Characterization of branched polymers by size exclusion chromatography coupled with multiangle light scattering detector. I. Size exclusion chromatography elution behavior of branched polymers

The elution behavior of branched macromolecules during their separation by size exclusion chromatography (SEC) was studied. The elution behavior of branched polymers was investigated using samples of randomly branched polystyrene and star branched poly(benzyl methacrylate) of different levels of branching by means of a SEC chromatograph coupled with a multiangle light scattering detector. Abnormal SEC elution behavior was found to be typical for highly branched polymers. After a normal elution at small elution volumes the molar mass and root mean square radius of the eluting molecules increased with increasing elution volume. Several SEC experiments were carried out to find explanation for this effect and SEC separation was compared with the separation by thermal field flow fractionation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1588–1594, 2001     

Reliability of molecular weight determination methods for oligomers investigated using certified polystyrene reference materials

Using polystyrene certified reference materials (CRMs) whose molecular weights range from 500 to 2400, we investigated the reliability of molecular weight determination by size-exclusion chromatography (SEC), SEC coupled with multi-angle light scattering detection (SEC-MALS), conventional static light scattering (SLS), matrix-assisted laser desorption/inonization time-of-flight mass spectrometry (MALDI-TOFMS), and ¹H NMR. Average molecular weights determined by these methods were compared with the certified values which were determined by supercritical fluids chromatography with relative standard uncertainty less than 1%. The comparison showed that recent SEC with calibration constructed by uniform polystyrenes can provide just the same average molecular weights as certified ones within the standard uncertainty. ¹H NMR was also found to be a powerful technique to determine number-average molecular weight accurately. Average molecular weights measured by SEC-MALS and SLS nearly agreed with certified values except for lower molecular weights. Although MALDI-TOFMS provided average molecular weights in agreement with certified values, the polydispersity given by MALDI-TOFMS were found to be very small for all the polystyrenes.     

SEC-MALS method for the determination of long-chain branching and long-chain branching distribution in polyethylene

This paper systematically describes a LCB determination method that can quantify both LCB content and LCB distribution across the molecular weight distribution in polyethylene homopolymers as well as copolymers. Coupling size-exclusion chromatography with multi-angle light scattering (SEC-MALS), this method quantifies molecular weights (MW) and radii of gyration (R_g) simultaneously. The number of LCB per molecule and LCB frequency as a function of MW can be calculated by comparing R_g of a branched polymer with that of a linear control at the same MW using the Zimm-Stockmayer approach. Because the presence of short-chain branching in copolymers results in changes in R_g of the copolymers, their LCB contents cannot be obtained before the short-chain branching (SCB) effect is corrected. Using well-characterized linear PE copolymers as standards, an empirical method is successfully established in this paper to correct the SCB effect. Consequently, this method can be applied to determine LCB in PE copolymers as well. Some practical aspects, such as the selection of formalism for data processing, the LCB detection sensitivity and precision, and long-term reproducibility of this method are also discussed. Finally, examples are given to demonstrate how this method is applied to determine LCB and LCB distribution in practical PE homopolymers and copolymers.     

Study of mechanical and rheological behaviors of linear and branched polycarbonates blends

A study of the mechanical and rheological properties of linear and branched polycarbonates blends is presented. Phase separations of the blends were checked through DSC and SEM, and, subsequently, mechanical and rheological properties were investigated. Phase separations were not observed in the blends. The mechanical properties were examined through tensile, flexural, and impact tests. All the mechanical properties of the blends were relatively independent of the compositions. For study of the rheological properties, melt viscosity, storage and loss moduli, and melt tension of the blends with various compositions were examined at various temperatures. The dependence of the viscosity on the molecular weight was also studied. As the content of branched polycarbonate increases, the dependence of the viscosity on the molecular weight and the shear thinning behavior became more marked. Melt tensions were also increased as the branched polycarbonate content increased in the blends for all tested temperatures. In this study, the blend systems which have same mechanical properties but different rheological properties can be obtained through blending of linear and branched polycarbonates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1814–1824, 2001     

Preparation and characterization of polyamide‐6 with three‐branched chains

With trimesinic acid as a molecular weight regulator, the hydrolytic polymerization of ?‐caprolactam was carried out, and nylon‐6 or polyamide‐6 with three‐branched chains was obtained. Through a systematic study of the effects of conditions such as the reaction time and concentration of trimesinic acid on the polymerization, we found that the conversion of caprolactam was almost insensitive to the initial concentrations of the regulators, but the relative viscosity of the polymer decreased with increasing trimesinic acid. Characterization investigations showed that differential scanning calorimetry curves changed from a single peak for normal nylon‐6 to one main peak and one shoulder or one small peak for the branched polymer; the melting point of the star‐shaped nylon‐6 decreased with an increasing amount of trimesinic acid, whereas its crystallization temperature was higher than that of linear‐chain nylon‐6. A wide‐angle X‐ray diffraction study indicated that the crystal structure of the star‐shaped nylon‐6 still belonged to the α form, and the crystallizability of the branched polymer with an elevated amount of trimesinic acid during polymerization did not seem to be weakened; the characteristic absorption of infrared spectra provided indirect evidence for the existence of branched chains in the polymer. Moreover, the mechanical properties of star‐shaped nylon‐6 and linear‐chain nylon‐6 were compared. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3184–3193, 2001     

Randomly branched styrene/divinylbenzene copolymers. II. Solution properties and structure

The [η] of randomly branched PSty/DVB continually decreases from linear polystyrene with increasing conversion. On the other hand, the relation of the 〈S²〉 to M of both low and high conversion series is equivalent, although the actual size is smaller than that of linear polystyrene of the same M. This fact, in conjunction with the previously published reactivity ratios, allows the following interpretation of the mechanism of copolymerization: namely, that branched molecules are formed in which the center core is higher in DVB content than is the periphery. Only about 1/7 of the available DVB units act as effective tetrafunctional branch points. An analysis of GPC data correlated with light scattering and viscosity dimensions allows the g value to be determined in the lightly and highly branched fractions. The viscosity ration is related to g^x, where x is 0.65 for low conversion fractions (A series) and becomes 1.41 for high conversion fractions (B series). This change in exponent is postulated to arise from an increase in branching density as conversion increases. The ratio of the hydrodynamic radius to the radius of gyration is higher for branched than for linear polymers. The theta temperature (θ) in cyclohexane for randomly branched polystyrene compared to linear polystyrene is always higher and can be as much as 2° higher.     

Physicochemical study by multi-angle light scattering of water-soluble methacryloylaminophenylarsonate copolymers

The properties of aqueous solutions of polyelectrolytes of sodium o- and p-methacryloylaminophenylarsonate (o- and p- MAPHA-Na) with acrylamide (AAD) or sodium methacrylate (MA-Na): poly(sodium o-methacryloylaminophenylarsonate) (poly(o-MAPHA-Na)), poly(sodium o-methacryloylaminophenylarsonate-co-acrylamide) (poly(o-MAPHA-Na-co-AAD)) (26:74), poly(sodium o-methacryloylaminophenylarsonate-co-sodium methacrylate) (poly(o- MAPHA-Na-co-AM-Na) (35:65) and (14:86), and poly(sodium p-methacryloylaminophenylarsonate-co-sodium methacrylate) (poly(p- MAPHA-Na-co-AM-Na)) (34:66) were studied by off-line, multi-angle light scattering, and in-line using size exclusion chromatography coupled with multi-angle light scattering (SEC-MALS) and refractometric (RI) detection. The M_w value corresponding to the homopolymer poly(o-MAPHA-Na) was 1,300,000 g/mol and for the copolymers the M_w and gyration radius values were decreased when the AAD or AM-Na comonomer composition increased. The macromolecular parameters obtained using SEC-MALS were in agreement with the values measured in the off-line mode. Also, SEC-MALS experiments allowed examination of the radius of gyration-M_w relationship in order to determine the polyelectrolyte conformation (ρ) in solution; these values fell between 0.7-0.53, indicating that the polyelectrolytes are random coils at θ-conditions. In addition, the effect of the pH on the macromolecular parameters was evaluated. At pH 4.5, the M_w and gyration radius values corresponding to poly(o-MAPHA-Na) and poly(o-MAPHA-Na-co-AAD) (26/74) remained very close to those measured at pH 7. However, <r _g ²?>?values for poly(o-MAPHA-Na-co-AM-Na) copolymers at pH 4.5 were less than pH 7, indicating that the presence of AM-Na reduced the size of the copolymer through intermolecular interactions.     

Characterization of structure of comblike polymer by pyrolysis gas chromatography and Fourier transform infrared spectroscopy

The characterization of branching in comblike polymers using high‐resolution pyrolysis gas chromatography (HRPGC) and Fourier transform infrared spectroscopy (FTIR) is investigated. The branching type can be identified from characteristic peaks of monomer and a group of dimers in pyrograms derived from α‐ and β‐scission of branched atoms. By resolving the overlapping bands between 2800–3000 cm^?1, the relative absorbance of CH₂ can be used to calculate the average branch length L. This method is helpful in evaluating the property of drag‐reduction agents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 359–363, 2001     

Influence of branching on the thermal behavior of poly(butylene isophthalate)

The thermal behavior of linear and randomly branched poly(butylene isophthalate) samples was investigated by thermogravimetric analysis and differential scanning calorimetry. As to the thermal stability, it was found to be good and similar for all the samples. The thermal analysis carried out using DSC technique showed that the melting temperature of the polymers decreased with increasing branching unit content, although the glass‐transition temperature was practically not affected by ramifications. The multiple endotherms typical of linear PBI were also observed in branched samples and were found to be influenced both by temperature and degree of branching. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the polymers were obtained. The presence of a crystal‐amorphous interphase was evidenced only for the branched samples and the interphase amount was found to increase as the branching unit content was increased. Isothermal melt crystallization kinetics was analyzed according to Avrami's treatment. The introduction of branching points was found to decrease the overall crystallization rate of poly(butylene isophthalate). Values of Avrami's exponent n close to 3 were obtained for all the samples, in agreement with a crystallization process originating from predetermined nuclei and characterized by three dimensional spherulitic growth. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2001–2010, 2002; DOI 10.1002/app.10517     

Influence of shearing history on the rheological properties and processability of branched polymers. III. An amorphous long-chain branched polymer

Viscoelastic properties of branched polymers vary with their shearing history; notwithstanding, their primary molecular parameters do not change. According to a recent study, such viscoelastic variation was believed to be observed only with crystalline long-chain branched polymers such as low-density polyethylene or polyacetal. That is, the origin of the viscoelastic variation was attributed to the presence of specific entanglements at the branching points, which was formed during the crystallization process. However, the viscoelastic variation of the long-chain branched polymers is the phenomenon at temperatures well above their melting points, namely, it is considered that whether the long-chain branched polymers are crystalline or not is not essential for the occurrence of the viscoelastic variation. Thus, the influence of the shearing history on the rheological properties of an amorphous long-chain branched polymer was investigated in this paper, and it was found that, irrespective of their crystallinity, the viscoelastic properties of long-chain branched polymers vary according to their shearing history.     

Preparation and properties of branched polybutylenesuccinate

To obtain long branched polybutylene succinate (PBS), modified PBSs were prepared by introducing a branching agent, trimethylol propane (TMP), to the polycondensation system of succinic acid and 1,4‐butanediol. Molecular parameters such as absolute molecular weight and root‐mean‐square (RMS) radius of the modified PBSs were measured by gel permeation chromatography (GPC) with a multiangle laser light‐scattering (MALLS) detector. The RMS radius of TMP05, PBS prepared by incorporating 0.5 wt % TMP during polycondensation, was the smallest of all PBSs tested at the same molecular weight. The notable shear thinning and much reduced loss tangent for TMP05 qualitatively supported the difference in their molecular structures predicted by GPC. The analytical results indicated that introducing 0.5 wt % TMP produced PBS with chain branches long enough to produce molecular entanglements. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1388–1394, 2001     

High molecular weight tail and long‐chain branching in low‐density polyethylenes

The composition of the high molecular weight tail in branched low‐density polyethylenes made by both tubular and autoclave reactors was studied in detail using size‐exclusion chromatography (SEC) coupled with a viscosity detector (VD) and a two‐angle light‐scattering detector (LSD). The detection of a second peak at very small elution volumes in the light‐scattering chromatogram but not in the refractive index chromatogram and viscosity chromatogram is due to high molecular weight species. It is also indicative of a change in the long‐chain branching distribution. It was found that the intrinsic viscosity contraction factor g′ scales with the radius of the gyration contraction factor, g, with the exponent, ε, having a value in the range 0.4–1.4. Furthermore, ε shows significant molar mass dependence. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2815–2822, 2001     

Dynamic mechanical properties of binary blends of different polyethylenes. II. Isothermal treatment

The relaxation processes and thermal properties of a series of blends of a highly linear high-density polyethylene (HDPE) with several branched high-density, linear low-density (LLDPE), and low-density polyethylenes (LDPE) have been measured as a function of crystallization temperature, T_c, and content of branched polyethylene (BPE). The influence of composition on the dynamic mechanical spectrum of the HDPE has been rationalized taking into account the dilution with increasing content of BPE of those crystals formed during the isothermal crystallization. The influence of the type of second constituent (HDPE, LLDPE or LDPE) on the relaxation process of the HDPE has been explained in terms of segregation material data.     

Synthesis,separation and characterization of knotted ring polymers

Knotted ring polystyrene (PS) with molecular weight of 380 k was successfully synthesized by intramolecular cyclization reaction in cyclohexane under extremely diluted condition. Crude product was confirmed to include linear precursor molecule, single ring molecules, and various intermolecular-reacted byproducts by SEC and interaction chromatography characterizations. The crude product was fractionated repeatedly several times by high performance interaction chromatography and finally highly-purified knotted ring molecules were obtained. It has been found by SEC-MALS that the chain dimension of the knotted ring polymers is evidently smaller than those of linear and the trivial ring polymer, while knotted polymer molecules have the same absolute molecular weight as the corresponding counterparts.     

Cuticular lipids of insects: VIII. Alkanes of the mormon cricketAnabrus simplex

The cuticular hydrocarbons of the Mormon cricket,Anabrus simplex, are all saturated and consist of n-alkanes (29+%), 3-methylalkanes (12%), internally branched monomethylalkanes (26+%), and dimethylalkanes (28+%). The principal n-alkane is the C₂₉ component, with a range from C₂₃ to C₃₃. The 3-methylalkanes range from C₂₈ to C₃₂, and the internally branched monomethyl-and dimethylalkanes range from C₂₉ to C₃₉. When the branched alkanes ofA. simplex are compared to those from other insects in the order Orthoptera, interesting patterns of methyl branching are observed. Scientific Journal Series 631, Agricultural Experiment Station, University of Montana, Bozeman, Montana 59715.     

SEC-MALS characterization of cyclization reaction products: Formation of knotted ring polymer

Cyclization reaction products by the end-to-end ring closure of telechelic polystyrenes (PSs) with molecular weight of 47 k and 380 k in THF (good solvent) and also in cyclohexane (poor solvent) were characterized by SEC connected with multi-angle light scattering (MALS). By comparison of the SEC peaks of the monomeric rings from 47 k-PSs in THF and cyclohexane, there is no essential difference both in molecular weight and in molecular weight distribution between the two monomeric rings formed. On the other hand, comparing the data for monomeric rings from 380 k-PSs in THF and cyclohexane by SEC-MALS, it has been found that the ring formed in cyclohexane has the same molecular weight as that of the ring formed in THF, while the former reveals the lower radius of gyration than that of the ring formed in THF. These results clearly indicate the evidence of the formation of knotted ring polymers by experiment for the first time.     

Synthesis of branched poly(lactide) using polyglycidol and thermal, mechanical properties of its solution-cast film

Branched poly(lactide)(PLA)s with various lengths of graft chain were synthesized by ring-opening polymerization of l- or d-lactide (l- or d-LA) in bulk using polyglycidol as a macroinitiator. The properties of polymer films of branched PLLA or PDLA obtained and their stereocomplex were investigated through thermal analysis and tensile testing. The branched PLLA or PDLA film exhibited a lower glass transition temperature (T_g), melting temperature (T_m), crystallinity, Young's modulus and a higher strain at break than the corresponding linear PLLA or PDLA film. The branched PLLA/branched PDLA stereocomplex film showed a high maximum stress and a high Young's modulus keeping its high strain at break. Moreover, the usefulness of branched PLLA or PDLA as a plasticizer of linear PLLA was investigated with 1:9 blend or stereocomplex film prepared from the branched PLLA or branched PDLA and linear PLLA. The blend or linear PLLA/branched PDLA stereocomplex film showed a higher strain at break compared with linear PLLA film. The mechanical properties of the blend or linear PLLA/branched PDLA stereocomplex film could easily be controlled by changing the molecular weight of branched PLA.     

Novel synthesis of branched polystyrenes by quasi‐living radical copolymerization using photofunctional inimer

Branched polystyrenes were prepared by quasi‐living radical copolymerization of N,N‐diethylaminodithiocarbamoylmethylstyrene (inimer: DTCS) with styrene under UV irradiation. DTCS monomers play an important role in this copolymerization system as an inimer capable of initiating living radical polymerization of the vinyl group. Two monomers (DTCS and styrene) showed equal reactivity toward both propagating species, and the copolymer composition was the same as the comonomer feed. This result means that both the branching and chain length of the hyperbranched molecules can be controlled statistically by the feed monomer ratios. The compact nature of the branched macromolecules is demonstrated by viscosity measurements compared to the linear analogues. © 2001 Society of Chemical Industry     

Polymerization of lactams,XLI. Molecular characterization of linear and branched polycaprylolactam

Samples of linear polycaprylolactam have been prepared and fractionated, and the [η]-M_w relationship has been established in m-cresol. Statistically branched samples have been obtained by copolymerizing 8-caprylolactam with bislactams. The degree of branching as well as the branching ability of different bislactams are discussed and compared with the corresponding data for branched polycaprolactams.     

Nonisothermal crystallization kinetics of ethylene–butene copolymer/low‐density polyethylene blends

Nonisothermal crystallization kinetics of the blends of three ethylene–butene copolymers with LDPE was studied using differential scanning calorimetry (DSC) and kinetic parameters such as the Avrami exponent and the kinetic crystallization rate (Z_c) were determined. It was found that the pure components and the blends have similar Avrami exponents, indicating the same crystallization mechanism. However, the crystallization rate of the blends was greatly influenced by LDPE. The Z_c of all the blends first increases with increasing LDPE content in the blends and reaches its maximum, then descends as the LDPE content further increases. The crystallization rate also depends on the short‐chain branching distribution (SCBD) of the ethylene–butene copolymers. The Z_c of the pure component with a broad SCBD is smaller, but its blends have a larger crystallization rate due to losing highly branched fractions after blending with LDPE. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 123–129, 2001