METHOD FOR PRODUCING AMINO METHYLATED BEAD POLYMERIZATES FROM N-CARBOXYLIC ACID METHYLPHTHALIMIDE ESTERS

Abstract

The invention relates to a process for preparing aminomethylated bead polymers from N-carboxymethylphthalimides, which are used as anion exchangers or can be converted further to chelate resins.

Claims

1. A process for preparing aminomethylated bead polymers, the process comprising: a) converting monomer droplets composed of a mixture comprising at least one monovinylaromatic compound, at least one polyvinylaromatic compound, and at least one initiator to a bead polymer; b) reacting the bead polymer from step a) with N-carboxymethylphthalimide in the presence of aliphatic saturated or unsaturated carboxylic anhydrides or carboxylic acids or in the presence of mixtures of aliphatic saturated or unsaturated carboxylic anhydrides and at least one aliphatic saturated or unsaturated carboxylic acid, and in the presence of at least one Friedel-Crafts catalyst, to give a phthalimidomethylated bead polymer, and the amount of the compounds used: N-carboxymethylphthalimide, bead polymer, aliphatic, saturated or unsaturated carboxylic anhydrides or carboxylic acids or mixtures thereof and Friedel-Crafts catalysts collectively in the reaction mixture is greater than 80% by weight, based on the total amount of the reaction mixture, and hydrolyzing the phthalimidomethylated bead polymer to give an aminomethylated bead polymer.

2. The process according to claim 1, wherein the monovinylaromatic compounds are styrene, α-methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, bromostyrene, chloromethylstyrene, or vinylnaphthalene, or mixtures of these compounds.

3. Process according to claim 1, wherein the polyvinylaromatic compounds are divinylbenzene, divinyltoluene, or trivinylbenzene, or mixtures of these compounds,

4. The process according to wherein the monovinylaromatic compound is styrene and the polyvinylaromatic compound is divinylbenzene.

5. The process according to claim 1, wherein the N-carboxymethyphthalimide is N-acetoxymethylphthalimide.

6. The process according to claim 1, wherein the Friedel-Crafts catalysts are a mixture of iron(III) chloride and sulphuric acid.

7. The process according to claim 1, further comprising using 2 to 5 mol of N-carboxymethylphthalimide per mole of Friedel-Crafts catalyst.

8. The process according to claim 1, further comprising using 10.sup.−3 mol to 0.03 mol of N-carboxymethylphthalimide per gram of bead polymer.

9. The process according to claim 1, further comprising using N-carboxymethylphthalimides in an amount of 1,6 to 2,5 mol per mole of carboxylic anhydrides or carboxylic acid.

10. The process according to claim 1, wherein the carboxylic anhydrides and carboxylic acids are a mixture of acetic anhydride and acetic acid.

11. The process according to claim 10, wherein a ratio of acetic anhydride to acetic acid is 3:1 to 0:1.

12. The process according to claim 1, further comprising collectively using the N-carboxymethylphthalimide compounds, the bead polymer, the carboxylic anhydrides or carboxylic acids or mixtures thereof, and the Friedel-Crafts catalysts in an amount greater than 95% by weight in the reaction mixture, based on the total amount of the reaction mixture.

13. The process according to claim 1, further comprising conducting process step c) with aqueous or alcoholic solutions of an alkali metal hydroxide at temperatures between 100° C. and 250° C.

14. The process according to claim 1, further comprising using a porogen in step a).

15. The process according to claim 1, wherein the carboxylic acid is acetic acid.

Description

EXAMPLES

Example 1

[0081] 1.1 Preparation of the Heterodisperse Macroporous Bead Polymer based on Styrene, Divinylbenzene and Ethylstyrene

[0082] Such a heterodisperse bead polymer is used in Example 5 of U.S. Pat. No. 3,989,650.

[0083] At room temperature, the reactor is initially charged with 1112 ml of demineralized water. 72 ml of a 2% by weight aqueous Walocel solution are metered into the initial charge. Walocel is a hydroxyethyl methyl cellulose. This solution is prepared by introducing the hydroxyethyl methyl cellulose solid into an initial charge of water while stirring and then stirring for a further 4 hours. After the aqueous Walocel solution has been metered in, the mixture is stirred for a further 30 minutes. Subsequently, 7.5 grams of disodium hydrogenphosphate*12 H.sub.2O are metered in. The mixture is stirred for a further 30 minutes.

[0084] With the stirrer stationary, the organic phase consisting of 865.1 grams of styrene, 94.9 grams of 80.95% by weight divinylbenzene, 576 grams of isododecane and 7.68 grams of 75% by weight dibenzoyl peroxide is metered in. The solution had been prepared separately beforehand.

[0085] The above mentioned mixture is polymerized to completion with stirring by increasing the temperature in accordance with a temperature programme beginning at 25° C. and ending at 95° C.

[0086] The mixture is cooled down, and the suspension is applied to a sieve, washed with demineralized water and dried in a laboratory vacuum cabinet at 80° C. for 48 hours.

[0087] Weight yield based on the total amount of monomers used: 957.2 grams

[0088] 1.2 Preparation of N-acetoxymethylphthalimide

[0089] 945.8 grams of acetic anhydride are initially charged at room temperature. 1025.8 grams of N-methylolphthalimide are metered into the initial charge, then 14.2 grams of monosulphuric acid are metered in. The suspension is heated to 80° C. A solution arises, which is stirred at 80° C. for 30 minutes.

[0090] 1.3 Preparation of a Phthalimidomethylated Heterodisperse Macroporous Bead Polymer

[0091] At 80° C. , 450 grams of the heterodisperse bead polymer from Example 1.1 are metered into the mixture from 1.2 within 2 minutes. The suspension is heated to 120° C. and stirred at this temperature for a further 2 hours. Then the mixture is cooled down to 60° C., 115.9 g of monosulphuric acid are metered in within 2 hours. Then 300.5 g of iron(III) chloride are metered in within 5 minutes. The mixture is stirred at 60° C. for a further hour. The mixture is heated to 115° C. and stirred at this temperature for a further as hours.

[0092] The mixture is cooled down to 80° C. 1500 ml of demineralized water are metered in. The mixture is stirred at 95° C. for 2 h. Then the mixture is cooled down and applied to a sieve, The phthalimidomethylated bead polymer is washed with water.

[0093] Volume yield: 2320 ml

[0094] Dry weight: 0.4911 gram per ml

[0095] Nitrogen content 5.6% by weight based on the total amount of the phthalimidomethylated bead polymer

[0096] 1.4 Preparation of an Aminomethylated Heterodisperse Macroporous Bead Polymer

[0097] 1380 grams of demineralized water and 1190 grams of 50% by weight aqueous sodium hydroxide solution are initially charged at room temperature.

[0098] 2296 ml of phthalimidomethylated head polymer from 1.3 are metered into the initial charge. The suspension is heated in an autoclave to 180° C. for 2 hours with stirring and stirred at this temperature for a further 8 hours. After cooling, the suspension is applied to a sieve. The resultant aminomethylated bead polymer is washed with demineralized water.

[0099] Volume yield: 1640 ml

[0100] Dry weight: 0.3378 gram per ml

[0101] HCl number: 2.85 mol/liter of resin

Example 2

[0102] 2.1 Preparation of the Monodisperse Macroporous Bead Polymer Based on Styrene, Divinylbenzene And Ethylstyrene

[0103] A 10 l glass reactor is initially charged with 3000 g of deionized water, and a solution of 10 g of gelatin, 16 g of disodium hydrogenphosphate dodecahydrate and 0.73 g of resorcinol in 320 g of deionized water is added and mixed in. The mixture is brought to 25° C. Subsequently, while stirring, a mixture of 3200 g of microencapsulated monomer droplets having a narrow particle size distribution, composed of 3.6% by weight of divinylbenzene and 0.9% by weight of ethylstyrene (used in the form of a commercial isomer mixture of divinyibenzene and ethylstyrene with 80% divinylbenzene), 0.5% by weight of dibenzoyl peroxide, 56.2% by weight of styrene and 38.8% by weight of isododecane (technical isomer mixture having a high proportion of pentamethylheptane) is given, the microcapsule consisting of a formaldehyde-hardened complex coacervate composed of gelatin and a copolymer of acrylamide and acrylic acid, and 3200 g of aqueous phase having a pH of 12 are added.

[0104] The mixture is stirred and polymerized to completion by increasing the temperature in accordance with a temperature program beginning at 250 and ending at 95° C. The mixture is cooled, washed over a 32 μm sieve and then dried at 80° C. under reduced pressure, This gives 1893 g of a polymer in bead form.

[0105] 2.2 Preparation of a Phthalimidomethylated Heterodisperse Macroporous Bead Polymer

[0106] 598 g of acetic acid, 441 g of acetoxymethylolphthalimide and 157 g of bead polymer from Example 2.1 are initially charged, heated to 60° C. and stirred at this temperature for 1 h. Subsequently, 143.1 g of FeCl.sub.3 are added and the mixture is stirred at 0.5 h. Thereafter, the temperature is increased to 110° C. and the mixture is stirred at this temperature for 10 h. The mixture is cooled down to 60° C., 360 g of acetic acid are added and the mixture is applied to a sieve, Washing is effected once more with 360 g of acetic acid at 60° C., and the mixture is applied to a sieve and washed with demineralized water.

[0107] Volume yield: 1010 ml

[0108] Nitrogen content: 5.9%

[0109] 2.2 Preparation of an Aminomethylated Heterodisperse Macroporous Bead Polymer

[0110] 988 ml of phthalimidomethylated bead polymer are hydrolysed analogously to Example 1.4.

[0111] Volume yield: 720 ml

[0112] HCl number: 227 mol/l

[0113] Aminomethylated resin—amount of base/grams of bead polymer: 10.4

[0114] Summary of Results

TABLE-US-00001 In the presence of a swelling agent (1,2-dichloroethane) No as per U.S. Pat. No. swelling Parameter 3,989,650 Example 5 agent Yield of aminomelthylafed resin 3.6 3.68 in ml per gram of bead polymer Aminomethyleted resin—HCl 2.4 2.65 number in mol/l Aminomethylated resin— 8.64 9.76 amount of base/grams of bead polymer Conversion level of the 64.8 75.8 phthalimide used to aminomethylated groups in %

[0115] The process claimed therefore allows, without use of swelling agents, higher yields of aminomethylated bead polymer to be obtained than is known from U.S. Pat. No. 3,989,650.