稀土催化丁二烯-异戊二烯共聚合过程中的原位环化反应

采用 Nd( naph) 3- Al( C2 H5) 3- ( t- C4 H9) Cl三组分稀土催化剂进行丁二烯 ( BD) -异戊二烯( IP)的顺式共聚合 ,在聚合过程中引入有机氯代烃 ( RCl) ,以与聚合液中的烷基铝作用生成阳离子活性种 ,引发已生成的共聚物的环化反应及单体的环聚反应 ,得到可溶性无凝胶且含有环聚成分的环化共聚合产物 .考察了 RCl用量、单体组成、稀土催化剂用量、反应温度等对原位环化反应的影响 .以红外光谱、核磁共振光谱对环化产物的结构进行了初步分析 。

钕-铝双金属配合物催化异戊二烯聚合的原位环化反应

Function of chloride and effect of various alkylaluminiums, Cl/Al molar ratio, solvents on cyclization in situ of isoprene polymerization catalyzed by Nd Al bimetallic complex were studied. The structure of cyclized products was characterized by means of IR and 1H NMR. The results indicated that in the course of isoprene polymerization with rare earth catalytic system, the function of alkylchloride introduced is terminating cis polymerization and generating cationic species with alkyl aluminums to initiate cyclization in situ . Soluble cyclized polyisoprene was obtained with fragments of cyclopolyisoprene.

螺环型硅钛树脂的合成与表征

以端羟基聚二甲基硅氧烷为原料、钛酸四丁酯为Ti源,合成了螺环型硅钛树脂。采用FT-IR(红外光谱)法、1H-NMR(核磁共振氢谱)法、GPC(凝胶渗透色谱)法、元素分析法和TGA(热失重分析)法等对产物的结构和性能进行了表征,并探讨了反应时间对反应进程的影响。研究结果表明:螺环型硅钛树脂的初始分解温度为300℃,800℃时的残炭率为27%左右,说明该硅钛树脂的热稳定性较好;聚合物在不同温度热解时,其热解速率在热解时间为5~20 min时相对最大,400℃之后热失重现象明显减弱且失重率较小;合成硅钛树脂的聚合速率很大,并且主要的聚合反应是环聚反应。

Optimization of reaction for synthesis of polyisobutylene amine between amination agent and epoxy polyisobutylene

An optimization study on the amination reaction of epoxy polyisobutylene for synthesis of polyisobutylene amine is presented. The experimental results indicate that n-butanol and ethylenediamine are the suitable solvent and amination agents for the reaction, respectively. The reaction yield of the amination reaction is notably increased with the enhanced molar ratio of either n-butanol against epoxy polyisobutylene or ethylenediamine against epoxy polyisobutylene. Also, the yield is enhanced with increasing temperature and time during the experimental range. Strikingly, the yield reaches as high as 91. 30% under optimal conditions; with the molar ratio of ethylenediamine, n-butanol and PIBO of 10∶ 6∶ 1, the reaction temperature of 150 ℃ and the reaction time of 6 h. In addition, the yield of the reaction is slightly decreased with the enhanced water content of the system. Accordingly, the mass concentration of water should be controlled within 1. 7% during the reaction.

Effect of catalyst on structure of(PEO)_8LiClO_4-SiO_2 composite polymer electrolyte films

(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra,contact angle method and TEM.The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10-5and 1.1×10-5S/cm respectively at 30℃.The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2,and influences the surface energy and conductivity of CPE films directly.Meanwhile,the ionic conductivity is related to the surface energy.

Hydrothermal synthesis and catalytic performance of bulky titanium silicalite-1 aggregates assembled by bridged organosilane

A facile and effective method to synthesize TS‐1zeolite aggregates has been presented.The crystallization of silanized seeds and nanocrystallites led to large and irregular TS‐1zeolite aggregates ranging from5to40μm in size,based on the special sol‐gel chemistry of bridged organosilane.Epoxidation of1‐hexene and cyclohexene was used as a probe reaction to investigate the catalytic performance of the resulting materials.These TS‐1zeolite aggregates possessed both the conventional nanoparticle properties of TS‐1zeolites and variable surface hydrophilic/hydrophobic features,which enhanced the catalytic properties of hydroperoxides for alkene epoxidation.Moreover,the large aggregates effectively simplified the separation procedure during preparation and catalytic reactions.

COX-2 polymorphisms-765G→C and-1195A→G and colorectal cancer risk

AIM： TO determine the possible modulating effect of the COX-2 polymorphisms, -765G→C and -1195A→G, on the risk of colorectal cancer （CRC） in a Dutch population. METHODS： This case-control study includes 326 patients with CRC and 369 age- and gender-matched controls. Genotypes of the COX-2 polymorphisms -7dEG→C and -1195A→G were determined by polymerase chain reaction-based restriction fragment length polymorphism. COX-2 genotypes and haplotypes were analyzed and odds ratios with 95% confidence intervals were estimated by logistic regression. RESULTS： The -765GG genotype was associated with an increased risk of developing CRC （OR, 1.45; 95% CI, 1.03-2.04）. No significant difference was observed in the genotype distribution of the -1195A→G polymorphism between patients and controls. The GG/AC haplotype was present significantly less often in patients than in controls （OR 0.44; 95% CI, 0.22-0.85）. When the AC, AG and GG haplotypes were investigated separately, the AC haplotype showed a tendency to be less frequent in patients than in controls （OR（AG/AC） 0.78; 95% CI, 0.57-1.06）. CONCLUSION： The -765GG genotype is associated with an increased risk of developing CRC and the G6/ AC haplotype seems to protect against CRC. These findings suggest a modulating role for the COX-2 polymorphisms -765G→C and -1195A→G in the development of CRC in a Dutch population.

Research on the Mechanism of Accelerator for Photocurable Resin in 3D Printing

The photopolymerization kinetics of cycloaliphatic epoxide and oxetane with accelerators were investigated with Real-time Fourier transform infrared spectroscopy(RT-FTIR).The consumption rates of epoxy group and oxetane group as a function of time were obtained by monitoring of the absorption peaks in the 789 cm-1 and 981 cm-1.The effect of accelerators type and the accelerating mechanism were discussed.In general,benzyl alcohol and its analogues with electron-donating substituents are useful accelerators for the cationic polymerization of cycloaliphatic epoxide and oxetane.Activated monomer mechanism and free-radical chain-induced decomposition of onium salt cationic photoinitiator account for the observed accelerating effect on the polymerization rate.

Ring Polymer Molecular Dynamics of the C(^(1)D)+H_(2) Reaction on the Most Recent Potential Energy Surfaces

Ring polymer molecular dynamics(RPMD)calculations for the C(^(1)D)+H_(2)reaction are performed on the Zhang-Ma-Bian ab initio potential energy surfaces(PESs)recently constructed by our group,which are unique in very good descriptions of the regions around conical intersections and of van der Waals(vdW)interactions.The calculated reaction thermal rate coefficients are in very good agreement with the latest experimental results.The rate coefficients obtained from the ground˜a^(1)A′ZMB-a PES are much larger than those from the previous RKHS PES,which can be attributed to that the vdW saddles on our PESs have very different dynamical effects from the vdW wells on the previous PESs,indicating that the RPMD approach is able to include dynamical effects of the topological structures caused by vdW interactions.The importance of the excited˜b^(1)A′′ZMB-b PES and quantum effects in the title reaction is also underscored.

Comparison of Single Loop and Dual Loop PP Reactors and PP Product Development

The present status of PP technology in China is presented. Through a review of single loop and dual loop PP reactor technology as well as development and utilization of PP products it is concluded that import of PP technology should be based on the demand of PP products and market trend with consideration of local conditions. The existing problems and future development of PP technology in China are discussed.

Brayton Power Cycles for Electricity Generation from Fusion Reactors

Brayton power cycles for fusion reactors have been investigated, using Helium in classical configurations and CO2 in a recompression layout. Thermal sources from the reactor have strongly constrained the cycle configurations, hindering use of a recuperator in Helium cycles and conditioning the outlet turbine temperature in CO2 ones. In both cycles, it is possible to take advantage of the exhaust thermal energy by coupling the Brayton to a Rankine cycle, with an organic fluid in the helium case （iso-butane has been investigated） and steam in the CO2 case. The highest efficiency achieved with Helium cycle is 38.5% using Organic Rankine Cycle and 32.6% with Helium alone. The efficiency changes from 46.7% using Rankine cycle to 41% with CO2 alone. The Helium cycle is highly sensitive to turbine efficiency and in a moderate way to compressor efficiency and pressure drops, being nearly insensitive to thermal effectiveness in heat exchangers. On the other hand, CO2 is nearly insensitive to all the parameters.

Recoverable Mn~Ⅲ (salen) supported on diamine modified zirconium poly(styrene-isopropenyl phosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins

Chiral Mn Ⅲ (salen) (Jacobsen's catalyst) was axially immobilized onto a new type of organic polymer-inorganic hybrid materialzirconium poly(styrene-isopropenyl phosphonate)-phosphate(ZPS-IPPA) with different linkage lengths and evaluated as catalysts for the epoxidation of unfunctionalized olefins. The results demonstrated that the prepared catalysts exhibited moderate to good activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the immobilized catalysts were relatively stable and could be conveniently separated from the reaction system by simple precipitation in hexane. Moreover, higher enantioselectivity was obtained with catalyst 2c than that of homogeneous counterpart catalyzed even after eight times. The excellent recycling of the catalyst was attributed to its structure feature of ZPS-IPPA which is different from either pure polystyrene or pure zirconium phosphates.

Recent advances of the Bergman cyclization in polymer science

The Bergman cyclization has strongly impacted on a number of fields including pharmaceutics, synthetic chemistry, and material science. The diradical intermediates stemmed from enediynes can not only cause DNA cleavage under physiological conditions but also function as monomer or initiator participants in polymer science. The homo-polymerization of enediynes through the Bergman cyclization to fabricate conjugated polymers is a fascinating strategy due to the advantages of facial operation, high efficiency, tailored structure, and catalyst-free operation. Moreover, conjugated polymers generated through the Bergman cyclization show many remarkable properties, such as excellent thermal stability, good solubility, and processability, which enables these polymers to be further manufactured into carbon-rich materials. Recent times have seen extensive efforts devoted to the application of the Bergman cyclization in polymer science and materials chemistry. A variety of synthetic strategies have been developed to fabricate structurally unique materials via the Bergman cyclization, including the fabrication of rod-like polymers with polyester, dendrimers and chiral imide side chains, functionalization of carbon nanomaterials by surface-grafting conjugated polymers, formation of nanoparticles by intramolecular collapse of single polymer chains, and the construction of carbon nanomembranes with different morphologies. Future developments involving the Bergman cyclization in polymer science, probably by altering the reaction mechanism to precisely control the microstructure of polymeric products, are also proposed in this review article.

Schiff base aluminum catalysts containing morpholinomethyl groups in the ring opening polymerization of rac-lactide

A series of Schiff base aluminum(III) complexes bearing morpholinomethyl substituents were synthesized. Comprehensive investigations on their stereoselective and kinetic features in the ring opening polymerization of lactide were carried out. The ring opening polymerization proved to be first-order in the catalyst and the monomer. Linear relationships between the numberaverage molecular weight of the polylactide and the monomer conversion were consistent with a well-controlled polymerization. The propagation rate was strongly affected by morpholinomethyl substituents on the salicylaldehyde moiety.

Polyrotaxane-based triblock copolymers synthesized via ATRP of N-isopropylacrylamide initiated from the terminals of polypseudorotaxane of Br end-capped pluronic 17R4 and β-cyclodextrins

Thermo-responsive polyrotaxane （PR）-based triblock copolymers were synthesized via the atom transfer radical polymeriza- tion （ATRP） of N-isopropylacrylamide initiated with self-assemblies made from a distal 2-bromoisobutyryl end-capped Plu- ronic 17R4 （PPOI4-PEG24-PPOI4） with a varying amount of β-cyclodextrins （β-CDs） in the presence of Cu（I）C1/PMDETA at 25 ~C in aqueous solution. The molecular structure was characterized by means of ~H NMR, FTIR, WXRD, GPC, TGA and DSC analyses. About half of [3-CDs are still entrapped on the Pluronic 17R4 chain while the number of incorporated NIPAAm monomers is nearly a double feed value in the resulting copolymers. The aggregate morphologies in aqueous solution were evidenced by TEM observations. A two-step thermo-responsive transition arising from a combination of a polypseudorotaxane middle block with poly（N-isopropylacrylamide） flanking blocks was also demonstrated by turbidity measurements. Given their thermo-responsive behavior in aqueous solution, these PR-based triblock copolymers show the potential to be used as smart materials for the controlled drug delivery systems, biosensors, and the like.