Analysis of dielectric observations of KCl-charged poly(methyl methacrylate) microcapsules using a two-component model consisting of KCl-permeable and KCl-impermeable capsules

Dielectric measurements were carried out on aqueous suspensions of poly(methyl methacrylate) microcapsules charged with KCl solutions to examine the KCl permeability of the microcapsules. The specimens exhibited three kinds of dielectric relaxation. Two kinds of dielectric relaxation were observed immediately after washing the specimens with distilled water. These overlapped each other when the specimen was left standing in the measuring cell for a long time. Their relaxation frequencies were affected by the KCl concentration of the suspending medium in which the specimen was kept before washing. Another relaxation was observed distinctly when the spepcimens were washed thoroughly with distilled water. Its relaxation frequency was affected by the KCl concentration of the charged solution. These results were explained by assuming that the specimens were mixtures of KCl-permeable and KCl-impermeable capsules. The theoretical analysis procedure was devised in the light of dielectric theory of interfacial polarization to estimate the parameters which characterize the structure of the specimens.     

Optical CO(2) sensor of the combination of colorimetric change of alpha-naphtholphthalein in poly(isobutyl methacrylate) and fluorescent porphyrin in polystyrene

An optical CO₂ sensor based on the overlay of the CO₂ induced absorbance change of pH indicator dye α-naphtholphthalein in poly(isobutyl methacrylate) (polyIBM) layer with the fluorescence of tetraphenylporphyrin (TPP) in polystyrene layer is developed. The observed luminescence intensity from TPP at 655 nm increased with increasing the CO₂ concentration. The ratio I₁₀₀/I₀ value of the sensing film consisting of α-naphtholphthalein in polyIBM and TPP in polystyrene layer, where I₀ and I₁₀₀ represent the detected luminescence intensities from a layer exposed to argon and CO₂ saturated conditions, respectively, that the sensitivity of the sensor, is estimated to be 192. The response and recovery times of the sensing film are less than 6.0 s for switching from argon to CO₂, and for switching from CO₂ to argon. The signal changes are fully reversible and no hysterisis is observed during the measurements. The highly sensitive optical CO₂ sensor based on fluorescence intensity changes of TPP due to the absorption change of α-naphtholphthalein in polyIBM layer with CO₂ is achieved.     

SBS与甲基丙烯酸丁酯本体接枝反应的研究

本文研究了以过氧化苯甲酰(BPO)为引发剂,甲基丙烯酸丁酯(BMA)既作溶剂又作为单体与苯乙烯-丁二烯嵌段共聚物(SBS)进行接枝共聚反应。用红外光谱、核磁共振谱及透射电镜表征了接枝共聚物(SBS-g-BMA)的组成及结构,讨论了时间、温度及SBS和BPO的用量对接枝的影响。     

Polymer-Titanium hybrids obtained by radical polymerization and Sol-Gel process

The possibility to prepare hybrids made by poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA) and/or poly(ethyl acrylate) (PEtA) with TiO₂ was studied. The processes of polymer formation-radical polymerization and sol-gel process for inorganic network —were achieved simultaneously. Due to a high reactivity of titanium isopropoxide (TIP) in the sol-gel process, a complexant comonomer, allyl acetoacetate (AlAcAc), was used. Covalent bonds between polymer and inorganic chains were obtained by addition of trialkoxysilane derivates with vinyl (VTES) or methacryloyl (MPTS) groups. The presence of TIP inhibits the radical polymerization of vinyl acetate (VAc). The PVAc-TiO₂ hybrids were produced by the sol-gel process of TIP in the presence of pre-obtained PVAc. Except for VTES and MPTS, trialkoxysilane derivates with methyl (MeTES), octyl (OTES) and phenyl (PTES) groups were used. The thermal stability of hybrids is strongly affected by TiO₂ presence and by the type of trialkoxysilane derivates. The thermal stability of PVAc hybrids decreases in the presence of TiO₂ inorganic network. The glass transition temperature of polymers increases in the presence of the inorganic network.     

Kinetic aspects of the Diels-Alder reaction between poly(styrene-co-furfuryl methacrylate) and bismaleimide

The crosslinking Diels-Alder reaction between styrene-furfuryl methacrylate copolymer samples (poly(ST-co-FM)) and bismaleimide (BM) at 25 °C in chloroform was studied by following the decay in UV absorbance of the maleimide (MI) group at 320 nm. Reaction conditions were changed by using copolymers with different mole fraction of FM, F_FM, and by employing different initial molar ratios of reactants (furan group within FM and MI group within BM). Second order kinetics were obeyed. ¹³C NMR spectra showed that, even when all reactants had been converted to an insoluble crosslinked network, unreacted MI groups remained, presumably in the form of singly reacted pendant BM molecules. The fractions of MI groups remaining unreacted were found to be 0.49, 0.34 and 0.22 for FM:MI mole ratios in the initial mixture of 2, 1 and 0.5 respectively, when using a copolymer of F_FM=0.1354. An attempt was also made to follow the kinetics of network formation by ¹³C NMR spectroscopy, using the peak areas for reacted and unreacted MI and FM groups, but many of the findings were subject to some uncertainty for reasons, which are discussed. However, because the peak areas were considered reliable for unreacted MI groups, the rate constant, k, was evaluated, thereby. Overall using UV and NMR the values of k lay within the interval (0.8-3.6) × 10⁻⁵ dm³ mol⁻¹ s⁻¹.     

用含偶氮基的聚苯乙烯大分子引发剂合成两亲性嵌段共聚物

采用含偶氮基的聚苯乙烯预聚物（ＰＳ ＡＣＰＣ）作为引发剂，合成了苯乙烯（Ｓｔ）分别与甲基丙烯酸（ＭＡＡ）、甲基丙烯酸（β 羟丙酯）（ＨＰＭＡ）的嵌段共聚物，考察了ＰＳ ＡＣＰＣ引发第二单体的聚合反应行为，以及影响第二单体转化率和均聚物含量、共聚物组成的因素．用溶解性、凝胶渗透色谱（ＧＰＣ）、红外光谱（ＩＲ）、核磁共振（ＮＭＲ）、动态接触角（ＤＣＡ）等表征了嵌段共聚物．     

青霉素酰化酶在甲基丙烯酸缩水甘油酯共聚物上的固定化

 用共价键合法将青霉素酰化酶固定化在珠状多孔的甲基丙烯酸缩水甘油酯（GM）共聚物上，研究了固定化反应时间、温度、pH值和酶液用量对固定化青霉素酰化酶的表观活性、表观偶联效率、活性回收及稳定性的影响．将GM共聚物载体加入到磷酸缓冲液（0．1mol／L，pH10．8）与青霉素酰化酶液（每克干载体用酶液1ml）的混合溶液中，在30℃下反应72h，单位质量（干重）固定化酶的表观活性为348U／g，表观偶联效率为66．7％，活性回收为31．7％．     

Quantitative aspects of gradient HPLC of copolymers from styrene and ethyl methacrylate

Summary Prerequisite of quantitative evaluation in chromatography is equivalence of sample composition and detector signal. This includes complete retention and proper elution of all sample constituents. In polymer HPLC, complete retention requires a poor starting eluent, a sufficiently active column, and a low ratio of injection volume to column volume. On small pore columns, insufficient retention caused the polymer to elute either in the interstitial volume (sample exclusion), together with the sample solvent, or immediately after the solvent plug.Stat-copoly(styrene/ethyl methacrylate) samples are more difficultly retained thanstat-copoly(styrene/acrylonitrile) specimes. With the former copolymer it could be shown that incomplete retention did not cause sample demixing. In order to gain complete retention, non-exclusion HPLC of polymers should be performed with columns whose solvent volume is at least 50 times as large as the injection volume. This consequence is of practical importance in chromatographic cross-fractionation where rather large volumes of SEC eluate are injected into the apparatus for gradient HPLC.     

Determination of thermodynamic properties of macroporous glycidyl methacrylate‐based copolymers by inverse gas chromatography

Macroporous crosslinked poly(glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) (PGME) was synthesized by suspension copolymerization and modified by ring‐opening reaction of the pendant epoxy groups with ethylene diamine (EDA). Inverse gas chromatography (IGC) at infinite dilution was applied to determine the thermodynamic interactions of PGME and modified copolymer, PGME‐en. The specific surface areas of the initial and modified copolymer samples were determined by the BET method, from low‐temperature nitrogen adsorption isotherms. The specific retention volumes, V, of 10 organic compounds of different chemical nature and polarity (nonpolar, donor, or acceptor) were determined in the temperature range 333–413 K. The weight fraction activity coefficients of test sorbates, , and Flory–Huggins interaction parameters, , were calculated and discussed in terms of interactions of sorbates with PGME and PGME‐en. Also, the partial molar free energy, , partial molar heat of mixing, , sorption molar free energy, ΔG, sorption enthalpy ΔH, and sorption entropy, ΔS, were calculated. Glass transitions in PGME and PGME‐en, determined from IGC data, were observed in the temperature range 373–393 K and 363–373 K, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2524–2533, 2005     

Emulsion polymerization of methyl methacrylate under pulsed microwave irradiation

Emulsion polymerization of methyl methacrylate (MMA) under pulsed microwave irradiation (PMI) with higher peak pulse power was studied. The effects of various parameters of PMI on the polymerization were analyzed and compared with that under conventional heating (CH) process. The results were summarized, as compared with that under CH, as follows. The amount of initiator used to reach constant conversion reduced by 50% at the same polymerization time; at the same initiator concentration 0.15 and 0.2 wt.%, the polymerization rate increased by 131% and 163%, respectively. The molecular weight of polymer obtained was 1.1-2.0 times larger than that under CH; at the same irradiation energy, the conversion achieved using a lower pulse power was greater than that using a higher pulse power. There seemed to be a factor of the irradiation energy efficiency; in other words, for the monomer conversion, the irradiation energy of low pulse power had a higher efficiency. The conversion achieved using a 3.5 μs pulse width was almost the same as that using a 1.5 μs pulse width. The results indicated that PMI had a significant non-thermal effect on the emulsion polymerization of MMA so as to effectively enhance the polymerization rate. The glass transition temperature (T_g), the polydispersity index (PDI) and the regularity of the polymer obtained using two processes were similar, indicating that the physical properties and microstructure of the polymer were not modified by the use of microwaves.