Cationic ring-opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms

The ring-opening polymerization of hexamethylcyclodisilazane (D_2NMe), initiated by methyl triflate in 1,2-dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D_4NMe). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D_3NMe). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back-biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.     

Microfabrication by X‐ray‐induced polymerization above the lower critical solution temperature

A polymer synthesis method is presented in which chain growth driven by exothermic reaction stimulates a gradual chain collapse. The globular precipitates in such systems can be restrained from coalescing by polymerizing in a quiescent environment. Time‐resolved small‐angle scattering study of the methacrylic acid polymerization kinetics in a quiescent system above its lower critical solution temperature (LCST) in water reveals the following features of this method: (a) growing oligomers remain as rigid chains until a critical chain length is reached, at which they undergo chain collapse, (b) radius of gyration increases linearly with time until a critical conversion is reached, and (c) radius of gyration remains constant after the critical conversion, even while conversion is gradually increasing. Following this self‐stabilizing growth mechanism, we show that nanoparticles can be directly synthesized by polymerizing N‐isopropylacrylamide above its LCST in water. The average size of nanoparticles obtained from a polymer–solvent system is expected to be the maximum extent of reaction spread at that monomer concentration. This hypothesis was then verified by polymerizing N‐isopropylacrylamide above their LCST in water, but by initiating the reaction with X‐rays shielded by a mask. The microfabricated patterns conform well to the size and shape of the mask used confirming that the growing chains do not propagate beyond the exposed regions as long as the reaction temperature is maintained above the LCST. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 429–425, 2006     

纳米镓/聚甲基丙烯酸甲酯复合材料的原位超声合成与表征

超声作用于低熔点金属镓,使其超细化为纳米级的镓粒子,并采用无引发剂的乳液聚合方法制备出GA/聚甲基丙烯酸甲酯(PMMA)纳米复合粒子,并分析了其微观结构。结果表明纳米镓的形态和结构因有无表面改性剂而不同;乳液聚合得到的纳米镓复合粒子是核壳结构型,粒子大小为50~80 NM,内核金属镓粒径为30~50 NM,与聚合物存在一定的化学作用。     

有机镍化合物催化烯烃聚合的研究进展

综述了有机镍化合物如烯丙基镍、乙酰丙酮镍、茂镍、二亚胺镍等催化烯烃聚合的研究进展。有机镍化合物可催化烯烃、α-烯烃(如乙烯、丙烯等)的齐聚及聚合、催化极性单体(如甲基丙烯酸甲酯、降冰片烯等)以及位阻较大的环烯烃、取代二烯烃、苯乙烯等的均聚和共聚。     

用两亲聚合物制备大颗粒苯丙乳液

分别以两亲聚合物P(C9-AA)和P(DCPD-St-α-St-AA)作乳化荆，研究了制备大颗粒(约1μm)及具有一定稳定性的苯丙乳液的方法，讨论了乳化剂，温度及引发剂用量对乳液性能的影响。结果表明，以P(C9-AA)作乳化剂时，引发剂用量为单体质量的1．2％，90℃时可以合成性能良好的苯丙乳液；以P(DCPD-St-α-St-AA)作乳化荆时，引发剂用量为单体质量的1．2％，80℃时可以合成性能良好的苯丙乳液。     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Restraining the associations of anthracene fluorophore by chemically linking to poly(methyl methacrylate)

Associations (dimer or aggregate) of anthracene (An) fluorophores tend to interrupt the monomer emission and reduce the quantum yield (Φ_PL); therefore, poly(methyl methacrylate) (PMMA) chain was used in this study to chemically link to anthracene and to block the mutual associations among the anthracene fluorophores. With this aim, the target polymers were prepared by anionic polymerizations with 9,10‐dibromoanthracene/s‐butyllithium as initiating system to proceed polymerizations of methyl methacrylate (MMA) directly or in the presence of 1,1‐diphenylethylene (DPE). Use of DPE before addition of MMA produces stable initiating anionic species and avoids potential side reactions during polymerization; however, it also introduces four β‐phenylene rings around the central anthracene ring, which interfere with the corresponding emission pattern and reduce the Φ_PL (32%) value due to potential interactions between phenylene rings and anthracene. On the contrast, polymerization without participation of DPE results in polymer with central anthracene ring directly connected to two PMMA chains, which gives clean vibronic emission pattern with limited association emissions and enhanced Φ_PL (52%) value. Physical blending of anthracene by PMMA is less efficient to restrain the associations and results in a film of lower Φ_PL (20%). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of branched polyacrylonitrile through self‐condensing vinyl copolymerization

Branched polyacrylonitrile (PAN) was prepared through a self‐condensing vinyl copolymerization of acrylonitrile and 2‐(2‐bromopropionyloxy)ethyl acrylate (BPEA). The branched architecture of the product was confirmed by NMR spectra and the average degree of branching (DB ) was estimated. Through a comparison of the intrinsic viscosity of the product with that of its linear analogue, the contraction factor g′ was calculated. It was found that the viscosity of the branched PAN was obviously lower that that of linear PAN. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of three crosslinkers on colored pH‐responsive core–shell latexes

Environmentally responsive hydrogels have become attractive research subjects for many applications. In this work, a series of pH‐sensitive and color‐changing nanoparticles (nanogels) with core–shell structures were synthesized. The cores were blue latex particles synthesized by a miniemulsion technique with styrene and methacrylic acid as monomers and Neozapon Blue 807 as a dye. The shell was a pH‐sensitive polymer that was precipitation‐polymerized onto the core from 2‐(diethylamino) ethyl methacrylate with N,N′‐methylenebisacrylamide, poly(propylene glycol) diacrylate, and divinylbenzene as crosslinking agents. In the resultant latexes, the color was observed to change from deep blue to pale blue as the pH of the system was changed from a high of 10 to a low of 3. The synthesized latexes and particles (gels) were then characterized with an ultraviolet–visible spectrometer, dynamic light scattering, Fourier transform infrared, and nuclear magnetic resonance. Atomic force microscopy was also used to investigate the different morphologies of the particles after the synthesized latexes were dried at different pH values. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(methyl methacrylate)/silica nanocomposite through emulsion polymerization using dimethylaminoethyl methacrylate

Polymer/Silica nanocomposite latex particles were prepared by emulsion polymerization of methyl methacrylate (MMA) with dimethylaminoethyl methacrylate (DM). The reaction was performed using a nonionic surfactant and in the presence of silica nanoparticles as the seed. The polymer‐coated silica nanoparticles with polymer content and number average particle sizes ranged from 32 to 93 wt % and 114–310 nm, respectively, were obtained depending on reaction conditions. Influences of some synthetic conditions such as MMA, DM, surfactant concentration, and the nature of initiator on the coating of the silica nanoparticles were studied. Electrostatic attraction between anionic surface of silica beads and cationic amino groups of DM is the main driving force for the formation of the nanocomposites. It was demonstrated that the ratio of DM/MMA is important factor in stability of the system. The particle size, polymer content, efficiency of the coating reaction, and morphology of resulted nanocomposite particles showed a dependence on the amount of the surfactant. Zeta potential measurements confirmed that the DM was located at the surface of the nanocomposites particles. Thermogravimeteric analysis indicated a relationship between the composition of polymer shell and polymer content of the nanocomposites. The nanocomposites were also characterized by FTIR and differential scanning calorimetry techniques. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008