Free-radical propagation rate coefficients

The pulsed laser polymerization-size-exclusion chromatography (PLP-SEC) technique has become the International Union of Pure and Applied Chemistry (IUPAC)-recommended method for the accurate determination of propagation rate coefficients, k_p, for radical polymerization. The fundamental insight provided by Heuts, Gilbert, and Radom into the relevance of transition state dynamics allows for an adequate understanding of the dependence of k_p on radical chain length, solvent environment, and monomer conversion. The associated entropic effects are particularly pronounced in aqueous solution, but are also found in less polar media and with non-polar monomers. Moreover, these arguments are applicable towards the interpretation of copolymerization reactivity ratios. The addition of sodium hydroxide to aqueous solutions of (meth)acrylic acid yields partially and even fully ionized systems with clearly reduced k_p, which indicates the action of repulsive forces between the equally charged monomer and radical species. Increasing the concentration of monomer as well as the addition of salts may reverse this effect and increase k_p due to counterion activity.     

Solid-state NMR studies on phase behavior and motional mobility in binary blends of polystyrene and poly(cyclohexyl methacrylate)

The phase behavior and motional mobility in binary blends of polystyrene (PS) and poly(cyclohexyl methacrylate) (PCHMA) have been investigated by solid state ¹³C NMR techniques. The blend miscibility has been studied by examining the ¹H spin-relaxation times in the laboratory frame (T₁^H) and in the rotating frame (T_1ρ^H) for the PCHMA/PS blends with various compositions and pure components. The T_1ρ^H results show that PCHMA and PS are intimately mixed at the molecular level within the blends at all compositions. In addition, according to the results of carbon T_1ρ relaxation time measurements, we conclude that mixing is intimate enough to cause a reduction in local chain mobility for PS, but an increase in side chain mobility for PCHMA.     

Phase behavior on the binary and ternary mixtures of poly(cyclohexyl acrylate) and poly(cyclohexyl methacrylate) in supercritical CO2

High‐pressure phase behavior was measured for the CO₂–cyclohexyl acrylate and CO₂–cyclohexyl methacrylate system at 40, 60, 80, 100, and 120°C and pressure up to 206 bar. This system exhibits type I phase behavior with a continuous mixture‐critical curve. The experimental results for the CO₂–cyclohexyl acrylate and CO₂–cyclohexyl methacrylate system were modeled using the Peng–Robinson equation of state. Experimental cloud‐point data, at a temperature of 250°C and pressure of 2800 bar, were presented for ternary mixtures of poly(cyclohexyl acrylate)–CO₂–cyclohexyl acrylate and poly(cyclohexyl methacrylate)–CO₂–cyclohexyl methacrylate systems. Cloud‐point pressures of poly(cyclohexyl acrylate)–CO₂–cyclohexyl acrylate system were measured in the temperature range of 40 to 180°C and at pressures as high as 2200 bar with cyclohexyl acrylate concentrations of 22.5, 27.4, 33.2, and 39.2 wt %. Results showed that adding 45.6 wt % cyclohexyl acrylate to the poly(cyclohexyl acrylate)–CO₂ mixture significantly changes the phase behavior. This system changed the pressure–temperature slope of the phase behavior curves from the upper critical solution temperature (UCST) region to the lower critical solution temperature (LCST) region with increasing cyclohexyl acrylate concentration. Poly(cyclohexyl acrylate) did not dissolve in pure CO₂ at a temperature of 250°C and pressure of 2800 bar. Also, the ternary poly(cyclohexyl methacrylate)–CO₂–cyclohexyl methacrylate system was measured below 187°C and 2230 bar, and with cosolvent of 27.4–46.7 wt %. Poly(cyclohexyl methacrylate) did not dissolve in pure CO₂ at 240°C and 2500 bar. Also, when 53.5 wt % cyclohexyl methacrylate was added to the poly(cyclohexyl methacrylate)–CO₂ solution, the cloud‐point curve showed the typical appearance of the LCST boundary. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1117–1125, 2004     

Graft chain propagation rate coefficients of acrylic acid in melt graft copolymerization with linear low density polyethylene

Graft chain propagation rate coefficients (k_p,g) for grafting AA onto linear low density polyethylene (LLDPE) in the melt in ESR tubes have been measured via Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy in the temperature range from 130 to 170 °C. To exclude the effect of homopolymerization on the grafting, the LLDPE was pre-irradiated in the air by electron beam to generate the peroxides and then treated with iodide solution to eliminating one kind of peroxides, hydroperoxide. The monomer conversion is determined by FTIR and the chain propagation free-radical concentration is deduced from the double integration of the well-resolved ESR spectra, consisting nine lines in the melt. The temperature dependence of k_p,g is expressed:

     

Copolymers of 2-hydroxyethyl methacrylate and methyl methacrylate: an electron beam resist study

The electron beam development characteristics of copolymers of HEMA and MMA are reported. A copolymer with 4% of HEMA was found to have comparable sensitivity and enhanced contrast compared with conventional PMMA and this material would appear to be useful in lithographic applications.     

Comparative study of poly(2,3 and 4 methyl cyclohexyl methacrylate)s. Dielectric relaxation spectroscopy (DRS)

The relaxation properties of poly(methyl cyclohexyl methacrylate)s (P2MCHMA), (P3MCHMA), (P4MCHMA) were analyzed. Dielectric spectroscopy (DS) techniques were used for this purpose. These polymers exhibit prominent α peaks, associated to the dynamic glass transitions, and then poorly defined β-relaxations and two other relaxation zones labelled as γ- and δ-relaxation in order of decreasing temperatures. The α relaxation processes were analyzed by means of the free volume theory, using the Vogel-Fulcher-Tammann-Hesse (VFTH) equation and in terms of the Havriliak-Negami (HN) empirical equation. Previously to these analyses, conductive contributions to the loss permittivity were subtracted. The apparent activation energies for the secondary processes under study have been calculated by means of Arrhenius. Comparison with previous relaxation results of poly(cyclohexyl methacrylate) (PCHMA), i.e. the polymer without substituents in the cyclohexyl ring, has been also carried out. In this way, changes in the glass transition absorptions as well as in the secondary processes have been discussed.     

Elastic and swelling behavior of 2-hydroxyethyl methacrylate,diethylene glycol methacrylate,and methacrylic acid copolymers

The elastic and swelling behavior of copolymers of 2-hydroxyethyl methacrylate, diethylene glycol methacrylate, and methacrylic acid crosslinked with ethylene glycol dimethacrylate has been studied. In the range of copolymer composition studied, Young's modulus of the swollen networks increases with the content of methacrylic acid, and its dependence on the content of diethylene glycol methacrylate passes through a maximum. The concentrations of the elastic network chains and determined from Young's moduli of swollen networks are much higher than those calculated from stoichiometry. This effect is attributed to the presence of additional physical crosslinks due to water-induced ordering of the hydrophobic backbone chains. Both the elastic and swelling behavior of the polymers mentioned above are decisive for their application in the preparation of soft contact lenses. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2141–2148, 1997     

Comparative study of localized side group in poly(2,3 and 4 methyl cyclohexyl methacrylate)s. TSDC measurements

By means of thermal sampling techniques, the fine structure of the γ-relaxation zone of poly(methyl cyclohexyl methacrylate)s (P2MCHMA), (P3MCHMA), (P4MCHMA) were analyzed. Results reveal that in this relaxation zone, at least two peaks are present. These peaks are attributed to the cis and trans isomers. Loss permittivity of the polymers under study in this relaxation zone has been reproduced from the partial depolarization data by using the elementary relaxation times and activation energies. Results are in relatively good agreement with the experimental data previously obtained. Molecular mechanic calculations have been carried out in order to elucidate the characteristics and molecular origin of the relaxations observed in this zone. An interpretation of the height of the peaks associated to the cis- and trans-isomer in terms of strain energy (SE) have been carried out.     

松香甘油酯与甲基丙烯酸-2-羟乙酯的反应研究

松香甘油酯中的共轭双键可以与甲基丙烯酸-2-羟乙酯(HEMA)发生Diels-Alder加成发应,同时松香甘油酯具有一定的酸值,其中未反应的松香可与HEMA进行酯化反应。研究了反应温度和物料配比对加成反应和酯化反应的影响,并对产物进行了红外光谱(FT-IR)分析和热重分析。实验结果表明,反应温度升高,加成反应和酯化反应的速率会加快,230℃是理想的反应温度;随着n(HEMA)∶n(松香甘油酯)比值的增加,产物的酸值和溴值下降,当n(HEMA)∶n(松香甘油酯)=3.0∶1时,溴值(65.2 g Br/100 g)和酸值(2.95 mg KOH/g)最低;FT-IR分析表明HEMA已经连接到松香甘油酯的分子上;热重分析表明加成物的初始分解温度提高了10℃,而最终分解温度下降了11.8℃。     

Physico-chemical characterization of hybrid polymers obtained by 2-hydroxyethyl(methacrylate) and alkoxides of zirconium

Hybrid monolithic materials were prepared through polymerisation of 2-hydroxyethyl methacrylate (HEMA) mixed with zirconium alkoxides (Zr(OBuⁿ)₄, Zr(OPrⁿ)₄ and Zr(OEt)₄), modified by acetylacetonate groups. The molar ratio HEMA/Zr varied between 1 and 4. Thermo-Gravimetry coupled with Mass Spectroscopy (TG-MS) analyses, ¹³C MAS NMR and Dynamical Mechanical Thermal Analysys (DMTA) indicated the polymeric chains were interconnected by the inorganic component.The presence of zirconium alkoxides modified substantially the poly-HEMA properties. Glass transition temperature of hybrid materials derived from butoxy and propoxy was found in the range 50-80 °C, depending on the composition. The typical swelling of p-HEMA in the water, was suppressed by the presence of zirconium compounds. After immersion in distilled water, hybrid polymers showed an initial slight weight increase, followed by a small mass loss, which increases proportionally to the length of alkoxyl group (ethoxide(propoxide(butoxide) and reaches a constant value after about 40 days. The hybrids remained always rigid and transparent. Flexural modulus and strength of about 400-900 and 4-8 MPa were measured.     

松香与甲基丙烯酸-β-羟乙酯的酯化反应和加成反应研究

研究了松香与甲基丙烯酸-β-羟乙酯(HEMA)的酯化反应和加成反应,探讨了阻聚剂、催化剂种类和用量、反应温度和原料配比等对酯化反应和加成反应的影响,并采用红外光谱(FT-IR)法和热重分析(TGA)法分别表征了产物的分子结构和酯化物的热稳定性。结果表明:松香分子中的羧基和双键分别与HEMA分子中的羟基和双键发生了酯化反应和加成反应;氧化锌是酯化反应较好的催化剂,当w(氧化锌)=1.0%(相对于松香而言)、反应温度为220℃时,有利于酯化反应的进行;HEMA用量越多,越有利于加成反应的进行;FT-IR表明已成功制取了松香与HEMA的反应产物,TGA表明该产物的热稳定性明显提高。     

Synthesis and characterisation of N-toluyl methacrylatoethyl carbamates,homopolymers and copolymers with methyl methacrylate

The paper describes the synthesis of N-2/4-toluyl methacrylatoethyl carbamates using 2/4-toluyl isocyanate and 2-hydroxyethyl methacrylate. Homopolymerisation and copolymerisation of these novel monomers with methyl methacrylate was carried out using benzoyl peroxide as an initiator and tetrahydrofuran as solvent. Photopolymerisation of N-4-toluyl methacrylatoethyl carbamate could be carried out without the use of photosensitiser. Structural characterisation of copolymers was done using ¹H-NMR. Thermal stability of copolymers was evaluated in a nitrogen atmosphere by dynamic thermogravimetry.     

丙烯酰胺类共聚物水凝胶的合成及性能研究

用自由基聚合法合成了不同摩尔配比的HEMA／AM共聚物水凝胶材料。研究了单体组成、温度、pH值、离子强度等因素对凝胶溶胀性能的影响。结果表明：水凝胶的溶胀速度较快;水凝胶在pH值小于4及pH值大于9的酸、碱溶液中发生水解,导致水凝胶的饱和含水量大幅增加,而在弱酸性溶液中几乎没有变化;水凝胶的饱和含水量对离子强度的变化不够敏感;随着温度的升高水凝胶的饱和含水量略有减少,说明此类水凝胶对温度的敏感性也较弱。     

Poly (2-hydroxyethyl methacrylate)-based hydrogels for slow release of pralidoxime chloride

Pralidoxime chloride (PAM-Cl)-loaded poly (2-hydroxyethyl methacrylate) (PHEMA)-based hydrogels were prepared by bulk copolymerization of 2-hydroxyethyl methacrylate (HEMA) with different mol fractions (0.02–0.10) of trimethylsilyl methacrylate. Characterization of the gels was done by dynamic swelling measurements. It was found that copolymerization does not alter the swelling mechanism of PHEMA and it essentially remains Fickian in nature. In vitro drug-release studies show the increase in release time from 6 to 12 h on incorporation of a 0.1 mol fraction of trimethylsilyl methacrylate on the PHEMA backbone. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 267–270, 1997     

温度及pH敏感共聚/粘土纳米复合水凝胶的合成与性能研究

以无机粘土为交联剂制备了具有温度、pH双重敏感性的聚（N-异丙基丙烯酰胺-co-甲基丙烯酸-β-羟乙酯）/粘土纳米复合水凝胶（P（NIPA-co-HEMA）/clay）,并用红外和X衍射对其结构和形态进行了表征。在弱碱性（pH=7.4）和25℃条件下,分别研究了温度和不同pH缓冲溶液对该凝胶溶胀度的影响,测定了纳米复合水凝胶的力学性能。结果表明：水凝胶的粘土已被剥离成单片层,且均匀分散在凝胶网络中,起交联作用;P（NIPA-co-HEMA）/clay具有良好的温度、pH双重敏感特性;凝胶的断裂伸长率〉1000%。     

Structural characteristics and properties of silica/poly(2-hydroxyethyl methacrylate) (PHEMA) nanocomposites prepared by mixing colloidal silica or tetraethyloxysilane (TEOS) with PHEMA

Two methods were used to prepare the silica/poly(2-hydroxyethyl methacrylate) (PHEMA) nanocomposites: one was the direct mixing of colloidal silica with PHEMA using methanol as a co-solvent (colloidal silica/PHEMA) and the other was the adding of the inorganic precursor, tetraethyloxysilane (TEOS), to the PHEMA/methanol solution, followed by the sol-gel process with an acid-catalyst (TEOS/PHEMA). The structure of the colloidal silica/PHEMA hybrid consisted of nano-silica uniformly dispersed in the PHEMA phase with slight inter-molecular hydrogen bonding. The structure of TEOS/PHEMA hybrid was similar to a semi-interpenetrated network with PHEMA chains tethered into the nano-silica network by inter- and intra-molecular hydrogen bonding. Consequently, the TEOS/PHEMA hybrid gels exhibited a smoother surface, higher transparency, and better thermal stability than the colloidal silica/PHEMA hybrid gels.     

自由基聚合反应动力学常数测定技术

自由基聚合是一类重要的聚合反应,其反应动力学常数的获取对于聚合机理研究、聚合物链结构定制、反应过程调控都有着重要的意义。综述了自由基聚合中最重要的链增长和链终止反应速率常数的测定方法,着重介绍连续脉冲激光引发结合凝胶渗透色谱测定链增长反应速率常数、单脉冲-连续脉冲激光耦合结合近红外光谱与电子顺磁共振波谱测定链终止反应速率常数,涵盖了各方法的检测原理、要求和适用条件,讨论了增长自由基链长对链增长和链终止反应速率常数的影响。此外,对链增长和链终止反应速率常数检测方法的提升和新方法的开发进行了展望。     

Inverse emulsion polymerization-assisted designing of superparamagnetic poly (2-hydroxyethyl methacrylate) nanoparticles and magnetically triggered release of cisplatin

Superparamagnetic nanocarriers of poly (2-hydroxyethyl methacrylate) (PHEMA) were prepared by carrying out benzoyl peroxide (BPO) initiated inverse emulsion-free radical polymerization of HEMA in the presence of poly (vinyl alcohol) (PVA) and subsequent in situ precipitation of magnetite within the PHEMA matrix. The as-prepared nanoparticles were characterized by FTIR and UV–visible spectroscopy, vibrating sample magnetometry (VSM), particle size and zeta potential analysis, and transmission electron microscopy, respectively. The PHEMA nanocarriers were investigated for their blood compatibility, and cytotoxicity response to L929 cells. The superparamagnetic nanoparticles were loaded with an anticancer drug cisplatin and the release profiles of the drug were examined as a function of various experimental parameters like composition of the PHEMA nanocarriers, percentage of drug loading, and strength of the externally imposed magnetic field. The kinetics of the drug release process was also investigated, and the obtained release data were applied to different mathematical kinetic models to explore the nature of the release mechanism.     

Network characteristics of homopolymer and some copolymers of poly(2-hydroxyethyl methacrylate)

Soluble poly(2-hydroxyethyl methacrylate) and copolymers of 2-hydroxyethyl methacrylate with n-butyl acrylate and 2-hydroxypropyl acrylate of varying compositions were synthesised by solution polymerisation. The polymers were characterised by dilute solution viscometry and shear viscosity. Crosslinked membranes were prepared from these polymers by introducing crosslinks in solution state through the reaction with 1,6-hexamethylene diisocyanate at a number of different crosslinker concentrations. The membranes swollen in dimethylformamide and water were characterised by performing equilibirium swelling measurements and calculating polymer volume fraction, the molecular mass between crosslinks (M?^c) and equilibrium water content (EWC) at 25°C. The calculation of M?^c used an expression developed by Peppas & Lucht for equilibrium swelling. This is a modified equation of the original Flory–Rehner expression, that allows non-Gaussian distribution of chain lengths. The variation of M?^c with crosslinker concentration and copolymer composition is discussed in terms of structural and molecular characteristics of these highly crosslinked networks.     

Interaction between Poly(2- hydroxyethyl methacrylate) and High Energy Excimer Laser Radiation

Poly(2-hydroxyethyl methacrylate) was prepared by bulk polymerization and then exposed to ablation by 193-nm pulsed radiation provided by an ArF excimer laser. The etch curve, i.e. ablation rate versus radiation fluence, presents two changes in the slope, which are consistent with a presumably characteristic behaviour of addition polymers with a strong tendency towards thermal depolymerization. Samples exposed to two fluences, each in the vicinity of one of the inflection points, were analysed by X-ray photoelectron spectra (XPS) at two different take-off angles. The results suggest that the ablation mechanism may vary when the fluence changes. At the higher fluence (280mJ/cm²), depolymerization is the dominant process and the material left after etching displays almost no change in the O/C atomic ratio. At the lower fluence (80mJ/cm²), cleavage of the pendant group is dominant and the O/C ratio decreases significantly, especially on the polymer surface.