Method for producing amido-methylated vinyl-aromatic bead polymers

Patent metadata

Field	Value
Publication number	US-11485809-B2
Application number	US-201716311296-A
Country	US
Kind code	B2
Filing date	Jun 9, 2017
Priority date	Jun 29, 2016
Publication date	Nov 1, 2022
Grant date	Nov 1, 2022

Abstract

The invention relates to a method of producing amidomethylated vinylaromatic bead polymers.

First claim

What is claimed is:

1. A method of producing amidomethylated vinylaromatic bead polymers, the method comprising contacting
at least one condensed formaldehyde,
at least one vinylaromatic bead polymer, and
at least one compound of formula (I) or salts thereof

where
R 1 ═—CH—(C 1 -C 6 -alkyl) or —CH 2 —, and R 2 ═—CH—(C 1 -C 6 -alkyl) or —CH 2 —, or
R 1 and R 2 are two carbon atoms of an aromatic C 6 -ring optionally substituted by one or two C 1 -C 6 -alkyl radials, or
R 1 and R 2 each represent —CH═,
in the presence of
at least one protic acid, wherein said protic acid is sulfuric acid having a concentration of at least 93 wt. %, and
at least one compound of the formula (II)

where
R 3 ═C 1 -C 4 -alkyl, F, Cl, or wholly or partly chlorinated or wholly or partly fluorinated C 1 -C 4 -alkyl,
X═Cl or F, and
m=0, 1 or 2.

2. The method as claimed in claim 1 , wherein the compounds of the formula (II) are selected from chlorobenzotrifluoride, dichlorobenzotrifluoride, benzotrifluoride, or mixtures thereof.

3. The method as claimed in claim 1 , wherein the condensed formaldehyde is paraformaldehyde or trioxane or mixtures thereof.

4. The method as claimed in claim 1 , wherein the vinylaromatic bead polymer is a styrene/divinylbenzene copolymer.

5. The method as claimed in claim 1 , wherein the compound of the formula (I) is phthalimide or salts thereof.

6. The method as claimed in claim 1 , wherein the vinylaromatic bead polymer comprises a monodisperse, vinylaromatic bead polymer.

7. The method as claimed in claim 1 , wherein the vinylaromatic bead polymer comprises a macroporous, monodisperse, vinylaromatic bead polymer.

8. The method as claimed in claim 1 , wherein a ratio of amounts of the compounds of formula (II) to the compounds of formula (I) is 3.5:1 to 9:1.

9. The method as claimed in claim 1 , wherein a ratio of amounts of the aromatic groups in the vinylaromatic bead polymer to the compounds of formula (I) is 0.5:1 to 1.8:1.

10. The method as claimed in claim 1 , wherein a ratio of amounts of the compounds of formula (I) to the condensed formaldehyde is 0.95:1 to 1.1:1.

11. The method as claimed in claim 1 , wherein a ratio of amounts of the compounds of formula (I) to the protic acid is 10:1 to 1:10.

12. The method as claimed in claim 1 , wherein the contacting is done at a temperature of 20° C. to 40° C.

13. The method as claimed in claim 1 , wherein:
a ratio of amounts of the compounds of formula (II) to the compounds of formula (I) is 2:1 to 10:1;
a ratio of amounts of the aromatic groups in the vinylaromatic bead polymer to the compounds of formula (I) is 0.2:1 to 2.5:1;
a ratio of amounts of the compounds of formula (I) to the condensed formaldehyde is 0.7:1 to 1.3:1; and
a ratio of amounts of the compounds of formula (I) to the protic acid is 10:1 to 1:10.

14. The method as claimed in claim 13 , wherein:
a ratio of amounts of compounds of formula (II) to the compounds of formula (I) is 3.5:1 to 9:1;
a ratio of amounts of aromatic groups in the vinylaromatic bead polymer to the compounds of formula (I) is 0.5:1 to 1.8:1;
a ratio of amounts of compounds of formula (I) to condensed formaldehyde is 0.95:1 to 1.1:1; and
a ratio of amounts of the compounds of formula (I) to the protic acid is 1:1 to 1:10.

15. The method as claimed in claim 1 , wherein:
the compound of the formula (II) is selected from the group consisting of benzotrifluoride, pentafluoroethanebenzene, pentachloroethanebenzene, 4-chlorobenzotrifluoride, 3-chlorobenzotrifluoride, 2-chlorobenzotrifluoride, dichlorobenzotrifluoride, difluoroethanebenzene, 3,4-dichlorobenzotrifluoride, heptafluoropropanebenzene, 1,1-difluoropentachloropropanebenzene, and mixtures of these compounds;
the protic acid is selected from the group consisting of hydrochloric acid, sulfuric acid, oleum, nitric acid, nitrous acid, sulfurous acid, aliphatic or aromatic methane, benzene or toluenesulfonic acids, phosphoric acid, oxalic acid, acetic acid and formic acid;
the condensed formaldehyde is selected from compounds of formula (III)

where n is =8 to 100, or trioxane, or mixtures thereof;
the vinylaromatic bead polymer is a copolymer derived from monomeric units of:
monoethylenically unsaturated compounds selected from the group consisting of styrene, vinyltoluene, ethylstyrene, a-methylstyrene, chlorostyrene, chloromethylstyrene, and mixtures thereof; and
multifunctional ethylenically unsaturated compounds selected from the group consisting of divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, trivinylnaphthalene, and mixtures thereof; and
the compound of the formula (I) is phthalimide, succinimide, maleimide, salts of phthalimide, succinimide, and maleimide, and mixtures thereof.

16. The method as claimed in claim 15 , wherein:
the compounds of the formula (II) are selected from chlorobenzotrifluoride, dichlorobenzotrifluoride, benzotrifluoride, or mixtures thereof;
the protic acid is sulfuric acid;
the condensed formaldehyde is paraformaldehyde or trioxane or mixtures thereof;
the vinylaromatic bead polymer is a styrene/divinylbenzene copolymer; and
the compound of the formula (I) is phthalimide or salts thereof.

17. The method as claimed in claim 16 , wherein:
a ratio of amounts of the compounds of formula (II) to the compounds of formula (I) is 2:1 to 10:1;
a ratio of amounts of the aromatic groups in the vinylaromatic bead polymer to the compounds of formula (I) is 0.2:1 to 2.5:1;
a ratio of amounts of the compounds of formula (I) to the condensed formaldehyde is 0.7:1 to 1.3:1; and
a ratio of amounts of the compounds of formula (I) to the protic acid is 10:1 to 1:10.

18. The method as claimed in claim 17 , wherein:
a ratio of amounts of compounds of formula (II) to the compounds of formula (I) is 3.5:1 to 9:1;
a ratio of amounts of aromatic groups in the vinylaromatic bead polymer to the compounds of formula (I) is 0.5:1 to 1.8:1;
a ratio of amounts of compounds of formula (I) to condensed formaldehyde is 0.95:1 to 1.1:1; and
a ratio of amounts of the compounds of formula (I) to the erotic acid is 1:1 to 1:10.

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Koop Bernd

Classifications

• C08F8/12

  Hydrolysis · CPC title

• C08F8/30 Primary

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08F212/36

  Divinylbenzene · CPC title

• C08K5/41

  Compounds containing sulfur bound to oxygen · CPC title

• C08F212/08 Primary

  Styrene · CPC title