Copolymer analysis by UV spectroscopy

An extensive and detailed analysis of copolymers was made by developing a rapid spectrophotometric method. Successful analysis of composition in styrene-p-methoxystyrene, styrene-p-chlorostyrene, and styrene-p-fluorostyrene copolymers were performed by UV spectrometry. Their absorption bands were investigated either with respect to pure polystyrene or with respect to the homopolymer of the other constituent at the same wavelength. Attempts to analyze copolymers of styrene-4-vinylpyridine and styrene-N-vinylcarbazole by similar methods were unsuccessful.     

Dipole moments of copolymers in relation to the distribution of polar monomer unit sequences

A method for evaluating the dipole moments of copolymers in relation to the distribution of polar unit sequences is proposed. Experimental data on the synthesis and dipole moments of styrene-p-chlorostyrene and styrene-p-methoxystyrene copolymers were used to calculate the effective dipole moment of a polar unit in a copolymer. For this purpose, we assumed the following effective moment values for the corresponding polar unit sequences along the copolymer chains: when both of the nearest neighbours are polar, μ_PP, when one of the nearest neighbours is polar and the other is non-polar, μ_PS, and when both of the nearest neighbours are non-polar, μ_SS. The relative magnitudes of μ_SS, μ_PS and μ_PP calculated for both copolymers reflect the influence of dipole-dipole interactions on the effective dipole moment of a polar unit in a copolymer molecule.     

Multi-directional blending for heterogeneous objects

This paper presents a novel multi-directional blending method for heterogeneous object design. Contrary to earlier studies, this paper introduces material blending through multiple features with different heterogeneous material composition. Feature-based method is used to represent and design heterogeneous objects with multi-directional material composition. The Voronoi diagram of multiple curves is constructed to generate bisector of the geometric domain. Then, metamorphosis from the bounding curve to multiple internal curves is performed using dynamic programming based optimization approach in two steps. First, optimum curve matching between internal curves and enclosing Voronoi cells is obtained. Then, an optimum ruling line alignment and insertion technique between the Voronoi diagram and the bounding curve is developed. Metamorphosis through complex concavities is also achieved. Finally, multi-directional material composition is mapped based on a set of relations.     

Complex assembly variant design in agile manufacturing. Part I: System architecture and assembly modeling methodology

In the distributed and horizontally integrated manufacturing environment found in agile manufacturing, there is a great demand for new product development methods that are capable of generating new customized assembly designs based on mature component designs that might be dispersed at geographically distributed partner sites. To cater for this demand, this paper addresses the methodology for complex assembly variant design in agile manufacturing. It consists in fundamental research in two parts: (i) assembly modeling; and (ii) assembly variant design methodology. This paper, the first of a two-part series, presents the assembly variant design system architecture and the assembly modeling methodology. First, a complementary assembly modeling concept is proposed with two kinds of assembly models, the hierarchical assembly model and the relational assembly model. The first explicitly captures the hierarchical and functional relationships between constituent components whereas the second explicitly captures the mating relationships at the form-feature-level. These models are complementary in the sense that each of them models only a specific aspect of assembly-related information but together they include the required assembly-related information. They are further specialized to accommodate the features of assembly variant design. As a result, two kinds of assembly models, the assembly variants model and the assembly mating graph are generated. These assembly models serve as the basis for assembly variant design which is discussed in the companion paper.     

Electro‐induced polymerization of acrylamide initiated by the potassium permanganate–titriplex VI redox system

The polymerization of acrylamide (AAm) was carried out with a potassium permanganate–Titriplex VI redox initiator system with and without electrolysis. Because of the high metal‐ion concentration in general, low‐molecular‐weight polymers were obtained (weight‐average molecular weight = 2600–4000). The effect of potassium permanganate and AAm concentrations and temperature on the polymerization yield was studied and compared with results obtained under the same experimental conditions used for electrolysis. The results of Fourier transform infrared spectroscopy, atomic absorption spectrometry, and scanning electron microscopy (SEM) results are given. SEM micrographs of the polymer obtained by electrochemical methods exhibited smoother surfaces than those obtained by nonelectrolytic methods. In the absence of potassium permanganate, there was no polymerization under experimental conditions. A possible reaction mechanism is suggested. The electro‐induced system resulted in about a 50% increase in the yield. Manganese content in the electro‐induced and chemical polymerization systems were 2.7 and 8.2%, respectively, supporting the yield increase in the electro‐induced system. A graphite electrode was used and resulted in a high yield and a fibrous polymeric structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1526–1534, 2001     

Synthesis and characterization of uv-curable acrylated urethane prepolymers,I. Effects of reactive diluents and relative humidity on physical properties

A UV-curable acrylated urethane prepolymer was synthesized from tolylene-2,4-diisocyanate (TDI), a polyether polyol (Arcol 1131) and endcapped with 2-hydroxyethyl methacrylate (HEMA) by addition reaction in the presence of dibutyltin dilaurate as catalyst. UV curing was performed with either diethylene glycol diacrylate or thiodiethylene glycol diacrylate as reactive diluent. The effects of reactive diluent types, their concentrations and the humidity of environment on mechanical properties of cured films were investigated. Changes in the tensile strength, elongation and Young's modulus values of the cured films upon addition of reactive diluents with different concentrations were related to the effect of the diluent on the crosslinking density of cured films. The increase of relative humidity from 50 to 95% caused a decrease of tensile strength and Young's modulus values of cured films. It is proposed that the decrease of these physical properties in high relative humidity is due to the formation of hydrogen bonding in polymer chains caused by water molecules.     

Acrytonitrile block copolymers

Summary Acrylonitrile was polymerized by an insertion process on being added to solutions containing the adduct of the reaction of tetrakis(dimethylamino) titanium (T4) and azobisisobutyronitrile (AIBN). The obtained azo-linked polyacrylonitrile has appropriate initiating functionality for a subsequent vinyl polymerization.     

Estimation of the equation of state exchange energy and entropy parameters of a polymer-solvent pair by intrinsic viscosity measurements

The intrinsic viscosity data of linear poly(4-chlorostyrene) in n-propylbenzene and isopropylbenzene were used to estimate the equation of state exchange energy (X₁₂) and entropy (Q₁₂) parameters. The quantities estimated for X₁₂ were 6.7 and 8.1 J cm^?3 and those of Q₁₂ were ?0.069 and ?0.063 J cm^?3 deg^?1 in n-propylbenzene and isopropylbenzene, respectively. The average values of the chain unperturbed dimension constant (K_o) and the characteristic ratio (C_x) were found to be 0.55 × 10^?3 dl mol^1/2g^?3/2 and 10.54, respectively, from the intrinsic viscosities measured at the corresponding θ-temperatures.     

Studies of linear polymer dimensions of poly(4-chlorostyrene) in various solvents around the θ temperatures by intrinsic viscosity

Intrinsic viscosities of poly(4-chlorostyrene) solutions in isopropyl-benzene and n-propylbenzene at temperatures above and below the theta (θ) temperatures of these solvents were measured using a capillary viscometer. The viscosity measurements were performed on three poly(4-chlorostyrene) samples having molecular weights (M?;_v) 1.75 × 10⁶, 6.5 × 10⁵ and 2.7 × 10⁵. A smooth and continuous contraction below the θ temperatures was observed for both solvents. The temperature dependence of [/eta] can be represented by a master curve in a plot of α³/eta|/tau|M^1/2 (g^1/2 mol^?1/2) versus |/tau|M^1/2 (g^1/2 mol^?1/2), where α/eta = [/eta(T)]/[/eta(θ)]^1/3 is the expansion factor and /tau = (T - θ)/T is the reduced temperature. A universal plot of reduced viscosity size (α/eta) versus reduced blob parameter (N/N_c) shows the achievement of collapsed state for T<θ. The prediction of thermal blob theory is also verified for T > θ. The temperature dependence of intrinsic viscosity, both below and above the θ temperature, exhibits similar behaviour to the temperature dependence of dipole moments for both of these solvents.     

Polyaminocarboxylic acids–Ce(IV) redox systems as an initiator in acrylamide polymerization

Acrylamide polymerization by Ce(IV)-polyaminocarboxylic acids, i.e., EDTA, DTPA, EGTA, and NTA, which have strong chelating properties, have been studied at different [H⁺], initiator concentration, and reaction time. Initiation of polymerization proceeds through the formation of the free radical after decarboxylation of the carboxyl group of polyaminocarboxylic acid. Results also indicate that the termination of the polymerization reaction is mainly mutual termination. Decrease of the rate of disappearance of the cerium(IV) is in the order of DTPA ≥ EDTA > NTA > EGTA. © 1993 John Wiley & Sons, Inc.