Ammeline–melamine–formaldehyde resins. Preparation and properties

Ammeline–melamine–formaldehyde resins (AMF Resins) containing 5–100 mol % of ammeline, were synthesized by polymerization of the preformed sodium salt of ammeline, melamine, and formaldehyde in basic medium by three methods. These resins, when cured, constitute a new class of thermosets. The rate of hydroxymethylation of the amino groups of the ammeline salt with formaldehyde was somewhat larger then that of the amino groups on melamine. At higher pH values ammeline insolubility was not a problem. The AMF resin composition was approximately equal to the mol ratio of the components originally charged. Both ammeline and melamine were consumed over the entire reaction period. Thus, it is possible to make approximately uniform random ammeline-melamine-formaldehyde resins (AMF) with any mol ratio of ammeline salt to melamine. By controlling the pH of the solution from which the resins were isolated, the (SINGLE BOND) O⁻ Na⁺/(SINGLE BOND) OH ratio could be varied. Resin melting points varied widely with the mol fraction of ammeline and the (SINGLE BOND) O⁻ Na⁺/(SINGLE BOND) OH ratio. AMF resin solubilities, shelf lives, cloud points, and water tolerance depended upon the method of preparation, pH, and other factors. The sodium salt of ammeline was hydroxymethylated in water more readily than ammeline. More highly methylolated ammeline species were readily formed in solution but upon precipitation only bis-N-hydroxymethylammeline was isolated. © 1996 John Wiley & Sons, Inc.     

Properties of ethylene–propylene–vinyl chloride graft copolymers. I. Viscoelasticity of ethylene–propylene copolymers

The viscoelastic behavior of two different ethylene–propylene copolymers was studied as a function of the molar ratios of the components and the distribution of the lengths of the ethylene and propylene sequences. The glass transition temperatures T_g agree with the values calculated from relations between T_g and component ratio established by other authors. The copolymer with longer ethylene and propylene sequences was found to exhibit a relaxation spectrum with a slope less steep than ?0.5. This broadening is explained by the broader distribution of friction factors of the statistical segments in this copolymer and by differences in crystallike nearest-neighbor packing.     

Hydrogenated polybutadiene–polymethyl methacrylate (HPB–PMMA) block copolymer. I. Synthesis of polybutadiene–polymethyl methacrylate (PB–PMMA) block copolymer

To get hydrogenated polybutadiene-polymethyl methacrylate (HPB-b-PMMA) block copolymer to be used as a compatibilizer for blends of polyolefin/polar polymer, PB-b-PMMA was synthesized by anionic-free radical mechanism transformation polymerization. Selective extraction, gradient elution thin layer chromatography, and oil-oil emulsion separation techniques were tried to attempt to separate the copolymerization products. Hydrogenation of the PB sequence in PB-b-PMMA yielded HPB-b-PMMA. The compatibilizing function of PB-b-PMMA was shown in blending experiments. © 1993 John Wiley & Sons, Inc.     

Boc–Pro–Hyp–Gly–OBzl and Boc–Ala–Hyp–Gly–OBzl,two repeating triplets found in collagen

The protected tripeptides benzyl N‐{2‐[N‐(tert‐butoxy­carbon­yl)­prol­yl]‐4‐hydroxy­prol­yl}glycinate or Boc–Pro–Hyp–Gly–OBzl, C₂₄H₃₃N₃O₇, and benzyl N‐{2‐[N‐(tert‐butoxy­carbon­yl)­alan­yl]‐4‐hydroxy­prol­yl}glycinate or Boc–Ala–Hyp–Gly–OBzl, C₂₂H₃₁N₃O₇, are the minimum repeating triplets found in collagen. Within the crystal structure of each are two independent peptide mol­ecules with similar structures. The peptides are arranged anti­parallel to one another and inter­act through hydrogen bonds involving the main chains and the 4‐hydroxy­prolyl groups. The structures exhibit characteristics of a triple helix, but the peptides tend to assume a sheet‐like structure.     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. II. Dynamic mechanical properties

A variety of new polymeric materials ranging from soft rubbers to hard, tough, and brittle plastics were prepared from the cationic copolymerization of regular soybean oil, low saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and divinylbenzene initiated by boron trifluoride diethyl etherate (BF₃ · OEt₂) or related modified initiators. The relationship between the dynamic mechanical properties of the various polymers obtained and the stoichiometry, the types of soybean oils and crosslinking agents, and the different modified initiators was investigated. The room‐temperature storage moduli ranged from 6 × 10⁶ to 2 × 10⁹ Pa, whereas the single glass‐transition temperatures (T_g) varied from approximately 0 to 105 °C. These properties were comparable to those of commercially available rubbery materials and conventional plastics. The crosslinking densities of the new polymers were largely dependent on the concentration of the crosslinking agent and the type of soybean oil employed and varied from 74 to 4 × 10⁴ mol/m³. The T_g increased and the intensity of the loss factor decreased irregularly with an increase in the logarithmic crosslinking densities of the polymers. Empirical equations were established to describe the effect of crosslinking on the loss factor in these new polymeric materials. The polymers based on conjugated LoSatSoy oil, styrene, and divinylbenzene possessed the highest room‐temperature moduli and T_g 's. These new soybean oil polymers appear promising as replacements for petroleum‐based polymeric materials. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2721–2738, 2000     

Dilute solution properties of styrene–acrylonitrile and styrene–methyl methacrylate copolymers. I. Intrinsic viscosity–molecular weight relations

Styrene–acrylonitrile (St–AN) copolymers of three compositions—27.4 mole-% (SA₁); 38.5 mole-% (SA₂); and 47.5 mole-% (SA₃) acrylonitrile—and styrene–methyl methacrylate (St–MMA) copolymer (SM) of 46.5 mole-% methyl methacrylate were prepared by bulk polymerization at 60°C with benzoyl peroxide as the initiator, and were then fractionated. The molecular weights of unfractionated and fractionated samples were determined by light scattering in a number of solvents. The [η] versus M?_w relations at 30°C were established for SA₁, SA₂, SM, and polystyrene (PSt) in ethyl acetate (EAc), dimethyl formamide (DMF), and γ-butyrolactone (γ-BL), and for SA₃ in methyl ethyl ketone (MEK), DMF, and γ-BL. Second virial coefficients A₂ and the Huggins constant were determined. From values of A₂ and the exponent a of the Mark–Houwink relation it is seen that the solvent power for samples SA₁, SA₂, and PSt is in the order EAc < γ-BL < DMF, while for sample SA₃ the solvent power is in the order MEK < γ-BL < DMF. The solvent power decreases with an increase in AN content. The solvent power of the three solvents used for SM copolymer sample is practically the same within experimental errors. From the a values it is concluded that in a given solvent the copolymer chains are more extended than the corresponding homopolymers.     

Generation of free radicals at subzero temperatures. III. Polyamine–hydroperoxide–iron system

The mechanism of the reaction of tetraethylenepentamine (TEPA) with cumene hydroperoxide (CHP) and iron ions was investigated. It was found that (1) TEPA did not reduce Fe(III); (2) TEPA was consumed by this reaction; (3) both Fe(II) and Fe(III) were effective for this reaction. It was shown that though the O? O bond of a hydroperoxide could be cleaved only at elevated temperatures, it could be easily cleaved by the reaction with the iron–TEPA complex. The function of this iron–TEPA complex is discussed.