Low molar mass cyclic poly(L-lactide)s: separate transesterification reactions of cycles and linear chains in the solid state.

L-Lactide (LA) was polymerized with neat tin(II) 2-ethylhexanoate (SnOct) in toluene at 115 °C at low concentration with variation of the LA/Cat ratio. Cyclic polylactides (cPLAs) with number average molecular weights () between 7000 and 17 000 were obtained. MALDI-TOF mass spectrometry also revealed the formation of a few percent of linear chains.

High linear poly(l-lactide)s prepared alcohol-initiated ROPs of l-lactide.

Alcohol-initiated ROPs of l-lactide were performed in bulk at 160 °C for 72 h with variation of the catalyst or with variation of the initiator (aliphatic alcohols). Spontaneous crystallization was only observed when cyclic Sn(ii) compounds were used as a catalyst. Regardless of initiator, high melting crystallites with melting temperatures ( ) of 189-193 °C were obtained in almost all experiments with Sn(ii) 2,2'-dioxybiphenyl (SnBiph) as catalyst, even when the time was shortened to 24 h.

About the transformation of low into high poly(l-lactide)s by annealing under the influence of transesterification catalysts.

Cyclic polylactides were prepared in bulk at 170 °C, crystallized at 120 °C and then annealed at temperatures between 130 and 170 °C with variation of catalyst, catalyst concentration and annealing time. The transformation of the initially formed low melting (L ) crystallites, having melting temperatures ( ) < 180 °C into high melting (H ) crystallites having values > 189 °C was monitored by means of DSC measurements and characterized in selected cases by SAXS measurements. It was confirmed that the formation of H crystallites involves a significant growth of the thickness of the lamellar crystallites along with smoothing of their surface.

The Ring-Opening Polymerization-Polycondensation (ROPPOC) Approach to Cyclic Polymers.

A new concept called ring-opening polymerization-polycondensation (ROPPOC) is presented and discussed. This synthetic strategy is based on the intermediate formation of chains having two end groups that can react with each other. The ROPPOC syntheses are subdivided into three groups according to the nature of the chain ends: two ionic end groups, one ionic and one covalent chain end, and a combination of two reactive covalent end groups may be involved, depending on the catalyst.

Thermorheological and mechanical properties of copolymers of lactide, isosorbide, and different phthalic acids.

The thermal, rheological, and mechanical behavior of copolymers of lactide, isosorbide, and three different phthalic acids are studied in a wide range of compositions. A linear behavior in glass transition temperature (Tg) with respect to the mole fraction of isosorbide and phthalate content in the copolymers is observed. This behavior is in quantitative agreement with the well-known Di Marzio-Gibbs equation, which correlates the Tg with the mole fraction of flexible bonds in the monomers.

Non-stoichiometric polycondensations and the synthesis of high molar mass polycondensates.

This report presents a general overview of non-stoichiometric step-growth polymerizations (polycondensations). Three kinds of non-stoichiometric polycondensations are defined and discussed for a(2) + b(2) monomer combinations. Depending on the kinetic scenario and on the experimental conditions, the excess of one monomer either strongly reduces or strongly enhances the average degree of polymerization (DP) relative to a stoichiometric polycondensation under identical conditions.

Simultaneous chain-growth and step-growth polymerization-a new route to cyclic polymers.

Reinvestigation of numerous ring-opening polymerizations by means of MALDI-TOF mass spectrometry has evidenced that cyclic polymers were formed as the only reaction products or, at least, in large fractions. This finding is ascribed to the intermediate formation of difunctional chains having active end groups that can react with each other. Due to the low concentration of these difunctional chains cyclization is favored over chain extension according to the Ruggli-Ziegler dilution principle.

Cyclic and multicyclic polymers by three-dimensional polycondensation.

The recent confirmation that polycondensations (and other step-growth polymerizations) of difunctional monomers involve cyclization reactions at any concentration and at any stage of the polymerization also has consequences for three-dimensional polycondensations on multifunctional monomers. It is demonstrated that tree-shaped (hyperbranched) oligomers are gradually transformed into star-shaped polymers with a cyclic core, when the conversion increases. Polycondensations of "a(2) + b(3)" or "a(2) + b(4)" monomer combinations yield multicyclic polymers, when gelation can be avoided.

Synthesis of eight- and star-shaped poly(epsilon-caprolactone)s and their amphiphilic derivatives.

Spirocyclic tin dialkoxides are unique initiators for the ring-expansion polymerization of lactones leading to complex, but well-defined macromolecular architectures. In a first example, epsilon-caprolactone (epsilon CL) was polymerized, followed by the resumption of polymerization of a mixture of epsilon CL and epsilon CL alpha-substituted by a chloride (alpha Cl epsilon CL), so leading to "living" eight-shaped chains. Upon hydrolysis of the alkoxides, a four-arm star-shaped copolyester was formed, whose each arm was grafted by conversion of the chloride units into azides, followed by the Huisgen's [3+2] cycloaddition of alkyne end-capped poly(ethylene oxide) (PEO) onto the azide substituents.

Polypeptides and 100 years of chemistry of alpha-amino acid N-carboxyanhydrides.

Syntheses and polymerizations of alpha-amino acid N-carboxyanhydrides (NCAs) were reported for the first time by Hermann Leuchs in 1906. Since that time, these cyclic and highly reactive amino acid derivatives were used for stepwise peptide syntheses but mainly for the formation of polypeptides by ring-opening polymerizations. This review summarizes the literature after 1985 and reports on new aspects of the polymerization processes, such as the formation of cyclic polypeptides or novel organometal catalysts.

Synthesis of trimethoxy- or triethoxysilane-endcapped polylactones via a bismuth(III)hexanoate-catalyzed one-pot-procedure.

It was shown that bismuth(III)hexanoate (Bi(OHex)3) efficiently and selectively catalyzes the addition of tetra(ethylene glycol) (TEG) onto the isocyanate group of 3-isocyanatopropyl triethoxysilane, IPTES. delta-Valerolactone (deltaVL), epsilon-caprolactone (epsilonCL) and D,L-lactide were polymerized by initiation with TEG/Bi(OHex)3. The resulting telechelic polyesters were in situ functionalized with IPTES or with 3-isocyanatopropyl trimethoxysilane, IPTMS.

Copolymerizations of epsilon-caprolactone and glycolide-a comparison of tin(II)octanoate and bismuth(III)subsalicylate as initiators.

Copolymerizations of epsilon-caprolactone (epsilonCL) and glycolide (GL) were conducted in bulk at 120 degrees C with variation of the reaction time. Either Sn(II) 2-ethylhexanoate (SnOct(2)) or bismuth(III)subsalicylate (BiSS) were used as initiators combined with tetra(ethylene glycol) as co-initiator. The resulting copolyesters were analyzed by (1)H and (13)C NMR spectroscopy with regard to the total molar composition and to the sequence of the comonomers.

Multiblock copolymers of L-lactide and trimethylene carbonate.

Sequential copolymerizations of trimethylene carbonate (TMC) and l-lactide (LLA) were performed with 2,2-dibutyl-2-stanna-1,3-oxepane as a bifunctional cyclic initiator. The block lengths were varied via the monomer/initiator and via the TMC/l-lactide ratio. The cyclic triblock copolymers were transformed in situ into multiblock copolymers by ring-opening polycondensation with sebacoyl chloride.

Telechelic and star-shaped poly(L-lactide)s by means of bismuth(III) acetate as initiator.

L-lactide was polymerized as concentrated solution in chlorobenzene with Bi(OAc)3 as initiator. When tetra(ethylene glycol) was added as co-initiator (CoI), telechelic polylactides having two CH-OH end groups were obtained. With 1,1,1-tri(hydroxy methyl)propane (THMP) as co-initiator, three-armed stars having three CH-OH end groups were formed.

Polylactones 57. Biodegradable networks based on A-B-A triblock segments containing poly(ethylene glycol)s-syntheses and drug release properties.

Condensation of Bu(2)Sn(OMe)(2) with poly(ethylene glycol)s yielded macrocyclic tin alkoxides which were, in turn, used as cyclic initiators for the ring-expansion polymerization of epsilon-caprolactone, D,L-lactide, or trimethylene carbonate. The resulting cyclic triblock copolymers were in situ cross-linked with trimesoyl chloride. The lengths of the A-B-A triblock segments were varied via the monomer-initiator ratio (M/I) or via the lengths of the poly(ethylene glycol)s.

Polylactones. 59. Biodegradable networks via ring-expansion polymerization of lactones and lactides with a spirocyclic tin initiator.

Spirocyclic tin initiators were prepared by condensation of commercial hydroxyethylated pentaerythritol with Bu(2)Sn(OMe)(2). These tin-containing spirocycles served as initiators for the ring-expansion polymerization of epsilon-caprolactone, beta-D,L-butyrolactone or D,L-lactide. The in situ polycondensation of these expanded spirocycles with terephthaloyl chloride or sebacoyl chloride yielded the desired biodegradable networks with elimination of the Bu(2)Sn group.