Kinetic approach to radiation-induced grafting in the polyethylene–styrene system. III

The method of investigation reported in previous papers was applied to preirradiation methods of reaction in vapor and in liquid. The absorption dose was varied from 2 to 0.1 Mrad. The monomer concentrations during reactions were determined gravimetrically. The patterns of increase of the degree of grafting did not change as the dose was varied in the liquid but changed considerably with dose in the vapor. The monomer concentration during the reaction did not vary with dose in the liquid but did so in the vapor. A model calculation was applied and improved to make the monomer concentration agree with that in the experiment. An attempt was made to describe the mechanism involved. There were some differences between the calculated values and the experimentally obtained ones, but the outline of the reaction mechanism was explained satisfactorily.     

Kinetic approach to radiation–induced grafting in the polyethylene–styrene system

To investigate the mechanism of radiation-induced grafting in this system, the increase of monomer concentration in the polyethylene film in styrene vapor was evaluated by measuring the weight increase and formulated to be V([M_∞] ? [M]). The decay of radical concentration was also measured by ESR and the rate constant of the decay was determined. The alkyl type radical was affected only a little by styrene, while the allyl type radical was much affected by styrene. A new computer investigation method was proposed to clarify the reaction mechanism. The data obtained were substituted into differential equations and used to calculate the pattern of increase of the degree of grafting for the preirradiation method with reaction in the vapor phase. Results of these calculations suggest that only allyl type radicals induce grafting reactions and that the grafting reaction seldom occurs in the region of grafted polystyrene.     

Kinetics of radiation-induced grafting reactions. II. Cellulose acetate–styrene systems

Kinetics of grafting reactions of styrene to preirradiated cellulose acetate have been studied by labeling the active sites with bromine atoms. The dilution of styrene monomer with methanol affected grafting reactions remarkedly: e.g., as the concentration of methanol in monomer solutions increased, the growth rates of individual graft radicals decreased while the average lifetimes increased. The integrated amounts of active sites which participated in grafting reactions were also affected by the constitution of monomer solutions and varied roughly in proportion to the extents of swelling of cellulose acetate. Grafting yields for styrene/methanol = 1/1 were higher than for 3/1 and 1/3 throughout the duration of grafting reactions, which is due not only to the high molecular weight of graft chains but also to the large number of graft chains for the 1/1 system compared to the other systems.     

Radiation-induced grafting in the polyethylene–styrene system and differential thermal analysis of the grafted samples

The graft polymerization of styrene onto high-density polyethylene films was carried out by γ-irradiation in the vapor phase. Two methods were used for grafting in these experiments: a preirradiation method and a simultaneous irradiation method. The effects of these grafting methods on the reaction mechanism of grafting and on the properties of the grafted samples were investigated. The amounts of styrene homopolymer in the grafted samples is under 2% in the case of the preirradiation method and above 10% in the case of the simultaneous irradiation method. The activation energies were calculated to be 18 kcal/mole for grafting in the preirradiation method and 15 kcal/mole for weight increase of polyethylene films in styrene vapor. The difference in the dimensional expansion between in the direction of stretching and the direction prependicular to it is smaller with preirradiation grafting than with grafting by the simultaneous irradiation method. Differential thermal analysis of the grafted films shows an endothermic peak due thermal decomposition which decreases gradually from 450°C to 415°C with increase in degree of grafting from 30 to 60%. The lowering of this peak temperature appears at a lower degree of grafting when the preirradiation method is used. On the basis of these results, it is concluded that the reaction rate of radiation-induced grafting in the vapor phase depends closely upon the processes of adsorption, dissolution, and diffusion of styrene monomer in polyethylene films; in the case of simultaneous irradiation method, the reaction proceeds comparatively uniformly in the amorphous region, while in the case of the preirradiation method, the reaction proceeds mainly at the boundary of the crystalline and amorphous regions.     

Kinetics of radiation-induced grafting reactions. I. Polyethylene–styrene systems

By means of bromine labeling and ESR, the grafting reactions of styrene onto preirradiated polyethylene have been investigated. Not all the radicals produced by irradiations participate in grafting reactions all together, but they are rendered active bit by bit by the swelling of crystalline parts of polyethylene. The growing rates for polystyryl graft chains at 20°C decrease from 4 monomer units/active site/sec to one-fourth the initial value after 100 min. On the contrary, the average lifetimes increase from <10³ sec to >2.6 × 10³ sec. The number-average molecular weight of graft chains also increases with reaction times and rises to 3.5 × 10⁵ after 90 min at 20°C.     

Kinetic approach to radiation-induced grafting in the polyethylene-styrene system. V. The behavior of initiator radicals

With high-density polyethylene (HDPE) and low-density polyethylene (LDPE) films the grafting reactions were performed by the preirradiation method. By holding the total absorption dose constant irradiation time was varied. The initial rate of grafting decreased with irradiation time. The relative concentration of alkyl radical in the polyethylene film also decreased with irradiation time, but the relative concentration of allyl increased. The differences in the ESR spectrum before and after the introduction of styrene indicate that the allyl-type radical reacted with styrene. To elucidate these results the allyl radical in the amorphous region was considered.     

Kinetic approach to radiation-induced grafting in the polyethylene-styrene system. IV. Comparison between high density polyethylene and low density polyethylene

The investigation method reported in earlier articles was applied to preirradiation methods of the reaction of low-density polyethylene (LDPE) in liquid and vapor and compared with high-density polyethylene (HDPE). Monomer concentrations during reactions and monomer feed rates were determined gravimetrically. Increasing patterns of the degree of grafting were obtained and compared. Monomer concentration during the reactions was lower in LDPE than HDPE and radical decay was more rapid in LDPE. A model calculation was applied to this experiment and a schematic explanation was attempted. The differences between the reaction mechanisms of HDPE and LDPE are explained.     

Effect of swelling on radiation-induced grafting of styrene to polyethylene

The radiation-induced grafting of low-density polyethylene in contact with styrene solution was studied. The effect of the degree of swelling of the polymer on the rate of grafting was investigated by diluting the styrene with methanol and with n-octane. For styrene-methanol solution, the rate of grafting was found to increase with degree of swelling, passing through a maximum when the sorbed solvent reaches 6.2 wt-% (70 vol-% methanol in the outside solution) and decreasing therafter. The methanol fraction of the sorbed liquid is far too small to cause precipitation of the grafted chains and inhibition of their termination rate. The dilution of styrene by octane has no effect on the swelling of polyethylene, but it decreases the grafting rate over the entire concentration range. The results are explained in terms of the concentration of sorbed monomer and the viscosity of the amorphous region of the polyethylene swollen by nonpolar liquids. Supporting evidence for the mechanism is presented in the form of grafting kinetic data as a function of dose rate (2.8 × 10²?9.5 × 10⁴ rad/hr), and post-irradiation grafting measurements for polyethylene in methanol-styrene (70/30, v/v). The data indicate that at the maximum grafting rate an optimum is achieved between a high concentration of sorbed monomer and a low viscosity for the poorly swelled polymer matrix.     

Free-radical grafting of monomers to polydienes. II. Kinetics and mechanism of styrene grafting to polybutadiene

A kinetic analysis of the grafting reaction has shown that, provided rubber radicals are not involved in termination reactions, the observed normal kinetics of styrene polymerization are to be expected. An expression relating the graft fraction with the rubber and monomer concentrations has been derived and its validity verified from the results reported in Part I. The observation that the molecular weight of the ungrafted PBD falls during the reaction has been explained on a theoretical basis.     

Kinetics of radiation-induced grafting reactions. III. Poly(isobutylene oxide)—styrene systems

Graft polymerization of styrene onto preirradiated poly(isobutylene oxide) was carried out at 25°C. The concentration of active sites for grafting was estimated by means of ESR and by the activation analysis of bromine atoms bound to the chain ends. Kinetic data such as differential amount of active sites (DACT), growth rate (GR), and average lifetime (τ) were obtained to calculate the molecular weight distribution of graft chains by the Monte Carlo simulation method. The number-average molecular weight of the graft chain was calculated from the equation, M _n = 2GRτ (mw), which agreed well with the observed value.     

Kinetics and mechanism of grafting of undecylenic acid onto acrylonitrile–butadiene–styrene terpolymer

The graft copolymerization of undecylenic acid onto acrylonitrile–butadiene–styrene terpolymer (ABS) was initiated with benzoyl peroxide (BPO) in a 1,2‐dichloroethane solution. IR spectra confirmed that undecylenic acid was successfully grafted onto the ABS backbone. The influence of the concentrations of undecylenic acid, BPO, and ABS on the graft copolymerization was studied. A reaction mechanism was proposed: the grafting most likely took place through the addition of poly(undecylenic acid) radicals to the double bond of the butadiene region of ABS. A monomer cage effect on the graft reaction was observed to depend on the 1.5 power of the monomer concentration from the experimental results of the initial rate of graft copolymerization. The initial rate of graft copolymerization was written as R_p = 1.77 × 10⁻³[P][I₂][M]^2.5/([P]+2.75[M]^2.5)². © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 486–494, 2001     

Kinetic investigation of the bromate–ascorbic acid–malonic acid system

According to our experiments the bromide ion concentration exhibits in the bromate–ascorbic acid–malonic acid–perchloric acid system three extrema as a function of time. To describe this peculiar phenomenon, the kinetics of four component reactions have been studied separately. The following rate equations were obtained: Bromate–ascorbic acid reaction: Bromate–bromide ion reaction: Bromide–ascorbic acid reaction: Bromine–malonic acid reaction: k₄ = 6 × 10^?3 s^?1, k_-4 ≥ 1.7 × 10³ s^?1, k₅ ≥ 1 × 10⁷M^?1 · s^?1 Taking into account the stoichiometry of the component reactions and using these rate equations, the concentration versus time curves of the composite system were calculated. Although the agreement is not as good as in the case of the component reactions, it is remarkable that this kinetic structure exhibits the three extrema found.     

Radiation-induced postpolymerization of trioxane in the solid state. II. Kinetic study of radiation-induced postpolymerization of trioxane in dry and high-vacuum system

A kinetic study of the radiation-induced postpolymerization of trioxane in the solid state has been made. Trioxane was purified by sublimation through Ag₂O and Na–K alloy in vacuo and was both irradiated and polymerized in a super-dry system under high vacuum. In the present study it was found that the initial rate of polymerization is larger than that reported previously. It is reasonably suggested that the postpolymerization of trioxane consists of two stages, i.e., a very large rate at the first stage and a relatively small one at the second stage. By using the kinetic scheme proposed previously kinetic parameters at the second stage were determined. It was found that trioxane can be postpolymerized even at a temperature below 30°C with good reproducibility and that the overall activation energy of the polymerization was less than 15 kcal/mole. No chain-transfer reaction seems to occur except at low temperatures. These results have been discussed in comparison with data reported previously.     

Changes in row structure of extruded polyethylene film in grafting with styrene. II. Copolymer morphology

The morphology of extruded high-density polyethylene film grafted with styrene was studied by transmission electron microscopy of thin stained sections. Near the film surface grafted polystyrene was confined to amorphous layers between lamellar crystals of polyethylene. In the film interior separate polystyrene domains were also formed and became predominant in grafting in diluted styrene. The deciding factor for the location of grafted polystyrene is the chain length because only long chains can coalesce in large separate zones. The polystyrene zones expand by cracking the stacks of lamellae along the lamellar normals. Straightening of the twisted crystalline lamellae of polyethylene occurred in grafting. “Bubbles” of styrene homopolymer were formed under conditions of high monomer concentration. The effect of staining the graft by the Kanig method² was also discussed.     

The polymerization of styrene oxide by the triisobutylaluminum–water system

Styrene oxide has been polymerized by the triisobutylaluminum–water catalyst system. Kinetic studies of the effects of varying the monomer, triisobutylaluminum, and water concentrations in benzene solutions have been made. Styrene oxide was consumed in two reactions: an initial fast one producing trimer and a slower reaction forming higher molecular weight polymer.     

Organic–inorganic polymeric nanocomposites involving novel titanium tetraisopropylate in polyethylene–octene elastomer

The new nanocomposites, by means of an in situ sol–gel process consisting of metallocene polyethylene–octene elastomer (POE) and titanium tetraisopropylate (TTIP), were investigated. In addition, the acrylic acid grafted POE (POE‐g‐AA) was studied as an alternative to POE. Fourier transform infrared (FTIR) spectroscopy, a dynamic mechanical analyzer (DMA) spectrometer, an X‐ray diffractometer (XRD), differential scanning calorimetry (DSC), a thermogravimetric analyzer (TGA), an Instron mechanical tester, and a scanning electron microscope (SEM) were used to characterize and examine the samples. The results indicate that the POE‐g‐AA/TiO₂ hybrid could have a positive effect on the properties of the POE/TiO₂ hybrid because the carboxylic acid groups of acrylic acid should act as coordination sites for the titania phase to form a Ti? O? C chemical bond. The strength of interfacial bonding between the polymer chains and the ceramic phase depended on the amount of TiO₂, as shown by the change in glass‐transition temperature (T_g) with TiO₂ content. The result of mechanical and thermal tests showed that both the tensile strength and the T_g increased to a maximum value and then decreased with an increasing of TiO₂ because excess particles (e.g., greater than 10 wt % TiO₂) might cause separation or segregation between the organic and inorganic phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4272–4280, 2004