Method for producing amino methylated bead polymerizates

Patent metadata

Field	Value
Publication number	US-10975235-B2
Application number	US-201716309672-A
Country	US
Kind code	B2
Filing date	Jun 9, 2017
Priority date	Jun 22, 2016
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

The invention relates to a process for preparing aminomethylated bead polymers using condensed formaldehydes and carbonyl halides.

First claim

What is claimed is:

1. A process for preparing aminomethylated bead polymers, the process comprising:
a) converting monomer droplets comprising at least one monovinylaromatic compound, at least one polyvinylaromatic compound, and at least one initiator to a bead polymer,
b) contacting the bead polymer with:
at least one compound of the formula (I) or salts thereof

where R 1 =C 1 -C 3 -alkyl or H, and

at least one compound of the formula (II) or the cyclic condensates thereof

where n=2 to 100,

in a reaction mixture comprising at least one Friedel-Crafts catalyst, at least one aliphatic saturated or unsaturated carbonyl halide, and additional aliphatic saturated or unsaturated carboxylic acids,

to give a phthalimidomethylated bead polymer, and
c) hydrolyzing the phthalimidomethylated bead polymer to give an aminomethylated bead polymer.

2. The process according to claim 1 , wherein the at least one monovinylaromatic compound is selected from the group consisting of styrene, α-methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, bromostyrene, chloromethylstyrene, vinylnaphthalene, and mixtures of these compounds.

3. The process according to claim 1 , wherein the at least one polyvinylaromatic compound is selected from the group consisting of divinylbenzene, divinyltoluene, trivinylbenzene, and mixtures of these compounds.

4. The process according to claim 1 , wherein the at least one monovinylaromatic compound is styrene, and the at least one polyvinylaromatic compound is divinylbenzene.

5. The process according to claim 1 , wherein R 1 =H.

6. The process according to claim 1 , wherein n=8 to 30.

7. The process according to claim 1 , wherein the at least one carbonyl halide comprises at least one of: aliphatic and saturated monocarbonyl chlorides that are liquid at temperatures between 10° C. and 60° C.; and aliphatic and saturated monocarbonyl bromides that are liquid at temperatures between 10° C. and 60° C.

8. The process according to claim 1 , wherein the bead polymer is contacted with the at least one compound of the formula (I) or salts thereof and the at least one compound of the formula (II) or the cyclic condensates thereof in the presence of a mixture of acetyl chloride and acetic acid.

9. The process according to claim 8 , the acetyl chloride and acetic acid are present in the mixture at a ratio of acetyl chloride to acetic acid of 1:1 to 1:10.

10. The process according to claim 1 , wherein the Friedel-Crafts catalyst is used in an amount of 1 to 5 mol per mole of the compound of the formula (I).

11. The process according to claim 1 , wherein the at least one carbonyl halide is used in an amount of 0.001 to 0.05 mol per gram of the bead polymer.

12. The process according to claim 1 , wherein the at least one carbonyl halide is used in an amount of 1 to 4 mol per mole of compounds of the formula (I).

13. The process according to claim 1 , wherein the compounds of the formula (I) are used in an amount of 0.01 to 0.05 mol per gram of the compounds of the formula (II).

14. The process according to claim 1 , the conversion in step a) is carried out in the presence of at least one porogen.

15. The process according to claim 1 , wherein the amounts of the compounds of the formula (I), the compounds of the formula (II), the bead polymer, the aliphatic saturated or unsaturated carbonyl halides, the Friedel-Crafts catalysts, and any carboxylic acids used, together are greater than 96% by weight in the reaction mixture, based on the total amount of the reaction mixture.

16. The process according to claim 1 , wherein:
the at least one monovinylaromatic compound is selected from the group consisting of styrene, α-methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, bromostyrene, chloromethylstyrene, vinylnaphthalene, and mixtures of these compounds;
the at least one polyvinylaromatic compound is selected from the group consisting of divinylbenzene, divinyltoluene, trivinylbenzene, and mixtures of these compounds;
R 1 =H;
n=8 to 30;
the at least one carbonyl halide comprises at least one of: aliphatic and saturated monocarbonyl chlorides that are liquid at temperatures between 10° C. and 60° C.; and
aliphatic and saturated monocarbonyl bromides that are liquid at temperatures between 10° C. and 60° C.; and
the bead polymer is contacted with the at least one compound of the formula (I) or salts thereof and the at least one compound of the formula (II) or the cyclic condensates thereof in the presence of a mixture of both an aliphatic carbonyl halide, and an aliphatic carboxylic acid.

17. The process according to claim 16 , wherein:
the at least one monovinylaromatic compound is styrene, and the at least one polyvinylaromatic compound is divinylbenzene;
the conversion in step a) is carried out in the presence of at least one porogen;
the aliphatic carbonyl halide is acetyl chloride and the aliphatic carboxylic acid is acetic acid, and the acetyl chloride and acetic acid are present at a ratio of acetyl chloride to acetic acid of 1:1 to 1:10;
the Friedel-Crafts catalyst is used in an amount of 1 to 5 mol per mole of the compound of the formula (I);
the at least one carbonyl halide is used in an amount of 0.001 to 0.05 mol per gram of the bead polymer;
the at least one carbonyl halide is used in an amount of 1 to 4 mol per mole of compounds of the formula (I); and
the compounds of the formula (I) are used in an amount of 0.01 to 0.05 mol per gram of the compounds of the formula (II).

18. The process according to claim 17 , wherein the amounts of the compounds of the formula (I), the compounds of the formula (II), the bead polymer, the Friedel-Crafts catalyst, the acetyl chloride, and the acetic acid, together are greater than 96% by weight in the reaction mixture, based on the total amount of the reaction mixture.

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Koop Bernd
• Rezkallah Areski
• Martin Georg
• Vanhoorne Pierre
• Klipper Reinhold
• Baljak Sladjana

Classifications

• B01J41/14 Primary

  obtained by reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• C08F2800/20

  as weight or mass percentages · CPC title

• B01J41/07

  in the weakly basic form · CPC title

• C08F8/12

  Hydrolysis · CPC title

• C08F212/14

  substituted by heteroatoms or groups containing heteroatoms · CPC title