Oxygen permeability and surface free energy properties of silicone-containing copolymers of methyl methacrylate

Novel organofunctional siloxanes from γ-methacryloxypropyltrimethoxysilane (MPTMS) were synthesized by transesterification reactions with high monohydric alcohols, branched alcohols, ether alcohols, phenol, and mandelic acid. The factors effecting the substitution ratios were determined. Copolymers of these siloxanes with methyl methacrylate (MMA) were prepared by bulk copolymerization in glass molds and their swelling, thermal, oxygen permeability, and surface free energy characteristics were investigated in order to determine the effect of the substituted group on the produced copolymer. The changes in these properties by the crosslinking of the copolymer with ethylene glycol dimethacrylate (EGDM) were also investigated. The copolymers containing branched, nonpolar, and lengthy pendant groups were found to be highly oxygen permeable possibly due to the introduction of larger free volume by these groups. The surface energy analysis showed that the main variation was found to be in γ values rather than γ values and only ether alcohol substitution increased γ values to a greater extent.     

Surface-free energy analysis of hydrolyzed ethylene-vinyl acetate copolymers

Ethylene-vinyl acetate (E-VA) copolymers containing 12, 28, and 40 wt% of vinyl acetate, ethylene-vinyl acetate-vinyl alcohol terpolymers obtained by partial hydrolysis of (E-VA) copolymers and ethylene-vinyl alcohol (E-VOH) copolymers obtained by complete hydrolysis of (E-VA) copolymers were investigated by one-liquid contact-angle method. The polar force component of surface-free energy (γ) of copolymers drastically increased by the substitution of the acetate groups with hydroxyl groups. The dispersion force component (γ) of copolymers increased only slightly with the hydrolysis degree and deviated largely from the additivity law in regards of the surface area functions. The surface-free energy analysis of the cross-linked ethylene-vinyl alcohol and surface-hydrolyzed ethylene-vinyl acetate copolymers was also carried out.     

Nonlinear programming methods to determine surface free energy components of polymers using harmonic mean approximation

The dispersion and polar surface free energy components, γ and γ, and the critical surface free energy, γ_c, of polymers were determined from contact angle data by the application of a nonlinear programming method using harmonic mean approximation. The surface free energy components of the probe liquids, γ and γ, which reflect the conditions of the maximized interaction parameter, Φ, were also simultaneously determined by this method.     

Surface free energy analysis of ethylene-vinyl acetate copolymers

Ethylene-vinyl acetate copolymers containing 4, 11, and 19 wt. % of vinyl acetate (VAc), polyethylene, and poly(vinyl acetate) were investigated by the two-liquid contact-angle method at 20°C. The dispersion force component of surface free energy γ increased drastically with the increase of VAc content, and deviated largely from the additivity law in regards of the surface area fractions of ethylene and VAc. On the other hand, the nondispersive (i.e., mainly due to hydrogen bonding) interaction free energy between solid and water I increased linearly with the concentration of VAc on the surface.     

Surface activity and micellar behavior of dimethylamino‐ and trimethylammonium‐ tipped oxyethylene–oxybutylene diblock copolymers in aqueous media

Surface activity and micellar behavior in aqueous media in the temperature range 20–50°C of the two block copolymers, Me₂N(CH₂)₂OE₃₉B₁₈, (DE₄₀B₁₈) and I^?Me₃N⁺(CH₂)₂OE₃₉B₁₈, (TE₄₀B₁₈) in the premicellar and postmicellar regions have been studied by surface tensiometry, viscometry, and densitometry. Where E represents an oxyethylene unit while B an oxybutylene unit. Various fundamental parameters such as, surface excess concentrations (Γ_m), area per molecule (a) at air/water interface and standard Gibbs free energy for adsorption, ΔG have been investigated for the premicellar region at several temperatures. The thermodynamic parameters of micellization such as, critical micelle concentrations, CMC, enthalpy of micellization, ΔH, standard free energy of micellization ΔG, and entropy of micellization ΔS have also been calculated from surface tension measurements. Dilute solution viscosities have been used to estimate the intrinsic viscosities, solute‐solvent interaction parameter and hydration of micelle. Partial specific volume and density of the micelle were obtained from the density measurements at various temperatures. The effect of modifying the end group of the hydrophilic block was investigated by comparing the behavior of trimethylammonium‐ and dimethylamino‐tipped copolymers, designated TE₄₀B₁₈, and DE₄₀B₁₈, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and electrochemistry of grafted copolymers of cellulose with 4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone,and 9-vinylcarbazole

Some new cellulosic materials, suitable for the adsorption of noble metal ions, were syn-thesized by chemical and electrochemical modification of cellulose. The polymerizable groups were introduced in cellulose with ∼ 80% yield of substitution by esterification with acryloyl chloride. The vinyl monomers (4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone, and 9-vinylcarbazole) were readily grafted into cellulose acrylate via radical polymerization in acetonitrile. The grafted copolymers of cellulose with 4-vinylpyridine and 4-vinylimidazole were reacted with methyl iodide and the corresponding 1-methylpyridinium iodide ( 6 ) and 3-methylimidazolium iodide ( 7 ) copolymers of cellulose were obtained. Copolymers 6 and 7 were transformed into new polymeric regents, differing in anions (ClO, CF₃COO⁻, NO, p-TsO⁻, BF, PF) by using a supporting electrolyte carrying the desired anions through the ion-exchange-electrochemical oxidation of the released iodide at a controlled anodic potential. © 1996 John Wiley & Sons, Inc.     

Surface characterization of poly(ethylene terephthalate) film by inverse gas chromatography

The gas-chromatographic retention of a series of n-alkanes at effectively zero coverage was measured on a poly(ethylene terephthalate) film surface, and the free energy of adsorption per—CH₂—segment of n-alkane at zero surface coverage, Δ?, was calculated. This quantity is a direct measure of the London (nonpolar) interactions of the surface. A value of 40 mN/m for γ^1/2, the London Component of the polyester surface free energy, may be estimated from the gas-chromatographic results, in good agreement with results from contact angle measurements. The complete adsorption isotherm and spreading pressure for n-decane were also measured by finite-concentration gas chromatography. The method is restricted to polar or crystalline polymers, where the n-alkane does not penetrate the bulk of the material during the measurements.     

Synthesis of ultraviolet‐curable modified polysiloxane and its surface properties

A novel ultraviolet (UV)‐curable monomer α,ω‐dichloropolysiloxane was synthesized by the telomerization of dichlorodimethylsilane and octamethylcyclotetrasiloxane (D₄). The products with very low peel strength (<0.332 N/cm) could be used as release agents in pressure‐sensitive adhesives. Moreover, the values of the dispersion component of surface energy (γ) from the films of UV‐curable prepolymers (26.40–33.75 mJ/m²) were determined and the effects of γ on the reduction of adhesion were investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2135–2139, 2002     

Synthesis,characterization, and thermodynamic properties of poly(3‐mesityl‐2‐hydroxypropyl methacrylate)

Poly(3‐mesityl‐2‐hydroxypropyl methacrylate) (PMHPMA) was synthesized in a 1,4‐dioxane solution with 2,2′‐azobisisobutyronitrile as the initiator at 60°C. The homopolymer and its monomer were characterized with ¹H‐ and ¹³C‐NMR, Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and elemental analysis techniques. According to size exclusion chromatography analysis, the number‐average molecular weight, weight‐average molecular weight, and polydispersity index of PMHPMA were 65,864 g/mol, 215,375 g/mol, and 3.275, respectively. According to thermogravimetric analysis, the carbonaceous residue value of PMHPMA was 14% at 500°C. The values of the specific retention volume, adsorption enthalpy, sorption enthalpy, sorption free energy, sorption entropy, partial molar free energy, partial molar heat of mixing, weight fraction activity coefficient of solute probes at infinite dilution (Ω), and Flory–Huggins interaction parameter (χ) were calculated for the interactions of PMHPMA with selected alcohols and alkanes by the inverse gas chromatography method at various temperatures. According to Ω and χ, selected alcohols and alkanes were nonsolvents for PMHPMA at 423–453 K. Also, the solubility parameter of PMHPMA (δ₂) was found to be 24.24 and 26.33 (J/cm³)^0.5 from the slope and intercept of (δ/RT) ? χ/V₁ = (2δ₂/RT)δ₁ ? δ/RT at 443 K, respectively [where δ₁ is the solubility parameter of the probe, V₁ is the molar volume of the solute, T is the column temperature (K), and R is the universal gas constant]. The glass‐transition temperature of PMHPMA was found to be 386 and 385 K by inverse gas chromatography and differential scanning calorimetry techniques, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 101–109, 2006     

Surface free energy analysis of polymers and its relation to surface composition

The dispersion force component of surface free energy, γ, and the nondispersive interaction free energy between solid and water, I, were determined by the two-liquid contact-angle method, i.e., by the measurement of contact angles of water drops on plain solids in hydrocarbon, for commercialy available organic polymers such as nylons, halogenated vinyl polymers, polyesters, etc. A method to estimate the I values from the knowledge of the polymer composition is also proposed, on the basis of the assumption of the spherical monomer unit and the sum of interactions between functional groups and water molecules at the surface.     

Corona-discharge treatment of polymeric films,II: Chemical studies

Polymeric films, chiefly polyethylenes, were subjected to corona-discharge treatment in a continuous treater at commercial rates in a program covering wide ranges of the main processing factors (2). Electron-spin-resonance measurements on freshly treated films found no free radicals. Reactions of the treated surfaces with a free-radical compound, diphenyl picryl hydrazyl (DPPH) were studied, focusing mainly on the rate effects. The evidence indicates that corona treatment produces fairly stable peroxide structures of the forms RO₂R and RO₃R on polyethylene surfaces. RO₃R reacts rapidly with DPPH alone, while RO₂R undergoes a slower reaction after addition of the catalyst, triethylene diamine. DPPH is capable of detecting as few as 10¹³ peroxide groups per square centimeter. Activation energies were 12 kcal/mole for the uncatalyzed reaction and 16 kcal/mole for the amine-catalyzed reaction. As with the physical effects reported earlier (2), the production of peroxides is most strongly dependent on the energy delivered to the film during treatment. This energy is proportional to the quotient of corona current and web speed, I/S, Regression analysis showed that air-gap thickness, relative humidity, and number of electrodes used also were significant factors, while dielectric thickness and corona frequency were not. We found that-γ, the polar component of surface energy of the treated film, which is nearly zero for untreated polyethylenes, is exponentially related to the concentrations of both RO₂R and RO₃R with a correlation coefficient for 92 specimens tested of 0.88. We believe this is the first strong evidence linking treatment factors, at commercial levels of treatment, to chemistry of the treated surface and linking both of those to changes in physical behavior of the surface.     

Cationic grafting from carbon black. III. Grafting of polyesters from carbon black by ring-opening polymerization of lactones initiated by CO+ClO groups on carbon black

It was found that the cationic ring-opening polymerization of δ-valerolactone (VL), ε-caprolactone (CL), and β-propiolactone (PL) was initiated by carbon black containing CO⁺ClO groups, which were introduced by the reaction of COCl groups with AgClO₄. The polyester was propagated from CO⁺ClO groups and effectively grafted onto carbon black surface. The polymerizability of these lactones by CO⁺ClO groups decreased in the following order: VL > CL > PL. The increasing temperature of the polymerization caused an increase in the rate of the chain transfer reaction of the growing chains and brought about the decrease of grafting ratio of polyester onto carbon black.     

Influence of anionic form on thermooxidation of TMAHP–cellulose

With the help of DTA, DTG elementary analysis of carbonized residues and ESR spectroscopy the influence of anionic form on thermooxidation of trimethylammoniumhydroxyprophyl (TMAHP)–cellulose was studied. At 300°C the percentage of carbon in carbonized residue thermolyzed in oxidative atmosphere is higher than for the sample degraded in inert atmosphere. The percentage of hydrogen decreases simultaneously. The concentration of free radicals in thermolyzed residue also increases due to the presence of oxygen. We propose that oxygen is abstracting the hydrogen atoms from polysaccharide and unpaired electrons on carbon atoms are produced. At 400°C the percentage of carbon in residues prepared at inert atmosphere is higher than for residue formed at oxidative atmosphere. Also the concentration of free radicals in thermolyzed residues obtained in inert atmosphere is greater than for those from oxidative ones. That is why suppose that at this temperature oxygen is bonded to polysaccharide residue and free radicals are terminated. From the semiquantitative DTA we can make the following sequence of samples according to their increasing thermooxidative effect: unmodified cellulose < A–HSO < A–Br^? < A–I^? < A–NO < A–H₂PO < A–CH₃COO^? < A–HCO < A–F^? < A–Cl^?1 < A–OH^p?.     

Study on the surface properties of grafted polyethylene particles by inverse gas chromatography

Inverse gas chromatography (IGC) studies on the surface of polyethylene (PE) particles grafted with acrylic acid and acryl amide have been reported. Surface properties of the virgin and grafting‐modified PE were compared by IGC. The dispersive contributions of the surface free energy γ and the K_A and K_B parameters expressing the ability of the stationary phase to act as Lewis acid or Lewis base were calculated. The results showed that the γ value increased significantly after grafting. The PE samples grafted with acrylic acid and acrylamide showed a predominantly basic character while the virgin PE was acidic. All of these suggested that the surface of PE has been modified through the grafting reaction, and thus is expected to improve its adhesions with other polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Spherulitic crystallization behavior of linear low‐density polyethylene

In this study the crystallization behavior of linear low‐density polyethylenes (LLDPEs) (ethylene‐α‐olefin copolymers) was studied by polarized light microscopy. A modified Hoffman‐Lauritzen (MHL) expression is proposed whereby the equilibrium melting temperature, T (T), is replaced with the melting temperature of the crystal stem is replaced with the maximum possible stem length, T. It successfully describes the crystalline spherulitic growth kinetics for both homogeneous and heterogeneous LLDPEs. In addition to regimes III and II, another regime (IM) was found in the high crystallization temperature range. Linear growth behavior of crystalline spherulites was observed in regime III, and nonlinear growth behavior was found in regimes II and IM. The basal surface free energy can be estimated from the short chain branching polydispersity (SCBP) for LLDPEs with excluded comonomers. Polym. Eng. Sci. 45:74–83, 2005. © 2004 Society of Plastics Engineers.     

Studies on acrylate copolymer soap‐free waterborne coatings crosslinked by metal ions

Acrylate copolymers containing hydrophobic monomers (methyl methacrylate, butyl acrylate, styrene, or divinyl benzene) and hydrophilic monomer (acrylic acid) were synthesized by solution polymerization, and neutralized to form the soap‐free hydrosol. The waterborne coating was prepared from the hydrosol crosslinked by M(NH₃) (M²⁺ was Zn²⁺ , Cu²⁺, Ni²⁺ or Co²⁺). ¹³C‐NMR analysis was used to identify the copolymer. The result of GPC showed that the molecular weight of the copolymer was within the range of thermosetting resin for coating. The factors affecting the crosslinking degree of the coating films were studied by DSC and gravimetric analysis. The results indicated that the appropriate crosslinking agent was Zn(NH₃), and the optimum curing condition was heating at 80°C for 30 min. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 91–96, 1999     

Adiabatic compressibility of polyelectrolytes: Poly(N-dimethylaminoethyl methacrylate) and its copolymer with acrylic acid

The adiabatic compressibility of poly(N-dimethylaminoethyl methacrylate) and of three copolymers of N-dimethylaminoethyl methacrylate and acrylic acid, ranging in composition from 33 to 58 mole-% amino groups, has been studied. The ?V of the polymer shows a slight decrease (2.4 cc/mole), while the ?K is found to have increased considerably (51 × 10^?4 cc bar^?1 mole^?1) compared to that of the monomer. The latter is apparently due to the more compressible nature of the polymer than that of its monomer. The experimentally observed ?K₂⁰ and ?V₂⁰ values for the three copolymers containing 58%, 43%, and 33% amino groups are ?2.5 × 10^?4 cc bar^?1 mole^?1 and 164.5 cc/mole, ?32 × 10^?4 cc bar^?1 mole^?1 and 177.5 cc/mole, and ?55 × 10^?4 cc bar^?1 mole^?1 and 211.3 cc/mole, respectively, whereas the calculated values are less by 19.4 × 10^?4 cc bar^?1 mole^?1 and 3.2 cc/mole, 49.5 × 10^?4 cc bar^?1 mole^?1 and 19.9 cc/mole, and 73 × 10^?4 cc bar^?1 mole^?1 and 16.4 cc/mole, respectively. This decrease is attributed to the interaction of acid and base groups in the molecules. The ?K₂⁰ and ?V₂⁰ values have been resolved into their ionic components ?K and ?V. Since the magnitude of electrostriction is higher in fully neutralized salt than in unneutralized salt, the ?K_2i⁰ and ?V_2i⁰ values are lower as expected. The difference in these values for the polybase and its salt is 23.7 × 10^?4 cc bar^?1 mole^?1 and 7.5 cc/mole, respectively, which may be due to the electrostrictive effect. In excess NaCl (1.0M), the magnitude of electrostriction is somewhat reduced and ?V_2i⁰ and ?V_2i⁰ approach values more or less equal to those of the unneutralized polymer. The 100% neutralized hydrochloride salt of poly(N-dimethylaminoethyl methacrylate) shows greatly increased reduced viscosity over that of the feebly basic parent polymer due to the characteristic polyelectrolytic expansion in dilute aqueous solution. The copolymer containing excess amount of amino groups (58%) shows similar behavior, while the other two copolymers containing fewer amino groups (43% and 33%) show a contraction of chains, which may be ascribed in interaction of the carboxyl ions that are freshly formed on dilution with the amino groups in the copolymer chain.     

Surface tension versus barrier property for fluorinated surfaces

The barrier property of fluorinated surfaces was compared to the surface tension measurements. A relationship between barrier property and the solvent's surface tension was developed. However, other properties of both the solvent and the polymer contribute to barrier property. The surface tension of the polymer surface was separated into nonpolar, polar, and hydrogen bonding forces. By estimating the % γ of various solvent mixtures, the % γ_S^D was estimated for the polymer surface.     

Über die Katalyse der Cooxidation von cis-Oct-4-en und n-Butyraldehyd

The Catalysis of the Co-Oxidation of cis-Oct-4-ene and n-Butyric Aldehyde The co-oxidation of cis-oct-4-ene and n-butyric aldehyde in the absence of catalysts, or in the presence of molybdenum and Co(acac)₃, resp., was studied in dependence on the aldehyde/olefin ratio, on the temperature and other reaction conditions. Under the same conditions, the noncatalyzed co-oxidation converted 50%, the MoO₂(acac)₂-catalyzed one 68%, and the Co(acac)₃-catalyzed one 40% of the reacted olefin into the epoxide. The cis/trans-epoxide ratio in the molybdenum-catalyzed co-oxidation was nearly 2 independent of the aldehyde/olefin ratio. In the non-catalyzed co-oxidation the cis/trans-epoxide ratio depends linearly on the aldehyde/olefin ratio (cis/trans E. = 0,58 + 0,90 n/n). From these dependences we can conclude that the homolytic mechanism of epoxide formation decreases and the polar mechanism (Priležaev-reaction) increases with increasing aldehyde/olefin ratio. Optimization of the epoxide yields according to a Box-Hunter experimental plan gave the following reaction conditions to yield 95% epoxide based on reacted olefin: 70°C, Δn_S/n = 0,49, n/n = 3,5 · 10⁻³, n/n = 0,53. The co-oxidation in the presence of other molybdenum catalysts of the chloro-nitrosyl-complex type and of the carbonyl-complex type as well as the co-oxidation with other aldehydes were studied, too.     

Oxidation of aqueous sulfur dioxide catalyzed by poly-4-vinylpyridine–Cu(II) complex. Part 1: Homogeneous phase oxidation

The oxidation of aqueous sulfur dioxide in the presence of polymer-supported copper(II) catalyst is also accompanied by homogeneous oxidation of aqueous sulfur dioxide catalyzed by leached copper(II) ions. Aqueous phase oxidation of sulfur dioxide of low concentrations by oxygen in the presence of dissolved copper(II) has therefore been studied. The solubility of SO₂ in aqueous solutions is not affected by the concentration of copper(II) in the solution. In the oxidation reaction, only HSO is the reactive S(IV) species. Based on this observation a rate model which also incorporates the effect of sulfuric acid on the solubility of SO₂ is developed. The rate model includes a power-law type term for the rate of homogeneous phase reaction obtained from a proposed free-radical chain mechanism for the oxidation. Experiments are conducted at various levels of concentrations of SO₂ and O₂ in the gas phase and Cu(II) in the liquid phase. The observed orders are one in each of O₂, Cu(II) and HSO. This suggests a first-order termination of the free radicals of bisulfite ions.