Process for preparing aminomethylated bead polymers

Patent metadata

Field	Value
Publication number	US-2016108199-A1
Application number	US-201514918714-A
Country	US
Kind code	A1
Filing date	Oct 21, 2015
Priority date	Oct 21, 2014
Publication date	Apr 21, 2016
Grant date	—

Abstract

Aminomethylated bead polymers for use as ion exchangers, especially as anion exchangers, or for the preparation of chelate resins, are prepared in the presence of 1,3-dichloropropane as solvent and swelling agent

First claim

What is claimed is:

1 . A process for preparing aminomethylated bead polymers, the process comprising:
a) converting monomer droplets composed of a mixture comprising at least one monoethylenically unsaturated aromatic compound, at least one multiethylenically unsaturated compound, and at least one initiator to bead polymer; b) contacting the bead polymer with:
compounds of the formula (I) or salts thereof

where R 1 =C 1 -C 3 -alkyl or H, and
compounds of the formula (II)

where n=1 to 100,
in the presence of a swelling agent and solvent comprising 1,3-dichloropropane, and
in the presence of protic acids, to give a phthalimidomethylated bead polymer; and
c) hydrolysing the phthalimidomethylated bead polymer to produce aminomethylated bead polymer.

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

3 . The process according to claim 1 , wherein the multiethylenically unsaturated aromatic compounds comprise divinylbenzene, divinyltoluene, trivinylbenzene, octadiene, or triallyl cyanurate, or mixtures of these compounds.

4 . The process according to claim 1 , wherein the monoethylenically unsaturated aromatic compound is styrene and the multiethylenically unsaturated compound is divinylbenzene.

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

6 . The process according to claim 1 , wherein n in the compound of the formula (II)=8 to 100.

7 . The process according to claim 1 , wherein the swelling agent and solvent comprises greater than 90% by weight of the 1,3-dichloropropane.

8 . The process according to claim 1 , wherein step b) is conducted at a temperature of about 55° C. to about 75° C.

9 . The process according to claim 1 , wherein step b) further comprises:
swelling the bead polymer of step a) in the 1,3-dichloropropane; combining the swelled bead polymer, the compounds of the formula (I), and the compounds of the formula (II) to form a mixture; and adding the protic acid to the mixture.

10 . The process according to claim 1 , wherein an amount of the compounds of the formula (I) is about 3.5 to about 1.7 mol per mole of protic acid.

11 . The process according to claim 1 , wherein an amount of the 1,3-dichloropropane is about 3.5 to about 13 mol per mole of compounds of the formula (I).

12 . The process according to claim 1 , wherein an amount of the 1,3-dichloropropane is about 7.5 to about 13 mol per mole of bead polymer.

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

14 . The process according to claim 1 , wherein step a) further comprises converting the monomer droplets in the presence of a porogen to produce a macroporous aminomethylated bead polymer.

15 . The process according to claim 1 , wherein the swelling agent and solvent is 100% 1,3-dichloropropane.

16 . The process according to claim 1 , wherein:
the monoethylenically unsaturated aromatic compounds is selected from a group consisting of styrene, α-methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, bromostyrene, chloromethylstyrene, alkyl acrylates, alkyl methacrylates vinylnaphthalene, and mixtures of these compounds; the multiethylenically unsaturated aromatic compounds is selected from a group consisting of divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, trivinylnaphthalene, 1,7-octadiene, 1,5-hexadiene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate triallyl cyanurate, and mixtures of these compounds; the initiator is selected from a group consisting of dibenzoyl peroxide, dilauroyl peroxide, bis(p-chlorobenzoyl) peroxide, dicyclohexyl peroxydicarbonate, tert-butyl peroctoate, tert-butyl peroxy-2-ethylhexanoate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-amylperoxy-2-ethylhexane, 2,2′-azobis(isobutyronitrile), and 2,2′-azobis(2-methylisobutyronitrile) and mixtures of these compounds; the monomer droplets are microencapsulated with polyesters, natural polyamides, synthetic polyamides, polyurethanes, or polyureas; R 1 =H; n in the compound of the formula (II)=8 to 100; and the swelling agent and solvent comprises at least 95% by weight 1,3-dichloropropane and at least one further swelling agent and/or solvent.

17 . The process according to claim 16 , wherein the at least one further swelling agent and/or solvent additional comprises at least one swelling agent and/or solvent selected from the group consisting of: 1,2-dichloroethane, 1,2-dichloropropane, 1,4-dichlorobutane, 1,6-dichlorohexane, methylene chloride, carbon tetrachloride, trichloroethane, chlorobenzene, 1,2-dichlorobenzene, nitropropane, nitrobenzene, cyclohexane, and methylcyclohexane.

18 . The process according to claim 16 , wherein:
step b) is conducted at a temperature of about 55° C. to about 75° C.; an amount of the compounds of the formula (I) is about 3.5 to about 1.7 mol per mole of protic acid; an amount of the 1,3-dichloropropane is about 3.5 to about 13 mol per mole of compounds of the formula (I); an amount of the 1,3-dichloropropane is about 7.5 to about 13 mol per mole of bead polymer, and the method further comprises:
in process step a) converting the monomer droplets in the presence of a porogen to produce a macroporous aminomethylated bead polymer,
in process step b):
swelling the bead polymer of step a) in the 1,3-dichloropropane;
combining the swelled bead polymer, the compounds of the formula (I), and the compounds of the formula (II) to form a mixture; and
adding the protic acid to the mixture; and

conducting process step c) in the presence of aqueous or alcoholic solutions of an alkali metal hydroxide at temperatures of about 100° C. to about 250° C.

19 . The process according to claim 18 , wherein the monoethylenically unsaturated aromatic compound is styrene and the multiethylenically unsaturated compound is divinylbenzene, and the selling agent and solvent is 100% 1,3-dichloropropane.

Assignees

• Lanxess Deutschland Gmbh

Inventors

• Klipper Reinhold
• Vanhoorne Pierre

Classifications

• C08F8/30

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08F2800/20

  as weight or mass percentages · CPC title

• C08F8/12

  Hydrolysis · CPC title

• B01J45/00

  Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties (ion-exchange chromatography processes B01D15/36) · CPC title

• C08F8/44

  Preparation of metal salts or ammonium salts · CPC title