Phase separation studies in RIM polyurethanes catalyst and hard segment crystallinity effects

Polyurethanes were prepared from pure 4,4′-diphenylmethane diisocyanate (MDI), 1,4-butane diol (BDO) or 1,2-ethane diol (EDO) and α,ω-hydroxyl poly(propylene oxide) (PPO) by reaction injection moulding (RIM). Hard segment (MDI + BDO or EDO) level was 45–50 wt%. The PPO had about 20% ethylene oxide copolymerized in at the chain ends to provide 80% primary OH end groups. M_n was varied from 2000 to 4000. Dibutyl tin dilaurate catalyst and mould temperature were varied. Dynamic mechanical, wide-angle X-ray, differential scanning calorimeter, molecular weight and tensile elongation measurements were made on the RIM polyurethanes. At low reaction rates (low catalyst or temperature) highly crystalline, well phase separated but low molecular weight polymers were produced. At high catalyst or temperature levels more poorly phase separated but high molecular weight, tough polymers resulted. Higher M_n PPO gave better phase separation and EDO gave higher melting temperatures. Preventing hard segment crystallinity by substituting asymmetric MDI or glycols resulted in phase compatibility.     

复合聚合物微粒乳液的制备与应用

对种子乳液聚合中加料方式、单体亲水性、引发剂等因素对复合微粒聚合物形成的影响作了介绍 ,总结了聚合物微粒形态预测的热力学和动力学方法。同时 ,讨论了复合聚合物微粒设计的原理并评述了其应用情况     

LLDPE及其催化剂技术进展

综述了线性密度聚乙烯（LLDPE）研究的最进展情况，特别对乙烯原位聚合工艺和后过渡金属镍、钯催化剂进行了详细的叙述，对我国LLDPE的生产提出了自己的看法。     

Halogen-induced charge transfer polymerization of pyrrole in aqueous media

Simultaneous polymerization and doping of pyrrole have been carried out in the presence of a halogenic electron acceptor, bromine (Br₂) or iodine (I₂), in aqueous dispersion or in a two-phase solvent system. The morphology of the polypyrrole (PPY) so produced is granular and porous. The electrical conductivity of the PPY-I₂ charge transfer (CT) complex is of the order of 10¹ ohm⁻¹ cm⁻¹ while that of the PPY-Br₂ complex is about one order of magnitude less. Both complexes are stable in the atmosphere. The physicochemical properties of the PPY-I₂ and PPY-Br₂ CT complexes prepared under various experimental conditions are examined in detail.     

新型阳离子聚丙烯酰胺微粒的研究--含PEO支链阳离子聚丙烯酰胺微粒的合成、助留性能及作用机理

本文采用反相微乳液聚合的方法合成了丙烯酰胺(AM)/丙烯酰氧基乙基三甲基氯化铵(AD-AMQUAT)/聚氧乙烯大单体(PEO-A)/N,N'-亚甲基双丙烯酰胺(Bis)的四元共聚物微粒.研究了该微粒助留剂的结构与性能.这种微粒和纸纤维能够通过离子键和氢键作用显著地增强助留效果.     

Control of structure and tack properties of acrylic pressure‐sensitive adhesives designed by a polymerization process

Free radical emulsion polymerization of methyl methacrylate (MMA) and 2‐ethylhexyl acrylate (EHA) results in the synthesis of pressure‐sensitive adhesives (PSAs) with good tack properties. Management of both the copolymer composition and the polymerization process allows one to control the behavior of the PSA. Semicontinuous (SC) processes create polymer particles whose instantaneous composition is close to that of the feed particle The SC Mixture process (continuous feeding with comonomer blends) affords nearly homogeneous latex particles and PSA films. The SC Gradient process (separate feedings at inversely varying rates) affords heterogeneous particles and films. The Batch process leads to somewhat heterogeneous films, but the hard (MMA‐rich) microdomains are made compatible with their soft (EHA‐rich) matrix because of the assumed formation of tapered‐type copolymers. Tack measurements indicate the importance of the particle and film structures. Too much hardness or softness leads to unacceptable lacks of adhesion and cohesion, respectively. Homogeneous structures prove adequate, but their tack properties collapse with rising temperature. Heterogeneous structures, with extensive phase segregation, prove unsatisfactory because they lack adhesion and cohesion. Finally, the association of well‐balanced composition and compatible heterogeneity is the criterion for suitable PSA behavior. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2749–2756, 2003     

丙烯酸酯与甲基丙烯酸酯的共聚及性能研究

采用悬浮聚合法，以丙烯酸－２－乙基－己酯与甲基丙烯酸十二酯为单体，合成了共聚型高吸油性树脂。研究了共聚单体的配比、交联剂用量、引发剂用量诸因素对高吸油性树脂的性能影响。制得的树脂可以吸其自身质量的１１．８倍的煤油、１４．７倍的苯、６．５倍的泵油。     

Surface tailoring of an ethylene propylene diene elastomeric terpolymer via plasma‐polymerized coating of tetramethyldisiloxane

In the research presented here, we explore the use of a low‐energy plasma to deposit thin silicone polymer films using tetramethyldisiloxane (TMDSO) (H(CH₃)₂? Si? O? Si? (CH₃)₂H) on the surface of an ethylene propylene diene elastomeric terpolymer (EPDM) in order to enhance the surface hydrophobicity, lower the surface energy and improve the degradation/wear characteristics. The processing conditions were varied over a wide range of treatment times and discharge powers to control the physical characteristics, thickness, morphology and chemical structure of the plasma polymer films. Scanning electron microscopy (SEM) shows that pore‐free homogeneous plasma polymer thin films of granular microstructure composed of small grains are formed and that the morphology of the granular structure depends on the plasma processing conditions, such as plasma power and time of deposition. The thicknesses of the coatings were determined using SEM, which confirmed that the thicknesses of the deposited plasma‐polymer films could be precisely controlled by the plasma parameters. The kinetics of plasma‐polymer film deposition were also evaluated. Contact angle measurements of different solvent droplets on the coatings were used to calculate the surface energies of the coatings. These coatings appeared to be hydrophobic and had low surface energies. X‐ray photoelectron spectroscopy (XPS) and photoacoustic Fourier‐transform infrared (PA‐FT‐IR) spectroscopy were used to investigate the detailed chemical structures of the deposited films. The optimum plasma processing conditions to achieve the desired thin plasma polymer coatings are discussed in the light of the chemistry that takes place at the interfaces. Copyright © 2004 Society of Chemical Industry     

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