Evaluation of long chain branching of polyphenylene sulfide using gel permeation chromatography with triple detection

The increasing polyphenylene sulfide (PPS) world demand due to its unique mechanical and chemical properties has augmented the pressure on development of analytical methods to evaluate its molecular weight distribution and structure. This article presents gel permeation chromatography with triple detection (GPC3D) performed in chloronaphthalene at 210°C on a commercially available instrument as a possible method to elucidate the structure properties of linear and branched PPS. The procedure allows measurement in a single run of the true molecular weight distributions and intrinsic viscosities, the Mark-Houwink parameters, and the number of long chain branches.     

Effect of polyborazine additive on thermolysis of polyphenylsilane and polyvinylsilane

To improve the ceramic residue yields and processabilities of polyphenylsilane (PPS) and polyvinylsilane (PVS), polyborazine (PBN) was employed as an additive. The ceramic residue yield of PPS increased from an original 39wt% to 65wt%, and of PVS from an original 26wt% to 64wt% by simply heating with 1wt% PBN at 70 °C. Furthermore, low viscous PPS and PVS were transformed into highly viscous polymers, which were found to be suitable for hand drawing into green fibers. The enhanced properties were attributed to an increased molecular weight, as analyzed by GPC. ¹H-NMR and ²⁹Si-NMR spectra suggested that dehydrocoupling of SiH₃ in PVS and SiH in PPS by PBN was responsible for the improved ceramic yields.     

SOLUTION PROPERTIES OF LADDER-LIKE POLYMER POLYPHENYLSILSESQUIOXANES

Solution properties of ladder-like polymer polyphenylsilsesquioxane (PPS) were studied by measurement of intrinsic viscosity, small angle laser light scattering and gel permeation chromatography. It was found that PPS can be modeled with a wormlike continuous cylinder rather than a wormlike coil. A plot of (M~2/[η])~(1/3) vs. M~(1/2) was employed in obtaining the persistence length (2λ)~(-1) and effective hydrodynamic diameter. When MW≤5×10~5, Mark-Houwink equation is adequate in describing the relationship between MW and [η] with αabout unity. This implies that PPS chain is semi-stiff. For GPC experiments, it was shown that universal calibration can be applied in PPS. When molecular weights of PPS are sufficiently high, their molecular weight distributions are often very broad.     

Polymerization of α-Methylstyrene in Cyclohexane with Potassium as Initiator. IV. Thermodynamic Study and Gel-Permeation Chromatographic Analyses of the Polymers

Polymerization of α-methylstyrene in cyclohexane containing traces of tetrahydrofuran (THF) has been carried out at 40°C with potassium as initiator. The conversion of monomer to polymer was very slow, and a solution with [M]₀ of 5.15 mole/ liter, carrying 0.110 mole/liter of the living ends [LE], required two months to reach a stationary state. The gel-permeation chromatographic (GPC) analyses of these polymers showed them to have multimodal distributions which could be split into components D+A, B, and C similar to those found for poly-α-methylstyrene prepared in THF and α-dioxane as solvents. Furthermore, under identical conditions of [M]₀ and [LE], the GPC distributions of poly-α-methylstyrene prepared in cyclohexane, p-dioxane, and THF were the same, in spite of their different dielectric constants. Under identical conditions of [M]₀ but with different [LE], the effect of excessive [LE] on the GPC distributions of the polymers prepared in cyclohexane was not limited to the component D+A as was the case when THF or p-dioxane were the solvents, but also on the component C which increased its contribution [P]_e to the polymer.     

Two-dimensional gel permeation chromatography (2D GPC) correlation studies of the aggregate-aggregate interactions in acid-catalyzed triethoxysilyl-terminated polystyrene systems. The effect of specific catalysts on growth process

A set of time resolved gel-permeation chromatography (GPC) profiles, for the reaction mixture of a well-defined polymeric silane coupling agent, triethoxysilyl-terminated polystyrene with molecular weight equal to 8000 (TESi-PS (8000)), catalyzed by HCl (0.1 mol/kg) in tetrahydrofuran (THF), was measured over a long time scale (1–768 h). The GPC profiles were then converted to two-dimensional (2D) correlation spectra. The 2D GPC correlation spectra were compared with those for the CH₃SO₃H (0.1 mol/kg)-catalyzed TESi-PS (8000)-THF system. It has been demonstrated that predominant production of less-reactive oligomers in the HCl-catalyzed system hinders further growth of the oligomer, while formation of reactive oligomers leads to further growth of polymeric precursors in the CH₃SO₃H-catalyzed system.     

A new solvent system for gel-permeation chromatography of poly(ethylene terephthalate)

A new solvent system comprising a mixture of nitrobenzene and tetrachloroethane has been developed for determining the molecular size distribution of poly(ethylene terephthalate) (PET) by gel-permeation chromatography (GPC). Unlike hot m-cresol, which until now has been the standard GPC solvent for PET, the nitrobenzene–tetrachloroethane mixture can be used at room temperature and thus minimizes polymer degradation and distribution equilibration. Results with this new system reveal reproducibly discernible differences between PET samples prepared by melt and solid-state polymerization, differences not previously noted in GPC reports based on the use of m-cresol.     

Molecular weight analysis of pitches and polymeric pitches by gel-permeation chromatography

The technique of gel-permeation chromatography (GPC) has been developed as a method for measuring molecular weight distribution in pitch materials. Molecular weight calibration data were obtained from measurements made on GPC fractions collected from a standard pitch. By solubilization of the polymeric portion of pitch through a reduction with lithium in ethylenediamine, the molecular weight range for analysis was extended to in excess of 3000. Mass spectroscopy has been used to further analyze some of the GPC fractions. The GPC calibration data can be employed, with the aid of computer analysis, to determine quantitatively number-average molecular weights M?_n weight-average molecular weights M?_w, and molecular weight distribution D (= M?_w/M?_n) in pitch materials.     

Laser photolysis studies of β-bond cleavage of phenacyl phenyl sulfide in acetonitrile

Photo-induced β-bond dissociation of phenacyl phenyl sulfide (PPS) has been investigated in acetonitrile by laser photolysis techniques. Direct excitation of PPS at 295 K provided the acetylmethyl and phenylthiyl radicals with a quantum yield (Φ_rad) of 0.18, whereas triplet sensitization using xanthone revealed an efficiency for β-cleavage of triplet PPS (α _rad) of ≥0.64. From disagreement between the Φ_rad and α _rad values, it was concluded that both the lowest excited single and triplet states are reactive for β-bond dissociation in PPS. The photochemical processes of excited PPS, including β-cleavage, are discussed in detail.     

Low-density polyethylene: Variation of branching frequency with molecular weight and its influence on molecular weight as determined by gel-permeation chromatography

A method for determining long-chain branching frequency and molecular weight averages for unfractionated low-density polyethylene (LDPE) by the combined use of gel-permeation chromatography (GPC) and intrinsic viscosity data has been reported (GPC–IV method). The method assumes that the number of long branches λ per unit molecular weight is a constant independent of molecular weight. Recent data reported on λ as a function of molecular weight M in commercial LDPE indicate that this assumption is not generally valid, and concern has been expressed as to the size of the errors in molecular weights calculated using this assumption. The errors associated with assuming that λ is constant were evaluated in this study by first determining the way in which λ varies with M for two typical commerical LDPE resins by fractionation and application of the GPC–IV method to representative fractions. The experimentally determined relations between λ and M were then employed in the calculation of molecular weight and molecular size averages from GPC–IV data on the original unfractonated samples. Although it was found that λ increases with molecular weight for both samples, the results indicate that the error involved in assuming that λ is a constant is no greater than the precision with which molecular weight averages can be evaluated by GPC.     

Synthesis and Characterization of Monodisperse α,ω-Divinylpolydimethylsiloxane and ω-Vinylpolydimethylsiloxane

Abstract

ω-Vinylpolydimethylsiloxanes (ω-PDMS) and α,ω-divynilpolydimethylsiloxanes (α,ω-PDMS) have been synthesized by anionic polymerization of hexamethylcyclotrisiloxane (D3). The reactions were carried out in n-hexane and tetrahydrofuran (THF), respectively. The initiator was n-butyl-lithium (n-BuLi); tetrahydrofuran was used as an electron donor compound to promote the polymerization of D3. The synthesized polymers have been characterized by infrared (FTIR), proton nuclear magnetic resonance spectroscopy (NMR), light scattering (LALLS), and gel permeation chromatography (GPC). Molecular weights ranging from 20,000 to 100,000 were obtained with relatively narrow molecular weight distributions; Mw/Mn < 1.25.     

Synthesis and characterization of graft copolymers containing poly(p-phenylene) main chains and mesogen-jacketed liquid-crystalline polystyrene side chains

A series of novel comblike mesogen-jacketed liquid-crystalline graft copolymers, poly(p-phenylene)-g-poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PPP-g-PMPCS) copolymers, have been designed and successfully synthesized by a Yamamoto coupling reaction and subsequent atom transfer radical polymerization (ATRP). ¹H NMR spectroscopy, ultraviolet–visible spectra, and gel permeation chromatography (GPC) have been used to confirm the molecular structure of the macroinitiator and the copolymers. A study of the polymerization kinetics of ATRP has shown that the molecular weight of the copolymer increases linearly with the conversion of the monomer, whereas the polydispersity remains narrow (≤1.28), indicating that the ATRP of 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene is well controlled. Thermogravimetric analysis and differential scanning calorimetry (DSC) measurements have indicated that the PPP-g-PMPCS copolymers have better thermal stabilities than the macroinitiator, and their thermal stabilities increase with increasing molecular weight. The liquid-crystalline behavior has been examined with polarized optical microscopy, DSC, one-dimensional wide-angle X-ray diffraction (1D WAXD), and two-dimensional wide-angle X-ray diffraction (2D WAXD). The results show that all the comblike copolymers exhibit obvious liquid-crystalline behaviors, even though the GPC molecular weight of the segments of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) have been determined to be far less than the critical value of linear PMPCS. Moreover, 1D WAXD measurements show that the temperature at which the comblike mesogen-jacketed liquid-crystalline copolymers can transform into a liquid-crystalline phase is low; about 20 °C in comparison with the linear ones. 2D WAXD analysis has revealed that these comblike copolymers should be assigned to a hexatic columnar nematic (Φ_HN) phase. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2543–2555, 2007     

Two-dimensional gel permeation chromatography (2-D GPC) correlation studies of the aggregate–aggregate interactions in acid-catalyzed triethoxysilyl-terminated polystyrene systems: weak catalysis by HNO<Subscript>3</Subscript>

Time-resolved gel-permeation chromatography (GPC) profiles were measured over a long period of time (t=0–768 h) for the HNO₃-catalyzed reaction mixture of a well-defined polymeric silane coupling agent, triethoxysilyl-terminated polystyrene. The results showed that HNO₃ catalyzes the rate of polymerization, but only to a small extent. Two-dimensional (2-D) GPC correlation spectra were calculated from time-resolved GPC profiles and were used to examine the mechanism of polymerization. The resolution enhancement obtained by 2-D correlation provided ample evidence for existence of four monomeric components. It has been demonstrated that dynamic variation in the population of these components occurs over a long reaction time, reflecting the mechanism of a slow polymerization process.     

NOVEL MOLECULAR PHOSPHORUS SULFIDES WITH S/P HIGHER THAN 2.5. I. GENESIS AND CHARACTERIZATION BY PHYSICAL AND CHEMICAL METHODS

Abstract

PS _x alloys (x = 2.75 to 71.5), prepared by heating P₄S₁₀ with excess sulfur at 300–312°C, have been extensively extracted by carbon disulfide at room temperature. The solutions have been shown by ³¹P NMR to contain, besides P₄S₁₀ and P₄S₉, a number of novel species, hereafter called soluble Phosphorus Poly-(or Per-)sulfides (PPS). Electronic and IR spectra are reported. All attempts at separating pure individual PPS have failed. Soluble PPS are metastable, with a definite tendency to polymerize. They are selectively desulfurized by Ph₃P. They decolorize Diphenylpicrylhydrazyl instantly. NMR monitored experiments led to a classification of soluble PPS according to their rate of hydrolysis.     

Poly(P-phenylene sulfide) hexafluoroarsenate: A novel conducting polymer

Poly(p-phenylene sulfide) (PPS) is a melt- and solution-processible polymer which on treatment with AsF₅ forms a blue-black material with a conductivity of 1–10 Ω^?1 cm^?1. Thermopower measurements indicate that the resulting polymer is p type, consistent with partial oxidation of the PPS by the AsF₅. The rate and extent of this doping process prove to be particularly sensitive to the degree of crystallinity of the starting polymer. There is also evidence of crosslinking of the polymer chains during the reaction with AsF₅. The details of both the chemistry and physics of the doping of PPS and several of its derivatives are presented.     

Phase separation in semicrystalline blends of poly(phenylene sulfide) and poly(ethylene terephthalate). II. Effect of poly(phenylene sulfide) homopolymer solubilization of PPS‐graft‐PET copolymer on morphology and crystallization behavior

The morphology and crystallization behavior of poly(phenylene sulfide) (PPS) and poly(ethylene terephthalate) (PET) blends compatibilized with graft copolymers were investigated. PPS‐blend‐PET compositions were prepared in which the viscosity of the PPS phase was varied to assess the morphological implications. The dispersed‐phase particle size was influenced by the combined effects of the ratio of dispersed‐phase viscosity to continuous‐phase viscosity and reduced interfacial tension due to the addition of PPS‐graft‐PET copolymers to the blends. In the absence of graft copolymer, the finest dispersion of PET in a continuous phase of PPS was achieved when the viscosity ratio between blend components was nearly equal. As expected, PET particle sizes increased as the viscosity ratio diverged from unity. When graft copolymers were added to the blends, fine dispersions of PET were achieved despite large differences in the viscosities of PPS and PET homopolymers. The interfacial activity of the PPS‐graft‐PET copolymer appeared to be related to the molecular weight ratio of the PPS homopolymer to the PPS segment of the graft copolymer (M_H/M_A). With increasing solubilization of the PPS graft copolymer segment by the PPS homopolymer, the particle size of the PET dispersed phase decreased. In crystallization studies, the presence of the PPS phase increased the crystallization temperature of PET. The magnitude of the increase in the PET crystallization temperature coincided with the viscosity ratio and extent of the PPS homopolymer solubilization in the graft copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 599–610, 2000     

Nonisothermal crystallization kinetics of poly (phenylene sulphide) in composites with a liquid crystalline polymer

The article deals with the melting and nonisothermal crystallization behavior of neat poly (phenylene sulphide) (PPS) and its composites with a thermotropic liquid crystalline polymer (TLCP)—Vectra A950, prepared by melt mixing and probed by differential scanning calorimetry. The various macrokinetic models namely, the Ozawa, the modified Avrami, the Tobin, and the Mo models were applied to describe the crystallization kinetics under nonisothermal conditions. The kinetic crystallizabilty of PPS/TLCP composites calculated using the approach of Ziabicki varies depending on these two composite composition‐induced effects. Similarly Mo model predicts that to obtain a higher degree of crystallizabilty for PPS/TLCP composites, a higher cooling rate should be used. The effective energy barrier based on the differential isoconversional method of Friedman is found to be an increasing function of relative degree of melt conversion. The effect is explained in terms of nucleation theory proposed by Wunderlich to crystallization of polymers. The Lauritzen–Hoffman parameters are estimated using G = 1/t_0.5 effective activation energy equation proposed by Vyazovkin and Sbirrazzuoli. The K_g values estimated from latter equations are more comparable with values obtained using isothermal crystallization data than 1/t_0.5 method. Furthermore, the kinetic analysis using this equation shows a regime transition from regime II to regime III for 100/00, 90/10, 80/20 PPS/TLCP composites, basically attributed to reduced mobility of PPS chains in composites. This regime II to III transition is accompanied by a morphological transition from defective spherulitic sheaf‐like structures to ordered sheaf‐like structures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1070–1100, 2010     

Concentration-resolved 2D correlation gel permeation chromatography study of aggregate-aggregate interactions in the polymerization products of triethoxysilyl-terminated polystyrene silane-coupling agent

Concentration-resolved 2D correlation gel permeation chromatography (GPC) has been used to examine the intricate details of the HCl-catalyzed polymerization of a polymeric silane-coupling agent (SCA), triethoxysilyl-terminated polystyrene (TESiPS). The concentration-resolved 2D correlation GPC maps directly reflect the marked difference in the aggregate-aggregate interactions of dilute and concentrated monomeric units, which govern the differences in the polymerized products. There is an optimum concentration of SCA for the enhancement of interfacial strength and subsequent polymerization. Thus, the concentration-resolved 2D correlation GPC technique can be used as a powerful tool for elucidation of aggregate-aggregate interactions and reaction mechanisms in a surface- or interface-enhanced reaction system. It has been shown that the yield value of polymerization products can be improved to a marked extent by choosing a high initial monomer concentration, due to the increase in the production of oligomers. Multiple reaction processes are promoted by the self-assembly of the monomeric and oligomeric components.     

Synthesis of poly(p‐phenylene sulfide) from bis(4‐bromophenyl) disulfide

Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006     

Method of determining the degree of branching from the gel permeation chromatogram for star-shaped SBS thermoplastic block copolymers

A novel GPC calculation method has been developed for characterizing star-shaped styrene–butadiene block copolymers (SBS). This method enables us to determine the degree of branching (number of arms per molecule) of the synthesized polymer without the need of a priori measurement of the true molecular weights of the SBS star polymer and its linear polymeric arm. To illustrate the simplicity of this method, nearly monodispersed three-arm and four-arm model star polymers have been purposely synthesized by linking living diblock polymeric arms of the polystyrene-block-polybutadiene type with silicon tetrachloride as the multifunctional linking agent. The good agreement between the degree of branching calculated from the GPC chromatogram and that actually measured by MALL (multiple angle laser light scattering) has corroborated the validity of the calculation method. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3393–3401, 1997     

Effect of sulfur-containing phenols and amines on the decomposition of hydroperoxides

The effect of polyphenol sulfides (PPS) and dithiolthione, the sulfur-containing derivative of acetone anil, on the decomposition of cumyl andn-decyl hydroperoxides (DHP) studied. The decomposition of cumyl hydroperoxide (CHP) in the presence of PPS is a complex multistep autocatalytic process during which an efficient catalyst for CHP decomposition is formed from the initial PPS. The PPS catalyst for CHP decomposition is deactivated in the reaction with peroxy radicals. Kinetic characteristics of the reaction between polyphenol sulfides and CHP are determined. Dithiolthione catalytically decomposes CHP and reacts with n-decyl hydroperoxide DHP in the stoichiometric ratio