Main chain and segmental dynamics of semi interpenetrating based on polyisoprene and poly(methyl methacrylate)

Main chain and segmental dynamics of polyisoprene (PI) and poly(methyl methacrylate)(PMMA) chains in semi IPNs were systematically studied over a wide range of temperatures (above and below T-g of both polymers) as a function of composition, crosslink density, and molecular weight. The immiscible polymers retained most of its characteristic molecular motion; however, the semi IPN synthesis resulted in dramatic changes in the motional behavior of both polymers due to the molecular level interpenetration between two polymer chains. ESR spin probe method was found to be sensitive to the concentration changes of PMMA in semi IPNs. Low temperature spectra showed the characteristics of rigid limit spectra, and in the range of 293-373 K.complex spectra were obtained with the slow component mostly arisingout of the PMMA rich regions and fast component from the PI phase. We found that the rigid PMMA chains closely interpenetrated into thehighly mobile PI network imparts motional restriction in nearby PI chains, and the highly mobile PI chains induce some degree of flexibility in highly rigid PMMA chains. Molecular level interchain mixing was found to be more efficient at a PMMA concentration of 35 wt.%. Moreover, the strong interphase formed in the above mentionedsemi IPN contributed to the large slow component in the ESR spectra at higher temperature. The shape of the spectra along with the data obtained from the simulations of spectra was correlated to the morphology of the semi IPNs. The correlation time measurement detected the motional region associated with the glass transition of PI and PMMA, and these regions were found to follow the same pattern of shifts in a-relaxation of PI and PMMA observed in DMA analysis. Activation energies associated with the T-g regions were also calculated. T-50G was found to correlate with the T-g of PMMA, and the volume of polymer segments undergoing glass transitional motion was calculated to be 1.7 nm(3).C-13 T-1 rho measurements of PMMA carbons indicate that the molecular level interactions were strong in semi IPN irrespective of the immiscible nature of polymers. The motional characteristics of H atoms attached to carbon atoms in both polymers were analyzed using 2D WISE NMR. Main relaxations of both components shifted inward, and both SEM and TEM analysis showed the development of a nanometer sized morphology in the case of highly crosslinked semi IPN. (C) 2010 Elsevier Ltd. All rights reserved.

COMPATIBILIZATION OF HIGH-DENSITY POLYETHYLENE/POLYISOPRENE BLENDS WITH POLYETHYLENE/POLYISOPRENE THREAD-THROUGH COPOLYMERS

The compatibilization of high density polyethylene (HDPE)/polyisoprene (PI) blends with polyethylene/polyisoprene (PE/PI) ''thread-through'' copolymers was investigated. The proliferating structure of PE/PI with segments chemically identical to HDPE and PI, respectively, is different from that of graft copolymers. Studies showed that the dispersed domain size in the blends was significantly reduced and interfacial adhesion was improved by the compatibilization action of the copolymer. In the differential scanning calorimetry (DSC) analysis, the crystallization peak of HDPE in the blends became broad with adding the copolymer and fractionated crystallization appeared in the HDPE/PI blend compatibilized with the copolymer at a weight ratio of 30/70 while it appeared in the blend without copolymer at a weight ratio of 20/80. DMA results showed that by adding the copolymer, both the glass transition temperature (T-g) of the PI component and the alpha-relaxation of HDPE shifted to lower temperature, demonstrating the enhanced penetration of the two components. Mechanical properties of the blends were improved, especially the elongation at break, by the presence of the copolymers. The characteristic yielding at the fractured surface of the blends compatibilized with the copolymer indicates the fractural behavior of the material changed from brittle to tough.

PREPARATION AND PROPERTIES OF THREAD-THROUGH COPOLYMERS OF POLYETHYLENE WITH POLYISOPRENE

Graft copolymers of polyethylene (PE) with polyisoprene (PI) were synthesized through polymerization of ethylene in toluene solution of PI (cis-1,4-: 95%; 3,4-: 5%) using a homogeneous V(acac)3/Et3Al2Cl3 catalyst. Copolymers are formed when the growing po

Synthesis and Characterization of Magnetic Composites Based on Cis-Polyisoprene and CoFe(2)O(4) Nanoparticles

CoFe(2)O(4) nanoparticles were obtained by the co-precipitation method. They were further modified by the adsorption of ricinoleic acid (RA). The non-modified and modified CoFe(2)O(4)/RA nanoparticles were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman, and Fourier transform infrared (FTIR) spectroscopy. The modified particles present a mean diameter < 20 nm. The adsorption of RA on the CoFe(2)O(4) surface is characterized by the IR absorptions of the RA while in the Raman spectrum the predominant signals are those from the CoFe(2)O(4). The cis-polyisoprene (PI) composite was prepared by dissolving PI in cyclohexane followed by the addition of a magnetic fluid based on CoFe(2)O(4)/RA nanoparticles dispersed in cyclohexane. After solvent evaporation a magnetic composite was obtained and characterized by AFM, Raman, and FTIR measurements. AFM images show uniformly CoFe(2)O(4)/RA particles distributed in the PI matrix. Raman spectra obtained for the composites reveal the characteristic Raman peaks of PI and CoFe(2)O(4) nanoparticles.

Nanostructures and nanoporosity in thermoset epoxy blends with an amphiphilic polyisoprene-block-poly(4-vinyl pyridine) reactive diblock copolymer

Nanostructured thermoset blends were prepared based on a bisphenol A-type epoxy resin and an amphiphilic reactive diblock copolymer, namely polyisoprene-block-poly(4-vinyl pyridine) (PI-P4VP). Infrared spectra revealed that the P4VP block of the diblock copolymer reacted with the epoxy monomer. However, the non-reactive hydrophobic PI block of the diblock copolymer formed a separate microphase on the nanoscale. Ozone treatment was used to create nanoporosity in nanostructured epoxy/PI-P4VP blends via selective removal of the PI microphase and lead to nanoporous epoxy thermosets; disordered nanopores with the average diameter of about 60 nm were uniformly distributed in the blend with 50 wt% PI-P4VP. Multi-scale phase separation with a distinctly different morphology was observed at the air/sample interface due to the interfacial effects, whereas only uniform microphase separated morphology at the nanoscale was found in the bulk of the blend.

Analysis of natural cis- and trans-polyisoprene mixtures by near-infrared spectrophotometry

Natural trans- and cis-polyisoprenes and mixtures of these polymers were analysed by near-infrared spectrophotometry. The relative absorptivity data versus the amount of isomers in synthetic mixtures showed a non-linear behaviour. The results are compared with literature data from polyisoprenes extracted from other vegetal species. (C) 2000 Elsevier B.V. Ltd. All rights reserved.

High-Pressure Micellar Solutions of Polystyrene-block-polybutadiene and Polystyrene-block-polyisoprene in Propane Exhibit Cloud-Pressure Reduction and Distinct Micellization End Points

Micellar solutions of polystyrene-block-polybutadiene and polystyrene-block-polyisoprene in propane are found to exhibit significantly lower cloud pressures than the corresponding hypothetical nonmicellar solutions. Such a cloud-pressure reduction indicates the extent to which micelle formation enhances the apparent diblock solubility in near-critical and hence compressible propane. Concentration-dependent pressure-temperature points beyond which no micelles can be formed, referred to as the micellization end points, are found to depend on the block type, size, and ratio. The cloud-pressure reduction and the micellization end point measured for styrene-diene diblocks in propane should be characteristic of all amphiphilic diblock copolymer solutions that form micelles in compressible solvents.

Direct probe of end-segment distribution in tethered polymer chains

End-tethered chains made of an adsorbed diblock copolymer of polystyrene (PS)-polyisoprene (PI) bearing an end-segment including a Ge atom are built by the Langmuir-Schaeffer technique. They are studied both in the dry state and in a good solvent for the PI chain using grazing incidence X-ray standing waves. The analysis of the signal provides a direct measurement of the end-segment distribution which is found to be singular and mostly localized to a plane in the dry case. In the good solvent case, end-segments are found to span the entire assembly and compare very well with results obtained by Kreer et al.

稀土催化剂合成窄分子量分布聚异戊二烯的研究

本论文利用传统的稀土催化剂组成，探讨了稀土催化剂的配制方式，配制出稳定的均相催化剂；深入探讨了影响聚异戊二烯分子结构的因素，合成了高顺式、高分子量、窄分子量分布且具有与天然橡胶相似的拉伸结晶特点的聚合物；讨论了催化剂活性中心的形成机理；均相催化剂用于丁二烯-异戊二烯共聚合可制备窄分子量分布的无规共聚物。 1. NdCl3•3iPrOH/MMAO催化体系：可在较低的MMAO (Al/Nd < 40)用量下，高收率地合成高的顺式-1,4含量(> 96%)、非常高的分子量(Mn > 100×104)、相当窄的分子量分布(Mw/Mn < 2.0)的聚异戊二烯。与烷基铝助催化剂如Al(i-Bu)3和Al(i-Bu)2H相比，在顺-1,4含量相同的情况下，MMAO体系所得聚合物的分子量最高，分子量分布最窄。催化剂形成配位阳离子性质的活性中心。 2. Nd(vers)3/Al(i-Bu)2H/Al(i-Bu)2Cl催化体系：可在适当的陈化条件下配制出稳定的均相催化剂，该均相催化剂可在较低的Al/Nd用量(Al/Nd = 10)和催化剂用量([Nd] = 0.20 mM)下，高收率(> 80%)地合成高顺式-1,4含量(> 96%)、高分子量(Mn > 50×104)、窄分子量分布(Mw/Mn < 3.0)的聚合物。均相催化剂的活性中心为配位阳离子性质的单活性中心。 3. Nd(vers)3/MMAO/Al(i-Bu)2H/Al(i-Bu)2Cl催化体系：在相当低的MMAO用量(Al/Nd = 10，总铝量Al/Nd = 20)下，仍具有高的催化活性，所得聚合物的分子量较高(Mn 52.4×104)，分子量分布较窄(Mw/Mn < 3.0)，顺-1,4结构含量可达96%。通过调节Al(i-Bu)2H和MMAO用量可以控制聚合物的分子量及分子量分布。 4. Nd(vers)3/Al(i-Bu)3/Al(i-Bu)2Cl催化体系：用Al(i-Bu)3代替Al(i-Bu)2H作助催化剂，可在各种加料方式下高收率地获得高顺-1,4含量(96%)、非常高分子量(Mn > 100×104)、窄分子量分布(Mw/Mn < 3.0)的聚异戊二烯，且所得异戊橡胶在高顺-1,4含量(96%)、高分子量(Mn ≥ 90×104)、窄分子量分布(Mw/Mn ≤ 2.1)时存在拉伸结晶现象，性能接近甚至超过天然橡胶。 5. Nd(vers)3/AlR3(Al(i-Bu)2H, Al(i-Bu)3)/Al(i-Bu)2Cl催化体系在一定条件下，可获得高顺式-1,4含量(丁二烯和异戊二烯的顺-1,4含量均可达99.9%)、高分子量(Mn > 50×104)、窄分子量分布(Mw/Mn < 3.0)的丁二烯-异戊二烯共聚物。只是用Al(i-Bu)3作助催化剂时，均相和非均相催化剂均可得到高顺式、更高分子量(Mn > 100×104)、更窄分子量分布(Mw/Mn < 1.8)的共聚物。两单体的竞聚率为：对于Al(i-Bu)2H体系，rBD = 0.923，rIP = 0.612；对于Al(i-Bu)3体系，rBD = 1.02，rIP = 0.919。表明聚合物为无规共聚物。

Effect of Shear Flow on the Formation of Ring-Shaped ABA Amphiphilic Triblock Copolymer Micelles

We have investigated the effect of Shear flow on the formation of rill.-shaped ABA triblock copolymer (P4VP(43)-b-PS260-b-P4VP(43)) micelles. The results reveal that Shear flow Plays an important role in the formation of the rings Both ring size and its, distribution are found to be dependent sensitively on the stirring rate. Sizable rings are more likely to be formed at moderate stirring rate, Interestingly, the ring formation mechanism is also dependent oil the Shear flow. Copolymers are likely to form rings via end-to-end cylinder connection at low stirring rates, whereas they tend to form rings via the pathway of the rod-sphere-vesicle-ring it high stirring rates.

Synthesis of the first rare earth metal bis(alkyl)s bearing an indenyl functionalized N-heterocyclic carbene

Treatment of indenyl-modified imidazolium bromide [C9H7CH2CH2(NCHCHN(C6H2Me3-2,4,6)CH)Br] ((IndH-NHC-H)Br) with rare earth metal tetra(alkyl) lithium (Ln(CH2SiMe3)(4)Li(THF)(4)) or with (trimethylsilylmethyl)lithium (LiCH2SiMe3) and rare earth metal tris(alkyl)s (Ln(CH2SiMe3)(3)(THF)(2)) sequentially afforded the first NHC-stabilized monomeric rare earth metal bis(alkyl) complexes (Ind-NHC)Ln(CH2SiMe3)(2) (1, Ln = Y; 2, Ln = Lu; 3, Ln = Sc) via double-deprotonation reactions. Complexes 1-3 are THF-free isostructural monomers. The monoanionic Ind-NHC species bond to the central metal ion in a eta(5):kappa(1) constrained geometry configuration (CGC) mode, which combine with the two cis-located alkyl moieties to form a tetrahedron ligand core, leading to the chirality of the complexes. Under the presence of activators AlEt3 and [Ph3C][B(C6F5)(4)], complex 2 showed catalytic activity toward the polymerization of isoprene to afford 3,4-regulated polyisoprene (91%).