Method and catalyst system for preparing polymers and block copolymers

Patent metadata

Field	Value
Publication number	US-10696797-B2
Application number	US-201816019246-A
Country	US
Kind code	B2
Filing date	Jun 26, 2018
Priority date	May 17, 2013
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

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 copolymerising anhydrides and epoxides.

First claim

The invention claimed is:

1. A method for producing a block copolymer, said block copolymer having a first and second block, using a single catalytic system, wherein the single catalytic system comprises a catalyst of formula (I):

Wherein:
[M] is a metal complex having at least one metal atom M coordinated by a ligand system;
M is Zn, Cr, Co, Mn, Mg, Fe, Ti, Ca, Ge, Al, Mo, W, Ru, Ni, or V;
Z is absent, or is independently 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;
the method comprising the steps of:
a) providing a mixture comprising:
i. an epoxide;
ii. a first monomer or combination of monomers selected from a group (i) to (iii):
Monomer (i): a lactide and/or a lactone,
Monomer (ii): an anhydride, or
Monomer (iii): carbon dioxide, and

iii. 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:
Monomer (i): a lactide and/or a lactone,
Monomer (ii): an anhydride, or
Monomer (iii): carbon dioxide; and

b) contacting the mixture with the single catalytic system;
wherein the rate of insertion of the first monomer or combination of monomers into the bond between the metal complex [M] and the ligand —Z—R is faster than the rate of insertion of the second monomer or combination of monomers into the bond between the metal complex [M] and the ligand —Z—R;
wherein when the first monomer or combination of monomers is Group (i), either —Z—R is -E-R, or the mixture comprises a compound [Y],
wherein when the second monomer or combination of monomers is Group (i), the mixture comprises a compound [Y]; and
wherein compound [Y] 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-.

2. The method according to claim 1 , wherein the mixture further comprises a third monomer or combination of monomers selected from a group which is different from the first and second monomers or combination of monomers:
Monomer (i): a lactide and/or a lactone,
Monomer (ii): an anhydride, or
Monomer (iii): carbon dioxide;
wherein the rate of insertion of the first and second monomers are as claimed in claim 1 , and wherein the rate of insertion of the third monomer or combination of monomers into the bond between the metal complex [M] and the ligand —Z—R is slower than the rate of insertion of the first and second monomers or combination of monomers into the bond between the metal complex [M] and the ligand —Z—R; and

wherein when the third monomer or combination of monomers is Monomer (i), the reaction mixture comprises a compound [Y].

3. 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.

4. The method according to claim 1 , wherein the catalyst has the following formula:

wherein
R 1 and R 2 are each 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, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted haloalkyl, an optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted alicyclic, or an 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 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, 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;
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 .

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

6. The method according to claim 1 , wherein M is Zn(II) or Mg(II).

7. 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 ],

Assignees

• Ip2Ipo Innovations Ltd

Inventors

• Williams Charlotte Katherine
• Romain Charles
• Kember Michael

Classifications

• C08G63/823

  for the preparation of polylactones or polylactides · CPC title

• C08G63/64

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

• C08G63/08 Primary

  Lactones or lactides · CPC title

• C08G63/42 Primary

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

• C08G63/82

  characterised by the catalyst used · CPC title