C 7 -C 12 -alkanols consist.
  • n-heptanol isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol, 2-propylheptanol, n-undecanol, isoundecanol, n-dodecanol or isododecanol.
  • Particularly preferred C 7 -C 12 alkanols are 2-ethylhexanol, isononanol and 2-propylheptanol, especially 2-ethylhexanol. Further preferred alkanols are the compounds listed herein.
  • a suitable commercially available plasticizer of the general formula (A.III) is, for example, di- (2-ethylhexyl) terephthalate (DOTP), which is sold under the brand name Palatinol® DOTP, by BASF Corp., Florham Park, NJ, USA, is offered.
  • DBP di- (2-ethylhexyl) terephthalate
  • the compounds of the general formula (A.IV) can either be obtained commercially or prepared by methods known in the art, for example as described in EP 1171413 B1.
  • ester compounds of the general formula (I.IV) are prepared by esterification of corresponding aliphatic dicarboxylic acids with the corresponding aliphatic alcohols by conventional methods known to those skilled in the art, as already described above for the preparation of the compounds of the general formula (Al ) and others.
  • Suitable derivatives are, for.
  • a preferred acid halide is the acid chloride.
  • Suitable transesterification catalysts are the customary catalysts customarily 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 butyltin 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 zircon
  • the amount of transesterification catalyst used is 0.05 to 5 wt .-%, preferably 0.10 to 1 wt .-%.
  • 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.
  • each of these reactors may be equipped with a distillation column, or it may be fed, preferably from the last boilers of the transesterification reactor cascade, the evaporated alcohol mixture via one or more manifolds of a distillation column.
  • the higher-boiling alcohol recovered in this distillation is preferably returned 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. If desired, the filtrate may be subjected to further workup to isolate and / or purify the product.
  • the product is separated by distillation.
  • Preferred titanium (IV) alcoholates are tetrapropoxy titanium, tetrabutoxy titanium or mixtures thereof.
  • the alcohol component is preferably used at least in twice the stoichiometric amount, based on the di (C 1 -C 4 -alkyl) ester used.
  • the transesterification can 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 especially 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 resulting products involved in the reaction.
  • the transesterification is carried out without adding an inert gas.
  • the process for the preparation of the compounds of the general formula (A.IV) has in common that, starting from the corresponding aliphatic dicarboxylic acids or suitable derivatives thereof, an esterification or a transesterification is carried out, the corresponding C 4 -C 12 alkanols are used as starting materials.
  • These alcohols may be pure substances or mixtures of isomers whose composition and degree of purity depends on the particular process with which they are prepared.
  • the C 4 -C 12 -alkanols which are used to prepare the compounds (A.IV) contained in the plasticizer composition can be straight-chain or branched or consist of mixtures of straight-chain and branched C 4 -C 12 -alkanols , These include n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol, 2-propylheptanol, n-undecanol, isoundecanol, n-dodecanol or isododecanol.
  • Preferred C 7 -C 12 -alkanols are 2-
  • the preferred C 7 -C 12 -alkanols which are used for the preparation of the compounds (A.IV) contained in the plasticizer composition may be straight-chain or branched or of mixtures of straight-chain and branched C 7 -C 12 -alkanols consist. 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 2-ethylhexanol, isononanol and 2-propylheptanol, isononanol and in particular 2-ethylhexanol.
  • Further preferred alkanols are the compounds listed herein.
  • the aliphatic dicarboxylic acids and aliphatic alcohols used for preparing the compounds of the general formula (A.IV) can either be obtained commercially or prepared by synthesis routes known from the literature.
  • the compounds of the general formula (A.V) can either be obtained commercially or prepared by processes known in the art, for example as described in EP 1171413 B1.
  • the 1, 2-Cyclohexandicarbonklareester usually obtained by nuclear hydrogenation of the corresponding phthalic acid esters.
  • the nuclear hydrogenation can after the in the
  • WO 99/32427 described method.
  • a particularly suitable nuclear hydrogenation process for example, also describes WO 201 1082991 A2.
  • 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 take place by customary processes known to the person skilled in the art.
  • the process for preparing the compounds of general formula (AV) has in common that, starting from phthalic acid, 1, 2-cyclohexanedicarboxylic acid or suitable derivatives thereof, an esterification or a transesterification is carried out, wherein the corresponding C 7 -C 12 alkanols be used as starting materials.
  • These alcohols are generally not pure substances but mixtures of isomers whose composition and degree of purity depends on the particular process with which they are prepared.
  • C 7 -C 12 -alkanols which are used for the preparation in the composition according to the invention 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. Particular preference is given to C 8 -C 11 -alkanols, in particular 2-ethylhexanol, isononanol and 2-propylheptanol. Further preferred alkanols are the compounds listed herein.
  • the carbodiimide compounds of the general formulas (B.l) and (B.ll) are prepared in a manner known per se. In a typical synthesis variant, the corresponding isocyanate compounds are preferably used. Conventional methods are known to the person skilled in the art, for example from "Carbodiimide” by Werner Rasshofer in Houben-Weyl Methods of Organic Chemistry Vol. VIII, 4th Edition, pages 883-914 and "Carbodiimide” by S. Peterson /
  • EP 0850985 various synthesis routes known which lead to the corresponding carbodiimide compounds of the general formulas (B.l) and (B.ll).
  • Preferred alcohol compounds in particular heptanol, octanol, nonanol, decanol, undecanol and dodecanol, are described below.
  • the heptanols used to prepare the compounds in question may 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 obtained by the rhodium- or preferably cobalt-catalyzed hydroformylation of dimerpropene, obtainable, for example, by B. after the Dimersol® process, and subsequent hydrogenation of the obtained isoheptanals are prepared to an isoheptanol mixture. According to its production, the isoheptanol mixture thus obtained 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 can be present in situ under the conditions of the hydroformylation reaction in the hydroformylation reaction mixture Influence of synthesis gas z.
  • rhodium salts as well as complex rhodium carbonyl compounds, in particular complexes with organic phosphines, such as triphenylphosphine, or organophosphites, preferably chelating biphosphites, such as.
  • organic phosphines such as triphenylphosphine
  • organophosphites preferably chelating biphosphites, such as.
  • chelating biphosphites such as.
  • cobalt-catalyzed hydroformylation of these olefins generally homogeneously cobalt carbonyl compounds which are soluble in the reaction mixture and form under the conditions of the hydroformylation reaction under the action of synthesis gas in situ from cobalt salts are used.
  • 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 hexene 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 T1O2 included.
  • Such catalysts are z.
  • DE-A 3228881, DE-A 2628987 and DE-A 2445303 Particularly advantageous is the hydrogenation of Isoheptanale with an excess of hydrogen of 1, 5 to 20% above the amount of hydrogen required stoichiometrically for the hydrogenation of Isoheptanale, at temperatures of 50 to 200 ° C and at a Hydrogen pressure of 25 to 350 bar performed and to avoid side reactions the hydrogenation feed according to DE-A 2628987 a small amount of water, advantageously in the form of an aqueous solution of an alkali metal hydroxide or carbonate according to the teaching of WO 01087809 added.
  • 2-ethylhexanol which has been the largest amount of plasticizer alcohol 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, Vol. A 10, pp. 137-140, VCH Verlagsgesellschaft GmbH, Weinheim 1987).
  • Substantially straight-chain octanols can be obtained by 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 isooctanol alcohol due to its method of preparation, is not a uniform chemical compound, but is a mixture of isomers of differently branched C 8 -alcohols, for example of Dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 4,5-dimethyl-1-hexanol, 3-methyl-1-heptanol and 5-methyl-1-heptanol, depending on the conditions of preparation used and process in different proportions in isooctanol can be present.
  • Isooctanol is usually prepared by the codimerization of propene with butenes, preferably n-butenes, and subsequent hydroformylation of the resulting mixture of heptenic isomers.
  • the octanal isomer mixture obtained in the hydroformylation can subsequently be hydrogenated to the isooctanol in a conventional manner.
  • 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 chloride compound, for example, ethylaluminum dichloride.
  • phosphine ligands for the nickel complex catalyst z.
  • tributylphosphine Triisopropylp- 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 Pp. 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, with similar properties Hepten 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).
  • Octol® process Hydrocarbon Processing, February 1986, pp. 31-33
  • a well-suited specific nickel-Hete- rogenkatalysator for Olefindimermaschine or codimerization is z.
  • WO 9514647 discloses.
  • Bronsted acidic 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, eg. For example, diatomaceous earth impregnated with phosphoric acid or diatomaceous earth as used by the PolyGas® process for olefin or oligomerization (Chitnis et al., Hydrocarbon Engineering 10, No. 6, June 2005).
  • Bronsted-acid catalysts which are very well suited for the codimerization of propene and butenes to heptenes are zeolites, of which the EMOGAS® process is based on the PolyGas® 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. converted into n-octanal or octanal isomer mixtures. 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 nolen.
  • Substantially straight-chain 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-octene can, for example, via an ethylene enoligomerization by means of a homogeneous in the reaction medium - 1, 4-butanediol-soluble nickel ckelkomplexkatalysator with z.
  • This process is also known by the name Shell Higher Olefins Process or SHOP process (see Weisermel, Arpe: Industrielle Organische Chemie, 5th edition, page 96, Wiley-VCH, Weinheim 1998).
  • Isononanol which is used for the synthesis of the diisononyl esters of the general formulas (I) and (II) contained in the plasticizer composition according to the invention, is not a uniform chemical compound but a mixture of differently branched isomeric C 9 -Alcohols which, depending on the nature of their preparation, in particular also of the starting materials used, may have different degrees of branching.
  • the isononanols are prepared by dimerization of butenes to isooctene mixtures, subsequent hydroformylation of the isooctene mixtures and hydrogenation of the resulting isononanal mixtures to form isononanol mixtures, as in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A1, pp. 291-292, VCH Verlagsgesellschaft GmbH, Weinheim 1995, explained.
  • 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 isooctene and hydrogenation of the resulting 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, 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 by industrially established processes to form the fuel additive methyl tert-butyl ether ( MTBE) or isobutyl tert-butyl ether for the recovery of pure isobutene.
  • MTBE methyl tert-butyl ether
  • isobutyl tert-butyl ether for the recovery of 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% by weight 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 described above in connection with the production of isoheptene mixtures, for example by means of heterogeneous, Bronsted-acid catalysts, as described in US Pat PolyGas® or EMOGAS® method, by means of the Dimersol® process using homogeneously dissolved in the reaction medium nickel complex catalysts or by heterogeneous, nickel (II) oxide-containing catalysts according to the Octol® process or the method according to WO 9514647.
  • the resulting isooctene mixtures are converted into isononanal mixtures by the known processes 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 above-mentioned in connection with the isoheptanol preparation cata- tors hydrogenated to the suitable Isononanolgemischen.
  • 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.
  • n-nonanol with the value 0 methyl octanols (a branch) with the value 1 and dimethylheptanols (two branches) with the value 2 to the iso index 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 concomitant quantification of their percentage in the isononanol mixture, determined by standard methods of gas chromatographic analysis.
  • they are expediently trimethylsilylated before the gas chromatographic analysis by standard methods, for example by reaction with N-methyl-N-trimethylsilyltrifluoroacetamide.
  • capillary columns with polydimethylsiloxane as the stationary phase.
  • Such capillary pillars are commercially available and only a few routine tests are required by a person skilled in the art in order to select a product which is optimally suitable for this separation task from the wide range of commercial offerings.
  • the corresponding diisononyl esters are generally esterified with isononanols having an iso-index of 0.8 to 2, preferably from 1, 0 to 1, 8 and more preferably from 1, 1 to 1, 5, which can be prepared by the above-mentioned methods.
  • compositions of isononanol mixtures are given below, as they can be used for the preparation of the compounds in question, wherein it should be 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 , whose composition may vary due to the production of butenes and may vary from variations 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 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:
  • 0.70 to 2.70 wt.% Preferably 0.90 to 2.50 wt.%, Particularly preferably 1.20 to 2.20 wt.% Of 3,6,6-trimethylhexanol;
  • an isononanol mixture prepared by cobalt-catalyzed hydroformylation followed by hydrogenation using an ethylene-containing butene mixture as raw material by means of the polygas® or EMOGAS® process-produced isooctene mixture may be used in the range of the following compositions vary depending on the composition of the raw materials and variations in the reaction conditions used:
  • Isodecanol which is used to synthesize the diisodecyl esters in question, is not a single chemical compound but a complex mixture of differently branched isomeric decanols.
  • 2-Propylheptanol which is used for the synthesis of the corresponding di (2-propylheptyl) ester, may be pure 2-propylheptanol or propylheptanol isomer mixtures, as generally formed in the industrial preparation of 2-propylheptanol and commonly also referred to as 2-propylheptanol.
  • 2-propylheptanol can be obtained by aldol condensation of n-valeraldehyde and subsequent hydrogenation of the 2-propylheptenal formed, for example according to US Pat. No. 2,921,089.
  • commercially available 2-propylheptanol contains, in addition to the main component 2-propylheptanol, one or more of the 2-propylheptanol isomers, as a result of production, 2-propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-isopropylheptanol, 2-propylheptanol.
  • 2-propylheptanol for example 2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methyl-heptanol and / or 2-ethyl-2,5-dimethylhexanol in 2-propylheptanol, is possible.
  • the starting material for the preparation of 2-propylheptanol can be any of a variety of hydrocarbon sources, for example 1-butene, 2-butene, raffinate I - an alkane obtained from the C 4 cut of a cracker after removal of allenes, acetylenes and dienes.
  • Alkene mixture containing in addition to 1- and 2-butene still significant amounts of isobutene - or raffinate II, which is obtained from raffinate I by separation of isobutene and as olefin components except 1- and 2-butene only small proportions of Contains isobutene.
  • mixtures of raffinate I and raffinate II can also be used as raw material for 2-propylheptanol preparation.
  • These olefins or olefin mixtures can be hydroformylated according to conventional methods with cobalt or rhodium catalysts, where 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 can vary within relatively wide limits depending on the catalyst used and the hydroformylation conditions.
  • n- and iso-valeraldehyde are formed in an n / iso ratio of generally 10: 1 to 20: 1, whereas, when using phosphite ligands, for example according to US Pat. No. 5,288,918 or WO 05028407, or phosphosamidite ligands, for example according to WO 0283695, modified rhodium hydroformylation catalysts almost exclusively n-valeraldehyde is formed.
  • phosphite ligands for example according to US Pat. No. 5,288,918 or WO 05028407
  • phosphosamidite ligands for example according to WO 0283695
  • Rh / TPP catalyst system converts 2-butene 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 with the mentioned phosphite ligand or Phosphoramidite ligand-modified rhodium catalysts wherein predominantly n-Valeralde- hyd 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.
  • the C 5 -aldehydes obtained, depending on the starting materials and catalysts used, ie n-valeraldehyde optionally in admixture with iso-valeraldehyde, 3-methylbutanal and / or valaldehyde, may, if desired, be separated completely or partly into the individual components by distillation before the aldol condensation so that there is also a possibility here of influencing and controlling the isomer composition of the C10 alcohol component of the ester mixtures used 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 n-valeraldehyde as the only condensation product 2-propylheptenal, whereas when using a mixture of isomeric C 5 - aldehydes an isomeric mixture of the products of Homoaldolkondensation same Aldehydmoleküle and the crossed aldol condensation different valeraldehyde isomers is formed.
  • a basic catalyst such as an aqueous solution of sodium or potassium hydroxide
  • aldol condensation can be controlled by the targeted implementation of individual isomers so that predominantly or completely a single aldol condensation isomer is formed.
  • the aldol condensation products in question can then be hydrogenated, usually after prior, preferably distillative removal from the reaction mixture and, if desired, 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 in question may be esterified with pure 2-propylheptanol.
  • mixtures of 2-propylheptanol with said propylheptanol isomers are used for preparing these esters, 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 of 60 to 98% by weight of 2-propylheptanol, 1 to 15% by weight of 2-propyl-4-methylhexanol and 0.01 to 20 wt .-% of 2-propyl-5-methyl-hexanol and 0.01 to 24 wt .-% of 2-isopropylheptanol, wherein the sum of the proportions of the individual constituents does not exceed 100 wt .-%.
  • 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 %
  • 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 Wt .-% 2-isopropyl-5-methyl-hexanol, wherein the sum of the proportions of the individual components does not exceed 100 wt .-%.
  • the proportions of the individual components add up to 100 wt .-%.
  • Preferred mixtures of 2-propylheptanol with the propylheptanol isomers include those with 85 to 95 wt .-% of 2-propylheptanol, 5 to 12 wt .-% of 2-propyl-4-methyl-hexanol and 0.1 to 2 wt .-% 2-propyl-5-methylhexanol and 0.01 to 1 wt .-% 2-isopropylheptanol, wherein the sum of the proportions of the individual components does not exceed 100 wt .-%.
  • the proportions of the individual components add up to 100 wt .-%.
  • the isomeric acid composition of the alkylester groups or alkylether groups corresponds in practice to the composition of the propylheptanol isomer mixtures used for the esterification.
  • the undecanols which are used to prepare the compounds in question may be straight-chain or branched or may 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.
  • 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 via the SHOP process previously mentioned in the preparation of 1-octene.
  • the 1-decene obtained in the SHOP process can undergo skeletal isomerization, e.g. Example by means of acidic zeolitic molecular sieves, as in
  • WO 9823566 which form mixtures of isomeric decenes whose rhodium or preferably cobalt-catalyzed hydroformylation and subsequent hydrogenation of the resulting isoundecanal mixtures leads to the isoundecanol used to prepare the corresponding compounds.
  • the hydroformylation of 1-decene or isodecene mixtures by means of rhodium or cobalt catalysis can be carried out as described above in connection with the synthesis of C 7 - to C 10 -alcohols.
  • the C 7 - to C 5 -alkyl alcohols or mixtures thereof thus obtained can be used as described above for the preparation of the compounds (I) or diester compounds of the general formula (II) used according to the invention.
  • Substantially straight-chain dodecanol can advantageously be obtained via the Alfol® or Epal® process. These methods include oxidation and hydrolysis 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 lengths, the desired n-dodecanol can be obtained after the C 12 -alkyl alcohol fraction has been removed by distillation.
  • 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 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 purification by distillation of the hydrogenation effluent, the isododecanols thus obtained or mixtures thereof, as described above, can be used to prepare the diester compounds in question.
  • Suspension PVC brand name Inovyn® 271 PC from INOVYN ChlorVinyls Limited, London, UK
  • Polyester softener based on adipic acid, 1,4-butanediol, neopentyl glycol and isononanol trade name Palamoll® 656 from BASF SE, Ludwigshafen, Germany
  • Polyester softener based on adipic acid, 1,4-butanediol, neopentyl glycol and isononanol trade name Palamoll® 654 from BASF SE, Ludwigshafen, Germany
  • Polyester plasticizers based on adipic acid, 1,2-propanediol, neopentyl glycol and isononanol trade name Palamoll® 652 from BASF SE, Ludwigshafen, Germany
  • Polyester plasticizers based on adipic acid, 1,2-propanediol and n-octanol Brand Name Palamoll® 638 from BASF SE, Ludwigshafen, Germany
  • Acetyl tributyl citrate trade name Citrofol® Bll from Jungbunzlauer GmbH, Ladenburg, Germany
  • Pentaerythritol tetravalerate trade name Pevalen® from Perstorp Oxo AB, Stenungsund, Sweden
  • Elastostab® H05 from BASF SE, Ludwigshafen, Germany Carbodiimide based on 4,4'-bis (diisocyanato) -dicyclohexylmethane, trade name Carbodilite® HMV 15CA from Nisshinbo Chemical Inc., Tokyo, Japan
  • Ba-Zn stabilizer brand name Reagens® SLX / 781 from Reagens S.p.A., Bologna, Italy
  • PVC homopolymeric suspension PVC
  • plasticizer and optionally hydrolysis stabilizer and 2 g of Ba / Zn stabilizer were mixed according to the formulations according to Table 1 with a hand mixer at room temperature.
  • the mixture was then plasticized on an oil-heated laboratory mixer mill (Collin, automatic mill type 150, diameter: 252 mm, width: 450 mm) and processed into a rolled skin.
  • the temperature of the two rolls was 180 ° C in each case; the speeds were 15 revolutions / min. (front roller) and 12 revolutions / min. (rear roller); the rolling time was 5 minutes.
  • the test serves to quantitatively measure the compatibility of plasticizers in plasticized PVC formulations. It is carried out at elevated temperature (70 ° C or 80 ° C) and 100% relative humidity. The data obtained are evaluated against the storage time.
  • specimens with a size of 75 x 110 x 0.5 mm are used.
  • the films are punched on the broadside, labeled (soldering iron) and weighed.
  • the finished weighed slides are hung on a wire frame and placed in a glass tub, which is about 5 cm filled with water (deionized water). It should be noted that the films do not touch each other. The lower edges of the foils must not be allowed to hang in the water.
  • the glass trough is sealed with a polyethylene film so that it does not escape steam, so that the water vapor that later forms in the glass trough can not escape. The water level in the glass basin is checked daily and possibly missing water is replaced.
  • each 2 films of the glass pan are removed and air-conditioned for 1 h hanging freely suspended in the air.
  • the films are then cleaned superficially with methanol.
  • the films are dried for 16 h at 70 ° C in a drying oven with forced convection hanging freely. After removal from the drying oven, the films are air-conditioned for 1 hour and then weighed. The arithmetic mean of the weight losses of the foils is given in each case.
  • the number average and weight average molecular weights were measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the GPC was performed on a GPC system Infinity 1100 Agilent Technologies, consisting of pump, column heating, columns and with a detector DRI Agilent 1200.
  • the eluent is tetrahydrofuran (THF), which at a flow rate of 1 ml / min by a column combination of two tempered at 35 ° C columns PLgel Mixed-E from Agilent flows.
  • THF tetrahydrofuran
  • the samples dissolved in THF at a concentration of 2 mg / ml are filtered through a Macherey-Nagel PTFE-20/25 (0.2 ⁇ m) filter prior to injection. 100 ⁇ l were injected.
  • the evaluation of the measured values obtained was carried out using a calibration curve previously obtained with narrowly distributed polystyrene standards from Polymer Laboratories with molecular
  • plasticizer About 1.5 g of plasticizer were added in 50 ml of a 0.1 molar ethanolic KOH solution, and an additional 20 ml of toluene were added in order to reduce the loss in mass. Subsequently, the sample was tempered for different lengths in a heating block at 95 ° C. After the end of the experiment, 20 ml of ethanol were added and the sample was cooled for 5 minutes. Then the titration is carried out with 0.1 molar hydrochloric acid. Under the same conditions, but without a sample, an active value was determined in each experiment. The saponification of the product was calculated from the difference between the effective value and the sample consumption.
  • the saponification rate was based on the saponification degree after 60 minutes.
  • Table 2 Results of the compatibility test of the formulations or the soft PVC films after 28 days in a tropical test at 70 ° C

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition contenant : A) un composant de plastifiant, contenant au moins un plastifiant qui présente au moins un groupe ester d'acide carboxylique, B) un composant de stabilisation de l'hydrolyse, contenant au moins un composé carbodiimide, qui présente au moins un groupe carbodiimide de formule -N=C=N-, les deux atomes de N du groupe carbodiimide étant à chaque fois liés à un atome de carbone hybridé en sp3, C) un composant polymère contenant un ou plusieurs polymères choisis parmi les homopolymères et les copolymères de poly(chlorure de vinyle).
PCT/EP2019/056910 2018-03-29 2019-03-20 Composition de pvc, contenant au moins un plastifiant, qui présente au moins un groupe ester d'acide carboxylique, et au moins un composé carbodiimide WO2019185409A1 (fr)

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Cited By (1)

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CN114044994A (zh) * 2022-01-13 2022-02-15 赛立特(南通)安全用品有限公司 一种柔性缓冲材料及其制备方法和用途

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