Reverse-phase polymerisation process

Patent metadata

Field	Value
Publication number	US-9765167-B2
Application number	US-201414908925-A
Country	US
Kind code	B2
Filing date	Jul 29, 2014
Priority date	Jul 31, 2013
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

A reverse-phase suspension polymerization process for the manufacture of polymer beads comprising forming aqueous monomer beads comprising an aqueous solution of water-soluble ethylenically unsaturated monomer or monomer blend and polymerizing the monomer or monomer blend to form polymer beads while suspended in a non-aqueous liquid, and recovering polymer beads, in which the process comprises, providing in a vessel ( 1 ) a volume ( 2 ) of non-aqueous liquid wherein the volume of non-aqueous liquid extends between at least one polymer bead discharge point ( 3 ) and at least one monomer feed point ( 4 ), feeding the aqueous monomer or monomer blend through orifices ( 5 ) into, or onto, the non-aqueous liquid to form aqueous monomer beads, allowing the aqueous monomer beads to flow towards the polymer bead discharge point subjecting the aqueous monomer beads to polymerization conditions to initiate polymerization to form polymerizing beads, wherein the polymerizing beads have formed polymer beads when they reach the polymer bead discharge point, removing a suspension of the polymer beads in non-aqueous liquid from the vessel at the polymer bead discharge point and recovering water soluble or water swellable polymer beads from the suspension. The invention also relates to the apparatus suitable for carrying out a reverse-phase suspension polymerization and polymer beads obtainable by the process or employing the apparatus.

First claim

The invention claimed is:

1. A reverse-phase suspension polymerisation process for the manufacture of polymer beads comprising forming aqueous monomer beads comprising an aqueous solution of water-soluble ethylenically unsaturated monomer or monomer blend and polymerising the monomer or monomer blend to form polymer beads while suspended in a non-aqueous liquid, and recovering polymer beads, in which the process comprises:
providing in a vessel a volume of non-aqueous liquid wherein the volume of non-aqueous liquid extends between at least one polymer bead discharge point and at least one monomer feed point,
feeding the aqueous monomer or monomer blend through orifices into, or onto, the non-aqueous liquid to form aqueous monomer beads,
allowing the aqueous monomer beads to flow towards the polymer bead discharge point,
subjecting the aqueous monomer beads to actinic radiation from at least one actinic radiation source to initiate polymerisation to form polymerising beads, wherein the polymerising beads have formed polymer beads when they reach the polymer bead discharge point, wherein an intensity of the actinic radiation is in the range of 30 to 1,000 mW/cm 2 , wherein the non-aqueous liquid and the monomer beads are at a temperature of below 30° C. when polymerization is initiated,
removing a suspension of the polymer beads in non-aqueous liquid from the vessel at the polymer bead discharge point and recovering water soluble or water-swellable polymer beads from the suspension.

2. The process according to claim 1 in which the polymerisation conditions comprises subjecting the aqueous monomer beads to ultraviolet light from at least one ultraviolet light source or to at least one light source that comprises at least one light emitting diode (LED).

3. The process according to claim 1 , further comprising subjecting the polymer beads removed from the vessel at the polymer bead discharge point to a post polymerisation stage.

4. The process according to claim 1 in which the aqueous monomer or monomer blend is fed into the non-aqueous liquid.

5. The process according to claim 1 in which the vessel comprises a wall or walls which comprise at least one ultraviolet light translucent section or ultraviolet light transparent section.

6. The process according to claim 5 in which the transparent section comprises borosilicate glass or quartz glass.

7. The process according to claim 5 in which at least one light source is mounted externally to the vessel such that the ultraviolet light enters the vessel through the transparent section of the vessel.

8. The process according to claim 1 in which at least one light source is mounted inside the vessel.

9. The process according to claim 8 in which at least one light source is submerged within the non-aqueous liquid.

10. The process according to claim 1 in which the aqueous monomer or monomer blend comprises a photoinitiator selected from the group consisting of 2,2′-Azobis (N,N′-dimethyleneisobutyramidine) dihydrochloride, 2,2′-Azobis(2-amidinopropane) Dihydrochloride, 2,2′-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride, 2,2′-Azobis(1-imino-1-pyrrolidino-2-ethylpropane)dihydrochloride, 2,2′-Azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 4,4′-Azobis(4-cyanovaleric acid) and 2,2′-Azobis(2-methylpropionitrile).

11. The process according to claim 1 , in which an amphipathic polymeric stabiliser is included in the non-aqueous liquid.

12. The process according to claim 1 , wherein the water-soluble ethylenically unsaturated monomer or monomer blend comprises at least one monomer selected from the group consisting of acrylamide, methacrylamide, N-vinyl pyrrolidone, 2-hydroxy ethyl acrylate, acrylic acid (or salts thereof), methacrylic acid (or salts thereof), itaconic acid (or salts thereof), maleic acid (or salts thereof), 2-acrylamido-2-propane sulphonic acid (or salts thereof), vinyl sulphonic acid (or salts thereof), allyl sulphonic acid (or salts thereof), dimethyl amino ethyl acrylate (or acid salts or quaternary ammonium salts thereof), dimethyl amino ethyl methacrylate (or acid salts or quaternary ammonium salts thereof), dimethyl amino propyl acrylamide (or acid salts or quaternary ammonium salts thereof), dimethyl amino propyl methacrylamide (or acid salts or quaternary ammonium salts thereof) and combinations of any of the above.

13. The process according to claim 12 in which at least one monomer has been prepared by a chemically catalysed process, a biologically catalysed process, or a biological process.

14. The process according to claim 12 in which the acrylamide has been prepared by a biological catalysed process or a biological process.

15. The process according to claim 1 in which the so formed polymer beads are ground to produce a polymer powder.

16. The process according to claim 1 in which the process is performed in a continuous mode.

17. The process according to claim 1 , wherein the aqueous monomer or monomer blend is fed into, or onto, the non-aqueous liquid through a grid of regularly spaced orifices.

18. The process according to claim 1 , wherein the aqueous monomer or monomer blend is extruded as droplets through a grid of regularly spaced orifices into, or onto, the non-aqueous liquid.

19. The process according to claim 1 , wherein the outer cylinder has a cross-sectional diameter which is at least 0.05 m greater than that of the inner cylinder.

20. The process according to claim 1 , wherein the outer cylinder has a cross-sectional diameter which is at least 0.1 m greater than that of the inner cylinder.

21. The process according to claim 1 , wherein the vessel is an annular gap between concentric inner and outer cylinders or a rectangular space.

22. The process according to claim 1 , wherein the vessel is an annular gap between concentric inner and outer cylinders.

23. The process according to claim 1 , wherein the vessel is an annular gap between concentric inner and outer cylinders or a rectangular space.

Assignees

• Basf Se

Inventors

• Haschick Robert
• Jelicic Aleksandra
• Barratt John Scott
• Hesse Pascal
• Soetje Oliver
• Fonseca Zepeda Gabriela Eugenia
• Keelapandal Ramamoorthy Shankara Narayanan
• Langlotz Bjoern

Classifications

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C08F2/32

  Polymerisation in water-in-oil emulsions · CPC title

• C08F226/10

  N-Vinyl-pyrrolidone · CPC title

• B01J19/244

  Concentric tubes · CPC title

• B01J4/007

  provided with moving parts · CPC title