Method and catalyst system for preparing polymers and block copolymers

Patent metadata

Field	Value
Publication number	US-10030106-B2
Application number	US-201414891148-A
Country	US
Kind code	B2
Filing date	May 16, 2014
Priority date	May 17, 2013
Publication date	Jul 24, 2018
Grant date	Jul 24, 2018

Abstract

The present invention provides methods for producing block copolymers, either by the sequential addition of monomers, or using a “one-pot” method. The invention also relates to novel methods for producing polyesters by ring opening lactides and/or lactones and by copolymerizing anhydrides and epoxides.

First claim

The invention claimed is:

1. A method for producing a block copolymer, using a single catalytic system, wherein the single catalytic system comprises a catalyst of formula (IA):

wherein
R 1 and R 2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl ether group, a thioether group, a sulfoxide group, a sulfinate group, an acetylide group, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted haloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alicyclic, or optionally substituted heteroalicyclic;
R 3 is optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted arylene, optionally substituted heteroarylene, or optionally substituted cycloalkylene, wherein each alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, and heteroalkynylene may optionally be interrupted by aryl, heteroaryl, alicyclic, or heteroalicyclic;
R 4 is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylheteroaryl, or optionally substituted alkylaryl;
R 5 is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylheteroaryl, or optionally substituted alkylaryl;
E 1 is C, E 2 is O, S or NH; or E 1 is N and E 2 is O;
Z is absent or selected from -E-, -EX(E)-, or EX(E)E-;
X is C or S;
Each E is independently selected from O, S or NR Z , wherein R Z is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylaryl, or optionally substituted alkylheteroaryl;
R is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, silyl, or a polymer; and when Z is absent, R may additionally be selected from halide, phosphinate, azide, or nitro;
each G is independently absent or a neutral or anionic donor ligand which is a Lewis base; and
M is Zn(II), Cr(II), Co(II), Mn(II), Mg(II), Fe(II), Ti(II), Cr(III)-Z—R, Co(III)-Z—R, Mn (III)-Z—R, Fe(III)-Z—R, Ca(II), Ge(II), Al(III)-Z—R, Ti(III)-Z—R, V(III)-Z—R, Ge(IV)-(—Z—R) 2 , or Ti(IV)-(—Z—R) 2 ;
the method comprising the steps of:
a) forming a first block by polymerising a first monomer or combination of monomers selected from the groups (i) to (iii):
Group (i): a lactide and/or a lactone,
Group (ii): an epoxide and an anhydride, or
Group (iii): an epoxide and carbon dioxide,

b) optionally contacting the catalyst of formula (IA) with a compound [Y] which is capable of converting the group —Z—R, wherein Z is absent or a group selected from -E-X(E)- or -E-X(E)E-, to a group —Z—R wherein Z is -E-;
c) forming a second block by polymerising a second monomer or combination of monomers selected from a different group (i) to (iii) to that selected for the first monomer or combination of monomers:
Group (i): a lactide and/or a lactone,
Group (ii): an epoxide and an anhydride, or
Group (iii): an epoxide and carbon dioxide,

 wherein when the first monomer or combination of monomers is Group (i), Z is -E-; and
 wherein when the first monomer or combination of monomers is group (ii) or Group (iii)-, and the second monomer or combination of monomers is Group (i), step b) is performed after step a).

2. The method according to claim 1 , wherein the first monomer or combination of monomers is Group (i), and Z—R is -E-R, the second monomer or combination of monomers is Group (ii) or Group (iii), and the second monomer or combination of monomers is added to the reaction after step a) has been performed.

3. The method according to claim 1 , wherein the first monomer or combination of monomers is Group (ii) or Group (iii), the second monomer or combination of monomers is Group (i), and step b) is performed after step a) and before step c).

4. The method according to claim 3 , wherein the second monomer or combination of monomers is added to the reaction with the first monomer or combination of monomers, or after step a) has been performed.

5. The method according to claim 1 , wherein the compound [Y] is a compound having a three, four or five membered saturated ring and at least one heteroatom selected from O, S or N.

6. The method according to claim 1 , wherein each E is O.

7. The method according to claim 1 , wherein M is Zn or Mg.

8. The method according to claim 1 , wherein the catalyst is selected from:

[L 1 Mg 2 Cl 2 (methylimidazole)],
[L 1 Mg 2 Cl 2 (dimethylaminopyridine)],
[L 1 Mg 2 Br 2 (dimethylaminopyridine)],
[L 1 Zn 2 (F 3 CCOO) 2 ],
[L 1 Zn 2 (OOCC(CH 3 ) 3 ) 2 ],
[L 1 Zn 2 (OC 6 H 5 ) 2 ],
[L 1 Fe 2 Cl 4 ],
[L 1 Co 2 (OAc) 3 ],
[L 1 Zn 2 (adamantyl carbonate) 2 ],
[L 1 Zn 2 (pentafluorobenzoate) 2 ],
[L 1 Zn 2 (diphenylphosphinate) 2 ],
[L 1 Zn 2 (bis(4-methoxy)phenyl phosphinate) 2 ],
[L 1 Zn 2 (hexanoate) 2 ],
[L 1 Zn 2 (octanoate) 2 ],
[L 1 Zn 2 (dodecanoate) 2 ],
[L 1 Mg 2 (F 3 CCOO) 2 ],
[L 1 Mg 2 Br 2 ],
[L 1 Zn 2 (C 6 F 5 ) 2 ],
[L 1 Zn 2 (C 6 H 5 ) 2 ], and
[L 1 Zn 2 (OiPr) 2 ].

9. The method according to claim 1 , wherein the catalyst system comprises a chain transfer agent.

10. The method of claim 6 , wherein the compound [Y] is an epoxide, an aziridine, an episulfide, an oxetane, a thietane, an azetidine, a saturated furan, a saturated thiophene, a pyrrolidine, or a saturated four-membered carbon ring where two adjacent carbon atoms are replaced by —Y—C(Y)—, wherein each Y is independently selected from O, S or NR Y , and wherein R Y is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alicyclic, optionally substituted heteroalicyclic, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkylaryl, or optionally substituted alkylheteroaryl.

11. The method of claim 5 , wherein the compound [Y] is an epoxide.

Assignees

• Imperial Innovations Ltd

Inventors

• Williams Charlotte Katherine
• Romain Charles
• Kember Michael

Classifications

• C08G63/823

  for the preparation of polylactones or polylactides · CPC title

• C08G63/08 Primary

  Lactones or lactides · CPC title

• C08G63/82

  characterised by the catalyst used · CPC title

• C08G63/42 Primary

  Cyclic ethers (C08G59/00 takes precedence); Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters · CPC title

• C08G63/64

  Polyesters containing both carboxylic ester groups and carbonate groups · CPC title