Continuous flow polymerisation process

Patent metadata

Field	Value
Publication number	US-8946360-B2
Application number	US-201113825530-A
Country	US
Kind code	B2
Filing date	Aug 12, 2011
Priority date	Sep 22, 2010
Publication date	Feb 3, 2015
Grant date	Feb 3, 2015

Abstract

The present invention relates to a process for continuously preparing polymer by RAFT solution polymerization, the process comprising: introducing into a flow reactor a reaction solution comprising one or more ethylenically unsaturated monomers, RAFT agent, non-reactive solvent and free radical initiator; and promoting RAFT polymerization of the one or more ethylenically unsaturated monomers within the reactor so as to form a polymer solution that flows out of the reactor.

First claim

The invention claimed is:

1. A process for continuously preparing polymer by RAFT solution polymerisation, the process comprising:
introducing a reaction solution comprising one or more ethylenically unsaturated monomers, RAFT agent, non-reactive solvent and free radical initiator into bundled flow lines or a coiled flow line of a tubular flow reactor; and
promoting RAFT polymerisation of the one or more ethylenically unsaturated monomers within the tubular flow reactor so as to form a polymer solution that flows out of the tubular flow reactor.

2. The process according to claim 1 , wherein the tubular flow reactor is in the form of a capillary tubular flow reactor.

3. The process according to claim 1 , wherein the bundled or coiled flow lines have an internal diameter of no more than 2.2 mm.

4. The process according to claim 1 , wherein the bundled or coiled flow lines have an internal diameter of no more than 1 mm.

5. The process according to claim 1 , wherein the bundled or coiled flow lines are made of metal.

6. The process according to claim 1 which further comprises introducing the resulting polymer solution into a flow reactor or a region of a flow reactor, together with a reaction solution comprising one or more ethylenically unsaturated monomers and free radical initiator; and
promoting RAFT polymerisation of the one or more ethylenically unsaturated monomers within the reactor so as to form a block copolymer solution that flows out of the reactor.

7. The process according to claim 6 , wherein the flow reactor or the region of a flow reactor into which the resulting polymer solution is introduced is coupled to the tubular flow reactor into which the reaction solution is introduced.

8. The process according to claim 1 , wherein the RAFT polymerisation is promoted by applying heat to the tubular flow reactor.

9. The process according to claim 1 , wherein RAFT agent is represented by general formula (II) or (III):

where Z and R are groups, and R* and Z* are x-valent and y-valent groups, respectively, that are independently selected such that the agent can function as a RAFT agent in the polymerisation of the one or more ethylenically unsaturated monomers; x is an integer ≧1; and y is an integer ≧2.

10. The process according to claim 9 , wherein R is selected from optionally substituted, and in the case of R* a x-valent form of optionally substituted: alkyl, alkenyl, alkynyl, aryl, acyl, carbocyclyl, heterocyclyl, heteroaryl, alkylthio, alkenylthio, alkynylthio, arylthio, acylthio, carbocyclylthio, heterocyclylthio, heteroarylthio, alkylalkenyl, alkylalkynyl, alkylaryl, alkylacyl, alkylcarbocyclyl, alkylheterocyclyl, alkylheteroaryl, alkyloxyalkyl, alkenyloxyalkyl, alkynyloxyalkyl, aryloxyalkyl, alkylacyloxy, alkylcarbocyclyloxy, alkylheterocyclyloxy, alkylheteroaryloxy, alkylthioalkyl, alkenylthioalkyl, alkynylthioalkyl, arylthioalkyl, alkylacylthio, alkylcarbocyclylthio, alkylheterocyclylthio, alkylheteroarylthio, alkylalkenylalkyl, alkylalkynylalkyl, alkylarylalkyl, alkylacylalkyl, arylalkylaryl, arylalkenylaryl, arylalkynylaryl, arylacylaryl, arylacyl, arylcarbocyclyl, arylheterocyclyl, arylheteroaryl, alkenyloxyaryl, alkynyloxyaryl, aryloxyaryl, alkylthioaryl, alkenylthioaryl, alkynylthioaryl, arylthioaryl, arylacylthio, arylcarbocyclylthio, arylheterocyclylthio, arylheteroarylthio, and a polymer chain.

11. The process according to claim 9 , wherein Z is selected from optionally substituted, and in the case of Z* a y-valent form of optionally substituted: F, Cl, Br, I, alkyl, aryl, acyl, amino, carbocyclyl, heterocyclyl, heteroaryl, alkyloxy, aryloxy, acyloxy, acylamino, carbocyclyloxy, heterocyclyloxy, heteroaryloxy, alkylthio, arylthio, acylthio, carbocyclylthio, heterocyclylthio, heteroarylthio, alkylaryl, alkylacyl, alkylcarbocyclyl, alkylheterocyclyl, alkylheteroaryl, alkyloxyalkyl, aryloxyalkyl, alkylacyloxy, alkylcarbocyclyloxy, alkylheterocyclyloxy, alkylheteroaryloxy, alkylthioalkyl, arylthioalkyl, alkylacylthio, alkylcarbocyclylthio, alkylheterocyclylthio, alkylheteroarylthio, alkylarylalkyl, alkylacylalkyl, arylalkylaryl, arylacylaryl, arylacyl, arylcarbocyclyl, arylheterocyclyl, arylheteroaryl, aryloxyaryl, arylacyloxy, arylcarbocyclyloxy, arylheterocyclyloxy, arylheteroaryloxy, alkylthioaryl, arylthioaryl, arylacylthio, arylcarbocyclylthio, arylheterocyclylthio, arylheteroarylthio, dialkyloxy- , diheterocyclyloxy- or diaryloxy- phosphinyl, dialkyl-, diheterocyclyl- or diaryl- phosphinyl, cyano (i.e. —CN), and —S—R, where R is as defined in claim 9 .

12. The process according to claim 1 , wherein the reaction solution is degassed to remove oxygen prior to polymerisation being promoted.

13. The process according to claim 9 , wherein Z is selected from optionally substituted, and in the case of Z* a y-valent form of optionally substituted: F, Cl, Br, I, alkyl, aryl, acyl, amino, carbocyclyl, heterocyclyl, heteroaryl, alkyloxy, aryloxy, acyloxy, acylamino, carbocyclyloxy, heterocyclyloxy, heteroaryloxy, alkylthio, arylthio, acylthio, carbocyclylthio, heterocyclylthio, heteroarylthio, alkylaryl, alkylacyl, alkylcarbocyclyl, alkylheterocyclyl, alkylheteroaryl, alkyloxyalkyl, aryloxyalkyl, alkylacyloxy, alkylcarbocyclyloxy, alkylheterocyclyloxy, alkylheteroaryloxy, alkylthioalkyl, arylthioalkyl, alkylacylthio, alkylcarbocyclylthio, alkylheterocyclylthio, alkylheteroarylthio, alkylarylalkyl, alkylacylalkyl, arylalkylaryl, arylacylaryl, arylacyl, arylcarbocyclyl, arylheterocyclyl, arylheteroaryl, aryloxyaryl, arylacyloxy, arylcarbocyclyloxy, arylheterocyclyloxy, arylheteroaryloxy, alkylthioaryl, arylthioaryl, arylacylthio, arylcarbocyclylthio, arylheterocyclylthio, arylheteroarylthio, dialkyloxy- , diheterocyclyloxy- or diaryloxy- phosphinyl, dialkyl-, diheterocyclyl- or diaryl- phosphinyl, cyano (i.e. —CN), and —S—R, where R is as defined in claim 10 .

Assignees

• Chiefari John
• Hornung Christian
• Saubern Simon
• Commw Scient Ind Res Org

Inventors

• Chiefari John
• Hornung Christian
• Saubern Simon

Classifications

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08F120/56

  Acrylamide; Methacrylamide · CPC title

• C08F4/00

  Polymerisation catalysts · CPC title

• C08F120/54

  Amides {, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide} · CPC title

• B01J19/243

  spirally, concentrically or zigzag wound · CPC title