Reactive polymers, 51. The temperature behaviour of macroporous methacrylate sorbents

The behaviour of macroporous methacrylate copolymers was investigated in the temperature range between 20 and 270°C. On the basis of retention of methyl alcohol and n-decane a discontinuity at 40°C was recorded in all cases, interpreted by the increasing mobility of chains of surface layers of the polymer globules. This temperature agrees with the reported T_g value of poly(glycidyl methacrylate) and is independent of further substitution of the polymer chain with ionogenic groups. At 210–250°C depolymerization takes place; in the case of methacrylic acid copolymers cyclic anhydrides are formed, while in the case of esters alkyls are eliminated. Modified copolymers of 2,3-dihydroxypropyl methacrylate with ionogenic groups are more stable thermally — the depolymerization proceeds under the same conditions to a smaller degree. Heating is connected with changes in the morphology of particles and pores, and also in the polarity of the polymers noticeable by the ratio of retentions of alcohols and paraffins and by the heat of dissolution.     

Water effect on the morphology of EVOH copolymers

The effect of water on the morphology of four ethylene vinyl alcohol copolymers (EVOH) with different ethylene contents was studied by differential scanning calorimetry (DSC). EVOH film samples equilibrated in controlled atmospheres at different relative humidities (RH) and 23°C were analyzed. Under dry conditions, the glass transition temperature (T_g) was unaffected by copolymer ethylene content. As RH increases, T_g decreases. It seems that the presence of water within the polymer matrix results in plasticization of the polymer. T_g varies from around 50°C (dry) to below room temperature. EVOH copolymers are glassy polymers when dry and rubbery polymers at high RHs. Fox and Gordon–Taylor's equations well describe T_g depletion at low water uptake, although severe water gain results in a considerable T_g decrease, which is not predicted by these theories. Melting temperature, T_m, and enthalpy, ΔH_m, were also analyzed. When dry, T_m decreases as ethylene content increases. No significant water effect was found on either T_m or ΔH_m. Hence, crystallinity seems to be unaffected by water presence. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1201–1206, 1999     

A new class of transparent polymeric materials. II. Synthesis and properties of poly(N-cyclohexylmaleimide-alt-isobutene) modified with lauryl methacrylate

Transparent polymeric materials with high heat resistance and low water absorption were designed based on the alternating copolymers of N-substituted maleimide (RMI) with isobutene (IB). The N-substituent of the maleimide significantly affected the glass transition temperature (T_g) and water absorption of the copolymers. Poly(N-cyclohexylmaleimide-alt-JB) [poly(CHMI-IB)] showed a T_g value as high as 192°C and relatively low water absorption. Furthermore, the incorporation of a small amount of lauryl methacrylate in the copolymers was confirmed to reduce the water absorption of the copolymer drastically, although it decreased the T_g of the copolymers at the same time. Poly(CHMI-IB), containing 4 mol % lauryl methacrylate, showed a good balance of excellent transparency, high heat resistance, acceptable mechanical properties, and low water absorption. The heat deflection temperature was as high as 141°C. The water absorption at 23°C after immersion for 14 days was 0.56% and the dimensional change after 7 days was 0.06%. They are half and one-quarter of those of poly(methyl methacrylate), respectively. © 1996 John Wiley & Sons, Inc.     

COLLAPSE OF STRUCTURE DURING DRYING OF CELERY

ABSTRACT

Collapse of structure of foodstuffs during air drying affects quality. In many materials the soluble components, mainly sugars, are an important part of the tissue in which case collapse may be related to their glass transition temperature (T_g). It has been speculated that collapse occurs at a temperature (T_c) related to, but greater than, T_g. Plant tissues with high moisture contents, such as celery, have low T_gS. Therefore considerable collapse is expected at drying temperatures.

The aim of this study was to determine how air drying temperature affected the quantity characteristics of the tissue. Celery, air dried at temperatures between 5 and 80°C, was examined for volumetric shrinkage, rehydration characteristics and porosity changes. significant shrinkage occurred at all drying conditions. At low water content collapse was limited, probably due to a higher collapse temperature. porosity development was insignificant during drying until the sample was very dry. Lower air-drying temperatures gave a product with improved quality characteristics.     

Predictors of glass transition in the biodegradable poly‐lactide and poly‐lactide‐co‐glycolide polymers

The biodegradable polylactide (PLA) and polylactide‐co‐glycolides (PLGAs) are being widely investigated for use as scaffolds in bone and ligament reconstruction. The glass transition temperatures (T_g) for these polymers are generally greater than 37°C, causing PLA and PLGA devices to possess brittle characteristics in physiological conditions. To evaluate the possibility of obtaining PLGA polymers with T_g values below 37°C, we evaluated the determinants of T_g in PLA and PLGA copolymers. The T_g, changes in specific heat capacity (ΔC_p), and enthalpic relaxation (ΔH_g) in two consecutive heating cycles were correlated with lactide/glycolide content and intrinsic viscosity [η] for PLA, PLGAs 90:10, 75:25, 65:35, and 50:50. A linear correlation was observed between T_g and intrinsic viscosity, with 0.1 dL/g increase in viscosity resulting in an increase in T_g by about 3.55°C. The selection of PLA and PLGA copolymers with [η] values <0.19 dL/g, corresponding to a viscosity average molecular weight of <70 kDa, will obtain PLA/PLGA polymers with T_g values below 37°C. The lowest attainable T_g values were found to be 28–30°C. Intrinsic viscosity also correlated with ΔC_p differences between aged and rapidly cooled polymers, and is therefore important in predicting free volume changes within these polymers upon aging. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1983–1987, 2006     

Development of cantaloupe (Cucumis melo) pulp powder using foam-mat drying method: Effects of drying conditions on microstructural of mat and physicochemical properties of powder

In this study, the effects of drying conditions on moisture content, water activity (a_w), dissolution time, solubility, hygroscopicity, β-carotene, color, glass transition temperature (T_g), and sticky point temperature (T_s) of foam-mat-dried cantaloupe pulp powders and microstructure of dried cantaloupe pulp foams were investigated. Drying was performed in three temperatures (40, 55, and 70°C) on 3- and 5-mm thicknesses. The analysis of scanning electron microscopy micrographs with grey-level co-occurrence matrix showed that there is wide porous structure of dried foams at higher speeds drying. The temperature increase reduced moisture content and a_w, and increased hygroscopicity, and thickness rise increased moisture content and a_w and consequently decreased powders’ hygroscopicity under the same thickness and drying temperature, respectively. Increase in drying temperature would increase the reconstitution speed of powders into water and therefore the dissolution time decreased. In addition, results showed that the powder produced at 40°C have higher β-carotene content than those of produced at 55 and 70°C. With increasing drying temperature from 40 to 70°C, Lightness parameter (L) was increased while redness parameter (a) was decreased. The T_g and T_s were compared by plotting them in a graph against moisture content. For all drying processes the T_s was higher than the T_g. The drying conditions at 70°C (higher drying temperature) and 3?mm (lower thickness) led to a shorter drying time and consequent lower energy demand to produce a powdered cantaloupe pulp with high stability (low moisture content, a_w, and high T_g and T_s) and reconstitution speed of powder into water.     

Poly(methyl methacrylate-co-acrylonitrile)

Stable macroradicals of methyl methacrylate were prepared by the azobisisobutyronitrile-initiated polymerization of methyl methacrylate in hexane whose solubility parameter value (δ) differed from that of the macroradical by more than 1.8 hildebrand units and in 1-propanol at temperatures below its theta temperature (84.5°C). The rates of heterogeneous polymerization in hexane and 1-propanol were much faster than that of the homogeneous polymerization in benzene. Stable macroradicals were not obtained in benzene which was a good solvent nor at temperatures above the glass transition temperature (T_t) of the macroradicals. Thus, stable macroradicals of butyl methacrylate (T_g20°C) and and methyl acrylate (T_g3°C) were not obtained at a polymerization temperature of 50°C. Good yields of block copolymers of methyl methacrylate and acrylonitrile were obtained by the addition of acrylonitrile to the methyl methacrylate macroradical in methanol, ethanol, 1-propanol and hexane at 50°C. The rate of formation of the block copolymer decreased in these poor solvents as the differences between the solubility parameter of the solvent and macroradical increased.The block copolymer samples prepared at temperatures of 50°C and above were dissolved in benzene which is a non-solvent for acrylonitrile homopolymer, but is a good solvent for poly(methyl methacrylate) and the block copolymer. The presence of acrylonitrile and methyl methacrylate in the benzene-soluble macromolecule was demonstrated by pyrolysis gas chromatography, infra-red spectroscopy and differential thermal analysis.     

Dynamic Mechanical Analysis of Amorphous-Phase Organization in Acrylic Polymers

Factors affecting polymer network organization were studied in highly crosslinked acrylics of the type used in dental adhesive resins. The variables tested were comonomer content and processing conditions. BisEMA (2,2,-bis[4-(2-methacryloyloxyethoxy)-phenyl]-propane) and BisEMA + TEGDMA (triethyleneglycol dimethacrylate) were cured with and without 25% comonomer. Comonomers had characteristics that are expected to influence intrachain organization in amorphous phases: TEGDMA, crosslinking; methyl methacrylate (MMA), monomer conversion; isobornyl methacrylate (IBM), low cure shrinkage; tetrahydrofurfuryl methacrylate (THFM), antiplasticization. Dynamic mechanical analysis temperature scans were run at 0.1 Hz 2h or 24h after ambient cure, or 24h postcure after heating at 75° or 125°C. After 24h, tan δ maxima occurred in ranges centering on approximately -30°, 75° and 150°C (T_g). Heating at 125°C nearly eliminated all peaks except T_g, reduced tan δ peaks and increased T_g by 0–14°. T_g increased in the order: TEGDMA>125°C>IBM>MMA>75°C>2h>24h>THFM. The ability to crosslink, and postcure heating at 125°C, were the more important factors found to increase intrachain organization in amine-promoted, unfilled BisEMA resins of the type used in dental sealants, luting cements and bulk-filling resin composite materials.     

Core–shell particles to toughen epoxy resins. I. Preparation and characterization of core–shell particles

A two-stage, multistep soapless emulsion polymerization was employed to prepare various sizes of reactive core–shell particles (CSPs) with butyl acrylate (BA) as the core and methyl methacrylate (MMA) copolymerizing with various concentrations of glycidyl methacrylate (GMA) as the shell. Ethylene glycol dimethacrylate (EGDMA) was used to crosslink either the core or shell. The number of epoxy groups in a particle of the prepared CSP measured by chemical titration was close to the calculated value based on the assumption that the added GMA participated in the entire polymerization unless it was higher than 29 mol %. Similar results were also found for their solid-state ^13C-NMR spectroscopy. The MMA/GMA copolymerized and EGDMA-crosslinked shell of the CSP had a maximum glass transition temperature (T_g) of 140°C, which was decreased with the content of GMA at a rate of −1°C/mol %. However, the shell without crosslinking had a maximum T_g of 127°C, which decreased at a rate of −0.83°C/mol %. The T_g of the interphasial region between the core and shell was 65°C, which was invariant with the design variables. The T_g of the BA core was −43°C, but it could be increased to −35°C by crosslinking with EGDMA. The T_g values of the core and shell were also invariant with the size of the CSP. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2069–2078, 1998     

Determination of the glass transition temperature of poly(styrene-co-divinylbenzene) by inverse gas chromatography

Inverse gas chromatography (i.g.c.) was used to characterize the supermolecular structure of modified, moderately crosslinked poly(styrene-co-divinylbenzene) (5–20 wt%) and to determine the interactions with normal alcohols (C₁C₆). For all copolymers a decrease of retention time with increasing molecular weight of alcohols from C₁ to C₃ followed by an increase for C₄ to C₆ alcohols was observed. It was found that with propanol or butanol the measured T_g values were close to those measured by d.s.c. The T_g values for poly(styrene-co-divinylbenzene) containing 5, 10 and 20 wt% divinylbenzene were: 102°C, 116°C and 133°C respectively. The highest alcohols (C₅ and C₆) acted as plasticizers and reduced the apparent T_g value. The relationship between the isosteric heat of adsorption and the number of carbon atoms in the alcohols was nonlinear with a minimum corresponding to butanol.     

Synthesis of bulk silicon oxynitride glass through nitridation of SiO2 aerogels and determination of Tg

The development of transparent glass for use in high-temperature applications is continuing. In this study, we synthesized bulk silicon oxynitride glasses (a-Si(O,N)_x) through the nitridation of SiO₂ aerogels containing methyl (CH₃-) groups and evaluated their bulk properties, including their glass transition temperature (T_g). Tetramethyl orthosilicate and methyltrimethoxysilane were added into the precursor gels, and those gels were subjected to a supercritical CO₂ drying process. The presence of CH₃-group in the gel avoided cracking during ammonolysis at 750°C–1400°C, and the transparency of the gel was remained even after ammonolysis at 1300°C. The ammonolysis successfully introduced nitrogen into the gels even at relatively low temperatures, for example, 750°C, and the highest nitrogen content (11.7 mass%) was achieved in the gel after ammonolysis at 1300°C. As the nitrogen-related signals in electron spectroscopy indicated presence of nitride ions (N³⁻) after ammonolysis and the infrared absorption signals attributed to Si–N bonds were enhanced with the increase of nitrogen concentration, we successfully obtained oxynitride glasses. Those oxynitride glasses showed increase of T_g with their nitrogen concentration.     

Study by thermal analysis of composites prepared from silica gel,furfuryl alcohol and acetaldehyde

Composites from furfuryl alcohol, acetaldehyde and silica gel were prepared with trifluoracetic acid as a catalyst. The composites were studied by TGA and DSC. The TGA results showed three main losses of weight, the first of which was ascribed to water. The percentage of polymer in the composites reached a limit value, independently of the ratio of furfuryl alcohol/acetaldehyde used. The layer of polymer that covers the silica was not completely cross‐linked. The composites contain soluble oligomers with 97: M _n < 580 g mol^?1, that could be extracted with THF. The soluble fraction of composites prepared from mixtures of furfurylic alcohol and acetaldehyde decreased as the proportion of the acetaldehyde increased. The DSC of the samples indicated a T_g between ?8 and ?15 °C that disappeared after an extraction with THF. The DSC of the oligomers removed showed a possible T_g at 13 °C and an exothermic peak between 70 and 170 °C which corresponded to an enthalpy of 326.1 J g^?1. © 2003 Society of Chemical Industry     

Synthesis and characterization of homo‐ and copolymers of 3‐(2‐cyano ethoxy)methyl‐ and 3‐[methoxy(triethylenoxy)]methyl‐3′‐methyl‐oxetane

Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF₃· Et₂O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and¹H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (T_g), the DSC data imply that the resulting copolymers have a lower T_g than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10^?5 S cm^?1 at room temperature and 2.79 × 10^?4 S cm^?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry     

Fast physical drying, high water and salt resistant coatings from non-drying vegetable oil

This paper reports fast physical drying, high water and salt resistances of coating materials from non-drying palm oleic acid. Short oil-length alkyd was synthesized and copolymerized with methyl methacrylate. Three copolymers of the alkyd and methyl methacrylate with different alkyd/MMA ratios were prepared via free radical polymerization. The copolymers were characterized by FTIR and H NMR spectroscopy, and glass transition temperatures (T_g) were measured by DSC. The decreasing amount of alkyd was noticed to increasing conversion and T_g. The overall thermal stability has increased with higher amount of alkyd in the copolymer. Moreover, incorporation of alkyd has improved the adhesion and film hardness of the coatings.     

Fast physical drying,high water and salt resistant coatings from non-drying vegetable oil

This paper reports fast physical drying, high water and salt resistances of coating materials from non-drying palm oleic acid. Short oil-length alkyd was synthesized and copolymerized with methyl methacrylate. Three copolymers of the alkyd and methyl methacrylate with different alkyd/MMA ratios were prepared via free radical polymerization. The copolymers were characterized by FTIR and H NMR spectroscopy, and glass transition temperatures (T_g) were measured by DSC. The decreasing amount of alkyd was noticed to increasing conversion and T_g. The overall thermal stability has increased with higher amount of alkyd in the copolymer. Moreover, incorporation of alkyd has improved the adhesion and film hardness of the coatings.     

Thermal analysis of styrene–alkyl methacrylate polymers. I. Glass transition temperatures

The glass transition temperatures (T_g's) of several polystyrenes and styrene–alkyl methacrylate copolymers and terpolymers were measured using thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). The polymers studied had number-average molecular weights from 3000 to 250,000 g/mole. The results indicate that the composition dependence of the T_g's for the copolymers and terpolymers can be satisfactorily described by a general Fox equation. In general, the measured T_g's of the copolymer and terpolymer samples depend more on the steric effects of the constituent pendent groups than on their molecular weights. The chain flexibility rather than the size of the pendent group is the determining factor in the glass transition properties of the styrene polymers.     

Novel poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers through atom transfer radical polymerization

Poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers have been synthesized successfully through atom transfer radical polymerization of methyl methacrylate using telechelic bromo‐terminated polyurethane/CuBr/N,N,N,N″,N″‐pentamethyldiethylenetriamine initiating system. As the time increases, the number‐average molecular weight increases linearly from 6400 to 37,000. This shows that the poly methyl methacrylate blocks were attached to polyurethane block. As the polymerization time increases, both conversion and molecular weight increased and the molecular weight increases linearly with increasing conversion. These results indicate that the formation of the tri‐block copolymers was through atom transfer radical polymerization mechanism. Proton nuclear magnetic resonance spectral results of the triblock copolymers show that the molar ratio between polyurethane and poly (methyl methacrylate) blocks is in the range of 1 : 16.3 to 1 : 449.4. Differential scanning calorimetry results show T_g of the soft segment at ?35°C and T_g of the hard segment at 75°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Water sorption on composites “LiBr in a porous carbon”

Water sorption equilibrium of LiBr confined to pores of a mesoporous synthetic carbon Sibunit and a macroporous expanded graphite (samples SWS-2C and SWS-2EG, respectively) was studied. Isobars of water sorption on these composites are measured at vapor pressure 6–81 mbar and temperature 30–145 °C. The type of sorption equilibrium for the two composites appears to be quite different. The isobars for SWS-2EG have a plateau corresponding to one molecule of H₂O adsorbed by one molecule of LiBr, which indicates the formation of crystalline hydrate LiBr·H₂O inside pores with a monovariant type of equilibrium. At lower temperatures, the equilibrium becomes divariant that is typical for LiBr–water solutions. On the contrary, the water sorption equilibrium for SWS-2C is divariant over the whole temperature and pressure range which means that no crystalline hydrates are formed inside Sibunit pores. In our opinion, this distinction results from differences in a pore structure of the host carbons. The composite sorption capacity can reach 0.6–1.1 g H₂O per 1 g of the dry sorbent at relative humidity 70%. The advanced sorption capacity makes the sorbents promising for gas drying, thermal storage of energy and other applications.     

Dielectric properties of copolymers based on cyano monomers and methyl α‐acetoxyacrylate

With the aim of developing dielectric polymers containing CN groups with strong dipole moment, alternating and statistical copolymers of the cyano monomers vinylidene cyanide (VCN), acrylonitrile and methacrylonitrile with methyl α‐acetoxyacrylate (MAA) were synthesized and characterized. The copolymer's composition and microstructure were analysed by NMR spectroscopy, SEC and elemental analysis. The reactivity ratios calculated from the Q–e Alfrey–Price parameters for these copolymers indicated the alternating and statistical structures confirmed by NMR analysis. The copolymers have glass transition temperatures T_g in the range 83–146 °C and are stable up to 230 °C. The thermal stability of the copolymers depends on the nature of the cyano monomers. Their molecular dynamics were investigated by dielectric relaxation spectroscopy. We revealed a weak relaxation β at sub‐T_g temperature for poly(VCN‐co‐MAA) usually originating from molecular motions that are restricted to the scale of a few bond lengths. Strong α‐relaxation processes occurred above T_g for these copolymers. This primary relaxation was associated with cooperative movements of the polar groups (CN) at the time of mobility of the principal chains. The activation energy of the α‐relaxation process was also calculated. The values of the dielectric increment Δε for these copolymers were determined by Cole–Cole plots and indicated that the copolymers exhibit interesting dielectric properties compared with similar cyano materials. The polarity–permittivity relationship was also established. © 2012 Society of Chemical Industry     

Accelerant‐promoted free radical polymerization of methacrylates by stabilized nitroxide unimolecular initiators: synthesis and characterization

BACKGROUND: This investigation evaluates the effectiveness of initiator adducts for living and controlled polymerization of methacrylates, crosslinking of dimethacrylates and thermal stabilities of the resulting polymers. Adducts of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy with benzoyl peroxide and with azobisisobutyronitrile were prepared and evaluated as stabilized unimolecular initiators for the free radical polymerization of methacrylate monomers using sulfuric acid as catalyst. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Successful polymerization was achieved at 70 and 130 °C with reaction times ranging from 45 min to 120 h. The dispersity (D) of poly(methyl methacrylate) (PMMA) was 1.09–1.28. The livingness and extent of control over polymerization were confirmed with plots of M_n evolution as a function of monomer conversion and of the first‐order kinetics. The glass transition temperature (T_g) for PMMA was 123–128 °C. The degradation temperature (T_d) for PMMA was 350–410 °C. T_d for poly(TEGMA) was 250–310 °C and for poly(EBPADMA) was 320–390 °C. CONCLUSION: The initiators are suitable for free radical living and controlled polymerization of methacrylates and dimethacrylates under mild thermal and acid‐catalyzed conditions, yielding medium to high molecular weight polymers with low dispersity, high crosslinking and good thermal stability. Copyright © 2008 Society of Chemical Industry