Radiation-Induced Degradation of a Series of Poly(vinyl Ethers)

The degradative effects of γ-radiation on diethyl ether solutions of poly(alkyl vinyl ethers) under a variety of conditions were studied by polymer molecular weight measurements. Poly(methyl vinyl ether) (PMVE), poly(ethyl vinyl ether) (PEVE), poly(isopropyl vinyl ether) (PIPVE), and poly(isobutyl vinyl ether) (PIBVE) exhibited similar degradative behavior, with G_(SC) values between 0.3 and 0.9 scissions/100 eV at 0°C. Chemically polymerized and radiation-polymerized PEVE samples gave comparable results. Chain degradation was much more pronounced for samples of poly(tert-butyl vinyl ether) (PTBVE) which yielded a G_(SC) value of 3.6 at 0°C. Degradation experiments conducted on PEVE in air resulted in significantly higher rates of scission: G_(SC) = 5.6 scissions/100 eV at 0°C. Chain scission was not measurably influenced by changing the solvent from diethyl ether to di-isopropyl ether. Increased polymer concentration was found to reduce the rate of polymer degradation.     

A detailed surface analytical study of degradation processes in (meth)acrylic polymers

The present study investigates the degradation behavior of various high‐molecular‐weight acrylic polymers (50,000 < M_n/g mol^?1 < 100,000), namely poly(methyl methacrylate) (PMMA), poly(n‐butyl methacrylate) (PBMA), poly(n‐butyl acrylate) (PBA), and poly(lauryl methacrylate) (PLMA), under extreme environmental conditions. These polymers were synthesized via various polymerization techniques to create different end‐groups. The polymers chosen are readily applicable in the formulation of surface coatings and were degraded under conditions which replicate the harsh Australian climate, where surface coatings may reach temperatures of up to 95 °C and are exposed to broad‐spectrum UV radiation of up to 1 kW m^?2. The degradation behavior of the polymeric materials on their surface was followed via ATR‐IR spectroscopy, high resolution FTIR microscopy, and X‐ray photoelectron spectroscopy. The extent of the observed thermal and photo‐oxidation is directly related to the length of the ester side group, with the degradation susceptibility decreasing in the order of PLMA > PBMA/PBA > PMMA, with PMMA still stable even after 5 months exposure to the harshest condition used (UV light at 95 °C). The general degradation mechanism involves the loss of the ester side groups to form methacrylic acid followed by cross‐linking. The effect of the variable end groups was found to be minimal. The results from this study are in good agreement with previous studies of low‐molecular‐weight model polymers under identical conditions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of novel degradable photocrosslinked poly(ether‐anhydride) networks

New degradable poly(ether‐anhydride) networks were synthesized by UV photopolymerization. Dicarboxylated poly(ethylene glycol) (PEG) or poly(tetramethylene glycol) (PTMG) was reacted with an excess of methacrylic anhydride to form dimethacrylated macromers containing anhydride linkages. The percent of conversion for the macromer formation was more than 80% at 60 °C after 24 h. ¹H NMR and IR spectroscopies show the presence of anhydride linkages in the macromer. In vitro degradation studies were carried out at 37 °C in PBS with crosslinked polymer networks formed by UV irradiation. All PEG‐based polymers degraded within 2 days, while PTMG‐based polymers degraded by 50% of the initial weight after 14 days. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1277–1282, 2000     

In situ polymerization and morphology of polypyrrole obtained in water‐soluble polymer templates

Several water‐soluble polymers were used as templates for the in situ polymerization of pyrrole to determine their effect on the generation of nanosized polypyrrole (PPy) particles. The polymers used include: polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(vinyl butyral), polystyrene sulfonic acid, poly(ethylene‐alt‐maleic anhydride) (PEMA), poly(octadecene‐alt‐maleic anhydride), poly(N‐vinyl pyrrolidone), poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), poly(N‐isopropyl acrylamide), poly(ethylene oxide‐block‐propylene oxide), hydroxypropyl methyl cellulose, and guar gum. The oxidative polymerization of pyrrole was carried out with FeCl₃ as an oxidant. The morphology of PPy particles obtained after drying the resulting aqueous dispersions was examined by optical microscopy, and selected samples were further analyzed via atomic force microscopy. Among the template polymers, PVA was the most efficient in generating stable dispersions of PPy nanospheres in water, followed by PEO and PEMA. The average size of PPy nanospheres was in the range of 160 nm and found to depend on the molecular weight and concentration of PVA. Model reactions and kinetics of the polymerization reaction of pyrrole in PVA were carried out by hydrogen ¹H NMR spectroscopy using ammonium persulfate as an oxidant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Poly(itaconates) monolayers behavior at the air/water interface. Study at different surface concentration

Polymer monolayers spread at the air/water interface were obtained for: poly(monooctyl itaconate) (PMOI), poly(monodecyl itaconate) (PMDI), poly(monododecyl itaconate) (PMDoI), poly(monobenzyl itaconate) (PMBzI), poly(methyldodecyl itaconate) (PMeDoI) and the alternating copolymer (monooctyl itaconate-alt-maleic anhydride) (MOI-alt-MA). By monolayer compression at constant temperature, the respective Langmuir isotherms for these polymers were obtained. For all polymers the zero-pressure limiting area per repeating unit (ru) Ao, and the collapse pressure π_c were determined. At low surface polymer concentrations, the monolayers characterization was carried out according to the surface pressure expressed as a function of the surface concentration. The behavior observed was described by the virial expansion development. At the semidilute region, the surface pressure variation was expressed in terms of the scaling laws as a power function of the surface concentration.     

Study on modification of polymers with the aid of the Schmidt reaction

A study of the Schmidt reaction on several polymers with pendant carboxylic and ketone moieties was carried out. Four polymers were used as starting materials: (1) poly(methyl vinyl ketone), (2) poly(acrylic acid), (3) a copolymer of methyl vinyl ketone and acrylic acid, and (4) a copolymer of styrene and acrylic acid. Most reactions were conducted in an acetic acid medium with the exception of one reaction on poly(acrylic acid) which was done in dioxane and another on copolymer of styrene and acrylic acid done in chloroform. It was found that a Schmidt reaction on poly(acrylic acid) in acetic acid solution will lead to intermolecular reactions of the intermediate with the solvent in preference to reactions with neighboring carboxyl groups on the polymer backbone. A tendency of poly(acrylic acid) to form cyclic anhydrides under these reaction conditions interferes with the yield of acetamide units.     

Interaction of polyanions with electroneutral liposomes in a slightly acidic medium

In this study, the interaction between poly(styrene sulfonic acid), polyacrylic acid, poly(meth-acrylic acid), poly(L-glutamic acid), poly(vinyl sulfate), and ternary copolymer of styrene with maleic anhydride and methacrylic acid (3: 2: 1), as well as DNA with lipid vesicles composed of zwitterion (electroneutral) lipid phosphatidylcholine, has been investigated. The methods of centrifuge ultrafiltration and dynamic light scattering reveal that, at pH 4.2, all polyacids under study are effectively adsorbed on the phospholipid membrane. The polymer-membrane complex is stabilized by hydrogen bonds and hydrophobic interactions in addition to electrostatic bonds. Even though, to a greater or lesser extent, all polyacids are capable of undergoing adsorption on the membrane in a slightly acidic medium, their effect on the membrane permeability is substantially different and is correlated with the ability of a polymer to form multiple interactions with phospholipid molecules. Poly(acrylic acid), poly(methacrylic acid), poly(styrene sulfonic acid), and the ternary copolymer of styrene with maleic anhydride and methacrylic acid can produce the membrane pores that are permeable to low-molecular-mass compounds. At the same time, poly(L-glutamic acid), poly(vinyl sulfate), and DNA exert no effect on the membrane permeability, although they are sorbed on the membrane surface.     

An electron spin resonance study on γ-irradiated poly( -lactic acid) and poly( -lactic acid)

The effect of gamma irradiation on poly( -lactic acid) ( -PLA) and poly( -lactic acid) ( -PLA), has been examined using ESR spectroscopy and through analysis of the changes in molecular weight. The G values for radical formation of both polylactic acids have been calculated at 77 and 300 K; G(R) = 2.0 at 77 K and G(R) = 1.5 at 300 K for -PLA and G(R) = 2.4 at 77 K and G(R) = 1.2 at 300 K for -PLA. The ESR spectrum at 300 K for the polymers was assigned to one radical, resulting from H atom abstraction from the quaternary carbon atom. The G values for crosslinking and scission have also been determined for the polymers at 300 K; G(S) = 2.3 and G(X) = 0.0 for -PLA, G(S) = 2.4 and G(X) = 0.28 for -PLA.     

Reversible addition fragmentation chain transfer polymerization of sterically hindered monomers: Toward well‐defined rod/coil architectures

The sterically hindered monomers dibutyl itaconate (DBI) and dicyclohexyl itaconate (DCHI) were polymerized via reversible addition fragmentation chain transfer (RAFT) free‐radical polymerization. S,S′‐Bis(α,α′‐dimethyl‐α″‐acetic acid) trithiocarbonate, cumyl dithiobenzoate, and cumyl phenyldithioacetate have been used as RAFT agents to mediate a series of polymerizations at 65 °C yielding rod polymers ranging in number average molecular weight from 9000 to 92,000 g mol^?1. The progress of the polymerization was followed via online Fourier transform–near infrared spectroscopy. The polydispersity indices of the obtained rod polymers were relatively high at 1.4–1.7. The RAFT polymerizations of the hindered monomers used in the present study displayed both ideal living and hybrid behavior between conventional and living polymerization, depending on the RAFT agent used. DCHI rod polymers generated via the RAFT process were subsequently reinitiated in the presence of styrene to produce a range of BAAB and A‐B rod‐coil block copolymers of molecular weights up to 164,000 g mol^?1. The chain extension yields molecular weight distributions that progressively shift to higher molecular weights and are unimodal. Thermogravimetric analysis of the pDCHI‐block‐pStyrene copolymers indicates thermal degradation in two separate steps for the pDCHI and pStyrene blocks. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2432–2443, 2004     

Equilibrium study of polymer–polymer complexation of poly(methacrylic acid) and poly(acrylic acid) with complementary polymers through cooperative hydrogen bonding

The degree of linkage, θ, defined as the ratio of the binding groups to the total of potentially interacting groups and the stability constant K of the polymer–polymer complexes in the systems poly(methacrylic acid)–poly(ethylene glycol), poly(acrylic acid)–poly(ethylene glycol), and poly-(methacrylic acid)–poly(vinyl pyrrolidone) in aqueous and aqueous alcohol media were determined as a function of temperature by potentiometric titration. It was found that θ and K are strongly dependent on chain length, temperature, and medium and that hydrophobic interaction is a significant factor in the stabilization of the complexes. The enthalpy and entropy changes and the cooperativeness parameter of the systems were calculated. A mechanism for the complexation in terms of cooperative interaction was proposed.     

Chemical modification of poly(ethylene‐co‐methyl acrylate‐co‐maleic anhydride) for cathodic electrodepositions

This study is concerned with the development of new polymers that could be deposited via cathodic electrocoating methods on metal surfaces. The synthetic strategy is based on the incorporation of cationic functionalities into commercial polymers. Polyalkyl acrylic or methacrylic ester copolymers were reacted with primary or secondary amines and aminoalkanols or their mixtures. Depending on the proportion of the acrylic or methacrylic ester in the starting material and the extent of the chemical modification, the resulting amide functionalized polymers are soluble or dispersible in water and could be used as aqueous dispersions for cathodic electrodepositions. Hindered amine catalysts, such as diazabicyclo[2.2.2]octane, accelerate the chemical transformation leading to higher level of functionalization. Among different amines screened, mixtures of oleylamine and ethanolamine proved to produce the best results. A poly(ethylene‐co‐methyl acrylate‐co‐maleic anhydride) [poly(E‐co‐MA‐co‐MAH)] was aminolyzed in solution with a mixture of 50/50 (mol % ratio) of oleylamine/ethanolamine and used to generate aqueous dispersions via phase inversion from methyl isobutyl ketone solutions. These dispersions exhibit particle sizes in the submicron range and zeta potential values indicating a good stability. They could be electrodeposited to give films of high elasticity according to the nanomechanical tests. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Radiation degradation of methyl α-chloroacrylate–methacrylonitrile copolymers

The radiation degradation behavior of methyl α-chloroacrylate (MCA) and methacrylonitrile (MCN) copolymers has been investigated as part of a program to develop high-sensitivity polymeric resists for integrated circuit manufacture. High-molecular-weight copolymers were prepared by emulsion techniques. Several different copolymer compositions were prepared varying from 19 to 68 mole % MCA. These copolymers were fractionated and then subjected to γ irradiation from a ⁶⁰Co Source. The G_s - G_s, G_s - 4G_s values were determined from M?;F>n_k^?1 and G_u^?1 versus dose plots, and the G_fs and G_s Values were then calculated. Molecular weights of both unirradiated and irradiated polymers were analyzed by membrane osmometry and gel permeation chromatography. All copolymers exhibited higher degradation susceptibilities than that of poly(methyl methacrylate) (PPMA), which has G_x = 1.3. The individual G_x and G_x values of the copolymers were found to fall between those of the two homopolymers, poly(methyl α-chloroacrylate) (G_x = 6.0) and polymethacrylonitrile (G_x ～ 3.1). The dependence of G_x and G_x values on molecular weight was minor. The crosslinking susceptibility of the poly(methyl α-chloroacrylate) (G_x ～ 0.8), was greatly decreased by copolymerization with MCN. Relatively small amounts of MCN caused a large drop in G_x, i.e., G_x ～ 0.15 at 32% MCN and G_x ～ 0.03 at 51% MCN. The observation could be attributed to the decreasing probability that crosslinking sites, in the MCA monomer units on adjacent chains, would lie in close proximity.     

Poly(dialkoxyethyl itaconates)

The oxidative and non-oxidative degradation of poly(di-methoxy-), poly(di-ethoxy-), poly(di-iso-propoxy-) and poly(di-n-butoxyethyl itaconate) were investigated by thermogravimetry. Characteristic degradation temperatures and apparent activation energies of degradation were determined for the non-oxidative degradation of all the investigated polymers. It was not possible to determine these characteristics in the presence of oxygen as the degradation was accompanied by a secondary exothermic reaction. Based on examination of the monomers, it is supposed that the exothermic reaction is a repolymerisation of the monomers released during the earlier stages of polymer degradation.     

Head-to-head vinyl polymers. XI. Preparation and characterization of poly(methyl acrylate) and poly(methyl methacrylate) consisting of head-to-head and head-to-tail units through cyclopolymerization of acrylic and methacrylic anhydrides

Acrylic anhydride (AAn) and methacrylic anhydride (MAAn) were polymerized with radical initiator in polar solvents at high temperatures. The polymers obtained were found to consist of five-and six-membered ring structures by comparing IR spectra of the polymers with those of model compounds, succinic anhydride, and glutaric anhydride. Hydrolysis and methylation of the polymers gave new polymers composed of head-to-head (HH) and head-to-tail (HT) methyl acrylate (MA) or methyl methacrylate (MMA) units. The content of HH unit of these HH/HT polymers was determined by ¹H-NMR and ¹³C-NMR spectra. The softening, glass transition, and thermal degradation temperatures of the poly(MA) with HH and HT units were found to somewhat increase with increasing of the content of the HH units. On the other hand, the glass transition and thermal degradation temperatures of the poly(MMA) with HH and HT units increased similarly, but the softening temperature decreased as the content of the HH units increased.     

One-step functionalization of multi-walled carbon nanotubes by radiation-induced graft polymerization and their application as enzyme-free biosensors

This paper describes the functionalization of multi-walled carbon nanotubes (MWNTs) by radiation-induced graft polymerization (RIGP) of vinyl monomers with functional groups and the application of these MWNTs in enzyme-free biosensors. The vinyl monomers used were acrylic acid (AAc), methacrylic acid (MAc), glycidyl methacrylate (GMA), maleic anhydride (MAn), and 4-vinylphenylboronic acid (VPBAc). Tubular-type MWNTs were obtained via RIGP of various vinyl monomers. The poly(VPBAc)-grafted MWNTs (PVBAc-g-MWNTs) were used as sensing sites in enzyme-free glucose sensors for the detection of glucose without enzymes. The PVBAc-g-MWNTs electrode displayed an excellent linear response to glucose concentration in the range 1.0–10 mM. The functionalized MWNTs prepared by RIGP can be used as biosensor materials.     

Studies of reactions with polymers. V. The reaction mechanism and resultant structure of PVA with PAN in DMSO without any catalyst

The reaction of polyacrylonitrile with poly(vinyl alcohol) in dimethyl sulfoxide without any catalyst was studied, and it showed that the adjacent nitrile groups on polyacrylonitrile could be linked up to form conjugated carbon-nitrogen sequence by the presence of poly(vinyl alcohol). However, no such reaction occurred when poly(vinyl alcohol) was replaced by i-propanol or poly(vinyl alcohol) graft copolymers. The structure of the resulting polymers were proposed by means of IR, UV, ¹H, and ¹³C-NMR spectroscopies. On the basis of the results, the effect of polymer feed and polymerization condition on this reaction were discussed. The compositions were determined by elemental analysis. The viscosity and thermal analysis of the products were also determined. At feed weight ratios of poly(vinyl alcohol) to polyacrylonitrile above one-half, gels were obtained.     

Polymers derived from fluoroketones. III. Monomer synthesis,polymerization, and wetting properties of poly(allyl ether) and poly(vinyl ether)

The synthesis and polymerization of a series of perhaloalkyl allyl and vinyl ethers derived from perhaloketones is described. Data on the critical surface tension of wetting (γ_c) for high molecular weight polymers of heptafluoroisopropyl vinyl ether and low molecular weight poly(heptafluoroisopropyl allyl ether) is also presented. Preparation of the allyl ethers is a one-step, high-yield displacement reaction between the potassium fluoride–perhaloacetone adduct and an allyl halide, such as allyl bromide. The vinyl ethersare prepared by a two-step process which involves displacement of halide from a 1,2-dihaloethane with a KF–perhaloacetone adduct and dehydrohalogenation of the 1-halo-2-perhaloalkoxyethane to a vinyl ether. Low molecular weight polymers were obtained with heptafluoroisopropyl allyl ether by using a high concentration of a free-radical initiator. The low molecular weight poly(heptafluoroisopropyl allyl ether) had a γ_c of 21 dyne/cm. No polymer was obtained with tributylborane–oxygen or with VCl₃–AIR₃, with gamma radiation, or by exposure to ultraviolet light. High molecular weight polymers were obtained from heptafluoroisopropyl vinyl either by using either lauryl peroxide or ultraviolet light but not by exposure to BF₃–etherate. The γ_c for poly(heptafluoroisopropyl vinyl ether) ranged from 14.2 to 14.6 dyne/cm., and the significance of this value is discussed in relation to the γ_c for poly(heptafluoroisopropyl acrylate).     

Head-to-head vinyl polymers. III. Preparation and characterization of head-to-head poly(acrylic acid) and its esters

Head-to-head (h-h) poly(acrylic acid) (PAA) and some h-h poly(alkyl acrylates) (PRA) with methyl, ethyl, n-propyl, n-butyl, isobutyl and 2-ethylhexyl substituents were prepared by hydrolysis or esterifications of the alternating copolymer of ethylene with maleic anhydride. In general, these esterification reactions became increasingly difficult as the carbon chain in the alcohols lengthened or branched. The softening, glass transition, and degradation temperatures of the h-h polymers obtained were somewhat higher than those of the corresponding head-to-tail (h-t) polymers. The main degradation products of both h-h and h-t PRA were identified by pyrolytic gas chromatography as the alcohol and monomer. In addition, the relative ratios of the amounts of alcohol to monomer were larger for h-h than for the corresponding h-t polymers.     

Adhesive polymer: Intermacromolecular interaction in fluid solution studied by fluorescence depolarization method

The fluorescence depolarization of the anthryl groups attached to poly(styrene-maleic anhydride) [P(St-MA)] has been examined in mixtures of various acrylic adhesive polymers with toluene for weight fractions ranging from 0 to 0.25. It is clear that the relative mean rotational relaxation time of the anthryl groups sharply increases with increasing concentration of poly(2-ethylhexylacrylate) (PEHA) containing about 5% acrylic acid units and 10% vinyl acetate units. It may be concluded that an excellent adhesive polymer is made with acrylic acid units as agents for intra- and interaction and vinyl acetate units as depression agents for acrylic acid units and agents for strong PEHA-P(St-MA) interaction.     

Stereoregularity of poly(vinyl ether)

α-Methylvinyl isobutyl and methyl ethers were polymerized cationically and the structure of the polymers was studied by NMR. Poly(α-methylvinyl methyl ether) polymerized with iodine or ferric chloride as catalyst was found to be almost atactic, whereas poly(α-methylvinyl isobutyl ether) polymerized in toluene with BF₃OEt₂ or AlEt₂Cl as catalyst was found to be isotactic. In both cases, the addition of polar solvent resulted in the increase of syndiotactic structure as is the case with polymerization of alkyl vinyl ether. tert-Butyl vinyl ether was polymerized, and the polymer was converted into poly(vinyl acetate), the structure of which was studied by NMR. A nearly linear relationship between the optical density ratio D₇₂₂/D₇₃₆ in poly(tert-butyl vinyl ether) and the isotacticity of the converted poly(vinyl acetate) was observed.