RAFT polymers

Patent metadata

Field	Value
Publication number	US-9650450-B2
Application number	US-201214365551-A
Country	US
Kind code	B2
Filing date	Dec 14, 2012
Priority date	Dec 14, 2011
Publication date	May 16, 2017
Grant date	May 16, 2017

Abstract

The invention provides for a process for removing thiocarbonylthio groups from polymer prepared by RAFT polymerization, the process comprising:
introducing into a flow reactor a solution comprising the RAFT polymer in solvent; and promoting a reaction within the flow reactor that removes the thiocarbonylthio groups so as to form a solution that flows out of the reactor comprising the RAFT polymer absent the thiocarbonylthio groups.

First claim

The invention claimed is:

1. A process for removing thiocarbonylthio groups from a polymer prepared by RAFT polymerisation, the process comprising:
introducing into bundled flow lines or a coiled flow line of a tubular flow reactor a solution comprising a RAFT polymer in solvent;
and promoting a reaction within the flow reactor that removes the thiocarbonylthio groups so as to form a solution that flows out of the reactor comprising the RAFT polymer absent the thiocarbonylthio groups, wherein the reaction within the flow reactor that removes the thiocarbonylthio groups is promoted by:
(i) increasing the temperature of the solution comprising the RAFT polymer to remove the thiocarbonylthio groups by thermolysis;
(ii) irradiating the solution comprising the RAFT polymer; or
(iii) introducing a reagent into the solution comprising the RAFT polymer, wherein,
(a) the reagent is provided in the form of a solution and is introduced into the solution comprising the RAFT polymer; or
(b) the reagent is provided on a solid support and the solution comprising the RAFT polymer is passed over the solid support.

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

3. The process according to claim 1 , wherein the flow reactor comprises one or more flow lines through which the solution comprising the RAFT polymer passes, the one or more flow lines having an internal diameter of about 1 mm.

4. The process according to claim 1 , wherein up to 90% of thiocarbonylthio groups are removed from the RAFT polymer.

5. The process according to claim 1 , wherein the polymer prepared by RAFT polymerisation is formed by introducing into a flow reactor reaction solution comprising one or more ethylenically unsaturated monomers, RAFT agent, solvent and free radical initiator; and promoting RAFT polymerisation of the one or more ethylenically unsaturated monomers so as to form within the flow reactor a solution comprising the RAFT polymer in solvent.

6. The process according to claim 5 , 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.

7. The process according to claim 6 , 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.

8. The process according to claim 6 , 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, dialkyloxydiheterocyclyloxy- or diaryloxy-phosphinyl, dialkyl-, diheterocyclyl- or diaryl-phosphinyl, cyano (i.e. —CN), and —S—R, where R is as defined in claim 6 .

9. The process according to claim 1 , wherein the solution introduced into the tubular flow reactor is degassed to remove oxygen.

Assignees

• Commw Scient Ind Res Org

Inventors

• Chiefari John
• Hornung Christian
• Postma Almar
• Saubern Simon

Classifications

• C08F8/00 Primary

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title

• B01J19/243

  spirally, concentrically or zigzag wound · CPC title

• C08F6/10

  Removal of volatile materials, e.g. solvents {(C08F6/001, C08F6/003, C08F6/005, C08F6/006, C08F6/008, C08F6/02, C08F6/04 take precedence)} · CPC title

• B01J19/242

  in series · CPC title

• B01J19/2425

  in parallel · CPC title