EP3983470A1 - Procédé de carbonylation d'époxydes - Google Patents

Procédé de carbonylation d'époxydes

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Publication number
EP3983470A1
EP3983470A1 EP20729779.7A EP20729779A EP3983470A1 EP 3983470 A1 EP3983470 A1 EP 3983470A1 EP 20729779 A EP20729779 A EP 20729779A EP 3983470 A1 EP3983470 A1 EP 3983470A1
Authority
EP
European Patent Office
Prior art keywords
iii
particularly preferably
carbene
butyl
tert
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20729779.7A
Other languages
German (de)
English (en)
Inventor
Jens Langanke
Leven MATTHIAS
Christoph Gürtler
Suresh RAJU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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Filing date
Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3983470A1 publication Critical patent/EP3983470A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0264—Phosphorus acid amides
    • B01J31/0265—Phosphazenes, oligomers thereof or the corresponding phosphazenium salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0286—Complexes comprising ligands or other components characterized by their function
    • B01J2531/0291—Ligands adapted to form modular catalysts, e.g. self-associating building blocks as exemplified in the patent document EP-A-1 479 439
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/13—Potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/60—Groups characterized by their function
    • B01J2540/64—Solubility enhancing groups

Definitions

  • the invention relates to a process for the carbonylation of epoxides in the presence of catalyst systems, the carbonylation taking place in the presence of carbon monoxide, and the catalyst system containing a molybdenum-based compound.
  • Another subject matter of the invention are carbonylation products and carbonylation secondary products and the use of catalyst systems according to the invention for the carbonylation of epoxides.
  • DE 10235316 A1 discloses a process for the production of lactones by catalytic carbonylation of oxiranes, a catalyst system comprising a) at least one carbonation catalyst A composed of neutral or anionic transition metal complexes of
  • WO 2006/058681 A2 describes a process for the production of enantiomerically enriched lactones by catalytic carbonylation of lactones to anhydrides in the presence of a neutral or anionic transition metal complex.
  • JP2013173090 describes the carbonylation of epoxides using immobilized catalyst systems.
  • EP 0176370 A1 describes a method for the preparation of lactones via the cyclizing esterification of unsaturated alcohols with carbon monoxide in the presence of a catalyst.
  • Mo is described as a component of a bimetallic catalyst system beta-lactones, i.e. cyclic 4-ring esters are neither described nor claimed.
  • Epoxides as possible substrates and / or intermediates are neither described nor claimed.
  • WO 2011/163309 A2 describes a two-stage process for the production of polyhydroxybutyrate and / or polyhydroxypropionate homopolymers with subsequent thermal decomposition to form unsaturated acids such as crotonic acid and / or acrylic acid.
  • unsaturated acids such as crotonic acid and / or acrylic acid.
  • the corresponding beta-lactones are produced by carbonylating epoxides and in the second stage they are converted into the corresponding homopolymers.
  • Cobalt and molybdenum compounds differ significantly in their regulatory classification.
  • the US federal agency OSHA prescribes a time-weighted average value for occupational exposure limits of ⁇ 0.1 ppm for cobalt carbonyls and cobalt hydrocarbonyls (cf. Clinical Toxicology, 1999, 37, 201-216), whereas a time-weighted average value for exposure limit values for soluble molybdenum compounds is 5 ppm and for insoluble molybdenum compounds is 10 ppm (cf. Clinical Toxicology, 1999, 37, 231-237).
  • a chemically more stable catalyst system should be used, so that longer storage and / or technically simpler storage, handling and use compared to the cobalt-based systems described above from the prior art is possible.
  • cobalt is in the very sensitive oxidation state -1 and can be degraded extremely easily with oxidants of all kinds, as well as hydroxy compounds or water.
  • the catalyst systems of the invention should be characterized by better technical availability and lower toxicity compared to the cobalt-based systems, with direct further processing of the carbonylation products to carbonylation secondary products, for example conversion to polyurethanes, without prior separation of the catalyst system is possible.
  • the object according to the invention is achieved by a process for the carbonylation of epoxides in the presence of catalyst systems, the carbonylation taking place in the presence of carbon monoxide, characterized in that the catalyst system contains a molybdenum-based compound.
  • the molybdenum-based compound is used in amounts of 0.0001 mol% to 20 mol% based on the amount of substance of epoxide.
  • the molybdenum-based compound has an oxidation state of zero.
  • the molybdenum-based compound is anionic.
  • the molybdenum-based compound contains one or more carbonyl ligands, preferably one to six, particularly preferably two to five.
  • the molybdenum-based compound has a further ligand (L) other than the carbonyl ligand, the following being more functional Relationship between the carbonyl ligand of the molybdenum-based compound with a total of 6 ligands and the ligand (L) of the molybdenum-based compound for mononuclear molybdenum-based compounds typically results:
  • the ligand (L) is one or more compound (s) and is selected from the group consisting of hydrido, such as (H), halide, such as F, CI, Br and I, pseudohalide, such as For example CN, N3, OCN, NCO, CNO, SCN, NCS and SeCN, inorganic N-ligands such as NC, NO, NO2, NO3, NH 2 , NCH 3 , NCCH 3 and NCCF 3 , pseudochalcogenides, carboxylates such as for example OTf, OAc and HCOO, other inorganic anions such as OH and HSO4, allyl compounds such as T
  • dienes such as butadienes (C4C6), cyclic C5 ligands, such as cyclopentadienyl (Cp, r
  • Alkyl compounds such as C (Ph) (Ph) (as Fischer carbene), C (OMe) (Ph) (as Fischer carbene), C (OEt) (NHPh) (as Fischer Carbenes)
  • NHC-carbenes such as, for example, 1,3-dimesitylimidazol-2-ylidenes (IMes, NHC-carbenes) and 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-ylidenes (SIMes, NHC-carbene), amines such as NH
  • the ligand (L) is one or more compound (s) and is selected from the group consisting of H, F, CI, Br, I, CN, NC, SCN, N 3 , NO 2 , N0 3 , NH 2 , OTf, OAc, OH, HSO4, r
  • the catalyst system contains an additional Fewis acid.
  • Fewis acids contain one or more coordinatively unsaturated metal atoms as the Fewis acidic center, e.g. Aluminum, tin, zinc, bismuth, vanadium, chromium, molybdenum, tungsten, iron, cobalt, nickel, rhodium, iridium, palladium, platinum, copper or zinc. But the semimetal boron also forms the Fewis acid center of Fewis acids.
  • Coordinatively unsaturated Fewis acid centers are characterized by the fact that nucleophilic molecules can bind to them. Coordinatively unsaturated Fewis acid centers can already be present in the compound used as catalyst or form in the reaction mixture, e.g. by splitting off a weakly bound nucleophilic molecule.
  • Mo (V) chloride is used simultaneously as Fewis acid and precursor for generating a catalyst system according to the invention (cf. example 14 according to the invention).
  • a catalyst system according to the invention cf. example 14 according to the invention.
  • part of Mo (V) can be reduced to Mo (0) and thereby forms the inventive molybdenum component of the catalyst system of the form [Mo (CO) n (Cl) m ] m .
  • the remaining portion of Mo (V) chloride serves as the Fewis acid according to the invention.
  • the synthesis of the catalyst systems can also take place in the reaction mixture itself and / or under reaction conditions. This procedure is referred to as for the in-situ generation of a catalyst system and was carried out in example 15 according to the invention.
  • the Fewis acid is cationic or charge-neutral, preferably cationic.
  • the Lewis acid is cationic.
  • the cationic Lewis acid is an unsubstituted dicyclopentadienyl metal cation, a substituted dicyclopentadienyl metal cation, an unsubstituted metal-porphyrin cation, a substituted metal-porphyrin cation, an unsubstituted metal-salen Cation, a substituted metal-salen cation, an unsubstituted metal-salphen-cation and / or a substituted metal-salphen-cation.
  • the Lewis acids can be simple inorganic, organometallic or organic compounds, such as BF 3 , AlCh, FeCk B (CH 3 ) 3 , B (OH) 3 , BPh 3 , B (OR) 3 , SiCL, SiF, PF 4 , CO2, S0 3 etc. and adducts of these compounds.
  • Lewis acids of more complex structure in which the Lewis acidic center is coordinated by complex ligands, are also known and are preferably used in one embodiment of the process according to the invention.
  • the ligands play the role, in particular, of having a stabilizing and / or strengthening effect on the Lewis acidic centers through partial coordinative saturation of the Lewis acidic center or the Lewis acidic centers.
  • a distinction can be made between electronic and steric effects of the ligand molecules. Square-planar and square-tetrahedral coordination polyhedra between N and / or O ligand (s) and Lewis acidic centers are particularly suitable for this.
  • Cyclopentadienyl metal complexes Lewis acids based on unsubstituted and substituted porphyrin, chlorine and corrin complexes, Lewis acids based on unsubstituted and substituted halls, Salpn, Salan, Salalen, Salph, Salphen and Salqu complexes, Lewis acids based of unsubstituted and substituted pincer complexes, Lewis acids based on unsubstituted and substituted pincer-diiminopyridine complexes are particularly preferred as Lewis acids in one embodiment of the method according to the invention.
  • Cyclopentadienyl metal complexes which are complexes between one or more metals and one or more cyclopentadienyl derivative ligands (C5R5), are characterized by the presence of so-called h 5 metal-lagnd bonds.
  • cyclopentadienyl metal complexes Cp complexes
  • pentamethylcyclopentadienyl metal complexes Cp * complexes
  • dicyclopentadienyl metal complexes ((Cp) 2 complexes) and di-pentamethyl-cyclopentadienyl Metal complexes ((Cp *) 2 complexes) suitable as Lewis acids.
  • the substituents are selected independently of one another from the group consisting of hydrogen (—H), methyl, tert.
  • the substituents are selected independently of one another from the group consisting of hydrogen (—H), methyl, tert.
  • Lewis acids based on unsubstituted and substituted pincers complexes with the Lewis acidic center selected from the groups of aluminum, tin, zinc, bismuth, vanadium, chromium, molybdenum, manganese, tungsten, iron, cobalt, Nickel, ruthenium, rhodium, iridium, indium, cerium, lanthanum, yttrium, gadolinium, palladium, platinum, copper and zinc.
  • the Lewis acidic center selected from the groups of aluminum, tin, zinc, bismuth, vanadium, chromium, molybdenum, manganese, tungsten, iron, cobalt, Nickel, ruthenium, rhodium, iridium, indium, cerium, lanthanum, yttrium, gadolinium, palladium, platinum, copper and zinc.
  • the ligands of these tweezer complexes have the general formula Inorganic linker) -E- (organic linker) -A, where A is selected from the group of the elements P, N and S and where E is selected from the group of elements C, B and N, and are tridentate.
  • Lewis acids based on unsubstituted and substituted pincer-diiminopyridine complexes with the Lewis acidic center selected from the groups of aluminum, tin, zinc, bismuth, vanadium, chromium, molybdenum, manganese, tungsten, iron , Cobalt, nickel, ruthenium, rhodium, iridium, indium, cerium, lanthanum, yttrium, gadolinium, palladium, Platinum, copper and zinc.
  • the ligands of these DIP complexes are in the form of diiminopyridine and its derivatives.
  • the catalyst system has the structure (I), (II), (III), (IV), (V), (VI), and / or (VII):
  • X H, F, CI, Br, I, CN, NC, SCN, NCS, CP, N 3 , N0 2 , N0 3 , NH 2 , OTf, OH or HS0, preferably H, F, CI, Br, I, CN, N 3 , or OTf, very particularly preferably CI or Br;
  • M Cr (III), Al (III), Fe (III), Co (III), Mn (III), V (III), In (III), Ga (III), Y (III), Ru ( III), La (III), Ce (III), Gd (III) or Ir (III), preferably Cr (III), Al (III), Fe (III), Co (III), Mn (III), or Ga (III), very particularly preferably Cr (III) or Al (III); with Ri and R 2 independently selected from the group of hydrogen (-H), methyl, tert.
  • X H, F, CI, Br, I, CN, NC, SCN, NCS, CP, N 3 , NO2, NO3, NH 2 , OTf, OH or HSO4, preferably H, F, CI, Br, I, CN, N3, or OTf, very particularly preferably CI or Br;
  • M Cr (III), Al (III), Fe (III), Co (III), Mn (III), V (III), In (III), Ga (III), Y (III), Ru ( III), La (III), Ce (III), Gd (III) or Ir (III), preferably Cr (III), Al (III), Fe (III), Co (III), Mn (III), or Ga (III), very particularly preferably Cr (III) or Al (III); with R selected from the group of hydrogen (-H), methyl, tert.
  • X H, F, CI, Br, I, CN, NC, SCN, NCS, CP, N 3 , N0 2 , N0 3 , NH 2 , OTf, OH or HSO4, preferably H, F, CI, Br, I, CN, N 3 , or OTf, very particularly preferably CI or Br;
  • Ri and R independently selected from the group consisting of hydrogen (-H), methyl, tert. Butyl, phenyl, nitro, bromine, chlorine, hydroxy, diethylamino and methoxy preferably Ri is R selected from the group of hydrogen (-H), methyl or tert. Butyl, very particularly preferably tert. Butyl.
  • the catalyst system has the structure (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV) and / or (XVI) : (VIII)
  • the epoxide of the present invention can be an epoxide having 2-45 carbon atoms.
  • the epoxide is selected from at least one compound from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2 , 3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, epoxides of C6-C22 ⁇ -olefins, such as 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide , 2-methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide , 1-dodecene
  • Examples of derivatives of glycidol are phenyl glycidyl ether, cresyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether and 2-ethylhexyl glycidyl ether.
  • the epoxide is ethylene oxide and / or propylene oxide.
  • the carbonylation process is carried out in the presence of a suspending agent, preferably an aprotic suspending agent.
  • the suspending agents used according to the invention do not contain any H-functional groups. All polar-aprotic, weakly polar-aprotic and non-polar-aprotic solvents, which in each case contain no H-functional groups, are suitable as suspending agents. A mixture of two or more of these suspending agents can also be used as suspending agents.
  • polar aprotic solvents may be mentioned at this point as examples: 4-methyl-2-oxo-1,3-dioxolane (hereinafter also referred to as cyclic propylene carbonate or cPC), 1,3-dioxolan-2-one (hereinafter also called cyclic ethylene carbonate or cEC), methyl formate, ethyl formate, isopropyl formate, propyl formate, ethyl acetate, isopropyl acetate, n-butyl acetate, methyl oxalate, 2,2-dimethoxypropane, acetone, methyl ethyl ketone, acetonitrile, benzonitrile, diethyl carbonate, dimethyl carbonate, dimethyl sulfoxide, n-butyl acetate, Dimethylformamide, dimethylacetamide and / V-methylpyrrolidone.
  • cPC cyclic propylene carbonate
  • the group of non-polar and weakly polar aprotic solvents include e.g. Ethers such as Dioxolane, dioxane, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, tert-amyl methyl ether, butyl methyl ether, methyl propyl ether, dimethyl ether, diisopropyl ether, ethyl methyl ether, methyl phenyl ether, dimethoxymethane, diethoxymethane, diemethoxyethane 12 (glyme), [ Cyclopentyl methyl ether, triglyme, tetraglyme,
  • Diethylene glycol dibutyl ether 2-methyltetrahydrofuran and tetrahydrofuran
  • esters such as ethyl acetate and butyl acetate
  • hydrocarbons such as pentane, n-hexane, benzene and alkylated benzene derivatives (e.g. toluene, xylene, ethylbenzene) and chlorinated hydrocarbons such as chloroform, Dichlorobenzene, fluorobenzene, difluorobenzene, methylene chloride, and carbon tetrachloride.
  • Preferred suspending agents are 4-methyl-2-oxo-l, 3-dioxolane, l, 3-dioxolan-2-one, 2-methyltetrahydrofuran, tetrahydrofuran, dioxanes, diemethoxyethane (glyme), diethyl ether, ethyl acetate, methyl ethyl ketone, / V- Methylpyrrolidone, acetonitrile, sulfolane, dimethyl sulfoxide, dimethylformamide, toluene, xylene, ethylbenzene, dichlorobenzene, fluorobenzene, chlorobenzene and difluorobenzene and mixtures of two or more of these suspending agents are used, 4-methyl-2-oxo-1,3-dioxolane, l , 3-dioxolan-2-one, 2-methyltetrahydrofuran, tetrahydro
  • the process is carried out at temperatures from 0 ° C to 200 ° C, preferably 60-190 ° C and particularly preferably 80-180 ° C
  • Another object of the present invention are carbonylation products by reacting epoxides with carbon monoxide by the process according to the invention, the molar proportion of cyclic anhydrides based on the epoxide used is less than 5 mol%, the proportion of cyclic anhydrides using the part disclosed in the experimental H-NMR method was determined, with particular reference to Example 24.
  • Carbonylation products include reaction products of epoxides with carbon monoxide such as 4-ring lactones, beta-butyrolactone as a reaction product of propylene oxide and CO and propiolactone as a reaction product of ethylene oxide and CO, and polyhydroxyalkanoates as a polymerization product of 4-ring lactones, especially polyhydroxybutyrate Beta-butyrolactone and polyhydroxypropionate from propiolactone and their copolymers, which in addition to the above-mentioned polyester repeat units also have polyether repeat units, are to be understood.
  • carbonylation products also include reaction products of epoxides with carbon monoxide to give corresponding cyclic ester ether compounds, in particular dioxepanone and
  • Dioxocanedione compounds in particular 1,4-dioxepan-5-one, 2,7-dimethyl-1,4-dioxepan-5-one, 2,6-dimethyl-1,4-dioxepan-5-one, 3,6- Dimethyl- 1, 4-dioxepan-5-one, 3,7-dimethyl- 1, 4-dioxepan-5 - one, l, 5-Dioxocane-2,6-dione, 3,8-dimethyl-l, 5- dioxocane-2,6-dione, 3,7-dimethyl-l, 5-dioxocane-2,6-dione and 4,8-dimethyl-l, 5-dioxocane-2,6-dione.
  • polyhydroxybutyrate short: PHB
  • PHB polyhydroxybutyrate
  • PGP Polyhydroxypropionate
  • Repeat unit formed from PO and / or n polyether repeat unit formed from EO (* end groups and / or others
  • the present invention also provides a process for the production of carbonylation products, preferably polyurethanes, by reacting the carbonylation products according to the invention with epoxides, polyisocyanants and / or polycarboxylic acids, preferably with polyisocyanates.
  • the present invention also relates to the use of the molybdenum-based catalyst systems according to the invention for the carbonylation of epoxides.
  • the invention relates to a process for the carbonylation of epoxides in the presence of catalyst systems, characterized in that the catalyst system contains a molybdenum-based compound.
  • the invention in a second embodiment, relates to a method according to the first embodiment, the molybdenum-based compound containing one or more carbonyl ligands, preferably one to six carbonyl ligands, particularly preferably two to five carbonyl ligands.
  • the invention relates to a method according to the first or second embodiment, the molybdenum-based compound having a further ligand (L) other than the carbonyl ligand.
  • the invention relates to a method according to one of the first to third embodiments, wherein the ligand (L) is one or more compound (s) and is selected from the group consisting of H, F, CI, Br, I, CN , NC, SCN, N3, NO2, NO3, NH2, OTf, OAc, OH, HSO4, t -CsHs, butadienes (C 4 C 6 ), cyclopentadienyl (Cp, r
  • the invention relates to a method according to one of the first to fourth embodiments, the molybdenum in the molybdenum-based compound having an oxidation state of zero.
  • the invention relates to a method according to one of the first to fifth embodiments, the catalyst system containing an additional Lewis acid.
  • the invention relates to a method according to the sixth embodiment, wherein the Lewis acid is cationic or charge-neutral, preferably cationic.
  • the invention relates to a method according to the seventh embodiment, wherein the Lewis acid is cationic.
  • the invention relates to a method according to the eighth embodiment, wherein the cationic Lewis acid is an unsubstituted dicyclopentadienyl metal cation, a substituted dicyclopentadienyl metal cation, an unsubstituted metal porphyrin cation, a substituted metal porphyrin Cation, an unsubstituted metal-salen cation, a substituted metal-salen cation, an unsubstituted metal-salphen cation and / or a and substituted metal-salphen cation.
  • the cationic Lewis acid is an unsubstituted dicyclopentadienyl metal cation, a substituted dicyclopentadienyl metal cation, an unsubstituted metal porphyrin cation, a substituted metal porphyrin Cation, an unsubstituted metal-salen cation, a substituted metal-salen
  • the invention relates to a method according to the eighth or ninth embodiment, wherein the molybdenum-based compound is anionic.
  • the invention relates to a process according to one of the first to tenth embodiments, wherein the catalyst system has the structure (I), (II), (III), (IV), (V), (VI), and / or ( VII) has:
  • Ri and R 2 independently selected from the group of hydrogen (-H), methyl, tert. Butyl, phenyl, nitro, bromine, chlorine, hydroxy, diethylamino and methoxy, preferably Ri equal to R 2 selected from the group of hydrogen (-H), methyl or tert. Butyl, very particularly preferably tert. Butyl;
  • X H, F, CI, Br, I, CN, NC, SCN, NCS, CP, N 3 , N0 2 , N0 3 , NH 2 , OTf, OH or HS0, preferably H, F, CI, Br, I, CN, N 3 , or OTf, very particularly preferably CI or Br;
  • Q Li, Na, K, Rb, Cs, Cu or Ag, preferably Li, Na, K or Rb, very particularly preferably Na; and / or (VII)
  • M Cr (III), Al (III), Fe (III), Co (III), Mn (III), V (III), In (III), Ga (III), Y (III), Ru ( III), La (III), Ce (III), Gd (III) or Ir (III), preferably Cr (III), Al (III), Fe (III), Co (III), Mn (III), or Ga (III), very particularly preferably Cr (III) or Al (III); with Ri and R 2 independently selected from the group of hydrogen (-H), methyl, tert. Butyl, phenyl, nitro, bromine, chlorine, hydroxy, diethylamino and methoxy, preferably Ri equal to R 2 selected from the group of hydrogen (-H), methyl or tert.
  • Butyl very particularly preferably tert. Butyl.
  • the invention relates to carbonylation products obtainable according to at least one of the first to eleventh embodiment, the molar proportion of cyclic anhydrides based on the epoxide used being less than 5 mol%, the proportion of cyclic anhydrides using the 1H-NMR method disclosed in the experimental section was determined.
  • the invention relates to a process for preparing carbonylation products, preferably polyurethanes, by reacting the carbonylation products according to the twelfth embodiment with epoxides, polyisocyanants and / or polycarboxylic acids, preferably with polyisocyanates.
  • the invention relates to the use of the catalyst systems containing a molybdenum-based compound according to one of the first to eleventh embodiments for the carbonylation of epoxides.
  • the invention relates to a method according to one of the first to twelfth embodiment, wherein the catalyst system has the structure (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV) and / or (XVI) has:
  • Trifluoromethanesulfonic acid in short: TfOH, 98%, Alfa Aesar
  • Celite® 545 abbreviated: Celite, Acros Organics
  • 1,4-Dioxanes in short: Dioxanes, dry, 99.8%, Sigma Aldrich Chemie GmbH
  • Molybdenum (V) chloride 99.6%, Alfa Aesar
  • the same procedure was used for polyhydroxypropionate.
  • ARCOL® POLYOL 1004 (PET 1004 for short) from Covestro was used as the polyether reference polymer for quantitative IR and NMR analysis. It is a bifunctional polyether polyol based on PO with an average MW of approx. 435 g / mol.
  • PHB polyhydroxybutyrate
  • a reference polymer for quantitative IR and NMR analysis is based on Tetrahedron Asymmetry, 2003, 14, 3249-3252 or Polym. Chem., 2014, 5, 161-168.
  • 3.8 mL of ⁇ -butyrolactone and 40 mL of toluene were placed in a Schlenk flask under an Ar protective gas atmosphere, 0.07 mL each of methanol and trifluoromethanesulfonic acid were added and the mixture was then stirred at 30 ° C. for 2 h.
  • PHB polyhydroxypropionate
  • PHB polyhydroxypropionate
  • propiolactone and 40 mL toluene were placed in a Schlenk flask, 0.07 mL each of methanol and trifluoromethanesulfonic acid were added and the mixture was then stirred at room temperature for 0.5 h. It was then quenched with 0.15 mL diisopropylethylamine, filtered and toluene and Washed diethyl ether.
  • the reference polymer PHP was finally dried in a high vacuum and analyzed by means of IR and NMR.
  • catalyst system 3 of formula (X): Mo (CO) 6 (0.095 g, 0.36 mmol) and (TPP) CrCl (1 g, 1.67 mmol) were placed in an aluminum foil-wrapped Schlenkko Iben with a reflux condenser under an Ar protective gas atmosphere, and 40 mL THF were added and then refluxed for 3 h. It was cooled to room temperature, and the resulting reaction mixture was concentrated in vacuo until it was completely dry, washed twice with hexane and dried again. The catalyst system 3 was obtained in 53% (0.19 g, 0.17 mmol) isolated yield and examined by means of IR. Characteristic carbonyl bands at 2060, 1932 and 1871 cm 1 were identified.
  • catalyst system 5 of the formula (XII):
  • the intermediate product Li [Cp * Mo (CO) 3] was prepared analogously to that for catalyst system 4.
  • Li [Cp * Mo (CO) 3] (0.27 g, 0.83 mmol) and salphene complex salt B (0.5 g, 0.83 mmol) were then placed in a Schlenk flask under an Ar protective gas atmosphere, 40 mL THF were added and the mixture was stirred overnight. The resulting reaction mixture was filtered through Celite and then concentrated in vacuo until completely dry.
  • the catalyst system 5 was obtained in 44% (0.38 g, 0.37 mmol) isolated yield and examined by means of IR. Characteristic carbonyl bands were identified at 1916 and 1865 cm 1 .
  • Mo (CO) 6 (1 g, 3.80 mmol) and 10.5 mL THF were then placed in a Schlenk flask, cooled to -60 ° C. and the previously prepared sodium naphthenate solution was added dropwise while stirring. After the addition was complete, the mixture was slowly warmed to room temperature and stirred for a further 24 h.
  • the reaction mixture was then concentrated in vacuo until completely dry, waxed three times with hexane and again concentrated in vacuo until completely dry.
  • the catalyst system 8 (formula: Na [Mo (CO) s]) was obtained with 87% (0.86 g, 3.30 mmol) isolated yield and examined by IR. Characteristic carbonyl bands at 1864 and 1733 cm 1 were identified.
  • the catalyst system, suspension medium, naphthalene as an internal standard and epoxide were weighed into a Schlenk tube and stirred under a countercurrent of Ar protective gas. The total volume of the mixture was 2-5 mL. This mixture was then completely transferred into a 10 mL pressure reactor under a gentle CO gas countercurrent. The desired CO pre-pressure was set with stirring, heated to the reaction temperature and the initial pressure at the reaction temperature was determined. At the end of the reaction time, the final pressure at reaction temperature was determined and the pressure reactor was then cooled with the aid of a water / ice mixture. The remaining residual pressure was slowly released and a sample of the reaction mixture was immediately taken for analysis.
  • the test was carried out as described in the general test procedure. 1 mol% of the catalyst system 1, THF as suspension medium, naphthalene as internal standard (0.009 mmol) and PO (0.924 mmol, 0.9 M) were used. The reaction was carried out at 120 ° C., an initial pressure of 80 bar and a reaction time of 23 h. A PO conversion of 85% was determined in the reaction mixture by means of NMR. The formation of 3% beta-butyrolactone was detected by GC analysis of the reaction mixture. The non-volatile components were not isolated and not analyzed separately.
  • the test was carried out as described in the general test procedure. 2 mol% of the catalyst system 1, DME as the suspension medium, naphthalene as the internal standard (0.2 mmol) and PO (2 mmol, 0.9 M) were used. The reaction was carried out at 120 ° C., an initial pressure of 80 bar and a reaction time of 19 h. A PO conversion of 69% was determined in the reaction mixture by means of NMR. The non-volatile components of the reaction mixture were isolated and analyzed. A polymer yield of 7% with a proportion of 14% by weight PHB in the polymeric product was determined.
  • the test was carried out as described in the general test procedure. 0.1 mol% of the catalyst system 1, DME as suspension medium, naphthalene as internal standard (1 mmol) and PO (10 mmol, 1.8 M) were used. The reaction was at 150 ° C, 70 bar
  • the test was carried out as described in the general test procedure. 1 mol% of the catalyst system 1, DME as suspension medium, naphthalene as internal standard (1 mmol) and PO (10 mmol, 1.8 M) were used. The reaction was at 150 ° C, 70 bar
  • Example 10 Carbonylation of Ethylene Oxide Using Catalyst System 1
  • the test was carried out as described in the general test procedure. 1 mol% of the catalyst system 1, a 2: 1 mixture (v / v) of THF and DME as suspension medium, naphthalene as internal standard (0.9 mmol) and EO (9.92 mmol, 2 M) were used .
  • the reaction was carried out at 120 ° C., an initial pressure of 70 bar and a reaction time of 65 h.
  • An EO conversion of 97% was determined in the reaction mixture by means of NMR.
  • the non-volatile components of the reaction mixture were isolated and analyzed. A polymer yield of> 99% with a proportion of 2 wt .-% PHP in the polymeric product was determined. The mass balance based on EO was> 99%.
  • the test was carried out as described in the general test procedure. 0.4 mol% of the catalyst system 1, no suspending agent, naphthalene as internal standard (1 mmol) and PO (10 mmol) were used. The reaction was carried out at 120 ° C., an initial pressure of 80 bar and a reaction time of 19 h. A PO conversion of 89% was determined in the reaction mixture by means of NMR. The non-volatile components of the reaction mixture were isolated and analyzed. A polymer yield of> 8% with a proportion of 4% by weight PHB in the polymeric product was determined.
  • the test was carried out as described in the general test procedure. 1 mol% of the catalyst system 2, DME, naphthalene as internal standard (1 mmol) and PO (10 mmol, 1.8 M) were used. The reaction was carried out at 150 ° C., an initial pressure of 70 bar and a reaction time of 65 h. A PO conversion of 54% and the formation of 2.5% acetone were determined by means of NMR in the reaction mixture.
  • the test was carried out as described in the general test procedure. 1 mol% of the catalyst system 3, THF, naphthalene as internal standard (0.4 mmol) and PO (4 mmol, 0.9 M) were used. The reaction was carried out at 150 ° C., an initial pressure of 75 bar and a reaction time of 21 hours. A PO conversion of 78% and the formation of 2.3% acetone were determined in the reaction mixture by means of NMR. The non-volatile components of the Reaction mixtures were isolated and analyzed. A polymer yield of 48% with a proportion of 14% by weight PHB in the polymeric product was determined.
  • Example 14 Carbonylation of propylene oxide using molybdenum (V) chloride for the in-situ generation of a catalyst system
  • the test was carried out as described in the general test procedure. 5 mol% molybdenum (V) chloride, DME, naphthalene as internal standard (1 mmol) and PO (10 mmol, 1.8 M) were used. The reaction was carried out at 150 ° C., an initial pressure of 130 bar and a reaction time of 68 h. A PO conversion of 100% was determined in the reaction mixture by means of NMR. The non-volatile components of the reaction mixture were isolated and analyzed. A polymer yield of 46% with a proportion of 20 wt.% PHB in the polymeric product was determined.
  • Example 15 Carbonylation of propylene oxide using molybdenum hexacarbonyl and salphen complex salt A for the in-situ generation of a catalyst system
  • the test was carried out as described in the general test procedure. 1 mol% each of the two air-stable compounds molybdenum hexacarbonyl and salphen complex salt A, DME, naphthalene as internal standard (0.4 mmol) and PO (4 mmol, 1.8 M) were used. The reaction was carried out at 150 ° C., an initial pressure of 93 bar and a reaction time of 19 h. A PO conversion of 30% was determined in the reaction mixture by means of NMR. The non-volatile components of the reaction mixture were isolated and analyzed. A proportion of 4 wt.% PHB was determined in the polymeric product.
  • the test was carried out as described in the general test procedure. 1 mol% of the catalyst system 5, THF, naphthalene as internal standard (0.4 mmol) and PO (4 mmol, 0.9 M) were used. The reaction was carried out at 150 ° C., an initial pressure of 103 bar and a reaction time of 63 h. A PO conversion of 30% was determined in the reaction mixture by means of NMR. The non-volatile components of the reaction mixture were isolated and analyzed. A polymer yield of 13% with a proportion of 25% by weight PHB in the polymeric product was determined.
  • Example 18 Carbonylation of propylene oxide without the use of a catalyst system
  • the experiment was carried out as described in the general experiment procedure, but without the addition of a catalyst system.
  • DME, naphthalene as internal standard (1 mmol) and PO (10 mmol, 1.8 M) were used.
  • the reaction was carried out at 150 ° C., an initial pressure of 70 bar and a reaction time of 5 h.
  • a PO conversion of 2% was determined in the reaction mixture by means of NMR. Only traces of polymer could be found, but they did not contain any PHB.
  • the test was carried out as described in the general test procedure. 5 mol% molybdenum hexacarbonyl, 5 mol% boron trifluoride as etherate, THF, naphthalene as internal standard (1 mmol) and PO (10 mmol, 1.7 M) were used. The reaction was carried out at 80 ° C., an initial pressure of 62 bar and a reaction time of 24 hours. A PO conversion of 100% and the formation of 1% propanal and 3% 2-methyl-2-pentenal were determined in the reaction mixture by means of NMR. The non-volatile components of the reaction mixture were isolated and analyzed. A polymer yield of 84% was determined with a proportion of 3% by weight PHB in the polymeric product.
  • the test was carried out as described in the general test procedure. 5 mol% of the catalyst system 7, THF, naphthalene as internal standard (0.1 mmol) and PO (1 mmol, 0.9 M) were used. The reaction was carried out at 120 ° C., an initial pressure of 80 bar and a reaction time of 46 h. A PO conversion of 100% was determined in the reaction mixture by means of NMR. Only traces of PHB could be detected.
  • Example 23 Carbonylation of propylene oxide using catalyst system 8 and boron trifluoride
  • the test was carried out as described in the general test procedure. 2 mol% of the catalyst system 8, 2.4 mol% boron trifluoride as etherate, DME, naphthalene as internal standard (0.2 mmol) and PO (2 mmol, 0.9 M) were used. The reaction was carried out at 120 ° C., an initial pressure of 75 bar and a reaction time of 45 h. A PO conversion of 72% was determined in the reaction mixture by means of NMR. Only traces of PHB could be detected.
  • the test was carried out as described in the general test procedure. 1 mol% of the catalyst system 10, THF, naphthalene as internal standard (0.2 mmol) and PO (2 mmol, 0.9 M) were used. The reaction was carried out at 120 ° C., an initial pressure of 82 bar and a reaction time of 15 h. A PO conversion of 100%, the formation of 77% Methyl succinic anhydride and 2% acetone could be detected in the reaction mixture by means of NMR. Only traces of polymer and no PHB could be detected. The characterization and quantification of methylsuccinic anhydride is based on the specific H-NMR signals and their integrals in relation to the PO / internal standard used:

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Abstract

L'invention concerne un procédé de carbonylation d'époxydes en présence de systèmes catalyseurs, la carbonylation ayant lieu en présence de monoxyde de carbone et le système catalyseur contenant un composé à base de molybdène. L'invention concerne également des produits de carbonylation et des produits de la réaction de carbonylation, ainsi que l'utilisation de systèmes catalyseurs selon l'invention pour la carbonylation d'époxydes.
EP20729779.7A 2019-06-12 2020-06-05 Procédé de carbonylation d'époxydes Withdrawn EP3983470A1 (fr)

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