Temperature dependence of unperturbed dimensions for isotactic poly(2-hydroxyethyl methacrylate)

The unperturbed dimensions of isotactic poly(2-hydroxyethyl methacrylate) (PHEMA) were evaluated from intrinsic viscosity measurements in water, ethanol, 1-propanol, 2-propanol, and 2-butanol under θ conditions over the temperature range of 3.7–32.1°C. The smallest value of unperturbed dimensions (K_θ) and the largest negative temperature dependence of unperturbed dimensions and the polymer–solvent interaction parameter (B) were obtained in aqueous θ solvent relative to the corresponding organic θ solvents. These results were interpreted by the hydrophobic interaction between the hydrophobic groups of isotactic PHEMA and water solvent. The temperature coefficient of the unperturbed dimensions, d ln〈r〉/dT, obtained in this study has a negative value of ?1.44 × 10^?3 deg^?1 under chemically similar θ solvents such as ethanol, 1-propanol, 2-propanol, and 2-butanol where specific solvent effects are eliminated or minimized. In order to obtain the thermodynamic parameters for mixing between isotactic PHEMA and solvents, the plots of the polymer–solvent interaction parameter versus reciprocal absolute temperature (1/T) were carried out. Both the entropy of dilution and enthalpy of dilution show the negative values for water, methanol, and t-butanol, whereas the positive ones for ethanol, 1-propanol, 2-propanol, and 2-butanol. This result indicates that the solution of isotactic PHEMA behave as exothermal systems in the former class of solvents and endothermal ones in the latter class of solvents.     

Coupling reaction of poly(α-methylstyryl) anion with (MMA–α-methylstyrene) block copolymer

(MMA–α-methylstyrene)block copolymer was reacted with poly(α-methylstyryl)anion at ?78°C in a mixture of good tetrahydrofuran (THF) and poor methylcyclohexane solvents. The reaction conditions were chosen so as to produce graft copolymers made up of a backbone (AB-type block copolymer) and a single branched chain (1:2 graft copolymer). Gel permeation chromatograph (GPC), osmotic pressure measurement, and elemental analysis were used for the characterization of 1:2 graft copolymer. It appeared that poly(α-methylstyryl)anion reacted with the end pendant groups located farthest away from the branched point of AB-type block copolymer, when the dimensions of AB-type block copolymer molecule are small.     

Cationic polymerization of α-methylstyrene from polydienes. I. Synthesis and characterization of poly(butadiene-g-α-methylstyrene) copolymers

The preparation of poly(butadiene-g-α-methylstyrene) copolymers was investigated with three different alkylaluminum coinitiators. The alkylaluminum compounds in conjunction with polybutadiene which contained a low concentration of labile chlorine atoms initiated the polymerization of α-methylstyrene to produce graft copolymers. Trimethylaluminum gave higher grafting efficiencies than diethylaluminum chloride at comparable monomer conversions. Triethylaluminum produced only very low monomer conversions (<5%), even at long reaction times, and for this reason was not studied extensively. The number of grafts per polybutadiene backbone was determined for a number of copolymers and found to increase slightly as the allylic chlorine concentration in the polybutadiene backbone was increased. In all cases, however, only a low percentage of the available labile chlorine sites along the polybutadiene backbone resulted in grafted α-methylstyrene side chains. The addition of small quantities of water to the polymerization solvent greatly enhanced the grafting rate and ultimate monomer conversion during the synthesis of these poly(butadiene-g-α-methylstyrene) copolymers. The mechanistic role of water during these grafting reactions is unknown at the present time.     

Metal-catalyzed oxidation of poly(α-methylstyrene) during surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) was used to characterize thin films of poly(α-methylstyrene) (PMS) spin-coated onto silver island films supported by glass substrates. At laser powers of a few tens of milliwatts, SERS spectra of thin films of PMS (about 100 Å) were weak, and only the bands near 1010 and 1040 cm^?1 were observed. At laser powers of about 100 mW, additional bands characteristic of PMS were observed near 720 and 1610 cm^?1. However, oxidative degradation of the PMS films to form graphite-like substances was also observed at the higher laser powers. When the thickness of the PMS films was increased to several hundred angstroms, degradation of the films was inhibited, but the intensity of the Raman scattering remained constant, indicating that the observed SERS was an interfacial rather than bulk effect. Degradation during SERS experiments was also inhibited by overcoating PMS films with much thicker films of poly(4-styrene sulfonate) (PSS). Scattering from the PSS overlayers was not observed as long as the thickness of the PMS films was greater than several tens of angstroms, again showing that the SERS was an interfacial effect. Oxidative degradation of the PMS films was also inhibited by adding a few percent of the antioxidant 2,6-di-tert-butyl-4-methylphenol to the polymer. Bands related to sulfite contaminants adsorbed onto the silver island films were observed near 640 and 940 cm^?1. These bands disappeared when PSS, but not PMS, was spin-coated onto the SERS substrates, indicating a strong interaction between PSS and silver.     

Infinite-dilution oscillatory flow birefringence properties of polystyrene and poly(α-methylstyrene) solutions

Oscillatory flow birefringence (OFB) measurements have been carried out for an extensive series of solutions containing narrow-distribution, atactic, linear polystyrenes PS (10, 000 or 390, 000 M_w) or poly(α-methylstyrene) PMS (400,000 M_w) in a high-viscosity solvent, Aroclor 1248. The concentration ranges examined are such that the concentration dependence is obtained in both the “dilute” and “semidilute” regimes; the data are sufficiently precise to permit extrapolation to obtain for the first time the infinite-dilution properties. Various plotting formats are explored to determine an appropriate extrapolation procedure. The infinite-dilution OFB properties are compared with the bead-spring model (Zimm) theory which predicts quantitatively the frequency dependence of the observed properties for the PS and PMS solutions studied except for the high-frequency regime. The sensitivity and precision of the OFB experiment is such that the extrapolation curves–and the resulting infinite-dilution properties–show substantially less scatter than comparable visco-elasticity (VE) data. There is no evidence of a change in the character of the concentration dependence for the range of concentrations studied.     

Cationic polymerization of α-methylstyrene in dichloromethane initiated with system 2,5-dichloro-2,5-dimethylhexane-BCl3. I. Molecular weight distribution and stereoregularity of poly (α-methylstyrene)

In the polymerization of α-methylstyrene (α-MeSt) in dichloromethane in the temperature interval between ?60 and ?20°C the polymer yield decreased with increasing temperature depending on the initiating system used (I-IV) in the series II > I > IV > III, where I was a freshly prepared solution of 2,5-dichloro-2,5-dimethylhexane (DDH) with BCl₃ in dichloromethane, was the same solution as in the preceding case, but stored at room temperature one month and then used, III was a freshly prepared BCl₃ solution in dichloromethane, and IV was the initiation system “H₂O”/BCl₃. The polymer samples synthesized at ≤ ?30°C had a bimodal molecular weight distribution (MWD), which was attributed to the different participation of ionic pairs and free ions in the propagation reaction. The stereoregularity of the polymer observed (ca. 85% syndiotactic and ca. 15% heterotactic triads) determined from the ₁H-NMR spectra was not affected by the difference in the initiation system. MWD of the polymer samples was investigated by the GPC method     

Study of the thermal degradability of poly(α-methylstyrene) with modified end groups

To induce degradabilities in polymers in response to environmental conditions, endm odification reactions of poly(α-methylstyrene) (PMS) derivatives were carried out. 2-Phenylallyl halide derivatives such as 2-phenylallyl bromide, 2-(p-tolyl)allyl bromide, and α-trifluoromethylstyrene were found to be suitable end-modification agents. For example, the ω-2-phenylallyl-PMS derivative was prepared with almost quantitative functionality by the reaction of the living PMS derivative with 2-phenylallyl bromide. In a similar way, ω-3,3-difluoro-2-phenylallyl- and ω-2-(4-toly)allyl-PMS derivatives were synthesized. Based on thermogravimetric analysis, the onset of the degradation temperature of the endmodified PMS derivatives decreased in the following order: ω-hydrogen- > ω-3,3-difluoro-2-phenylallyl- > ω-2-phenylallyl- > ω-2-(p-tolyl)allyl-PMS. Actually, the onset temperature of ω-2-(p-tolyl)allyl-PMS derivatives was 50°C lower than that of ω-H-PMS derivatives. These results indicate that the active species is produced effectively at the endunsaturated bond, which initiates depolymerization of the polymer at rather low temperatures. Therefore, it is concluded that a 2-phenylallyl substituent at the end of the PMS chain induces effective degradation through a radical mechanism.     

Solution properties,unperturbed dimensions,and chain flexibility of poly(1‐adamantyl acrylate)

Poly(1‐adamantyl acrylate) (PAdA) exhibits much higher glass transition and degradation temperatures than other polyacrylates. However, the quantitative evaluation of the stiffness of this polymer chain has not been reported previously. In this study, the dilute solution properties and conformational characteristics of PAdA were evaluated using viscometry and scattering techniques. The unperturbed dimensions of this polymer were evaluated using the Burchard–Stockmayer–Fixman extrapolation and the touched‐bead wormlike chain model. The PAdA chain has a comparable persistence length, diameter per bead and characteristic ratio to poly(methyl methacrylate) and polystyrene. All these results indicate that PAdA is less flexible than common polyacrylates. In addition, the second virial coefficients (A₂) of PAdA in different solvents obtained by static light scattering were compared. Among the solvents investigated, tetrahydrofuran is a moderate solvent. Radius of gyration of a polymer sample in the various solvents ranged from 16.8 to 30.3 nm. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1526–1531     

Dilatometric constant for polymerization of α-methylstyrene

By measurement of the specific volume of solutions of poly-α-methylstyrene in α-methylstyrene monomer at 25°C, the dilatometric constant was found to be K_D = (0.002007 ± 0.000030)%^?1. Estimation of the temperature dependence resulted in the equation (K_D)_t = 1.81 × 10^?3 + 7.82 + 10^?6 t, where t denotes temperature in °C.     

Synthesis of poly(γ-methoxypropylmethylsilylene) and poly(γ-methoxypropylmethylsilylene-co-di-n-hexylsilylene)

The synthesis of γ;-methoxypropylmethyldichlorosilane, and its subsequent polymerization and copolymerization with di;-n;-hexyldichlorosilane through the reductive coupling with sodium has been accomplished. The resulting polymers contain methyl ether side groups that allow further synthetic transformations on the polysilane backbone. For poly (γ;-methoxypropylmethylsilylene) these groups impart solubility characteristics different than typical alkyl and aryl substituted polysilanes. These new polymers and copolymers have been characterized by GPC and ¹H-, ¹³C-, and ²⁹Si-NMR. © 1994 John Wiley & Sons, Inc.     

Cationic polymerization of α-methylstyrene oxide

The polymerization of α-Methyl Styrene Oxide initiated by trityl hexachloroantimonate is reported upon. Data is presented on side reactions, percent yield and molecular weight of polymer produced in the polymerization.     

Electroinitiated copolymerization of indene and α-methylstyrene

Electroinitiated cationic copolymerization of indene and α-methylstyrene in dichloromethane has been investigated by constant potential electrolysis. The effects of copolymerization potential and the temperature on the copolymer composition was also studied. Constant potential electrolysis was found to be a suitable method to study the potential effects on copolymer compositions and the reactivity ratios of the monomers. The reactivity ratios were calculated according to integrated Lewis–Mayo equation.     

Free radicals in γ-irradiated poly-α-methylstyrene

Electron spin resonance (ESR) spectra were observed at ?160°C and at room temperature for γ-irradiated poly-α-methylstyrene. The spectrum observed at room temperature has been attributed to the radical species while that at ?160°C results from the same radical and superposition of the spectrum due to the radical ?H₂-C(CH₃)(C₆H₅)-. The radicals which are stable at room temperature could be used to graft vinyl acetate.     

Polyisobutylene-containing block polymers by sequential monomer addition. X. Synthesis of poly(α-methylstyrene-b-isobutylene-b-α-methylstyrene) thermoplastic elastomers

Preparatory to triblock synthesis experiments, the cationic polymerization of α-methylstyrene (αMeSt) was investigated using the 2-chloro-2,4,4-trimethylpentane (TMPCI)/TiCl₄ initiating system in the presence of triethylamine (Et₃N) as electron donor (ED) and CH₃Cl/n-hexane mixed solvent in the ?80 to ?40°C range. Conversions are influenced by temperature, [TiCl₄], [Et₃N], and [αMeSt]. The polymerization of αMeSt is living at ?80°C: Both termination and chain transfer to monomer are frozen out, however, initiation is slow relative to propagation. Highly syndiotactic (>94%) Pα Mest was obtained. At?60deg;C initiator efficiency is ca. 100%, but termination becomes evident. Et₃N may act both as Ed and as proton scavenger. Novel poly(α-methystyrene-b-isobutylene-b-α-methylstyrene) (PαMeSt-PIB-PαMeSt) triblocks have been synthesized by adding αMeSt to biliving polyisobutylene carbocations (⊕PIB⊕) in the ?80 to ?40°C range. The effects of temperature, solvent polarity, and [Et₃N] on the block copolymerization have been investigated. At ?80°C, the rate of crossover from ⊕PIB⊕ to αMeSt is lower than that of propagation of PαMeSt⊕, so that the triblock is contaminated by PIB and PIB-b-PαMeSt. At ?60°C, crossover occurs preferentially. The rate of propagation relative to that of crossover is also reduced by lowering the solvent polarity and increasing the [Et₃N]. High crossover efficiency and blocking efficiency can be obtained under optimum blocking conditions. The triblocks are novel thermoplastic elastomers (TPEs). © 1994 John Wiley & Sons, Inc.     

Polymerization of α-methyleneindane: A cyclic analog of α-methylstyrene

α-Methyleniedane (MI), a cyclic analog of α-methylstyrene which does not undergo radical homopolymerization under standard conditions, was synthesized and subjected to radical, cationic, and anionic polymerizations. MI undergoes radical polymerization with α,α′-azobis(isobutyronitrile) in contrast to α-methylstyrene, owing to its reduced steric hindrance, though the polymerization is slow even in bulk. Cationic and anionic polymerization of MI with BF₃OEt₂ and n-butyllithium, respectively, proceed rapidly. The thermal degradation behavior of the polymer depends on the polymerization conditions. The anionic and radical polymers are heteortactic-rich. Reactivity ratios in bulk radical copolymerization on MI (M₂) with methacrylate (MMA, M₁) were determined at 60°C (r₁ = 0.129 and r₂ = 1.07). In order to clarify the copolymerization mechanism, radical copolymerization of MI with MMA was investigated in bulk at temperatures ranging from 50 to 80°C. The Mayo–Lewis equation has been found to be inadequate to describe the result due to depolymerization of MI sequences above 70°C.     

Nuclear magnetic relaxation of α-13C nuclei of helical poly(γ-hexyl-L-glutamate) and poly(γ-benzyl-L-glutamate)

Spin-lattice relaxation times (T₁), spin-spin relaxation times (T₂), and nuclear Overhauser enhancements (NOE), at 75.5 MHz are reported for α-¹³C nuclei of poly (γ-benzyl-L -glutamate) in deuterated dimethylformamide at 60°C and of poly(γ-hexyl-L -glutamate) in cyclohexanone at 48 and 79°C. It is shown that for molecular weights above 10⁵, the polypeptides cannot be considered as essentially rigid helices with internal librational motions; additional backbone flexing motions contribute to the relaxation behavior.