PMMA‐modified divinylester/styrene resins: Phase diagrams and morphologies

Binary and ternary experimental cloud‐point curves (CPCs) for systems formulated with a low molar mass synthesized divinylester (DVE) resin, styrene (St), and poly(methyl methacrylate) (PMMA) were determined. The CPCs results were analyzed with the Flory–Huggins (F‐H) thermodynamic model taking into account the polydispersity of the DVE and PMMA components, to calculate the different binary interaction parameters and their temperature dependences. The St‐DVE system is miscible in all the composition range and down to the crystallization temperature of the St; therefore, the interaction parameter expression reported for a higher molar mass DVE was adapted. The interaction parameters obtained were used to calculate the phase diagrams of the St‐PMMA and the DVE‐PMMA binary systems and that of the St‐DVE‐PMMA ternary system at three different temperatures. Quasiternary phase diagrams show liquid–liquid partial miscibility of the St‐PMMA and DVE‐PMMA pairs. At room temperature, the St‐DVE‐PMMA system is miscible at all compositions. Final morphologies of PMMA‐modified cured St‐DVE materials were generated by polymerization‐induced phase separation (PIPS) mechanism from initial homogeneous mixtures. SEM and TEM micrographs were obtained to analyze the generated final morphologies, which showed a direct correlation with the initial miscibility of the system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4539–4549, 2006     

两步法合成大粒径丁苯胶乳

研究了聚甲基丙烯酸甲酯（MMA）对丁苯（BS）胶乳的附聚作用以增大丁苯胶乳粒径；探讨了无机盐、体系pH值及体系中MMA胶乳与BS胶乳的固含量比（R值）对附聚后丁苯胶乳的粒径及稳定性的影响。结果表明：适当添加无机盐可以稳定胶乳体系，最佳用量（质量分数）为0．1％～0．2％；适当增大体系pH值，可增大胶乳粒径；在附聚过程中，当R值在两个附聚峰附近时，可增大丁苯胶乳的粒径。     

Influence of composition and molecular mass on the morphology,crystallization and melting behaviour of poly(ethylene oxide)/poly(methyl methacrylate) blends

Results are reported on the influence of composition and molecular mass of components on the isothermal growth rate of spherulites, on the overall kinetic rate constant, on the primary nucleation and on the thermal behaviour of poly(ethylene oxide)/poly(methyl methacrylate) blends. The growth rate of PEO spherulites as well as the observed equilibrium melting temperatures decrease, for a given T_c or ΔT, with the increase of PMMA content.Such observations are interpreted by assuming that the polymers are compatible in the undercooled melt, at least in the range of crystallization temperatures investigated. Thermodynamic quantities such as the surface free energy of folding σ_e and the Flory-Huggins parameter χ₁₂ have been obtained by studying the dependence of the radial growth rate G and of the overall kinetic rate constant K from temperature and composition and the dependence of the equilibrium melting temperature depression ΔT_m upon composition, respectively.     

定向MWNTs/PMMA的原位聚合制备及耐磨损性

采用原位聚合方法制备了定向碳纳米管/聚甲基丙烯酸甲酯复合材料,并且研究了该复合物的耐磨损性.对定向碳纳米管及其复合物进行了傅立叶红外吸收光谱分析、扫描电镜及光学显微镜观察.采用砝码质量法评价了复合物的耐磨损性.分析结果表明,混酸处理后定向碳纳米管附带了-OH、-COOH基等极性基团.混酸处理后定向碳纳米管束状结构被破坏,定向碳纳米管可以单管形态分散于基体中,碳纳米管表面包覆着PMMA.砝码质量法耐磨损性测试结果表明,定向碳纳米管的加入可提高PMMA复合物的耐磨损性和耐划痕性,当定向碳纳米管用量为0.7%时,复合物的耐磨损性能提升了54%.     

VAc／MMA半连续乳液共聚合的研究：Ⅰ种子乳液共聚合

以过硫酸铵为引发剂，十二烷基硫酸钠为乳化剂，于７０℃下进行了ＶＡｃ＝ＭＭＡ种子乳液共聚合。试验考察了组分和操作条件对体系稳定性，聚合速度及组成分布等的影响，同时，从理论上给出了加料速率与体系稳定性因子间的关系。     

A RIS treatment of the mean-square dipole moment of PMMA chains in consideration of the pendant ester group orientations

According to the six-state scheme proposed by Vacatello and Flory, the mean-square dipole moments 〈M²〉/x (x: number of monomeric units) of poly(methyl methacrylate) (PMMA) chains and their temperature dependence were calculated by the matrix algebra method of rotational isomeric state theory. To take account of the orientation effect of polar ester groups, the statistical weight matrices, U′ and U″, were recast into an expanded form. A Bernoullian probability λ introduced to measure the preference between the two alternative orientations (χ=0 and χ=π) of the side ester groups was found to give rise to a large effect on the mean-square dipole moment of polymers. When the skeletal bonds of a meso dyad are both in trans, an exceptionally strong dipole-dipole interaction may take place. If the two adjacent ester groups adopt the same orientation, the dipoles must be situated nearly parallel to each other in a close proximity. Such repulsive interactions may be alleviated by taking a staggered conformation, i.e. (χ,χ′)=(0,π) or (π,0). Such neighbor-dependent correlation inherent to the meso dyad is considered by assigning a parameter λ′ to the proper element of the U_m″ matrix. The values of 〈M²〉/x observed at 30 °C were satisfactorily reproduced by adopting λ=0.270 and λ′=0.865. The thermal coefficients were found to be reconciled with the available experimental data by allowing the orientation parameters λ and λ′ to be slightly temperature dependent. The stereochemical characteristics of the chain terminals were examined in order to extend the treatment to include the dipole moment of PMMA oligomers.     

氯化聚乙烯对氯丁橡胶与甲基丙烯酸甲酯接枝共聚反应的影响

研究了高氯氯化聚乙烯(HCPE)对氯丁橡胶与甲基丙烯酸甲酯接枝共聚及其反应产物的影响。结果表明,HCPE能加快聚合速率,提高转化率、接枝效率和接枝度。含HCPE的产物,含有较高分子量的级份,分子量分布较宽,树脂相的分布比较均匀,并具有较好的机械性能和较高的粘接强度。     

MDYB-3有机玻璃裂纹扩展温度效应试验研究

随着对飞机性能要求的提高,对机用有机玻璃的要求愈来愈高.目前飞机舱盖玻璃表面温度在-55℃～100℃范围内变化,因此,研究飞机舱盖MDYB-3有机玻璃温度效应具有十分重要的意义.文中采用CT(compact tension)试样对MDYB-3有机玻璃在-50℃～90℃范围内进行裂纹扩展试验,研究温度对MDYB-3有机玻璃裂纹扩展速率的影响.应用线弹性断裂力学理论,分析不同环境温度下裂纹扩展速率与等效应力强度因子ΔK之间的关系.试验结果表明,MDYB-3有机玻璃随着温度升高,裂纹扩展速率减小,断裂韧度增大;低温时MDYB-3有机玻璃表现为脆性,裂纹扩展十分平滑,断面垂直于拉伸方向,温度较高时MDYB-3有机玻璃表现为粘性,裂纹扩展面凹凸不平.     

溶致相分离法制备液晶光开关研究

以溶致相分离的方法制备了聚甲基丙烯酸甲酯（PMMA）基聚合物分散液晶（PDLC）,并对影响其光开关效应的因素做了较为系统的研究。结果表明,液晶含量从40％增到50％使得PDLC体系的透过率从62％升高到80％,从而减弱了光开关效应。进一步增加液晶含量不提高体系的透过率,却使光开关效应愈发不明显;固化温度从室温（22℃）增大到液晶清亮点附近（55℃）,则显著提高了光开关效应。