Search results for "Condensation"

Effect of core-forming molecules on molecular weight distribution and degree of branching in the synthesis of hyperbranched polymers

1998

The polydispersity index, the molecular weight distribution (MWD), and the degree of branching ( ) are calculated for hyperbranched polymers obtained in self-condensing vinyl polymerization of AB* monomers in the presence of a core-forming molecule (i.e. a multifunctional initiator, Bf*). Two cases are considered:  (a) batch polymerization, i.e., with all components mixed together; (b) semibatch polymerization, i.e., slow addition of the monomer to the core-forming molecule. The results obtained for the latter case are also valid for polycondensation of AB2 monomers. The presence of core-forming molecules leads to a considerable narrowing of the MWD's, the polydispersity index decreasing wi…

Synthesis of Defined Poly(silsesquioxane)s: Fast Polycondensation of Trialkoxysilanes in a Continuous-Flow Microreactor

2009

The polycondensation of trialkoxysilanes to PSSQs in a microreactor setup is demonstrated. While continuous-flow processes involving microreactors found various applications in chain growth polymerization, their influence on step-growth polymerization is less explored, and the polycondensation of multifunctional monomers has not been studied in detail. We found significantly increased yields and a decreased polydispersity of the obtained polymers in comparison to the batch process. By variation of the residence time molecular weights could be adjusted reproducibly ranging from M n =1900 to 11000 g · mol -1 . Thus, the microreactor setup offers for the first time the possibility to synthesiz…

New ferrocene-containing copolyesters

1995

We have synthesized four new ferrocene monomers (three diols and one diester). The redox potential of these ferrocene derivatives varies between 0 mV and 230 mV due to different degrees of ring alkylation. Amorphous and liquid crystalline copolyesters were prepared with these monomers in the polymer main chain. Cyclovoltammetric measurements show that the redox potential of the ferrocene units is increased by about 40 mV upon polymer formation (esterification). Since the ester group is 4 to 6 σ-bonds away from the ferrocene unit this increase is probably caused by some charge-transfer interaction through space. First rheological measurements show an unusual rubber-like behaviour of the ferr…

Redox Materials by the Covalent Entrapment of Redox-Active Dirhodium(II,II) Species in a Siloxane Network

2004

Hydrolysis and polycondensation of the coupling agent (aminopropyl)triethoxysilane (APS), axially coordinated to the redox-active complex [Rh 2 (form) 2 (CH 3 COO) 2 -(APS) 2 ], lead to the insertion of redox-active inorganic microdomains into a siloxane network; the new polymers undergo cyclic redox reactions indicating that dirhodium(II,II) centres retain their redox activity even when incorporated into siloxane networks.

Synthesis of Oxetane-Functional Aliphatic Polyesters via Enzymatic Polycondensation

2012

Synthesis, characterization, and thermal properties of a series of oxetane-functional aliphatic polyesters are investigated. The incorporation of the acid-sensitive 3,3-bis(hydroxymethyl)oxetane (BHMO) into polymers is achieved by using the enzyme CALB (Candida antarctica Lipase B) as a catalyst. This mild synthetic strategy provides well-defined, oxetane-functional polyesters. The enzymatic polycondensation allows for the synthesis of a series of aliphatic polyesters containing various ratios of the difunctional monomers sebacic acid, 1,8-octanediol, and BHMO with molecular weights between 5000–9800 g mol−1 and polydispersity indices (Mw/Mn) in the range of 1.25 and 1.92. Furthermore, cros…

Vitamin C Loaded Polyethylene: Synthesis and Properties of Precise Polyethylene with Vitamin C Defects via Acyclic Diene Metathesis Polycondensation

2020

A polyethylene-like polymer with an in-chain vitamin C group was synthesized by olefin metathesis polymerization. Here, we describe both the synthesis and a comprehensive physical characterization. Because of the olefin metathesis synthesis, the vitamin C groups are equidistantly arranged in the polyethylene (PE) main chain. Their separation was adjusted to 20 CH2 units. After hydrogenation, a semicrystalline polymer is obtained that is soluble in polar solvents. Because of its size and steric effect, the vitamin C acts as a chain defect, which is expelled from the crystal lattice, yielding a lamellar crystal with a homogeneous thickness corresponding to the interdefect distance. The physic…

Poly(silicate)-metabolizing silicatein in siliceous spicules and silicasomes of demosponges comprises dual enzymatic activities (silica polymerase an…

2007

Siliceous sponges can synthesize poly(silicate) for their spicules enzymatically using silicatein. We found that silicatein exists in silica-filled cell organelles (silicasomes) that transport the enzyme to the spicules. We show for the first time that recombinant silicatein acts as a silica polymerase and also as a silica esterase. The enzymatic polymerization/polycondensation of silicic acid follows a distinct course. In addition, we show that silicatein cleaves the ester-like bond in bis(p-aminophenoxy)-dimethylsilane. Enzymatic parameters for silica esterase activity are given. The reaction is completely blocked by sodium hexafluorosilicate and E-64. We consider that the dual function o…

1990

Adsorption of water vapor by poly(styrenesulfonic acid), sodium salt: isothermal and isobaric adsorption equilibria

2004

Abstract Air conditioning and dehumidifying systems based on sorption on solids are of great interest, especially in humid climates, because they allow reduction of thermal loads and use of chlorofluorocarbons. Previous studies have shown that hydrophilic polymers such as sulfonic polymers can have very high performance in water adsorption from air. The aim of this study was to characterize the water vapor adsorption properties of fully sulfonated and monosulfonated poly(styrenesulfonic acid), sodium salt, and to elucidate the mechanism of adsorption on these materials. Adsorption isotherms have been determined by TGA between 298 and 317 K for pressures ranging from 0.1 to 45 hPa. They have…

(S)-Mandelic acid enolate as a chiral benzoyl anion equivalent for the enantioselective synthesis of non-symmetrically substituted benzoins

2011

A strategy for the enantioselective synthesis of non-symmetrically substituted benzoins from (S)-mandelic acid and aromatic aldehydes has been developed. This strategy is based on a diastereoselective aldol reaction of the lithium enolate of the 1,3-dioxolan-4-one derived from (S)-mandelic acid and pivalaldehyde with aromatic aldehydes, which gives the corresponding aldols in good yields. Subsequent hydroxyl group protection as MEM ethers, basic hydrolysis of the dioxolanone ring, oxidative decarboxylation of the α-hydroxy acid moiety, and hydroxyl group deprotection provides chiral non-symmetrically substituted benzoins with high enantiomeric excesses.