Showing papers in "Journal of Polymer Science Part A in 1978"

Applications of ESCA to polymer chemistry. XVII. Systematic investigation of the core levels of simple homopolymers

Abstract: The core levels of a series of 83 homopolymers have been studied by electron spectroscopy for chemical analysis (ESCA). Comparisons of the experimentally determined core-level binding energies with theoretical calculations using the ground-state potential model in the complete neglect of differential overlap (CNDO/2) self-consistent field molecular orbital (SCF MO) formalism have been made on the C1s and O1s core levels for the oxygen-containing polymers in the series. A comparison of the ground-state potential model (GPM) and relaxation potential model (RPM) on a series of six model compounds representative on the series of polymers is given. Compilations are given of binding energies of C1s, O1s, N1s, Cl2p, S2p, Si2p, and Br3d levels for typical structural features of common occurrence in polymer systems. These data, taken in conjunction with that previously published on fluoropolymers, provide a sound basis for the development of ESCA as a fingerprint tool in the elaboration of features of structure and bonding in polymers in general.

Particle nucleation in emulsion polymerization. I. A theory for homogeneous nucleation

Abstract: This paper is the first in a series intended to clarify the particle nucleation mechanisms in emulsion polymerization. The theory for particle nucleation by precipitation of oligomeric radicals from the water phase is discussed and a model based on the diffusion, propagation and termination steps is presented. The physical factors that influence the capture rate of oligomers in particles are discussed, and qualitative expressions for the electrostatic repulsion and reversible diffusion are derived. These factors are shown to be able to explain the relatively slow absorption rate of oligomers in particles and micelles. A kinetic model for simultaneous particle nucleation and limited flocculation is presented. Numerical integration of this model shows that the particle number goes through a maximum and that simultaneous nucleation and flocculation of primary particles may take place after Interval I in an emulsion polymerization is finished.

Influence of the fire retardant ammonium polyphosphate on the thermal degradation of poly(methyl methacrylate)

Abstract: The thermal degradation of ammonium polyphosphate (APP), a commercial fire retardant, and its blends with poly(methyl methacrylate) (PMMA) have been studied by thermal volatilization analysis (TVA) and the degradation products identified. APP degrades under vacuum in three stages. Initially it condenses to an ultraphosphate ( 370°C). In the presence of APP, the normal depolymerization of PMMA to monomer competes with degradation reactions which form high-boiling chain fragments, methanol, carbon monoxide, dimethyl-ether, carbon dioxide, hydrocarbons, and char. These additional reactions are initiated principally by the PPA. Intramolecular cyclization occurs, resulting in the formation of anhydride, and ester groups are eliminated, methanol and carbon monoxide being evolved. Further degradation of the modified polymer leads to the other volatile products and the char.

Dye‐sensitized photoinitiated cationic polymerization

Abstract: Several dyes have been discovered which sensitize the photolysis of diaryliodonium salts at visible wavelengths. By using the combination of a dye and a diaryliodonium salt, visible light can be used to photoinitiate cationic polymerization. In this article, the dye-sensitized photopolymerizations of cyclohexene oxide, epichlorohydrin, and 2-chloroethyl vinyl ether are described.

Thermal degradation of the polyurethane from 1,4-butanediol and methylene bis(4-phenyl isocyanate)

Abstract: A polyurethane prepared from 1,4-butanediol (BD) and methylene bis(4-phenyl isocyanate) begins to evolve volatile degradation products at approximately 240°C By a combination of thermal analysis methods (TVA, TG, and DSC) and examination of the volatile and involatile products by using a combination of GLC and infrared and mass spectrometric analysis, it is shown that the total reaction comprises a primary depoly-condensation process in which the two monomers are formed, followed by the subsequent reaction of these monomers to form the volatile products, tetrahydrofuran, dihydrofuran, carbon dioxide, water, butadiene, hydrogen cyanide, and carbon monoxide and residual carbodiimide and urea structures A mechanism, which accounts for all these products, has been formulated and tested

Relationships on the effect of water on glass transition temperature and young's modulus of nylon 6

Abstract: The glass transition temperature Tg of nylon 6 decreases monotonically toward a finite value Tgl upon increase of the moisture content. The mechanism of this decrease entails the reversible replacement of intercaternary hydrogen bonds in the accessible regions of the polyamide. The limiting glass transition temperature Tgl is approached when the moisture content approaches Wl, which corresponds to the amount of water required for complete interaction with all accessible amide groups. Denoting with Tg0 the glass transition temperature of the dry polymer, the effect of water on Tg is represented by the equation, Tg = (ΔTg)0 exp{−[ln(ΔTg)0]W/τWl} + Tgl, where (ΔTg)0 = Tg0 −Tgl, and τ = W(Tgl+1)/Wl. This equation appears to be generally applicable to hydrophilic polymers, since correspondingly calculated data are also in very good agreement with experimental data for polymers such as nylon 66, poly(vinyl alcohol), and polyN-vinylpyrrolidone. The effect of water of Young's modulus E of nylon 6 is represented by an analogous relationship, and the quantity In[(E−El)/(Tg−Tgl)] is a linear function of the moisture content.

Polymerization of cyclic esters of phosphoric acid. VI. Poly(alkyl ethylene phosphates). Polymerization of 2-alkoxy-2-oxo-1,3,2-dioxaphospholans and structure of polymers

Abstract: Five-membered cyclic esters of phosphoric acid of the general formula: CH2CH(R)OP(O)-(OR′)O polymerize readily to solid, soluble polymers of high molecular weight without any rearrangement known for various tri- and pentavalent organophosphorus monomers 1H-, 13C-, and 31P-NMR spectra of polymers confirmed their linear structure: where R is H, with R′ = CH3, C2H5, n-C3H7, i-C3H7; n-C4H9, CCl3CH2, or C6H5, or R is CH2Cl and R′ is C2H5 The use of n-C4H9Li, (C5H5)2Mg, or (i-C4H9)3Al as initiators leads to polymers with Mn = 104–105

Structure and extinction of counterflow diffusion flames above condensed fuels: Comparison between poly(methyl methacrylate) and its liquid monomer, both burning in nitrogen–air mixtures

Abstract: Since poly(methyl methacrylate) is known to depolymerize largely to its monomer when heated, the chemical kinetics in the gaseous diffusion flame produced by this polymer in a fire may coincide with that of burning liquid methyl methacrylate. To test this hypothesis, flat diffusion flames were probed and extinguished adjacent to surfaces of each of these fuels. Profiles of temperature and of concentrations of stable chemical species are reported, as are gas velocities of approach flow required to produce extinction for various oxygen/nitrogen ratios of the stream. Results revealed structural differences attributable to differing thermal properties of the fuels. Many fuel species were observed in the gas phase, their profiles being partially rationalized on the basis of a suggested decomposition mechanism for gaseous methyl methacrylate. Overall kinetic parameters for gasphase combustion, obtained by use of extinction results in a previously developed theory, are nearly the same for the polymer and monomer but appear to differ by amounts exceeding experimental uncertainties. It is suggested that this may be traced to small differences in fuel species leaving the condensed phase which, for the polymer, is covered by a thin, two-phase region.

ESCA applied to polymers. XVIII. RF glow discharge modification of polymers in helium, neon, argon, and krypton

Abstract: The crosslinking of an ethylene–tetrafluoroethylene copolymer by exposure to a variety of inert gas plasmas, excited by an inductively coupled radiofrequency (RF) field, has been studied. The rates for direct and radiative energy-transfer processes are determined within the framework of a kinetic model of the system and are shown to have a strong dependence on the sustaining gas, as do the average depths of penetration of the ions and metastable species. Helium is found to be the most efficient gas for the crosslinking of the outermost few monolayers whereas the crosslinking of the subsurface and bulk polymer is best effected by neon. Madelung charge potential calculations have been performed to simulate the experimentally determined x-ray photoelectron spectroscopy (ESCA) spectra to elucidate several features of the mechanisms involved.

Thermooxidative degradation of polyethylene. I and II. Structural changes occurring in low‐density polyethylene, high‐density polyethylene, and tetratetracontane heated in air

Abstract: Samples of low-density polyethylene (LDPE), high-density polyethylene (HDPE), and tetratetracontane (n-C44H90) free from additives were heated in air at temperatures between 120 and 180°C. As a comparison, “as received” HDPE containing unspecified additives has also been included. The structural changes have been studied with gel chromatography, viscometry, infrared spectroscopy, differential scanning calorimetry, and gravimetric measurements. LDPE, HDPE, and n-C44H90 follow the same course of thermooxidative degradation when they are free from additives and present in the molten state. Both molecular-diminishing and enlargement reactions occur. At temperatures below 150°C molecular enlargement is not observed until after rather long exposure times, whereas at higher temperatures enlargement occurs immediately. The difference is because “peroxide curing” becomes increasingly important above 150°C, whereas ester formation is operating at all temperature levels. Degradation below Tm is restricted to the amorphous phase that results in a different degradation pattern. In accelerated testing work extrapolations of the Arrhenius type in the prediction of structural change are thus not justified, even within the actual narrow temperature range. Neither are changes in commonly used standards like carbonyl content justified as a measure of the changes; for example, in mechanical properties. The stabilizer in the unpurified HDPE not only influences the induction period but also the course of the thermooxidative degradation.

Urea-formaldehyde resins. III. Constitutional characterization by 13C fourier transform NMR spectroscopy

Abstract: 13C Fourier transform NMR has been used to characterize a random chemical structure of ureaformaldehyde resins. By comparison of 13C chemical shifts with synthesized standard derivatives from urea and formaldehyde the analysis of reacted formaldehyde was completed. In a 13C spectrum of resin each signal due to reacted formaldehyde (e.g., methylol group, methylene group, and dimethylene ether group) was isolated. Measurement of a 13C spectrum of resin by the gated decoupling of proton without nuclear Overhauser effect made a quantitative analysis of reacted formaldehyde possible. In this quantitative analysis a 13C quantity of carbonyl groups in urea residue can be directly compared with that of each combined formaldehyde.

Estimation of monomer reactivity ratios by nonlinear least-squares procedure with consideration of the weight of experimental data

Abstract: To obtain the optimum values of the monomer reactivity ratios for the copolymerization systems with largely different reactivities between both monomers, a nonlinear least-squares procedure which took into account the weights of experimental data, was proposed and discussed. The weights of the data were treated for the errors arisen from the amounts of monomers charged, the densities of monomers, the weights of copolymer formed, and the composition of copolymer. The least-squares procedure with the consideration of the weights was applicable to both differentiated equation and integrated equation derived by Lewis and Mayo. This procedure was applied to radical copolymerizations of α-substituted crotonic esters with styrene, and reasonable monomer reactivity ratios were obtained. It was noted that errors from the copolymer composition were more important than those from the other factors and that the use of the integrated equation was recommended even when the copolymers were isolated at low conversions.

Optical resolution of mandelic acid derivatives by column chromatography on crosslinked cyclodextrin gels

Abstract: Crosslinked α- and β-cyclodextrin gels (α-CD-E and β-CD-E) were used for the chromatographic resolution of racemic mandelic acid and its derivatives. β-CD-E bound L-(+)-isomers preferentially over D-(−)-isomers and resolved DL-methyl mandelate to give a D-(−)-isomer of 100% optical purity in the first fraction. Mandelic acid, ethyl mandelate, and O-methylated mandelic acid yielded resolutions of 65–83% in initial fractions. α-CD-E, on the contrary, bound D-(−)-isomers more strongly than L-(+)-isomers, resolving DL-methyl mandelate to a smaller extent than β-CD-E. Binding of DL-mandelic acid and DL-methyl mandelate on β-CD-E was studied quantitatively by the equilibrium method. β-CD-E has a similar binding capacity to starch with 1:1 stoichiometry but bound much more strongly than starch. β-CD-E has the same mode of selectivity as starch for the asymmetric binding of the mandelic acid derivatives, but α-CD-E has a reverse selectivity to β-CD-E and starch.

Modification of properties of ion-exchange membranes. IV. Change of transport properties of cation-exchange membranes by various polyelectrolytes

Abstract: A change in electrodialytic transport properties of various cation exchange membranes was observed after the membranes had been adsorbed or ion-exchanged with various cationic polyelectrolytes. Transport properties measured in this report were the relative transport number of calcium ion to sodium ion PCaNa, the current efficiency of cations, and the electric resistance of the membrane during the electrodialysis. Weakly basic and strongly basic cationic polyelectrolytes of various molecular weights were used. Though PCaNa of any cation exchange membrane decreased by the adsorption or ion exchange of any cationic polyelectrolyte, the degree of the decrease in PCaNa changed with species and molecular weight of polyelectrolytes and species of cation-exchange membranes. Weakly basic polyelectrolytes and low molecular weight, strongly basic polyelectrolytes were effective in producing a marked decrease in PNaCa of any cation exchange membrane. The effect of strongly basic polyelectrolytes of high molecular weight on PCaNa was weak in most cases. However, if it was possible to make the polyelectrolyte adhere to the surface of the membrane to form a compact coiled structure, any cationic polyelectrolyte was effective in producing a remarkable decrease in PCaNa of any cation-exchange membrane.

Storage stability of reactive phenolic dispersions

Abstract: Storage stability of an aqueous phenolic dispersion resin has been studied by accelerated methods with chemical kinetics and centrifugation. The activation energy of the resin advancement reaction was 25.6 kcal/g mole. Results indicate that the chemical and physical properties of the dispersion resin do not change significantly in a storage period of 4.5 months under normal conditions (25°C). Under refrigeration (4°C) the product is stable indefinitely for all practical purposes.

Improved methods of estimating monomer reactivity ratios in copolymerization by considering experimental errors in both variables

Abstract: Existing methods of calculating monomer reactivity ratios in copolymerization are reviewed briefly, evaluated, and classified according to their mathematical and computational similarities. More attention is paid to procedures based on the integrated copolymer equation with which calculation of r values is performed most often by electronic computer. Unfortunately, until now all procedures have shown shortcomings because the real-error structure of the observations has not been taken into account. A new algorithm that does account correctly for measurement errors in both variables is described. A computational method is illustrated for copolymerization data obtained from quantitative gas chromatographic analysis of the monomer feed throughout the reaction. It is shown that the actual error structure of the variables corresponds to the assumed error structure. Reliability of the estimates is substantially increased, compared with the existing methods. Standard deviations of the monomer reactivity ratios are given and appear to be in good agreement with reality.

13C NMR spectroscopic study of epoxidized 1,4‐polyisoprene and 1,4‐polybutadiene

Abstract: Partly epoxidized cis- and trans-1,4-polyisoprenes and cis-and trans-1,4-polybutadienes were prepared, and their 13C NMR spectra examined. All the prominent resonances in the spectra of the epoxidized polymers were assigned by using lanthanide shift reagent and off-resonance decoupling experiments. A 13C NMR method of quantitative assessment of the epoxide content was developed following determination of relative spin-lattice relaxation time (T1) and nuclear Overhauser effect (NOE) parameters of the various carbons in the epoxidized polyisoprenes and polybutadienes.

Viscoelasticity of rubber‐resin mixtures

Abstract: The dynamic viscoelastic response of blends in various proportions of natural rubber with each of two tackifier resins, a poly(β-pinene) and a pentaerythritol ester of hydrogenated rosin, has been investigated. Results are presented in the form of master curves of the modulus G′r and the viscosity η′r against frequency. The two resins show remarkably similar behavior in modifying the viscoelastic behavior of the rubber; the most obvious effects of increasing resin concentration are (a) a displacement of the transition zone toward lower frequencies, (b) a reduction in width and eventual elimination of the “rubbery plateau,” and (c) a displacement of the terminal zone in the direction of higher frequencies. The effect (a) is interpreted in molecular terms as a restriction of segmental motion and may be quantitatively evaluated in terms of reduced fractional free volume and increased monomeric friction coefficient. Effects (b) and (c) are explicable in terms of reduced average molecular weight, with consequent reduction in entanglement coupling and resistance to viscous flow. Quantitative analysis of the results, using relaxation time spectra, lends support to the iso-free-volume theory of the glassy state and shows a correlation between fractional free volume and monomeric friction coefficient.

An investigation of the thermolysis mechanism of model urethanes

Abstract: The products of pyrolysis in a helium atmosphere of a model urethane foam based on PAPI and propoxylated trimethylol propane were investigated by using GC/MS and GC/CIMS. Chemical-ionization mass spectrometry was used because it produces primarily protonated molecular ions (M + 1) with little fragmentation which facilitated the identification of the polyol decomposition products. Identification of the polyol pyrolysis fragments has led to the formulation of a detailed polyol thermolysis mechanism. This mechanism shows the polyol to decompose by a systematic route of reactions rather than by a random breakdown.

Microstructure determination of poly‐(1,3‐pentadiene) by a combination of infrared, 60‐MHz NMR, 300‐MHz NMR, and X‐ray diffraction spectroscopy

Abstract: A quantitative procedure has been developed for characterizing the complete microstructure of polymers of 1,3-pentadiene, including the tacticity of any crystalline component. This can be accomplished by a combination of infrared spectroscopy, X-ray crystallinity, and 300-MHz NMR spectroscopy. A series of high structural purity polymers were synthesized with a series of previously unreported mixed microstructures. These samples were characterized by using the three techniques mentioned, including the previously unreported 300-MHz NMR data. With those results a 60-MHz NMR/IR method of spectroscopy was developed to determine the composition of poly(1,3-pentadiene)s in terms of percent cis-1,2-, cis-1,4-, trans-1,4-, and 3,4-pentadiene units.

Preparation and degradation of salts of poly(methacrylic acid). I. Lithium, sodium, potassium, and caesium salts

Abstract: The polymers of lithium, sodium, potassium, and caesium salts of methacrylic acid have been prepared by free radical polymerization of the respective monomers in methanol solution. The degradation behavior of the polymers has been investigated by thermal volatilization analysis, thermogravimetry, and product analysis. These materials are stable to about 350°C under programmed heating at 10°C/min in vacuo. The principal degradation products are monomer, the corresponding isobutyrate, carbonate, oxide, carbon dioxide, and a fraction of liquid volatiles that is complex and contains a variety of aldehydes and ketones. The mechanism of degradation is discussed in detail.

Degradation of polymer mixtures. IX. Blends of polystyrene with polybutadiene

Abstract: The degradation of cis-1,4-polybutadiene, polystyrene, and blends of PB and PS has been studied by thermogravimetry, thermal volatilization analysis, and differential scanning calorimetry. Volatile products have been investigated and separated by subambient TVA and characterized spectroscopically. In the degradation of the blends, there is no change in the nature of the volatile products of degradation, but the rate of degradation of the PS component is markedly reduced. The PB component is the first to break down, and during the initial period of degradation of the PB, the PS degradation is apparently inhibited. It is suggested that some of the volatile products of decomposition of PB, most notably 4-vinylcyclohexene, may diffuse into the PS phase in the blend and act as radical inhibitors.

Synthesis of N-substituted bisitaconimide monomers for use as thermosetting polyimide resins

Abstract: Two monomeric N-substituted bisitaconimides, N,N′-bisitaconimido-p,p′-diphenylmethane and N,N′-bis(itaconimido-p,p′-diphenyl ether), were synthesized from the corresponding diamines. The synthesis was accomplished by reaction of the diamine with itaconic anhydride and cyclocondensation of the resultant bisitaconamic acid. Attempts to use p,p′-diaminodiphenylsulfone as the diamine gave N,N′-biscitraconimido-p,p′-diphenylsulfone and N-citraconimido-N′-itaconimido-p,p′-diphenylsulfone instead of the bisitaconimide. The two bisitaconimides polymerize thermally at 180°C and 225°C, respectively, and yield tough polymers with very high thermal stability.

Distribution of polymer deposition in plasma polymerization. II. Effect of reactor design

Abstract: The effects of relative positions of the monomer inlet and the r.f. coil, and of the inlet and outlet, on the distribution of polymer deposition in plasma polymerization of ethylene were investigated using an electrodeless glow discharge by a 13.5-MHz radiofrequency source. The diffusional transport of active species created under the r.f. coil, diffusional transport of polymer forming species, and flow of gas in the system are important factors that determine the distributions of polymer deposition observed in plasma polymerization of ethylene. The mechanisms of polymer deposition are discussed in conjunction with postulated plasma polymerization mechanisms.

Acetylation of DMSO:PF solutions of cellulose

Abstract: Three different techniques for esterifying solutions of cellulose dissolved in mixtures of dimethyl sulfoxide (DMSO) and paraformaldehyde (PF) were evaluated and are herein described. The evaluation and development of suitable synthetic procedures and the characteristics of the resulting acetylated cellulose are reported. Glacial acetic acid (glacial HOAc), acetyl chloride (AcCl), and acetic anhydride (Ac2O) were compared as acetylating agents for solutions of cellulose in DMSO:PF, and it was demonstrated that mixtures of pyridine (Py) and Ac2O rapidly acetylated the cellulose to yield beige to amber acetone-soluble cellulose acetates which were partially oxidized. These thermoplastic resins exhibited softening points between 80 and 110°C and thermal stabilities (in nitrogen atmospheres) similar to those of native celluloses (350 to 375°C). Degree of acetyl substitution (DS) values ranged from 0 to 2.0 as a function of acetylation time.

Synthesis and study of block copolycondensates containing polysiloxane and unsaturated polyester blocks in the chain. II. Poly(unsaturated esters‐b‐siloxanes) with blocks linked by SiC bonds and poly(butadienes‐b‐siloxanes)

Abstract: Poly(unsaturated esters-b-siloxanes) whose blocks are linked by SiC bonds and poly(butadienes-b-siloxanes) have been obtained by polycondensation of ω,ω′-diepoxy polydimethylsiloxanes and ω,ω′-dicarboxylic poly(unsaturated esters). The reaction between polysiloxanes with SiH end groups and allylepoxy has been studied; the resulting ω,ω-diepoxy polysiloxanes have the expected structure. The polycondensation of oligomers with, respectively, epoxy and carboxylic end groups has been studied and the optimal conditions established. The samples with SiC bonds are not affected by hydrolysis in pure water. The poly(siloxanes-b-unsaturated esters) can be cured by UV light.