# US 2018/0022837 A1 · Reverse-phase polymerisation process incorporating a microfluidic device > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2018/0022837 A1 - Document ID: US20180022837A1 - Status: Published application - Kind: A1 - Application number: 15/547,343 - Filed: 2016-01-28 - Published: 2018-01-25 - Earliest claimed: 2015-01-30 - Assignees: BASF SE - Applicants: BASF SE - Inventors: Robert HASCHICK; Aleksandra JELICIC; Gabriela Eugenia FONSECA ZEPEDA; Anna RECKMANN; Christian HOLTZE; Bernd STRUBEL - Web page: https://patentgrep.com/patent/US20180022837A1 ## CPC - C08F 2/32: Polymerisation in water-in-oil emulsions - B01J 19/0093: {Microreactors, e.g. miniaturised or microfabricated reactors (laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027)} - C08F 20/34: Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate} - C08F 120/34: Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate} - B01J 2219/00833: Plastic - B01J 2219/00894: More than two inlets - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract Disclosed herein is a polymerization process involving the steps of generating monomer micro-volumes in a microfluidic device, feeding the monomer micro-volumes through the at least one first microfluidic channel towards a monomer feed point at which the monomer micro-volumes enter into or onto a volume of a non-aqueous liquid and form aqueous monomer droplets, allowing the aqueous monomer droplets to flow towards a polymer bead discharge point, initiating polymerisation of the aqueous monomer droplets to form polymerising beads, removing a suspension of the polymer beads in the 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 present disclosure also includes an apparatus for performing the polymerization process and water soluble or water swellable polymer beads obtained by the polymerization process. ## Claims ### Claim 1 A reverse-phase suspension polymerisation process for the manufacture of polymer beads comprising forming aqueous monomer droplets of an aqueous solution comprising 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, the process comprising: 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, generating monomer micro-volumes in at least one microfluidic device, said monomer micro-volumes being separated by non-aqueous liquid in at least one first microfluidic channel, feeding the monomer micro-volumes through the at least one first microfluidic channel towards the at least one monomer feed point at which the monomer micro-volumes enter into or onto the volume of non-aqueous liquid and form aqueous monomer droplets, allowing the aqueous monomer droplets to flow towards the polymer bead discharge point, initiating polymerisation of the aqueous monomer droplets to form polymerising beads, wherein the polymerising 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, wherein: the at least one microfluidic device (5) comprises at least one second microfluidic channel conveying non-aqueous liquid; at least one third microfluidic channel conveying the aqueous solution comprising water soluble ethylenically unsaturated monomer or monomer blend; and at least one intersection between the at least one third microfluidic channel and the at least one second microfluidic channel; the at least one first microfluidic channel is in communication with the at least one intersection, and the monomer micro volumes are formed at the at least one intersection before being fed through the at least one first microfluidic channel towards the monomer feed point. ### Claim 2 (depends on 1) The process according to claim 1, wherein the polymer beads removed from the vessel at the polymer bead discharge point are subjected to a post polymerisation stage. ### Claim 3 (depends on 1) The process according to claim 1, wherein the monomer micro-volumes are obtained in the microfluidic device employing at least one of the techniques selected from the group consisting of hydrodynamic flow focusing, coaxial shear flow, crossflow shear in cross junction, co-flow junction and T-junction microchannel geometries. ### Claim 4 (depends on 1) The process according to claim 1, wherein the at least one second and at least one third microfluidic channels each intersect the first microfluidic channel are substantially non-right angles. ### Claim 5 (depends on 1) The process according to claim 1, wherein the at least one second and at least one third microfluidic channels each intersect the first microfluidic channel are substantially at right angles. ### Claim 6 (depends on 1) The process according to claim 1, wherein the diameter of the at least one first microfluidic channel is between 30 μm and 3500 μm. ### Claim 7 (depends on 1) The process according to claim 1, wherein the diameter of the at least one second microfluidic channel and the diameter of the at least one third microfluidic channel are each independently selected from diameters in the range of from 10 μm to 5000 μm. ### Claim 8 (depends on 1) The process according to claim 1, wherein the monomer micro-volumes are formed by delivering a flow of the aqueous solution comprising water-soluble ethylenically unsaturated monomer or monomer blend from the at least one third microfluidic channel into the at least one intersection. ### Claim 9 (depends on 1) The process according to claim 1, wherein the process is conducted in two or more vessels in parallel. ### Claim 10 (depends on 1) The process according to claim 1, wherein the aqueous monomer or monomer blend and/or the non-aqueous liquid contains a polymerisation initiator. ### Claim 11 (depends on 1) The process according to claim 1, wherein the suspension of the polymer beads in the non-aqueous liquid removed at the polymer bead discharge point has a concentration of at least 10% polymer beads on total weight of suspension. ### Claim 12 (depends on 1) The process according to claim 1, wherein the aqueous polymer beads are produced at a rate of at least 15 kg/hour, preferably at a rate of at least 20 kg/h. ### Claim 13 (depends on 1) The process according to claim 1, wherein an amphipathic stabiliser is included in the non-aqueous liquid. ### Claim 14 (depends on 1) 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), vinyl formamide and combinations of any of the above. ### Claim 15 (depends on 14) The process according to claim 14, wherein at least one monomer has been prepared by a chemically catalysed process, a biologically catalysed process or a biological process. ### Claim 16 (depends on 14) The process according to claim 14, wherein the acrylamide has been prepared by a biological catalysed process or a biological process. ### Claim 17 (depends on 1) The process according to claim 1, wherein the so formed polymer beads are ground to produce a polymer powder. ### Claim 18 (depends on 1) The process according to claim 1, wherein the process is performed in a continuous mode. ### Claim 19 An apparatus suitable for a reverse-phase suspension polymerisation process for the manufacture of polymer beads from an aqueous solution comprising water-soluble ethylenically unsaturated monomer or monomer blend, the apparatus comprising: a vessel comprising a monomer feed point and a polymer bead discharge point, which vessel is suitable for containing a volume of non-aqueous liquid between the monomer feed point and the polymer bead discharge point, at least one microfluidic device suitable for generating monomer micro-volumes, said monomer micro volumes being separated by non-aqueous liquid in at least one first microfluidic channel, a feeder for feeding the monomer micro-volumes through the at least one first microfluidic channel towards the at least one monomer feed point, a droplet feeder for enabling the monomer micro-volumes to enter into or onto the volume of nonaqueous liquid and forming aqueous monomer droplets, a droplet discharge line for allowing the aqueous monomer droplets to flow towards the polymer bead discharge point, an initiator for initiating polymerisation of the aqueous monomer droplets such that they form polymerising beads which have formed polymer beads when they reached the polymer bead discharge point, a suspension remover for removing a suspension of aqueous polymer beads in non-aqueous liquid at polymer bead discharge point, and a polymer bead recoverer for recovering water-soluble or water swellable polymer beads from the suspension, wherein: the at least one microfluidic device comprises at least one second microfluidic channel suitable for conveying non-aqueous liquid; at least one third microfluidic channel suitable for conveying the aqueous solution comprising water soluble ethylenically unsaturated monomer or monomer blend; and at least one intersection between the at least one third microfluidic channel and the at least one second microfluidic channel; the at least one first microfluidic channel is in communication with the at least one intersection, and a micro-volume former is provided for forming the monomer micro-volumes at the at least one intersection before being fed through the at least one first microfluidic channel towards the monomer feed point. ### Claim 20 (depends on 1) Water soluble or water swellable polymer beads obtainable by the process of claim 1.