BoPhoz类膦-氨基膦配体在Rh-催化β-脱氢氨基酸酯的不对称氢化反应中的应用

将BoPhoz类膦-氨基膦配体应用在Rh-催化β-脱氢氨基酸酯的不对称氢化反应中,考察了配体结构及反应条件对反应结果的影响,并在优化的条件下研究了各种底物的适用范围,产物的对映选择性达81％ee．     

Preparation and properties of water‐absorbent composites of chloroprene rubber,starch, and sodium acrylate

The effects of the amounts of starch, sodium acrylate (NaAA) and dicumyl peroxide (DCP) on the properties of chloroprene rubber (CR)/starch/NaAA composites prepared by melting method were investigated. The results showed that the addition of starch improved the mechanical properties, but decreased the water‐absorbing capacity of the composite, most likely due to the decrease in the local concentration of the main water‐absorbing material sodium polyacrylate and the increase in crosslinking density of the composite resulting from the reaction between starch and CR. This reaction was verified by the vulcanized curves, DSC curves, and the cut surface morphology. The as‐prepared composite demonstrated higher water‐absorbing capacity, resulting from the incorporation of NaAA. The mechanical properties decreased with increasing the DCP loading, and the water‐absorbing ratio is the maximum at 1.0 phr DCP. The tensile strength of the composite decreased significantly after water immersion, due to the absorbed water acting as a plasticizer. The extracted component from composites after water immersion is mainly sodium polyacrylate according to Fourier transform infrared (FT‐IR) spectroscopy analysis. The morphology of the composites before and after water immersion was observed by optical transmission microscopy (OTM). The results indicated that the starch exhibits a good dispersion state, and the water‐absorbing capacity results primarily from sodium polyacrylate. Copyright © 2010 John Wiley & Sons, Ltd.     

Poly(D,L-lactide)-block-poly(2-hydroxyethyl acrylate) block copolymers as potential biomaterials for peripheral nerve repair: in vitro and in vivo degradation studies

The properties of poly(D ,L ‐lactide)‐block‐poly(2‐hydroxyethyl acrylate) (PLA‐b‐PHEA) block copolymers by means of in vitro / in vivo (rat) degradation are investigated and compared to those of PLA homopolymer. Over 12 weeks, we observe mass loss and molecular weight decrease. In vitro and in vivo findings are very similar for each polymer tested. When a short PHEA block is used (PLA‐b‐PHEA 15 000–3 000 g · mol^?1, 85/15 wt%), the degradation process is found to be very similar to that of homo‐PLA, and to be typical of a bulk erosion mechanism, with no mass loss observed until week 7 and continuous decrease of molar mass within this timeframe. For a longer PHEA block length within the block copolymer (PLA‐b‐PHEA 15 000–7 500 g · mol^?1, 65/35 wt%), the degradation mechanism is modified, with a significant mass loss observed at early times and only a slight decrease in molar mass. The latter finding is related to the pronounced hydrophilicity and softness of the material induced by the PHEA block, which allow easy diffusion and rapid leakage of the degradation residues from the material towards the aqueous medium. Schwann cells are found to better adhere on spin‐coated films of PLA‐b‐PHEA (85/15 wt%) than on PLA ones. These results show the potential of such hydrophilized PLA‐based copolymers for use in peripheral nerve repair.

     

Modification of porous suspension‐PVC particles by stabilizer‐free aqueous dispersion polymerization of absorbed acrylate monomers

The present study describes modification of porous PVC particles by polymerization of a monomer/crosslinker/peroxide solution absorbed within the PVC particles. The modifying crosslinked polymers include butyl acrylate (BA) crosslinked with ethylene glycol dimethacrylate (EGDMA) and ethylhexyl acrylate (EHA) crosslinked with EGDMA. The monomer solution is blended with the PVC particles by dry‐blending. The monomer absorbed particles are then polymerized in a stabilizer‐free aqueous dispersion‐polymerization. The modified semi‐IPN PVC particles have better stability than the neat PVC particles in packed columns for absorption of halo‐organics from water, etc. The modified semi‐IPN PVC particles are melt processable and thus have the potential of being interesting and useful modified rigid PVC materials. The modified PVC particles characterization includes polymerization yield, non‐extractables and porosity measurements and also morphology and dynamic mechanical behavior (DMTA). PBA and PEHA polymerization has shown high yield levels. The high conversion of BA and EHA within the particle, is partly due to their low solubility in water. The levels of non‐extractable fractions found are indicative of low chemical interaction between the polyacrylate/PVC phases in the particle. The modified PVC particle's porosity levels indicate that BA and EHA partly polymerize within the PVC particles' bulk and partly in the pores as crusts covering the PVC pore surfaces. This finding is supported by SEM observations of unetched and etched freeze fractured surfaces. Higher crosslinking levels of the polyacrylate modification promote compatibility with the PVC particles' bulk. DMTA measurements show two loss modulus peaks for the 0.5%EGDMA blends in the glass transition temperature region, suggesting imcompatibility. However, at 5%EGDMA a single transition is found exhibiting enhanced compatibility owing to the high degree of crosslinking, which prevents phase separation. Copyright © 2002 John Wiley & Sons, Ltd.     

On-line detection of emulsion polymerization by solid-state NMR spectroscopy

 The on-line detection of emulsion polymerization processes by means of solid-state NMR spectroscopy is demonstrated for the first time using poly(butyl acrylate) as a model system. Relatively short time intervals are accessible via ¹H detection while the use of ¹³C NMR spectroscopy results in an increased spectral resolution. Details of sample preparation and experimental techniques are given, while remaining artifacts of the preliminary results will be addressed in further investigations. Received: 7 November 1997 Accepted: 5 January 1998     

Preparation and physical properties of novel nonionic surfactants and their grafting copolymers with linear low density polyethylene (LLDPE)

Three nonionic surfactants, S1, S2, and S3 and their acrylates, AS1, AS2, and AS3, were synthesized with poly(ethylene oxide) and diols such as glycol, 1,6‐hexanediol, and 1,10‐decanediol as the main starting materials. Their chemical structures were characterized by means of Fourier transform infrared (FTIR) spectroscopy and ¹H NMR. The surface activity and surface tension (γ) of S1, S2, and S3 were evaluated by a drop weight method. The surface tension was found to decrease with the length of the lipophilic spacer in the molecular chains (γ_S1 < γ_S2 < γ_S3). AS1, AS2, and AS3 were adopted as functionalizing monomers and grafted onto linear low density polyethylene (LLDPE) with a melt reactive extrusion procedure. The graft degrees of LLDPE were determined by FTIR. Three grafted LLDPE samples with grafting degrees of 1.16% (AS1), 0.82% (AS2), and 0.71% (AS3) were prepared. Thermal and rheological properties of grafted LLDPE samples were studied with differential scanning calorimetry and a rotational rheometer. Crystallization rates of grafted LLDPE were faster than that of plain LLDPE at a given crystallization temperature because graft chains could act as nucleating agents. The isothermal crystallization behavior of grafted LLDPE was in accordance with the Avrami model only in the first stage, and deviated from the model with an increase in the crystallization time. Shear thinning at high shear rates and shear thickening at low shear rates were observed for the grafted LLDPE. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 314–322, 2005     

Interpolymer association between hydrophobically modified poly(sodium acrylate) and poly(N-isopropylacrylamide) in water: The role of hydrophobic interactions and polymer structure

The association between hydrophobically modified poly(sodium acrylate) (HMPA) and poly(N-isopropylacrylamide) (PNIPAM) in aqueous solution was studied using turbidimetry, viscometry and fluorescence measurements. Both the polymeric and the amphiphilic nature of the HMPA influence the association process. The tendency for association, as reflected by the increase in the cloud point and the reduced viscosity of PNIPAM, increases with the length of the alkyl group and the degree of substitution of HMPA. The fluorescence study, using pyrene as a probe, ascertains that the association is of hydrophobic nature and the association process is gradual and less cooperative than the association of PNIPAM with ionic surfactants. When high molar mass HMPA is used, the hydrophobic association between HMPA and PNIPAM leads to the formation of a reversible network with significantly enhanced thickening properties as compared to the thickening ability of the corresponding pure HMPA in aqueous solution.     

Synthesis of a thermoresponsive shell‐crosslinked 3‐layer onion‐like polymer particle with a hyperbranched polyglycerol core

A novel thermoresponsive shell crosslinked three‐layer onion‐like polymer particles were prepared using hyperbranched polyglycerol (PG) as parents compound, the periphery hydroxyl groups of PG were transformed into trithiocarbonates (? SC(S)S? ) first; then, it was used as chain transfer agent to prepare star‐like block copolymer of N‐isopropyl acrylamide (NIPA) and N,N‐dimethylaminoethyl acrylate (DMA) in sequence via reversible addition fragmentation chain transfer (RAFT) process. Thus, a three‐layer polymer, PG? [SC(S)S? (DMA)? b? (NIPA)]_n, was obtained. The middle layer of poly(DMA) was then crosslinked with 1,8‐diiodoctane, and the resulting onion‐like three‐layer polymer showed a lower critical solution temperature (LCST) in water because of the outer layer of poly(NIPA). The LCST value only slightly depended on the crosslinking degree. Finally, the ? SC(S)S? were transformed into thiols by sequential treating with sodium borohydride and formic acid; thus, the core molecule was chemically detached from the crosslinked shell and a novel shell crosslinked polymer particle was obtained. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5652–5660, 2005     

Optimization of the synthesis of poly(octadecyl acrylate) by atom transfer radical polymerization and the preparation of all comblike amphiphilic diblock copolymers

The atom transfer radical polymerization of octadecyl acrylate (ODA) has been investigated and optimized to produce polymers with predetermined molecular weights and narrow polydispersities (<1.2). The poor solubility of the catalytic system formed with conventional ligands such as the N‐(n‐propyl)‐2‐pyridylmethanimine and 2,2′‐bipyridine with Cu(I)Br in nonpolar reaction conditions gave poor control over molecular weight characteristics in ODA polymerizations. The use of N‐(n‐octyl)‐2‐pyridylmethanimine in combination with Cu(I)Br yielded a more soluble catalyst that improved control over the polymerization. The products from the polymerizations were further improved when an initiator, octadecyl 2‐bromo‐2‐methyl‐propanoate, similar in structure to the monomer, was used. Together, these modifications produced polymerizations that showed true controlled character as well as products with predetermined molecular weights and narrow polydispersities. Diblock copolymers of PODA were prepared with methyl methacrylate (MMA) and olig(oethylene glycol) methyl ether methacrylate (OEGMA). The PODA‐block‐POEGMA copolymers are the first examples of all comblike amphiphilic block copolymers. One of PODA‐block‐POEGMA copolymer samples has been shown to self‐assemble as micelles in a dilute aqueous solution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1129–1143, 2005