Provided herein are heterogeneous catalysts suitable for use in carbonylation reactions, including the production of acrylic acid from ethylene oxide and carbon monoxide on an industrial scale. The production may involve various unit operations, including, for example: a beta-propiolactone production system configured to produce beta-propiolactone from ethylene oxide and carbon monoxide; a polypropiolactone production system configured to produce polypropiolactone from beta-propiolactone; and an acrylic acid production system configured to produce acrylic acid with a high purity by thermolysis of polypropiolactone.

Catalyst systems suitable for tetramerizing ethylene to form 1-octene may include a catalyst including a reaction product of a chromium compound and a ligand having the structure according to Formula (II). In Formula (II), A and C may be independently chosen from phosphorus, arsenic, antimony, bismuth, and nitrogen; B may be a linking group between A and C; and R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may be independently chosen from a (C.sub.1-C.sub.50) hydrocarbyl or a (C.sub.1-C.sub.50) heterohydrocarbyl. The catalyst system may include a co-catalyst including a reaction product of an organoaluminum compound and an antifouling compound. The antifouling compound may include one or more quaternary salts; one or more organic acids, organic acid salts, esters, anhydrides, or combinations of these; one or more chlorinated hydrocarbons, chloro-aluminum alkyls, or combinations of these; one or more polyether alcohols; or one or more non-polymeric ethers.

There is a process for the preparation of polypropylene carbonate having the step of copolymerization of propylene oxide and carbon dioxide (CO.sub.2) in the presence of a catalytic system including: at least one catalyst selected from complexes of a transition metal having general formula (I):

##STR00001## at least one co-catalyst selected from: (a) ionic compounds having general formula (II):

##STR00002## and (b) ionic compounds having general formula (III)

##STR00003##

According to one embodiment, a catalyst system that reduces polymeric fouling may include at least one chromium compound, at least one aluminum compound, and at least one antifouling agent or a derivative thereof. The antifouling agent may have a structure including a central aluminum molecule bound to an R1 group, bound to an R2 group, and bound to an R3 group. One or more of the chemical groups R1, R2, and R3 may be antifouling groups having the structure —O((CH.sub.2).sub.nO).sub.mR4, a phosphonium or phosphonium salt, a sulfonate or sulfonate salt, a sulfonium or sulfonium salt, an ester, an anhydride, a polyether, or a long-chained amine-capped compound, where n is an integer from 1 to 20, m is an integer from 1 to 100, and R4 is a hydrocarbyl group. The chemical groups R1, R2, or R3 that do not include an antifouling group, if any, may be hydrocarbyl groups.

Disclosed are a catalyst system capable of selectively oligomerizing olefins including ethylene and a method for preparing an olefin oligomer by using the same and, specifically, a novel catalyst system capable of trimerizing and tetramerizing olefins, unlike olefin oligomerization catalyst systems that have been reported so far, and a method for preparing an olefin oligomer by using the same. The present invention provides a catalyst system for olefin oligomerization, the catalyst system comprising: a ligand compound represented by chemical formula 1; a chromium compound; a metal alkyl compound; and an aliphatic or alicyclic hydrocarbon solvent.

The present disclosure provides novel methods of making aluminum complexes with utility for promoting epoxide carbonylation reactions. Methods include reacting neutral metal carbonyl compounds with alkylaluminum complexes.

A nanocage-confined catalyst has the formula: NC-m[M(Salen1)X]-n[M′(Salen2)]. NC is a material having a nanocage structure, and M(Salen1)X and M′ (Salen2) are active centers, respectively; each occurrence of M is independently selected from the group consisting of Co ion, Fe ion, Ga ion, Al ion, Cr ion, and a mixture thereof. Each occurrence of M′ is independently selected from Cu ion, Ni ion and a mixture thereof, m is 0 to 100; n is 0 to 100, with the proviso that at least one of m and n is not 0; each occurrence of Salen1 and Salen2 is independently a derivative of Shiff bases; X is an axial anion selected from the group consisting of substituted or unsubstituted acetate, substituted or unsubstituted benzene sulfonate, substituted or unsubstituted benzoate, F—, Cl—, Br—, I—, SbF6-, PF6-, BF4-, and a mixture thereof.

Provided herein are metal-organic frameworks having a repeating core structure that generally includes a linker coordinated to a secondary building unit through O-metal-O bonds. The linkers create a framework with a plurality of pores, where a cobalt carbonyl moiety occupies at least a portion of the plurality of pores. Provided are also methods of making such metal-organic frameworks via a solvothermal reaction. The metal-organic frameworks are suitable for use in carbonylation reactions, such as carbonylation of epoxides. The metal-organic frameworks may be used for producing acrylic acid from ethylene oxide and carbon monoxide on an industrial scale. The production may involve various unit operations, including for example a beta-propiolactone production system configured to produce beta-propiolactone from ethylene oxide and carbon monoxide; a polypropiolactone production system configured to produce polypropiolactone from beta-propiolactone; and an acrylic acid production system configured to produce acrylic acid with a high purity by thermolysis of polypropiolactone.

An oxo-nitrogenated iron complex having general formula (I) or (II) wherein: R.sub.1 and R.sub.2 identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R.sub.3, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X.sub.1 and X.sub.2, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups, —OCOR.sub.4 groups or —OR.sub.4 groups wherein R.sub.4 is selected from linear or branched C.sub.1-C.sub.20, preferably C.sub.1-C.sub.15, alkyl groups. Said oxo-nitrogenated iron complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

A transition metal-based heterogeneous carbonylation reaction catalyst has an excellent catalytic activity and selectivity in the carbonylation reaction and is easily separated from a product, by crosslinking polymerizing a transition metal-based homogeneous catalyst unit through a Friedel-Craft reaction. The catalyst may be used in a method for preparing lactone. The transition metal-based heterogeneous carbonylation reaction catalyst allows to produce lactone or succinic anhydride with an epoxide compound while showing a high selectivity, and can be applied in industrial very usefully due to easy separation from the product and thus reusing thereof.