Liquid chromatography of polymers under limiting conditions of desorption II. Tandem injection and quantitative molar mass determination

Liquid chromatography under limiting conditions of desorption (LC LCD) is a method which allows molar mass independent elution of various synthetic polymers. A narrow, slowly moving zone of small molecules, which promotes full adsorption of one kind of polymer species within column (an adsorli) acts as an impermeable barrier for the fast moving macromolecules. The latter accumulate on the barrier edge and elute nearly in total volume of liquid within column. At the same time, transport of less adsorptive macromolecules is not hampered so that these are eluted in the size exclusion (SEC) mode. As result, polymers differing in their polarity and adsorptivity can be easily separated without molar mass interference. Three methods of barrier creation are discussed and compared. It is shown that a fraction of sample may elute unretained if the adsorli sample solvent is used as a barrier in connection with a narrow-pore column packing. One part of excluded macromolecules likely breaks-out from the adsorli zone and this results in partial loss of sample and distortion of the LC LCD peaks. This problem can be avoided if the adsorli zone is injected immediately before sample solution. Applicability of the LC LCD method for polymer separation has been demonstrated with a model mixture of poly(methyl methacrylate) (adsorbing polymer) and polystyrene (non adsorbing polymer) using bare silica gel as a column packing with a combination of tetrahydrofuran (a desorption promoting liquid -a desorli) and toluene (adsorli). It has been shown that the LC LCD procedure with tandem injection allows simple and fast discrimination of polymer blend components with good repeatability and high sample recovery. For quantitative determination of molar masses of both LC LCD and SEC eluted polymers, an additional size exclusion chromatographic column can be applied either in a conventional way or in combination with a multi-angle light scattering detector. A single eluent is used in the latter column, which separates the mixed mobile phase, system peaks and the desorli zone from the polymer peaks so that measurements are free from disturbances caused by the changing eluent composition. The resulting LC LCD x SEC procedure has been successfully applied to poly(methyl methacrylate) samples.     

Separation of parent homopolymers from diblock copolymers by liquid chromatography under limiting conditions of desorption 4. Role of eluent and temperature

Liquid chromatography under limiting conditions of desorption (LC LCD) enables fast, base-line discrimination of both parent homopolymers from various diblock copolymers in one single step. The low molecular admixtures are fully separated, as well. General rules are discussed in detail for selection of mobile phases and temperature applied in LC LCD of block copolymers. Typical practical separation examples are presented. It is shown that both the composition of the well-selected LC LCD mobile phase and the temperature of experiment may vary in a broad range without affecting the basics of method. This implies that the method is robust and user friendly.     

Conductive polymer composites (CPC): influence of processing conditions,shear rate and temperature on electrical properties of poly(butylene terephthalate)/poly(amide12-b-tetramethyleneglycol) – carbon black blends

Conductive Polymer Composites (CPC) have been obtained by blending two immiscible polymers, poly(butylene terephthalate) (PBT) and poly(amide12-b-tetramethyleneglycol) (PEBAX) with carbon black (CB). The extrusion process allows to obtain anisotrope co-continuous structures of various morphologies depending on composition and experimental conditions. It is possible to enhance CPC conductivity with appropriate processing temperature (T_p) and screw speed (Ω), without changing the composition of the blend. The best results are obtained with Ω =5 rpm and T_p=260°C. PBT/PEBAX-CB resistivity evolution with T_p and Ω doesn't follow a linear law as expected from previous studies with poly(butylene terephthalate)/poly(ethylene)-CB and poly(butylene terephthalate)/poly(ethylene-co-ethyl acrylate)-CB systems. CB distribution has a more important impact on conductivity than polymers phase morphology. A good control of these parameters is essential to reproduce and optimize electrical properties.     

以热致液晶聚合物微纤增强的原位复合材料

用４种热致液晶聚合物分别与聚丙烯,聚对苯二甲酸丁二酯,聚碳酸酯,聚醚砜和聚砜搭配,在各聚合物对的“加工窗口“温度范围内熔融共混并挤塑得到６种共混物。藉流变仪,扫描电子显微镜,偏光显微镜,动态力学谱仪等重点研究了原位复合材料中微纤结构的形成,组分特性,熔体粘度,挤塑温度和浓度等因素对各向异性结构形成的贡献,以及液晶聚合物对聚合物结晶的诱导作用和两相间的相互作用。     

Liquid chromatography with tandem mass spectrometry method for trace level analysis of migrated secondary alkanesulfonate from poly(tetramethylene terephthalate) into food simulants

Secondary alkanesulfonate has been widely used as an antistatic additive in polymers for producing anti‐dust food packaging containers. Currently, no reported method exists for accurate quantification of secondary alkanesulfonate in ethanolic and acidic food simulants. A new liquid chromatography with tandem mass spectrometry method was developed to quantify the migrated amount of secondary alkanesulfonate at trace levels in food simulants from a poly(tetramethylene terephthalate) containing secondary alkanesulfonate. The poly(tetramethylene terephthalate) samples loaded with the antistatic additive were exposed to various food simulants. The collected extracts were directly analyzed by liquid chromatography with tandem mass spectrometry in electrospray ionization negative mode. As secondary alkanesulfonate is a mixture containing C14 to C17 chain lengths, it was separated on a Poroshell 120 EC‐C8 column adopting methanol water gradient program. The migration of secondary alkanesulfonate ranged from 58 to 329 ppb; which is well within the allowed permissible regulatory limits and the adopted method was validated by conducting spiking studies and acceptable recoveries were obtained. The developed method was not only sensitive to detect lower levels of the migrated antistatic additive, but it also avoided more cumbersome sample preparation methodologies like sample enrichment and other derivatization approaches.     

Miscibility and properties of poly(l-lactic acid)/poly(butylene terephthalate) blends

Binary blends of poly(l-lactide) (PLLA) and poly(butylene terephthalate) (PBT) containing PLLA as major component were prepared by melt mixing. The two polymers are immiscible, but display compatibility, probably due to the establishment of interactions between the functional groups of the two polyesters upon melt mixing. Electron microscopy analysis revealed that in the blends containing up to 20% of poly(butylene terephthalate), PBT particles are finely dispersed within the PLLA matrix, with a good adhesion between the phases. The PLLA/PBT 60/40 blend presents a co-continuous multi-level morphology, where PLLA domains, containing dispersed PBT units, are embedded in a PBT matrix. The varied morphology affects the mechanical properties of the material, as the 60/40 blend displays a largely enhanced resistance to elongation, compared to the blends with lower PBT content.     

粘度比对刚性链高分子与柔性链高分子共混物微结构的影响

粘度比对刚性链高分子与柔性链高分子共混物微结构的影响何嘉松,卜文胜,张洪志,许向青（中国科学院化学研究所,北京,１０００８０）（化工部北京化工研究院,北京,１０００１３）关键词高分子共混物,热致液晶聚合物,聚合物加工影响柔性链高分子与柔性链高分子共混...     

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.     

Effects of comonomer sequential structure on thermal and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate)s

In this work, new investigations on the effect of comonomer sequential structure on the thermal and crystallization behaviors and biodegradability have been implemented for the biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST) as well as aliphatic poly(butylene succinate) (PBS). At first, these copolyesters were efficiently synthesized from dimethyl succinate and/or dimethyl terephthalate and 1,4‐butanediol via condensation polymerization in bulk. Subsequently, their molecular weights and macromolecular chain structures were analyzed by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. By means of differential scanning calorimeter (DSC) and wide‐angle X‐ray diffractometer (WAXD), thermal and crystallization behaviors of these synthesized aromatic–aliphatic copolyesters were further explored. It was demonstrated that the synthesized copolyesters were revealed to have random comonomer sequential structures with thermal and crystallization properties strongly depending on their comonomer molar compositions, and that crystal lattice structures of the new crystallizable copolyesters shifted from the monoclinic crystal of semicrystalline PBS to triclinic lattice of the poly(butylene terephthalate) (PBT) with increasing the terephthalate comonomer composition, and the minor comonomer components were suggested to be trapped in the crystallizable component domains as defects. In addition, the enzymatic degradability was also characterized for the copolyesters film samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1635–1644, 2006     

Miscibility and Crystallization in Binary Crystalline Blends of Poly(butylene terephthalate) with Poly(butylene terephthalate-e-caprolactone)

Poly(butylene terephthalate)/poly(butylene terephthalate-e-caprolactone) is a new A/AxB1-x binary crystalline blend with intra-molecular repulsion interaction. Using the mean-field binary interaction model, the value of interaction parameter between the butylene terephthalate and caprolactone structural unit was first reported to be 0.305. This blend exhibited different crystallization behavior from a typical homopolymer/copolymer blend, which was carefully investigated by di?erential scanning calorimetry. It was found that poly(butylene terephthalate-e-caprolactone) copolymers have a great effect on the pure poly(butylene terephthalate) chain mobility and poly(butylene terephthalate) crystalline lattice packing. In the meantime, the crystallization of butylene terephthalate segments in copolymers was restricted by the previously formed poly(butylene terephthalate) crystallites. The two constituents for blending can not form a co-crystal in the range of composition even if they have the same butylene terephthalate unit. It can be concluded that longersegments in a copolymer would be beneficial for the formation of a co-crystal in blends.     

Effect of carbon nanotube modification on poly(butylene terephthalate)-based composites

The influence of the chemical modification of carbon nanotubes on the mechanical, thermal and electrical properties of poly(butylene terephthalate)-based composites was investigated. Polymer composites based on poly(butylene terephthalate) were obtained via in situ polymerisation or extrusion. Commercially available multi-walled carbon nanotubes (Nanocyl NC7000) at different loadings (mass %: 0.05, 0.25, 1, 2) were used as fillers. The functionalisation process took place under a chlorine atmosphere followed by a reaction with sodium hydroxide. The effect of carbon nanotube modification was analysed according to the changes in the polymer thermal and mechanical properties. An addition of modified carbon nanotubes in the amount of 0.05 mass % improved the mechanical properties of the composites in terms of both Young’s modulus and tensile strength by 5–10 % and 17–30 % compared with composites with unmodified carbon nanotubes and neat poly(butylene terephthalate), respectively. The in situ method of composite preparation was a more effective technique for enhancing the matrix-filler interactions, although a significantly lower amount of fillers were used than in the extrusion method.     

Characterization of PBT/POSS nanocomposites prepared by in situ polymerization of cyclic poly(butylene terephthalate) initiated by functionalized POSS

Novel poly(butylene terephthalate) (PBT)/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were synthesized by ring‐opening polymerization of cyclic poly(butylene terephthalate) initiated by functionalized POSS with various feed ratios. The impact of POSS incorporation on melting and crystallization behaviors of PBT/POSS nanocomposites was investigated by means of X‐ray diffraction and differential scanning calorimetry. It was found that the novel organic–inorganic association result in the significant alterations in the melting and crystallization behavior of PBT. Thermal studies confirmed that the incorporation of POSS can enhance the thermal stability of the polymers, and the copolymer glass transition temperature increased with the increasing of POSS macromonomer content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1853–1859, 2010     

TG-DTA/FT-IR method for analyzing thermal decomposition mechanism of polyesters

An attempt to estimate the thermal decomposition mechanism of polymers using the simultaneous TG-DTA/FT-IR system was summarized. The library search of FT-IR spectra at various temperatures and of the subtraction spectrum obtained by subtracting the spectra at different temperatures were used to determine the types of evolved gases from poly(ethylene terephthalate) and poly(butylene terephthalate) at given stages of decomposition. The quantitative analysis of evolved gases was carried out using the specific gas profiles at the specific absorption band. The kinetic parameters were estimated from both TG and spectroscopic curves measured at various heating rates.     

Multiple dark-field STEM: A new method for beam-sensitive polymers

A new method for recording multiple dark-field transmission electron micrographs using a scanning transmission electron microscope fitted with a quadrant detector is described. Simultaneous multiple recording is particularly advantageous when studying electron beamsensitive polymers and images of crystals of poly(butylene terephthalate) are presented by way of example. Resolution levels of ca. 10 nm are demonstrated.     

Liquid crystalline conjugated polymers and their applications in organic electronics

This article describes the syntheses and electro‐optical applications of liquid crystalline (LC) conjugated polymers, for example, poly(p‐phenylenevinylene), polyfluorene, polythiophene, and other conjugated polymers. The polymerization involves several mechanisms: the Gilch route, Heck coupling, or Knoevenagel condensation for poly(p‐phenylenevinylene)s, the Suzuki‐ or Yamamoto‐coupling reaction for polyfluorenes, and miscellaneous coupling reactions for other conjugated polymers. These LC conjugated polymers are classified into two types: conjugated main chain polymers with long alkyl side chains, namely main‐chain type LC polymers, and conjugated polymers grafting with mesogenic side groups, namely side‐chain type LC conjugated polymers. In general, the former shows higher transition temperature and only nematic phase; the latter possesses lower transition temperature and more mesophases, for example, smectic and nematic phases, depending on the structure of mesogenic side chains. The fully conjugated main chain promises them as good candidates for polarized electroluminescent or field‐effect devices. The polarized emission can be obtained by surface rubbing or thermal annealing in liquid crystalline phase, with maximum dichroic ratio more than 20. In addition, conjugated oligomers with LC properties are also included and discussed in this article. Several oligo‐fluorene derivatives show outstanding polarized emission properties and potential use in LCD backlight application. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2713–2733, 2009     

The enzymatic degradation of commercial biodegradable polymers by some lipases and chemical degradation of them

Biodegradable polyesters, poly(butylene succinate adipate) (PBSA), poly(butylene succinate) (PBS), poly(ethylene succinate) (PES), poly(butylene succinate)/poly(caprolactone) blend (HB02B) and poly(butylene adipate terephthalate) (PBAT), were evaluated about degradability for enzymatic degradation by lipases and chemical degradation in sodium hydroxide solution. In enzymatic degradation, PBSA was the most degradable by lipase PS, on the other hand, PBAT containing aromatic ring was little degraded by eleven kinds of lipases. In 1N NaOH solution, degradation rate of PES with ethylene unit was extremely fast, in comparison with other polyesters. Interestingly the degradation rate of PBSA in enzymatic degradation by lipase PS was faster than in chemical degradation.     

Separation and characterization of functional poly(n-butyl acrylate) by critical liquid chromatography

The separation of functional poly(n-butyl acrylate) (PnBA) polymers based on the number of end-groups under critical liquid chromatography (LC) conditions has been studied using a bare-silica column. The (near-) critical solvent compositions for non-, mono-, and difunctional (telechelic) carboxyl-PnBAs were determined in normal-phase LC, using mixtures of acetonitrile, acetic (or formic) acid, and dichloromethane of varying composition. Some formic or acetic acid had to be added to the mobile phase to elute PnBA polymers with carboxyl end-groups. The critical solvent compositions obtained were not exactly the same for non-, mono-, and difunctional PnBA polymers. These were unusual experimental observation, but they were in agreement with theoretic predictions. Nevertheless, low-molecular-mass PnBA samples were successfully separated according to the carboxyl functionality at (near-) critical conditions. With the aid of mass spectrometry (MS), the (near-) critical separation of low-molecular-mass PnBA polymers was confirmed to be mainly based on the carboxyl functionality. Calibration curves for evaporative light-scattering detection (ELSD) were used for quantitative analysis of carboxyl-functional PnBA polymers. The results proved that nearly ideal functionalities (average number of carboxyl end-groups per molecule up to 1.99) were achieved for telechelic PnBAs prepared by one-step reversible addition-fragmentation chain-transfer (RAFT) polymerization of PnBA.     

Laser-induced breakdown spectroscopy for polymer identification

This study aims at differentiating several organic materials, particularly polymers, by laser induced breakdown spectroscopy. The goal is to apply this technique to the fields of polymer recycling and cultural heritage conservation. We worked with some usual polymers families: polyethylene (PE), polypropylene (PP), polyoxymethylene, (POM), poly(vinyl chloride), polytetrafluoroethylene, polyoxyethylene (POE), and polyamide for the aliphatic ones, and poly(butylene terephthalate), acrylonitrile–butadiene–styrene, polystyrene, and polycarbonate for the aromatic ones. The fourth harmonic of a Nd:YAG laser (266 nm) in ambient air at atmospheric pressure was used. A careful analysis of the C₂ Swan system (0,0) band in polymers containing no C–C (POM), few C–C (POE), or aromatic C–C linkages led us to the conclusion that the C₂ signal might be native, i.e., the result of direct ablation from the sample. With use of these results, aliphatic and aromatic polymers could be differentiated. Further data treatments, such as properly chosen line ratios, principal component analysis, and partial least squares regression, were evaluated. It was shown that many polymers could be separated, including PE and PP, despite their similar chemical structures.     

高特PET-PBT共混单丝的结构与性能

采用一定比例的聚对苯二甲酸丁二醇酯(PBT)对聚对苯二甲酸乙二醇酯(PET)进行共混改性纺制大直径单丝,通过对共混单丝的力学性能、扫描电子显微镜及热性能分析,研究了共混比例、后拉伸工艺对共混物的相容性和拉伸强度的影响.结果表明:通过PET-PBT共混,提高了单丝的勾结强度;液体冷却温度、拉伸倍率及拉伸温度是影响共混单丝...     

Sequential analysis of polyesters by stepwise chemical degradation: Preparation of degradation products

Model reactions for the sequential analysis of polyesters, especially those of the poly(ethylene terephthalate) and poly(butylene terephthalate) type, by stepwise chemical degradation were performed. The cyclic degradation products, containing the reagent and an ethylene terephthalate or butylene terephthalate unit, terephthalic acid mono(2-{o{N-<N′-[4-(iminomethyl-) benzoyl-]> 2′-(imino)ethoxycarbonyl-}iminobenzoyl-} oxyalkyl) ester N″-lactams, were deliberately synthesized.