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.     

电化学聚合研究进展

电化学聚合是近年来发展起来的一种新型的聚合方法，它除了可以合成一些常用方法所不能合成的聚合物外，还能改变某些聚合物的性能．现已广泛用于导电高分子的研究中．并具有潜在的工业化前景。本文从机理及应用方面综述了电化学聚合方法的研究进展。     

3,9-二羟甲基-3′,9′-二苯基-1,5,7,11-四氧杂螺环[5,5]十一烷的合成及聚合反应

利用苯乙醛与甲醛之间的坎尼扎罗反应合成２－苯基－２－羟甲基丙二醇，进而合成新的螺环化合物：３，９－二羟甲基－３′，９′－二苯基－１，５，７，１１－四氧杂螺环［５，５］十一烷．通过红外光谱、核磁共振氢谱和元素分析证实了它的组成和结构．在三氟化硼单乙胺络合物的作用下，该化合物能够进行双开环聚合反应．用膨胀计法跟踪测试了在聚合反应过程中它的体积膨胀率约为３．８％，并对聚合反应机理作了初步探讨．     

正交试验优化复合纳滤膜复合条件

采用聚砜基膜，以哌嗪水溶液与均苯三甲酰氯正己烷有机溶液发生界面聚合反应，在聚砜基膜上形成一超薄脱盐层，从而制备聚哌嗪酰胺复合纳滤膜．制备过程中影响复合纳滤膜性能的因素是多方面的．着重讨论了水相浓度、有机相浓度、有机相处理时间的影响．采用正交试验法对制备条件进行优化，制得性能较佳的复合纳滤膜．     

Biomimetic micropatterning of silica by surface-initiated polymerization and microcontact printing

Micropatterns of silica on a gold substrate were generated by a biomimetic approach, namely, the biosilicification of silicic acids. The procedure consists of three simple steps: pattern generation of a polymerization initiator, (BrC(CH(3))(2)COO(CH(2))(11)S)(2), by microcontact printing; surface-initiated, atom-transfer radical polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) from the patterned area; and polycondensation of silicic acids. The tertiary amine-containing polymer, pDMAEMA, aided in the spatially controlled polycondensation of silicic acids on surfaces in the presence of phosphate ions, and micropatterns of silica on a gold substrate were successfully generated in combination with the technique of microcontact printing. The procedure could be extended to the controlled fabrication of silica patterns with any size, shape, or thickness.     

P(MMA-AN)/TiO2复合粒子的制备及光催化性能

采用原位乳液聚合方法制备了基于共价键结合的P(MMA-AN)/TiO2复合粒子,红外光谱和热失重分析结果表明P(MMA-AN)在TiO2表面接枝率为15.9%。以甲基橙溶液为目标污染物,研究了P(MMA-AN)/TiO2复合粒子和TiO2对甲基橙的吸附和光催化降解甲基橙溶液的性能,结果表明:两种粒子对甲基橙的吸附都很少;在相同时间内,P(MMA-AN)/TiO2复合粒子对甲基橙溶液的降解性能优于TiO2,紫外光照180 min后,P(MMA-AN)/TiO2复合粒子对甲基橙溶液的降解率达到了88%,而TiO2仅为74%。     

低临界胶束浓度PEGMA-b-PCL的制备及其 药物缓释性能

以ε-己内酯（ε-CL）为疏水链段,聚乙二醇甲醚甲基丙烯酸酯（PEGMA）为亲水链段,4-氰基-4-[(十二烷基硫基硫羰基)硫基]戊酸（CDPA）为可逆加成-断裂链转移（RAFT）试剂,在以甲苯为溶剂、N2氛围、80 ℃、反应24 h的条件下,通过RAFT聚合法制备了两嵌段聚合物PEGMA-b-PCL。将其自组装为胶束用作纳米药物载体,并以姜黄素（Cur）为胶束负载药物。考察了两嵌段聚合物结构、分子量及分布,表征了胶束载体粒径、形貌,测试了胶束载体的载药和释药性能。结果表明,不同嵌段聚合物相对分子质量范围为478~7318,此类聚合物具有较低的临界胶束浓度（CMC）,在常规条件下（pH=7.4）其范围为0.920~1.600 μg/mL。胶束载体粒径范围为:68.34~186.30 nm。当n(CDPA)∶n(ε-CL)=1∶200时,胶束载药量和包封率最高,可达12.05%和75.26%。在不同pH值环境下,药物缓释性能可达15 d,其中pH=5.0时释药量可达35.38%。