用甲基丙烯酸改善PMMA光纤芯材的耐热性

用甲基丙烯酸(MAA)改性PMMA,使其维卡软化点提高了20~23℃,透光率未降低。     

High glass transition and thermal stability of new pyridine-containing polyimides: Effect of protonation on fluorescence

A new diamine monomer containing heterocyclic pyridine and triphenylamine groups, 4-(4,4′-diaminotriphenylamine)-2,6-bis(4-methylphenyl)pyridine (4), was synthesized by Chichibabin and nucleophilic fluoro-displacement reactions. The diamine was used to prepare a series of novel polyimides via polycondensation with various aromatic tetracarboxylic dianhydrides in N-methyl-2-pyrrolidinone. The polyimide 4a derived from the diamine 4 with 4,4′-hexafluoroisopropylidenediphthalic anhydride and having high T_g (313 °C), mechanical, and thermal properties was soluble in various organic solvents, such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, pyridine, chloroform, tetrahydrofuran, at room temperature. The polyimide (4a) could be cast into a self-standing film from DMAc solution and was thermally converted into tough and flexible film. The film had high tensile modulus of 2.2 GPa and exhibited excellent thermal stability in both nitrogen and air (T_d¹⁰ > 550 °C). The pristine polymer exhibited the UV-vis absorption bands in the region 240-400 nm and protonated polymer exhibited absorption in the region 390-500 nm. The protonated polymer possessed strong orange fluorescence (around 600 nm) in THF solution after protonation with acids as excited at 438 nm. The fluorescent intensity was influenced by the acid concentrations and the chemical structure of conjugated bases. The fluorescent intensity at 600 nm increased as acid concentration from a lower to a moderate concentration and decreased at higher concentrations.     

N-异丙基丙烯酰胺高分子水凝胶研究进展

N-异丙基丙烯酰胺基高分子水凝胶的研究进展做了综述。简要介绍了该类水凝胶的合成方法,重点分析了不同共聚单体及交联剂对水凝胶溶胀性能和环境响应性的影响,尤其是快速响应水凝胶的合成方法和N-异丙基丙烯酰胺/天然大分子水凝胶的特点。本文也简单介绍了该类水凝胶在不同领域内的应用。     

pH值对N-异丙基丙烯酰胺与甲基丙烯酸共聚形成微凝胶的影响

在pH值为4．0和7．0的水介质中分别采用乳液聚合法使N-异丙基丙烯酰胺（NIPAM）和甲基丙烯酸（MAA）共聚,合成了具有温度／pH双重刺激响应性的P（NIPAM—CO—MAA）共聚微凝胶。傅立叶红外变换光谱、元素分析和电位滴定分析结果表明,在pH为4．0条件下合成的微凝胶中MAA单元含量偏高,微凝胶的粒径随着MAA用量的增加而增大,而pH为7．0时合成的微凝胶的粒径随着单体MAA用量的增加而减小。通过动态激光光散射测试P（NIPAM—CO—MAA）微凝胶的动力学直径随介质温度或pH值的变化关系发现,pH为4．0条件下合成的微凝胶具有更明显的pH刺激响应性,其温度刺激响应性受介质pH值的影响较大,表明MAA单元有可能更均匀地分布于微凝胶聚合物网络中。     

Permeability of heterogeneous membranes based on methacrylic acid

The permeability of H⁺, Na⁺, insulin, and hemoglobin through porous membranes made of crosslinked poly(methacrylic acid) was investigated at different pH values on both sides of the membrane. It was shown that a change in the charge of the protein during its transport through the membrane might raise the driving force of the process so much that the permeability coefficient of the protein through the membrane would be higher than in solution. In the case reported here, the flow of the protein may be regarded as partial electrophoresis in a porous medium.     

The glass transition behaviour and thermodynamic properties of amorphous polystyrene

The effect of molecular weight (MW) and thermal history on the heat capacity (c_p) of amorphous polystyrene over the temperature range from 200–440 K has been measured using differential scanning calorimetry (d.s.c.) General equations are given that show the influence of MW on c_p in both the glassy and liquid states. An enthalpic definition of the glass temperature reflects changes in the glass structure, due to thermal history, that are not found using conventional d.s.c. constructions. Thermodynamic and statistical mechanical theories give reasonable approximations to the observed T_g-MW curve but small systematic deviations are found. The effect of thermal history on T_g can be reproduced using a MW-dependent activation enthalpy.     

Mg-substituted hydroxyapatite nanopowders: Synthesis,thermal stability and sintering behaviour

This paper reports a systematic investigation on Mg-substituted hydroxyapatite (Ca_10?xMg_x(PO₄)₆(OH)₂) nanopowders produced by precipitation of Ca(NO₃)₂·4H₂O and Mg(NO₃)₂. The Mg content ranged between 0.6 and 2.4 wt%. Semicrystalline Mg-substituted hydroxyapatite powders made up of needle-like nanoparticles were obtained, the specific surface area ranged between 87 and 142 m²/g. Pure hydroxyapatite nanopowder decomposed around 1000 °C. Mg-substituted hydroxyapatites were thermally stable up to 660 °C (x = 1.0), 760 °C (x = 0.5) and 840 °C (x = 0.25) showing a distinct decreased thermal stability with respect to the pure sample.A relevant displacement of the sintering curve at lower temperature as a function of Mg content was observed, comparing to the behaviour of a pure HAp material, synthesized following the same procedure, and ascribed to the β-TCP formation.     

The potentiometric behaviour of copolymers of methacrylic acid in water-ethanol solutions

Summary The synthesis is reported of copolymers of styrene with methacrylic acid and of methyl methacrylate with methacrylic acid by radical copolymerization, of copolymers of methyl methacrylate with methacrylic acid by partial alkaline hydrolysis of poly(methyl methacrylate), and of block copolymers of styrene with methacrylic acid. Modified titration curves of all these copolymers were recorded in water and water-ethanol solutions. In a solution containing 50 mass.% ethanol, only small differences could be observed between the potentiometric behaviour of the individual copolymers and polymethacrylic acid. Also, there were no essential differences in any of the solvents used between the potentiometric behaviour of block copolymers of styrene with methacrylic acid, on the one hand, and polymethacrylic acid, on the other. On the contrary, maxima and minima were always observed on the modified titration curves of statistical copolymers with a higher content of the hydrophobic comonomer in solutions with a high water content. Thus, using the modified titration curves, it is possible to decide whether a given copolymer is of the block or statistical type.     

Synthesis and characterization of hydrogels based on gamma irradiation of acrylic acid and methacrylic acid

In this work, hydrogels based on different ratios of acrylic acid (AAc) and methacrylic acid (MAc) monomers were prepared by gamma radiation copolymerization. The hydrogels were characterized by IR spectroscopy and thermogravimetric analysis (TGA). The effect of temperature and pH on the degree of swelling of AAc/MAc hydrogels was also studied. The results showed that the gel fraction of AAc is relatively higher than MAc, while the gel fraction of AAc/MAc hydrogels decreased slightly with increasing the ratio of MAc monomer in the initial solution. The IR spectroscopic analysis indicates the formation of copolymer networks and the presence of hydrogen bonding. The thermal study showed that PAAc hydrogel displayed higher thermal stability than PMAc and AAc/MAc hydrogels, over the studied compositions. The results showed that PAAc hydrogel reached equilibrium swelling state in water after 4 h, whereas PMAc and AAc/MAc hydrogels reached the equilibrium after 7 h. In this regard, AAc/MAc hydrogels showed degree of swelling in water lower than PAAc and higher than PMAc hydrogels. It was found that the swelling of the hydrogels based on AAc and MAc monomers or their copolymers increases with increasing temperature up to 50°C. Moreover, it was observed that the degree of swelling of hydrogels were not affected by increasing the pH values up to 4 and increased greatly within the pH values from 5 to 9. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Poly(butylene terephthalate) modified with ethoxylated bisphenol S with increased glass transition temperature and improved thermal stability

Novel copolyesters have been prepared by polycondensation and by melt mixing of poly(butylene terephthalate) with an ethoxylated bisphenol S. No side reactions occur during the synthesis of the samples, as proved by NMR analysis. The polyesters were examined by TGA and DSC. The insertion of the bisphenol S (sulfonyldiphenol) group significantly improved the thermal stability of the polymer. The thermal analysis carried out using DSC technique showed that the T_m of the copolymers decreased with increasing co-unit content, differently from T_g, which on the contrary increased, exceeding in some cases 100 °C, and crystallization rate decreased. A polymer containing only terephthalate moieties and ethoxylated bisphenol S has been prepared for the first time.     

Synthesis of thermal stability and wear resistance of glass ceramics

Translated from Steklo i Keramika, No. 5, pp. 12–13, May, 1990.     

Morphology and glass transition of thin polylactic acid films

The aim of this study is to highlight the effect of the morphology of polylactic acid (PLA) thin films on the glass transition in this confined geometry. For that purpose, poly(L ‐lactic acid) and poly(D ‐lactic acid) polymer films were prepared on different surfaces such as mica and silicon surfaces by using two different solvents. The films exhibit different morphologies starting from individual macromolecular chains at very low concentration to homogeneous films at higher concentrations. Globular to elongated rodlike structures of the PLA macromolecules were observed according to the polarity of the surface and the solvent. The T_g of PLA enantiomeric film, determined by adhesion force using atomic force microscopy (AFM) as a function of temperature, was confirmed by ellipsometric measurements. Surprisingly, this value is independent of the morphology of thin enantiomeric film. A balance between the attractive surface effects and a decrease of the crystallinity of PLA on the mobility in the amorphous region will be discussed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of sepiolite on glass transition temperature and melting behaviour of semicrystalline polymer blends

Summary Thermal analysis of blends poly(vinylidene fluoride) (PVF₂) with poly(methyl methacrylate) (PMMA) or polystyrene (PS) filled with sepiolite was carried out to examine the effects of the filler on properties such as melting behaviour and glass transition temperature. For the compatible PVF₂/PMMA system, the presence of the filler did not cause any substantial changes in the thermal behaviour of the blend. In the non-compatible PVF₂/PS system, some compatibilization is achieved in the blend, indicated by PVF₂ melting point depression as well as by a shift of the glass transition of the homopolymers in the blend.     

Self-assembly of hydrophobic polybetaine based on (tridecyl)aminocrotonate and methacrylic acid

Novel polymeric betaine based on tridecylaminocrotonate and methacrylic acid was synthesized by Michael addition reaction. The obtained products were abbreviated as CROtriDA-MAA and with respect to its potassium salt as CROtriDA-MAA-K. The structure of CROtriDA-MAA was established by ¹H NMR and FTIR spectroscopy. The hydrodynamic, molecular and conformational properties of CROtriDA-MAA-K in solutions and morphology in solid state were evaluated by methods of GPC, DLS, zeta-potential, surface enhanced ellipsoidal microscopy (SEEC), optical microscopy. Meanwhile, the long alkyl “tails” (tridecyl) located in side polymeric chains are responsible for self-assembling behavior. Several types of self-assembled structures in water at different pH and in water–DMSO mixture were observed. The dendritic structure with wide trunks and few side branches is formed at pH 3. The “Maltese cross-like” aggregates were found at pH 6.5. The tree-like fractal patterns are formed at pH 12. The self-assembled coiled-ribbon-like and tubular-like aggregates were observed in water–DMSO mixtures.     

Glass transition behavior of latex interpenetrating polymer networks based on methacrylic/acrylic pairs

Interpenetrating polymer networks (IPN's) of poly(alkyl methacrylates) and poly(alkyl acrylates) have been synthesized in latex form. Dynamic mechanical spectroscopy studies on these materials revealed extraordinarily broad glass transition regions, illustrating the semicompatible nature of these materials. In a true synergistic effect, the value of tan δ remains high and nearly constant over a broad temperature range for select compositions, emphasizing their potential value in noise and vibration damping applications. Compositionally identical latex IPN pairs were prepared by slow and rapid addition of monomer. The mechanical behavior of the resulting materials was similar and can be explained in terms of the core-shell model. A 50/50 isomeric homologous series of compositions was examined. After taking into account the relative difference between the glass transition temperatures of the methacrylic/acrylic pair, no substantial change in compatibility was noted throughout the series. Because the acrylic monomer II is roughly equally solvated by both the previously formed methacrylic polymer I and the nascent acrylic polymer II, extensive polymer I/polymer II mixing is encouraged, and sharp phase separation discouraged in these materials.     

Apparent anomalous thermal behavior of polymers undergoing a glass transition

Glass transitions in certain polymer samples were detected as a step change in a DTA trace in the exothermic sense. This anomaly is explained as a manifestation of the volume relaxation shown to occur at the glass transition in internally strained samples.     

Studies on thermal stability and behaviour of polyacetal and thermoplastic polyurethane elastomer blends

The influence of thermoplastic polyurethane (TPU) elastomer on the rigidity of polyacetal (polyoxymethylene, POM) was studied by determining heat deflection temperature (HDT). The higher the content of TPU in the POM/TPU blend, the lower the HDT of the blend, as would be expected. A comparative study of the recycle capability of POM and the blends was carried out by measuring melt flow index (MFI) on each successive extrusion. Stress-strain behaviour of the virgin material and that obtained after fourth-time extrusion was analysed for POM and the blends. The effect of γ-radiation on the mechanical behaviour of the blends was investigated. The kinetics of thermal degradation of POM, TPU and their blends was studied. The kinetic parameters, viz. activation energy and the order of reaction, were established. The values of the activation energy of the blends were found to be higher than those of the POM and TPU, indicating improved stability of the resultant blends.     

Phase transition and thermal stability of ceramics from Na-based geopolymers

Geopolymer ceramics undergo a series of thermal phase transitions, progressing from an amorphous geopolymer gel to a crystalline phase, and eventually to an amorphous glass phase as the temperature increases. However, there is a lack of mechanism understanding regarding to the crystallization process and the subsequent thermal degradation. Here, we fundamentally investigated the kinetics of nepheline formation in Na-based geopolymer systems and its thermal stability up to 1400°C. Nepheline crystallization is controlled by bulk nucleation and three-dimensional crystal growth based on the Avrami factor of 4.64, where the activation energy of nepheline formation is 350.59 kJ/mol. High thermal stability of geopolymer ceramics is achieved due to the appearance of nepheline up to 1400°C with the Si/Al ratio ranging from 1.40 to 1.94, while melting and amorphous structure are formed above a higher Si/Al ratio of 2.22. The nature of sintering for geopolymer ceramics consists of shrinkage, expansion and shrinkage corresponding to dehydroxylation, crystallization, and densification, leading to a thermal shrinkage of 21% at 1400°C.     

Highly porous thermal insulation material based on liquid glass

The studies show that liquid glass, due to its high adsorption capacity and low bloating temperature, can be used to manufacture thermal insulation materials. The synthesis methods for highly porous materials by the low-temperature bloating of liquid glass and a filler were proposed for the first time. The proposed techniques contribute to the uniform bloating throughout the volume and the homogeneity of the thermal insulation material for the equipment and pipelines.