Plasticizer composition containing furan derivatives and 1,2-cyclohexanedicarboxylic
ester
BACKGROUND OF THE INVENTION
The present invention relates to a plasticizer composition which comprises at least one
furan derivative and at least one 1,2-cyclohexanedicarboxylate ester, molding
compounds which comprise a thermoplastic polymer or an elastomer and such a
plasticizer composition and the use of these plasticizer compositions and molding
compounds.
PRIOR ART
To achieve desired processing or use properties, so-called plasticizers are added to
many plastics in order to make these softer, more flexible andlor more ductile. In
general, the use of plasticizers serves to shift the thermoplastic range of plastics to
lower temperatures, in order to obtain the desired elastic properties in the range of
lower processing and use temperatures.
Polyvinyl chloride (PVC) is among the most produced plastics in terms of quantity.
Because of its multiplicity of possible uses, it is nowadays found in a large number of
products in everyday life. A great commercial importance is therefore ascribed to PVC.
Originally, PVC is a plastic which is rigid and brittle up to ca. 80°C, which via the
addition of heat stabilizers and other additives is used as rigid PVC (PVC-U). Only by
the addition of suitable plasticizers is soft PVC (PVC-P) obtained, which can be used
for many use purposes for which the rigid PVC is unsuitable.
Further important thermoplastic polymers in which plasticizers are usually to be found
are for example polyvinyl butyral (PVB), homo- and copolymers of styrene, polyacrylates,
polysulfides or thermoplastic polyurethanes (PU).
Whether a substance is suitable for use as a plasticizer for a particular polymer largely
depends on the properties of the polymer to be plasticized. As a rule, plasticizers are
desired which have high compatibility with the polymer to be plasticized, i.e. impart
good thermoplastic properties to this and only have a low tendency to evaporation
and/or sweating (high permanence).
A large number of different compounds for plasticizing PVC and other plastics are
obtainable on the market. Because of their good compatibility with PVC and their
advantageous use properties, phthalate diesters with alcohols of different chemical
structure, such as for example diethylhexyl phthalate (DEHP), diisononyl phthalate
(DINP) and diisodecyl phthalate (DIDP) were often used in the past as plasticizers.
Short-chain phthalates, such as for example dibutyl phthalate (DBP), diisobutyl
phthalate (DIBP), benzyl butyl phthalate (BBP) or diisoheptyl phthalate (DIHP), are also
used as fast fusers, e.g. in the production of so-called plastisols. Apart from the shortchain
phthalates, dibenzoate esters such as dipropylene glycol dibenzoate can also be
used for the same purpose. A further class of plasticizers with good gelling properties
are for example the phenyl and cresyl esters of alkylsulfonic acids, which are
obtainable under the trademark Mesamoll@.
Plastisols are initially a suspension of finely powdered plastics in liquid plasticizers.
Here the rate of dissolution of the polymer in the plasticizer at ambient temperature is
very low. Only on heating to higher temperatures does the polymer dissolve
appreciably in the plasticizer. In the process, the individual isolated plastic aggregates
swell and fuse into a highly viscous three-dimensional gel. This process is described as
gelling and takes place beyond a certain minimum temperature, which is described as
the gelling or dissolution temperature. The gelling step is not reversible.
Since plastisols exist in liquid form, these are very often used for coating a great variety
of materials, such as for example textiles, glass non-wovens, etc. In such cases, the
coating is very often built up of several layers.
In industry, therefore, the procedure often used in the processing of plastisol products
is that one layer of plastisol is applied and directly afterwards the plastic, in particular
PVC, is gelled with the plasticizer above the dissolution temperature, thus a solid layer
consisting of a mixture of gelled, partly gelled and non-gelled plastic particles is formed.
The next layer is then applied onto this gelled layer and after application of the last
layer the whole structure is processed as a whole to the completely gelled plastic
product by heating to higher temperatures.
Apart from plastisols, dry powder mixtures of plasticizer and plastics can also be
produced. Such dry blends, in particular based on PVC, can then be further processed
at elevated temperatures, e.g. by extrusion, to granules or processed to the completely
gelled plastic product by conventional molding processes, such as injection molding,
extrusion or calendering.
In addition, because of the increasing technical and economic demands on the
processing of thermoplastic polymers and elastomers, plasticizers which have good
gelling properties are also desired.
Particularly in the production and processing of PVC plastisols, for example for the
production of PVC coatings, it is inter alia desirable to have a plasticizer with a low
gelling temperature available as a fast fuser. In addition, high storage stability for the
plastisol is desirable, in other words the non-gelled plastisol should exhibit only a slight
5 or no viscosity increase with time at ambient temperature. These properties should as
far as possible be attained by addition of a suitable plasticizer with rapid gelling
properties, whereby the use of further viscosity-decreasing additives andlor of solvents
should be unnecessary.
10 However, as a rule fast fusers often have compatibility with the polymers to which they
are added which requires improvement, and likewise a permanence which also still
requires improvement. Hence in order to arrive at the desired plasticizer properties the
use is also known of mixtures of plasticizers, for example at least one plasticizer which
imparts good thermoplastic properties, but gels less well, in combination with at least
15 one fast fuser.
Furthermore, there is the need to replace at least some of the phthalate plasticizers
mentioned at the outset, since these are suspected of being harmful to health. This
applies especially for sensitive use fields such as children's toys, food packaging or
20 medical articles.
In the prior art, various alternative plasticizers with different properties are known for
various plastics and especially for PVC.
25 A class of plasticizers known from the prior art, which can be used as an alternative to
phthalates, is based on cyclohexanepolycarboxylic acids, as described in WO
99132427. In contrast to their non-hydrogenated aromatic analogs, these compounds
are toxicologically harmless and can also be used in sensitive use fields. The
corresponding lower alkyl esters as a rule have fast fusing properties.
30
WO 00178704 describes selected dialkyl cyclohexane-1,3- and 1,Cdicarboxylate esters
for use as plasticizers in synthetic materials.
US 7,973,194 B1 teaches the use of dibenzyl cyclohexane-l,Cdicarboxylate, benzyl
35 butyl cyclohexane-l,4-dicarboxylate and dibutyl cyclohexane-l,4-dicarboxylate as fast
fusing plasticizers for PVC.
A further class of plasticizers are the esters of 2,5-furandicarboxylic acid (FDCS).
WO 201211 13608 describes C5 dialkyl esters of 2,5-furandicarboxylic acid and use
thereof as plasticizers. These short-chain esters are also especially suitable for the
production of plastisols.
5 WO 201211 13609 describes C7 dialkyl esters of 2,5-furandicarboxylic acid and use
thereof as plasticizers.
WO 201 11023490 describes CS dialkyl esters of 2,5-furandicarboxylic acid and use
thereof as plasticizers.
10
WO 201 11023491 describes Clo dialkyl esters of 2,5-furandicarboxylic acid and use
thereof as plasticizers.
R. D. Sanderson et al. (J. Appl. Pol. Sci., 1994, Vol. 53, 1785-1793) describe the
15 synthesis of esters of 2,5-furandicarboxylic acid and use thereof as plasticizers for
plastics, in particular polyvinyl chloride (PVC), polyvinyl butyral (PVB), polylactic acid
(PLA), polyhydroxybutyric acid (PHB) or polyalkyl methacrylate (PAMA). Specifically,
the di(2-ethylhexy1)-, di(2-octyl)-, dihexyl- and dibutyl esters of 2,5-furandicarboxylic
acid are described and their plasticizing properties characterized by dynamic
20 mechanical thermal analyses.
The present invention is based on the objective of providing a plasticizer composition
for thermoplastic polymers and elastomers which on the one hand imparts good
thermoplastic properties and on the other hand good gelling properties, i.e. a low
25 gelling temperature. The plasticizer composition should thereby in particular be suitable
for the preparation of plastisols. The plasticizer composition should have high
compatibility with the polymer to be plasticized, possess high permanence, and also be
toxicologically harmless.
30 Surprisingly, this problem is solved by means of a plasticizer composition comprising
a) at least one compound of the general formula (I),
wherein
X is *-(C=O)-0-, *-(CH2),-0- or *-(CH2),-0-(C=O)-, wherein * represents the
linkage point with the furan ring and n has the value 0, 1 or 2;
and
R1 and R2 are mutually independently selected from C4 alkyl and C5-Cs cycloalkyl,
wherein the cycloalkyl residues are unsubstituted or can be substituted with
at least one C1-Clo alkyl residue substituted,
10 b) at least one compound of the general formula (II),
0
wherein
R~ and R4 are mutually independently selected from branched and unbranched
C7-C12 alkyl residues.
A further subject of the invention are molding compounds which comprise at least one
20 thermoplastic polymer or elastomer and one plasticizer composition, as defined
previously and below.
A further subject of the invention is the use of a plasticizer composition, as defined
previously and below, as a plasticizer for thermoplastic polymers, in particular polyvinyl
25 chloride (PVC), and elastomers.
A further subject of the invention is the use of a plasticizer composition, as defined
previously and below, as a plasticizer in plastisols.
30 A further subject of the invention is the use of these molding compounds for the
production of molded articles and films.
DESCRIPTION OF THE INVENTION
The plasticizer compositions according to the invention have the following advantages:
5 - The plasticizer compositions according to the invention are characterized by high
compatibility with the polymer to be plasticized, in particular PVC.
- The plasticizer compositions according to the invention impart to the polymer to
be plasticized a high permanence.
10
- The plasticizer compositions according to the invention are advantageously
suitable for the obtention of a large number of very diverse and complex
processing and use properties of plastics.
15 - The plasticizer composition according to the invention is advantageously suitable
for the production of plastisols.
- The compounds (I) present in the plasticizer composition according to the
invention are very suitable as fast fusers, on the basis of their exceptionally low
dissolution temperatures according to DIN 53408. Small quantities of the
compounds (I) in the plasticizer composition according to the invention are
already sufficient to reduce the temperature necessary for gelling a thermoplastic
polymer and/or to increase the rate thereof.
25 - The plasticizer compositions according to the invention are suitable for use for
the production of molded articles and films for sensitive use fields such as
medicinal products, food packaging, products for the interior sector, for example
homes and vehicles, toys, child care articles, etc.
30 - For the production of the compounds (I) present in the plasticizer compositions
according to the invention, readily accessible educts can be used. A particular
economic and ecological advantage lies in the possibility of being able to use
both petrochemical raw materials available in large quantities and also renewable
raw materials for the production of the compounds (I) used according to the
invention. Thus for example the starting materials for the furan nuclei are
obtainable from naturally occurring carbohydrates such as cellulose and starch,
whereas the alcohols usable for the introduction of the side-chains are available
from large-scale industrial processes. Thus on the one hand the demand for
"sustainable" products can be covered, on the other hand, however, profitable
production is also possible.
- The methods for the production of the compounds (I) used according to the
invention are simple and efficient, hence these can be prepared without difficulty
on the large industrial scale.
5
As mentioned above, it was surprisingly found that the compounds of the general
formula (I) present in the plasticizer composition according to the invention, in particular
the C4 dialkyl esters of furandicarboxylic acid, have very low dissolution temperatures
and excellent gelling properties. Thus their dissolution temperatures according to DIN
10 53408 lie markedly below the dissolution temperatures of the corresponding dialkyl
esters of phthalic acid and have at least equally good rapid gelling properties.
It was found that the compounds (I), especially in combination with 1,2-cyclohexanedicarboxylate
esters of the general formula (II), are suitable for improving the gelling
15 behavior of thermoplastic polymers and elastomers. Also, small quantities of the
compounds (I) in the plasticizer composition according to the invention are already
sufficient to reduce the temperature necessary for gelling and/or to increase the gelling
rate.
20 In the context of the present invention, a fast fuser is understood to mean a plasticizer
which has a dissolution temperature according to DIN 53408 of less than 120°C. Such
fast fusers are used in particular for the production of plastisols.
In the context of the present invention, the expression "C1-Clo alkyl" comprises straight-
25 chain or branched CI-Clo alkyl groups. Preferably however these are straight-chain or
branched C1-Cs alkyl groups. These include methyl, ethyl, propyl, isopropyl, n-butyl,
isobutyl, sec.-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-
dimethylpropyl, 1,l -dimethylpropyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 2-hexyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,
30 2,3-dimethylbutyl, 1, l-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-
trimethylpropyl, 1,2,2-trimethylpropyl, 1 -ethylbutyl, 2-ethylbutyl, 1 -ethyl-2-methylpropyl,
n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, l-propylbutyl, n-octyl and the like.
Particularly preferably, however, they are straight-chain or branched C1-C5 alkyl
groups.
35
The expression "C4 alkyl" comprises straight-chain and branched C4 alkyl groups.
Preferably, C4 alkyl is selected from n-butyl, isgbutyl, sec.-butyl and tert.-butyl.
Particularly preferably, C4 alkyl is n-butyl or isobutyl.
The expression "C7-C12 alkyl" comprises straight-chain and branched C7-CI2 alkyl
groups. Preferably c 7 - C ~al kyl is selected from n-heptyl, I-methylhexyl, 2-methylhexyl,
I-ethylpentyl, 2-ethylpentyl, I-propylbutyl, 1-ethyl-2-methylpropyl, n-octyl, isooctyl, 2-
ethylhexyl, n-nonyl, isononyl, 2-propylhexyl, n-decyl, isodecyl, 2-propylheptyl, nundecyl,
isoundecyl, n-dodecyl, isododecyl and the like. Particularly preferably, C7-CI2
alkyl is n-octyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2-propylheptyl, n-undecyl or
isoundecyl.
In the sense of the present invention, the expression 11C5-C6 cycloalkyl" comprises
cyclic hydrocarbons with 5 to 6, in particular with 6 carbon atoms. These include
cyclopentyl or cyclohexyl.
Substituted C5-C6 cycloalkyl groups can, depending on their ring size, have one or
more (e.g. 1, 2, 3, 4 or 5) C1-Clo alkyl substituents. Examples of substituted C5-C6
cycloalkyl groups are 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, 2-, 3- and
4-methylcyclohexyl, 2-, 3- and 6ethylcyclohexyI, 2-, 3- and 4-propylcyclohexyl, 2-, 3-
and 4-isopropylcyclohexyI, 2-, 3- and 4-butylcyclohexyl, 2-, 3- and 4-sec.-butyl
cyclohexyl and 2-, 3- and 4-tert.-butylcyclohexyl.
Preferably the groups X in the compounds of the general formula (I) have the same
meaning.
In a first preferred embodiment, in the compounds of the general formula (I), the groups
X both are *-(C=O)-0-.
In a further preferred embodiment, in the compounds of the general formula (I) the
groups X both are *-(CH2)-0-(C=O)-.
In a further preferred embodiment, in the compounds of the general formula (I) the
groups X both are *-(CH2),-0-, wherein n is 0, 1 or 2. Particularly preferably, n is 1.
Preferably, in the compounds of the general formula (I) the residues R1 and R2 mutually
independently are an unbranched or branched C4 alkyl residue.
Particularly preferably, in the compounds of the general formula (I) the residues R' and
R2 mutually independently are n-butyl or isobutyl.
In a preferred implementation, in the compounds of the general formula (I) the residues
R1 and R2 have the same meaning.
Preferred compounds of the general formula (I) are selected from
di-(n-butyl) 2,5-furandicarboxylate,
di-n-butyl ether of 2,5-di(hydroxymethyl)furan,
25-di(hydroxymethy1)furan di-n-butanoate,
di-(isobutyl) 2,5-furandicarboxylate,
di-isobutyl ether of 2,5-di(hydroxymethyl)furan,
2,5-di(hydroxymethy1)furan di-isobutanoate
and mixtures of two or more than two of the aforementioned compounds.
A particularly preferably compound of the general formula (I) is di-(n-butyl) 2,5-furandicarboxylate.
In a further preferred embodiment, in the compounds of the general formula (11) the
residues R3 and R4 have the same meaning.
Preferably, in the compounds of the general formula (11) the residues R3 and R4 both
are 2-ethylhexyl, both are isononyl or both are 2-propylheptyl.
A particularly preferably compound of the general formula (11) is di-(isononyl) l,2-cyclohexanedicarboxylate.
By adaptation of the contents of the compounds (I) and (11) in the plasticizer
composition according to the invention, the plasticizer properties can be matched to the
relevant use purpose. For use in specific use fields, it can in some cases be helpful to
ad to the plasticizer compositions according to the invention further plasticizers
different from the compounds (I) and (11). For this reason, the plasticizer composition
according to the invention can optionally comprise at least one further plasticizer
different from the compounds (I) and (11).
The additional plasticizer different from the compounds (I) and (11) is selected from
dialkyl phthalate esters, aryl alkyl phthalate esters, 1,2-cyclohexanedicarboxylate
esters different from compounds (II), dialkyl terephthalate esters, trialkyl trimellitate
esters, alkyl benzoate esters, dibenzoate esters of glycols, hydroxybenzoate esters,
esters of saturated mono- and dicarboxylic acids, esters of unsaturated dicarboxylic
acids, amides and esters of aromatic sulfonic acids, alkylsulfonate esters, glycerin
esters, isosorbide esters, phosphate esters, citrate triesters, alkylpyrrolidone
derivatives, 2,5-furandicarboxylate esters different from compounds (I), 2,5-
tetrahydrofurandicarboxylate esters, epoxidized plant oils and epoxidized fatty acid
monoalkyl esters, and polyesters of aliphatic andlor aromatic polycarboxylic acids with
at least dihydric alcohols.
Suitable dialkyl phthalate esters which can advantageously be mixed with the
compounds (I) and (II), mutually independently have 4 to 13 C atoms, preferably 8 to
13 C atoms, in the alkyl chains. A suitable alkyl aralkyl phthalate ester is for example
benzyl butyl phthalate. Suitable 1,2-cyclohexanedicarboxylate esters different from the
compounds (11) mutually independently have respectively 3 to 6 C atoms, preferably 4
to 6 C atoms, in the alkyl chains. Suitable dialkyl terephthalate esters preferably
mutually independently have respectively 4 to 13 C atoms, in particular 7 to 11 C
atoms, in the alkyl chains. Suitable dialkyl terephthalate esters are for example di-(nbutyl)
terephthalate dialkyl ester, di-(2-ethylhexyl) terephthalate dialkyl esters, di-
(isononyl) terephthalate dialkyl esters or di-(2-propylheptyl) terephthalate dialkyl esters.
Suitable trialkyl trimellitate esters preferably mutually independently have respectively 4
to 13 C atoms, in particular 7 to 11 C atoms, in the alkyl chains. Suitable alkyl benzoate
esters preferably mutually independently have respectively 7 to 13 C atoms, in
particular 9 to 13 C atoms, in the alkyl chains. Preferred alkyl benzoate esters are for
example isononyl benzoate, isodecyl benzoate or 2-propylheptyl benzoate. Suitable
dibenzoate esters of glycols are diethylene glycol dibenzoate and dibutylene glycol
dibenzoate. Suitable esters of saturated mono- and dicarboxylic acids are for example
esters of acetic acid, butyric acid, valeric acid, succinic acid or lactic acid and the
mono- and dialkyl esters of glutaric acid, adipic acid, sebacic acid, malic acid or tartaric
acid. Suitable dialkyl adipate esters preferably mutually independently have
respectively 4 to 13 C atoms, in particular 6 to 10 C atoms, in the alkyl chains. Suitable
esters of unsaturated dicarboxylic acids are for example esters of maleic acid and
fumaric acid. Suitable alkylsulfonate esters preferably have an alkyl residue with 8 to
22 C atoms. These include for example the phenyl or cresyl esters of pentadecylsulfonic
acid. Suitable isosorbide esters are isosorbide diesters, which are preferably
mutually independently respectively esterified with C8-CI3 carboxylic acids. Suitable
phosphate esters are tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl
phosphate, isodecyl diphenyl phosphate, bis-(2-ethylhexyl) phenyl phosphate and 2-
ethylhexyl diphenyl phosphate. In the citrate triesters, the OH group can be present in
free or carboxylated form, preferably acetylated. The alkyl residues of the acetylated
citrate triesters preferably mutually independently have 4 to 8 C atoms, in particular 6
to 8 C atoms. Suitable are alkylpyrrolidone derivatives with alkyl residues of 4 to 18 C
atoms. Suitable dialkyl 2,5-furandicarboxylate esters different from the compounds (I)
mutually independently have respectively 7 to 13 C atoms, preferably 8 to 12 C atoms,
in the alkyl chains. Suitable dialkyl 2,5-tetrahydrofurandicarbylate esters mutually
independently have respectively 7 to 13 C atoms, preferably 8 to 12 C atoms, in the
alkyl chains. Suitable epoxidized plant oils are for example epoxidized fatty acids from
epoxidized soya oil, for example. obtainable from Galata-Chemicals, Lampertheim,
Germany. Epoxidized fatty acid monoalkyl esters, for example obtainable under the
trademark re~lex~o'"f 'P olyOne, USA, are also suitable. The polyesters of aliphatic and
aromatic polycarboxylic acids are preferably polyesters of adipic acid with polyhydric
alcohols, in particular dialkylene glycol polyadipates with 2 to 6 carbon atoms in the
alkylene residue.
In all the above-mentioned cases, the alkyl residues can each be linear or branched
and in each case be the same or different. Reference is made to the general
statements made at the outset concerning suitable and preferred alkyl residues.
The content of the at least one further plasticizer different from the compounds (I) and
(11) in the plasticizer composition according to the invention is usually 0 to 50 wt.%,
preferably 0 to 40 wt.%, particularly preferably 0 to 30 wt.% and in particular 0 to 25
wt.%, based on the total quantity of the at least one further plasticizer and the
compounds (I) and (11) in the plasticizer composition.
In a preferred embodiment, the plasticizer composition according to the invention
comprises no further plasticizer different from the compounds (I) and (11).
Preferably, the content of compounds of the general formula (I) in the plasticizer
composition according to the invention is 1 to 50 wt.%, particularly preferably 2 to 40
wt.% and in particular 3 to 30 wt.%, based on the total quantity of the compounds (I)
and (11) in the plasticizer composition.
Preferably, the content of the compounds of the general formula (11) in the plasticizer
composition according to the invention is 10 to 99 wt.%, particularly preferably 50 to 98
wt.% and in p'articular 70 to 97 wt.%, based on the total quantity of the compounds (I)
and (11) in the plasticizer composition.
In the plasticizer composition according to the invention, the weight ratio between
compounds of the general formula (I) and compounds of the general formula (11)
preferably lies in the range from 1 :I 00 to 1:1, particularly preferably in the range from
1 :50 to 1 :2 and in particular in the range from 1 :30 to 1 :2.
Molding com~ounds
A further subject of the present invention relates to a molding compound, comprising at
least one polymer and a plasticizer composition as previously defined.
In a preferred embodiment, the polymer present in the molding compound is a
thermoplastic polymer.
As thermoplastic polymers, all thermoplastically processable polymers are possible. In
particular, these thermoplastic polymers are selected from:
- homo- or copolymers which comprise at least one monomer incorporated by
polymerization, which is selected from C2-CI0 monoolefins, such as for example
ethylene or propylene, 1,3-butadiene, 2-chloro-l,3-butadiene, vinyl alcohol and
C2-CI0 alkyl esters thereof, vinyl chloride, vinylidene chloride, vinylidene fluoride,
tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and
methacrylates with alcohol components of branched and unbranched C1-Clo
alcohols, vinyl aromatics such as for example styrene, (meth)acrylonitrile, a,Pethylenically
unsaturated mono- and dicarboxylic acids, and maleic anhydride;
- homo- and copolymers of vinyl acetals;
- polyvinyl esters;
- polycarbonates (PC);
- polyesters, such as polyalkylene terephthalates, polyhydroxyalkanoates (PHA),
polybutylene succinates (PBS) and polybutylene succinate adipates (PBSA);
- polyethers;
- polyether ketones;
- thermoplastic polyurethanes (TPU);
- polysulfides;
- polysulfones;
and mixtures thereof.
Polyacrylates with the same or different alcohol residues from the group of the C4-C8
alcohols, particularly butanol, hexanol, octanol and 2-ethylhexanol, polymethyl
rnethacrylate (PMMA), methyl methacrylate-butyl acrylate copolymers, acrylonitrilebutadiene-
styrene copolymers (ABS), ethylene-propylene copolymers, ethylenepropylene-
diene copolymers (EPDM), polystyrene (PS), styrene-acrylonitrile
copolymers (SAN), acrylonitrile-styrene-acrylate (ASA), styrene-butadiene-methyl
methacrylate copolymers (SBMMA), styrene-maleic anhydride copolymers, styrenemethacrylic
acid copolymers (SMA), polyoxymethylene (POM), polyvinylalcohol
(PVAL), polyvinyl acetate (PVA), polyvinyl butyral (PVB), polycaprolactone (PCL), polyhydroxybutyric
acid (PHB), polyhydroxyvaleric acid (PHV), polylactic acid (PLA),
ethylcellulose (EC), cellulose acetate (CA), cellulose propionate (CP) or cellulose
acetatelbutyrate (CAB) can for example be mentioned.
Preferably, the at least one thermoplastic polymer present in the molding compound
according to the invention is polyvinyl chloride (PVC), polyvinyl butyral (PVB) or homoand
copolymers of vinyl acetate, homo- and copolymers of styrene, polyacrylates,
thermoplastic polyurethanes (TPU) or polysulfides.
Depending on which thermoplastic polymer or thermoplastic polymer mixture is present
5 in the molding compound, different quantities of plasticizer are used. As a rule, the total
plasticizer content in the molding compound is 0.5 to 300 phr (parts per hundred resin
= parts by weight per hundred parts by weight polymer), preferably 0.5 to 130 phr,
particularly preferably 1 to 35 phr.
10 In particular, the at least one thermoplastic polymer present in the molding compound
according to the invention is polyvinyl chloride (PVC).
Polyvinyl chloride is obtained by homopolymerization of vinyl chloride. The polyvinyl
chloride (PVC) used according to the invention can for example be produced by
15 suspension polymerization, microsuspension polymerization, emulsion polymerization
or bulk polymerization. The production of PVC by polymerization of vinyl chloride and
production and composition of plasticized PVC are for example described in
"BeckerlBraun, Kunststoff-Handbuch, Volume 211: Polyvinyl Chloride", 2nd Edition, Carl
Hanser Verlag, Mijnchen.
20
For the PVC plasticized according to the invention, the K value, which characterizes
the molecular mass of the PVC and is determined according to DIN 53726, mostly lies
between 57 and 90, preferably between 61 and 85, in particular between 64 and 75.
25 In the context of the invention, the content of PVC in the molding compounds according
to the invention is about 20 to 95 wt.%, preferably about 45 to 90 wt.% and in particular
about 50 to 85 wt.%.
If the thermoplastic polymer in the molding compounds according to the invention is
30 polyvinyl chloride, the total plasticizer content in the molding compound is 1 to 300 phr,
preferably 5 to 130 phr, particularly preferably 10 to 120 phr and in particular 15 to 100
phr.
A further subject of the present invention relates to molding compounds comprising at
35 least one elastomer and at least one plasticizer composition as previously defined.
Preferably, the elastomer present in the molding compounds according to the invention
is at least one natural rubber (NR), or at least one synthetically produced rubber, or
mixtures thereof. Preferred synthetically produced rubbers are for example
polyisoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR),
nitrile-butadiene rubber (NBR) or chloroprene rubber (CR).
Rubbers or rubber mixtures which can be vulcanized with sulfur are preferable.
5
In the context of the invention, the content of elastomer in the molding compounds
according to the invention is about 20 to 95 wt.%, preferably about 45 to 90 wt.% and in
particular about 50 to 85 wt.%.
10 In the context of the invention, the molding compounds which comprise at least one
elastomer, in addition to the above components, can comprise other suitable additives.
For example, they can comprise reinforcing fillers such as carbon black or silicon
dioxide, other fillers, a methylene donor such as hexamethylenetetramine (HMT), a
methylene acceptor, such as phenol resins modified with cardanol (from cashew nuts),
15 a vulcanizing or crosslinking agent, a vulcanization or crosslinking accelerator,
activators, various types of oil, anti-ageing agents and various other additives which
are for example mixed into tire and other rubber compounds.
If the polymer in the molding compounds according to the invention is rubbers, the
20 content of the plasticizer composition according to the invention, as defined above, in
the molding compound is 1 to 60 phr, preferably 1 to 40 phr, particularly preferably 2 to
30 phr.
Additives moldina com~ound
25
In the context of the invention, the molding compounds comprising at least one
thermoplastic polymer can comprise other suitable additives. For example, they can
comprise stabilizers, lubricants, fillers, pigments, flame retardants, light stabilizers,
propellants, polymeric processing aids, impact modifiers, optical brighteners, antistatic
30 agents or biostabilizers.
Below, some suitable additives are described in more detail. However, the examples
presented do not represent any limitation of the molding compounds according to the
invention, but serve only for illustration. All content information is stated in wt.% based
35 on the total molding compound.
As stabilizers, all usual PVC stabilizers in solid and liquid form are possible, for
example usual CaIZn, BaIZn, Pb or Sn stabilizers and also acid-binding layer silicates
such as hydrotalcite.
The molding compounds according to the invention can have a content of stabilizers
from 0.05 to 7%, preferably 0.1 to 5%, particularly preferably from 0.2 to 4% and in
particular from 0.5 to 3%.
Lubricants should become active between the PVC pastilles and counteract frictional
forces during mixing, plasticizing and molding.
As lubricants, the molding compounds according to the invention can comprise all
lubricants usual for the processing of plastics. For example, hydrocarbons, such as
oils, paraffins and PE waxes, fatty alcohols with 6 to 20 carbon atoms, ketones,
carboxylic acids, such as fatty acids and montanic acid, oxidized PE wax, metal salts of
carboxylic acids, carboxylic acid amides and carboxylate esters, for example with the
alcohols ethanol, fatty alcohols, glycerin, ethanediol and pentaerythritol and long-chain
carboxylic acids as the acid component are possible.
The molding compounds according to the invention can have a content of lubricant
from 0.01 to lo%, preferably 0.05 to 5%, particularly preferably from 0.1 to 3% and in
particular from 0.2 to 2%.
Fillers chiefly influence the compressive, tensile and bending strength and the rigidity
and thermal deformation resistance of plasticized PVC favorably.
In the context of the invention, the molding compounds can also comprise fillers, such
as for example carbon black and other organic fillers, such as natural calcium
carbonates, for example chalk, limestone and marble, synthetic calcium carbonates,
dolomite, silicates, silicic acid, sand, diatomaceous earth, and aluminum silicates, such
as kaolin, mica and feldspar. Preferably, calcium carbonates, chalk, dolomite, kaolin,
silicates, talc or carbon black are used as fillers.
The molding compounds according to the invention can have a content of fillers from
0.01 to 80%, preferably 0.1 to 60%, particularly preferably from 0.5 to 50% and in
particular from 1 to 40%.
The molding compounds according to the invention can also comprise pigments in
order to adapt the product obtained to different possible uses.
In the context of the present invention, both inorganic pigments and also organic
pigments can be used. As inorganic pigments, for example cobalt pigments such as
CoO/AI2O3, and chromium pigments, for example Cr203, can be used. As organic
pigments, for example monoazo pigments, condensed azo pigments, azomethine
pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, dioxazine
pigments and aniline pigments are possible.
The molding compounds according to the invention can have a content of pigments
from 0.01 to lo%, preferably 0.05 to 5%, particularly preferably from 0.1 to 3% and in
particular from 0.5 to 2%.
In order to reduce flammability and to decrease smoke evolution during combustion,
molding compounds according to the invention can also comprise flame retardants.
As flame retardants, for example antimony trioxide, phosphate esters, chloroparaffin,
aluminum hydroxide, boron compounds, molybdenum trioxide, ferrocene, calcium
carbonate or magnesium carbonate can be used.
The molding compounds according to the invention can have a content of flame
retardants from 0.01 to lo%, preferably 0.1 to 8%, particularly preferably from 0.2 to
5% and in particular from 0.5 to 2%.
In order to protect articles produced from the molding compounds according to the
invention against damage in the surface region due to influence of light, the molding
compounds can also comprise light stabilizers, e.g. UV absorbers.
In the context of the present invention, for example hydroxybenzophenones,
hydroxyphenylbenzotriazoles, cyanoacrylates or so-called "hindered aminine light
stabilizers" (HALS), such as the derivatives of 2,2,6,6-tetramethylpiperidine, can be
used as light stabilizers.
The molding compounds according to the invention can have a content of light
stabilizers, e.g. UV absorbers, from 0.01 to 7%, preferably 0.1 to 5%, particularly
preferably from 0.2 to 4% and in particular from 0.5 to 3%.
Production of the C O ~ D O U o~f ~thSe general formula (1)
The production of the compounds of the general formula (I) present in the plasticizer
compositions according to the invention is described below.
Production of the diesters of 2,5-furandicarboxylic acid
Compounds of the general formula (I.1),
wherein R' and R~ have the aforesaid meanings, are obtainable by a method in which
5
a) optionally 2,5-furandicarboxylic acid or an anhydride or acid halide thereof is
reacted with a C1-C3 alkanol in presence of a catalyst with obtention of a di-(C1-
C3 alkyl) 2,5-furandicarboxylate,
10 b) 2,5-furandicarboxylic acid or an anhydride or acid halide thereof or the di-(C1-C3
alkyl) 2,5-furandicarboxylate obtained in step a) is reacted with at least one
alcohol R1-OH and, if R1 and R2 different meanings, additionally with at least one
alcohol R2-OH in presence of at least one catalyst with obtention of a compound
of the formula (1.1).
15
Concerning suitable and preferred embodiments of the residues R' and R2 reference is
made to the previous statements in their entirety.
Suitable C1-C3 alkanols for use in step a) are for example methanol, ethanol, n-
20 propanol or mixtures thereof.
In step b) of the process, the 2,5-furandicarboxylic acid or the di-(C1-C3 alkyl) 2,5-
furandicarboxylate obtained in step a) is subjected to an esterification or
transesterification with at least one alcohol R1-OH and, if R' and R2 have different
25 meanings, additionally with at least one alcohol R2-OH to give the compounds of the
formula (I. 1).
Esterification
30 The conversion of the 2,5-furandicarboxylic acid (FDCS) into the corresponding di-(C1-
C3 alkyl) 2,5-furandicarboxylates andlor ester compounds of the general formulae (1.1)
can be effected by usual methods known to those skilled in the art. These include the
reaction of at least one alcohol component, selected from CI-C3 alkanols or the
alcohols RI-OH and R2-OH respectively, with FDCS or a suitable derivative thereof.
35 Suitable derivatives are for example the acid halides and acid anhydrides. A preferred
acid halide is the acid chloride. As esterification catalysts, the catalysts usual for this
can be used, e.g. mineral acids such as sulfuric acid and phosphoric acid; organic
sulfonic acids, such methanesulfonic acid and p-toluenesulfonic acid; amphoteric
catalysts, in particular titanium, tin (IV) or zirconium compounds, such as
tetraalkoxytitaniums, e.g. tetrabutoxytitanium, and tin (IV) oxide. The water forming
5 during the reaction can be removed by usual measures, e.g. by distillation.
WO 02138531 describes a process for the production of esters of polybasic carboxylic
acids, in which a) in a reaction zone, a mixture essentially consisting of the acid
component or an anhydride thereof and the alcohol component is heated to boiling in
presence of an esterification catalyst, b) the alcohol and water-comprising vapors are
10 separated by rectification into an alcohol-rich fraction and a water-rich fraction, and c)
the alcohol-rich fraction is returned to the reaction zone and the water-rich fraction is
discharged from the process. The process described in WO 02138531 and the catalysts
disclosed therein are also suitable for the esterification.
15 The esterification catalyst is used in an effective quantity, which usually lies in the
range from 0.05 to 10 wt.%, preferably 0.1 to 5 wt.%, based on the sum of acid
component (or anhydride) and alcohol component.
Further suitable processes for the production of the compounds of the general formula
20 (1.1) by esterification are for example in US 6,310,235, US 5,324,853, DE-A 2612355 or
DE-A 1945359. Reference is made to said documents in their entirety.
As a rule, the esterification of FDCS is preferably effected in presence of the abovedescribed
alcohol components, by means of an organic acid or mineral acid, in
25 particular concentrated sulfuric acid. For this, the alcohol component is advantageously
used in at least double the stoichiometric quantity, based on the quantity of FDCS or a
suitable derivative thereof in the reaction mixture.
The esterification can as a rule be effected at ambient pressure or decreased or
30 increased pressure. Preferably, the esterification is performed at ambient pressure or
decreased pressure.
The esterification can be performed in the absence of an added solvent or in presence
of an organic solvent.
35
If the esterification is performed in presence of a solvent, this is preferably an organic
solvent inert under the reaction conditions. These include for example aliphatic
hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic
hydrocarbons or ethers. Preferably the solvent is selected from pentane, hexane,
40 heptane, ligroin, petroleum ether, cyclohexane, dichloromethane, trichloromethane,
tetrachloromethane, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes,
dibutyl ether, THF, dioxan and mixtures thereof.
The esterification is usually performed in a temperature range from 50 to 250°C.
5
If the esterification catalyst is selected from organic acids or mineral acids, the
esterification is usually performed in a temperature range from 50 to 160°C.
If the esterification catalyst is selected from amphoteric catalysts, the esterification is
10 usually performed in a temperature range from 100 to 250°C.
The esterification can be effected in the absence or in presence of an inert gas. An
inert gas is as a rule understood to be a gas which under the given reaction conditions
enters into no reactions with the educts, reagents and solvents involved in the reaction
15 or the products arising. Preferably the esterification takes place without the introduction
of an inert gas.
Transesterification:
20 The transesterification of the di-(Cl-C3 alkyl) 2,5-furandicarboxylates to the
corresponding ester compounds 1.1 according to the process step b) can be effected by
usual processes known to those skilled in the art. These include the reaction of the di-
(C1-C3) alkyl ester with at least one C4 alkanol or C5 to C6 cycloalkanol or mixtures
thereof in presence of a suitable transesterification catalyst.
25
As transesterification catalysts, the usual catalysts commonly used for transesterification
reactions, which are mostly also used in esterification reactions, are possible.
These for example include mineral acids, such as sulfuric acid and phosphoric acid;
organic sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid; or
30 specific metal catalysts from the group of the tin (IV) catalysts, for example dialkyltin
dicarboxylates such as dibutyltin diacetate, trialkyltin alkoxides, monoalkyltin
compounds such as monobutyltin dioxide, tin salts such as tin acetate or tin oxides;
from the group of the titanium catalysts, monomeric and polymeric titanates and
titanium chelates such as tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl
35 orthotitanate and triethanolamine titanate; from the group of the zirconium catalysts,
zirconates and zirconium chelates such as tetrapropyl zirconate, tetrabutyl zirconate,
and triethanolamine zirconate; and lithium catalysts such as lithium salts, lithium
alkoxides; or aluminum(lll), chromium(lll), iron(ll I), cobalt(ll), nickel(l1) and zinc(ll)
acetylacetonate.
40
The quantity of transesterification catalyst used is about 0.05 to 5 wt.%, preferably
about 0.1 to 1 wt.%. The reaction mixture is preferably heated to the boiling point of the
reaction mixture, so that the reaction temperature lies between 20°C and 200°C
depending on the reactants.
5
The transesterification can be effected at ambient pressure or decreased or increased
pressure. Preferably the transesterification is performed at a pressure from 0.001 to
200 bar, particularly preferably 0.01 to 5 bar. The lower-boiling alcohol eliminated
during the transesterification is preferably distilled off continuously in order to shift the
10 equilibrium of the transesterification reaction. The distillation column required for this is
as a rule directly connected to transesterification reactor, preferably it is installed
directly on this. In case of the use of several transesterification reactors connected in
series, each of these reactors can be equipped with a distillation column, or preferably
the vaporized alcohol mixture can be passed to one distillation column from the last
15 vessels of the transesterification reactor cascade via one or more collector pipes. The
higher boiling alcohol recovered in this distillation is preferably returned again to the
transesterification.
In case of the use of an amphoteric catalyst, its separation is generally effected by
20 hydrolysis and subsequent separation of the metal oxide formed, e.g. by filtration.
Preferably, after the reaction has taken place, the catalyst is hydrolyzed by washing
with water and the precipitated metal oxide filtered off. If desired, the filtrate can be
subjected to a further workup for isolation andlor purification of the product. The
product is preferably separated by distillation.
2 5
The transesterification of the di-(C1-C3 alkyl) 2,5-furandicarboxylates is preferably
effected in presence of the alcohol component and in presence of at least one titanium
(IV) alcoholate. Preferred titanium (IV) alcoholates are tetrapropoxytitanium,
tetrabutoxytitanium or mixtures thereof. Preferably, the alcohol component is used in at
30 least double the stoichiometric quantity, based on the di-(Cl-C3 alkyl) ester used.
The transesterification can be performed in the absence or in presence of an added
organic solvent. Preferably, the transesterification is performed in presence of an inert
organic solvent. Suitable organic solvents are those mentioned above for the
35 esterification. These include in particular toluene and THF.
The temperature during the transesterification preferably lies in a range from 50 to
200°C.
The transesterification can be effected in the absence or in presence of an inert gas.
An inert gas is as a rule understood to be a gas which under the given reaction
conditions enters into no reactions with the educts, reagents and solvents involved in
the reaction or the products arising. Preferably, the transesterification is performed
5 without introduction of an inert gas.
A particularly suitable embodiment of the process comprises:
a) reaction of 2,5-furandicarboxylic acid with methanol in presence of concentrated
10 sulfuric acid with obtention of dimethyl 2,5-furandicarboxylate,
b) reaction of the dimethyl 2,5-furandicarboxylate obtained in step a) with at least
one alcohol R'-OH in presence of at least one titanium (IV) alcoholate to give the
compounds of the general formula (1.1).
15 Production of the C4 diether and C4 diester derivatives of the formula (1.2) and (1.3)
respectively
compounds of the general formula (1.2) or (1.3),
wherein R' and R2 have one of the aforesaid meanings and n has the value 1 or 2, are
obtainable by a process in which either
25
a) 2,5-di-(hydroxymethy1)furan (n = I ) or 2,5-di-(hydroxyethy1)furan (n = 2) is reacted
with at least one alkylating agent R'-z and, if R' and R2 have different meanings,
additionally with at least one alkylating agent R2-Z, wherein Z is a leaving group,
in presence of a base to give compounds of the formula (1.2),
b) 2,5-di-(hydroxymethyl)furan (n = 1 ) or 2,5-di-(hydroxyethy1)furan (n = 2) is reacted
with at least one acid halide R'-(C=O)X and, if R' and RZ have different
meanings, additionally with at least one acid halide R2-(c=o)x, wherein X is Br or
CI, in presence of at least one tertiary amine, to give compounds of the formula
(1.3).
As a rule, the alkylation is performed in presence of an organic solvent inert under the
reaction conditions. Suitable solvents are those previously mentioned for the
esterification. Preferred solvents are aromatic hydrocarbons, such as toluene.
5
The leaving group Z preferably is a residue which is selected from Br, CI, or the tosyl,
mesyl or triflyl group.
Particularly preferably, the leaving group Z is Br.
10
The alkylating agents R1-z and R2-z are commercially available or can be produced
from the corresponding alcohols by suitable reactions or procedures familiar to those
skilled in the art. For example, the alkyl bromides R'-B~a nd R2-~prr eferably used for
this process can be produced in known manner on the large industrial scale from the
15 corresponding alcohols R1-OH or R2-OH using hydrogen bromide (HBr).
As suitable bases, inorganic andlor strong organic bases are possible. These for
example include inorganic bases or base formers, such as hydroxides, hydrides,
amides, oxides and carbonates of the alkali and alkaline earth metals. These include
20 LiOH, NaOH, KOH, Ms(OH)~C, a(OH)2, LiH, NaH, sodium amide (NaNH2),l ithium
diisopropylamide (LDA), Na20, K2C03, Na2C03 and Cs2C03; and organometallic
compounds such as n-BuLi or tert.-BuLi. NaOH, KOH, K2C03 and Na2C03 are
preferable.
25 Here the base is preferably used in at least two-fold stoichiometric excess, based on
the 25-di-(hydroxymethy1)furan or. 2,5-di-(hydroxyethy1)furan. Particularly preferably,
an at least fourfold stoichiometric excess of base is used.
The alkylation can be performed in the absence or in presence of an organic solvent.
30 As a rule, the reaction is performed in presence of an inert organic solvent, such as
pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, dichloromethane,
trichloromethane, tetrachloromethane, benzene, toluene, xylene, chlorobenzene,
dichlorobenzenes, dibutyl ether, THF, dioxan and mixtures thereof.
35 The alkylation can as a rule be effected at ambient pressure, decreased pressure or
increased pressure. Preferably, the alkylation is performed at ambient pressure.
Preferably, the alkylation is performed in a temperature range from 30 to 200"C,
preferably 50 to 150°C.
40
The alkylation can be effected in the absence or in presence of an inert gas.
Preferably, no inert gas is used in the alkylation.
In a specific suitable embodiment of the alkylation, 2,5-di-(hydroxymethy1)furan or 2,5-
5 di-(hydroxyethy1)furan are converted into the diether compounds of the general formula
(1.2) in presence of an at least fourfold excess of base in an inert organic solvent and
with at least one alkyl bromide R1-Br or R2-Br respectively. Concerning the residues R1
and R2, reference is made to the previous statements. An alkali metal hydroxide, in
particular KOH, is preferably used as the base.
10
For the production of the ester compounds of the general formula (1.3)' 2,5-di-
(hydroxymethy1)furan or 2,5-di-(hydroxyethy1)furan is preferably converted to the
compounds of the formula (1.3) with at least one acid halide R'-(C=O)X and, if R1 and
R2 have different meanings, with at least one acid halide R2-(c=o)x, wherein X is Br or
15 CI, in presence of at least one tertiary amine.
Apart from these processes, still further common esterification methods are available to
those skilled in the art, as previously described in case of the esterification of FDCS.
20 For the production of the ester compounds of the general formula (1.3), all types of
tertiary amines familiar to those skilled in the art can be used. Examples of suitable
tertiary amines are:
- from the group of the trialkylamines: trimethylamine, triethylamine, tri-n-
25 propylamine, diethylisopropylamine, diisopropylethylamine and the like;
- from the group of the N-cycloalkyl-N,N-dialkylamines: dimethylcyclohexylamine
and diethylcyclohexylamine;
- from the group of the N,N-dialkylanilines: dimethylaniline and diethylaniline;
- from the group of the pyridine and quinoline bases: pyridine, a-, P- and y-picoline,
30 quinoline and C(dimethy1amino)pyridine (DMAP).
Preferred tertiary amines are trialkylamines and pyridine bases, in particular
triethylamine and C(dimethylamino)pyridine (DMAP) and mixtures thereof.
35 The esterification can be effected at ambient pressure, or at decreased or increased
pressure. Preferably, the esterification is performed at ambient pressure.
The esterification can be performed in the absence or in presence of an organic
solvent. Preferably, the esterification is performed in presence of an inert organic
40 solvent, as previously defined.
The esterification is usually performed in a temperature range from 50 to 200°C.
The esterification can be effected in the absence or in presence of an inert gas.
5
In a preferred embodiment of the process for the production of the compounds 1.3, 2,5-
di-(hydroxymethy1)furan is converted to compounds of the formula (1.3) with an acid
chloride R~-(c=o)CI in presence of triethylamine and/or DMAP and an inert organic
solvent.
10
For the production of the compounds of the general formula (I), C4 alkanols and C5-C6
cycloalkanols are used as educts.
Preferred C4 alkanols can be straight-chain or branched or consist of mixtures of
15 straight-chain and branched butanols. These include l-butanol, 2-butanol, 2-methyl-lpropanol
or 2-methyl-2-propanol and mixtures thereof. Preferable are I -butanol or 2-
methyl-I -propanol.
The C5-C6 cycloalkanols are selected from cyclopentanol or cyclohexanol and mixtures
20 thereof. Cyclohexanol is preferable.
Depending on their ring size, substituted CS-C6 cycloalkanols can have one or more
(e.g. 1, 2, 3, 4 or 5) C1-Clo alkyl substituents. Examples of Cs to C6 cycloalkanols are 2-
and 3-methylcyclopentanol, 2- and 3-ethylcyclopentanol, 2-, 3- and 4-methyl-
25 cyclohexanol, 2-, 3- and 4-ethylcyclohexanol, 2-, 3- and 4-propylcyclohexanol, 2-, 3-
and 4-isopropylcyclohexanol, 2-, 3- and 4-butylcyclohexanol, 2-, 3- and 4-sec.-
butylcyclohexanol and 2-, 3- and 4-tert.-butylcyclohexanol.
The furan-2,5-dicarboxylic acid (FDCS, CAS No. 3238-40-2) used for the production of
30 the compounds of the general formula (I) can either be obtained commercially or
produced by synthesis routes known in the literature. Thus, possibilities for the
synthesis are found in the publication by Lewkowski et al. published on the Internet
with the title "Synthesis, Chemistry and Application of 5-hydroxymethylfurfural and its
derivatives" (Lewkowski et a/., ARKIVOC 2001 (i), pages 17-54, ISSN 1424-6376).
35 Common to most of these syntheses is an acid-catalyzed reaction of carbohydrates, in
particular glucose or fructose, preferably fructose to give 5-hydroxymethylfurfural (5-
HMF), which can be separated from the reaction mixture by process technology
operations, such as for example the two-phase procedure. Similar results were
described for example by Leshkov et a/. in Science 2006, Vol. 312, pages 1933-1937
40 and by Zhang et a/. in Angewandte Chemie 2008, Vol. 120, pages 9485-9488. In a
further step, the 5-HMF can then be oxidized to FDCS, as for example cited by
Christensen in ChemSusChem 2007, Vol. 1, pages 75-78.
2,5-bis(hydroxymethy1)furan (CAS No. 1883-75-6) can also either be obtained
5 commercially or synthesized. The synthesis described take place starting from 5-HMF,
which can be reduced in two steps via 2,5-bis(hydroxymethy1)furan (2,5-BHF)
(Lewkowski eta/., ARKIVOC 2001 (i), pages 17-54, ISSN 1424-6376).
2,5-bis(hydroxyethy1)furan can be obtained by reduction of the methyl 2,5-
10 furandiacetate. Methyl 2,5-furandiacetate can be synthesized from 2,5-bis(hydroxymethyl)
furan (2,5-BHF) via suitable reactions familiar to those skilled in the art, such as
for example analogously to the process described by Rau et a/. in Liebigs Ann. Chem.,
Vol. 1984 (8. 1984), pages 1504-1 51 2, ISSN 0947-3440. In thk, 2,5-bis(chloromethyl)-
furan is prepared from 2,5-BHF by reaction with thionyl chloride, which is converted to
15 2,5-bis(cyanomethy1)furan by the action of KCN in benzene in presence of [18]crown-6.
The 2,5-bis(cyanomethy1)furan can then be saponified to the 2,5-furandiacetic acid and
esterified with methanol to the dimethyl ester converted directly into the methyl 2,5-
furandiacetate by alcoholysis with methanol (Pinner reaction). The methyl 2,5-
furandiacetate can then be reduced to 2,5-bis(hydroxyethy1)furan.
2 0
The preparation of the methyl 2,5-furandiacetate can also be effected analogously to
the process described by Kern et a/. in Liebigs Ann. Chem., Vol. 1985 (6. 1985), pages
1 168-1 174, ISSN 0947-3440.
25 Compounds of the aeneral formula (11)
The compounds of the general formula (11) can either be obtained commercially or
produced by processes known in the state of the art.
30 As a rule, the 1,2-cyclohexanedicarboxylate esters are mostly obtained by nuclear
hydrogenation of the corresponding phthalate esters. The nuclear hydrogenation can
be effected by the process described in WO 99132427. A particularly suitable nuclear
hydrogenation process is for example also described in WO 201 1082991 A2.
35 Furthermore, 1,2-cyclohexanedicarboxylate esters can be obtained by esterification of
1,2-cyclohexanedicarboxylic acid or suitable derivatives thereof with the corresponding
alcohols. The esterification can be effected by usual processes known to those skilled
in the art.
It is common to the processes for the production of the compounds of the general
formula (11) that, starting from phthalic acid, 1,2-cyclohexanedicarboxylic acid or
suitable derivatives thereof, an esterification or a transesterification is performed,
wherein the corresponding C7-CI2 alkanols are used as educts. These alcohols are as
5 a rule not pure substances, but rather an isomer mixture, the composition and purity
whereof depends on the particular processes by which these are produced.
Preferred C7-C12 alkanols which are used for the production of the compounds (11)
present in the plasticizer composition according to the invention can be straight-chain
10 or branched or consist of mixtures of straight-chain and branched C7-C12 alkanols.
These include n-heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, nnonanol,
isononanol, isodecanol, 2-propylheptanol, n-undecanol, isoundecanol, ndodecanol
or isododecanol. Particularly preferable C7-C12 alkanols are 2-ethylhexanol,
isononanol and 2-propylheptanol, in particular isononanol.
15
He~tanol
The heptanols used for the production of the compounds of the general formula (11) can
be straight-chain or branched or consist of mixtures of straight-chain and branched
20 heptanols. Preferably mixtures of branched heptanols, also described as isoheptanol,
which are obtainable by the rhodium- or preferably cobalt-catalyzed hydroformylation of
dimeric propene, e.g. by the DimersolO process, and subsequent hydrogenation of the
isoheptanals obtained to give an isoheptanol mixture, are used. Depending on its
production, the isoheptanol mixture thus obtained consists of several isomers.
25 Essentially straight-chain heptanols can be obtained by rhodium- or preferably cobaltcatalyzed
hydroformylation from 1-hexene and subsequent hydrogenation of the nheptanal
obtained to n-heptanol. The hydroformylation of 1-hexene or propene dimer
can be effected by methods known per se: in the hydroformylation with rhodium
catalysts homogeneously dissolved in the reaction medium, both uncomplexed
30 rhodium carbonyls, which are formed in situ in the hydroformylation reaction mixture
under the conditions of the hydroformylation reaction under the action of synthesis gas
for example from rhodium salts, and also complex rhodium carbonyl compounds, in
particular complexes with organic phosphines, such as triphenylphosphine, or
organophosphites, preferably chelatising biphophites, as for example described in US-
35 A 528891 8, be used as catalyst. In the cobalt-catalyzed hydroformylation of these
olefins, in general cobalt carbonyl compounds homogeneously soluble in the reaction
mixture, which are formed in situ from cobalt salts under the action of synthesis gas
under the conditions of the hydroformylation reaction, are used. If the cobalt-catalyzed
hydroformylation is carried out in presence of trialkyl- or triarylphosphines, the desired
heptanols are formed directly as the hydroformylation product, so that further
hydrogenation of the aldehyde function is no longer needed.
For the cobalt-catalyzed hydroformylation of 1-hexene or the hexene isomer mixtures,
the industrially established processes explained in Falbe, New Syntheses with Carbon
Monoxide, Springer, Berlin, 1980 on pages 162 - 168, such as the Ruhrchemie
process, the BASF process, the Kuhlmann process or the Shell process are for
example suitable. While the Ruhrchemie, BASF and the Kuhlmann processes operate
with non-ligand-modified cobalt carbonyl compounds as catalysts, and thereby obtain
hexanal mixtures, the Shell process (DE-A 1593368) uses phosphine or phosphite
ligand-modified cobalt carbonyl compounds as catalyst, which because of their
additional high hydrogenation activity lead directly to the hexanol mixtures.
Advantageous embodiments for performing the hydroformylation with non-ligandmodified
cobalt carbonyl complexes are described in detail in DE-A 21 39630, DEA
2244373, DE-A 2404855 and WO 01 014297.
For the rhodium-catalyzed hydroformylation of I-hexene or the hexene isomer
mixtures, the industrially established rhodium low pressure hydroformylation process
with triphenylphosphine ligand-modified rhodium carbonyl compounds, such as is the
subject of US-A 4148830, can be used. Advantageously, non-ligand-modified rhodium
carbonyl compounds can be used as the catalyst for the rhodium-catalyzed
hydroformylation of long-chain olefins such as the hexene isomer mixtures obtained
according to the afore-mentioned processes, wherein in contrast to the low pressure
process, a higher pressure of 80 to 400 bar has to be set. The implementation of such
rhodium high-pressure hydroformylation processes is described in e.g. EP-A 695734,
EP-B 880494 and EP-B 1047655.
The isoheptanal mixtures obtained after hydroformylation of the hexene isomer
mixtures are catalytically hydrogenated to isoheptanol mixtures in a manner in itself
usual. Preferably heterogeneous catalysts are used for this, which comprise as
catalytically active components metals and/or metal oxides of groups VI to VIII, and of
subgroup I of the periodic table of the elements, in particular chromium, molybdenum,
manganese, rhenium, iron, cobalt, nickel and/or copper, optionally deposited on a
support material such as A1203, Si02 and/or Ti02. Such catalysts are for example
described in DE-A 3228881, DE-A 2628987 and DE-A 2445303. Particularly
advantateously, the hydrogenation of the isoheptanals is performed with an excess of
hydrogen from 1.5 to 20% above the quantity of hydrogen stoichiometrically needed for
the hydrogenation of the isoheptanals, at temperatures from 50 to 200°C and at a
hydrogen pressure from 25 to 350 bar, and for avoidance of side reactions, in
accordance with to DE-A 2628987 a small quantity of water, advantageously in the
form of an aqueous solution of an alkali metal hydroxide or carbonate corresponding to
the teaching of WO 01087809 is added to the hydrogenation feed.
Octanol
5
2-ethylhexanol, which was for many years the plasticizer alcohol produced in the
greatest quantities, can be obtained via the aldol condensation of n-butyraldehyde to 2-
ethylhexenal and subsequent hydrogenation thereof to 2-ethylhexanol (see Ullmann's
Encyclopedia of Industrial Chemistry; 5th Edition, Vol. A 10, pp. 137 - 140, VCH
10 Verlagsgesellschaft GmbH, Weinheim 1987).
Essentially straight-chain octanols can be obtained by the rhodium- or preferably
cobalt-catalyzed hydroformylation of I-heptene and subsequent hydrogenation of the
n-octanal obtained to n-octanol. The I-heptene needed for this can be obtained from
15 the Fischer-Tropsch synthesis of hydrocarbons.
In contrast to 2-ethylhexanol or n-octanol, owing to the manner of its production the
alcohol isooctanol is not a homogeneous chemical compound, but rather an isomer
mixture of differently branched Ce alcohols, for example of 2,3-dimethyl-I-hexanol, 33-
20 dimethyl-I-hexanol, 4,s-dimethyl-I-hexanol, 3-methyl-1-heptanol and 5-methyl-lheptanol,
which can be present in the isooctanol in different proportions depending on
the production conditions used. lsooctanol is usually produced by the codimerization of
propene with butenes, preferably n-butenes, and subsequent hydroformylation of the
mixture of heptane isomers thereby obtained. The octanal isomer mixture obtained in
25 the hydroformylation can subsequently be hydrogenated to the isooctanol in a manner
in itself usual.
The codimerization of propene with butenes to isomeric heptenes can advantageously
be effected by the homogeneously catalyzed DimersolB process (Chauvin et al; Chem.
30 Ind.; May 1974, pp. 375 - 378), in which a soluble nickel-phosphine complex is used as
the catalyst in presence of an ethylaluminum chlorine compound, for example
ethylaluminum dichloride. As phosphine ligands for the nickel complex catalyst,
tributylphosphine, triisopropylphosphine, tricyclohexylphosphine and/or tribenzylphosphine
can for example be used. The reaction takes place at temperatures from 0
35 to 80°C, during which advantageously an pressure is set at which the olefins are
present dissolved in the liquid reaction mixture (Cornils; Hermann: Applied
Homogeneous Catalysis with Organometallic Compounds; 2nd Edition; Vol. 1 ; pp. 254 -
259, Wiley-VCH, Weinheim 2002).
Alternatively to the DimersolB process with nickel catalysts homogeneously dissolved
in the reaction medium, the codimerization of propene with butenes can also be
performed with heterogeneous NiO catalysts deposited on a support, whereby similar
heptane isomer distributions are obtained as in the homogeneously catalyzed process.
5 Such catalysts are for example used in the so-called OctolB process (Hydrocarbon
Processing, February 1986, pp. 31 - 33), and a very suitable specific heterogeneous
nickel catalyst for olefin dimerization or codimerization is for example disclosed in
WO 9514647.
10 Instead of catalysts based on nickel, Brernsted acid heterogeneous catalysts can also
1 be used for the codimerization of propene with butenes, whereby as a rule more highly
branched heptenes than in the nickel-catalyzed process are obtained. Examples of
catalysts suitable for this are solid phosphoric acid catalysts e.g. kieselguhr or
diatomaceous earth impregnated with phosphoric acid, such as are used by the
15 PolyGasB process for olefin di- or oligomerization (Chitnis et al; hydrocarbon
Engineering N, No. 6 - June 2005). Very suitable Brernsted-acid catalysts for the
codimerization of propene and butenes to heptenes are zeolites, which are utilized by
the EMOGASB process developed on the basis of the PolyGasB process.
20 The 1-heptene and the heptene isomer mixtures are converted into n-octanal or
octanal isomer mixtures by the known methods explained above in connection with the
production of n-heptanal and heptanal isomer mixtures by odium or cobalt-catalyzed
hydroformylation, preferably cobalt-catalyzed hydroformylation. These are then
hydrogenated to the corresponding octanols, e.g. by means of one of the catalysts
25 mentioned above in connection with the production of n-heptanol and isoheptanol.
Nonanol
Essentially straight-chain nonanol can be obtained by rhodium or preferably cobalt-
30 catalyzed hydroformylation from 1-octene and subsequent hydrogenation of the nnonanal
thereby obtained. The starting olefin 1-octene can for example be obtained via
an ethylene oligomerization by means of a nickel complex catalyst homogeneously
soluble in the reaction medium, 1 ,4-butanediol, with diphenylphosphinoacetic acid or 2-
diphenylphosphinobenzoic acid as ligands. This process is also known under the name
35 Shell Higher Olefins Process or SHOP process (see Weisermel, Arpe: lndustrielle
Organic Chemie; 5th Edition; p. 96; Wiley-VCH, Weinheim 1998).
The isononanol which is used for the synthesis of the diisononyl esters of the general
formula (11) present in the plasticizer composition according to the invention is not a
40 homogeneous chemical compound, but rather a mixture of differently branched
isomeric C9 alcohols, which, depending on the manner of their production, in particular
also the starting materials, can have different degrees of branching. In general, the
isononanols are produced by dimerization of butenes to isooctene mixtures,
subsequent hydroformylation of the isooctene mixtures and hydrogenation of the
isononanal mixtures thus obtained to isononanol mixtures, as explained in Ullmann's
Encyclopedia of Industrial Chemistry, 5" Edition, Vol. Al, pp. 291 - 292, VCH
Verlagsgesellschaft GmbH, Weinheim 1995.
As the starting material for the production of the isononanols, both isobutene, cis- and
trans-2-butene and also 1-butene or mixtures of these butene isomers can be used. In
the dimerization of pure isobutene mainly catalyzed by means of liquid, e.g. sulfuric or
phosphoric acid, or solid, e.g. phosphoric acid applied onto kieselguhr, SiOl or AI2O3 as
support material or zeolites or Brransted acids, the strongly branched 2,4,4-trimethylpentene,
also referred to as diisobutylene, is predominantly obtained, which after
hydroformylation and hydrogenation of the aldehyde yields highly branched
isononanols.
lsononalos with a lower degree of branching are preferable. Such low branching
isononanol mixtures are produced from the linear butenes 1-butene, cis- and/or trans-
2-butene, which optionally can comprise still smaller quantities of isobutene, via the
above-described route of butene dimerization, hydroformylation of the isooctene and
hydrogenation of the isononanal mixtures obtained. A preferred raw material is the socalled
raffinate II, which is obtained from the C4 cut from a cracker, for example a
steam cracker, which is obtained after elimination of allenes, acetylenes and dienes, in
particular 1,3-butadiene, through their partial hydrogenation to linear butenes or their
separation by extractive distillation, for example by means of N-methylpyrrolidone, and
subsequent Brransted acid-catalyzed removal of the isobutene present therein by
reaction thereof with methanol or isobutanol by established large-scale processes with
formation of the fuel additive methyl-tert.-butyl ether (MTBE) or of the isobutyl tert.-butyl
ether used for the obtention of pure isobutene.
As well as 1-butene and cis- and trans-2-butene, raffinate II still comprises n- and isobutane
and residual quantities of up to 5 wt.% of isobutene.
The dimerization of the linear butenes or of the butene mixture present in the raffinate II
can be effected by means of the common processes operated on the large industrial
scale, such as were explained above in connection with the generation of isoheptene
mixtures, for example by means of heterogeneous, Brransted acid catalysts, as used in
the PolyGasQ or EMOGASQ process, by means of the DimersolQ process using nickel
complex catalysts homogeneously dissolved in the reaction medium or by means of
heterogeneous, nickel(l1) oxide-containing catalysts by the Octal@ process or the
process according to WO 9514647. The isooctene mixtures thus obtained are
converted into isononal mixtures by the known process explained above in connection
with the production of heptanal isomer mixtures by rhodium- or cobalt-catalyzed
hydroformylation, preferably cobalt-catalyzed hydroformylation. These are then
hydrogenated to the suitable isononal mixtures e.g. by means of catalysts mentioned
above in connection with the production of isoheptanol.
The isononanol isomer mixtures thus produced can be characterized via their isoindex,
which can be calculated from the degree of branching of the individual isomeric
isononanol components in the isononanol mixture multiplied by the percentage content
thereof in the isononanol mixture. Thus for example n-nonanol with the value 0,
methyloctanols (one branching) with the value 1 and dimethylheptanols (two
branchings) with the value 2 contribute to the isoindex of an isononanol. The higher the
linearity, the lower is the isoindex of the isononanol mixture concerned. Accordingly,
the isoindex of an isononanol mixture can be determined by gas chromatographic
separation of the isononanol mixture into its individual isomers and associated
therewith quantification of their percentage content in the isononanol mixture,
determined by standard methods of gas chromatographic analysis. In order to increase
the volatility and improve the gas chromatographic separation of the isomeric nonanols,
these are advantageously trimethylsilylated by standard methods, for example by
reaction with N-methyl-N-trimethylsilyltrifluoroacetamide, before the gas
chromatographic analysis. In order to achieve as good a separation as possible of the
individual components in the gas chromatographic analysis, capillary columns with
polydimethylsiloxane as the stationary phase are preferably used. Such capillary
columns are commercially available, and it requires only a few routine experiments by
those skilled in the art in order to select an optimal product for this separation task from
the large number available on the market.
The diisononyl esters of the general formula (11) used in the plasticizer composition
according to the invention are in general esterified with isononanols with an isoindex
from 0.8 to 2, preferably from 1 .O to 1.8 and particularly preferably from 1.1 to 1.5,
which can be produced by the above-mentioned processes.
Purely by way of example, possible compositions of isononanol mixtures, such as can
be used for the production of the compounds of the general formula (11) used according
to the invention are stated below wherein it should be noted that the contents of the
isomers stated in detail in the isononanol mixture can vary depending on the
composition of the starting material, for example raffinate II, whose composition of
butenes can vary depending on the production process, and on fluctuations in the
production conditions used, for example the age of the catalyst used and temperature
and pressure conditions to be adapted thereto.
For example, an isononanol mixture which was produced by cobalt-catalyzed
5 hydroformylation and subsequent hydrogenation from an isooctene mixture generated
using raffinate II as raw material by means of the catalyst and process according to
WO 9514647 can have the following composition:
1.73 to 3.73 wt.%, preferably 1.93 to 3.53 wt.%, particularly preferably 2.23 to
3.23 wt.% 3-ethyl-6-methyl-hexanol;
0.38 to 1.38 wt.%, preferably 0.48 to 1.28 wt.%, particularly preferably 0.58 to
1.18 wt.% 2,6-dimethylheptanol;
2.78 to 4.78 wt.%, preferably 2.98 to 4.58 wt.%, particularly preferably 3.28 to
4.28 wt.% 3,5-dimethylheptanol;
6.30 to 16.30 wt.%, preferably 7.30 to 1 5.30 wt.%, particularly preferably 8.30 to
14.30 wt.% 3,6-dimethylheptanol;
5.74 to 11.74 wt.%, preferably 6.24 to 1 1.24 wt.%, particularly preferably 6.74 to
10.74 wt.% 4,6-dimethylheptanol;
1.64 to 3.64 wt.%, preferably 1.84 to 3.44 wt.%, particularly preferably 2.14 to
3.14 wt.% 3,4,5-trimethylhexanol;
1.47 to 5.47 wt.%, preferably 1.97 to 4.97 wt.%, particularly preferably 2.47 to
4.47 wt.% 3,4,5-trimethylhexanol, 3-methyl-4-ethylhexanol and 3-ethyl-4-methylhexanol;
4.00 to 10.00 wt.%, preferably 4.50 to 9.50 wt.%, particularly preferably 5.00 to
9.00 wt.% 3,4-dimethylheptanol;
0.99 to 2.99 wt.%, preferably 1.19 to 2.79 wt.%, particularly preferably 1.49 to
2.49 wt.% 4-ethyl-5-methylhexanol and 3-ethylheptanol;
2.45 to 8.45 wt.%, preferably 2.95 to 7.95 wt.%, particularly preferably 3.45 to
7.45 wt.% 4,5-dimethylheptanol and 3-methyloctanol;
1.21 to 5.21 wt.%, preferably 1.71 to 4.71 wt.%, particularly preferably 2.21 to
4.21 wt.% 4,5-dimethylheptanol;
1.55 to 5.55 wt.%, preferably 2.05 to 5.05 wt.%, particularly preferably 2.55 to
4.55 wt.% 5,6-dimethylheptanol;
1.63 to 3.63 wt.%, preferably 1.83 to 3.43 wt.%, particularly preferably 2.1 3 to
3.1 3 wt.% 4-methyloctanot;
0.98 to 2.98 wt.%, preferably 1 .I8 to 2.78 wt.%, particularly preferably 1.48 to
2.48 wt.% 5-methyloctanol;
0.70 to 2.70 wt.%, preferably 0.90 to 2.50 wt.%, particularly preferably 1.20 to
2.20 wt.% 3,6,6-trimethylhexanol;
- 1.96 to 3.96 wt.%, preferably 2.16 to 3.76 wt.%, particularly preferably 2.46 to
3.46 wt.% 7-methyloctanol;
1.24 to 3.24 wt.%, preferably 1.44 to 3.04 wt.%, particularly preferably 1.74 to
2.74 wt.% 6-methyloctanol;
- 0.1 to 3 wt.%, preferably 0.2 to 2 wt.%, particularly preferably 0.3 to 1 wt.% nnonanol;
- 25 to 35 wt.%, preferably 28 to 33 wt.%, particularly preferably 29 to 32 wt.%
other alcohols with 9 and 10 carbon atoms; with the proviso that the overall sum
of said components comes to 100 wt.%.
Correspondingly to the above statements, an isononanol mixture which was produced
by cobalt-catalyzed hydroformylation and subsequent hydrogenation using an
ethylene-containing butene mixture as raw material by means of the PolyGasQ or
EMOGASB process can vary in the range of the following compositions, depending on
the raw material composition and fluctuations in the reaction conditions used:
- 6.0 to 16.0 wt.%, preferably 7.0 to 15.0 wt.%, particularly preferably 8.0 to 14.0
wt.% n-nonanol;
- 12.8 to 28.8 wt.%, preferably 14.8 to 26.8 wt.%, particularly preferably 15.8 to
25.8 wt.% 6-methyloctanol;
- 12.5 to 28.8 wt.%, preferably 14.5 to 26.5 wt.%, particularly preferably 15.5 to
25.5 wt.% 4-methyloctanol;
- 3.3 to 7.3 wt.%, preferably 3.8 to 6.8 wt.%, particularly preferably 4.3 to 6.3 wt.%
2-methyloctanol;
- 5.7 to 11.7 wt.%, preferably 6.3 to 11.3 wt.%, particularly preferably 6.7 to 10.7
wt. % 3-ethylheptanol;
- 1.9 to 3.9 wt.%, preferably 2.1 to 3.7 wt.%, particularly preferably 2.4 to 3.4 wt.%
2-ethylheptanol;
1.7 to 3.7 wt.%, preferably 1.9 to 3.5 wt.%, particularly preferably 2.2 to 3.2 wt.%
2-propylhexanol;
- 3.2 to 9.2 wt.%, preferably 3.7 to 8.7 wt.%, particularly preferably 4.2 to 8.2 wt.%
3,5-dimethylheptanol;
- 6.0 to 16.0 wt.%, preferably 7.0 to 15.0 wt.%, particularly preferably 8.0 to 14.0
wt.% 2,s-dimethylheptanol;
- 1.8 to 3.8 wt.%, preferably 2.0 to 3.6 wt.%, particularly preferably 2.3 to 3.3 wt.%
2,3-dimethylheptanol;
- 0.6 to 2.6 wt.%, preferably 0.8 to 2.4 wt.%, particularly preferably 1 .I to 2.1 wt.%
3-ethyl-4-methylhexanol;
- 2.0 to 4.0 wt.%, preferably 2.2 to 3.8 wt.%, particularly preferably 2.5 to 3.5 wt.%
2-ethyl-4-methylhexanol;
WO 20151104309 34 PCTlEP2015l050207
- 0.5 to 6.5 wt.%, preferably 1.5 to 6 wt.%, particularly preferably 1.5 to 5.5 wt.%
other alcohols with 9 carbon atoms;
with the proviso that the overall sum of said components comes to 100 wt.%.
5 Decanol
The isodecanol which is used for the synthesis of the diisodecyl esters of the general
formula (11) present in the plasticizer composition according to the invention is not a
homogeneous chemical compound, but rather a complex mixture of differently
10 branched isomeric decanols.
These are in general produced by the nickel or Bransted acid-catalyzed trimerization of
propylene, for example by the PolyGas@ or the EMOGAS@ process explained above,
subsequent hydroformylation of the isononene isomer mixture thus obtained by means
15 of homogeneous rhodium or cobalt carbonyl catalysts, preferably by means of cobalt
carbonyl catalysts and hydrogenation of the resulting isodecanal isomer mixture, e.g.
by means of the catalysts and processes mentioned above in connection with the
production of C7-C9 alcohols (Ullmann's Encyclopedia of Industrial Chemistry; 5th
Edition, Vol. Al, p. 293, VCH Verlagsgesellschaft GmbH, Weinheim 1985). The
20 isodecanol thus produced is in general strongly branched.
The 2-propylheptanol which is used for the synthesis of the di(2-propylheptyl) esters of
the general formula (11) present in the plasticizer composition according to the invention
can be pure 2-propylheptanol or propylheptanol isomer mixtures, such as are in
25 general formed in the industrial production of 2-propylheptanol and commonly also
described as 2-propylheptanol.
Pure 2-propylheptanol can be obtained by aldol condensation of n-valeraldehyde and
subsequent hydrogenation of the 2-propylheptenal thus formed, for example according
30 to US-A 2921089. In general, depending on the production process, commercially
available 2-propylheptanol, as well as the main component 2-propylheptanol,
comprises one or more of the 2-propylheptanol isomers 2-propyl-4-methylhexanol, 2-
propyl-5-methylhexanol, 2-isopropyl-heptanol, 2-isopropyl-4-methylhexanol, 2-
isopropyl-5-methylhexanol and/or 2-propyl-4,4-dimethylpentanol. The presence of other
35 isomers of 2-propylheptanols, for example 2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-
methyl-heptanol and/or 2-ethyl-2,s-dimethylhexanol in the 2-propylheptanol, is
possible, because of the low rates of formation of the aldehydic precursors of these
isomers in the course of the aldol condensation, these are present in the 2-
propylheptanol only in trace amounts, if at all, and are of no practical importance for the
plasticizer properties of the compound produced from such 2-propyheptanol isomer
mixtures.
As the starting material for the production of 2-propylheptanol, a variety of carbon
sources can be used, for example I-butene, 2-butene, rafinate I - an alkanelalkene
mixture obtained from the C4 cut from a cracker after removal of allenes, acetylenes
and dienes, which as well as 1- and 2-butene still comprises considerable quantities of
isobutene or rafinate II, which is obtained from rafinate I by removal of isobutene and
as olefin components apart from 1- and 2-butene only still comprises small amounts of
isobutene. Of course, mixtures of rafinate I and rafinate II can also be used as raw
material for the production of 2-propylheptanol. These olefins or olefin mixtures can be
hydroformylated with cobalt- or rhodium catalysts by methods in itself usual, whereby
from I-butene a mixture of n- and iso-valeraldehyde - the name iso-valeraldehyde
designates the compound 2-methylbutanal - is formed, the nliso ratio whereof can very
within relatively wide limits depending on the catalyst used and the catalyst and
hydroformylation conditions. For example with use of a rhodium catalyst modified with
triphenylphosphine (RhITPP), n- and iso-valeraldehyde are formed from I-butene in an
nliso ratio of in general 10:l to 20:1, whereas with use of phosphite ligands, for
example according to US-A 5288918 or WO 05028407, or of rhodium hydroformylation
catalysts modified with phosphoamidite ligands, for example according to
WO 0283695, almost exclusively n-valeraldehyde is formed. While the RhITPP catalyst
system only very slowly converts 2-butene in the hydroformylation, so that most of the
2-butene can be recovered again from the hydroformylation mixture, the
hydroformylation of the 2-butene succeeds with the said phosphite ligand- or
phosphoramidite ligand-modified rhodium catalysts, and as a result n-valeraldehyde is
predominantly formed. On the other hand, isobutene present in the olefinic raw
material, albeit with differing rates, is hydroformylated to 3-methylbutanal by practically
all catalyst systems and depending on the catalyst to a lesser extent to pivalaldehyde.
Depending on the starting materials and catalysts used, the C5 aldehydes, i.e. nvaleraldehyde,
optionally mixed with iso-valeraldehyde, 3-methylbutanal and/or
pivalaldehyde, can if desired be completely or partially separated into the individual
components before the aldol condensation, so that here also a possibility exists of
influencing and controlling the isomer composition of the Clo alcohol component of the
ester mixture used according to the invention. Likewise, it is possible to feed the C5
aldehyde mixture as formed in the hydroformylation into the aldol condensation, without
the prior separation of individual isomers. In the aldol condensation, which can be
performed by means of a basic catalyst, such as an aqueous solution of sodium or
potassium hydroxide, for example by the processes described in EP-A 366089, USA
4426524 or US-A 543431 3, with the use of n-valeraldehyde 2-propylheptenal is
formed as the only condensation product, whereas with use of a mixture of isomeric C5
aldehydes an isomer mixture of the products of the homoaldol condensation of like
aldehyde molecules and the crossed aldol condensation of different valeraldehyde
isomers is formed. Of course, the aldol condensation can be controlled by the specific
5 conversion of individual isomers such that a single aldol condensation isomer is
predominantly or entirely formed. The aldol condensation products concerned can then
be hydrogenated to the corresponding alcohols or alcohol mixtures with conventional
hydrogenation catalysts, for example those mentioned above for the hydrogenation of
aldehydes, usually after prior separation from the reaction mixture, preferably by
10 distillation, and, if desired, purification by distillation.
As already mentioned, the compounds of the general formula (11) present in the
plasticizer composition according to the invention can be esterified with pure 2-propylheptanol.
In general, however, for the production of these esters, mixtures of the 2-
15 propylheptanol with said propylheptanol isomers is used, in which the content of 2-
propylheptanol is at least 50 wt.%, preferably 60 to 98 wt.% and particularly preferably
80 to 95 wt.%, in particular 85 to 95 wt.%.
Suitable mixtures of 2-propylheptanol with the propylheptanol isomers comprises for
20 example those of 60 to 98 wt.% 2-propylheptanol, 1 to 15 wt.% 2-propyl-4-methylhexanol
and 0.01 to 20 wt.% 2-propyl-5-methyl-hexanol and 0.01 to 24 wt.% 2-
isopropylheptanol, wherein the sum of the contents of the individual components does
not exceed 100 wt.%. Preferably, the contents of the individual components add up to
100 wt.%.
25
Further suitable mixtures of 2-propylheptanol with the propylheptanol isomers comprise
for example those of 75 to 95 wt.% 2-propylheptanol, 2 to 15 wt.% 2-propyl-4-methylhexanol,
1 to 20 wt.% 2-propyl-5-methyl-hexanol, 0'1 to 4 wt.% 2-isopropylheptanol,
0,1 to 2 wt.% 2-isopropyl-4-methylhexanol and 0,1 to 2 wt.% 2-isopropyl-5-methyl-
30 hexanol, wherein the sum of the contents of the individual components does not
exceed 100 wt.%. Preferably, the contents of the individual components add up to 100
wt.%.
Preferred mixtures of 2-propylheptanol with the propylheptanol isomers comprise those
35 with 85 to 95 wt.% 2-propylheptanol, 5 to 12 wt.% 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 contents of the individual components does not exceed 100 wt.%.
Preferably, the contents of the individual components add up to 100 wt.%.
With use of said 2-propylheptanol isomer mixtures instead of pure 2-propylheptanol for
the production of the compounds of the general formula (II), the isomer composition of
the alkyl ester groups or alkyl ether groups practically corresponds to the composition
of the propylheptanol isomer mixtures used for the esterification.
Undecanol
The undecanols which are used for the production of the compounds of the general
formula (11) present in the plasticizer composition according to the invention can be
straight-chain or branched or be constituted of mixtures of straight-chain and branched
undecanols. Preferably, mixtures of branched undecanols, also described as
isoundecanol, are used as the alcohol component.
Essentially straight-chain undecanol can be obtained by rhodium- or preferably cobaltcatalyzed
hydroformylation from 1 -decene and subsequent hydrogenation of the nundecanal
thereby obtained. The starting olefin 1-decene is produced via the SHOP
process previously mentioned in the of 1-octene.
For the production of branched isoundecanols, the 1-decene obtained in the SHOP
process can be subjected to skeletal isomerization, e.g. by means of acidic zeolitic
molecular sieve, as described in WO 9823566, whereby mixtures of isomeric decenes
are formed, rhodium- or preferably cobalt-catalyzed hydroformylation whereof and
subsequent hydrogenation of the isoundecanal mixtures leads to the isoundecanols
used for the production of the compounds (11) used according to the invention. The
hydroformylation of I-decene or isodecene mixtures by rhodium- or cobalt catalysis
can be effected as described above in connection with the synthesis of C7 to CI0
alcohols. The same applies analogously for the hydrogenation of n-undecanal or
isoundecanal mixtures to n-undecanol or isoundecanol respectively.
After purification of the output from the hydrogenation by distillation, the C7 to CI1 alkyl
alcohols or mixtures thereof thus obtained can be used as described above for the
production of the diester compounds of the general formula (11) used according to the
invention.
Dodecanol
Essentially straight-chain dodecanal can advantageously be obtained via the Alfol@ or
Epal@ process. These processes comprise the oxidation and hydrolysis of straightchain
trialkylaluminum compounds, which are built up stepwise starting from
triethylaluminum via several ethylation reactions using Ziegler-Natta catalyst. From the
mixtures of largely straight-chain alkyl alcohols of different chain length resulting
therefrom, the desired n-dodecanol can be obtained after extraction of the CI2 alkyl
alcohol fraction by distillation.
5 Alternatively, n-dodecanol can also be produced by hydrogenation of natural fatty acid
methyl esters, for example from coconut oil.
Branched isododecanol can be obtained analogously to the known processes for the
codimerization andlor oligomerization of olefins, as for example described in WO
10 00631 51, with subsequent hydroformylation and hydrogenation of the isoundecene
mixtures, as for example described in DE-A 433971 3. After purification of the output
from the hydrogenation by distillation, the isododecanols or mixtures thereof thus
obtained can be used, as previously described, for production of the diester
compounds of the general formula (11) used according to the invention.
15
Plastisol a~~lications
As already stated, because of its good gelling properties the plasticizer composition
according to the invention is particularly suitable for the production of plastisols.
20
A further subject of the invention therefore relates to the use of a plasticizer
composition, as previously defined, as plasticizer in a plastisol.
Plastisols can be produced from various plastics. In a preferred embodiment, the
25 plastisols according to the invention is a PVC plastisol.
The content of plasticizer composition according to the invention in the PVC plastisols
is usually 5 to 300 phr, preferably 50 to 200 phr.
30 Plastisols are usually brought into finished product form at ambient temperatures by
various processes such as coating processes, screen printing processes, molding
processes, such as the slush molding or rotation molding process, dipping processes,
spraying processes and the like. Next, the gelling is effected by heating, whereby a
homogeneous, more or less flexible product is obtained after cooling.
35
PVC plastisols are suitable in particular for the production of PVC films, for the
production of seamless hollow bodies and gloves, and for use in the textiles sector,
such as for example for textile coatings.
The PVC plastisols based on the plasticizer composition according to the invention are
especially suitable for the production of artificial leather, e.g. artificial leather for vehicle
manufacture, underbody protection for vehicles, joint seals, carpet backing coatings,
heavy duty coatings, conveyor belts, dip coatings and articles produced by dipping
5 processes, toys such as dolls, balls or play animals, anatomical models for training,
floor coverings, wall coverings, (coated) textiles such as latex clothing, protective
clothing or rain clothing such as waterproof jackets, tarpaulins, tents, coil coatings,
roofing felts, sealing compounds for closures, breathing masks and gloves.
10 Moldinq comwound uses
The molding compound according to the invention is preferably used for the production
of molded articles and films. These include in particular housings of electrical
appliances, such as for example kitchen appliances and computer housings, tools,
15 pipes, cables, hoses, such as for example plastic hoses, watering and irrigation hoses,
industrial rubber hoses or chemical hoses, wire sheathings, window profiles,
components for automobile construction, such as for example bodywork components,
vibration dampers for engines, tires, furniture, such as for example chairs, tables or
shelves, foam for pillow and mattresses, seals, composite films, such as films for
20 composite safety glass, in particular for automobile windows and window panes,
records, packaging containers, and adhesive tape films or coatings.
Apart from this, the molding compound according to the invention is also suitable for
the production of molded articles and films which come directly into contact with people
25 or foodstuffs. These are predominantly medicinal products, hygiene products, food
packaging, products for interiors, toys and childcare articles, sport and leisure products,
clothing or fibers for fabrics and the like.
The medicinal products which can be produced from the molding compound according
30 to the invention are for example tubes for enteral nutrition and hemodialysis, ventilation
tubes, infusion tubes, infusion pouches, blood pouches, catheters, tracheal tubes,
disposable syringes, gloves or breathing masks.
The food packaging which can be produced from the molding compound according to
35 the invention is for example cling film, food hoses, drinking water tubes, containers for
storing or freezing foods, cover gaskets, closure caps, crown caps or artificial wine
corks.
The products for the interior sector which can be produced from the molding compound
40 according to the invention are for example ground coverings, which can be built up
homogeneously or of several layers, consisting of at least one foamed layer, such as
for example floor coverings, sports floors or luxury vinyl tiles (LVT), artificial leather,
wall coverings or foamed or non-foamed wall coverings in buildings or facings or
console coverings in vehicles.
5
The toys and childcare articles which can be produced from the molding compound
according to the invention are for example dolls, inflatable toys such as balls, game
pieces, modeling clay, swimming aids, toy car covering hoods, nappy changing pads,
hot-water bottles, teething rings or bottles.
10
The sport and leisure products which can be produced from the molding compound
according to the invention are for example gymnastics balls, practice mats, seat
cushions, massage balls and rollers, shoes or shoe soles, balls, air mattresses or
drinking bottles.
15
The clothing which can be produced from the molding compounds according to the
invention are for example rubber boots.
Non-PVC applications
20
In addition, the present invention comprises the use of the plasticizer composition
according to the invention as an additive orland in additives, selected from: calendering
aids, rheological additives, surface-active compositions such as flow aids, film
formation aids, defoamants, antifoam agents, wetting agents, coalescing agents and
25 emulsifiers, lubricants such as lubricating oils, lubricating greases and lubricating
pastes, quenchers for chemical reactions, phlegmatizing agents, pharmaceutical
products, plasticizers in adhesives, impact modifiers and suspending agents.
The invention is explained in more detail on the basis of the figures described below
30 and the examples. However the figures and examples should not be understood as
limiting for the invention.
In the following examples and diagrams, the following abbreviations are used:
35 2,5-FDCS for 2,5-furandicarboxylic acid,
DlNP for diisononyl phthalate,
DMAP for 4-dimethylaminopyridine,
THF for tetrahydrofuran, and
phr for parts by weight per 100 parts by weight polymer.
40
DESCRIPTION OF DIAGRAMS
Figure 1:
5 Figure 1 shows the gelling behavior of PVC plastisols each with a total content of
plasticizer composition according to the invention of 60 phr. Here plasticizer
compositions according to the invention which comprise the commercially available
plasticizer Hexamoll@ DINCHo and different quantities of the fast fuser 2,5-FDCS
dibutyl ester were used. Additionally, the comparison is shown of the gelling behavior
10 of PVC plastisols which comprise exclusively the commercially available plasticizers
Hexamollo DINCHo or Palatinolo N (DINP). The viscosity of the plastisols as a
function of temperature is shown.
EXAMPLES
15
I) Production Exameles of Comeounds (I) Used According to the Invention:
Example 1
Synthesis of di-(n-butyl) 2,5-furandicarboxylate by direct esterification
20
445 g (6.00 mol, 4.0 equivalents) n-butanol in 500 g toluene were placed in a 2 L
round-necked flask equipped with a Dean-Stark water separator and a dropping funnel.
The mixture was heated to reflux with stirring and 234 g (1.50 mol, 1.0 equivalents) of
2,5-furandicarboxylic acid were added, followed by 11.5 g (0.12 mol, 8 mol.%) of 99.9%
25 sulfuric acid in 3 to 4 portions, whenever the reaction slowed. The course of the
reaction was followed on the basis of the quantity of separated water in the Dean-Stark
apparatus. After complete conversion, a sample was taken from the reaction mixture
and analyzed by GC. The reaction mixture was cooled to room temperature,
transferred into a separating funnel and washed twice with saturated NaHC03 solution.
30 The organic phase was washed with saturated common salt solution, dried with
anhydrous Na2S0, and the solvent removed under reduced pressure. The crude
product was purified by fractional distillation. The desired di-(n-butyl) 2,5-
furandicarboxylate could thereby be obtained in a yield of 80% and a purity of 98.9%.
The identity and purity of the final product was determined by NMR and GC-MS
35 analysis (GC separating column: Agilent J&W DB-5, 30 m x 0.32 mm x I .0 pm or Ohio
Valley OV-1701 60 m x 0.32 mm x 0.25 pm).
II) Ap~licationT echnolonv Tests:
1l.a) Determination of the dissolution temperature according to DIN 53408:
5 For the characterization of the gelling behavior of the compounds (I) used according to
the invention in PVC, the dissolution temperature was determined according to DIN
53408. According to DIN 53408, one drop of a slurry of 1 g PVC in 19 g plasticizer is
observed in transmitted light under a microscope equipped with a heatable microscope
stage. During this, the temperature is increased linearly from 60°C at 2°C per minute.
10 The temperature at which the PVC particles become invisible, i.e. their contours and
contrasts can no longer be discerned, is regarded as the dissolution temperature. The
lower the dissolution temperature, the better is the gelling behavior of the substance
concerned for PVC.
15 In the following table, the dissolution temperatures of the plasticizer di(n-butyl) 2,5-
furandicarboxylate and of Mesamoll@ TP-LXS 51 06 and of dibutyl phthalate as a
comparison are shown.
1 ) Mixture of phenyl alkylsulfonate esters from Lanxess Deutschland GmbH (CAS
20 NO. 91 082-17-6)
2) Di(n-butyl) benzene-l,2-dicarboxylate (CAS No. 84-74-2)
Ex. No.
1
V1
V2
As is clear from the table, di(n-butyl) 2,5-furandicarboxylate shows the lowest
dissolution temperature.
25
1l.b) Determination of the gelling behavior of PVC plastisols:
To investigate the gelling behavior of PVC plastisols based on the plasticizer
compositions according to the invention, PVC plastisols which comprise the
30 commercially available plasticizer Hexamoll@ DINCH@ and different quantities of the
fast fuser 2,5FDCS dibutyl ester (5 to 10 wt.%, based on the plasticizer composition
used) were produced according to the following formula:
Substance
Di(n-butyl) 2,5-furandicarboxylate
Mesamoll@ TP-LXS 51 067')
Dibutyl phthalate2)
Dissolution temperature
according to DIN 53408
[" C]
83
114
100
3) commercially available PVC from Solvin GmbH & Co. KG, produced by
suspension polymerization (K value as per IS0 1628-2: 73)
4) liquid Ba-Zn stabilizer from Reagens Deutschland GmbH
Additive
Solvin 372 NF~)
Plasticizer composition according
to the invention
Reagent SLX 7814)
5 Additionally, as a comparison, plastisols were produced which comprise exclusively the
commercially available plasticizers Hexamoll@ DINCH@ or Palatinol@ N (DINP).
phr
100
60
2
The production of the plastisols was effected by adding the PVC to the weighed
mixture of the plasticizer composition according to the invention and heat stabilizer with
10 stirring by means of a dissolver at ca. 800 revolutionslrninute. After completion of the
PVC addition, the mixture was homogenized for 2.5 minutes at 2500 revolutionslrninute
and then deaerated under vacuum in a desiccator.
In order to gel a liquid PVC plastisol and to convert it from the state of PVC particles
15 homogeneously dispersed in plasticizer into a homogeneous, solid soft PVC matrix, the
energy necessary for this must be supplied in the form of heat. In one processing
process, the parameters temperature and residence time are available for this. The
faster.the gelling proceeds (the index here is the dissolution temperature, i.e. the lower
this is, the faster the material gels), the lower the temperature (at equal residence time)
20 or the residence time (at equal temperature) that can be selected.
The investigation of the gelling behavior of a plastisol is carried out by an in-house
method with an Anton Paar MCRlOl rheometer. In this, the viscosity of the paste is
measured with heating at constant shear (rotation). The measurement is made with a
25 platelplate system (PP50) starting at 30°C at a shear rate of 10 11s and a heating rate
of 5"CIminute.
In general, the viscosity of a plastisol firstly decreases with increasing temperature and
reaches a minimum. Next, the viscosity increases again. The temperature at the
30 minimum of the curve and the steepness of the rise after minimum give indications as
to the gelling behavior, i.e. the lower the temperature at the minimum and the steeper
the subsequent rise, the better or faster the gelling takes place.
As can very clearly be discerned in figure 1, in comparison to the PVC plastisol which
35 comprises exclusively the commercially available plasticizer Hexamoll@ DINCHB, the
PVC plastisol with the plasticizer composition according to the invention, gels markedly
faster and at considerably lower temperatures. Furthermore, in the ungelled state, i.e.
at temperatures below the gelling temperature, the PVC plastisols which comprise the
plasticizer composition according to the invention have a markedly lower viscosity than
5 a PVC plastisol which comprises exclusively the commercially available plasticizer
Palatino103 N (DINP).
Patent Claims
1. A plasticizer composition, comprising
a) at least one compound of the general formula (I),
(1)
wherein
X is *-(C=O)-0-, *-(CHZ)~-Oo-r *-(CH2)n-O-(C=O)- , wherein *
represents the linkage point with the furan ring and n has the value 0,
1 or 2;
and
R1 and R2 are mutually independently selected from C4 alkyl and C5-Ce
cycloalkyl, wherein the cycloalkyl residues are unsubstituted or can
be substituted with at least one CI-Clo alkyl residue,
b) at least one compound of the general formula (II),
wherein
R3 and R4 are mutually independently selected from branched and
unbranched C7-C12 alkyl residues.
30
2. The plasticizer composition as claimed in claim 1, where in the compounds of the
general formula (I) R1 and R2 mutually independently are an unbranched or
branched C4 alkyl residue.
The plasticizer composition as claimed in any one of the preceding claims, where
in the compounds of the general formula (I) R1 and R2 both are n-butyl or both
are isobutyl.
The plasticizer composition as claimed in any one of the preceding claims, where
in the compounds of the general formula (I) the group X is *-(C=O)-0-.
The plasticizer composition as claimed in any one of the preceding claims, where
in the compounds of the general formula (11) R3 and R4 both are 2-ethylhexyl,
both are isononyl or both are 2-propylheptyl.
The plasticizer composition as claimed in any one of the preceding claims, where
the plasticizer composition optionally comprises a further plasticizer different from
the compounds (I) and (II), which is selected from dialkyl phthalate esters, alkyl
aralkyl phthalate esters, 1,2-cyclohexanedicarboxylate esters different from
compounds (II), dialkyl terephthalate esters, trialkyl trimellitate esters, alkyl
benzoate esters, dibenzoate esters of glycols, hydroxybenzoate esters, esters of
saturated mono- and dicarboxylic acids, esters of unsaturated dicarboxylic acids,
amides and esters of aromatic sulfonic acids, alkylsulfonate esters, glycerin
esters, isosorbide esters, phosphate esters, citric acid triesters, alkylpyrrolidone
derivatives, 25-furandicarboxylate esters different from compounds (I), 2,5-
tetrahydrofurandicarboxylate esters, epoxidized plant oils and epoxidized fatty
acid monoalkyl esters, and polyesters of aliphatic and/or aromatic polycarboxylic
acids with at least dihydric alcohols.
The plasticizer composition as claimed in any one of the preceding claims, where
the content of the compounds of the general formula (I) in the plasticizer
composition is 1 to 50 wt.%.
The plasticizer composition as claimed in any one of the preceding claims, where
the content of the compounds of the general formula (11) in the plasticizer
composition is 10 to 99 wt.%.
The plasticizer composition as claimed in any one of the preceding claims, where
the weight ratio between compounds of the general formula (I) and compounds of
the general formula (I I) is in the range from 1 : 100 to 1 : 1 .
A molding compound, comprising at least one polymer and one plasticizer
composition as defined in any one of claims 1 to 9.
11. The molding compound as claimed in claim 10, where the polymer is a
thermoplastic polymer which is selected from
homo- or copolymers which comprise at least monomer incorporated by
polymerization, which is selected from C2-CIO monoolefins, 1,3-butadiene,
2-chloro-I ,3-butadiene, vinyl alcohol and CZ-CIO alkyl esters thereof, vinyl
chloride , vinylidene chloride, vinylidene fluoride, tetrafluoroethylene,
glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of C1-
CIO alcohols, vinylaromatics (meth)acrylonitrile, maleic anhydride and a$-
ethylenically unsaturated mono- and dicarboxylic acids,
homo- and copolymers of vinyl acetals,
polyvinyl esters,
polycarbonates,
polyesters,
polyethers,
polyether ketones,
thermoplastic polyurethanes,
polysulfides,
polysulfones,
polyether sulfones,
cellulose alkyl esters,
and mixtures thereof.
25 12. The molding compound as claimed in claim 11, wherein the thermoplastic
polymer is selected from polyvinyl chloride (PVC), polyvinyl butyral (PVB), homoand
copolymers of vinyl acetate, homo- and copolymers of styrene, polyacrylates,
thermoplastic polyurethanes (TPU) or polysulfides.
30 13. The molding compound as claimed in any one of claims 11 or 12, where the
thermoplastic polymer is polyvinyl chloride (PVC).
14. The molding compound as claimed in claim 13, where the content of the
plasticizer composition in the molding compound is 1.0 to 300 phr.
35
15. The molding compound as claimed in one of claims 11 or 12, comprising at least
one thermoplastic polymer different from polyvinyl chloride, where the content of
the plasticizer composition in the molding compound is 0.5 to 300 phr.
40 16. The molding compound as claimed in claim 10, where the polymer is an
elastomer, preferably selected from natural rubbers, synthetic rubbers and
mixtures thereof.
17. The molding compound as claimed in claim 16, wherein the content of the
plasticizer composition in the molding compound is 1.0 to 60 phr.
5 18. The use of a plasticizer composition, as defined in any one of claims 1 to 9, as a
plasticizer for thermoplastic polymers and elastomers.
19. The use of a plasticizer composition, as defined in any one of claims 1 to 9, as a
plasticizer in a plastisol.
20. The use of a molding compound, as defined in any one of claims 10 to 17, for the
production of molded articles and films, such as for example housings of
electrical devices, computer housings, tools, pipes, cables, hoses, wire
coverings, window profiles, components for automobile construction, tires,
furniture, foam for pillows and mattresses, tarpaulins, seals, laminated films,
records, artificial leather, packing containers, adhesive tape films or coatings.
21. The use of a molding compound as defined in any one of claims 10 to 17, for the
production of molded articles and films which come directly into contact with
people or foods.
22. The use as defined in claim 21, where the molded articles and films which come
directly into contact with people or foods are medicinal . products, hygiene
products, food packaging, products for interiors, toys and childcare articles, sport
and leisure products, clothing or fibers for fabrics.