Effects of composition and sequential structure on thermal properties for copolymer of 3-hydroxybutyrate and lactate units

Copolymers of (R)-3-hydroxybutyrate (3HB) and (R)-lactate ((R)-2-hydroxypropionate: 2HP) units were synthesized by polycondensation reaction from methyl esters of 3HB and 2HP in the presence of titanium-based catalyst. Mixing of two monomers from the beginning of polymerization yielded random copolymers of 3HB and 2HP units. On the other hand, by controlling the time of mixing of two monomers, copolymers with blocking tendency were obtained. The structure and thermal properties of the obtained copolymers were characterized by ¹H and ¹³C NMR, X-ray diffraction, differential scanning calorimetry, and optical microscopy. Glass-transition temperature of the copolymers was mainly governed by the copolymer composition, and the values varied linearly with the composition. In contrast, the melting temperature was strongly depending on the sequential length of crystallizable monomeric unit, and the values were in inverse proportion to the number-averaged sequential length of crystallizable monomeric unit. The crystallinity of the copolymer samples was affected by both the composition and sequential length of crystallizable monomeric unit. The finding is valuable for design of copolymer molecules with desirable thermal properties by controlling both the copolymer composition and sequential structure.     

Correlation of Composition and DP of Some ThreeComponent Phenolic Block Copolymers with Their Titration Curves in Nonaqueous Media

Some three-component phenolic block copolymers have been prepared from the following three monomeric units: p-amino-phenol, p-chlorophenol, and p-creso1. Homopolymerization of these monomers has been done with formaldehyde in the presence of acid catalyst. The homopolymer samples were then condensed together with stoichiometric quantities of formaldehyde and acid catalyst. Several samples of the copolymers were also prepared by changing the composition of the feed during homopolymerization. Composition, DP, and the average number of a particular monomeric uhit in a block of a copolymer chain has been deduced from electrometric titration curves of the copolymers in nonaqueous media.

Simultaneous copolymerization of three different monomer species may give rise to a copolymer whose composition will depend on the relative reactivity of the monomers. In normal copolymerization the different monomers alternate in the chain either in a more or less regular or in a completely random manner. Some preliminary investigations on a few three-component random phenolic copolymers revealed that composition, DP, and dissociation behavior of such systems could be evaluated by electrometric titration techniques in nonaqueous media [1]. Since three-component copolymers as such are quite complex, it was therefore considered of interest to see whether such simple techniques could be used for getting information about these copolymers prepared under various conditions. Keeping this fact in view, block copolymers involving the following three monomeric units have been prepared: p-aminophenol (PAP), p-chlorophenol (PClP), and p-cresol (PC). Block copolymers have been prepared by combining the homopolymer chains of the three monomers with the aid of functional groups and formaldehyde. The feed composition of the homopolymers has also been varied to change the size of the blocks. The characteristic feature of these three-component copolymers is the presence of a phenolic OH group in each of its repeating units and the presence of -NH₂ and Cl groups as structural substi-tuents in some of the repeating units. One can thus deduce the composition of the copolymers from the quantitative estimation of C1 and -NHz groups. An attempt has been made in this paper to correlate composition, DP, size of some of the blocks in the copolymer chains, intramolecular hydrogen bonding, etc. with the features of electro-metric titration curves of the copolymers in nonaqueous media.     

Terpolymerization of maleic anhydride with vinyl monomers

The relative reactivity of vinyl monomers characterized by electron donor and electron acceptor properties in free radical terpolymerization with maleic anhydride has been compared on the basis of product composition analysis. Terpolymers containing ca. 50 mol % of maleic anhydride were obtained in systems containing two electron donor monomers and the relative reactivity of them increases in the following order: 1-hexene < propylene ≈ isobutylene < styrene < isoprene < 1,3-butadiene. In systems consisting of an electron donor monomer and two electron acceptor monomers (i.e., maleic anhydride and an acrylic monomer), the composition of the terpolymers formed depends essentially on the resonance stabilization of the electron donor monomer. With a rise of their resonance stabilization, the content of acrylic monomeric units decreases and the share of alternating sequences of the electron donor and maleic anhydride monomeric units increases. It was found that the relative reactivity of maleic anhydride in all such systems is much greater than that predicted on the basis of reactivity ratios determined in binary systems. The relative reactivity of the studied acrylic monomers decreases in the order: methyl methacrylate > methyl acrylate > acrylonitrile. In the presence of catalytic amounts of ZnCl₂ the content of acrylic monomeric units clearly increases in the products obtained, mainly as a result of homopropagation. The results obtained are discussed in terms of the classical mechanism of propagation and the complex participation model.     

关于聚皂共聚物组成的核磁共振研究

烷基甲基二烯丙基溴化铵共聚物是一种新型疏水改性的聚皂,应用多种核磁共振分析技术对其结构和共单体的组成进行了定量的讨论.研究结果表明,在测定化学结构和性质上比较接近的共单体组成时,核磁共振方法是一种有效的工具.     

Orientation and relaxation in uniaxially stretched styrene-co-methyl methacrylate random copolymers

Orientation and relaxation behavior in uniaxially stretched styrene-co-methyl methacrylate random copolymers was investigated. When compared at a reference temperature T = T_g + constant, orientation of methyl methacrylate units (MMA) decreases while styrene units orientation increases with a decrease in the styrene percentage. This behavior can be related to intermolecular interactions between MMA units and to the stiffness of styrene-MMA units, which do not undergo conformational changes upon stretching. Both monomer units relax the same in a given copolymer and chain relaxation increases when the styrene percentage increases. Orientation relaxation of styrene and MMA units can be reduced to two general relaxation master curves whatever the blend composition, when the results are compared at same monomeric friction coefficient. © 1994 John Wiley & Sons, Inc.     

A simple HPLC-MS method for the quantitative determination of the composition of bacterial medium chain-length polyhydroxyalkanoates

Bacterial poly(hydroxyalkanoates) (PHAs) vary in the composition of their monomeric units. Besides saturated side-chains, unsaturated ones can also be found. The latter leads to unwanted by-products (THF ester, secondary alcohols) during acidic cleavage of the polymer backbone in the conventional analytical assays. To prevent these problems, we developed a new method for the reductive depolymerization of medium chain-length PHAs, leading to monomeric diols that can be separated and quantified by HPLC/MS. Reduction is performed at room temperature with lithium aluminum hydride within 5-15 min. The new method is faster and simpler than the previous ones and is quantitative. The results are consistent with the ones obtained by quantitative (1)H NMR.     

Reduction of the hydrodynamic resistance to turbulent water flow with copolymers of acrylamide,acrylonitrile, and 2-acrylamido-2-methylpropanesulfonic acid

The influence of the ratio of acrylamide, acrylonitrile, and 2-acrylamido-2-methylpropanesulfonic acid monomeric units in the terpolymer on its molecular-mass characteristics was studied. The influence of the copolymer composition on its resistance to the action of CaCl₂ was determined. The capability of the synthesized terpolymers to reduce the hydrodynamic resistance to a liquid flow was evaluated with a laboratory capillary turbulent rheometer. The hydrodynamic resistance reduction effect depends on the molecular-mass characteristics of the terpolymers.     

Quantitative evaluation of photodegradation and racemization of poly(l-lactic acid) under UV-C irradiation

To obtain details of poly(l-lactic acid) (PLLA) photodegradation behavior, PLLA films were irradiated by UV-C light (λ = 253.7 nm) to directly excite carbonyl groups, resulting in a rapid decrease in the molecular weight accompanying a gradual decrease in the optical purity of monomeric units in the chains. The racemization during the photodegradation was first detected as a result of the chain scission by irradiation. From quantitative analyses of the molecular weight and the monomeric unit composition, it was found that the chain scission ratio and the d-lactate unit ratio increased in parallel during the irradiation, suggesting that approximately one d-lactate unit formed for every chain scission. From a mechanistic consideration, the racemization equilibrium was proposed to occur at both carboxyl and hydroxyl chain ends.     

Formation, 3D Structure,and Strength Characteristics of Interpenetrating Polymer Networks Based on Cold-Curing Oligomer-Oligomer Systems

The kinetics of low-temperature formation of interpenetrating polymer networks based on modified epoxy resins and copolymers of unsaturated oligoester resin with oligoether acrylates were studied in relation to the composition of the initial mixture. The influence of the parameters of the three-dimensional structure (cross-linking density, content of lattice points, number of monomeric units in cross-links) on the strength characteristics of the resulting polymer networks was examined, and the best conditions were found for preparing shockproof materials.     

Anionic copolymerization of 2,3,4,5,6-pentafluorostyrene and divinylbenzene

Anionic copolymerizations of 2,3,4,5,6-pentafluorostyrene (PFS) with 1,3-divinylbenzene (m-DVB) and 1,4-divinylbenzene (p-DVB) were performed by using lithium diisopropylamide as an initiator in order to synthesize the fluorine-containing linear polymer with pendant vinyl groups. The products were soluble copolymers possessing both PFS and DVB monomeric units, and the DVB monomeric unit in copolymer had pendant vinyl group. This copolymerization reaction took a much longer time than that of styrene with DVB. The copolymerization parameter of this system was examined from copolymer composition curves. In this system, m-DVB was found to be more reactive than p-DVB. The reactivity of copolymerization was largely influenced by the reactivity of active species. © 1993 John Wiley & Sons, Inc.     

Styrene-methyl acrylate copolymers and acrylate homopolymers in solution

Molecular weight determinations by light scattering and osmometry and intrinsic viscosity measurements were made in various solvents on fractions of styrene–methyl acrylate copolymers with different compositions and on acrylate homopolymers prepared by free-radical reaction. Relations between intrinsic viscosity [η] and molecular weight M thus established are compared with those reported by other authors. 2-Methylcyclohexanol was found to be a theta solvent for the copolymers and both parent homopolymers, and isoamyl acetate was a theta solvent for poly(methyl acrylate). From theta point viscosity data obtained with these solvents, unperturbed chain dimensions were estimated. The results are compared with the unperturbed dimensions estimated from the [η]–M relations obtained in good solvents. On the basis of the experimental data it was found that the unperturbed dimension depends linearly on the copolymer composition, in contrast to the case of styrene–methyl methacrylate copolymers. Composition dependences of the theta temperature and of the parameter describing the long-range interactions between nonadjacent segments in polymer chains were investigated. The result implies that long-range interactions between monomeric units never disappear even when those between the same monomeric units vanish. The Huggins constant for copolymer is discussed in terms of the excluded volume variable.     

Molar Mass and Structural Characteristics of Poly[(lactide-co-(aspartic acid)] Block Copolymers

Summary: We report on various synthetic procedures for the preparation of biodegradable and biocompatible poly(lactide-co-aspartic acid) block copolymers based on natural monomeric units – lactic acid and aspartic acid. Multiblock poly(lactide-co-aspartic acid) copolymers of different comonomer composition were synthesized by heating a mixture of L-aspartic acid and L,L-lactide in melt without the addition of any catalyst or solvent and with further alkaline hydrolysis of the cyclic succinimide rings to aspartic acid units. Diblock poly(lactide-co-aspartic acid) copolymers with different block lengths were prepared by copolymerization of amino terminated poly(β-benzyl-L-aspartate) homopolymer and L,L-lactide with subsequent deprotection of the benzyl protected carboxyl group by hydrogenolysis. The differences in the structure, composition, molar mass characteristics, and water-solubility of the synthesized multiblock and diblock poly(lactide-co-aspartic acid) copolymers are discussed.     

Influence of the composition of acrylamide–acrylonitrile–2-acrylamido-2-methylpropanesulfonic acid terpolymer on its resistance to high temperatures and salts

The influence of the ratio of the acrylamide, acrylonitrile, and 2-acrylamido-2-methylpropanesulfonic acid monomeric units in the terpolymer on its resistance to elevated temperatures and sensitivity to calcium salts was studied. The influence of the terpolymer composition on the chemical transformations occurring under the conditions of thermal and hydrothermal treatment was studied by TGA and IR spectroscopy. The degree of hydrolysis of the terpolymers influences their resistance to CaCl₂. The resistance of the terpolymers to CaCl₂ additions at their concentrations of up to 7 wt % is preserved at the content of 2-acrylamido-2-methylpropanesulfonic acid units higher than 20 mol %. The revealed features allow optimization of the structure of polymer systems used in drilling lubricants.     

Sequential analysis of polyesters by stepwise chemical degradation: Application to oligo and poly(alkylene terephthalate)s

A specifically tailored reagent was used to label the hydroxyl end groups of poly(ethylene/butylene terephthalate), which is synthesized by transesterification of the corresponding homopolymers. The terminal monomeric unit was then eliminated, together with the attached label, as a low molecular-weight cyclic compound. Specially synthesized reference compounds containing ethylene terephthalate and butylene terephthalate units enabled the terminal monomeric unit to be identified as butylene terephthalate, although the copolymer showed an otherwise random distribution. Despite the practical and theoretical reasons that restrict this sequential degradation to the last monomeric unit for polymers, the principle can be used in a wider range of applications if combined with selective degradation and separation by means of HPLC, which results in chemically uniform oligomers. The ultimate and penultimate monomeric units of ethylene/butylene terephthalate type oligomers can be identified using the cyclodegradation procedure described here. © 1993 John Wiley & Sons, Inc.     

Role of the polymer microstructure in the thermoreversible gelation of poly(vinyl chloride)

Gels of polyvinylchloride (PVC) and PVC copolymers of different microstructure and molar composition, were prepared in a series of diester-like solvents. The viscoelastic properties of these gels were evaluated as a function of temperature and the molecular structure was studied by small-angle neutron scattering. The degrees of proton association in the polymer solutions were determined by ¹H NMR spectroscopy by measuring the intensity of proton bands of CH₂ monomeric units. The body of experimental data shows clearly that there is a straight relation between molecular structure, viscoelastic properties of the gel, degree of polymer-solvent interaction and polymer microstructure.     

Engineering reverse saturable absorbers for desired wavelengths

A variety of applications exist for reverse saturable absorbers (RSAs) in laser science (RSAs are substances whose excited-state absorption cross section is larger than their ground-state absorption cross section at a given wavelength and possess a number of other properties). We propose an approach to designing RSAs at a desired wavelength by construction of dimers of dye molecules which absorb near the wavelength of interest. The dimer ground-state absorption is to a state in which the excitation is spread over both monomeric units and the excited-state absorption commences from this state to the doubly excited electronic state in which both monomeric units are excited.     

Circularly Polarized Luminescence in Supramolecular Assemblies of Chiral Bichromophoric Perylene Bisimides

Chiral bichromophoric perylene bisimides are demonstrated as active materials of circularly polarized emission. The bichromophoric system exhibited circularly polarized luminescence with dissymmetry factors typical of that of similar organic chiral chromophoric systems in the monomeric state. Variation in solvent composition led to the formation of stably soluble helical aggregates through intermolecular interactions. A large enhancement in the dissymmetry of circularly polarized luminescence was exhibited by the aggregated structures both in the solution and solid states. The sum of excitonic couplings between the individual chromophoric units in the self‐assembled state results in relatively large dissymmetry in the circularly polarized luminescence, thereby giving rise to enhanced dissymmetry factors for the aggregated structures. The spacer between chiral center and chromophoric units played a crucial role in the effective enhancement of chiroptical properties in the self‐assembled structures. These materials might provide opportunities for the design of a new class of functional bichromophoric organic nanoarchitectures that can find potential applications in the field of chiroptical memory and light‐emitting devices based on supramolecular electronics.     

Isotopically pure uniform polymers: The final step toward true uniformity in macromolecules

Computer‐based calculations were used to simulate the mass spectra for a number of uniform macromolecules having fixed, well‐defined chain lengths. The presence of naturally occurring carbon, hydrogen, oxygen, and halogen isotopes introduced significant levels of mass heterogeneity into these systems. For a given polymer, mass variability was demonstrated to be a function of both the elemental composition and degree of polymerization of the polymer chain. In many cases, these natural variations in mass exceeded the molecular weight of one or more monomeric repeat units along the polymer backbone, effectively blurring the mass distinction between uniform polymer constructs formed from N and N+1 repeat units. The significance of isotopic diversity and its potential impact on the synthesis and physiochemical properties of highly uniform macromolecules is also discussed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 923–935, 2002     

Interaction between oppositely charged polyelectrolytes in aqueous solution

Oppositely charged polyelectrolytes interact in solution, forming polyelectrolyte complexes, which often appear as gel-like precipitates. This kind of complex formation was studied by means of calorimetric and rheological measurements. The enthalpy effects, though being fairly small, give some information about the binding strength of counterions to the macroion. We studied the system poly(p-styrene sulfonate)/poly(trimethylammonium-2-ethyl methacrylate) (PSS-PTMA), varying systematically the low molar mass counterions of PSS. In every case, the maximum of enthalpy was found around a 1:1 (mol:mol monomer units) composition of the complexes, with the shape of enthalpy versus composition-curve indicating a stoichiometric interaction. The maximum enthalpy decreased with increasing atomic mass of the counterion when the alkaline metal salts of PSS were used and no change was made on the side of the cationic polyelectrolyte. The salts of the alkaline earth metals gave a distinctly higher enthalpy. On the contrary, viscosity measurements showed a very broad minimum as a function of composition, indicating that the formation of non-stoichiometric complexes is also occurring. The conclusion of these observations is that the complex formation is stoichiometric with respect to the monomeric units, but not necessarily stoichiometric with respect to the entire macromolecules.     

Block copolymers derived from azobiscyanopentanoic acid. IV. Synthesis of a polyamide–polystyrene block copolymer

Polyamides 6.10 and 6.6 (PA^* 6.10 and 6.6) containing small amounts of ? N?N? units in the main chains were prepared by interfacial polycondensation between hexamethylenediamine and sebacoyl chloride or adipoyl chloride with addition of azobiscyanopentanoyl chloride. Polyamide–polystyrene block copolymers (PA-b-PSt) were then prepared by decomposition of the ? N?N? units of PA^*, initiating radical polymerization of styrene in m-cresol. The average PA block length of PA-b-PSt thus formed was longer than that expected from the initially present PA segments between the ? N?N? units. This is probably due to recombination of PA radicals whose initiation efficiency is as low as 15%. The PSt blocks also had higher molecular weight (7000–79,000) in comparison with homopolystyrene produced from monomeric azobiscyanopentanoic acid used as an initiator due to higher viscosity of polymerization system. Variation of intrinsic viscosity and turbidimetric titration behavior along with the change in composition were also discussed.