Polymerization strategies to overcome limiting monomer conversion in silicone-acrylic miniemulsion polymerization

The limiting conversion phenomenon observed in high solid content silicone-modified acrylic miniemulsion polymerizations was investigated. It was found that the limiting conversion was mainly due to the formation of inactive radicals upon propagation of butyl acrylate radicals with the vinyl end groups of the polydimethylsiloxane. Polymerization strategies that allowed overcoming this problem and achieving high monomer conversion were implemented.     

间歇式液相本体聚丙烯装置计算机控制与管理系统

介绍一种间歇式液相本体聚丙烯装置计算机先进控制与管理系统。它是由“基本控制层”和“上位控制层”构成的经济适用型集散控制装置。该装置采用了多屏显示技术、网络通讯技术、PLC程控技术、ActiveX控件技术和面向对象程序设计方法、数据库技术以及闭环辩识、预测控制、反应优化、底层PID控制与上层先进控制无扰动自动切换等多种技术和控制方式，因而可以灵活有效地实现聚合反应的全过程自动化生产和安全保护。     

Polymerization behavior and polymer properties of eosin-mediated surface modification reactions

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eightfold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from fivefold lower eosin surface densities (2.8 versus 14 eosins/μm²) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities.     

CpTi(dbm)Cl_2催化烯烃聚合及其聚合物性质

开发了一种新型非茂聚烯烃催化剂———CpTi(dbm)Cl2,考察了催化剂在均相及负载条件下对乙烯及乙烯-1-己烯共聚的催化行为。催化剂在均相条件下对乙烯聚合的催化活性较低,但用MgCl2和MgCl2/SiO2复合双载体对催化剂进行负载后,催化乙烯聚合具有非常好的催化活性。催化剂还具有良好的共聚能力及良好的氢调敏感性。     

新型聚丙烯酸(934P、980)树脂的制备

详细研究了以乙酸乙酯和环己烷为溶剂，丙烯酸为单体，BPO，LPO，AIBN为引发剂，聚烯基多醚为交联剂，合成增稠能力强、透明度高的聚丙烯酸树脂。于混和溶剂存在下制得的聚合物，消除了以往由二氯甲烷为溶剂的反应介质中所得产品的毒性，可广泛应用于医药及日用化工等行业。     

水溶性聚偶氮酯的研究

用Ｐｉｎｎｅｒ合成方法制备了用ＰＥＧ４００封端的水溶性聚偶氮酯，并表征了其结构；研究了热分解反应动力学及用于乳液聚合的动力学。结果表明，该种引发剂具有引发速度快、热分解机理简单和具有辅助乳化作用等优点。     

Modelling of addition polymerization processes — Free radical,ionic, group transfer,and ziegler–natta kinetics

A brief review of addition polymerization processes is presented with a summary of the key characteristics classified by kinetic mechanism (free-radical, anionic, cationic, group transfer, or Ziegler–Natta), phase behavior, and reactor type. A practical approach to modelling in the industrial R & D environment is discussed in terms of a CAD package for polymerization processes.     

Effects of processing conditions on the curing of a vinyl ester resin

The effects of temperature, initiator, and accelerator levels on the curing of an epoxy bisphenol‐A vinyl ester resin Derakane® 411‐45 (formulated with styrene) were investigated by gel‐time and exotherm‐peak measurements on bulk samples. It was observed that the gel time was reduced as the initiator or accelerator ratio increased. Except at higher contents of the accelerator, a small kinetic plateau was seen in the gel curve and a shift of the maximum exotherm toward high temperatures in the DSC curves. This was explained by the dual role played by the accelerator species. A regression analysis of all gel‐time data showed a dependence of 3/2 order in the accelerator and first order in the initiator concentrations. Thus, for this polymerization initiation system, the gel time can be predicted for any initiator and cobalt levels and at any temperature within the ranges studied. The effect of the initiator on the unreacted styrene and vinyl ester was also examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1146–1154, 2002; DOI 10.1002/app.10403     

Radiation polymerization of acrylonitrile in a viscous system with styrene

Radiation polymerization of acrylonitrile in a viscous system with styrene was performed at ambient temperature by using γ‐rays. It is found that the overall rate of polymerization was accelerated after critical conversion due to the gel effect. As the molar fraction of styrene in monomer feed (f_St) is increased, both the total polymer conversion and molar fraction of acrylonitrile in the copolymer feed (F_AN) were decreased. The monomer reactivity ratios for acrylonitrile and styerne were determined to be r₁ (AN) = 0.25 and r₂ (St) = 2.0, respectively. The copolymers obtained were characterized by Fourier transformed infrared spectra (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), ¹H‐NMR, and pyrolysis mass spectrometry (PMS). It was found that the slight addition of styrene to acrylonitrile strongly changes crystallinity, morphology, and thermal decomposition of the resulting polymer. ¹H‐NMR measurment of AN/St copolymer showed the appearance of aromatic proton signals and shifted the resonance of the methylene proton to lower chemical shifts. The mass spectra of AN/St copolymers showed fragments of pyrolysates corresponding to oligonitriles with styrene end groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 268–275, 2002; DOI 10.1002/app.10324     

高分子量阴离子型聚丙烯酰胺的制备

介绍了聚丙烯酰胺的品种、性能及用途；研究了以丙烯酸为共聚单体，采用反相乳液聚合制备高分子量阴离子型聚丙烯酰胺胶乳的原理和方法；分析讨论了原料纯度、乳化剂和引发剂种类及操作条件等因素对产品性能的影响．