Thermal behavior of core‐shell rubber/styrene monomer gels

The thermal behavior of core‐shell rubber (CSR)/styrene monomer mixtures was studied using subambient differential scanning calorimetry (DSC). Interaction between the styrene and CSR material was observed as a depression of the freezing and melting points of the styrene monomer and as a shift in the glass transition temperature of the rubbery phase in the CSR materials. The depression of the freezing point of the styrene in the CSR/styrene mixtures was related to the size of the critical nuclei required for crystallization. The heat of crystallization was found to decrease linearly with decreasing styrene content, but calculations showed that not all of the styrene present in the mixtures crystallized upon cooling, confirming that there was an interaction between the CSR material and the styrene monomer. At temperatures below the glass transition temperature of the system, the mixtures contain a pure styrene crystalline phase and an amorphous CSR/styrene phase. The styrene was found to act as a plasticizer, reducing the glass transition temperature of the rubbery core material. The variation of the glass transition temperature of the CSR/styrene systems was determined with respect to the composition of the amorphous phase. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3136–3150, 2000     

Copolymerisation radiochimique du styrene avec l'acrylonitrile en solution

The radiation-initiated copolymerization of styrene and acrylonitrile was investigated at 20° in dimethylformamide (DMF) and in benzylalcohol solutions. The compositions of the copolymers were only slightly affected by these polar solvents. The influence of temperature on the copolymerization in DMF solutions was studied in greater detail. It was found that the acrylonitrile content in the copolymer obtained at -78° drastically increased as a result of an anionic polymerization of acrylonitrile. Fractional precipitation of the products obtained at -78° showed that they were not mixtures of polymers but were block copolymers containing long sequences of acrylonitrile units. This copolymer is assumed to arise as a result of the simultaneous growing of the two ends of a primary radical-ion, acrylonitrile adding to one end by an anionic mechanism while the free radical end initiates a random copolymerization of styrene and acrylonitrile. The anionic contribution to the over-all process was established. The anionic homopolymerization of acrylonitrile was studied in DMF, toluene and their mixtures. The rate was found to exhibit a maximum for 20% acrylonitrile in DMF. It was further noticed that significant amounts of DMF could be replaced by toluene or styrene without affecting the rate. The reduction in rate in more concentrated monomer solutions was attributed to an autoinhibition of acrylonitrile in its anionic polymerization.     

Regioselectivity in aqueous palladium catalysed hydroxycarbonylation of styrene: a catalytic and mechanistic study

Regioselectivity control was studied in palladium catalysed hydroxycarbonylation of styrene in neat water with water-soluble phosphines, mostly trisulfonated triphenylphosphine, TPPTS, but also N-bis(N',N'-diethyl-2-aminoethyl)-4-aminomethylphenyl-diphenylphosphine, N3P. The factor giving the highest changes in regioselectivity in the TPPTS system, under similar reaction conditions, is the temperature. In the N3P case, only a minor variation in the n/i ratio as a function of temperature is observed. Insitu normal- and high-pressure NMR experiments were performed to obtain further information about the catalytic cycle and the reaction intermediates. Two palladium hydride intermediates, a palladium eta3-benzylic complex and both the branched and linear palladium acyl complexes were identified in the HP NMR experiments. The hydroxycarbonylation in water using styrene as a substrate operates using a hydride mechanism for pathways leading to both linear and branched product. Insertion of styrene in the palladium-hydride bond gives an eta3-benzyl compound. A high CO pressure gives a kinetic preference for the iso-acyl in the next step. In the TPPTS system, at moderate temperatures, the hydrolysis of the iso-acyl is faster than its conversion to the thermodynamically more stable n-acyl. A low n/i therefore requires high pressures and reasonably low temperatures. The N3P ligand always favours the linear product since isomerisation of the iso-acyl to the n-acyl in this system is fast under all conditions investigated.     

Salt-catalyzed reaction between styrene oxide and silk fibroin

The addition reaction of styrene oxide (StO) with silk fibroin was studied in the presence of various salts in different solvents at 45–75°C. Some water was required to make StO react with silk padded with various salt solutions. The reaction rate increased with the salt concentration and reached a maximum value at a certain concentration of the salt. Padding with solutions of thiosulfate, cyanide, thiocyanate, bicarbonate, or carbonate resulted in high add-ons (to 65 mole/10⁵ g) and low solubilities in HCl and NaOH aqueous solutions. The weight gains increased with the epoxide concentration and reached a constant value at a certain concentration of StO solution in ethanol, while they decreased slightly with epoxide concentration over 10% of StO solution in n-hexane. Histidine, lysine, arginine, tyrosine, and aspartic and glutamic acids were found to react. The reaction rate decreased with increasing solubility parameter of the solvent used, reached a minimum value about at 10 or at the solubility parameter of the epoxide, and then increased with the parameter. The StO–silk reaction may depend on the distribution of StO between aqueous salt and an organic solvent phases, and on the swelling of silk fiber in different aqueous salt solutions or in various organic solvents. The mechanism for this epoxide-silk reaction and the reactivity difference between StO and phenyl glycidyl ether toward silk fibroin are discussed in the light of the observed phenomena.     

Dynamic mechanical properties of two copolymers of styrene and n-hexyl methacrylate

The storage (J′) and loss (J″) shear compliances have been measured for two random copolymers of styrene and n-hexyl methacrylate with styrene contents of 18% and 30% (by weight) in the frequency range 45–4400 Hz and the temperature range 31–107°C. The data at different temperatures were combined by the method of reduced variables, and the WLF coefficients were calculated from the temperature shift factors by the method of Pierson and Kovacs. The data were compared with earlier data for the two homopolymers. The thermal expansion coefficient of the fractional free volume, and the free volume at the glass transition temperature, varied monotonically with composition, but the fractional free volume at a reference temperature of 100°C appeared to pass through a maximum as a function of concentration. Comparison of isothermal plots of J′ at 100°C, plots of the relaxation spectrum at 100°C, the monomer friction coefficient and its temperature dependence, and isochronal plots of the storage shear moduls at 100 radians/see all show that the properties of poly(n-hexyl methacrylate) are very slightly affected by incorporation of 18% styrene and only moderately affected by 30% styrene. By contrast, comparison of styrene–butadiene rubber with 1,4-polybutadiene shows a very large effect of incorporation of 23.5% styrene. These differences may be associated with local packing relations of the comonomer residues and suggest that copolymer properties cannot be readily predicted from those of the component homopolymers.     

Adsorption of styrene at a binary solution-gas interface

The surface tension isotherms of styrene solutions in 2-propanol-water solvents are obtained experimentally. Isotherms of excess and absolute adsorption at the liquid-gas interfaces are also obtained. A thermodynamic model for the adsorption of styrene from 2-propanol-water binary solvent at the solutiongas interfaces is proposed on the basis of the stoichiometric approach. The isosteric adsorption heats are calculated using the experimental isotherms of surface tension and excess adsorption of styrene from 2-propanol-water binary solvent, and it is shown that the formation of the surface layer occurs according to a mechanism combining the processes of displacement adsorption between molecules of the components of the solvent, styrene, and 2-propanol.     

Metallocene-catalyzed ethene/styrene co- and terpolymerization with olefinic termonomers

Ethene was co- and terpolymerized with 1-octene and styrene using the methylalumoxane (MAO) activated halfsandwich metallocene Me₂Si(Me₄Cp)(N-t.-butyl)TiCl₂(Cp = cyclopentadienyl, Me = methyl) as catalyst. At temperatures of 40 and 60°C styrene concentration was varied in order to investigate the influence of the comonomers. Despite decreasing the overall activity with respect to ethene/1-octene copolymerization, polymerization activity was found to exibit a relative maximum with increasing styrene concentration. An explanation is given taking two different comonomer effects into account. Low styrene concentration promoted higher 1-octene incorporation compared to ethene/1-octene copolymerization but significantly lowered the molecular weight of the terpolymers. With constant ethene and 1-octene concentration it was possible to produce ethene/1-octene/styrene terpolymers with styrene content varying from 0 to 25 mol % and 1-octene content varying from 8 to 21 mol %. All terpolymers were amorphous. With constant ethene content it was found possible to vary their glass transition temperature with 1-octene/styrene molar ratio incorporated in the terpolymer. ¹³C-NMR spectroscopic microstructure analysis showed that no styrene/1-octene sequences were found in the terpolymer backbone. Furthermore terpolymerizations were conducted successfully incorporating norbornene, 1,5-hexadiene and propene as monomers in terpolymertization with ethene and styrene. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2549–2560, 1997     

Copolymerization with depropagation: A study of α-methyl styrene/methyl methacrylate in solution at elevated temperatures

In free-radical polymerization, solvents are routinely used to reduce the solution viscosity and molecular weight. In the case of the α-methyl styrene/methyl methacrylate copolymer system, reducing the monomer concentration also has significant effects on the copolymer composition and maximum conversion obtained. Reactivity-ratio studies as well as full-conversion-range data were provided, and the results were compared to similar data in the bulk phase from our earlier work. A 30 wt % toluene solution was used for all experimental conditions. Copolymer composition modeling results were also presented. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1753–1763, 2001     

Ageing of thermosets based on tung oil/styrene/divinylbenzene

New thermoset polymers prepared by cationic co-polymerization of tung oil with styrene and/or divinylbenzene were evaluated at different times after their preparation. The changes in the properties were correlated with the composition of the copolymers. The action of atmospheric oxygen on the fatty acid unsaturations produced chemical changes in these polymers, which affected the properties of the cured materials. These changes were analyzed by FTIR, dynamic mechanical properties and mechanical testing. An increase in the modulus with time for all the analyzed samples was observed, as well as a large effect on the glass transition temperature and, consequently, in the shape memory properties.     

Thermal properties in cured natural rubber/styrene butadiene rubber blends

Blends of natural rubber (NR) and styrene butadiene rubber (SBR) were prepared with sulfur and n-t-butyl-2-benzothiazole sulfonamide (TBBS) as accelerator, varying the amount of each polymer in the blend. Samples were analysed by rheometer curing at 433 K until their maximum torque was reached. The miscibility among the constituent polymers of the cured compounds was studied in a broad range of temperatures by means of differential scanning calorimetry, analyzing the glass transition temperatures of the samples. The specific heat capacity of the compounds was also determined. Thermal diffusivity of the samples was measured in the temperature range from 130 to 400 K with a new device that performs measurements in vacuum. The thermal results are explained on the basis of the structure formed during the vulcanization of the samples considering the variation of the crosslink density of each phase. Finally, a serial thermal conduction model that takes into account the contribution of each phase to the thermal diffusivity was used to fit the experimental results.     

分子水平研究不同嵌段结构苯乙烯/丁二烯共聚物的表面结构

利用具有准单分子层灵敏度的和频振动光谱(SFG)、原子力显微镜(AFM)和接触角(CA)测定技术研究链结构和溶剂对苯乙烯(S)/丁二烯(B)嵌段共聚物表面准分子层化学结构形成的影响.结果表明,两嵌段共聚物SB比三嵌段共聚物SBS更有利于聚丁二烯(PB)组分在膜表面富集.利用PB的选择性溶剂环己烷做溶剂时,SB膜表面层完全由纯的PB组分组成,而SBS表面则是聚苯乙烯(PS)与PB二组分共存.利用PS的选择性溶剂甲苯做溶剂时,SB与SBS表面都是PS与PB二组分共存,其中SBS表面PS组分的含量更高.原因是由于溶剂影响嵌段共聚物分子在溶液中的构象从而影响溶剂挥发后聚合物表面结构的形成.     

Thermal behaviour of styrene butadiene rubber/poly(ethylene-co-vinyl acetate) blends

The thermal behaviour of styrene butadiene rubber (SBR)/poly (ethylene-co-vinyl acetate) (EVA) blends was studied by using thermogravimetry (TG) and differential scanning calorimetry (DSC). The effects of blend ratio, cross-linking systems and compatibilization on the thermal stability and phase transition of the blends were analyzed. It was found that the mass loss of the blends at any temperature was lower than that of the components, highlighting the advantage of blending SBR and EVA. The addition of compatibilizer was also found to improve the thermal stability. DSC studies indicated the thermodynamic immiscibility of SBR/EVA system even in the presence of the compatibilizer. This is evident from the presence of two different glass transition temperatures, corresponding to SBR and EVA phases in both compatibilized and uncompatibilized blends.     

Effect of styrene oligomers on syndiospecific polymerization of styrene

Styrene oligomers, preferentially consisting of styrene dimers and trimers, are formed by a free radical mechanism at the thermal polymerization of stabilizer-free styrene during storage and at higher polymerization temperatures. The identity of several dimer and trimer fractions formed in such a free radical polymerization, their influence on a coordinative polymerization reaction, the syndiospecific polymerization of styrene, as well as their effect on the properties of the resulting polymers has been investigated.Styrene dimers and styrene trimers reduce the polymerization activity of the transition metal catalyst significantly, especially at low amounts of oligomers added to the styrene. This behavior is discussed with respect to a proposed mechanism involving complexation of the active transition metal species with the specific oligomer instead of the styrene monomer, resulting in increased steric hindrance towards insertion of a styrene molecule to the active site.Both oligomers reduce the molecular weight of the syndiotactic polystyrene, by acting as chain-transfer agents. The constancy of the polydispersity over the whole concentration range of added dimer or trimer indicates that the uniformity of the active sites of the coordinative polymerization is not significantly influenced by the presence of the oligomers.The thermal properties of the polymers demonstrate that the oligomers do not affect the high syndiospecificity of the active catalytic sites, whereas the increase in crystallization temperature with increasing amounts of styrene dimer or trimer is comparable to effects observed by the addition of crystallization nucleators to semicrystalline polymers.     

Anionic polymerization of styrene in ionic liquids

For the first time anionic polymerization of styrene has been successfully carried out at ambient temperatures in an ionic liquid, providing milder reaction conditions than classical methods. The addition of the zwitterion provides better dissociation of the metal cation based initiators and the IL based reaction allows the use of a much milder Lewis base initiator than is usually required. The present method also eliminates the traditional solvents and rigorous reaction conditions.     

Kinetics and mechanism of the benzoin isobutyl ether photoinitiated polymerization of styrene

The kinetics of the photopolymerization of styrene in bulk and in dilute systems in the presence of benzoin isobutyl ether as photoinitiator have been examined. The values of the intensity exponent, calculated at different temperatures or at different styrene concentrations, and the monomer exponent, calculated at various intensities, showed significant departure from those predicted by the ideal kinetic scheme, particularly at high intensity, at low temperature, or at low styrene concentrations. Low molecular weight polymer was the dominant product when high light intensity or low polymerization temperature was used. As the temperature was raised, however, or as the intensity was reduced, a high molecular weight polymer became progressively more important. Kinetic and molecular weight data suggest that at low temperature, high intensity, and/or at low monomer concentration, the benzoyl radical is the dominant initiating species; and the benzyl ether radical was consumed mainly in the termination step. At low intensity, high temperature and/or high monomer concentration, however, it appears that both benzoyl and benzyl ether radicals initiated polymerization.     

对甲苯磺酸/活性炭/双氧水体系选择氧化苯乙烯生成苯甲醛(英文)

以双氧水为氧化剂,研究了对甲苯磺酸和活性炭体系选择氧化苯乙烯生成苯甲醛反应性能。考察了反应时间、温度、催化剂用量、苯乙烯和双氧水摩尔比等对苯乙烯选择氧化性能的影响.结果表明,对甲苯磺酸和活性炭的用量和用量比是一个重要因素,但对甲苯磺酸的酸性对氧化反应活性影响不大.对甲苯磺酸和双氧水相互作用,经非自由基过程氧化苯乙烯.通过分解双氧水产生氢氧自由基,活性炭显著提高对甲苯磺酸和双氧水体系氧化苯乙烯活性.在惰性或还原气氛中高温处理活性炭能降低其表面含氧基团数量,增加碱性,有效分解双氧水,产生相对较多的OH自由基.与未处理的活性炭相比,高温处理的活性炭进一步提高了对甲苯磺酸和双氧水体系氧化苯乙烯活性,但降低了苯甲醛选择性.经磺化,在活性炭表面引入的–SO_3H基团比含氧基团(–OH,–COOH)更有效与双氧水作用氧化苯乙烯.     

The influence of tertiary aromatic amines on the BPO initiated cure of unsaturated epoxy polyesters with styrene studied by non-isothermal DSC

The influence of tertiary aromatic amines on the course of BPO initiated cure reaction of unsaturated epoxy polyesters with different styrene content has been studied by non-isothermal differential scanning calorimetry. Unsaturated epoxy polyesters prepared from cyclohex-4-ene-1,2-dicarboxylic anhydride, maleic anhydride and suitable aliphatic glycol: ethylene glycol or 1,4-butanediol or 1,6-hexanediol were dissolved in vinyl monomer (styrene) resulting in a styrene content of 20–80% by weight. The styrene solutions of polyesters were subjected to the cure reaction with suitable curing agent: benzoyl peroxide (BPO) used in various concentration (0.5–3.0 wt%) or the mixture of BPO/stoichiometric ratio of chosen tertiary aromatic amines: (N,N-dimethylbenzylamine (BDMA) or 2,4,6-tri(dimethylaminomethyl) phenol (DMP-30). The curing characteristic such as: temperature of the cure initiation (T _onset), peak maximum temperature (T _max), final cure temperature (T _end), heat generated during the cure reaction (ΔH) were evaluated. It has been found that the course of the cure reaction depended on the styrene content in prepared compositions and the initiating system used. The performed investigations confirmed that one of the applied tertiary aromatic amine: BDMA was an effective promoter for BPO decomposition process, causing a decrease in characteristic curing temperatures of unsaturated epoxy polyesters with styrene. The organic peroxide-amine interactions caused the promotion of BPO decomposition to benzoyloxy radicals at lower temperatures and thus accelerated the copolymerization process. However, DMP-30 was a very sluggish promoter for BPO decomposition, probably due to the presence of both hydroxyl group, their ortho-position to two of three amine groups and their branched structure. The redox reaction between BPO and DMP-30 probably resulted in non-radical products or radical formation which was incapable of initiating the polymerization reaction.     

Dynamic mechanical behaviour of styrene/butadiene copolymers and their blends

The dynamic mechanical behaviour of high impact polystyrene (PS-HI), styrene/butadiene/styrene block copolymer (SBS) and PS-HI + SBS blends were investigated. Dynamic mechanical analysis (DMA) was performed in the temperature range −100°C to 100°C. The primary viscoelastic functions were determined. The copolymers PS-HI and SBS as well as PS-HI+SBS blends were investigated in creep-fatigue regime and relaxation at temperatures 25, 30, 35, 40 and 45°C. Dynamic mechanical behavior of PS-HI, SBS and PS-HI + SBS blends depends on the copolymer and blends composition, the hard phase content, time and temperature. With the decrement of the hard phase PS concentration, the loss tangent of the soft phase increases while the loss tangent of the hard phase and the storage modulus decrease. All samples have a single T_g of the hard phase and a single T_g of the soft phase. The glass transition temperatures decrease as the content of the PS phase decreases. At the constant load the creep values increase and those of creep modulus decrease over a period of time, for all examined samples. These effects are more pronounced in samples with lower content of hard phase and at higher temperatures. The time-temperature correspondence principle was applied to create master curves for the reference temperature 25°C for the creep modulus of PS-HI, SBS and PS-HI + SBS blends on a time scale far outside of the range measured by DMA experiments. These results enable us to predict the useful life of our copolymers and their blends in a wide range of time and temperature.     

Living radical copolymerization of styrene/maleic anhydride

Styrene/maleic anhydride (MA) copolymerization was carried out using benzoyl peroxide (BPO) and 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Styrene/MA copolymerization proceeded faster and yielded higher molecular weight products compared to styrene homopolymerization. When styrene/MA copolymerization was approximated to follow the first‐order kinetics, the apparent activation energy appeared to be lower than that corresponding to styrene homopolymerization. Molecular weight of products from isothermal copolymerization of styrene/MA increased linearly with the conversion. However products from the copolymerization at different temperatures had molecular weight deviating from the linear relationship indicating that the copolymerization did not follow the perfect living polymerization characteristics. During the copolymerization, MA was preferentially consumed by styrene/MA random copolymerization and then polymerization of practically pure styrene continued to produce copolymers with styrene‐co‐MA block and styrene‐rich block. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2239–2244, 2000     

Temperature Effect on the Micelle Behavior of Styrene-Isoprene Block Copolymers in Selective Solvents

Abstract

Micelle formation by several styrene-isoprene two-block copolymers in selective solvents, viz., n-heptane, n-dodecane, N,N′-dimethylformamide, and N,N′ -dimethylacetamide, was studied by viscometry and photon correlation spectroscopy (PCS). Aggregation number and micellar weight were deduced by combining viscosity and PCS data. The temperature effect on the viscosity behavior of micellar solutions of block copolymers in different selective solvents is examined and explained. ¹H-NMR spectra of the copolymer in n-heptane were recorded at different temperatures to explain the characteristic features of micellar solutions.