Functionalized star-shaped polymers having PEO and/or polyglycidyl arms and their properties

The introduction of methacrylic, carboxylic and phosphate functional groups on the core and at the end of the poly(ethylene oxide) (PEO) arms in the PEO star-shaped polymers is described. In the polyglycidol (PGL) star-shaped polymers phosphate groups were attached to the PGL arms as side groups. Polymers were characterized by NMR and SEC analysis with triple detection. The conversion of the unsubstituted star-shaped polymers into functionalized has been confirmed by ¹H and ¹³C NMR spectra. The influence of the length of arms, their structure and the presence of functional groups on melting (T_m) and crystallization (T_c) temperatures and the degree of crystallinity (X_c) by differential scanning calorimetry (DSC) has been studied.     

Theory of chromatography of linear and cyclic polymers with functional groups

We discuss the chromatographic behavior of linear polymers and rings having specific (functional) adsorption-active groups. Functionalized eight-shaped, daisy-like and theta-shaped macromolecules are considered as well. By using a model of an ideal chain with point-type defects in a slit-like pore we derive equations for the distribution coefficient covering all modes of chromatography of functionalized polymers of any molar mass in both narrow and wide pores. Additionally simple approximate formulae are obtained for a number of important modes of chromatography; chromatograms are simulated for model mixtures of polydisperse non-functional and functional polymers. By using the theory we analyze separation of polymers by molar mass, functionality and topology. Although there is a principal possibility to use adsorption chromatography or size-exclusion chromatography (SEC), we conclude that the liquid chromatography at the critical condition (LCCC) is especially efficient for separation of polydisperse polymers by both functionality and topology. The theory predicts that functionalized linear and cyclic polymers can be separated from each others by LCCC even better than non-functionalized ones. The LCCC behavior of some other types of polymers such as comb-like and semicyclic ones is discussed as well.     

Topological separation of linear and star-shaped polystyrenes by off-line 2D chromatography. Stars having high molar mass arms and quantification of the star fraction

Off-line 2D separations on mixtures of linear and star-shaped polymers were performed using temperature gradient interaction chromatography (TGIC) as a first and SEC as a second dimension. The experiments resulted in clear separations of the linear and star shaped-structures for arm molar masses up to 42,000 g/mol. The resolution is nearly independent of the molar masses of the arms and depends only on the number of star arms. From the 2D chromatograms it is possible to determine the molar mass of the first branched structure, i.e. the three arm star. The evaluation of the relative peak volume allows a reliable estimation of the amount of branched structures in the complex mixture.     

线形和星形聚L-丙交酯大分子单体的合成

以辛酸亚锡为催化剂,分别以聚乙二醇、甲基丙烯酸羟乙酯、三羟甲基丙烷、季戊四醇、甘露醇和山梨醇等和L-丙交酯反应,得到末端为羟基的线形和星形聚L-丙交酯。通过和甲基丙烯酰氯反应,在上述线形和星形聚L-丙交酯成功引入双键,得到了相应的反应性大分子单体,其双键的存在经红外谱图和高锰酸钾试验得到证实。通过在过氧化二苯甲酰引发下的热交联,研究了上述大分子单体的反应性,发现端基数对交联产物的性质有一定影响。溶解试验、凝胶含量测定和热重分析表明,端基数目较多的大分子单体的交联产物有较高的凝胶含量,交联密度较大,热性能较好。     

Separation of parent homopolymers from diblock copolymers by liquid chromatography under limiting conditions of desorption 3. Role of column packing

The novel separation method, liquid chromatography under limiting conditions of desorption, LC LCD enables rapid one-step discrimination of both parent homopolymers from diblock copolymers. The low-molecular admixtures/impurities can be base-line separated, as well. The general rules for selection of the LC LCD columns are reviewed. Bare silica gel column packings are discussed in detail. Selected examples of separation are presented. They demonstrate that the principle of LC LCD separation is not affected by the particle size and initial purity of bare silica gel column packing nor by its effective pore diameter and volume. However, appropriate choice of the packing pore size facilitates base-line separation of particular sample constituents. Important may be the column history; columns saturated with previously adsorbed polymers may lose their performance. Up to a certain limit, success of the LC LCD separation does not depend on the column efficiency and reasonable results can be obtained even with the columns packed with rather big particles. This indicates possibility of the large-scale preparative applications and feasibility of the high-speed LC LCD separations.     

Study on the mechanism of hindered sedimentation by ‘unified theory on solid-liquid separation’

The entire procedure of hindered sedimentation has been calculated by the introduction of new boundary conditions to the ‘unified theory on solid-liquid separation.’ During this study, the hindered sedimentation was defined as ‘a process of sedimentation with transmission of the gravitational force between the particles due to contact.’ The lower concentration limit, on which the ‘unified theory on solid-liquid separation’ is based, could not be applied. To understand the mechanism of hindered sedimentation, variations in the porosity during sedimentation were calculated by using our theory.     

Comparison of the surface energetics data of eucalypt fibers and some polymers obtained by contact angle and inverse gas chromatography methods

This study compares two approaches to determine the surface energy of solids, and its acid-base components in particular: inverse gas chromatography (IGC) and analysis of contact angle data using the Good-van Oss theory. The comparison is made in the context of wood fibers from Eucalyptus globulus and Eucalyptus regnans pulped by the kraft and neutral sulfite semi-chemical (NSSC) processes, and of selected polymers. Contact angles on wood fibers were measured using the Wilhelmy method and on polymer samples using the sessile drop technique. For the dispersive component of the surface energy, the level of agreement between the two approaches was reasonable, using alkanes for the IGC measurements and diiodomethane for the Wilhelmy and sessile drop techniques. However, agreement was poor for the acid and base characteristics when monopolar probes were used for IGC and water, formamide, and diiodomethane for contact angle measurements. The Good-van Oss approach suggested that all fibers and polymers are monopolarly basic, whereas IGC measurements suggested that they are bipolar. When new values were used for the acid and base components of the surface energy of the liquid probes based on the values for water proposed by Della Volpe and Siboni, all samples still appeared strongly basic. This is inconsistent with the chemical nature of the lignocellulosic fibers. Thus, the Good-van Oss approach provides a poor indication of acid-base properties of the surfaces of solids in suggesting that lignocellulosic fibers and polymers are strongly basic. The above issues as well as potential problems in measuring the surface energy of lignocellulosic fibers using the three-liquid procedure and the Good-van Oss approach are discussed.     

Fast determination of critical eluent composition for polymers by gradient chromatography

Gradient chromatography was applied in order to calculate the composition at elution for different methacrylates on normal phase columns. In addition the composition at elution was determined for polyethyleneoxide on a reverse phase column. It is shown that high molar mass polymers elute for a given homopolymer irrespective of their molar mass at the same eluent composition, which varies only slightly with gradient slope. In general the composition at elution in gradient chromatography is expected to be slightly lower than the true critical composition. For high molar mass polymers we found this composition to be close to the critical composition determined by isocratic experiments. The difference between the composition at elution and the true critical composition for a variety of polymethacrylates and for polyethyleneglycol was found to be only between 0.2 and 5%. Thus, after estimating the composition at elution, only a small number of additional isocratic experiments is needed to find the exact critical composition.     

The use of soluble polymers to effect homogeneous catalyst separation and reuse

The use of soluble polymeric ligands for homogeneous catalysts separation is reviewed with emphasis on work from the author's laboratory. Examples discussed include polyethylene-bound catalysts, poly(alkene oxide)-bound catalysts, poly(N-isopropylacrylamide)-bound catalysts, fluorous polymer-bound catalysts and amphoteric polymer-bound catalysts. The utility of these systems is also discussed in the broader context of polymer-supported catalysis and the advantages and limitations of soluble polymeric ligands are discussed in this context.     

Characterization of star-shaped poly(l-lactide)s by liquid chromatography at critical conditions

A series of linear and star-shaped poly(l-lactide)s (PLA's) have been prepared by living polymerization of l,l-dilactide (LA) and analyzed by liquid chromatography at critical conditions (LC-CC). For the analysis of the PLA's LC-CC conditions have been used corresponding to silica gel as the stationary phase and a mixture of 1,4-dioxane/n-hexane (56.25/43.75 by vol%) at 50 °C as the mobile phase. At the critical point of adsorption, a series of linear C₄H₉-PLA-OH's having molar masses (M_n) in the range from 2.3×10³ to 7.4×10⁴, prepared by ring-opening polymerization of LA initiated with Sn(OC₄H₉)₂ (THF, 80 °C), showed no dependence of the elution volumes on molar mass. In subsequent experiments, star-shaped PLA's bearing various numbers of PLA-OH arms (R-(PLA-OH)_x) have been prepared in a controlled synthesis starting from various polyols (R-(OH)_x) containing exclusively primary hydroxyl groups: diethyleneglycol (x=2), trimethylolpropane (x=3), di(trimethylolpropane) (x=4), dipentaerithritol (x=6), and poly(3-ethyl-3-hydroxymethyloxetane) (〈x〉=13.4) and LA monomer. As coinitiator/catalyst tin(II) octoate (Sn(Oct)₂) has been used (bulk polymerization, 120 °C). ¹H NMR analysis of the resulting star-shaped polymers revealed that all OH-groups in the polyols started growth of the PLA chains. The series of star-shaped PLA's have been analyzed by LC-CC as well as by two-dimensional (2D) chromatography (i.e. LC-CC versus size exclusion chromatography (SEC)) with regard to possible structural imperfections. It has been shown, that the LC-CC elution volumes of the resulting R-(PLA-OH)_x increase with the number of PLA-OH arms, allowing discrimination of the individual R-(PLA-OH)_x's in their mixture. An exponential increase of the retention volume as a function of the number of arms has been found. Eventually, LC-CC measurements of the elution volumes carried out for acetylated star-shaped PLA's (R(PLA-OOCCH₃)_x) have shown that for the interactions of the R-(PLA-OH)_x macromolecules with the column packing the hydroxyl end-groups are mostly responsible.     

Adsorption of star polymers studied by a new numerical mean field theory

We present a systematic theoretical investigation of star-like polymers of various architectures near adsorbing surface, using a new numerical self-consistent mean field theory. The comparison of the experimentally reported adsorption profiles with the predictions of our method shows excellent agreement. The study of the structural properties of the formed brushes indicates that as the number of branches is increased the number of adsorbed polymers is significantly reduced. Mixtures of different kinds of star polymers show interesting behaviors as the more branched polymers try to develop in the outer region of brush. We also estimate the forces obtained when curved surfaces come close as a function of the distance between the surfaces.     

The application of simulated moving bed chromatography for the separation between 2,6- and 2,7-dimethylnaphthalene

The possibility of applying SMB chromatography for the separation of 2,6-DMN and 2,7-DMN was investigated by numerical simulation based on the single column chromatography experimental data. It was found that 2,6-DMN could be separated from 2,7-DMN in the ODS-modified silica gel by using methanol and water as the mobile phase. A systematic method of obtaining model parameters for the SMB simulation from single column chromatography experiments was presented. The adsorption isotherms of 2,6-DMN and 2,7-DMN were obtained by the pulse method. The mass transfer kinetics was very fast, indicating that the mobile phase and the stationary phase are very close to equilibrium for both 2,6-DMN and 2,7-DMN. SMB simulation was performed by using the model parameters. Pure 2,6-DMN and 2,7-DMN can be obtained by selecting suitable operating conditions, indicating that SMB chromatography can be employed to separate 2,6-DMN and 2,7-DMN. The influence of operating parameters (feed flow rates, raffinate flow rate, and switch time) was also investigated to recommend the optimum operating conditions.     

Simulation of GPC-distribution coefficients of linear and star-shaped molecules in spherical pores. 2. Comparison of simulation and experiment

Star-polymers with arm numbers ranging from 3 to 10 have been synthesized and characterized by conventional GPC and GPC-light-scattering. The GPC elution behavior of the stars was studied and compared with predictions from computer simulations. The comparison of simulated and experimental data shows reasonable agreement if the arms are sufficiently long. Thus, using computer simulations GPC calibration curves of non-linear topologies can be constructed based on the calibration curve of the corresponding linear polymer. For star polymers prepared by atom transfer radical polymerization we found additional peaks having twice the molecular weight of the peak that has been assigned to the star. The elution volumes of these peaks were in good agreement with an expected dumbbell topology that would arise from coupling of the arms of different stars.     

芳香醇类化合物高效液相色谱法的分离研究

采用高效液相色谱法对15种芳香醇及结构相近化合物进行了分离研究。在优化的色谱条件下,8种对映体和4种非手性芳香醇同系物得到了基线分离。与单纯的紫外检测器相比,旋光检测器可方便地得到手性对映体的左旋或右旋特性。有关分离机理得到了合理的解释。     

色谱技术与色谱试剂现状评述

在分析测试领域,用色谱分析的方法和应用越来越广泛,在今天对高质量产品的测定已涉及食品、医药、环保、生化和石油化工等等。色谱技术的发展和变化试剂有着很大的影响,尤其是从事生产制造、经营管理和分析使用者来说,了解色谱技术的发展和现状,来对待色谱试剂的新认识,有助于分析测试的正确性和可靠性的进一步提高。     

A novel two-dimensional network formed by complexation of cucurbituril with cadmium ions

The crystal structure of compound {3[Cd₂(C₃₆H₃₆N₂₄O₁₂)]·10Cl·10(H₂O)}·2Cl·39(H₂O) (1) is reported. It consists of complexes of cucurbituril and cadmium cations formed through ion-dipole interactions, in which a novel two-dimensional network is created by the complexation of cucurbituril and cadmium ions. Binding constants determined from voltammetric data indicate that Cd²⁺ has a high binding affinity for Q[6] ( by CV) and forms a 2:1 (M²⁺/Q[6]) complex.     

Preparative separation of four sesquiterpenoids from Curcuma longa by high-speed counter-current chromatography

A high-speed counter-current chromatography (HSCCC) method was developed for the preparative separation of four major sesquiterpenoids with similar structures, namely ar-turmerone, β-turmerone, α-turmerone, and E-α-atlantone, from the essential oil of Curcuma longa Linn. using a two-phase solvent system composed of n-heptane-ethyl acetate–acetonitrile–water (9.5/0.5/9/1, v/v). From a single HSCCC run, 1.7861 g of ar-turmerone, 0.4708 g of β-turmerone, 1.3427 g of α-turmerone, and 0.1650 g of E-α-atlantone were obtained. The purity of each compound was over 98% as determined by HPLC. The chemical structures of these compounds were determined by ¹H NMR and ¹³C NMR.     

Theory of chromatography of complex cyclic polymers: eight-shaped and daisy-like macromolecules

A theory of chromatography of eight-shaped, trefoil-shaped and daisy-like polymers is developed. For a model of an ideal chain in a slit-like pore exact equations and a number of approximate formulae for the distribution coefficient K of these polymers are derived. All modes of chromatography of complex macrocycles of arbitrary molar mass in both narrow and wide pores are covered by the theory. It is shown that complex macrocycles always elute after linear polymers and rings of the same contour length. The effective chromatographic radius of eight-shaped and daisy-like macromolecules, which determines retention in size-exclusion chromatography are calculated. The increase in the retention with molar mass is predicted for all types of macrocycles at the critical interaction condition. Non-monotonous molar mass dependences of K are found at pre-critical interaction. We simulate separation of complex cyclic polymers from linear and ring precursors, discuss possibilities to separate symmetric and asymmetric eights, and speculates on the use of chromatography for separating knotted and unknotted polymer rings. According to the theory, the chromatography under the critical and pre-critical interaction conditions is expected to be especially efficient in these and similar problems. Boundary conditions for the theory and its applicability to real systems are discussed.     

Termini and main-chain composition of monomethoxy-terminated poly(ethylene glycol) studied by two-dimensional column chromatography

Samples of poly(ethylene glycol) especially those with functionalized ends have dimeric, trimeric, and tetrameric components at twice, three times, and four times as high a molecular weight (MW) as that of the main component. We used two-dimensional column chromatography to evaluate the MW and identify the terminal groups in each component. The first step is high osmotic pressure chromatography to prepare a sufficient amount of fractions that contain different percentages of the multimeric components. In the second step, each of the fractions was characterized by using regular size exclusion chromatography and high-resolution NMR. Decomposition of the chromatogram combined with isolation of the terminal methoxy peak in the NMR spectrum led to unique identification of the terminal groups. We thus found that the monomeric component is monomethoxy-terminated whereas the dimeric and other multimeric components are mostly dihydroxy-terminated.