Organoaluminum compounds as the initiators and catalysts of chain polymerization processes

Abstract

Zwi¹zki glinoorganiczne jako inicjatory i katalizatory procesów polimeryzacji ³añcuchowejStreszczenie -Artyku³ stanowi przegl¹d literaturowy dotycz¹cy katalitycznej aktywnooeci zwi¹zków glinoorganicznych w procesach polimeryzacji anionowej, kationowej, rodnikowej oraz polimeryzacji i kopolimeryzacji koordynacyjnej z udzia³em monomerów heterocyklicznych, aldehydów, ditlenku wêgla i innych monomerów karbonylowych. Przedstawiono mechanizmy inicjowania tych procesów i struktury generowanych centrów aktywnych oraz omówiono szereg przyk³adów reakcji, w których zwi¹zki glinu skutecznie aktywuj¹ monomery i pozwalaj¹ na bardziej selektywny przebieg polimeryzacji. Zaprezentowano równie¿ mo¿liwooeci wykorzystania handlowo dostêpnych alumoksanów w syntezie polieterów, poliestrów i poliwêglanów. S³owa kluczowe: katalizatory glinoorganiczne, alumoksany, polimeryzacja ³añcuchowa, kopolimeryzacja. ORGANOALUMINUM COMPOUNDS AS THE INITIATORS AND CATALYSTS OF CHAIN POLYMERIZATION PROCESSESSummary -The paper presents a literature review on the catalytic activity of organoaluminum compounds in anionic, cationic and radical polymerization, as well as coordination polymerization and copolymerization involving heterocyclic monomers, aldehydes, carbon dioxide and other carbonyl monomers. The initiation mechanisms of these processes and the structures of the generated active sites have been presented and several examples of processes in which aluminum compounds efficiently activate the monomers and allow a more selective course of polymerization are discussed. Moreover, the possibility of application of commercially available alumoxanes in the synthesis of polyethers, polyesters and polycarbonates has been shown.

Inorganic heterocycles based on alumosilicate-sulfide ligand

“…Compound 4 started to decompose once out of the mother liquor, even under an inert atmosphere. 1 ,9.27;N,3.16. Found: C,61.4;H,9. A solution of 1 (0.50 g, 0.73 mmol) in toluene (10 mL) was prepared inside a glove box and kept for at least 30 min.…”

“…322.6°C (dec); 1 H NMR (300.53 MHz, C 6 D 6 , 20°C): d (ppm) À0.38 (s, 3 H, AlMe), 1.11 (d, 3 J H-H = 6.7 Hz, 3 H, CHMe 2 ), 1.12 (m,4 H,AlO(CH 2 CH 2 ) 2 ), 1.15 (d, 3 J H-H = 6.7 Hz, 3 H, CHMe 2 ), 1. 18 (s, 9 H, CMe 3 ), 1.22 (s, 9 H, CMe 3 ), 1.26 (d, 3 J H-H = 6.7 Hz, 3 H, CHMe 2 ), 1.27 (d, 3 J H-H = 6.7 Hz, 3 H, CHMe 2 ), 1.42 (m,4 H,(O(CH 2 CH 2 ) 2 ), 1.44 (d, 3 J H-H = 6.7 Hz, 3 H, CHMe 2 ), 1.56 (s, 3 H, Me), 1.61 (s, 3 H, Me), 1.71 (d, 3 J H-H = 6.7 Hz, 3 H, CHMe 2 ), 1.72 (d, 3 J H-H = 6.7 Hz, 6 H, CHMe 2 ), 3.53 (m, 2 H, AlO(CH 2 CH 2 ) 2 ), 3.56 (sept, 3 J H-H = 6.7 Hz, 1 H, CHMe 2 ), 3.58 (m,4 H,(O(CH 2 CH 2 ) 2 ), 3.62 (sept, 3 J H-H = 6.7 Hz, 1 H, CHMe 2 ), 3.77 (m, 2 H, AlO(CH 2 CH 2 ) 2 ), 3.81 (sept, 3 J H-H = 6.7 Hz, 1 H, CHMe 2 ), 4.04 (sept, 3 J H-H = 6.7 Hz, 1 H, CHMe 2 ), 4.88 (s, 1 H, c-H), 6 H,; 13 124.2,124.5,125.0,126.8,127.4,127.9,141.0,141.0,144.9,145.3,145.4, 13 g mol -1 ): C,63.28;H,8.85;N,3.51. Found: C,63.0;H,8.6;N,3.2%.…”

Diversity of transformation of heteroallenes on acenaphthene-1,2-diimine aluminum oxide

“…The high interest in these objects is due to the fact that these compounds are effective catalysts and co-catalysts in the polymerization of a wide range of organic molecules. [1][2][3] However, even the simplest co-catalyst in alkene polymerization, methylalumoxane (MAO), has not yet been structurally characterized, and its mechanism of action has not been fully understood. [4][5][6] It is known that MAOs containing simple Me-Al-O monomer units form various types of clusters, while the use of N,N-chelating ligands allows forming monomeric MAO derivatives.…”

Characterization of Isobutylaluminoxanes by Electrospray Ionization Mass Spectrometry

“…reactions of carbonyl compounds, including CO 2 , with aluminum alkyls . They find use as Lewis acidic catalysts of ring-opening polymerization and as additives or initiators of anionic and free radical polymerization, but by far their most important use is as cocatalysts for coordination polymerization using transition-metal catalysts. Poly(methylaluminoxane) (PMAO) is widely used for this purpose along with hydrocarbon-soluble versions known as modified methylaluminoxanes (MMAO), which are formed by step growth, copolymerization of trimethylaluminum (TMA) and higher aluminum alkyls such as triisobutylaluminum (TiBAl), or modification of PMAO by TiBAl .…”