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.     

杂多酸催化合成(甲基)丙烯酸异冰片酯的研究

采用杂多酸作为催化剂合成了特殊单体丙烯酸异冰片酯和甲基丙烯酸异冰片酯，并对反应条件进行了优化，使反应收率达到86．1％，纯度≥99％。同时在200L的反应釜中进行了放大试验，放大试验的收率达到86．3％，略优于小试水平，此外对产品的应用性能进行了检测，达到国外同类产品的标准，具有很好的应用前景。     

Rheology of poly(n‐butyl methacrylate) and its composites with calcium carbonate

Poly(n‐butyl methacrylate) (PBMA) composites with calcium carbonate (CaCO₃) were prepared by in situ radical copolymerization of butyl methacrylate (BMA) and methacrylic acid (MA) with precipitated calcium carbonate. To compare the different rheological behaviors of the monomer mixtures with CaCO₃ and the composites, the steady and dynamic viscosities of BMA/MA/CaCO₃ and poly(BMA/MA/CaCO₃) were measured by means of steady and oscillatory shear flows. The viscosity of the mixture BMA/MA/CaCO₃ was found to increase evidently with the increasing of CaCO₃%. The influence of MA% on viscosity of BMA/MA/CaCO₃ was slight. During the in situ polymerization, the viscosity of the reacting system was measured to be enhanced by a factor of about 10⁴ from the monomer/CaCO₃ mixture to composites. The dependency of zero‐shear viscosity on molar mass of PBMA was also investigated. The relation between the zero‐shear viscosity and molar mass is η₀ = 10^?15 M_w^3.5. The evolution of the viscosity with the temperature for both PBMA and its composites was obtained and time–temperature superposition was used to build master curves for the dynamic moduli. The flow activation energies were found to be 115.0, 148.6, and 178.7 kJ/mol for PBMA, composite PBMA/CaCO₃ (90/10), and PBMA/MA/CaCO₃ (89/1/10), respectively. The viscosity of the composites containing less than 10% CaCO₃ was lower than that of pure PBMA with the same molar mass. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1376–1383, 2003     

阳离子型丙烯酸树脂的合成及其水溶性研究

以自由基聚合法合成了阳离子型丙烯酸树脂，通过稳定性比较考察了甲基丙烯酸缩水甘油酯(GMA)用量及树脂中和度对树脂水溶性的影响，用Zeta电位研究了中和度对胶体稳定性的影响，采用激光光散射仪(LLS)测定了胶体颗粒在水分散液中的流体动力学半径及分布，研究表明：当GMA用量为15％(质量分数)，中和度为80％时．体系中胶体颗粒具有足够的亲水性和良好的稳定性。     

超支化聚酯的合成及光固化性能研究

通过甲基四氢苯酐和环氧丙醇的开环聚合反应，一步法制备超支化聚酯，聚酯的数均摩尔质量为1450～2600g／mol，支化度在0．41～0．71之间。用甲基丙烯酸缩水甘油酯改性，合成了UV固化超支化聚酯，并对其光固化性能进行了初步研究，发现超支化聚酯能有效降低固化膜的线收缩率，聚酯的官能度越高，固化膜的硬度越大，固化速度越快，在约1s的固化时问内凝胶率超过75％。     

Small‐angle X‐ray scattering study of modified porous suspension–poly(vinyl chloride) particles

Small‐angle X‐ray scattering (SAXS) was applied to investigate the microstructure of unmodified and modified porous commercial suspension‐type poly(vinyl chloride) (PVC) particles. The modified PVC particles were prepared by an in situ stabilizer‐free polymerization/crosslinking of particles absorbed with a monomer/crosslinker/peroxide solution. The modifying polymers include styrene with or without divinyl benzene (DVB) as a crosslinker and methyl methacrylate (MMA) with or without ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The SAXS method was used to highlight the effect of polystyrene (PS) on the microstructure of PVC particles and to evaluate the characteristic lengths, both in the PVC/PS and the PVC/XPS (PS crosslinked with 0 and 5% DVB, respectively) systems. A model is suggested, where during the synthesis modification process, swelling of PVC by styrene and styrene polymerization occur simultaneously. PVC swelling by styrene causes destruction of the PVC subprimary particles, whereas styrene polymerization leads to phase separation resulting from incompatibility of the polymers. It was further suggested that because of PVC swelling by styrene, structure of the subprimary particles is lost. Therefore the characteristic lengths of PVC/PS and PVC/XPS, as calculated from the SAXS measurements, were attributed to the size of the phase‐separated PS and XPS inclusions, respectively. The SAXS method also shows that PMMA and XPMMA do not influence the PVC microstructure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1024–1031, 2005     

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.     

Kinetic and molecular weight control for methyl methacrylate semibatch polymerization. II. Open control

The gel effect will bring a violent increase of conversion for methyl methacrylate (MMA) polymerization in a short time. It will be very dangerous for the reactor, as it causes an increase of molecular weight and broadens the molecular weight distribution. To unify the kinetics, molecular weight, and its distribution, on the basis of the mathematical models for semibatch polymerization of MMA, three controlled objectives that are the heat load distribution index, the change in molecular weight, and molecular weight distribution index are presented. Three materials (monomer, solvent, and chain transfer agent) and their flow rate and feeding mode are analyzed for the open control of kinetics, molecular weight, and its distribution. The optimum flow rate and mode are obtained. The heat load distribution index and molecular weight distribution index are even less than 2.0 and 2.2, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4399–4405, 2006     

Interpenetrating polymer networks based on polyol modified castor oil polyurethane and poly(2‐ethoxyethyl methacrylate): Synthesis,chemical, mechanical,thermal properties,and morphology

Interpenetrating polymer networks (IPNs) of glycerol modified castor oil polyurethane (GC‐PU) and poly(2‐ethoxyethyl methacrylate) poly(2‐EOEMA) were synthesized using benzoyl peroxide as initiator and ethylene glycol dimethacrylate (EGDM) as crosslinker. GC‐PU/poly (2‐EOEMA) interpenetrating polymer networks were obtained by transfer molding. The novel GC‐PU/poly (2‐EOEMA) IPNs are found to be tough films. These IPNs are characterized in terms of their resistance to chemical reagents thermal behavior (DSC, TGA) and mechanical behavior, including tensile strength, Young's modulus, shore A hardness, and elongation. The morphological behavior was studied by scanning electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1029–1034, 2004