Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Reexamination Certificate
1999-03-24
2001-04-03
Moore, Margaret G. (Department: 1712)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
C528S030000, C556S009000, C525S475000, C210S679000, C210S683000
Reexamination Certificate
active
06211408
ABSTRACT:
TECHNICAL FIELD
The present invention relates generally to macroporous organofunctional polysiloxane resins and more particularly to strong acid, silver or mercury-exchanged macroporous polysiloxane resins wherein at least one percent of its active sites have been converted to the silver or mercury form.
BACKGROUND ART
Ion exchange resins are well known in the art. Typically, such resins are used as acid catalysts to synthesize various products. There is shown, for example, in U.S. Pat. No. 5,504,234 to Omura et al. the method for the preparation of (meth) acryloxyalkyl group-containing linear organopolysiloxanes. Instead of using a conventional acidic catalyst, the reaction is promoted by the use of a cation-exchange resin in the H+ form which is readily removed from the polymerization mixture after completion of the reaction. The catalytic efficiency of the cation-exchange resin is further enhanced if the resin is swollen with a polar organic solvent such as tetrahydrofuran prior to its use in the process.
There is shown in U.S. Pat. No. 5,315,042 to Cipullo et al. a process for making bisphenol-A utilizing an ion exchange resin catalyst and an optional free mercaptan promotor. Bisphenol-A is continuously prepared by reaction of phenol and acetone in the presence of an acidic catalyst under accelerated flow conditions with increased throughput in order to increase initial reactivity. The acetone and bisphenol-A are separated from the effluent stream prior to depletion of the acetone whereby the residence time of the bisphenol-A is reduced and undesirable by-products and color are reduced.
In U.S. Pat. No. 5,105,026 to Powell et al. there is shown another process for preparing bisphenol-A. In the '026 patent the process generally includes reacting a carbonyl compound with a stoichiometric excess of a phenolic compound in the presence of an acidic catalyst, crystallizing bisphenol-A and using an acidic ion exchange resin catalyst to convert at least a portion of the by-product to bisphenol.
Ion exchange resins are also typically used to remove undesirable ionic compounds from various media. For example, cationic resins are used in their sodium or hydrogen form to remove undesirable metallic ions from drinking water. So also, such resins are used in their acid (H
+
) form in like applications in organic media. Anionic resins, on the other hand, can be used to remove undesirable anions from various liquid media as is shown, for example, in U.K. Patent Application No. 2,112,394, published Jul. 20, 1983 of Becker et al. This patent relates to the removal of iodide compounds from acetic acid by using anionic ion exchange resins and reports efficiencies of up to approximately 90 percent.
There is also known in the art various processes which employ silver-exchanged cationic ion exchange resins for various purposes as further discussed below.
There is shown in U.S. Pat. No. 5,464,559 to Marchin et al. a composition for treating drinking water for the purpose of disinfecting the water and/or removing iodide. A chelating resin having iminodiacetate chelating groups is employed and the resin is loaded with not over 0.5 mol of silver ions per mol of iminodiacetate.
U.S. Pat. No. 5,220,058 of Fish et al. Discloses a process for removing iodides from carboxylic acids and/or carboxylic acid anhydrides. The process described involves using an ion exchange resin in which thiol functional groups have been exchanged with silver, palladium or mercury.
In U.S. Pat. No. 4,615,806 to Hilton there is shown a preferred method for removing iodide compounds from non-aqueous media, such as acetic acid. The media is contacted with a macroreticulated (macroporous), strong-acid cation exchange resin which has at least one percent of its active sites converted to the silver or mercury form. By way of the method of the '806 patent, iodide compounds, both organic iodides and ionic iodides are quantitatively removed from acetic acid in short contact times (on the order of 100 seconds). The resins of the present invention may be used in practicing the process of U.S. Pat. No. 4,615,806 in order to remove iodide compounds from non-aqueous media such as acetic acid and acetic anhydride at elevated temperatures.
SUMMARY OF INVENTION
There is provided in accordance with the present invention a macroporous, strong-acid polysiloxane ion exchange resin wherein at least one percent of the active sites have been converted to the silver or mercury form. Although it may be possible to convert from 1 to 100 percent of the active sites of the resin to the silver or mercury form, generally speaking, at least 25% of the active sites of the resin are converted to the silver form. Typically 25 to 75% of the active sites are converted to the silver or mercury form as described hereinafter.
In general, the resins in accordance with the present invention have a pore volume of from about 1 to about 3 ml per gram. From about 1.5 to about 2 ml per gram of pore volume is typical. The macropores of the resins have a characteristic pore size of its macropores of from about 5 to about 100 nanometers (nm).
Characteristically, resins in accordance with the present invention are made up of repeat units of the formula I:
wherein n is an integer from 1 to 6. Typically the alkyl chains carrying the sulfonic acid group has three carbon atoms and thus n is commonly 3.
In another embodiment the macroporous, strong-acid polysiloxane ion exchange resins utilized in accordance with the present invention are made up of repeat units of the formula II:
where R is a methylene radical, n is an integer from 1 to 6, p is an integer from 2 to 4 and x is optionally a hydrogen atom or the radical -SH.
In yet another aspect in the present invention there is provided a method for removing iodide compounds from a non-aqueous organic medium comprising contacting the medium containing the iodide compounds with a macroporous, strong-acid, polysiloxane ion exchange resin where at least 1 percent of the active sites have been converted to the silver or mercury form. In a typical application of the inventive process, the organic medium is acetic acid or acetic anhydride and the iodide compounds include alkyl iodides. In a particularly preferred process in accordance with the present invention, hexyl iodide is removed from acetic acid.
DETAILED DESCRIPTION
The invention is described in detail below with reference to several embodiments. Such embodiments are illustrative only and do not limit the scope of the invention which is set forth in the appended claims.
The present invention, in a first aspect, is directed to macroporous, strong-acid, polysiloxane ion exchange resins where at least one percent of the active sites have been converted to the silver or mercury form. Polysiloxane resins are well known in the art, typically made by way of a sol-gel condensation process and are available from Degussa, A. G., Frankfurt, Am Main, under the trade name Deloxan ASP. These resins (prior to and after conversion to the silver or mercury form) have the properties set forth in the following Table 1:
TABLE 1
Macroporous Strong-Acid Polysiloxane Ion Exchange Resin
Trade Name:
Deloxan ASP
Resin Material:
Macroporous organofunctional polysiloxane
Functionality:
Chemically bonded sulfonic acid group
H+ capacity:
0.7-1.1 meq/g (dry substance)
Macroscopic
Attrition resistance spheres or micro spheres
appearance:
Particle size:
Variable, depending on application,
0.4-1.6 mm (fixed-bed)
0.1-0.4 mm (suspension)
Specific surface area:
400-600 m
2
/g (BET)
Pore Volume:
1.0-1.5 ml/g (pore size: 6-12 nm)
0.3-0.8 ml/g (pore size: >30 nm)
1.5-2.0 ml/g (total pore volume)
Bulk density:
0.8-1.2 kg/l (wet form, shipping weight)
0.20-0.35 kg/l (dry substance)
Water content:
60-80% (delivery form)
Typical True Density:
2.0 g/ml
Operating Temperature
Max. 230° C., depending on pH value, medium
Range:
and reaction conditions.
Operating pH range:
0-10 (temperature dependent)
Operating medium:
Aqueous and organic medium
Resistance to
Resistant to organic solvents and stro
Celanese International Corporation
Ferrell Michael W.
Moore Margaret G.
Mullen James J
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