乳液聚合中单体醋酸乙烯酯与保护胶体聚乙烯醇的接枝反应研究

研究了以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,聚乙烯醇与单体的接枝反应。探讨了引发剂用量、聚合反应温度、保护胶体聚合度等因素对接枝反应的影响。     

本体聚合中的预热和过滤

讨论了本体聚合中预热和过滤的顺序，对冷过滤、热过滤的优缺点进行了探讨，提出了建议     

原位聚合制备尼龙6/纳米SiO2复合材料研究

对原位聚合制备尼龙6／纳米SiO2进行研究。结果表明，无论是否对纳米SiO2复合材料进行偶联化处理，其表面均将在原位聚合过程中与尼龙6产生接枝；SiO2表面接枝物的生成，可在某种程度上造成体系结晶程度的降低，但复合体系的力学性能主要由SiO2粒子的分散程度、粒子和其体之间的相界面性质等因素决定；采用经偶联剂处理并具有较小粒径和较大比表面积的SiO2对尼龙6进行复合，可使复合体系的力学性能指标达到较高的水平，且硅烷偶联剂的最佳用是为SiO2的3％左右。     

用金属卟啉络合物引发合成高分子量聚醚

介绍了用四苯基卟啉铝络合物催化体系合成高分子量聚醚的方法。该聚合过程显示出一种持续特性。产物具有均一的链长和极窄的分子量分布，且数均分子量Ｍｎ可通过改变单体与引发剂的摩尔比来控制。     

Well-defined polymer precursors synthesized by RAFT polymerization of N,N-dimethylacrylamide/N-acryloxysuccinimide: random and block copolymers

N,N-dimethylacrylamide (DMA) and N-acryloxysuccinimide (NAS) were copolymerized by the reversible addition–fragmentation chain transfer (RAFT) polymerization technique, to obtain random and block copolymer precursors onto which different side-groups may be statistically grafted via the reactive NAS units. These reactive copolymers have interesting applications in various fields such as coatings and paints, water purification and biology. Random poly(DMA-co-NAS) copolymer chains were synthesized with a 75/25 molar ratio, high conversion, an excellent molecular weight (MW) control from 5000 to 130 000 g mol⁻¹, and low polydispersity index (M_w/M_n<1.1). Poly(DMA-b-NAS) block copolymers were synthesized by a two step method, in which a poly(DMA) homopolymer was prepared first and then used as macro-chain transfer agent to polymerize NAS. For example, a poly(DMA-b-NAS) sample was obtained with an average molecular weight of 44 300/7400 g mol⁻¹ corresponding to 447 DMA and 44 NAS units. Such block copolymers had not yet been synthesized by any controlled polymerization technique. They can be used to prepare polymers with exactly the same backbone and an increasing number of different side groups (e.g. hydrophobic, ionic or fluorescent).     

Novel fluorescent polynorbornenes with multi-functional armed structure by using highly stable block macroinitiators via a combination of living ring-opening metathesis polymerization and atom transfer radical polymerization

Novel organosoluble fluorescent polynorbornenes with multi-functional armed structure were designed and prepared by using highly stable block macroinitiators via a combination of living ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). A bromo-containing functional norbornene (NBMBr) was prepared from the Diels-Alder reaction of cyclopentadiene and allyl bromide. The diblock copolymer of 5-(N-carbazolyl methyl)bicycle[2.2.1]hept-2-ene (CbzNB) and NBMBr was successfully prepared using living ROMP and used as a novel macroinitiator [poly(CbzNB-b-NBMBr)] for ATRP. Carbazoyl-containing multi-functional armed copolymer with poly(methyl methacrylate) (PMMA) was prepared by using poly(CbzNB-b-NBMBr) as a macroinitiator for ATRP. Strong fluorescence emissions (370-450 nm) were observed in the low excimer-forming multi-functional armed fluorescent polynorbornenes. The fact is that low excimer-forming carbazole-containing polymeric compound would apparently be favorable in photoconductive materials. The multi-functional armed structure make this compound an attractive candidate for applications as multi-modified hole transport materials in molecular electronic devices. Multi-modification could be further considered to be carried out by using such a functional bromo group at the end of multi-arms.     

Radical entry mechanisms in redox-initiated emulsion polymerizations

The mechanisms and kinetics of radical entry in emulsion polymerizations utilizing redox initiation are investigated using polymerization rate data obtained by reaction calorimetry and electrospray mass spectroscopy analysis of initiator-derived aqueous-phase products. These data have been used to evaluate an initiation scheme for redox-initiated emulsion polymerizations of common monomers such as styrene and methyl methacrylate based around the oxidant, tert-butyl hydroperoxide. Redox initiators are broadly classed by the solubility of their radical products: Hydrophilic radicals enter by propagating to a critical degree of polymerization to become surface-active whilst more hydrophobic radicals may enter particles directly. When direct entry is applicable (the hydrophobic case), initiation efficiency will always be very high.     

Synthesis of thermosetting poly(phenylene ether) containing allyl groups

New thermosetting poly(2-allyl-6-methylphenol-co-2,6-dimethylphenol)s (3) have been developed by oxidative coupling copolymerization of 2-allyl-6-methylphenol (1) with 2,6-dimethylphenol (2), followed by thermal curing. Copolymerization was conducted in nitrobenzene in the presence of copper(I) chloride and pyridine as the catalyst under a stream of oxygen, producing high molecular weight copolymers (M_n∼50,000) with broad molecular weight distributions (M_w/M_n∼35). The structure of resulting copolymers 3 was characterized by IR, ¹H, and ¹³C NMR spectroscopy. Cross-linking reactions of copolymers were carried out by thermal treatment in the absence or presence of a peroxide (3 wt%, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-butane). The 10% weight loss and glass transition temperatures of the cured copolymers were 436 °C in nitrogen and 235 °C, respectively after curing at 70 °C for 1 h and 300 °C for 1 h. The average refractive index of the cured copolymer (3b) film was 1.5407, from which the dielectric constant (ε) at 1 MHz was estimated as 2.6. The ε and dissipation factor of copolymer-films at 1 MHz were directly measured from their capacitances as 2.5-2.6 and 0.0015-0.0019, respectively.     

Knowledge and Belief: Some Clarifications

The notions of knowledge and belief play an important role in philosophy. Unfortunately, the literature is not very consistent about defining these notions. Is belief more fundamental than knowledge or is it the other way around? Many accounts rely on the widely accepted strategy of appealing to the intuition of the reader. Such an argumentative methodology is fundamentally flawed because it lets the problems of common sense reasoning in through the front door. Instead, I suggest that philosophical arguments should be based on formal-computational models to (a) reduce the ambiguities and uncertainties that come with intuitive arguments and reasoning, and (b) capture the dynamic nature of many philosophical concepts. I present a model of knowledge and belief that lends itself to being implemented on computers. Its purpose is to resolve terminological confusion in favor of a more transparent account. The position I defend is an antirealist naturalized one: knowledge is best conceived as arising from experience, and is fundamental to belief.     

Controlling the diffusionless Lorenz equations with periodic parametric perturbation

Diffusionless Lorenz equations (DLE) are a simple one-parameter version of the well-known Lorenz model, which was obtained in the limit of high Rayleigh and Prandtl numbers, physically corresponding to diffusionless convection. A simple control method is presented to control chaos by using periodic parameter perturbation in DLE. By using the generalized Melnikov method, the parameter conditions could be obtained to guide the controlled DLE to a low-periodic motion. Moreover, the existence conditions of periodic orbits and homoclinic orbits in the system are given. Some results of the numerical simulation are also explained clearly by a rigorous analysis.