聚甲基丙烯酸甲酯(PMMA)微流控芯片DNA分析系统的研制

生物分析是微流控芯片分析最具进一步发展及商品化前景的分支领域之一。报道了基于聚甲基丙烯酸甲酯(PMMA)微流控芯片DNA分析系统的研制。采用简易热压法自制的PMMA芯片,以小型光纤式激光诱导荧光为检测器,以四触点可切换1 800 V高压电源为电驱动系统,以2%羟乙基纤维素(HEC)为筛分介质,通过用于DNA分析的TO-PRO-3荧光染料和激光诱导荧光检测器670 nm截止滤光片的选择,构建了微流控芯片DNA分析系统。芯片凝胶电泳分离φX174-HaeⅢRF DNA片段, 以603 bp片段计算理论塔板数n为1.14×106·m-1, 271/281 bp的分离度R为1.2。建立的PMMA微流控芯片DNA分析系统具有制作和运行成本低,芯片可重复使用,分析重现性好等特点。该研究可用于制作微型化便携式DNA分析仪,应用于临床诊断、疾病筛查等领域。     

Phase Separation in Poly(Methyl Methacrylate)-Epoxy Blend

Diglycidyl ether of bisphenol A (DGEBA) epoxy resin was modified with high molecular weight poly(methyl methacrylate) (PMMA). Morphological variations of a 2 wt% PMMA-modified epoxy mixture were studied by optical microscopy and scanning electron microscopy (SEM). A PMMA-epoxy blend cured at 100°C revealed that a secondary phase morphology was observed in both epoxy and PMMA phases from the early stages of the phase separation process. A morphology consisting of a rough striated continuous phase along with large smooth regions was observed by SEM, confirming the secondary phase separation. The dynamic mechanical thermal analysis showed that the PMMA modification of epoxy at such a low PMMA concentration of 2 wt% has no major influence on the glass transition temperature of the epoxy-rich phase. The PMMA-epoxy blend showed a slight increase in the flexural properties and the fracture toughness.     

Effect of Individualized Cellulose Fibrils on Properties of Poly(Methyl Methacrylate) Composites

Cellulose fibrils were manufactured from flax fibers using chemical treatments followed by cryo-crushing and ultrasonication techniques. The fibrils, consisting mainly of cellulose free from lignin, pectin and hemicellulose, were exploited as a biofiller in preparing poly(methyl methacrylate) (PMMA) matrix composites. The effects of incorporating cellulose fibrils on the physical and mechanical properties of the polymer matrix were investigated. In particular, the influence of the fibrils on the thermal stability and degradation of the composites was studied by means of thermogravimetric analysis carried out in both inert and oxidative atmospheres. The runs performed under air flow revealed the efficiency of the cellulose fibrils in delaying the polymer decomposition during thermal oxidation. The weight loss was slowed down in the composites of all compositions and the temperature of degradation increased with increasing the amount of the fibrils. The combustion properties of the fibril-based composites were evaluated by means of pyrolysis combustion flow calorimetry. The addition of cellulose fibrils into the PMMA matrix resulted in a noticeable decrease of the primary combustion parameters.     

Effect of Molecular Architecture on Physical Properties of Tree-Shaped and Star-Shaped Poly(Methyl Methacrylate)-Based Copolymers

The synthesis of star-like A(B)_n copolymers based on the hydrophilic poly(ethylene glycol) monomethyl ether (m-PEG, block A) and the hydrophobic poly(methyl methacrylate) (PMMA, blocks B) is reported. We obtained copolymers made of one m-PEG chain and 2 or 4 PMMA blocks using a combined “arm first”—“core first” approach. Such structures were called tree-shaped copolymers where the m-PEG was considered as the trunk and PMMA arms as the branches. Star-like copolymers (B)_nA-A(B)_n built by two tree-shaped fragments with a poly(propylene oxide) (PPO) as the central junction, were also synthesized according to a previously reported procedure. The latter were called star-shaped structures and the synthesis was performed to obtain architectures different from the tree-shaped one but characterized by a similar length of the PMMA arms. Microstructural analysis was carried out through ¹H-NMR and GPC, and the thermal and transport properties (sorption and diffusion) to liquid water were investigated and correlated to the molecular architecture of the two classes of copolymers.     

Effect of Solvent on the Miscibility of Polystyrene/Poly(Styrene-Co-Acrylonitrile) Blends at Different Temperatures

The effect of solvent and temperature on the miscibility of polystyrene (PS) and poly (styrene-co-acrylonitrile) (PSAN) was examined by the dilute-solution viscometry (DSV) method. The extent of miscibility of different PS/PSAN blend compositions (30/70, 50/50, and 70/30) in chloroform (CHCl₃) and N, N- dimethyl formamide (DMF) was discussed in terms of the signs of various viscosity (ΔB, μ, Δ[η], α, and β) parameters. Based on the sign convention of these interaction parameters, partial miscibility in DMF and almost immiscibility in CHCl₃ was indicated for the examined blend. The data obtained from the DSV method were then correlated with the ones obtained through density and refractive index measurements; good agreement was obtained. The study also revealed a relatively greater influence of temperature and composition on the miscibility of the blend in DMF than in CHCl₃.     

Thermal Stability and Degradation Kinetics of Poly(Methyl Methacrylate)/Sepiolite Nanocomposites by Direct Melt Compounding

Poly(methyl methacrylate) (PMMA) nanocomposites based on sepiolite modified with trimethyl hydrogenated tallow amine by an adsorption process were prepared by melt compounding using a corotating twin screw extruder. The morphology and dispersion of sepiolite in the PMMA were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal stability and the activation energies were investigated by thermogravimetric analysis/differential thermogravimetric (TGA/DTG). The XRD and TEM results show that the sepiolite was dispersed homogeneously in the PMMA matrix at a nanometer scale. The TGA analysis revealed that the addition of sepiolite improved the thermal stability of PMMA. The apparent activation energies were calculated by the method of Flynn–Wall–Ozawa in nitrogen at four different heating rates, showing that sepiolite increased the apparent activation energies by about 20 kJ/mol within the degree of conversion (α) of 0.35–0.9, as compared with the reference PMMA sample.     

Parametric Studies on the Grafting of Poly(Methyl Methacrylate) onto Organophilic Montmorillonite Using Silylated Clay Platelets

Poly(methyl methacrylate) (PMMA)/organophilic montmorillonite (Cloisite 30B) nanocomposites were synthesized by the chemical grafting of PMMA onto Cloisite 30B via solution polymerization of methyl methacrylate (MMA) with vinyl-modified organoclay. The effects of different parameters such as clay weight percent (CWP), solvent per monomer volume ratio, and dispersion time on the properties of the PMMA grafted Cloisite 30B were investigated using the Taguchi experimental design method. This method gives a much-reduced variance for the experiments with optimum setting of control parameters and provides a set of minimum experiments compared to the conventional methods. Qualitative evidence for the chemical grafting of the PMMA onto Cloisite 30B was confirmed by Fourier transform infrared spectroscopy (FT-IR). X-ray diffraction (XRD) was used to investigate interlayer changes of the clay in the grafted nanoplatelets. The exfoliated/intercalated morphology of the nanocomposites was confirmed by XRD. Furthermore, thermal properties were measured by thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). Statistical analysis of results revealed that clay weight percent and solvent per monomer ratio had significant effects on the properties of final products. The percent of grafted PMMA and storage modulus of PMMA/30B nanocomposites decreased with increasing clay content due to better dispersion of the clay at lower loadings. On the other hand, because of a tendency to formation of homopolymer and oligomers at higher solvent loadings; the percent of grafted PMMA, storage modulus and glass transition temperature of PMMA/30B nanocomposites decreased with an increase in solvent per monomer volume ratio. However, the obtained PMMA/30B nanocomposites at the optimum conditions, was exhibited a higher glass transition temperature, higher storage modulus and better thermal stability than the pure PMMA.     

无规聚甲基丙烯酸甲酯立构复合的红外光谱研究

用红外光谱研究了无规聚甲基丙烯酸甲酯的丙酮、苯、氯仿溶液成膜样品的立构复合状况。结果表明无规聚甲基丙烯酸甲酯在丙酮和苯中确能形成立构复合结构,结构的形成主要是依靠分子链中间规和等规链段的相互作用。对丙酮样品的退火实验表明,在退火过程中能够发生间规链段的自聚集现象。     

基于新型聚合物碳糊复合电极的电致化学发光研究

以甲基丙烯酸甲酯(MMA)预聚物作为石墨粉的粘合剂,完全聚合固化,制备并表征了聚合物碳糊复合电极.基于此电极考察了鲁米诺体系的电致化学发光行为.在最优条件下,鲁米诺在聚合物碳糊电极上的电化学响应比在传统的碳糊电极上明显增强,电致化学发光的稳定性和发光强度也大大增加.利用尿酸对该体系发光的强抑制作用,建立了尿酸的电致化学发光检测方法,线性范围为8×10-11-3×10-8mol/L,检出限为1.2×10-11 mol/L,应用于体液测定,结果满意.     

离子液体中聚氧化乙烯(PEO)相变过程中的氢键效应

我们把Flory-Huggins模型推广应用到聚合物/离子液体体系,研究聚氧化乙烯(PEO)在离子液体[EMIM][BF_4]中相变过程中的氢键效应,理论模型考虑了三种类型氢键(Ⅰ型:PEO-[EMIM]~+氢键,Ⅱ型:PEO-[BF_4]~-氢键和Ⅲ型:[EMIM]~+-[BF_4]~-氢键)的形成,分析了三种类型的氢键分数随温度、 PEO体积分数的变化.研究发现,三种类型的氢键分数随温度的升高而减少.在较小PEO体积分数条件下,增加PEO体积分数,Ⅰ型、Ⅱ型氢键分数轻微地减小;在较大PEO体积分数条件下,增加PEO体积分数,Ⅰ型、Ⅱ型氢键分数急剧减少.Ⅲ型氢键分数随着PEO体积分数的增加而急剧降低.由于三种氢键效应,第二维里系数A_2随温度的增加而减小.通过计算分析不同分子量的PEO在[EMIM][BF_4]中的相图发现,在PEO体积分数较低的条件下,Ⅰ型、Ⅱ型和Ⅲ型氢键是PEO相变的主要驱动力;在PEO体积分数较高的条件下,Ⅰ型和Ⅱ型氢键在PEO相变过程中起到主导作用.     

Effects of UV-irradiation on the thermo-mechanical properties of optical grade poly(methyl methacrylate)

We studied the evolution of the thermo-mechanical properties of poly(methyl methacrylate) (PMMA) materials exposed to ultra-violet (UV) light. To do so we measured important mechanical parameters including the fracture strength, the stress-strain relation, and Young's modulus as a function of the UV-irradiation dose. We concluded that the mechanical properties of PMMA are affected by UV light. The ductility disappears and the strength and strain at rupture strongly decrease (over 30%). The evolution of the Young's modulus is discussed as a function of the cross-linking degree of the materials. Moreover we observed the occurrence of surface damage, which in its turn enhances the degradation of these mechanical parameters.     

Electrical conductivity behaviour of pure and polyblends samples of polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA)

Electrical conductivity of pure PVC, PMMA and their polyblends samples has been studied in detail as a function of polarizing fields at constant temperatures. Different plots were drawn to investigate the nature of mechanism responsible for conduction. The nature of all the thermograms is nonlinear but similar for all temperatures. The plots have two slopes, i.e., ohmic conduction with slope of curve ≈1 at lower voltage region and a non-ohmic conduction with slope ≈1.9 at higher voltage region are observed. The increase in the conductivity and decrease in the activation energy, suggest that plasticization effect is taking place between the polymers when they are blended. Fowler–Nordheim plots are not consistent and showing negative and positive slopes simultaneously for lower as well as higher values of applied voltage. Theoretical and experimental values of β_SR and β_PF were calculated and the β_exp of pure and polyblend samples is in agreement with theoretically β_PF. The β_exp value lies close to β_PF, this shows that Poole–Frenkel mechanism is also effective. The calculated metal electrode potential barrier at a constant voltage suggests that the dominant charge carrier mechanism is Schottky–Richardson type. Hence in the present case both SR and PF mechanisms are seem to be operative.     

Enrichment of poly(methyl methacrylate) and its graft copolymer of polybutadiene on the surface of polypropylene blends

Poly(methyl methacrylate) (PMMA) and its graft copolymer of polybutadiene were used as the macromolecular surface modifiers of polypropylene. The enrichment and diffusion of the modifiers onto the surface of polypropylene blends were investigated using FTIR-ATR, CDA and SEM. It has been found that the selective aggregation of the modifier component on the surface of polypropylene was mainly affected by the content, molecular weight and size of the segregated domains. Lower content and higher surface energy die were in favor of the enrichment of the additive. PMMA with higher molecular weight showed larger domain phase and lower diffusion velocity which resulted in less enrichment on the surface of PP blends.     

Mechanical,Thermal, and Rheological Properties of EPDM-graft-methyl Methacrylate and Styrene (EPDM-g-MS)/Methyl Methacrylate-Styrene Copolymer (MS Resin) Blends

EPDM-graft-methyl methacrylate and styrene (EPDM-g-MS) were synthesized by solution graft copolymerization of methyl methacrylate (MMA) and styrene (St) onto ethylene-propylene-diene terpolymer (EPDM). EPDM-g-MS/MS resin blends (MES) tht were prepared by melt blending EPDM-g-MS and methyl methacrylate-styrene copolymer (MS resin). The mechanical properties, compatibility, thermal stabilities and rheological properties of MES were studied by the pendulum impact tester and the tension tester, differential scanning calorimetric (DSC), thermogravimetry analysis (TGA), and the capillary rheometry, respectively. The results showed that EPDM-g-MS had an excellent toughening effect on MS resin; the notched Izod impact strength of MES reached 20.7 kJ/m² when EPDM content in MES was 25 wt%, about 14 times that of MS resin. EPDM-g-MS and MS resin were partially compatible, and the compatibility increased with an increasing MMA/St ratio of EPDM-g-MS. MES had excellent heat-resistance, which increased as the EPDM content in MES and MMA/St ratio of EPDM-g-MS rose. MES melt flow confirmed pseudoplastic flow characteristics. The apparent viscosity (η _a ) of MES decreased with an increasing shearing rate (γ) and temperature, but increased with an increasing EPDM content in MES and MMA/St ratio of EPDM-g-MS. The flow activation energy of MES was lower than that of MS resin.     

Toughening Effect of Poly(ethene-co-1-butene)-graft-methyl Methacrylate and Acrylonitrile on Styrene-acrylonitrile Copolymer (SAN)

Poly(ethene-co-1-butene)-graft-methyl methacrylate-acrylonitrile (PEB-g-MAN), synthesized by suspension grafting copolymerization of methyl methacrylate and acrylonitrile onto PEB, was blended with styrene-acrylonitrile copolymer (SAN). The mechanical properties, phase structure, toughening mechanism, miscibility, and thermal stability of the SAN/PEB-g-MAN blends were studied using a pendulum impact tester, tension tester, scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TG). The results showed that PEB-g-MAN has an excellent toughening effect on SAN resin. The notched impact strength of the blends (containing 25 wt% PEB) was 63.3 kJ/m², which was nearly 60 times that of SAN resin. The brittle-ductile transition of SAN/PEB-g-MAN blends occurred when the weight percentage of PEB was between 17.5 and ～20 wt%. SAN and PEB-g-MAN were partially miscible. The toughening mechanism of the blends changed with the PEB content. When the PEB content was low, the toughening mechanism of the blends was branching and termination of cracks with slight cavitation. As the content of PEB increased, the toughing mechanism gradually changed from branching and termination of crack with slight cavitation to both branching and termination of crack and cavitation, to extensive cavitation, and finally to shear yielding accompanied by cavitation. The phase structure of the blends changed from a “sea-island’’ structure to a cocontinuous structure as the PEB content increased. ATG analysis showed that the thermal properties of the SAN resin in the blends were enhanced by adding the PEB-g-MAN.     

Temperature-controlled depth profiling in polymeric materials using cluster secondary ion mass spectrometry (SIMS)

Secondary ion mass spectrometry (SIMS) employing an SF₅⁺ polyatomic primary ion source was used to depth profile through poly(methylmethacrylate) (PMMA), poly(lactic acid) (PLA) and polystyrene (PS) thin films at a series of temperatures from −125 °C to 150 °C. It was found that for PMMA, reduced temperature analysis produced depth profiles with increased secondary ion stability and reduced interfacial widths as compared to analysis at ambient temperature. Atomic force microscopy (AFM) images indicated that this improvement in interfacial width may be related to a decrease in sputter-induced topography. Depth profiling at higher temperatures was typically correlated with increased sputter rates. However, the improvements in interfacial widths and overall secondary ion stability were not as prevalent as was observed at low temperature. For PLA, improvements in signal intensities were observed at low temperatures, yet there was no significant change in secondary ion stability, interface widths or sputter rates. High temperatures yielded a significant decrease in secondary ion stability of the resulting profiles. PS films showed rapid degradation of characteristic secondary ion signals under all temperatures examined.     

Enthalpy Relaxation Study of Poly(Vinyl Chloride) Films Based on the Time-Temperature Superposition Principle

Abstract

In the enthalpy relaxation of poly(vinyl chloride), a decrease in enthalpy upon the isothermal ageing was measured using the differential scanning calorimetry method as a function of ageing time (t_A) and ageing temperature. The range of the ageing temperature was from 56?°C (T_g ? 25?°C) to 72?°C (T_g ? 9?°C) where T_g denotes the glass transition temperature. The limiting value of the decrease in enthalpy was determined by applying a stretched exponential function to the measured enthalpy data. The relaxation function (?) was derived from the measured enthalpy and the construction of a master curve was tried by shifting the ? ? t_A curves of the respective ageing temperatures horizontally. Although there was no agreement between the shift factors (a_T) and the relaxation times of the ? ? t_A curves, the superposition was successfully constructed and the a_T values obtained for the poly(vinyl chloride) sample were found to be comparable to those reported for viscoelastic experiments over a broad temperature range above and below T_g carried out for different polymers. The origin of the decrease in enthalpy was briefly discussed in terms of the chain dynamics in the isothermal condition.     

Viscoelastic Behavior of Poly(Methyl Methacrylate-Co-Methyl Acrylate) Random Copolymer Studied by Dynamic Mechanical Analysis and Nanoindentation

The viscoelastic behavior of poly(methyl methacrylate) (PMMA) homopolymer and poly(methyl methacrylate-co-methyl acrylate) random copolymers was characterized by dynamic mechanical analysis and nanoindentation. Differential scanning calorimetric results showed only one glass transition, indicating the random distribution of comonomers in the copolymers. The α relaxation temperature (T_α) and activation energy (H_α) decreased with increasing content of methyl acrylate monomers (C_MA%). The β relaxation temperature (T_β) also decreased whereas the activation energy (H_β) showed only small variations compared with H_α. Moreover, the indention displacement and creep compliance strongly depended on C_MA%. Two creep stages were found in the creep compliance curves.     

红外光谱监测聚富马酸二羟丙酯及其共聚物的合成研究

聚富马酸二羟丙酯(PPF)是一种可生物降解的线形不饱和聚合物,其分子链上的双键在适当引发剂的作用下可以与其他烯类单体进行交联,生成具有三维网络结构的交联体,对组织起到支撑作用。先合成了中间体低聚物-富马酸二羟丙酯(PFP),然后采用熔融缩聚的方法通过低聚物PFP合成了聚合物PPF,并且在此基础上采用类似的方法合成了癸二酸二羟丙酯(PSP),再使PFP和PSP进行缩聚反应,生成包含癸二酸二羟丙酯链段的新的聚富马酸二羟丙酯的共聚物——聚(富马酸二羟丙酯共聚癸二酸二羟丙酯)P(PF-co-PS)。在合成的过程中用FTIR对中间体富马酸二丙二醇酯、癸二酸二羟丙酯以及PPF和P(PF-co-PS)的结构进行了表征。结果表明,随着聚合反应的进行,低聚物逐渐转化为聚合物PPF或P(PF-co-PS)。