EP3491053A1 - Composition de plastifiant - Google Patents

Composition de plastifiant

Info

Publication number
EP3491053A1
EP3491053A1 EP17742454.6A EP17742454A EP3491053A1 EP 3491053 A1 EP3491053 A1 EP 3491053A1 EP 17742454 A EP17742454 A EP 17742454A EP 3491053 A1 EP3491053 A1 EP 3491053A1
Authority
EP
European Patent Office
Prior art keywords
plasticizer
weight
disclosed
compound
ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17742454.6A
Other languages
German (de)
English (en)
Inventor
Matthias Pfeiffer
Boris Breitscheidel
Axel Grimm
Herbert Morgenstern
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3491053A1 publication Critical patent/EP3491053A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to a plasticizer composition containing at least one trimellitic acid trialkyl ester and at least one terephthalic acid tartyl ester, molding compositions containing at least one polymer and such plasticizer composition, plastisols containing at least one polymer and such plasticizer composition, and the use of these softener compositions, molding compositions and plastisols.
  • Polyvinyl chloride is one of the most widely produced plastics in terms of quantity.
  • PVC is usually a hard and brittle plastic up to about 80 ° C, which is used as rigid PVC (PVC-U) by adding heat stabilizers and other additives.
  • PVC-U rigid PVC
  • plasticizers can yield soft PVC (PVC-P), which can be used for many applications where rigid PVC is unsuitable.
  • PVC-P soft PVC
  • the use of plasticizers serves to lower the processing temperature of plastics and to increase their elasticity.
  • plasticizers are commonly used in other plastics.
  • Other plastics may be, for example, polyvinyl butyral (PVB), homopolymers or copolymers of styrene, polyacrylates, polysulfides or thermoplastic polyurethanes (TPU).
  • PVB polyvinyl butyral
  • TPU thermoplastic polyurethanes
  • plasticizers for plastics are, for example, ortho-phthalic acid esters, such as di-2-ethylhexyl phthalate, diisononyl phthalate or diisodecyl phthalate. Short-chain ortho-phthalates, however, increasingly come under pressure because of their toxicological properties.
  • plasticizers in addition to a high compatibility with the plastic to be softened, that is, they do not occur or only relatively slowly from the plastic to be plasticized, are also toxicologically largely harmless.
  • the object of the present invention is therefore to provide a plasticizer composition for plastics, for example PVC, based on DOTP, which has a high compatibility with the plastics to be plasticized and is toxicologically harmless.
  • the plasticizer composition should soften the plasticized with it Give good mechanical properties to plastics and show low volatility, both during processing and during use.
  • plasticizer composition comprising a) at least one compound of the general formula (I),
  • R 1a R 1b and R 1c are independently C3 to Cs alkyl
  • R 2a and R 2b are independently Cs-alkyl
  • An object of the disclosure is the use of the disclosed plasticizer composition as a plasticizer for plastics.
  • plasticizer composition as plasticizer for plastisols.
  • a molding composition containing at least one polymer and the disclosed plasticizer composition.
  • a plastisol is the subject of the disclosure containing at least one polymer and the disclosed softener composition.
  • a molding composition containing at least one polymer and the disclosed plasticizer composition for the production of moldings and films is the subject of the present disclosure.
  • a plastisol containing at least one polymer and the disclosed plasticizer composition for making molded articles and films is the subject of the present disclosure.
  • molded articles and films containing the disclosed plasticizer composition are the subject of the present disclosure.
  • the abbreviation phr parts per hundred resin
  • the weight percentage refers to the total weight if nothing else is stated.
  • a mixture is any mixture of two or more, for example a mixture may contain two to five or more.
  • a mixture can also contain an arbitrarily large number.
  • a gelling aid is a plasticizer
  • the dissolution temperature of the plasticizer or the mixture of different plasticizers according to DIN 53408 is not more than 125 ° C.
  • a compound of general formula (I) may be: .1 is 1, 2,4-benzenetricarboxylic acid tr ⁇ (n-propyl) ester
  • .3 is 1, 2,4-benzenetricarboxylic acid tr ⁇ (n-butyl) ester
  • .4 is 1, 2,4-benzenetricarboxylic acid tr ⁇ (iso-butyl) ester
  • .6 is 1, 2,4-benzenetricarboxylic acid tr ⁇ (2-methylbutyl) ester
  • a compound of general formula (II) may be:
  • a polymer may be an elastomer or a thermoplastic.
  • a thermoplastic can usually be processed thermoplastically.
  • thermoplastic may be, for example: TP.1 is a homopolymer or copolymer which contains in copolymerized form at least one monomer which is selected from C 2 to C 10 monoolefins, for example ethene, propylene, 1,3-butadiene, 2-chloro-1, 3-butadiene, vinyl alcohols or their C 2 - to C 10 -alkyl esters, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates or methacrylates with alcohol components of branched or unbranched C 1 to C 10 alcohols, vinyl aromatics, for example styrene , (Meth) acrylonitrile, ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acids and maleic anhydride.
  • monomer which is selected from C 2 to C
  • TP.2 is a polyvinyl ester
  • TP.3 is a polycarbonate
  • TP.4 is a polyether
  • TP.5 is a polyether ketone
  • TP.6 is a thermoplastic polyurethane
  • TP.7 is a polysulfide
  • TP.8 is a polysulfone
  • TP.9 is a polyester
  • TP.10 is a polyalkylene terephthalate
  • TP.1 1 is a polyhydroxyalkanoate
  • TP.12 is a polybutylene succinate
  • TP.13 is a polybutylene succinate adipate
  • TP.14 is a polyacrylate with identical or different alcohol radicals from the group of
  • C 4 - to Cs-alcohols such as butanol, hexanol, octanol, or 2-ethylhexanol
  • TP.15 is a polymethylmethacrylate
  • TP 16 is a methyl methacrylate-butyl acrylate copolymer
  • TP 17 is an acrylonitrile-butadiene-styrene copolymer
  • TP 18 is an ethylene-propylene copolymer
  • TP 19 is an ethylene-propylene-diene copolymer
  • TP 20 is a polystyrene
  • TP 21 is a styrene-acrylonitrile copolymer
  • TP 22 is an acrylonitrile-styrene-acrylate
  • TP 23 is a styrene-butadiene-methyl methacrylate copolymer
  • TP 24 is a styrene-maleic anhydride copolymer
  • TP 25 is a styrene-methacrylic acid copolymer
  • TP26 is a polyoxymethylene
  • TP 27 is a polyvinyl alcohol
  • TP 28 is a polyvinyl acetate
  • TP 29 is a polyvinyl butyral
  • TP 30 is a polyvinyl chloride
  • TP 31 is a polycaprolactone
  • TP 32 is polyhydroxybutyric acid
  • TP 33 is polyhydroxyvaleric acid
  • TP 34 is polylactic acid
  • TP 35 is ethylcellulose
  • TP 36 is cellulose acetate
  • TP 37 is cellulose propionate
  • TP 38 is Celite acetate / butyrate
  • polyvinyl chloride is obtained by homopolymerization of vinyl chloride.
  • the polyvinyl chloride contained in the disclosed molding composition can be prepared by, for example, suspension polymerization or bulk polymerization.
  • the polyvinyl chloride contained in the disclosed plastisol can be prepared, for example, by microsuspension polymerization or bulk polymerization.
  • the preparation of polyvinyl chloride by polymerization of vinyl chloride and preparation and composition of plasticized polyvinyl chloride are described, for example, in "Becker / Braun, Kunststoff-Handbuch, Volume 2/1: Polyvinyl chloride", 2nd edition, Carl Hanser Verlag, Kunststoff.
  • the K value which characterizes the molar mass of the polyvinyl chloride and is determined in accordance with DIN-EN 1628-2 (Nov 1999) is usually in the range from 57 to 90, preferably in the range from 61 to, for the polyvinyl chloride softened with the disclosed softener composition 85 and more preferably in the range of 64 to 80.
  • the present plasticizer composition is characterized by a high compatibility with the plastic to be softened.
  • the gelling behavior of the plasticized plastic can be positively influenced by the present plasticizer composition.
  • the present plasticizer composition may be characterized by low volatility, both in processing and during use of the final products.
  • the present plasticizer composition may have a beneficial effect on the mechanical properties of plasticized plastics therewith.
  • a measure of the elasticity of plasticized plastics is the Shore A hardness. The lower the Shore A hardness, the higher the elasticity of the plasticized plastic.
  • a measure of good gelling properties may be a low dissolution temperature and / or a low gelling temperature.
  • plasticizers in plasticized plastics characterizes the extent to which plasticizers tend to exude during use of the plasticized plastics, thereby impairing the performance properties of the plastics.
  • low volatility in processing may be reflected by low process volatility.
  • low volatility in use of the final product may be reflected in low film volatility.
  • the dissolution temperature / gelling temperature refers to the minimum temperature at which a substantially homogeneous phase forms between polymer and plasticizer.
  • the present disclosure is a plasticizer composition containing at least one compound of the general formula (I) and at least one compound of the general formula (II).
  • R 1a , R 1b and R 1c are independently C3 to C6 alkyl.
  • C3- to Cs-alkyl may be straight-chain or branched.
  • C3 to Cs-alkyl n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-methylbutyl or 3-methylbutyl.
  • R 1a , R 1b and R 1c are independently C 4 alkyl.
  • C 4 alkyl may be straight-chain or branched.
  • C 4 alkyl may be n-butyl or isobutyl.
  • R 1a, R 1 b and R 1c in a compound of general formula (I) are generally independently, R 1a, R 1 b and R 1c are the same in general.
  • the disclosed plasticizer composition contains at least one compound of general formula (I). Accordingly, the disclosed plasticizer composition may also contain a mixture of compounds of general formula (I).
  • the disclosed plasticizer composition may, for example, comprise a mixture of compounds of general formula (I) selected from 1.1, I.2, I.3, I.4, I.5, I.6 and I.7.
  • R 2a and R 2b are independently Cs-alkyl.
  • Ce-alkyl may be straight-chain or branched.
  • Cs-alkyl may be n-octyl, isooctyl, or 2-ethylhexyl.
  • R 2a and R 2b in a compound of general formula (II) are generally independent of each other, R 2a and R 2b are generally the same.
  • the disclosed plasticizer composition contains at least one compound of the general formula (II). Accordingly, the disclosed plasticizer composition may also contain a mixture of compounds of general formula (II).
  • the disclosed plasticizer composition may contain a mixture of compounds of the general formula (II) selected from 11.1 and II.2
  • a plasticizer composition may include, for example:
  • 1.7 XX a mixture of compounds 1.1 to I.7 and compound 11.1 or, a mixture of compounds 1.1 to I.7 and compound II.2 or, a mixture selected from compound 1.1, I.2, 13, I.4, I .5, I.6, and I.7 and a mixture selected from Compound 11.1 and II.2.
  • the content of at least one compound of the general formula (I) in the disclosed plasticizer composition is usually 5 to 70% by weight. It may be preferable that the content is 8 to 70% by weight, and more preferably 10 to 70% by weight.
  • the content of at least one compound of the general formula (I) in the disclosed softening composition may be, for example, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65% by weight.
  • Plasticizer composition is usually 30 to 95 weight percent. It may be preferable that the content is 30 to 92% by weight, and more preferably 30 to 90% by weight.
  • the content of at least one compound of the general formula (II) in the disclosed softening composition may be, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by weight.
  • the subject matter of the disclosure may thus be a plasticizer composition containing from 5 to 70% by weight of at least one compound of the general formula (I), and to 95 weight percent of at least one compound of general formula (II). It may be preferred that a plasticizer composition contains from 8 to 70 weight percent of at least one compound of general formula (I) and from 30 to 92 weight percent of at least one compound of general formula (II). It may further be preferred that a plasticizer composition contains from 10 to 70% by weight of at least one compound of the general formula (I) and from 30 to 90% by weight of at least one compound of the general formula (II).
  • a plasticizer composition within the scope of the disclosure may include
  • the weight ratio of the at least one compound of the general formula (I) and the at least one compound of the general formula (II) may be in the range of 1:19 to 7: 3. It may be preferred that the weight ratio is in the range of 1: 1.5 to 7: 3. Further, it may be preferable that the weight ratio is in the range of 1: 9 to 7: 3. Thus, the weight ratio of at least one compound of general formula (I) and at least one compound of general formula (II) may be in the range of 1: 15, 1: 5, 1: 1, or 2: 1.
  • a plasticizer composition may contain, in addition to at least one compound of the general formula (I) and (II), at least one plasticizer different from the compounds of the general formulas (I) and (II).
  • a plasticizer other than the compounds of the general formula (I) or (II) may, for example, be a terephthalic acid dialkyl ester having 4 to 7 carbon atoms in the alkyl chains, a terephthalic acid dialkyl ester having 9 to 13 carbon atoms in the alkyl chains Dialkyl phthalate, a cyclohexane-1,2-dicarboxylic acid dialkyl ester having 4 to 13 carbon atoms in the alkyl chains, a dialkyl cyclohexane-1, 3-dicarboxylate, a dialkyl cyclohexane-1, 4-dicarboxylate, a dialkyl malate, a dialkyl acetyl maleate , a benzoic acid alkyl ester, a dibenzoic acid ester, a saturated monocarboxylic acid alkyl ester, an unsaturated monocarboxylic acid ester, a saturated dicarboxylic acid diester, an uns
  • a terephthalic acid dialkyl ester which is different from the compound of the general formula (II), usually has 4 to 7 C atoms in the alkyl chains.
  • the alkyl chains of the dialkyl terephthalate different from the compound of general formula (II) may independently have a different number of C atoms.
  • a terephthalic acid dialkyl ester which is different from the compound of the general formula (II), usually has 9 to 13 C atoms in the alkyl chains.
  • a terephthalic acid dialkyl ester other than the compound of the general formula (II) may, for example, be diisononyl terephthalate.
  • a dialkyl phthalate may have 9 to 13 carbon atoms in the alkyl chains.
  • the alkyl chains can independently of one another have a different number of carbon atoms.
  • a dialkyl phthalate may be, for example, di-isononyl phthalate.
  • a cyclohexane-1,2-dicarboxylic acid dialkyl ester generally has 4 to 13 C atoms in the alkyl chains.
  • the alkyl chains of the cyclohexane-1,2-dicarboxylic acid dialkyl ester can independently of one another have a different number of C atoms.
  • a cyclohexane-1,2-di-carboxylic acid dialkyl ester may be, for example, di- (2-isononyl) -1,2-cyclohexanedicarboxylate, such as Hexamoll®DINCH®.
  • a cyclohexane-1, 3-dicarboxylic acid dialkyl ester may have 4 to 13 carbon atoms in the alkyl chains.
  • the alkyl chains of the cyclohexane-1, 3-dicarboxylic acid dialkyl ester may independently have a different number of carbon atoms.
  • a cyclohexane-1,4-dicarboxylic acid dialkyl ester may have 4 to 13 carbon atoms in the alkyl chains.
  • the alkyl chains of the cyclohexane-1, 4-dicarbon Aciddialkylesters may independently have a different number of carbon atoms.
  • a cyclohexane-1,4-dicarboxylic acid dialkyl ester may, for example, be di- (2-ethylhexyl) -cyclohexane-1,4-dicarboxylate.
  • An dialkyl malate or a dialkyl acetyl maleate may have from 4 to 13 carbon atoms in the alkyl chains.
  • the alkyl chains of the malic dialkyl ester or of the dialkyl acetyl malic ester may independently of one another have a different number of C atoms.
  • An alkyl benzoate may have 7 to 13 C atoms in the alkyl chain.
  • a benzoic acid alkyl ester may be, for example, isononyl benzoate, isodecyl benzoate, or 2-propylheptyl benzoate.
  • a dibenzoic acid ester may be, for example, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, or dibutylene glycol dibenzoate
  • a saturated monocarboxylic acid ester may be, for example, an ester of acetic acid, an ester of butyric acid, an ester of valeric acid, or an ester of lactic acid.
  • a saturated monocarboxylic acid ester may also be an ester of a monocarboxylic acid with a polyhydric alcohol.
  • pentaerythritol may be completely esterified with valeric acid.
  • An unsaturated monocarboxylic acid ester may be, for example, an ester of acrylic acid.
  • an unsaturated dicarboxylic acid diester may be an ester of fumaric acid.
  • An alkyl sulfonic acid ester may have 8 to 22 C atoms in the alkyl chain.
  • An alkylsulfonic acid ester may be, for example, a phenyl or cresyl ester of pentadecylsulfonic acid.
  • An isosorbide ester is usually an isosorbide diester which is esterified with Cs to Ci3 carboxylic acids.
  • An isosorbide diester may have different or identical Cs to C 13 alkyl chains.
  • a phosphoric acid ester may be tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecyldiphenyl phosphate, or bis-2 (2-ethylhexyl) phenyl phosphate, 2-ethylhexyldiphenyl phosphate.
  • the OH group may be present in free or carboxylated form, for example acetylated form.
  • the alkyl chains of the citric acid triester or of the acetylated citric acid triester independently of one another comprise 4 to 8 C atoms.
  • An alkylpyrrolidone derivative may have 4 to 18 carbon atoms in the alkyl chain.
  • a 2.5-furandicarboxylic acid dialkyl ester may have 5 to 13 carbon atoms in the alkyl chains.
  • the alkyl chains of 2,5-Furandicarbonklaredialkylesters may independently have a different number of carbon atoms.
  • a 2,5-tetrahydrofurandicarboxylic acid dialkyl ester may have 5 to 13 carbon atoms in the alkyl chains.
  • the alkyl chains of 2,5-Tetrahydrofurandicarbonklaredialkylesters can independently have a different number of carbon atoms.
  • a polyester having aromatic or aliphatic polycarboxylic acids may be a polyester based on adipic acid with polyhydric alcohols, such as dialkylene glycol polyadipates having 2 to 6 carbon atoms in the alkylene unit. Examples may be polyester adipates, polyglycol adipates and polyester phthalates.
  • the plasticizer composition disclosed contains at least one plasticizer different from those of the compound of the general formulas (I) and (II)
  • its content in the disclosed plasticizer composition is up to 50% by weight based on the total of all of Softener composition contained plasticizers. It may be preferable that the content in the disclosed plasticizer composition is up to 40% by weight. It may be further preferred that the content in the disclosed softening composition is up to 25% by weight. In general, however, it may be preferable that no plasticizer other than the compounds of the general formulas (I) and (II) is contained in the disclosed plasticizer composition.
  • a molding composition containing the disclosed plasticizer composition and at least one polymer.
  • the disclosed molding composition may accordingly also contain a mixture of polymers.
  • thermoplastic is included in the molding composition containing the disclosed plasticizer composition. Accordingly, the disclosed molding composition may also contain a mixture of thermoplastics.
  • a molding compound may contain, for example
  • thermoplastic properties are generally the routine activity of those skilled in the art.
  • the amount of the disclosed plasticizer composition in the disclosed molding composition is typically 0.5 to 300 phr. It may be preferred that the amount of the disclosed plasticizer composition in the disclosed molding composition is from 0.1 to 130 phr. It may be further preferred that the amount of the disclosed plasticizer composition in the molding composition is from 2.0 to 100 phr.
  • the amount of the disclosed plasticizer composition contained in the disclosed molding composition may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95 phr. When polyvinyl chloride is contained in the molding compound, the amount of the disclosed plasticizer composition in the disclosed molding composition is usually 5 to 300 phr.
  • the amount of the disclosed plasticizer composition in the disclosed molding composition is from 15 to 200 phr. It may be further preferred that the amount of the disclosed plasticizer composition in the disclosed molding composition is from 30 to 150 phr.
  • the amount of the disclosed plasticizer composition contained in the disclosed molding composition may be, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 1 15, 120, 125, 130, 135, 140, or 145 phr.
  • the disclosed molding composition contains 20 to 90 weight percent polyvinyl chloride. It may be preferred that the molding composition contains 40 to 90 weight percent polyvinyl chloride, and more preferably 45 to 85 weight percent.
  • the disclosed molding composition may contain 50, 55, 60, 65, 70, 75 or 80 weight percent polyvinyl chloride.
  • the disclosed molding composition containing at least one thermoplastic and the disclosed plasticizer composition may also contain other additives.
  • the disclosed plastisol containing at least one thermoplastic and the disclosed plasticizer composition may also contain other additives.
  • Additives may for example be stabilizers, lubricants, fillers, colorants, flame retardants, light stabilizers, blowing agents, polymeric processing agents, impact modifiers, optical brighteners, antistatic agents, biostabilizers or a mixture thereof.
  • the additives described below do not limit the disclosed molding composition or the disclosed plastisol, but are merely illustrative of the disclosed molding composition or the disclosed plastisol.
  • Stabilizers may be the usual polyvinyl chloride stabilizers in solid and liquid form, such as Ca / Zn, Ba / Zn, Pb, Sn stabilizers, acid-binding phyllosilicates, carbonates such as hydrotalcite, or mixtures thereof.
  • the disclosed molding composition or plastisol may contain stabilizer content of from 0.05 to 7 percent by weight based on the total weight of the molding material or the plastisol. It may be preferred that the content of stabilizers is from 0.1 to 5% by weight and more preferably from 0.5 to 3% by weight.
  • Lubricants are generally used to reduce the adhesion between the disclosed molding material or the disclosed plastisol and surfaces and, for example, are said to reduce friction when mixing, plasticizing or deforming.
  • As lubricants in the disclosed molding composition or in the disclosed plastisol all common lubricants used in plastics processing can be used.
  • Lubricants commonly used in plastics processing are, for example, hydrocarbons, such as oils, paraffins, PE waxes or mixtures thereof, fatty alcohols having 6 to 20 C atoms, ketones, carboxylic acids, such as fatty acids, montanic acids or mixtures thereof, oxidized PE waxes, metal salts of carboxylic acids, carboxylic acid amides, carboxylic acid esters resulting from the esterification of alcohols such as ethanol, fatty alcohols, glycerol, ethanediol or pentaerythritol with long-chain carboxylic acids.
  • the disclosed molding composition or plastisol may contain lubricity of 0.01 to 10 weight percent based on the total weight of the molding compound or plastic isolate.
  • the content of the lubricant is from 0.05 to 5% by weight, and more preferably from 0.2 to 2% by weight.
  • Fillers are generally used to positively influence the compressive, tensile and / or flexural strength, hardness and / or heat distortion resistance of the disclosed molding composition or plastisol.
  • fillers for example, carbon black and / or inorganic fillers may be present in the disclosed molding composition or in the disclosed plastisol.
  • Inorganic fillers may be natural calcium carbonates such as chalk, limestone, marbles, synthetic calcium carbonates, dolomite, silicates, silicic acid, sand, diatomaceous earth, aluminum silicates such as kaolin, mica, feldspar, or any mixture of two or more of the aforementioned fillers.
  • the disclosed molding composition or plastisol may contain from 0.01 to 80 percent by weight filler based on the total weight of the molding material or the plastisol. It may be preferable that the content of the filler is 0.01 to 60% by weight, and more preferably 1 to 40% by weight.
  • the disclosed molding composition or plastisol may contain 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 27, 30, 33, 36, or 39 percent by weight fillers.
  • Colorants may serve to tailor the disclosed molding composition or plastisol to different uses.
  • Colorants may be, for example, pigments and / or dyes.
  • inorganic and / or organic pigments may be included in the disclosed molding composition or in the disclosed plastisol.
  • Inorganic pigments may be cobalt pigments such as COO / Al 2 O 3 and / or chromium pigments such as Cr 2 O 3.
  • Organic pigments may be monoazo pigments, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments and / or dioxazine pigments.
  • the disclosed molding composition or plastisol may contain from 0.01 to 10 percent by weight coloring matter based on the total weight of the molding material or the plastisol. It may be preferable that the content of colorants is 0.05 to 5% by weight, and more preferably 0.1 to 3% by weight.
  • Flame inhibitors may serve to reduce the flammability of the disclosed molding material or plastisol and to reduce smoke on burning.
  • Flame inhibitors which may be included in the disclosed molding composition or in the disclosed plastisol may, for example, be antimony trioxide, chloroparaffin, phosphate esters, aluminum hydroxide and / or boron compounds.
  • the disclosed molding composition or plastisol may contain about 0.01 to 10 weight percent of flame retardants based on the total weight of the molding material or the plastisol. It may be preferable that the content of flame retardants is 0.2 to 5% by weight, and more preferably 0.5 to 2% by weight.
  • Light stabilizers such as UV absorbers, can serve to protect the disclosed molding material or plastisol by damage from the action of light.
  • Light stabilizers may, for example, be hydroxybenzophenones, hydroxyphenylbenzotriazoles, cyanoacrylates, hindered amine light stabilizers, such as derivatives of 2,2,6,6-tetramethylpiperidine or mixtures of the abovementioned compounds.
  • the disclosed molding material or plastisol may contain from 0.01 to 7 weight percent of light stabilizers based on the total weight of the molding material or the plastisol. It may be preferable that the content of the light stabilizer is 0.02 to 4% by weight, and more preferably 0.5 to 3% by weight.
  • the disclosed plasticizer composition and at least one elastomer may be included.
  • the disclosed plasticizer composition and a mixture of elastomers may also be included in the disclosed molding composition.
  • An elastomer may be, for example, a rubber.
  • a rubber may be a natural rubber or a synthetic rubber.
  • Synthetically produced rubber may be, for example, polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber.
  • the disclosed molding composition comprises at least natural rubber and / or at least one synthetic rubber, wherein the rubber or rubber mixture contained can be vulcanized with sulfur.
  • the disclosed molding composition contains at least one elastomer in a proportion of 20 to 95 percent by weight based on the total weight of the molding composition. It may be preferred that the disclosed molding composition contains at least one elastomer at a level of from 45 to 90 percent by weight. Further, it may be preferable that the disclosed molding composition contains at least one elastomer in a proportion of 50 to 85% by weight.
  • the disclosed molding composition may contain, for example, 55, 60, 65, 70, 75 or 80 percent by weight of at least one elastomer.
  • the amount of the disclosed plasticizer composition in the molding composition is usually 1 to 60 phr. It may be preferable that the amount of the disclosed plasticizer composition in the molding composition is 2 to 40 phr and further 3 to 30 phr. The amount of the disclosed plasticizer composition contained in the molding composition may be, for example, 5, 10, 15, 20 or 25 phr. Also, in the disclosed molding composition, a mixture of at least one thermoplastic and at least one elastomer may be included. Thus, in the disclosed molding composition, a mixture of polyvinyl chloride and at least one elastomer may be included.
  • the content of elastomer is generally 1 to 50 percent by weight, based on the total weight of the molding composition. It may be preferable that the content of the elastomer is 3 to 40% by weight based on the total weight of the molding compound. It may further be preferred that the content of elastomer is 5 to 30 percent by weight based on the total weight of the molding composition.
  • the disclosed molding composition may contain, for example, 10, 15, 20 or 25 percent by weight of elastomer.
  • the amount of plasticizer composition disclosed in the molding composition can vary widely to achieve the desired properties. It corresponds to the routine activity of those skilled in corresponding amounts of the disclosed
  • the amount of the disclosed plasticizer composition in the molding composition containing polyvinyl chloride and at least elastomer is 0.5 to 300 phr. It may be preferred that the amount of the disclosed plasticizer composition in the molding composition containing polyvinyl chloride and at least one elastomer is from 1 to 150 phr and further from 2 to 120 phr.
  • the amount of the disclosed plasticizer composition contained in the molding composition may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 , 90, 95, 100, 105, 1 10 or 1 15 phr.
  • a molding composition containing the disclosed plasticizer composition and at least one elastomer may also contain other additives.
  • Additives may be, for example, carbon black, silica, phenolic resins, vulcanizing or crosslinking agents, vulcanizing or crosslinking accelerators, activators, various oils, anti-aging agents or mixtures of said additives.
  • Further additives may be substances which, on the basis of his specialist knowledge, the skilled person would mix into tires or other rubber compounds in order to achieve a specific effect.
  • a plastisol containing the disclosed plasticizer composition and at least one polymer.
  • the disclosed plastisol may accordingly also contain a mixture of polymers.
  • a plastisol is a suspension of finely powdered polymer in liquid plasticizer, the rate of dissolution of the polymer in the liquid plasticizer being very low at room temperature.
  • a substantially homogeneous phase forms between polymer and plasticizer.
  • the individual isolated plastic aggregates swell and combine to form a three-dimensional highly viscous gel. This process is usually referred to as gelling and takes place from a certain minimum temperature. This minimum temperature is generally referred to as gelling or dissolving temperature.
  • the introduction of the necessary heat can be done via the parameters temperature and / or residence time.
  • thermoplastic is contained in a plastisol.
  • a plastisol may contain, for example Trimellitic acid trialkyl and
  • the plastisol may be necessary to include different amounts of the disclosed plasticizer composition in the plastisol to achieve the desired plastisol properties.
  • the setting of the desired plastisol properties is generally subject to the routine activity of the skilled person.
  • the proportion of the disclosed plasticizer composition in the plastisol is usually from 30 to 400 phr, preferably from 50 to 200 phr.
  • the content of plasticizers of the general formula (I) in a plastisol containing polyvinyl chloride is usually at least 10 phr, may preferably be at least 15 phr and may in particular be at least 20 phr.
  • the disclosed plasticizer composition can be used as a plasticizer for a polymer or a mixture of polymers.
  • the disclosed plasticizer composition can be used as a plasticizer for a thermoplastic or a mixture of thermoplastics.
  • the disclosed plasticizer composition can also be used as a plasticizer for an elastomer or blend of elastomers.
  • An elastomer may be a natural rubber or a synthetic one
  • Synthetically prepared rubber may be, for example, polyisoprene rubber, styrene-butadiene rubber, butadiene rubber, nitrile-butadiene rubber, chloroprene rubber, or any mixture thereof.
  • the disclosed plasticizer composition may also be used as a plasticizer for a blend containing at least one elastomer and at least one thermoplastic. Most commonly, the disclosed softener composition is used as a plasticizer for polyvinyl chloride or a blend of polymers containing polyvinyl chloride.
  • the disclosed plasticizer composition can be used as a plasticizer in a plastisol.
  • Most of the disclosed softening composition is used as a plasticizer in a plastisol containing polyvinyl chloride.
  • Shaped bodies may be, for example, containers, apparatus or foamed devices.
  • Containers may include, for example, housings of electrical appliances such as kitchen appliances or computer housings, pipes, hoses such as water or irrigation hoses, industrial rubber hoses, chemical hoses, wire or cable sheathing, tool sheathing, bicycle, scooter, wheelbarrow handles, metal coatings or packaging containers ,
  • Apparatus may be, for example, tools, furniture such as chairs, shelves, tables, records, profiles such as window profiles, floor profiles for outdoor use or profiles for conveyor belts, components for vehicle construction such as body components, underbody protection, vibration dampers, or erasers.
  • Foamed devices may be, for example, upholstery, mattresses, foams or insulating materials.
  • Films may include, for example, tarpaulins such as truck tarpaulins, roof tarpaulins, geomembranes, stadium roofs or tarpaulins, gaskets, composite films such as laminated safety glass films, self-adhesive films, laminating films, shrink films, outdoor flooring, tape foils, coatings, swimming pool sheeting, decorative sheeting, tablecloths or artificial leather ,
  • the disclosed molding composition can be used to make moldings or films which come into direct contact with humans or foods.
  • Shaped bodies or films which come into direct contact with humans or foods may be, for example, medical devices, hygiene products, food packaging, interior products, baby and children's products, childcare articles, sports or leisure products, clothing, fibers or fabrics.
  • Medical devices that can be made using the disclosed molding material may include, for example, enteral or hemodialysis tubes, breathing tubes, drainage tubes, infusion tubes, infusion bags, blood bags, catheters, tracheal tubes, disposable syringes, gloves, or respiratory masks.
  • Food packages that can be made using the disclosed molding composition may include, for example, cling film, food hoses, drinking water hoses, food storage or freezing containers, lid seals, caps, bottle caps or artificial wine corks.
  • Indoor products which can be produced using the disclosed molding composition can be, for example, floor coverings which are homogeneous or consist of several
  • Layers consisting of at least one foamed layer, such as floor coverings, mudflap mats, sports floors, luxury Vinyl Tiles (LVT), imitation leather, wall coverings, foamed or unfoamed wallpapers in buildings, carcasses or console covers in vehicles
  • foamed layer such as floor coverings, mudflap mats, sports floors, luxury Vinyl Tiles (LVT), imitation leather, wall coverings, foamed or unfoamed wallpapers in buildings, carcasses or console covers in vehicles
  • toys such as dolls, toy figures or kneading
  • inflatable toys such as balls or rings, stopper socks, buoyancy aids, stroller covers, changing pads, hot water bottles, teething rings or vials.
  • Sports or leisure products that can be made using the disclosed molding composition may be, for example, exercise balls, exercise mats, seat cushions, massage balls or rollers, shoes, shoe soles, balls, air mattresses, or water bottles.
  • Apparel that can be made using the disclosed molding composition can be, for example, latex clothing, protective clothing, rain jackets or rubber boots.
  • Piastisols are typically processed at ambient temperature by various methods, such as brushing, casting, such as the shell casting or rotary casting, dipping drive, printing process, such as screen printing, spraying and the like into the shape of the finished product. Subsequently, the gelation is carried out by heating, after cooling a homogeneous, more or less flexible product is obtained.
  • the disclosed plastisol can be used for the production of films, wallpapers, seamless hollow bodies,
  • Films may include, for example, truck tarpaulins, roof tarpaulins, covers in general, such as boat covers, stroller covers or stadium roofs, tarpaulins, geomembranes, tablecloths, coatings, swimming pool foils, artificial leather or decorative sheeting.
  • gloves can be gardening gloves, medical gloves, chemical gloves, protective gloves or disposable gloves.
  • the disclosed plastisol may be used, for example, to make gaskets such as gaskets, cowls or console covers in vehicles, dolls, toy figures or kneading, inflatable toys such as balls or rings, stopper socks, buoyancy aids, changing pads, exercise balls, exercise mats, seat cushions, vibrators, mas - Sawing balls or rolls, latex clothing, protective clothing, rain jackets or rubber boots are used.
  • gaskets such as gaskets, cowls or console covers in vehicles, dolls, toy figures or kneading
  • inflatable toys such as balls or rings, stopper socks, buoyancy aids, changing pads, exercise balls, exercise mats, seat cushions, vibrators, mas - Sawing balls or rolls, latex clothing, protective clothing, rain jackets or rubber boots are used.
  • the disclosed plastisol usually contains polyvinyl chloride.
  • the subject of the present disclosure is also the use of the disclosed plasticizer composition as a calendering aid or rheology aid.
  • the subject of the present disclosure is also the use of the disclosed plasticizer composition in surface-active compositions, such as flow or film binders, defoamers, antifoaming agents, wetting agents, coalescing agents or emulsifiers.
  • the disclosed plasticizer composition can also be used in lubricants such as lubricating oils, greases or lubricating pastes.
  • the disclosed softening composition can be used as a quenching agent for chemical reactions, phlegmatizers, in pharmaceutical products, in adhesives, in sealants, in printing inks, in impact modifiers or leveling agents.
  • the subject matter of the disclosure are molded articles or films containing the disclosed plasticizer composition. It is based on the use of molding materials for the manufacture of ment made of molded articles or films reference to moldings or films reference. The examples of moldings or films cited here are to be used to design the terms moldings or film in these sections.
  • Suitable derivatives are, for.
  • An acid halide may be, for example, an acid chloride.
  • the reaction can be carried out in the presence of an esterification catalyst.
  • esterification catalyst customary catalysts can be used, for.
  • mineral acids such as sulfuric acid or phosphoric acid
  • organic sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid
  • amphoteric catalysts in particular titanium, tin (IV) - or zirconium compounds, such as Tetraa Ikoxytitane, z.
  • tetra butoxytitanium, or tin (IV) oxide As tetra butoxytitanium, or tin (IV) oxide.
  • the resulting in the reaction water can be removed by conventional means, for. B. by distillation, are removed.
  • WO 02/038531 describes a process for preparing esters in which a) in a reaction zone, a mixture consisting essentially of the acid component or an anhydride thereof and the alcohol component is boiled in the presence of an esterification catalyst, b) the alcohol and water-containing vapors are separated into a fraction rich in alcohol and a fraction rich in water by rectification, c) the alcohol-rich fraction is returned to the reaction zone and the water-rich fraction
  • esterification catalysts the aforementioned catalysts are used.
  • the esterification catalyst is used in an effective amount, which is usually in the range of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the sum of acid component (or anhydride) and alcohol component.
  • Further detailed illustrations for carrying out esterification processes can be found, for example, in US Pat. No. 6,310,235 B1, US Pat. No. 5,324,853 A, DE-A 2612355 (Derwent Abstract No. DW 77-72638 Y) or DE-A 1945359 (Derwent Abstract No. DW 73-27151 U ). These documents are referred to in their entirety.
  • the esterification of the corresponding tricarboxylic acids for example
  • 1, 2,4-benzenetricarboxylic acid in the presence of the above-described alcohol components R 1a - OH, R 1b -OH and / or R 1c -OH by means of an organic acid or mineral acid, in particular concentrated sulfuric acid. It may be advantageous that the alcohol component is used at least in twice the stoichiometric amount, based on the 1, 2,4-benzenetricarboxylic acid or a derivative thereof.
  • the esterification can be carried out at ambient pressure or reduced or elevated pressure. It may be preferred that the esterification is carried out at ambient or reduced pressure.
  • the esterification may be carried out in the absence of an added solvent or in the presence of a solvent.
  • a solvent which is inert under the reaction conditions.
  • An inert solvent is generally understood as meaning a solvent which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed.
  • the inert solvent can form an azeotrope with water.
  • these include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons or ethers.
  • the solvent is selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes, di-butyl ether, THF, dioxane and mixtures thereof becomes.
  • 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. If the esterification catalyst is selected from amphoteric catalysts, the esterification is usually carried out in a temperature range of 100 to 250 ° C.
  • the esterification can take place in the absence or in the presence of an inert gas.
  • An inert gas is generally understood as meaning a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed. It may be preferred that the esterification takes place without the addition of an inert gas.
  • the alcohol and the acid are combined in a 2: 1 functional group molar ratio in a stirred flask together with the esterification catalyst aluminum tri-methyl sulfonate in a molar ratio of 400: 1 based on the acid without inert gas.
  • the reaction mixture is heated to boiling, preferably from 100 to 140 ° C.
  • the water formed in the reaction is distilled off azeotropically together with the alcohol and then separated off.
  • the alcohol is returned to the reaction mixture.
  • the 1, 2,4-benzenetricarboxylic acid and aliphatic alcohols used for the preparation of the compounds of the general formula (I) can either be obtained commercially or prepared by synthesis routes known from the literature.
  • the compounds of the general formula (I) can also be prepared by transesterification. Transesterification procedures and specific procedures are either known to those skilled in the art or are apparent to him by his general knowledge.
  • starting materials are compounds of the general formula (I) in which R 1a R 1b and R 1c independently of one another represent d- to C 2 -alkyl.
  • trialkyl tricarboxylates for example trimethyl trimellitate, triethyl trimellitate, dimethyl trimethyl end-trimethyl ester or methyl trimellitate or mixtures thereof, with at least one alcohol component selected from the alcohols R 1a -OH R 1b -OH and R 1c- OH, where R 1a , R 1b and R 1c is C 3 - to C 5 -alkyl, in the presence of a suitable transesterification catalyst.
  • transesterification catalysts for example, the usual, usually for
  • Transesterification reactions used catalysts into consideration which are usually used in esterification reactions. These include z.
  • mineral acids such as sulfuric acid or phosphoric acid
  • organic sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid
  • the special metal catalysts from the group of tin (IV) catalysts for example dialkyltin dicarboxylates such as dibutyltin diacetate, trialkyltin alkoxides, monoalkyltin compounds such as monobutyltin dioxide, tin salts such as tin acetate or tin oxides
  • titanium catalysts monomeric or polymeric titanates or titanium chelates such as tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate, triethanolamine titanate
  • zirconium catalysts zirconates or zirconium
  • the amount of transesterification catalyst used may generally be from 0.001 to 10% by weight. It may be preferable that the amount is 0.05 to 5% by weight.
  • the reaction mixture is usually heated to the boiling point of the reaction mixture, so that the reaction temperature, depending on the reactants in a temperature range of 20 to 200 ° C.
  • the transesterification can be carried out at ambient pressure or reduced or elevated pressure. It may be preferred that the transesterification is carried out at a pressure of 0.001 to 200 bar, and more preferably at a pressure of 0.01 to 5 bar.
  • the lower-boiling alcohol eliminated during the transesterification can be distilled off continuously in order to shift the equilibrium of the transesterification reaction.
  • the distillation column required for this purpose is usually in direct contact with the transesterification reactor.
  • the distillation column can be installed directly on the transesterification reactor.
  • each of these reactors may be equipped with a distillation column or, preferably from the last boilers of the transesterification reactor cascade, the vaporized alcohol mixture may be fed via one or more manifolds to a distillation column.
  • the recovered in this distillation higher boiling alcohol is preferably recycled back to the transesterification.
  • the transesterification of the tri (C 1 -C 2) -alkyl esters of corresponding tricarboxylic acids, for example 1, 2,4-benzenetricarboxylic acid, with at least one alcohol component selected from the alcohols R 1a -OH R 1b -OH and R 1c -OH, where R 1a , R 1b and R 1c are C 3 - to C 5 -alkyl, may preferably be carried out in the presence of at least one titanium (IV) -alcoholate.
  • Preferred titanium (IV) alcoholates are tetrapropoxy titanium, tetrabutoxy titanium or mixtures thereof. It may be preferred that the alcohol component is used at least in twice the stoichiometric amount, based on the tri- (C 1 -C 2 -alkyl) esters used.
  • the transesterification can be carried out in the absence or in the presence of an added solvent. It may be preferred that the transesterification is carried out in the presence of an inert solvent. Suitable solvents are those mentioned above for the esterification. These include especially toluene and THF.
  • the temperature in the transesterification is usually in a range of 20 to 200 ° C.
  • the transesterification can be carried out in the absence or in the presence of an inert gas.
  • An inert gas is generally understood as meaning a gas which, under the given reaction conditions, does not react with the starting materials, reagents, solvents or the products formed. It may be preferable that the transesterification is carried out without adding an inert gas.
  • Preparation of compounds of the general formula (II) The compounds of the general formula (II) can either be obtained commercially or prepared by methods which are either known to the person skilled in the art or can be deduced from his general knowledge.
  • terephthalic acid dialkyl esters are obtained by esterification of terephthalic acid or suitable derivatives thereof with the corresponding alcohols. Methods and specific procedures are either known to those skilled in the art or are apparent to him by his general knowledge.
  • the process for the preparation of the compounds of general formula (II) has in common that starting from terephthalic acid or suitable derivatives thereof, an esterification or a transesterification is carried out, wherein the corresponding Cs-alkanols are used as starting materials.
  • These alcohols are usually not pure substances, but mixtures of isomers whose composition and degree of purity depends on the particular method with which they are presented.
  • Preferred Cs-alkanols which are used for the preparation of the compounds (II) contained in the plasticizer composition according to the invention may be straight-chain or branched or consist of mixtures of straight-chain and branched Cs-alkanols. These include n-octanol, isooctanol or 2-ethylhexanol. It may be preferred that 2-ethylhexanol is used.
  • Octanol 2-ethylhexanol which was the plasticizer alcohol produced in the largest amounts for many years, can be obtained, for example, 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, for example, by the rhodium- or preferably cobalt-catalyzed hydroformylation of 1-heptene and subsequent hydrogenation of the resulting n-octanal to n-octanol.
  • the 1-epoxide required for this purpose can be obtained, for example, from the Fischer-Tropsch synthesis of hydrocarbons.
  • the isooctanol alcohol is generally not a uniform chemical compound but an isomeric mixture of differently branched Cs-alcohols, for example Dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 4,5-dimethyl-1-hexanol, 3-methyl-1-heptanol and 5-methyl-1-heptanol which, depending on the conditions of preparation used and can be present in different ratios in isooctanol method.
  • Isooctanol is usually prepared by the codimerization of propene with butenes, such as n-butenes, and subsequent hydroformylation of the resulting mixture of heptene isomers.
  • the octanal isomer mixture obtained in the hydroformylation can then be hydrogenated in a conventional manner to the isooctanol.
  • the codimerization of propene with butenes to isomeric heptenes can be carried out, for example, with the aid of the homogeneously catalyzed Dimersol® process (for example Chauvin et al., Chem. Ind., May 1974, pp. 375-378), in which the catalyst used is a soluble nickel Phosphine complex in the presence of an ethylaluminum chlorine compound, for example Ethylaluminiumdichlo- rid serves.
  • phosphine ligands for the nickel complex catalyst may, for.
  • tributylphosphine tri-isopropylphosphine, tricyclohexylphosphine and / or Tribenzylphosphin be used.
  • the reaction generally takes place at temperatures of 0 to 80 ° C., it being advantageous to set a pressure at which the olefins are dissolved in the liquid reaction mixture (for example Cornils, Hermann: Applied Homogeneous Catalysis with Organo metallic Compounds; 2nd edition, Vol 1, pages 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), a well-suited specific nickel heterogeneous catalyst for Olefindimermaschine or codimerization is z. As disclosed in WO 9514647.
  • catalysts based on nickel it is also possible to use brominated-acid heterogeneous catalysts for the codimerization of propene with butenes, as a rule higher-branched heptenes than in the nickel-catalyzed process are obtained.
  • catalysts suitable for this purpose are solid phosphoric acid catalysts z.
  • diatomaceous earth impregnated with phosphoric acid or diatomaceous earth as used for example by the PolyGas® process for Olefindi- or oligomerization (for example, Chitnis et al; Hydrocarbon Engineering ⁇ 0, No. 6 - June 2005).
  • Br ⁇ nsted-acidic catalysts are usually zeolites, which, for example, uses the further developed based on the PolyGas® process EMOGAS® process.
  • the 1-heptene and the heptene isomer mixtures are prepared by the known processes described above in connection with the preparation of n-heptanal and heptanal isomer mixtures by means of rhodium- or cobalt-catalyzed hydroformylation, preferably cobalt-catalyzed hydroformylation, in n-octanal or octanal isomer mixtures. These are then z.
  • homopolymeric emulsion PVC was used as Solvin® 367 NC and / or Vinnolit® P 70, isononylbenzot as Vestinol® INB, isodecylbenzoate as Jayflex® MB 10, di- (2-ethylhexyl) terephthalate as EASTMAN 168 TM, Diisononyl phthalate as Palatinol® N, trimellitic tri- (2-ethylhexyl) ester as Palatinol® TOTM and the Ba-Zn stabilizer as reagent SLX / 781 used.
  • the product properties are, as far as available from the data sheets of the manufacturers, indicated in the following table.
  • the acid number was determined (according to DIN EN ISO 21 14 06/2002). At a value of 55 mg KOH or below, part of the wet isobutanol was replaced with fresh, dry isobutanol and the reaction continued under reflux until the acid number had fallen below a value of 1 mg KOH. The reaction mixture was cooled to about 100 ° C and then a 20% aqueous sodium hydroxide solution was added and stirred for 30 minutes. The amount of aqueous sodium hydroxide solution required is calculated according to the acid number SZ:
  • the product was obtained as a light yellowish oil in a yield of 1920 g (98%) and a purity of 96%.
  • the following table gives the properties of the compounds as described above.
  • the dissolution temperature was determined in accordance with DIN 53408 (06/67). The lower the dissolution temperature, the better the gelling behavior of the substance in question for PVC.
  • compound I.3 and compound I.4 show a lower dissolving temperature for PVC than the gelling aids Vestinol® INB and Jayflex® MB10.
  • the dynamic viscosity is slightly higher.
  • 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester and 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester are compared with the plasticizers EASTMAN 168 TM, Palatinol® N and Palatinol® TOTM significantly lower solution temperature for PVC.
  • plastisols were the PVC and a mixture of the plasticizer compositions according to the invention.
  • Plasticizer di (2-ethylhexyl) terephthalate (as EASTMAN 168 TM) with 1, 2,4-benzenetricarboxylic acid tri- (n-butyl) ester (compound I.3) or 1, 2,4- Benzene tricarboxylic acid tris (iso-butyl) ester (compound I.4) in different proportions (EASTMAN 168 TM to 1, 2,4-benzenetricarboxylic acid tri- (n-butyl) ester (compound I.3) 88/12, 75/25 and 78/22, or EASTMAN 168 TM to 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4) 85/15), according to the following recipe produced:
  • plastisols were prepared as a comparison which, apart from PVC, exclusively contain the soft materials di (2-ethylhexyl) terephthalate (as EASTMAN 168 TM), diisononyl phthalate (as Palatinol® N) or trimellitic acid tri- (2-ethylhexyl) ester ( as Palatinol® TOTM) or plastisols containing 73% of the plasticizer EASTMAN 168 TM with 27% of the gelling assistant Vestinol® INB and a plastisol with 64% of the plasticizer EASTMAN 168 TM with 36% of the gelling agent Jayflex® MB 10.
  • EASTMAN 168 TM di (2-ethylhexyl) terephthalate
  • Palatinol® N diisononyl phthalate
  • trimellitic acid tri- (2-ethylhexyl) ester as Palatinol® TOTM
  • plastisols containing 73%
  • the viscosity measurements were carried out with an oscillatory and rotary rheometer MCR 302 from Anton Paar in an oscillation test.
  • the plastisols with the softening composition according to the invention gel at much lower temperatures than the plastisol containing exclusively Eastman 168 TM.
  • a composition of 88 wt.% Eastman 168 TM and 12 wt.% Of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester compound I.3
  • a gelling temperature of 150 ° C is achieved the gelation of the plasticizer Palatinol® ® N is and is sufficient for many plastisol applications.
  • the gelling temperature of the plastisols can be further significantly lowered.
  • the gelling temperature of 150 ° C is also reached, which corresponds to the gelling temperature of Palatinol ® N.
  • plastisols were prepared with a plasticizer composition comprising 12% by weight of 1, 2,4-benzenetricarboxylic acid tri- (n-butyl) ester (compound I.3) and 88% by weight Eastman 168 TM or from 15% 1, 2, 4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4 ) and 85% by weight Eastman 168 TM and with the softener compositions comprising 27% by weight Vestinol® INB and 73% by weight Eastman 168 TM and 36% by weight Jayflex® MB 10 and 64% by weight Eastman 168 TM. The following recipe was used.
  • Plastisols containing exclusively Eastman 168 TM, Palatinol® N or 1,2,4-benzenetricarboxylic acid tri (iso-butyl) ester were prepared as a comparison. The following recipe was used.
  • the liquid plastisol In order to be able to determine performance properties of the plastisols, the liquid plastisol must be converted into a processable, solid film. For this, the plastisol was pregelled at low temperature. The pre-gelation of the plastisols took place in a Mathis oven.
  • a new relay paper was clamped in the fixture at the Mathisofen.
  • the oven was preheated to 140 ° C; the gel time is set to 25 s.
  • the gap adjustment the gap between the paper and the doctor blade was adjusted to 0.1 mm with the thickness template.
  • the thickness gauge was set to 0.1 mm.
  • the gap was set to a value of 0.7 mm on the dial gauge.
  • the plastisol was applied to the paper and smoothed with a squeegee. Then the jig was driven into the oven via the start button. After 25 s, the clamping device drove out of the oven again.
  • the plastisol was gelled and the resulting film was peeled off the paper in one piece. The thickness of this film was about 0.5 mm.
  • 3 square specimens (49 ⁇ 49 mm) were punched out with a Shore hardness punching iron from the prefilm, weighed and then gelled for 2 minutes at 190 ° C. in a Mathis oven. After cooling, these specimens were reweighed and the% weight loss calculated. The specimens were always positioned exactly in the same position of the relay paper. For this purpose, a line was drawn across the paper at the height of the hole in the frame to which the template for the Petri dishes was attached. The position for the 3 specimens was aligned at this line. They lay evenly across the width on the paper centered on the line.
  • the process volatility of the plasticizer composition of the present invention is 12% by weight of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3) and 88% by weight of Eastman 168 TM or 15% 1, 2,4-benzenetricarboxylic acid tri (isobutyl) ester (Compound I.4) and 85% by weight Eastman 168 TM significantly lower than the process volatility of the 527% Vestinol softener compositions ® INB and 73% by weight Eastman 168 TM or 36% by weight Jayflex® MB 10 and 64% Eastman 168 TM.
  • significantly less plasticizer is lost during the processing of the plastisols.
  • the process volatility of the plasticizer composition according to the present invention comprises 12% by weight of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (compound I.3) and 88% by weight of Eastman 168 TM or 15% 1, 2, 4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) and 85% by weight Eastman 168 TM is slightly higher than that of the pure plasticizers Eastman 168 TM or Palatinol® N, and significantly lower than the process volatility of the pure gelling agent
  • the Shore A hardness of the plastisol sheet having the disclosed plasticizer composition is 12 weight percent of 1,2-tri (n-butyl) 2,4-benzenetricarboxylic acid (Compound I) 3) and 88% by weight Eastman 168 TM or 15% by weight 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4) and 85% by weight Eastman 168 TM lower than the Shore A hardness of the films of the plastisols with the softener compositions of 27 wt.% Vestinol® INB and 73 wt.% Eastman 168 TM and 36 wt.% Jayflex® MB 10 and 64 wt.% Eastman 168 TM ,
  • the use of the disclosed plasticizer compositions thus leads to a higher elasticity of the PVC articles.
  • the Shore A hardness of the disclosed plasticizer composition is 15% by weight of 1, 2,4-tricarboxylic acid tri- (isobutyl) ester (Compound I.4) and 85% by weight Eastman 168 TM significantly lower than the Shore A hardness of the films containing only the plasticizer Eastman 168 TM or the gelling aid 1, 2, 4-benzenetricarboxylic tri- (iso-butyl) ester.
  • plastisols having the disclosed plasticizer composition were prepared from 12% by weight of 1,2,3-tri (n-butyl) 1,4-benzenetricarboxylic acid ester (Compound I.3) and 88% by weight Eastman 168 TM resp 15% by weight of 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4) and 85% by weight of Eastman 168 TM and plastisols with the softener compositions of 27% by weight of Vestinol® INB and 73% by weight Eastman 168 TM and 36% by weight Jayflex® MB 10 and 64% by weight Eastman 168 TM prepared as described under II.c).
  • PVC plastisols were also prepared containing exclusively Eastman 168 TM Palatinol® N or 1,2,4-benzenetricarboxylic acid tri (iso-butyl) ester (compound I.4).
  • the plastisol was gelled directly at 190 ° C. for 2 minutes in the Mathis oven. On the approximately 0.5 mm thick films thus obtained, the film volatility test was carried out.
  • the film volatility of the disclosed plasticizer composition is 12% by weight of tri (n-butyl) 2,4-benzenetricarboxylate (compound I.3) and 88% by weight.
  • the disclosed plasticizer compositions therefore, less plasticizer escapes in the finished, plasticized PVC article.
  • the film volatility of the disclosed plasticizer composition was 12% by weight of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3) and 88% by weight of Eastman 168 TM and 15% by weight, respectively , 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) and 85% by weight Eastman 168 TM is comparable to that of the pure plasticizers Eastman 168 TM resp. Palatinol® N and significantly lower than that of the pure 1, 2,4-benzenetricarboxylic tri- (iso-butyl) ester (Compound I.3) and 88% by weight of Eastman 168 TM and 15% by weight, respectively , 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) and 85% by weight Eastman 168 TM is comparable to that of the pure plasticizers Eastman 168 TM resp. Palatinol® N and significantly lower than
  • plastisols having the disclosed softening composition were prepared from 12% by weight of 1, 2,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3) and 88% Eastman 168 TM and 15 respectively %
  • 1,4-benzenetricarboxylic acid tri (iso-butyl) ester Compound I.4
  • 85% by weight of Eastman 168 TM and plastisols with the plasticizer compositions of 100% by weight 1, 2, 4-benzenetricarboxylic acid tris (iso-butyl) ester (Compound I.4), 27% Vestinol® INB and 73% by weight Eastman 168 TM and 36% by weight Jayflex® MB 10 and 64% Eastman 168 TM as prepared under ll.c).
  • the test serves to qualitatively and quantitatively measure the compatibility of plasticized PVC formulations. It is carried out at elevated temperature (70 ° C) and humidity (100% rel. H). The data obtained are evaluated against the storage time.
  • test specimens 10 test specimens (foils) with a size of 75 ⁇ 1 ⁇ 10 ⁇ 0.5 mm were used per formulation. The films were punched on the broadside, labeled and weighed. The label must be smudge-proof and can z. B. done with the soldering iron. Testers
  • Warming cabinet, analytical balance, temperature measuring device with sensor for measuring the interior temperature of the heating cabinet, basin made of glass, metal frames made of stainless material;
  • Test medium water vapor formed at 70 ° C from demineralized water
  • the temperature in the interior of the heating cabinet was set to the required 70 ° C.
  • the test films were hung on a wire rack and placed in a glass pan about 5 cm high with water (deionized water). Only films of the same composition may be stored in a designated and numbered basin in order to avoid mutual interference and to facilitate removal after the respective storage periods.
  • the glass pan was sealed with a PE film so that it could not escape the water vapor that later formed in the glass pan.
  • the sweat performance of the disclosed softener composition is 12% by weight of 1,2,3,4-benzenetricarboxylic acid tri (n-butyl) ester (Compound I.3) and 88% by weight Eastman 168 TM or 15% by weight of 1, 2,4-benzenetricarboxylic acid tri (iso-butyl) ester (Compound I.4) and 85% by weight of Eastman 168 TM significantly better than the exudation behavior of the softener compositions of FIG.
  • Trialkyl trimellitates differing in carbon number in their alkyl chains were examined for their process volatility and film volatility.
  • the determination of the process volatility was carried out analogously to II.
  • C) the determination of the film volatility was carried out analogously to II.
  • plastisols with the following formulation were used:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition de plastifiant comprenant a) au moins un composé de formule générale (I), dans laquelle R1a, R1b et R1c représentent séparément les uns des autres alkyle C3 à C5, b) au moins un composé de formule générale (II), dans laquelle R2a et R2b représentent séparément alkyle C8.
EP17742454.6A 2016-08-01 2017-07-27 Composition de plastifiant Withdrawn EP3491053A1 (fr)

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EP16182123 2016-08-01
PCT/EP2017/068984 WO2018024596A1 (fr) 2016-08-01 2017-07-27 Composition de plastifiant

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CN109563309B (zh) * 2017-02-10 2020-11-03 株式会社Lg化学 增塑剂组合物和包含该增塑剂组合物的树脂组合物
CN110382643A (zh) 2017-03-01 2019-10-25 巴斯夫欧洲公司 包含pvc和增塑组分的涂覆剂组合物
EP3589707B1 (fr) 2017-03-01 2022-10-05 Basf Se Composition d'agent de revêtement à base de pvc et composants plastifiants
BR102018077549A2 (pt) * 2018-08-24 2020-03-10 Maria Eugênia Moniz de Aragão Gonzaga Composição, processo e produto resultante de solados para calçados

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DE1945359B2 (de) 1969-09-08 1973-05-10 Verfahren zur gewinnung von estern
DE2612355C3 (de) 1976-03-24 1983-11-17 Basf Ag, 6700 Ludwigshafen Verfahren zur Abtrennung von Katalysatoren aus rohen Weichmacherestern
US5324853A (en) 1993-01-19 1994-06-28 Exxon Chemical Patents Inc. Process for the production of plasticizer and polyolesters
DE4339713A1 (de) 1993-11-22 1995-05-24 Basf Ag Verfahren zur Oligomerisierung von Olefinen zu hochlinearen Oligomeren und Katalysatoren dafür
DE19721347B9 (de) 1997-05-22 2005-09-29 Celanese Chemicals Europe Gmbh Verfahren zur Herstellung von Esterweichmachern
DE10056179A1 (de) 2000-11-13 2002-05-29 Basf Ag Verfahren zur Herstellung von Estern mehrbasiger Säuren
US6675560B2 (en) * 2001-06-29 2004-01-13 Eastman Chemical Company PVC food wrap formed from dioctyl terphthalate plasticizer, method of forming same and method of wrapping food therewith
US8372912B2 (en) * 2005-08-12 2013-02-12 Eastman Chemical Company Polyvinyl chloride compositions
US20130089728A1 (en) * 2010-08-12 2013-04-11 Zeon Corporation Vinyl chloride resin composition for powder molding, and molded article and laminate of vinyl chloride resin
WO2014093438A1 (fr) * 2012-12-11 2014-06-19 Baxter International Inc. Compositions de pvc stabilisées par rayonnement et leur procédé de fabrication
US20160075671A1 (en) * 2013-04-12 2016-03-17 Basf Se Tetrahydrofuran derivatives and use thereof as plasticizers
WO2016153235A1 (fr) * 2015-03-20 2016-09-29 주식회사 엘지화학 Composition de plastifiant et composition de résine, et procédé pour les préparer
KR101901010B1 (ko) * 2015-03-20 2018-09-20 주식회사 엘지화학 가소제 조성물, 수지 조성물 및 이들의 제조 방법

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US20190161598A1 (en) 2019-05-30
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WO2018024596A1 (fr) 2018-02-08
CA3032594A1 (fr) 2018-02-08
RU2019105688A3 (fr) 2020-11-19

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