Mixture of diesters of adipic or phthalic acid with isomers...

Details Mixture of diesters of adipic or phthalic acid with isomers... Mixture of diesters of adipic or phthalic acid with isomers...

1999-11-26

2002-08-20

Killos, Paul J. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acid esters

C585S531000, C560S204000

Reexamination Certificate

active

06437170

ABSTRACT:

The present invention relates to a mixture of isomeric nonanol diesters of adipic or phthalic acid. The alcohol component of these diesters is formed from an isomeric nonanols mixture.
Long-chain alcohols, e.g. C
8
, C
9
and C
10
alcohols, are widely used for producing plasticizers. For this, the alcohols are reacted with polycarboxylic acids, such as phthalic acid or adipic acid, forming the corresponding esters. Commercially important representatives include adipates of C
8
, C
9
and C
10
alcohols, for example di(2-ethylhexyl) adipate, diisononyl adipates and diisodecyl adipates, and phthalates of C
8
, C
9
and C
10
alcohols, such as di(2-ethylhexyl) phthalate, diisononyl phthalates and diisodecyl phthalates.
Diisononyl adipates are used especially in films, profiles, synthetic leather, cables, lines or piping based on plasticized PVC. Diisononyl adipates are used in particular when the products are intended to be used at low temperatures.
Diisononyl phthalates are used especially in films, coatings and floorcoverings based on plasticized PVC. They are also used for producing PVC cable sheathing, for applications which include some at relatively high temperatures.
DE-A-20 09 505 discloses the use of isononanols in the form of bisisononyl esters of phthalic acid or adipic acid as plasticizers where the isononanols have been prepared from 2-ethyl-l-hexene in a known manner by the oxo synthesis, by reaction with carbon monoxide and hydrogen at elevated temperature and pressure in the presence of carbonyl complexes of metals of the 8th transition group of the Periodic Table, if desired followed by hydrogenation. The 2-ethyl-1-hexene is obtainable by dimerizing 1-butene with trialkyl aluminum compounds. The bisisononyl esters described are said to be suitable plasticizers for polyvinyl chloride and to have low volatility, low viscosity and to give good low-temperature resistance in the polyvinyl chloride compositions plasticized therewith.
U.S. Pat. No. 4,623,748 describes dialkyl adipates, inter alia diisononyl adipates, prepared by reacting propylene oligomers or butylene oligomers from the dimersol process in the presence of supported tantalum(V) halides/oxides as catalysts, reacting the resultant C
8
, C
9
or C
12
olefins to give C
9
, C
10
or, respectively, C
13
alcohols and esterifying these alcohols with adipic acid. The dialkyl adipates are said to have high flash points and to be suitable for use as lubricants.
GB 1,114,379 discloses an isomeric nonanols mixture which comprises n-nonanol and includes essentially no alcohols having more than one branch in their carbon skeleton. The mixture is prepared by hydroformylating an octene fraction obtained by polymerizing ethylene with catalysis by trialkylaluminum compounds, and then reducing the hydroformylation product.
WO 92/13818 describes the preparation of diisononyl phthalates starting from butenes and, where appropriate, from olefin mixtures comprising propene, via oligomerization on supported phosphoric acid catalysts at reaction temperatures of from 200 to 235° C. to give essentially octene-containing olefin mixtures, hydroformylation of these octene-containing olefin mixtures and subsequent hydrogenation to give essentially alcohol mixtures comprising isononanols, and esterification of these isononanol-containing alcohol mixtures using phthalic anhydride. The ester mixtures essentially comprising diisononyl phthalates are intended to be suitable as plasticizers for PVC.
DE 28 55 421 describes phthalates of C
9
alcohols, obtained by an oxo reaction of C
8
olefins, hydrogenation of the reaction product and esterification of the C
9
alcohols using phthalic anhydride, where from 3 to 20% of the C
8
olefins have an isobutane skeleton in each molecular chain and less than 3% of the olefins have quaternary carbon, and also more than 90% of the total amount of the C
9
olefins are present in the form of n-octenes, monomethylheptenes and dimethylhexenes. The C
9
phthalates are intended to be suitable as plasticizers for PVC.
EP 0 278 407 describes a C
9
alcohol mixture for plasticizers which comprises certain proportions of components with a specified GC retention behavior in relation to certain reference compounds. Plasticizers based on the C
9
alcohol mixture are intended to give advantageous resistance to low temperatures and good electrical insulation properties.
In using diisononyl esters as plasticizers in thermoplastic PVC-based molding compositions it is important that the resultant plasticized PVC compounds have both very high thermal stability and very good low-temperature flexibility properties. It is also important that there is little or no bleed-out of the plasticizers when they are used in the plasticized PVC compound. Neither the diisononyl esters described in the patent literature mentioned above nor commercially available plasticizers based on diisononyl esters comply with this combination of properties in an ideal manner.
It is an object of the present invention, therefore, to provide a mixture of isomeric nonanol diesters of a dicarboxylic acid, such that when the mixture is used as a plasticizer in PVC-based molding compositions, it gives good low-temperature flexibility properties and preferably high thermal stability of the molding compositions and preferably high compatibility.
We have found that this object is achieved by a mixture of isomeric nonanol diesters of a dicarboxylic acid selected from
a mixture of diesters of adipic acid in the
1
H NMR spectrum of which, observed in CDCl
3
, the ratio of the area under the resonance signals at chemical shifts in the range from 1.0 to 2.0 ppm with respect to TMS to the area under the resonance signals at chemical shifts in the range from 0.5 to 1.0 ppm with respect to TMS is from 1.20 to 5.00, and
a mixture of isomeric nonanol diesters of phthalic acid in the
1
H NMR spectrum of which, taken up in CDCl
3
, the ratio of the area under the resonance signals at chemical shifts in the range from 1.1 to 3.0 ppm with respect to TMS to the area under the resonance signals at chemical shifts in the range from 0.5 to 1.1 ppm with respect to TMS is from 1.00 to 4.00.
The isomeric nonanol diesters of adipic acid are also referred to as “diisononyl adipates” below and the isomeric nonanol diesters of phthalic acid are also referred to below as “diisononyl phthalates”, or both may be referred to simply as “diesters”.
The properties of the diisononyl adipates and the diisononyl phthalates and, respectively, their effect on the properties of their resultant plasticized molding compositions, are determined by the molecular structure, in particular by the structure of the isononyl groups of the alcohol component. It has been found that advantageous low-temperature flexibility properties and, at the same time, high compatibility are obtained if the isononyl groups of the alcohol component in the plasticizer have a particular ratio of methylene (CH
2
) and methylidene (CH) groups to methyl (CH
3
) groups. To distinguish the groups adequately from one another
1
H NMR spectroscopy may be used.
The diisononyl adipates or phthalates according to the invention have a specific ratio of methylene groups and methylidene groups to methyl groups in the isononyl radical. For the purposes of the present invention, this ratio is determined with the aid of
1
H NMR spectroscopy on a solution of the diisononyl adipates or phthalates in deuterochloroform (CDCl
3
). The spectra are observed by, for example, dissolving 100 mg of substance in 5 ml of CDCl
3
and placing the solution in an NMR sample tube of diameter 5 mm. The equipment used for the NMR spectroscopy in the present studies was of “DPX-400” type from Bruker. The spectra were observed with a delay of 1 second, 32 scans, a pulse length of 3.7 &mgr;s and a sweep width of 8278.146 Hz. The resonance signals are indicated in terms of the chemical shift with respect to tetramethylsilane (TMS) as internal standard. Comparable results are obtained using other commercially available NMR equipment with the same operating

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