Determining and correcting "moment bias" in gradient polymer elution chromatography

Gradient polymer elution chromatography (GPEC) is rapidly becoming the analytical method of choice for determining the chemical composition distribution (CCD) of synthetic polymers. GPEC can be performed in traditional (strict precipitation-redissolution mechanism) or interactive (normal- and reversed-phase) modes, and results may be qualitative, semi-quantitative, or fully quantitative. Quantitative approaches have thus far relied on colligative or end group techniques for determining the values of standards used in constructing the GPEC calibration curve. While the values obtained from said methods are number-averages, they are assigned to the peak apexes of the standards (i.e. assigned as peak averages). This creates a determinate error in the quantitation, referred to herein as "moment bias". In this paper we determine moment bias for a series of styrene-acrylonitrile (SAN) copolymers, where the distribution and averages of the AN% have been measured using normal-phase (NP) GPEC. We also correct for the effect via statistical treatment of the chromatographic data.     

Separation of poly-3-hydroxyvalerate-co-3-hydroxybutyrate through gradient polymer elution chromatography

Polyhydroxyalkanoates are biodegradable polyesters produced by bacteria that can have a wide distribution in molecular weight, composition of monomers, and functionalities. This large distribution often leads to unpredictable physical properties making commercial applications challenging. To improve polymer homogeneity and obtain samples with a clear set of physical characteristics, poly-3-hydroxyvalerate-co-3-hydroxybutyrate copolymers were fractionated using gradient polymer elution chromatography (GPEC) as opposed to extensively used bulk fractionation. Separation was achieved using a reversed-phase column with chloroform and ethanol as the solvent and non-solvent, respectively. A separation was also conducted on a normal-phase column to compare elution patterns between columns of varied polarity. The fractions were analyzed using Size Exclusion Chromatography (SEC) and NMR to determine the percentage of 3-hydroxyvalerate in the copolymer as well as its molecular weight. It was found that as the percentage of "good" solvent was increased in the mobile phase, the polymers eluted with decreasing percentage of 3-hydroxyvalerate and increasing molecular weight which indicates the importance of precipitation/redissolution in the separation. The elution pattern of the polymer remained unchanged when using both a normal- and reversed-phase column which also illustrates the dominance of precipitation/redissolution in GPEC of polyhydroxyalkanoates. As such, GPEC is shown to be an excellent choice to provide polyhydroxyalkanoate samples with a narrower distribution in composition than the original bulk copolymer sample.     

Morphology control in polymeric multiphase systems with block copolymers and structured latexes

Some application possibilities of block copolymers for the morphology control in polymeric multiphase systems are reviewed. The microdomain formation of block copolymers in the solid state is illustrated in the case of functionalized block copolymers and for interpolymer complexes. The preparation of “hairy latex” by emulsion polymerization in the presence of hydrophilic-hydrophobic block copolymers is shown in connection with their applications in the controlled agglomeration process of latexes and for the preparation of polymer particles having microvoids. The surface activity of block copolymers in polymeric oil-in-oil systems is illustrated for silicone oil filled polymers. These materials have a low kinetic friction coefficient and act as reservoir systems with the lubricant incorporated in the polymer matrix.     

A qualitative study to the influence of molar mass on retention in gradient polymer elution chromatography (GPEC)

Gradient Polymer Elution Chromatography (GPEC) appears to be a powerful method for the determination of chemical composition distributions (CCD) of high molar mass copolymers. In order to perform these experiments, molar mass dependence of the retention time must be minimized. It is shown that variation in solvent and non-solvent strength is a powerful method for adjusting the molar mass dependence. There appears to be a relation between molar mass dependence of retention behavior in GPEC on one hand and solubility under critical solvent conditions on the other hand. This phenomenon can be explained qualitatively from the important precipitation/redissolution mechanism in GPEC.     

Evaluation of polymers based on a silicone backbone as pseudostationary phases for electrokinetic chromatography.

The feasibility of polymeric phases based on a silicone polymer backbone as pseudostationary phases for electrokinetic chromatography has been investigated. Silicone phases were studied because of the range of chemistries that could be developed based on these backbones, and because successful development of silicone phases would make it possible to employ much of the stationary phase chemistry developed in the past thirty years. Three silicone polymer structures have been investigated, but only one had sufficient aqueous solubility to permit application in electrokinetic chromatography. This phase was characterized by a variety of methods and was shown to be a mixture of partially hydrolyzed poly(bis-(3-cyanopropyl) siloxanes. When employed as a pseudostationary phase, this material provided selective and efficient separations. The electrophoretic mobility of the silicone polymer is greater than that of sodium dodecyl sulfate (SDS) micelles and poly(sodium 10-undecenylsulfate), providing an extended migration time range. A striking characteristic of the polymer is that the electrophoretic mobility is greater than typical electroosmotic mobilities. The chemical selectivity of the phase is significantly different from that of SDS micelles or poly(sodium 10-undecenylsulfate). The silicone phase is a more cohesive, basic and polar phase than SDS micelles. In buffers modified with a high concentration of organic solvents, the chromatographic properties of the silicone polymer are inferior to those of the poly(sodium 10-undecenylsulfate). The greatest limitation of silicone polymers for this application appears to be limited aqueous solubility, which will make it difficult to realize a family of such polymers with different chemical selectivities.     

Preparation and Properties of Benzylsulfonyl-Containing Silicone Copolymers via Ring-opening Copolymerization of Macroheterocyclosiloxane and Cyclosiloxane

Ring-opening copolymerization (ROCP) of benzylsulfonyl macroheterocyclosiloxane (BSM) and five different cyclosiloxanes was systematically investigated. A general approach for the synthesis of benzylsulfonyl-containing silicone copolymers with various substituents, including methyl, vinyl, ethyl, and phenyl, was developed herein. A series of copolymers with variable incorporation (from 6 % to 82 %) of BSM were obtained by modifying the comonomer feed ratio and using KOH as the catalyst in a mixed solvent of dimethylformamide and toluene. The obtained copolymers exhibited various composition-dependent properties and unique viscoelasticity. Notably, the surface and fluorescent characteristics as well as the glass transition temperatures of the copolymers could be tailored by varying the amount of BSM. Unlike typical sulfone-containing polymers, such as poly(olefin sulfone)s, the prepared copolymers displayed excellent thermal and hydrolytic stability. The universal strategy developed in the present study provides a platform for the design of innovative silicone copolymers with adjustable structures and performance.     

Behavior of polymers at surfaces and interfaces as observed in simulated systems

Cooperative motion algorithm (CMA) is used to simulate polymer chains in three types of dense systems reflecting special cases of polymer behavior at surfaces and interfaces: polymer brushes with variable grafting density in the range 0–1, both in a neutral solvent and in a polymer melt, layers of end-functionalized polymers between parallel end-adsorbing walls, and copolymers of various distributions of comonomer units (random, block and gradient copolymers) at interfaces with noncompatible polymers.     

Poly(N-acylethylenimine) copolymers containing pendant pentamethyldisiloxanyl groups. III. Surface properties and abhesion

The surface properties and abhesion of both N/Si and U/Si series of random copolymers were studied by contact angle and peel strength measurements. When these copolymers are coated on clean glass slides, the contact angles of water on the polymer films are over 105° for copolymers with less than 50 mol % of Si , and 98-104° for those with more than 50 mol % of Si. All the polymers have similar critical surface energies, 21 dyn/cm (from hydrocarbon probes) and 20 dyn/cm (from EtOH/H₂O probes), within the experimental error. This demonstrates that the amide groups in the polymer backbones are buried and all the polymers have methyl surfaces. The copolymers with less than 50 mol % Si (for N/Si copolymers) or 20 mol % (for U/Si copolymers) are stable and show good abhesive properties toward Scotch magic tape at or below 50°C. The peel strengths of Scotch magic tape with the copolymer coated slides rise dramatically as the annealing temperatures approach to the melting points of the polymers.     

开环易位聚合合成瓶刷聚合物

瓶刷聚合物是一类具有独特侧链结构的梳形聚合物。功能性瓶刷聚合物在光子晶体、表面活性剂、医药载体、防污涂层以及智能材料等领域具有良好的应用价值。通过开环易位聚合合成瓶刷聚合物的方法具有合成步骤简单、聚合物接枝密度高和侧链组成均一等优点,在控制聚合物组成、分子量和分散性等方面具有显著优势。本文基于开环易位聚合,简述了合成瓶刷均聚物以及嵌段型、混合型和核-壳型三种类型的瓶刷共聚物的方法,并介绍了合成精确结构的瓶刷聚合物的新进展。     

Synthesis of diblock copolymers containing both polydiene and polyalcohol blocks

A wide range of functional diblock copolymers containing both functional polymer and hydrocarbon polymer, have been prepared by the combination of anionic polymerization and borane chemistry. The distinctive hydroboration reactivity between various polydienes enables us to selectively functionalize one polydiene segment in diblock copolymers which contain two different polydiene segments. In turn, the hydroborated polymers are valuable intermediate compounds which can be converted to a whole family of functional polymers with a variety of other functionalities under mild reaction conditions. The hydroxylated diblock copolymer is used as an example to demonstrate the chemistry. The two-phase nature of these copolymers is also shown by the observation of two distinctive glass transition temperatures associated with the individual polymer segments.     

Structure-Property Relationships in Rubber-Modified Styrenic Polymers

Styrenic polymers and copolymers are often impact modified with rubber particles. The efficiency of rubber toughening depends mainly on the size of the rubber particles and the degree of cross-linking. The deformation rate, the temperature, the orientation of the polymer molecules and the efficiency of rubber grafting also influence rubber toughening. It is thought that on impact, cavitation inside the rubber particles occurs which reduces the detrimental dilatational stress in the bulk polymer without forming cracks in the brittle matrix or at the rubber-matrix interface. Crazing and shearing are facilitated if the rubber particles can easily cavitate. This can be achieved by either avoiding too much cross-linking or by adding oil (silicone oil in the case of ABS) into the rubber particles, which acts as nuclei for void formation. An electron spectroscopic imaging method is described which allows visualizing the location of the oil. Already after cooling silicone oil modified ABS samples down to liquid nitrogen temperature rubber cavitation is observed. This cavitation is caused by the thermal stress developing due to the differences in thermal expansion coefficient between the rubber phase and the SAN-matrix and is facilitated by silicone oil. Voiding also leads to an increase of light scattering, which can be detected by an optical microscope using dark field illumination.     

A series of poly[N-(2-hydroxypropyl)methacrylamide] copolymers with anthracene-derived fluorophores showing aggregation-induced emission properties for bioimaging

A series of new poly[N-(2-hydroxypropyl)methacrylamide]-based amphiphilic copolymers were synthesized through a radical copolymerization of a monomeric/hydrophobic fluorophore possessing aggregation-induced emission (AIE) property with N-(2-hydroxypropyl)methacrylamide. Photophysical properties were investigated using UV-Vis absorbance and fluorescence spectrophotometry. Influences of the polymer structures with different molar ratios of the AIE fluorophores on their photophysical properties were studied. Results show that the AIE fluorophores aggregate in the cores of the micelles formed from the amphiphilic random copolymers and polymers with more hydrophobic AIE fluorophores facilitate stronger aggregations of the AIE segments to obtain higher quantum efficiencies. The polymers reported herein have good water solubility, enabling the application of hydrophobic AIE materials in biological conditions. The polymers were endocytosed by two experimental cell lines, human brain glioblastoma U87MG cells and human esophagus premalignant CP-A, with a distribution into the cytoplasm. The polymers are non-cytotoxic to the two cell lines at a polymer concentration of 1 mg/mL.     

TUNED MECHANICAL PROPERTIES ACHIEVED BY VARYING POLYMER STRUCTURE — KNOWLEDGE THAT GENERATES NEW MATERIALS FOR TISSUE ENGINEERING

By changing both the monomer composition and the polymer structure, we have varied the mechanical properties of resorbable polymers. The polymers were synthesized by ring-opening polymerization using L-lactide （LLA）, ε-caprolactone （εCL）, trimethylene carbonate （TMC） and 1,5-dioxepan-2-one （DXO） as monomers. Well-defined triblock copolymers, microblock copolymers and networks have been evaluated, and comparisons between them show that it is possible to tune the mechanical properties. Triblock copolymers with an amorphous middle block of poly（1,5-dioxepan-2- one） （PDXO） and semi-crystalline end-blocks of poly（ε-caprolactone） （PCL） were stronger and had a higher strain at break than triblock copolymers with poly（L-lactide） （PLLA） as end-blocks. Polymers with both DXO and TMC in the amorphous middle-block and PLLA as end-blocks showed a lower stress at break, but the material gained elasticity, a property which is very valuable in tissue engineering. Mechanical properties of networks, synthesized by a novel method, containing PDXO and PCL are also presented. Although it is difficult to compare them with the uncross-linked polymers, this is an additional way to modify and widen the properties.     

Theoretical study of cooperativity in multivalent polymers for colloidal stabilization

Multivalent polymers, i.e., copolymers with multiple binding sites, have been proposed recently for stabilization of fusogentic liposomes and other liposomal colloids useful for drug delivery. The performance of such polymers critically depends on their molecular architecture, in particular the strength and frequency of surface anchoring sites along the backbone of a highly soluble polymer. In this work, we investigate the adsorption and surface forces due to multivalent polymers based on coarse-grained polymer models. We find that for W-type polymers that form dangling tails when all anchoring segments are attached to a surface, increasing the chain length at fixed polymer composition leads to a stronger repulsive barrier in the polymer-mediated surface forces thereby increasing the ability of the polymer to stabilize colloidal particles. This prediction conforms to an earlier experiment indicating that increasing the number of hydrophobic anchors along poly(ethylene glycol) polymers results in the cooperative behavior for both surface adsorption and steric stabilization. For M-type multivalent polymers that have weakly anchoring sites placed at the ends, however, addition of binding sites at fixed polymer composition could lead to negative cooperativity, i.e., the more binding sites, the less the amount of adsorption or the weaker the ability of surface protection. The theory also predicts that polymers with two anchoring sites (e.g., telechelic copolymers) are most efficient for colloidal stabilization.     

甲壳型液晶高分子研究进展与展望

简要介绍了甲壳型液晶高分子的模型理论, 概述了当前国内外对甲壳型液晶高分子设计、 液晶相态、 性质及基于甲壳型液晶高分子的嵌段共聚物体系的设计和自组装性质等研究进展, 展望了今后的研究方向.     

Self-organization behavior of methacrylate-based amphiphilic di- and triblock copolymers

Amphiphilic di- and triblock copolymers having different hydrophilic-to-hydrophobic block length ratio were synthesized using ATRP. The self-assembly behavior of these AB and ABA block copolymers consisting of poly(n-butyl methacrylate) (B) and poly(2,2-(dimethylaminoethyl methacrylate) (A) was investigated using a combination of dynamic light scattering, negative-stain transmission electron microscopy, cryoelectron microscopy, and atomic force microscopy. Two populations of self-organized structures in aqueous solution, micelles and compound micelles, were detected for diblock copolymers. Triblock copolymers assembled into vesicular structures of uniform sizes. Furthermore it was found that these vesicles tended to compensate the high curvature by additional organization of the polymer chains outside of the membrane. The chain hydrophilicity of the polymers appeared to have a critical impact on the self-assembly response toward temperature change. The self-reorganization of the polymers at different temperatures is discussed.     

Block copolymers of styrene,isoprene, and ethylene oxide prepared by anionic polymerization. I. Synthesis and characterization

Anionic polymerization has been used as a technique for the synthesis of five-block copolymers of polystyrene (PS), polyisoprene (PI), and poly(ethylene oxide) (PEO). Two types of such polymers, PEO-PI-PS-PI-PEO and PEO-PS-PI-PS-PEO with varying PEO block length, have been prepared, using potassium naphthalene as the initiator and tetrahydrofuran as the solvent. The polymers were purified by extraction with ethyl acetate, diethyl ether, and water. After the addition of each monomer, a sample from the living polymer solution was taken and analyzed by spectroscopy (infared (IR) and proton magnetic resonance (PMR)), osmometry, and gel-permeation chromatography (GPC) to obtain information about composition, molecular weight and molecular weight distribution of the intermediate polymers. The five-block copolymers have also been characterized by the same techniques and by elemental analysis.     

Tuning the molecular properties of polybenzimidazole by copolymerization

In the present work, a series of novel random polybenzimidazole (PBI) copolymers consisting of m- and p-phenylene linkages are synthesized from various stoichiometric mixtures of isophthalic acid (IPA) and terephthalic acid (TPA) with 3,3',4,4'-tetraaminobiphenyl (TAB) by solution copolycondensation in polyphosphoric acid (PPA). The resulting copolymers are characterized by different techniques to obtain their molecular properties parameters. The monomer concentration in the polymerization plays an important role in controlling the molecular weight of the polymer. Surprisingly, a simple change in the dicarboxylic acid architecture from meta (IPA) to para (TPA) increases the molecular weight of the copolymers, which is maximum for the para homopolymer. The low solubility of TPA in PPA is found to be the dominating factor for obtaining the higher molecular weight polymer in the case of the para structure. FT-IR study shows that the introduction of the para structure enhances the conjugation along the polymer chain. The positive deviation of the copolymer composition from the feed ratio is due to the higher reactivity ratio of TPA than IPA, which is obtained from proton NMR studies. The incorporation of the para structure in the chain enhances the thermal stability of the polymers. The para homopolymer shows 59 degrees C lower glass transition temperature compare to the meta homopolymer indicating enhancement of the flexibility of the polymer chain due the introduction of the p-phenylene linkage in the backbone. The T(g) of the copolymers shows both positive and negative deviation from the expected T(g) calculated by the Fox equation. The enhanced conjugation of the polymer chains also influences the photophysical properties of the polymers in solution. All the PBI polymers exhibit strong fluorescence in dimethylacetamide solution. As expected, that all the polymers are amorphous in nature reveals that the copolymerization does not influence the packing characteristics of the PBI chains.     

Photoinitiating systems and their use in polymer synthesis

This paper on recent developments in the use of photoinitiating systems in polymer synthesis concentrates on: (i) the possiblity of controlled//living polymerization by photopolymerization, (ii) major photoinitiating systems for both cationic and radical polymerization and (iii) preparation of block copolymers and functional polymers by photoinduced processes. Much progress has been made in the past ten years in preparation of block copolymers by photoinduced reactions of either chromophoric groups incorporated into polymers or low‐molecular‐weight compounds with suitable functional groups present in polymer chains.     

Enhancement of thermoelectric properties of D-A conjugated polymer through constructing random copolymers with more electronic donors

Developing new D-A conjugated polymer system for thermoelectric (TE) application is highly desirable. Herein, a series of random copolymers by incorporating 3,4-ethylenedioxythiophene (EDOT) electron rich units into a diketopyrrolopyrrole (DPP) D-A conjugated polymer were designed and synthesized. Compared to the alternating conjugated copolymer PDPP-3T, the HOMO level of the random copolymers are increased as part of the electron deficiency acceptor DPP units in the polymer chain were superseded by electron rich EDOT, which could contribute to effective p-doping. Moreover, through incorporating EDOT to construct random copolymers, it can also induce an orientation change from face-on dominated to edge-on dominated orientation as well as enhance the packing of copolymer chains, which is beneficial to the charge transport. Under same doping condition, the electrical conductivities of the doped polymers increase and the Seebeck coefficient decrease as the increasing of EDOT content, resulting in an optimized power factor of 6.4 μW m⁻¹ K⁻² for the random polymer with EDOT content of 40% which is four times higher than that of alternating conjugated copolymer PDPP-3T. These results demonstrated that constructing random copolymers by incorporating more electronic donors into D-A conjugated polymers may be a promising strategy for developing TE conjugated polymers.