Cyclohexyl Methacrylate Research Articles

A molecular mechanics investigation into the mechanism of the low temperature relaxations of three poly(alkyl methacrylates)

The enthalpy curves for the rotation of the ester groups around the O-alkyl bonds in three-unit all- anti models of syndiotactic poly(ethyl methacrylate), poly(isopropyl methacrylate) and poly(cyclohexyl methacrylate) have been calculated using molecular mechanics. The abundance of conformers and the enthalpies of activation for their interconversion at 50 K have been related to the mechanical loss processes at low temperature with Hoffman's theory for a three site model with two equienergetic sites. The calculated activation energies compare well with the experimental values of the δ relaxations. The mechanical loss process is in all cases caused by the exchange of ester side chain positions by partial rotation around the O-alkyl bond.

Miscibility of poly(tetrahydropyranyl-2-methacrylate) and poly(cyclohexyl methacrylate) with styrenic polymers

The glass transition behaviour for blends of poly(tetrahydropyranyl-2-methacrylate) (PTHPMA) with poly(α-methylstyrene) (PαMS), polystyrene (PS) and poly( p-methylstyrene) (P pMS) has been studied by differential scanning calorimetry. The results indicate that PTHPMA/PαMS blends are fully miscible, whereas PTHPMA/P pMS blends are immiscible. The miscibility of PTHPMA/PS blends depends on their compositions. Lower critical solution temperature (LCST) behaviour was observed for all the miscible blends containing PTHPMA. Poly(cyclohexyl methyacrylate) was found to be miscible with PS, PαMS and P pMS, and none of the blends showed LCST behaviour.

Miscibility of polycarbonate with methyl methacrylate-based copolymers

Poly(methyl methacrylate) and bisphenol-A polycarbonate having high molecular weights do not form homogeneous mixtures above the glass transition temperature at equilibrium. This paper outlines a strategy for developing melt-processible, homogeneous blends of polycarbonate with an acrylic polymer through copolymerization. Nine different comonomers were copolymerized with methyl methacrylate and these polymers were blended with polycarbonate. Copolymers based on cyclohexyl methacrylate and phenyl methacrylate gave homogeneous mixtures with polycarbonate having cloud points (lower critical solution temperature behaviour) near or above the temperature range needed for melt processing. The thermal stability of the acrylic polymers was examined and in some cases a third monomer was used to obtain improvements.

Excimer fluorescence as a molecular probe of polymer blend miscibility. 9. Effects of guest concentration and annealing in blends of poly(2-vinylnaphthalene) with poly(cyclohexyl methacrylate)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTExcimer fluorescence as a molecular probe of polymer blend miscibility. 9. Effects of guest concentration and annealing in blends of poly(2-vinylnaphthalene) with poly(cyclohexyl methacrylate)William C. Tao and Curtis W. FrankCite this: Macromolecules 1990, 23, 13, 3275–3283Publication Date (Print):June 1, 1990Publication History Published online1 May 2002Published inissue 1 June 1990https://doi.org/10.1021/ma00215a013RIGHTS & PERMISSIONSArticle Views56Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

Density and concentration fluctuations in plasticized poly(cyclohexyl methacrylate)

Etude par spectroscopie de correlation photonique polarisee entre Tg et Tg×150 de la relaxation segmentaire primaire et de la diffusion cooperative dans le polymere contenant 5, 10 et 15% de phtalate de dioctyle. Les temps de relaxation primaire varient fortement avec la temperature, avec des parametres d'activation independants de la concentration du plastifiant. Les parametres d'activation de la relaxation lente diminuent lorsque la concentration du phtalate augmente

Thermal properties of copolymers of alkyl methacrylates with triallyl cyanurate

AbstractThe homo‐ and copolymers of triallyl cyanurate and methyl methacrylate, ethyl methacrylate, propyl methacrylate, n‐butyl methacrylate, and cyclohexyl methacrylate were synthesized by free radical bulk polymerization using benzoyl peroxide as the initiator. The thermal properties of the polymers have been studied. The influence of the triallyl cyanurate content on the thermal behaviour of the copolymers has been investigated.

Dielectric relaxation behaviour of poly(cyclohexylmethyl methacrylate) and poly(benzyl methacrylate)

The relaxation processes in poly(cyclohexylmethyl methacrylate) (PCMMA) and poly(benzyl methacrylate) (PBzMA) have been studied by dynamic dielectric techniques. The study includes the α-, γ- and δ-relaxations in the first polymer and the α-relaxation in the second one. The α-relaxation has been fitted to the empirical model of Havriliak and Negami, and the functional relation between the mean relaxation times and the temperature has been adjusted to the equation of Vogel. In the case of PCMMA two new relaxations labelled δ and γ in order of increasing temperature have been observed. The apparent activation energy of these relaxations are 5.5 and 11.8 kcal mol −1 respectively. The dielectric relaxation behaviours of PCMMA and PBzMA are discussed in relation to that of poly(cyclohexyl methacrylate) previously studied.

Préparation de microlatex acryliques par polymérisation photochimique de solutions micellaires et de microémulsions

AbstractMicrolatices of acrylic monomers, in the particle size range of 10–30 nm, were prepared by photopolymerization of micellar systems (monomer‐surfactant) and of microemulsions based on monomer‐surfactant‐cosurfactant. Formation of monomer containing microemulsions is shown for various surfactants in combination with alcohols as cosurfactants and the corresponding phase diagrams are given. Photopolymerization, in the presence of oil‐soluble initiators, was investigated for such systems based on cyclohexyl methacrylate (CHMA) and on tetramethylene dimethacrylate (BDMA). Crosslinked and non‐crosslinked colloidal polymer particles could be obtained, with a 5–10% solid content of polymer. The variation of particle size, and the molecular weight for non‐crosslinked systems, was studies as a function of initiator concentration, and monomer/surfactant ratio. The smallest particles (10–15 nm) are obtained for the system BDMA/lauryl sulfate (LS).

Studies on graft copolymerization of cyclohexyl methacrylate onto 1,2‐polybutadiene

AbstractThe free radical grafting of cyclohexyl methacrylate (CMA) onto 1,2‐polybutadiene (1,2‐PBD) in benzene solution at 60°C was studied. The graft copolymer was characterized by IR, NMR, DSC, and intrinsic viscosity measurements. The polymerization of CMA shows normal kinetic behavior when the PBD concentration is kept below 1.0 monomer mol/L. The rate of grafting was determined at different reaction times, monomer concentrations, initiator concentrations, backbone concentrations, temperatures, and concentrations of the zinc chloride additive. The performance of the graft copolymer used as adhesive was also investigated for bonding of PVC/PVC film.

Pulse radiolysis study of initiation and propagation in radiation induced polymerisation of cyclohexyl methacrylate

Initiation and individual propagation rate constants for the first few steps are determined for e - aq, OH radical and H atom reactions with cyclohexyl methacrylate as the monomer using the technique of pulse radiolysis. Though the rate constants for initiation are higher, the propagation rate constants for the transient species formed by reaction of OH radical and H atom are lower compared to that by reaction of e - aq with the monomer. It is also observed that in the case of e - aq reaction the first propagation step is about an order of magnitude faster than the second propagation step and propagation through radical-anionic form is much faster than its radical counterpart.

Relaxation processes in amorphous poly(cyclohexyl methacrylate) in the rubbery and glassy state studied by photon correlation spectroscopy

Relaxation processes in amorphous poly(cyclohexyl methacrylate) in the rubbery and glassy state studied by photon correlation spectroscopy

Preferential and total sorption in the systems methacrylic polymer/toluene + butyl chloride

AbstractViscometric, dialysis equilibrium differential refractometry. densitometric and light scattering measurements have been performed for three different polymethacrylates: poly(methyl methacrylate). poly(butyl methacrylate) and poly(cyclohexyl methacrylate) in toluene/butylchloride binary mixture at 298 K. We have measured the preferential and total sorption to the polymer chain by the solvents, the Mark‐Houwink‐Sakurada parameters and the B interaction parameter. We have drawn conclusions about the liquid‐liquid and polymer‐liquid interactions, trying to explain the influence of the polymer side group in its solution behaviour.

Organotin polymers.I. Copolymerization on tributyltin methacrylate with (hydroxy) alkyl methacrylates

AbstractCopolymers of tributyltin methacrylate (M1) with cyclohexyl methacrylate, ethoxyethyl methacrylate, ethyl methacrylate, 2‐hydroxyethyl methacrylate, and 2‐hydroxypropyl methacrylate were synthesized in solution at 55°C utilizing azobisisobutyronitrile initiator. Copolymer compositions were determined by tin analysis; monomer reactivity ratios were calculated by Kelen‐Tüdös method. Since the reactivity ratios indicate the distribution of different monomer units in the polymer chain, the measured values are compared and discussed. Preliminary results of the biotoxicity studies on some of the copolymers are also reported.

Variation in thermodynamic properties of polymethacrylates in binary mixtures

Viscometric, densitometric and light scattering measurements have been performed for poly(methyl methacrylate), poly( n-butyl methacrylate) and poly(cyclohexyl methacrylate) binary mixtures of toluene and n-butyl chloride at 298 K. The total sorption to the polymer chain by the solvents, the Mark-Houwink-Sakurada parameter and the interaction parameter, B, have been determined. Conclusions about the liquid-liquid and polymer-liquid interactions have been drawn, trying to explain the influence of the polymer side group on solution behaviour.

Radiation polymerisation of cyclohexyl methacrylate—I

Radiation polymerisation of cyclohexyl methacrylate has been carried out at various doses, dose rates and temperatures. The radical yield determined by induction period method using benzoquinone as a scavenger is 6.25. The dose rate exponent is found to be 0.517 indicating a bimolecular termination. The ( K p/K t 1 2 ) value is 0.268, which is an order of magnitude higher than for methyl methacrylate under identical conditions of dose rate and temperature. Energy of activation calculated on the basis of kinetic data is found to be 2.06 kcal/mol, which is also quite low. These results indicate the probability of the existence of an anionic initiation in addition to free radical initiation. Chain transfer constant to tonomer ( K tr / K p )is found to be 1.9 × 10 −4.

Radiation polymerisation of cyclohexyl methacrylate—II. role of ionic and radical scavengers

Radiation polymerisation of cyclohexyl methacrylate has been carried out in the presence of scavengers i.e. biphenyl, cyclohexanol and benzoquinone. In presence of biphenyl and cyclohexanol which are scavengers for electrons and anions no induction period was observed and the rates of polymerisation and molecular weights decreased to the same extent. In presence of benzoquinone, a scavenger for both anions and free radicals, an induction period was observed, decreasing both the molecular weights and the rates of polymerisation. From these results it is evident that the polymerisation takes place both by anions and free radicals. A very high chain transfer constant ( K tr / K p ) to benzoquinone equal to 23.06 was obtained.

Blends containing polymers of epichlorohydrin and ethylene oxide. Part I: Polymethacrylates

AbstractThe phase behavior of blends of various polymethacrylates with poly(epichlorohydrin) (PECH); poly(ethylene oxide) (PEO); and a copolymer of epichlorohydrin and ethylene oxide [P(ECH/EO)], was examined using differential scanning calorimetery (DSC), dynamic mechanical properties, and optical indications of phase separation on heating, namely lower critical solution temperature (LCST) behavior. Poly(methyl methacrylate) (PMMA), was shown to be miscible with PECH, PEO, and P(ECH/EO), while only PECH was found miscible with the higher polymethacrylates: poly(ethyl methacrylate), poly(n‐propyl methacrylate), poly(n‐butyl methacrylate), and poly(cyclohexyl methacrylate). However, even PECH was found to be only partially miscible with poly(isopropyl methacrylate). In many cases, unusually broad glass transitions were observed by DSC for blends which are believed to be the result of equilibrium composition fluctuations. All mixtures showed LCST behavior and based on this and excess volume measurements, to the extent possible, qualitative conclusions were made concerning the relative strength of the interactions among the various blend pairs. For PECH, it appears that the interaction with polymethacrylates decreases with increasing size of the alkyl pendant group, with poly(cyclohexyl methacrylate) being a possible exception. The interaction with PMMA is apparently about the same for PECH and PEO, but somewhat less for P(ECH/EO). The latter is consistent with an intrachain attraction of ECH and EO believed to exist. The reasons for similar interactions of PEO and PECH with PMMA are not understood; however, it is clear that the chlorine moiety of PECH is needed for miscibility with higher polymethacrylates.

Unperturbed dimensions of poly(cyclohexyl methacrylate) and their temperature coefficient

Unperturbed dimensions of poly(cyclohexyl methacrylate) and their temperature coefficient were studied. The influence of the character of solvent on the solubility of poly(cyclohexyl methacrylate) are discussed.

Gamma radiolysis of polycyclohexyl methacrylate

Polycyclohexyl methacrylate prepared by gamma ray initiation of cyclohexyl methacrylate was found to be a degrading type of polymer. The radiolytic products of the polymer are carbon monoxide, carbon dioxide, hydrogen, cyclohexyl formate, cyclohexane, and cyclohexanol with small traces of methane and cyclohexene. On the basis of the yields obtained, i.e. cyclohexane, cyclohexanol, cyclohexyl formate, and hydrogen, a mechanism has been proposed for the radiolytic degradation of the polymer. On the basis of the proposed mechanism for degradation, G(scission) should be ≈2.82. But the measured value using the molecular weight-radiation dose relationship is only ≈2.41. This indicates that the measured value is actually [ G( S) - G( X)] and not G( S) alone and some amount of crosslinking is also taking place along with degradation.

Dielectric and mechanical-dynamical studies on poly(cyclohexyl methacrylate)

The relaxation processes in poly(cyclohexyl methacrylate) have been studied by transient and dynamic dielectric means as well as by viscoelastic techniques. The study embraces also the effect of the thermal treatment on the α and β relaxations. The α relaxation has been fitted into the empirical model of Havriliak and Negami, and the functional relation between the mean relaxation times and the temperature has been adjusted to the equation of Vogel. The β relaxation is strongly hindered, so it is scarcely perceivable. The secondary γ relaxation was studied mainly by dielectric means. Its apparent activation energy does not depend on the temperature and amounts to 11.2 ± 0.2 kcal mol −1. It allows an application of the time-temperature superposition principle and its behaviour is thermorheologically simple. A δ relaxation with a temperature-independent apparent activation energy of 8.5 kcal mol −1 has been obtained