t-Butyl-Oxycarbonylated Diamines as Building Blocks for Isocyanate-Free Polyurethane/Urea Dispersions and Coatings.

t-Butyl-oxycarbonylated diamines ("di-Boc-carbamates") are investigated as dicarbamate monomers for diamine/dicarbamate polymerizations. Polyureas (PUs) and polyurethanes (PURs) with high molecular weights are prepared from stoichiometric polymerizations of diamines or diols with N-N'-di-t-butyl-oxycarbonyl isophorone diamine (DiBoc-IPDC) using KOt-Bu as a catalyst, while gelation is observed when an excess of DiBoc-IPDC is used with respect to the diamines or diols. Stable dispersions are obtained from PUs and PURs with 3,3'-diamino-N-methyldipropylamine (DMDPA) as internal dispersing agent.

Isocyanate-Free Approach to Water-Borne Polyurea Dispersions and Coatings.

Here, an isocyanate-free approach to produce polyureas from diamines and dicarbamates as monomers is reported. A side reaction limiting the molecular weight during the diamine/ dicarbamate polymerization, that is, N-alkylation of amine end groups, is investigated. Mitigation of the N-alkylation, either by enhancing the carbamate aminolysis rate or by substitution of dimethylcarbamates with more sterically hindered diethylcarbamates, affords polyureas with sufficiently high molecular weights to assure satisfactory mechanical properties.

Unique Base-Initiated Depolymerization of Limonene-Derived Polycarbonates.

The depolymerization of poly(limonene carbonate) (PLC) initiated by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was investigated.

Chemoselective Alternating Copolymerization of Limonene Dioxide and Carbon Dioxide: A New Highly Functional Aliphatic Epoxy Polycarbonate.

The alternating copolymerization of biorenewable limonene dioxide with carbon dioxide (CO2 ) catalyzed by a zinc β-diiminate complex is reported. The chemoselective reaction results in linear amorphous polycarbonates that carry pendent methyloxiranes and exhibit glass transition temperatures (Tg ) up to 135 °C. These polycarbonates can be efficiently modified by thiols or carboxylic acids in combination with lithium hydroxide or tetrabutylphosphonium bromide as catalysts, respectively, without destruction of the main chain.

Incorporation of isosorbide into poly(butylene terephthalate) via solid-state polymerization.

The biomass-based monomer isosorbide was incorporated into poly(butylene terephthalate) (PBT) by solid-state polymerization (SSP) using the macrodiol monomer BTITB-(OH) 2, which consists of isosorbide (I), terephthalic acid (T), and 1,4-butandiol (B) residues. This macromonomer can be synthesized by a simple one-pot, two-step reaction. Polymers with number-average molecular weights up to 100,000 g x mol (-1) were readily synthesized from various ratios of PBT/BTITB-(OH) 2.

Reactions of M[CH(SiMe3)2] (M = Na or K) with PhCN, and related chemistry.

A number of metal complexes containing one of the following ligands: the 1-azaallyl [N(R)C(Ph)C(H)R]- ([triple bond]L-), the 1,3-diazaallyl([triple bond]LL'-) and the isomeric beta-diketiminate [{N(R)C(Ph)]}2CH]- ( identical with LL-) have been prepared (R = SiMe(3)). These are the crystalline compounds H(LL) (2), Na(LL) (3), [Na(LL)(thf)2] (4), Na(L) (6), [Na(mu-LL')]8 (7), [K(mu-L)(eta6-C6H6)]2 (8), [K(mu-LL')(thf)]2 (9), [K(thf)2(mu-LL)](infinity) (10) and [Ni(LL')2] (11). A new synthesis of Na[C(H)R2] (1) involved Hg[C(H)R2]2 and Na/Hg as reagents.

Syntheses and structures of structurally diverse potassium beta-diketiminates derived from the ligand [(N(SiMe3)C(Ph))2CH].

The compounds [K((mu-N(SiMe3)C(Ph))2CH)(thf)2]infinity 1, [K(mu-N(SiMe3)C(Ph)C(H)C(Ph)NH)L]2 [L = (thf)2 2, tmen 3], [K(mu-NSi(Me)2C(Ph)C(H)C(Ph)N)(thf)3]2 4 and [K(N(H)C(Ph))2CH](thf)0.5 5 have been prepared from K[(N(SiMe3)C(Ph))2CH] and the X-ray structures of 1-4 are reported.