Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2002-06-24
2003-09-23
Acquah, Samuel A. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S301000, C525S437000
Reexamination Certificate
active
06624285
ABSTRACT:
Polyesters capped by isomeric nonanols, a process for their preparation, and their use as plasticizers
Plastics are mostly based on materials obtainable by polymerization of organic monomers. Depending on their chemical constitution and on the particular circumstances of the preparation process, these polymers have characteristic physical properties, such as flexibility.
In order to achieve controlled changes in the usage properties of the polymers, prior to their processing to give products for use it is also usual to incorporate additives, e.g. fillers, dyes, flame retardants and plasticizers. The plasticizers serve to maintain or further improve the flexibility of the resultant consumer articles.
One polymer for which the issues described here are of very particular significance is polyvinyl chloride, which is produced on a large scale industrially and is found in an endless variety of articles in daily use.
Depending on the group of chemicals to which a plasticizer belongs, its use can raise quite specific new areas of work for the skilled worker. One of these which is receiving particular attention is the discharge of plasticizers out of the materials, for example via bleeding, where the plasticizer mostly forms a liquid film on the surface of the material, or by evaporation. Another phenomenon is migration: the escape of the plasticizer from the material followed by permeation into a plastic with which it is in contact.
An important class of plasticizers is that of polyesters of dicarboxylic acids. They are used in particular in producing films, coatings, profiles, floorcoverings and cables based on plasticized PVC when relatively high requirements are placed on resistance to extraction, especially in contact with gasoline, or with oils or fats, and also on the UV resistance and volatility of the plasticizer.
There are known polyester plasticizers made from dicarboxylic acids and from diols and having terminal alcohol groups—from syntheses using an excess of diol—or terminal acid groups—from syntheses using an excess of dicarboxylic acid—these groups having been esterified, i.e. “capped”, with monocarboxylic acids or, respectively, monohydric alcohols.
RO-B 104 737 discloses a process for preparing aliphatic linear polyester plasticizers, by reacting adipic acid with propylene glycol and 2-ethylhexanol.
GB-A 1 173 323 describes PVC compositions comprising a plasticizer which may have been built up from adipic acid, 1,2-propanediol and isodecanol, for example.
U.S. Pat. No. 5,281,647 discloses a process for preparing a plasticizer, by reacting, for example, adipic acid with a sterically hindered diol, such as neopentyl glycol, and with another diol, for example a butylene glycol. The resultant product is then reacted with a mono alcohol, and the alcohol here may be a nonyl alcohol.
However, the known plasticizers of polyester type still have inadequate compatibility with PVC, and therefore suffer a considerable extent of discharge during use. Over the course of time this results in a marked reduction in flexibility, for example of plasticized PVC compounds prepared using these plasticizers. In addition, these known plasticizers exhibit a high degree of migration from materials of this type into other plastics with which they come into contact.
It is an object of the present invention, therefore, to provide plasticizers of polyester type which have good compatibility with plastics, in particular when processed into plasticized PVC compounds, and exhibit only a low tendency to migrate into other plastics with which they come into contact.
We have found that this object is achieved by means of polyesters suitable as plasticizers and obtained by reacting aliphatic dicarboxylic acids, neopentyl glycol, at least one other diol and a nonanol mixture, where the nonanol mixture is mainly composed of 1-nonanol, of monomethyloctanols, of dimethylheptanols and of monoethylheptanols.
Novel nonanol mixtures have also been found, as have a process for preparing the polyesters and the use of the polyesters as plasticizers for plastics or polymers.
For the purposes of the present invention, since the dicarboxylic acids, the neopentyl glycol, the other diol(s) and the nonanol mixture are reacted to give the polyesters of the invention, the composition of the polyesters in terms of the starting materials refers to dicarboxylic acid units, neopentyl glycol units, diol units and, respectively, nonanol units in the polyester.
According to the earlier German patent application with the official file reference number 19924339.5, the nonanol mixture used according to the invention is particularly advantageously obtainable in a process involving two or more stages and starting from a hydrocarbon mixture comprising butenes. In a first step, the butenes are dimerized to give a mixture of isomeric octenes. The octene mixture is then hydroformylated to give C
9
aldehydes and then hydrogenated to give the nonanol mixture. In this reaction sequence, specific, defined parameters have to be adhered to, at least during the butene dimerization, preferably during the butene dimerization and the hydroformylation.
It is preferable, therefore, that the isomeric octenes mixture is obtained by bringing a hydrocarbon mixture comprising butenes into contact with a heterogeneous catalyst comprising nickel oxide. The isobutene content of the hydrocarbon mixture is preferably 5% by weight or less, in particular 3% by weight or less, particularly preferably 2% by weight or less, and most preferably 1.5% by weight or less, based in each case on the total butene content. A suitable hydrocarbon stream is that known as the C
4
cut, a mixture of butenes and butanes, available in large quantities from FCC plants or from steam crackers. A starting material used with particular preference is that known as raffinate II, which is an isobutene-depleted C
4
cut.
A preferred starting material comprises from 50 to 100% by weight, preferably from 80 to 95% by weight, of butenes and from 0 to 50% by weight, preferably from 5 to 20% by weight, of butanes. The following makeup of the butenes can be given as a general guide to quantities:
1-butene
from 1 to 98% by weight,
cis-2-butene
from 1 to 50% by weight,
trans-2-butene
from 1 to 98% by weight, and
isobutene
up to 5% by weight.
Possible catalysts are catalysts known per se and comprising nickel oxide, as described, for example, by O'Connor et al. in Catalysis Today, 6, (1990) p. 329. Supported nickel oxide catalysts may be used, and possible support materials are silica, alumina, aluminosilicates, aluminosilicates having a layer structure and zeolites. Particularly suitable catalysts are precipitation catalysts obtainable by mixing aqueous solutions of nickel salts and of silicates, e.g. of sodium silicate and sodium nitrate, and, where appropriate, of other constituents, such as aluminum salts, e.g. aluminum nitrate, and calcining.
Particular preference is given to catalysts which essentially consist of NiO, SiO
2
, TiO
2
and/or ZrO
2
, and also, where appropriate, Al
2
O
3
. A most preferred catalyst comprises, as significant active constituents, from 10 to 70% by weight of nickel oxide, from 5 to 30% by weight of titanium dioxide and/or zirconium dioxide and from 0 to 20% by weight of aluminum oxide, the remainder being silicon dioxide. A catalyst of this type is obtainable by precipitating the catalyst composition at pH from 5 to 9 by adding an aqueous solution comprising nickel nitrate to an aqueous alkali metal waterglass solution which comprises titanium dioxide and/or zirconium dioxide, filtering, drying and annealing at from 350 to 650° C. For details of preparation of these catalysts reference may be made to DE-A 4339713. The entire content of the disclosure of that publication is incorporated herein by way of reference.
The hydrocarbon mixture comprising butenes is brought into contact with the catalyst, preferably at temperatures of from 30 to 280° C., in particular from 30 to 140° C. and particularly preferably from 40 to 130° C. This preferably takes place at
Breitscheidel Boris
Disteldorf Walter
Haller Christiane
Holzmann Jürgen
Morsbach Bernd
Acquah Samuel A.
BASF - Aktiengesellschaft
Keil & Weinkauf
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