Process for Preparing Polycarbonates by Polymerization of Five-Membered-Ring Cyclic Carbonates

• US 20160068630A1
• Filed: 04/29/2014
• Published: 03/10/2016
• Est. Priority Date: 04/29/2013
• Status: Abandoned Application

• Current Assignee: Centre National De La Recherche Scientifique, Total Research & Technology Feluy SA (Totalenergies Se)
• Original Assignee: Centre National De La Recherche Scientifique, Total Research & Technology Feluy SA (Totalenergies Se)
• Inventors: CARPENTIER, Jean-Francois, GUILLAUME, Sophie, GUERIN, William
• Application Number:
  US14/786,227
• Publication Number:
  US 20160068630A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C07D 317/36 Alkylene carbonates; Substituted alkylene carbonates
• CPC Class Codes: C07D 317/46 condensed with one six-membered ring
• CPC Class Codes: C08G 63/64 Polyesters containing both carboxylic ester groups and carbonate groups
• CPC Class Codes: C08G 64/30 using carbonates
• CPC Class Codes: C08G 64/305 and alcohols

Abstract

A process for the preparation of polycarbonates may include ring-opening polymerization of five-membered cyclic carbonates in the presence of a catalyst; a compound of formula (I), stereoisomers, racemics, or mixtures thereof; and optionally cyclic esters, stereoisomers, racemics, or mixtures thereof. Formula (I) is:

Each dotted bond “a” and “b” is a solid bond, a wedged bond, or a hashed wedged bond. R²¹ and R²², taken together with the carbon atoms 4 and 5 of the cyclic carbonate, may form a ring. The ring may be a C_5-9cycloalkylene, C_5-9cycloalkenylene, or C_6-12arylene. The ring may optionally be substituted with substituents including halo, hydroxyl, C_1-6alkyl, haloC_1-6alkyl, C_1-6alkoxy, haloC_1-6alkoxy, C_6-12aryl, C_1-6alkylthio, carboxyl, C_1-6alkoxycarbonyl, C_1-6alkylcarbonyloxy, amino; or mono- or di-C_1-6alkylamino.

Claims

1-15. -15. (canceled)

16. A process for preparing a polycarbonate or copolymer thereof, said process comprising homo- or copolymerizing in the presence of at least one catalyst, one or more compounds of formula (I), stereoisomers, racemics, or mixtures thereof;

optionally with one or more cyclic esters, stereoisomers, racemics, or mixtures thereof;

17. The process according to claim 16, wherein the catalyst is an organometallic catalyst of formula (II) or (III),

18. The according to claim 17, wherein the catalyst is selected from [(NNO)ZnEt], [BDI]Zn(N(SiMe₃)₂), [BDI]Zn(Et), and {[BDI]Zn(OR³⁰)}₂, wherein R³⁰ is C_1-6alkyl, and wherein [BDI]Zn(N(SiMe₃)₂) and [(NNO)ZnEt] have the following structures:

19. The process according to claim 16, wherein the catalyst is selected from complexes of formulae M(OSO₂CF₃)_m, M(N(OSO₂CF₃)₂)_m, M(R²³C(O)CR²³₂C(O)R²³)_m, and (R²⁴CO₂)_mM, wherein M is a metal of Group 2, 3, including the lanthanide series, or Group 12, 13, 15, wherein each R²³ is independently an optionally substituted C_1-12 alkyl, wherein each R²⁴ is independently a perfluorinated C_1-12alkyl or an aryl, and wherein m is the valence of M.

20. The process according to claim 16, wherein the catalyst is selected from the group consisting of dimeric phosphazene bases, or amines or guanidines, organic acids, sparteine, thiourea-amino derivatives, N-heterocyclic carbenes, 4-(dialkylamino)pyridines, amidines, phosphorus based phosphines, phosphazenium derivatives and phosphazenes, metal amides;

and compounds of general formula M¹(Y¹, Y², . . . Y^p)^q, in which M¹ is a metal selected from the group consisting of the elements of columns 3 to 12 of the periodic table of the elements, and the elements Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Ca, Mg and Bi;

wherein Y¹, Y2, . . . Y^p are each substituents selected from the group consisting of alkyls with 1 to 20 carbon atoms, aryls having from 6 to 30 carbon atoms, alkoxys having from 1 to 20 carbon atoms, aryloxys having from 6 to 30 carbon atoms, oxides, carboxylates, and halide groups, and wherein p and q are integers of from 1 to 6.

21. The process according to claim 20, wherein the catalyst is selected from the group consisting of 1,5,7-triazobicyclo-[4,4,0]dec-5-ene (TBD);

1,8-diazabicyclo[5.4.0]undec-7-ene (DBU);

4-dimethylaminopyridine (DMAP);

tert-butylimino-1,3-dimethylperhydro-1,3,2-diazaphosphine (BEMP);

Sn(Oct)₂;

Al(OiPr)₃;

Ti(OiPr)₄;

Ti(2-ethylhexanoate)₄;

Ti(2-ethylhexyloxide)₄;

Zr(OiPr)₄;

Bi(neodecanoate)₃;

(2,4-di-tert-butyl-6-(((2-(dimethylamino)ethyl)(methyl)amino)methyl)phenoxy)(ethoxy)zinc;

Zn(lactate)₂;

Y[N(SiMe₃)₂]₃;

[Y]+L1; and

[Y]+L2, wherein L1 is a tetradentate ligand of formula L1 and L2 is a tetradentate ligand of formula L2;

22. The process according to claim 16, wherein the process is performed in the presence of a compound of formula (IV),

R⁸—

OH 

 

(IV)

wherein R⁸ is selected from the group consisting of C_1-20alkyl, C_6-30aryl, and C_6-30arylC_1-20alkyl optionally substituted by one or more substituents selected from the group consisting of halogen, hydroxyl, and C_1-6alkyl.

23. The process according to claim 16, wherein the homo- or copolymerizing is in the presence of cyclic esters, wherein the cyclic esters are selected from the group consisting of lactones, cyclic carbonates, glycolides and lactides, wherein each group is unsubstituted or substituted with one or more substituents each independently selected from C_1-6alkyl and C_1-6alkoxy.

24. The process according to claim 16, wherein the homo- or copolymerizing is in the presence of cyclic esters, wherein the cyclic esters are selected from the group consisting of lactide;

trimethylene carbonate;

glycolide;

β

-butyrolactone;

δ

-valerolactone;

γ

-butyrolactone;

γ

-valerolactone;

4-methyldihydro-2(3H)-furanone;

alpha-methyl-gamma-butyrolactone;

ε

-caprolactone;

1,3-dioxolan-2-one;

propylene carbonate;

4-methyl-1,3-dioxan-2-one;

1,3-doxepan-2-one;

5-C_1-4alkoxy-1,3-dioxan-2-one; and

mixture thereof, wherein each group is unsubstituted or substituted with one or more substituents each independently selected from C_1-6alkyl and C_1-6alkoxy.

25. The process according to claim 16, wherein the process is performed in the presence or absence of a solvent.

26. The process according to claim 16, wherein the polycarbonate or copolymer thereof comprises recurring units of formula (VII3) or of formula (VII4),

27. An article comprising a polycarbonate or copolymer thereof prepared according to claim 16.

28. A process for preparing a polycarbonate or copolymer thereof, said process comprising copolymerizing in the presence of at least one catalyst, one or more compounds of formula (I), stereoisomers, racemics, or mixtures thereof;

with one or more cyclic esters, stereoisomers, racemics, or mixtures thereof;

29. The process according to claim 28, wherein two of said one or more substituents of the ring formed by R²¹ and R²² with the carbon atoms 4 and 5 are joined to form a ring fused to said C_3-9cycloalkylene, C_5-9cycloalkenylene, or C_6-12arylene;

wherein said ring formed by said two substituents is selected from the group consisting of C_3-9cycloalkyl, C_5-9cycloalkenyl, C_6-12aryl, and heterocyclyl, wherein each group is unsubstituted or substituted with one or more R⁴⁰, wherein each R⁴⁰ is independently selected from halo, hydroxyl, C_1-6alkyl, haloC_1-6alkyl, C_1-6alkoxy, haloC_1-6alkoxy, C_6-12aryl, C_1-6alkylthio, carboxyl, C_1-6alkoxycarbonyl, C_1-6alkylcarbonyloxy, amino;

or mono- or di-C_1-6alkylamino.

30. An article comprising a polycarbonate or copolymer thereof prepared according to claim 28.

31. A process for the synthesis of a compound of formula (I) a stereoisomer or racemate thereof,

32. A polycarbonate or copolymer thereof comprising a recurring unit of formula (VII1) and/or (VII2),

33. The polycarbonate or copolymer thereof according to claim 32, comprising recurring units each independently represented by the following formula (VIIA) or (VIIB) or (VIIC);

34. The polycarbonate or copolymer thereof according to claim 32, comprising recurring units each independently represented by the following formula (VIIA1) or (VIIB1) or (VIIC1);

35. An article comprising a polycarbonate or copolymer thereof according to claim 32.

36. A polycarbonate or copolymer thereof comprising recurring units of formula (VII3) or of formula (VII4),

37. An article comprising a polycarbonate or copolymer thereof according to claim 36.