Reversible addition–fragmentation chain‐transfer graft polymerization of styrene: Solid phases for organic and peptide synthesis

The γ‐initiated reversible addition–fragmentation chain‐transfer (RAFT)‐agent‐mediated free‐radical graft polymerization of styrene onto a polypropylene solid phase has been performed with cumyl phenyldithioacetate (CPDA). The initial CPDA concentrations range between 1 × 10^?2 and 2 × 10^?3 mol L^?1 with dose rates of 0.18, 0.08, 0.07, 0.05, and 0.03 kGy h^?1. The RAFT graft polymerization is compared with the conventional free‐radical graft polymerization of styrene onto polypropylene. Both processes show two distinct regimes of grafting: (1) the grafting layer regime, in which the surface is not yet totally covered with polymer chains, and (2) a regime in which a second polymer layer is formed. Here, we hypothesize that the surface is totally covered with polymer chains and that new polymer chains are started by polystyrene radicals from already grafted chains. The grafting ratio of the RAFT‐agent‐mediated process is controlled via the initial CPDA concentration. The molecular weight of the polystyrene from the solution (PS_free) shows a linear behavior with conversion and has a low polydispersity index. Furthermore, the loading of the grafted solid phase shows a linear relationship with the molecular weight of PS_free for both regimes. Regime 2 has a higher loading capacity per molecular weight than regime 1. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4180–4192, 2002     

Radiation-induced grafting of styrene vapor to polyethylene

The radiation-induced grafting of styrene vapor to low-density polyethylene film of 0.063 mm thickness was studied at 23°C at a dose rate of 1.98 × 10⁴ rad/hr. The concentration C of monomer in the film was measured as a function of pre-irradiation exposure time to monomer vapor. The concentration-dependent diffusion coefficient of styrene in polyethylene was calculated to be 4.9 × 10^?9 exp {2.0C/C₀} cm²/sec, where C₀ is the saturation concentration of styrene in the film, and a linear boundary diffusion coefficient for styrene vapor into polyethylene film was found to be 2.0 × 10^?7 cm/sec. The rate of grafting was determined as a function of the concentration of styrene absorbed in the film. The maximum graft yield was obtained with an initial styrene concentration in the film of 4 wt-%. Under conditions of low initial monomer concentration, the grafting rate increases with irradiation time. The results are compared with previously published data on grafting of polyethylene from methanol–styrene solutions. They are explained in terms of the viscosity of the amorphous region as a function of styrene content and the resistance to the diffusion of monomer at the film–vapor interface.     

Polymers from renewable resources. II. A study in the radio chemical grafting of poly(styrene‐alt‐maleic anhydride) onto cellulose extracted from pine needles

A binary mixture of styrene and maleic anhydride has been graft copolymerized onto cellulose extracted from Pinus roxburghii needles. The reaction was initiated with gamma rays in air by the simultaneous irradiation method. Graft copolymerization was studied under optimum conditions of total dose of radiation, amount of water, and molar concentration previously worked out for grafting styrene onto cellulose. Percentage of total conversion (Pg), grafting efficiency (%), percentage of grafting (Pg), and rates of polymerization (R_p), grafting (R_g), and homopolymerization (R_h) have been determined as a function of maleic anhydride concentration. The high degree of kinetic regularity and the linear dependence of the rate of polymerization on maleic anhydride concentration, along with the low and nearly constant rate of homopolymerization suggest that the monomers first form a complexomer which then polymerizes to form grafted chains with an alternating sequence. Grafting parameters and reaction rates achieve maximum values when the molar ratio of styrene to maleic anhydride is 1 : 1. Further evidence for the alternating monomer sequence is obtained from quantitatively evaluating the composition of the grafted chains from the FT‐IR spectra, in which the ratio of anhydride absorbance to aromatic (CC) absorbance for the stretching bands assigned to the grafted monomers remained constant and independent of the feed ratio of maleic anhydride to styrene. Thermal behaviour of the graft copolymers revealed that all graft copolymers exhibit single stage decomposition with characteristic transitions at 161–165°C and 290–300°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1763–1769, 1999     

Surface grafting of polyethylene by mutual irradiation in methyl acrylate vapor. II. High-energy electrons irradiation

Vapor-phase mutual grafting of methyl acrylate (MA) onto polyethylene (PE) at high dose rates from an electron accelerator yields the same surface graft structure as does the grafting at low dose rates from ⁶⁰Co sources; i.e., a homopolymer layer (consisting of only MA component) is easily formed on the inner graft copolymer layer (consisting of both MA and PE components) as a result of the continuously increasing surface graft composition. To produce the surface layer, 4-MeV electron irradiation with a linear electron accelerator requires only less than 3 min of irradiation time at dose rates of more than 2 Mrad/min, whereas γ irradiation with a ⁶⁰Co source requires at least 1 hr at dose rates of less than 2 × 10³ rad/min. The rate of monomer consumption (or polymerization) in the surface homopolymer layer shows no dependence of irradiation time and a positive dependence of dose rate. It has been suggested that this kinetic feature at the high dose rates shows some contribution of vapor-phase homopolymerization and subsequent deposition (onto the grafting surface) followed by recombination with the grafted side chain radicals, although secondary graft copolymerization from the grafted chain radicals is still the principal process for the growth of the surface homopolymer layer.     

Radiation-induced graft copolymerization of mixtures of styrene and acrylamide onto cellulose acetate. III. A kinetic study

The kinetics of graft copolyermization of styrene and acrylamide from their binary monomer mixtures onto gamma-irradiated cellulose acetate film was studied. The extent of grafting increased with a rise in reaction time and temperature. The nature of the radical site on the trunk polymer was acertained in a study of grafting at different temperatures when the trunk polymer was irradiated in the presence and absence of oxygen. The character of the radical was tested further in a study of the ESR spectrum. The variation in grafting rates and energies of activation required for graft copolyermization at various mole ratios of the monomers was observed. The grafting rates showed a maximum at 1:1 mol ratio of monomers which was also associated with minimum energy of activation. The Kk_t values in the system were dependent on the composition of monomers.     

Parameter Study for the Pre‐Irradiation Grafting of Styrene/Divinylbenzene onto Poly(tetrafluoroethylene‐co‐hexafluoropropylene) from Isopropanol Solution

Pre‐irradiation grafting of styrene/divinylbenzene (DVB) onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films from isopropanol (ⁱPrOH) solution was investigated with respect to the effect of irradiation dose, film thickness, cross‐linker concentration, and reaction temperature. A mathematical model was applied to the kinetic curves to extract information on the polymerization rate, the radical‐recombination rate, and the grafting through time. It turned out that the two closely correlated reaction rates for polymerization and radical recombination can be varied over a wide range by changing the irradiation dose, the cross‐linker concentration, and the reaction temperature. On the other hand, the time until the grafting front has progressed to the center of the film is mainly affected by the film thickness and the reaction temperature. The formation of homopolymer in the grafting solution increases steeply with temperature and cross‐linker concentration.     

γ-Radiation-induced ionic polymerization of pure liquid styrene

Pure liquid styrene, carefully purified and exhaustively dried, exhibits kinetic behavior under γ-irradiation that can best be described in terms of an ionic mechanism. This is based on the observed linear dependence of the rate of polymerization on the dose rate, the independence of molecular weight on the same parameter, and comparison with the thermal and ultraviolet initiated polymerization of monomer prepared under the same stringent conditions. The highest rate of conversion to polymer is 400%/hr. at a dose rate of 10⁶ rads/hr., corresponding to a G_(-monomer) ≈ 40,000.     

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.     

Pre‐Irradiation Grafting of Styrene/Divinylbenzene onto Poly(tetrafluoroethylene‐co‐hexafluoropropylene) from Non‐Solvents

Pre‐irradiation grafting of styrene/divinylbenzene (DVB) onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films was studied with respect to the influence of solvent. Particularly favorable grafting conditions with long radical lifetimes and reasonably high polymerization rates were achieved with solvents that are precipitants for the newly formed polystyrene, e.g., low‐molecular‐mass alcohols like ⁱPrOH, AcOH, their mixtures with H₂O, and H₂O/surfactant systems. Using one of these solvents significantly extended the range of accessible graft levels, and a specific degree of grafting was obtained at a much lower monomer concentration and irradiation dose than with grafting in a good solvent such as toluene. As practical consequences, the monomer was used more efficiently, and the radiation damage of the perfluorinated base material was reduced with the result of improved mechanical properties of the grafted films.     

Radiation-initiated homogeneous grafting of styrene to benzylcellulose

Graft copolymers of benzylcellulose and styrene were prepared by direct irradiation of benzylcellulose–styrene solutions with ⁶⁰Co γ-radiation. The solutions remained homogeneous during irradiation. The amount of styrene grafted to benzylcellulose increased in dilute solutions and was dose-dependent up to 4.0 MR. The graft copolymer consisted of both branched and linear structures with one in every 140–1020 benzylated anhydroglucose units carrying a grafted polystyrene chain. Grafted polystyrene was isolated from the graft copolymer by hydrolysis of the benzylcellulose substrate. The number-average molecular weight and molecular weight distribution of the grafted polystyrene were the same as those for hompolymer formed in the same solution, indicating that the substrate is fully accessible to the monomer and polymerization conditions are uniform throughout the solution during the grafting procedure. The existence of a true graft copolymer was proved by the solubility behavior, intrinsic viscosity, number-average molecular weight, and density-gradient sedimentation of the product of the grafting procedure. Column elution fractionation of the gross products of the grafting procedure failed to isolate the benzylcellulose–styrene copolymer which was eluted with ungrafted benzylcellulose.     

Radiation-induced grafting of styrene into poly(vinylidene fluoride) film by simultaneous method with two different solvents

Radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses of 1 and 2.5 kGy in the presence of a styrene/N,N-dimethylformamide (DMF) solution (1:1, v/v) and at doses of 20, 40 and 80 kGy in presence of a styrene/toluene solution (1:1, v/v) at dose rate of 5 kGy h^?1 was carried out by the simultaneous method under nitrogen atmosphere and room temperature, using gamma rays from a Co-60. The films were characterized before and after modification by calculated grafting yield (GY %), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). GY results shows that grafting increases with dose, and the grafting of styrene was confirm by FT-IR due to the new characteristic peaks and by the TG and DSC attributed to changes in thermal behavior of the grafted material. Results showed that the system allows the controlled grafting of styrene into PVDF using gamma rays at doses as low as 1 kGy in DMF.     

Effect of dose rate on radiation-induced polymerization of styrene adsorbed on silica gel

The effect of dose rate on the rate of polymerization and molecular weight distribution of radiation-induced polymerization of styrene adsorbed on silica gel was studied in a wide dose rate range of 4.4 × 10⁴ to 3 × 10⁸ rad/hr by γ rays of ⁶⁰Co and electron beams with a Cockcroft-Walton-type accelerator. Dose rate dependence on the initial rate of polymerization was about 1 below 3 × 10⁷ rad/hr, and it decreased gradually at high dose rates. Throughout the dose rate range, graft polymerizations and homopolymerizations by cationic and radical mechanisms proceeded simultaneously. Dose rate dependence of the cationic polymerization was 1 below 3 × 10⁷ rad/hr, while dose rate dependence of the radical polymerization was 0.65 below 3 × 10⁷ rad/hr. At high dose rates, molecular weight and fraction of graft polymer decreased, and fraction of cationic polymerization increased. A very high-molecular-weight graft polymer was formed above 4.4 × 10⁵ rad/hr at the initial stage of the polymerization. The dose rate dependence of this polymerization was larger than 1 and decreased with increase in dose rate. The polymerization seems to be related to an excitation of monomer or growing chain.     

Grafting onto wool. XXV. Effect of acids on γ-radiation-induced graft copolymerization of methyl methacrylate onto wool fiber

Graft copolymerization of methyl methacrylate (MMA) onto Himachali wool fiber has been investigated in aqueous medium by using γ irradiation from a 2100 Ci⁶⁰CO source as means of initiation. Graft copolymerization was carried out by the mutual method in nitrogen atmosphere as well as in air. Effect of mineral acids and acetic acid on percentage of grafting was studied. Percentage of grafting was determined as functions of total dose, concentration of monomer, and concentration of acids. Maximum percentage of grafting in the presence of acids occurred in nitrogen atmosphere at a total dose of 1.05 MR. All the acids were found to influence grafting and the reactivity of different acids towards graft copolymerization was found to follow the order: H₂SO₄ > HCl > HNO₃ > HC1O₄ > HOAc. An attempt has been made to explain the reactivity order of different acids in the light of the mechanism proposed for γ-irradiation-induced graft copolymerization of vinyl monomer onto wool fiber.     

Study of energy transfer to solvent in radiation graft polymerization of styrene onto polyethylene

The radiation-initiated graft polymerization of styrene onto polyethylene was studied to determine whether energy transfer to diluent was responsible for the previously observed high orders of dependence of the grafting rate on monomer concentration. n-Octane was used as the diluent instead of benzene. If energy transfer from excited polyethylene to benzene were present, it should not be with n-octane. The percent swelling of polyethylene by various n-octane–styrene mixtures was determined. The compositions of various n-octane–styrene mixtures absorbed inside polyethylene were determined by ultraviolet and refractive index measurements and found to be richer in styrene than the corresponding mixtures in which the polyethylene had been placed. The graft polymerization rates were determined at 0.000761, 0.0371, and 0.213 Mrad/hr and plotted against the inside styrene concentrations on a log-log scale to yield the kinetic orders of dependence of rate on monomer as 2,3, and 3, respectively. It was concluded that energy transfer to diluent was not responsible for the high-order dependence observed.     

Radiation Graft Copolymerization of a Mixture of Styrene and n-Butyl Acrylate on Natural Rubber Latex

The radiation graft copolymerization of a mixture of styrene (St) and n-butyl acrylate (NBA) monomers on natural rubber (NR) latex has been studied. An irradiation dose of about 18 kGy was needed to attain a conversion of about 80%. The tensile strength of the grafted NR film increases with increasing irradiation dose. A film tensile strength of about 155 kg/cm² was attained by irradiation of a mixture of St, NBA, and NR latex with a dose of about 14 kGy. At low concentrations of monomer in the latex, the Mooney viscosity of the film increases with increasing irradiation dose. At higher monomer concentration, grafting and homopolymerization proceed more favorably than crosslinking, and thus the Mooney viscosity decreases with increasing dose. Thermal analysis of the film showed that the grafted NR was more heat resistant than ungrafted NR.     

Grafting onto wool. IV. Effect of amines upon ceric ion-initiated grafting of poly(methyl acrylate)

Grafting of poly(methyl acrylate) onto wool has been carried out in an aqueous medium at 45 ± 1°C by using ceric ammonium nitrate (CAN) in the presence of triethylamine, diethylamine, n-butylamine, triethanolamine, and N,N-dimethylaniline. The percentage of grafting varied with the nature and concentrations of the amines. Reactivity of the different amines toward grafting reactions followed the order: triethylamine > diethylamine > n-butylamine > triethanolamine ≥ N,N-dimethylaniline. In the presence of N,N-dimethylaniline grafting did not occur. An attempt has been made to explain the observed reactivity of Ce⁴⁺ in various amine systems in graft copolymerization reactions.     

Kinetics of radiation-induced graft copolymerization of styrene with ethyl acrylate

The radiation-induced graft copolymerization of styrene with ethyl acrylate onto preirradiated polyethylene powder was carried out at 20°C. The grafting yield decreased in the following order: ethyl acrylate ? styrene > styrene–ethyl acrylate mixture. On the other hand, the amount of absorption of liquid monomers in polyethylene powder decreased as follows: styrene > styrene–ethyl acrylate mixture > ethyl acrylate. By kinetic analysis of the grafting yield and amount of absorption of monomers it was elucidated that the value K_p/K_t in an ethyl acrylate system (7.7 × 10^?2) was much larger than those in styrene–ethyl acrylate systems and in a styrene system (ca. 1.0 × 10^?2).     

Gamma radiation induced graft copolymerization of vinyl monomers onto poly(vinyl alcohol)

In an attempt to modify water-soluble synthetic polymers, graft Copolymerization of methylmethacrylate (MMA) and ethyl acrylate (EA) onto poly(vinyl alcohol), PVA, has been studied by using gamma irradiation from a Co⁶⁰ source as initiator. The graft copolymerization was carried out in an aqueous medium by the mutual method in air. The effect of total dose and concentration of vinyl monomers on percentage of grafting has been determined. Water plays a significant role in the enhancement of graft copolymerization and the optimum amount of water to afford maximum grafting has been evaluated. The effect of CH₃OH on aqueous grafting of MMA and EA by radiation method has been studied. The graft copolymer has been characterized by IR spectroscopic and thermogravimetric methods.     

Grafting polymerization of styrene onto alternating terpolymers based on chlorotrifluoroethylene,hexafluoropropylene, and vinyl ethers,and their modification into ionomers bearing ammonium side‐groups

The grafting polymerization of styrene initiated by the alkyl chloride groups of poly(CTFE‐alt‐VE) and poly[(CTFE‐alt‐VE)‐co‐(HFP‐alt‐VE] copolymers (where CTFE, HFP, and VE stand for chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), and vinyl ether (VE), respectively) followed by the chemical modification of the polystyrene grafts are presented. First, the fluorinated alternating copolymers were produced by radical copolymerization of CTFE (with HFP) and VE. Second, atom transfer radical polymerization enabled the grafting polymerization of styrene in the presence of the poly(CTFE‐alt‐VE)‐macroinitiator using the alkyl chloride group of CTFE as the initiation site. Kinetics of the styrene polymerization indicated that such a grafting had a certain controlled character. For the first time, grafting of polystyrene onto alternating fluorinated copolymers has been achieved. Differential scanning calorimetry thermograms of these graft copolymers exhibited two glass transition temperatures assigned to both amorphous domains of the polymeric fluorobackbone (ranging from ?20 to +56 °C) and the polystyrene grafts (ca. 95 °C). The thermostability of these copolymers increased on grafting. Thermal degradation temperatures at 5% weight loss were ranging from 193 to 305 °C when the polystyrene content varied from 81 to 27%. Third, chloromethylation of the polystyrene grafts followed by the cationization of the chloromethyl dangling groups led to original ammonium‐containing graft copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

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.