Dynamic Mechanical Properties and Adhesive Strengths of Emulsion Polymer by Power Feed Technique, I

Dynamic mechanical properties and adhesive strengths of power feed copolymer and random copolymer synthesized using styrene or methyl methacrylate and n-butyl acrylate were investigated. Although the two systems were synthesized from the same raw materials, power feed copolymer had a very broad transition compared with random copolymer. This fact was explained by the fact that the system synthesized through power feed method was an alloy of copolymers which are a continuous series from monomer A rich copolymers to monomer B rich copolymers. The dynamic mechanical behavior of film cast from solution was almost the same as that of emulsion film, which indicated more extensive application of power feed copolymer. In the P(nBA/St) system, power feed copolymer maintained its adhesive strengths over a wide temperature range compared with random copolymer. The absolute value, however, was not so high. This was due to the low cohesive strengths of the films.     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. III. Adhesive Joint Strengths of Grafted Power Feed Copolymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. Power feed copolymer had a very broad glass transition temperature compared with random copolymer, even if grafting and/or crosslinking were introduced to the system. This tendency was almost the same as the non-grafted power feed copolymer where only low molecular weight surfactant was used.

Adhesive joint strengths of power feed copolymers were evaluated compared with random copolymers. In the case of usual linear power feed copolymer, the adhesive joint strengths were not higher than those of random copolymer, which was considered to be due to the lower film strengths of the power feed copolymer. Power feed copolymer having grafting showed slightly higher adhesive joint strengths over a wide range of temperatures than random copolymer. When crosslinking was introduced to the system, power feed copolymer showed much higher adhesive joint strengths over a wide temperature range.     

Copolymerizations of macromonomer prepared by addition-fragmentation chain transfer polymerization of methyl acrylate trimer

Summary An oligomer of the methyl acrylate unsaturated trimer bearing 2-carbomethoxy-2-propenyl ω-end group (M _n = 1300, M _w/M _n = 1.7, and functionality > 0.7) was copolymerized as a macromonomer (0.02 mol/L) with styrene (1.0 mol/L) in benzene at 60 °C. The amounts of monomer and macromonomer in the feed simultaneously decreased with increasing time to indicate copolymer formation, and the macromonomer was found to be as reactive as styrene toward poly(styrene) radicals. The M _ns of the copolymers were 13900–22000 depending on conversion. No resonance due to the unsaturated <ω-end group bound to the poly(styrene) chain was detected by ¹H-NMR spectroscopy, indicating that no fragmentation of adduct radical of the end group to expel the poly(methyl acrylate trimer) radical. Polymerization of ethyl methacrylate (1.0 mol/L) in the presence of the macromonomer (0.02 mol/L) resulted in a mixture of the unreacted macromonomer and homopolymer of ethyl methacrylate. No end group bound to the poly(ethyl methacrylate) was detected by ¹H-NMR spectroscopy, excluding the possibility of addition fragmentation chain transfer to the macromonomer to expel an oligomer radical of the methyl acrylate trimer. Addition of the poly(methacrylate) radical to the macromonomer is extremely slow under the present conditions of copolymerization. Received: 27 March 2003/Revised version: 30 April 2003/ Accepted: 30 April 2003 Correspondence to Bunichiro Yamada     

Mechanism and kinetics of the free radical ring-opening polymerization of cyclic allylic sulfide lactones

The polymerization of 7-, 8- and 11-membered lactones, 6-methylene-1,4-oxathiepan-7-one, 3-methylene-1,5-oxathiocan-2-one and 3-methylene-1-oxa-5-thiacycloundecan-2-one in benzene at 70, 40–70 and 40–65 °C, respectively, is presented. All polymerizations proceeded with complete ring-opening up to approximately 25% conversion, where insoluble polymer was formed. Evidence is given attributing polymer double bond loss to crosslinking, although redistribution of the molecular weights via addition to polymer double bonds followed by β-fragmentation also appears to occur for polymerizations of the 8- and 11-membered lactones. Michael adducts of lactones with 2-methyl-2-propanethiol were prepared as models for chain-transfer products of hydrogen abstraction by carbon-centred radicals. Polymerization rates were found to increase marginally with ring size. Arrhenius parameters obtained for the polymerizations of the 8- and 11-membered lactones indicated that the addition step was more important than fragmentation in determining the rate of propagation.     

ESR study on radical polymerization of styrene

Summary Propagation rate constant (k_p) for styrene was evaluated at different chain lengths of the polymer radical based on the steady-state concentration of the polymer radical determined by means of ESR spectroscopy at 70°C. Over a range of degree of polymerization of the polymer radical from 40 to 410, the value of k_p, 480±10 L/mol·s, remained constant. A considerable increase in viscosity of the polymerization mixture did not affect this value.     

Effects of aging and moisture on the dynamic viscoelastic properties of oriental lacquer (urushi) film

The effects of aging and moisture on the dynamic viscoelastic properties of three oriental lacquer films were investigated. With aging over 1000 days at room temperature, the glass‐transition temperature of the lacquer films (T_α) shifted to higher temperatures, the maximum loss tangent (tanδ_α) decreased, and the storage modulus at 20°C (E) increased. These changes were analogous irrespective of lacquers. With increasing moisture content, E decreased and tanδ increased at room temperature. Although the equilibrium moisture content of the virgin lacquer (sap) film was higher than that of the clear lacquer film, its E and tanδ were more stable with an increase of moisture content. It was speculated that the polysaccharides aggregated in the sap film did not effectively contribute to the mechanical properties of the film, while their hygroscopicity resulted in higher moisture content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2288–2294, 2002     

Contribution of primary radical termination to radical polymerization of diethyl fumarate estimated from absolute rate constants

Summary Diethyl fumarate was radically polymerized under UV irradiation and concentration of the propagating radical was determined to be of the order of 10^-5 mol/L by scavenge with a stable free radical. The absolute rate constant for propagation (k_p) was evaluated from the overall rate of polymerization at 30°C: K_p =(2.9 ± 0.3) × 10^-2 L/mol · s. The rate constant for mutual termination of the polymer radical (k_t) was calculated from the decreasing rate of the radical concentration in the dark: k_t=8.0 L/mol·s. The k_t value determined is one twentieth of that evaluated previously by a rotating sector method. This discrepancy is accounted for by contribution of much faster primary radical termination.     

Mechanical relaxation processes of wood in the low-temperature range

The dynamic viscoelastic properties of untreated and chemically modified wood specimens were determined in the temperature range 123 to 293 K and at constant frequencies. Absolutely dry wood specimens exhibited one relaxation process labeled γ at around 180 K, being attributed to the motions of methylol groups in the amorphous region of the wood constituents. The changes in the γ process due to the chemical modifications were explained by the reduction in the original γ loss peak due to the decrease of methylol groups, and an additional relaxation induced by the other groups introduced. With moisture adsorption, an additional relaxation labeled β was induced at 220–240 K. It appeared only when the wood adsorbed moisture irrespective of chemical modifications, and its characteristics were not affected by the formaldehyde and PEG treatments involving the remarkable changes in the mobility of amorphous molecules. These results suggested that the dominant mechanism of β relaxation was not the segmental motions of the main chain, but the motion of the adsorbed water molecules. The positive activation entropy of the β relaxation was interpreted to reflect rearrangement of the adsorption sites required for the rotation of the adsorbed water molecules. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3338–3347, 2001     

Detailed studies of the initiation step in free radical polymerization of α-(substituted methyl)acrylates by electron paramagnetic resonance spectroscopy

Reactions of the adduct radical obtained by addition of the initiator-derived 2-carbomethoxy-2-propyl radical to methyl α-[(2-methyl-2-carbomethoxy)propyl]acrylate (the unsaturated dimer of methyl methacrylate (MMAD)) have been monitored by electron paramagnetic resonance spectroscopy. Rate constants for addition of the 2-carbomethoxy-2-propyl radical to MMAD, mutual reactions between the adduct radicals, and reactions of the adduct radical and the 2-carbomethoxy-2-propyl radical, and β-fragmentation of the adduct radical were evaluated by steady-state and non-steady-state kinetic analysis in tandem with computer modeling and simulations involving parameter optimization procedures. The resulting rate constants showed that addition and radical-radical reactions between low molecular weight radicals are suppressed due to the marked steric congestion of the carbon-carbon double bond and radical center, respectively, and that β-fragmentation can compete with radical-radical reactions of the adduct radicals depending on the radical concentration.     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. II. Chemical Structure of Grafted Power Feed Polymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through a non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. With the increase of PVA, grafting was also increased. Feeding method did not affect grafting nor grafting efficiency to a great extent. However, the amount of initiator had a negative correlation against grafting or grafting efficiency. From NMR spectroscopy, it was known that n-butyl acrylate monomer grafted onto PVA rather than copolymerized with styrene monomer. In order to increase the cohesive strengths of each phase, grafting was introduced to the power feed polymerization. In these cases, the chemical structure of grafted power feed polymer was investigated.