PROCESS OF PRODUCING AND USE OF A TREATED, PROMOTED ION EXCHANGE RESIN CATALYST

Abstract

The present invention relates to the treatment of a promoted strong acid ion exchange resin for use as an acid catalyst with an antioxidant to protect the resin from oxidative degradation and the use of said treated promoted ion exchange resin catalyst in chemical production processes.

Claims

1. A process for producing a treated promoted ion exchange resin catalyst comprising providing a promoted ion exchange resin catalyst having an attached thiol promoter, and contacting the promoted ion exchange resin catalyst with 2,6-di-t-butyl-.alpha.-dimethylamino-p-cresol to produce a treated promoted ion exchange resin.

2. The process of claim 1 wherein the ion exchange resin catalyst is a sulfonic acid-type cation-exchange resin catalyst.

3. The process of claim 2 wherein the cation-exchange resin catalyst is a sulfonated styrene-divinyl benzene copolymer.

4. The process of claim 1 wherein the amount of antioxidant incorporated into the cation-exchange resin catalyst is from 0.001 to 10 percent by weight.

5. The process of claim 1 wherein the 2,6-di-t-butyl-.alpha.-dimethylamino-p-cresol is bound.

6. The process of claim 1 wherein the thiol promoter is attached to the resin via an amine group of the promoter.

7. The process of claim 1, wherein the thiol promoter is selected from the group consisting of 2-mercaptomethylpyridine, cysteamine, and 4-aminobutanethiol.

8. The treated promoted ion exchange resin of claim 1.

9. The method of using the treated promoted ion exchange resin of claim 8 in a condensation reaction.

Description

EXAMPLES

Preparation of Resin for Testing

[0035] To establish a clean starting baseline, all the catalyst resins are given the same conditioning procedure in order to remove any residual acid from the plant process. A clean glass quart jar is filled with 350 mLs of fresh ion exchange resin and batch washed three times with 500 mLs of DI water. The resin is then charged to a 1 diameter jacketed glass column fitted with an FMI pump and a heating bath. The column is heated and maintained at 60 C. by the heating bath. The catalyst resin is backwashed by pumping 4 L of DI water through the column at 15 mL/min. After 4 liters of DI water has passed through the column the resin is transferred to a clean glass quart jar and batch washed again three times, but now with MilliQ H.sub.2O. After the last batch wash the resin is siphoned dry using house vacuum for 60 seconds. The freshly cleaned resin is now ready for testing.

Addition of Promoter:

[0036] To a clean 1 L round-bottomed flask equipped with a Teflon stirring paddle is transferred 150 g of conditioned resin along with enough DI water for fluid stirring. The promoter solution is prepared by adding 1.50 g of Cysteamine-95 to 13.5 g of DI water. The mixture is stirred vigorously until dissolved and then transferred to an addition funnel. The promoter solution is charged to the catalyst resin drop wise over 60 minutes with stirring at RT. Following the addition of the promoter solution the addition funnel is rinsed with DI water into the round-bottomed flask. The catalyst resin is stirred for another 30 minutes following the end of the promoter addition. After 30 minutes the resin is washed 3 times (batchwise) with 500 mLs DI water to remove any residual promoter solution and the sample is then transferred to a clean quart jar. The loaded resin is again batch washed 3 times with 500 mls MilliQ water to remove any effect of the standard DI water. A 50 g sample of the treated resin is then transferred to a clean 8 oz jar and run through the stability test as described below.

Addition of Antioxidant:

[0037] To a clean 1 L round-bottomed flask equipped with a Teflon stirring paddle is transferred 150 g of conditioned resin along with enough tap DI water for fluid stirring. The antioxidant solution is prepared by adding 1.0 g of Ethanox-703 to 113.6 g of DI water along with 0.7 g of 96% H.sub.2SO.sub.4. The mixture is stirred vigorously until dissolved. To the conditioned resin in the round-bottomed flask is charged 11.53 g of the prepared Ethanox-703 solution. The loading of the antioxidant onto the resin takes place while the resin is stirring at RT for 30 minutes in the round-bottomed flask. After 30 minutes the resin is batched washed 3 times with 500 mLs DI water to remove any residual antioxidant solution and transferred to a clean quart jar. The loaded resin is again batch washed 3 times with 500 mLs MilliQ water to remove any effect of the standard DI water. A 50 g sample of the treated resin is then transferred to a clean 8 oz jar and run through the stability test as described below.

General Procedure for Stability Testing the Resin Samples:

[0038] To a clean 8 oz jar is transferred 50 g of conditioned resin. The correct amount of MilliQ water is charged to the resin (depending on the resin solids). The jar is sealed and placed on an auto shaker for 20 minutes at 140 rpm. After shaking, the resin and MillQ water are separated by using a clean glass funnel and Whatman filter paper. For samples being tested after aging, the resin is stored as 30 C for the requisite amount of time (see table below) followed by separating the resin and MillQ water by using a clean glass funnel and Whatman filter paper. The MilliQ water is filtered into a clean 4 oz jar and the catalyst resin is siphoned dry and stored in the 8 oz jar. The effluent MilliQ water is then tested for pH , and conductivity. These values are recorded in Table 1 below

TABLE-US-00001 TABLE 1 Results of Stability Testing of Resins, Dependant on Order of Addition of Promoter and Antioxidant. Age Conductivity Resin Treatment (days) pH (S/cm) AMBERLYST 31 1. Promoter 3 7.44 5 2. Antioxidant AMBERLYST 31 1. Antioxidant 3 5.21 35 2. Promoter AMBERLYST 121 1. Promoter 3 7.44 8 2. Antioxidant AMBERLYST 121 1. Antioxidant 3 4.99 94 2. Promoter AMBERLYST 131 1. Promoter 3 7.54 5 2. Antioxidant AMBERLYST 131 1. Antioxidant 3 4.89 81 2. Promoter DOWEX CM-4 1. Promoter 3 5.62 28 2. Antioxidant DOWEX CM-4 1. Antioxidant 3 4.93 137 2. Promoter DOWEX 50WX4 1. Promoter 3 6.61 9 2. Antioxidant DOWEX 50WX4 1. Antioxidant 3 5.38 29 2. Promoter