Method and catalyst system for preparing polymers and block copolymers

Patent metadata

Field	Value
Publication number	US-2016108181-A1
Application number	US-201414891148-A
Country	US
Kind code	A1
Filing date	May 16, 2014
Priority date	May 17, 2013
Publication date	Apr 21, 2016
Grant date	—

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

1 . A method for producing a block copolymer, 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, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl;
R is hydrogen, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl, alkylheteroaryl, silyl or a polymer; and when Z is absent, R may additionally be selected from halide, nitro, azide and phosphinate;
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 (I) with a compound [Y] which is capable 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 . 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, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl;
R is hydrogen, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl, alkylheteroaryl, silyl or a polymer; and when Z is absent, R may additionally be selected from halide, phosphinate, azide and nitro;
the method comprising the steps of:
d) 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

e) 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], and
wherein when the second monomer or combination of monomers is Group (i), the mixture comprises a compound [Y].

6 . The method according to claim 5 , 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 5 , 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].

7 . 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, preferably 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, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl; more preferably wherein the compound [Y] is an epoxide.

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

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, or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alicyclic or heteroalicyclic;
R 3 is optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
R 4 is H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl,

Assignees

• Imp Innovations Ltd

Inventors

• Williams Charlotte Katherine
• Romain Charles
• Kember Michael

Classifications

• C08G63/42 Primary

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

• C08G81/00 Primary

  Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers (involving only carbon-to-carbon unsaturated bond reactions C08F299/00 {; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42}) · CPC title

• C08G63/82

  characterised by the catalyst used · CPC title

• C08G64/18 Primary

  Block or graft polymers · CPC title

• C08G63/64

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