Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3

Ti‐based Ziegler–Natta catalysts supported on MgCl₂ doped with AlCl₃ were prepared by the reaction of MgCl₂/AlCl₃–ethanol adduct with TiCl₄. No AlCl₃ crystallites were found in the AlCl₃‐doped catalysts by WAXD analysis, suggesting that AlCl₃/MgCl₂ solid solution was formed. The effect of doping on the catalyst performance in ethylene polymerization was investigated. The results showed that the catalysts based on AlCl₃‐doped MgCl₂ support exhibited a slightly higher activity than did the MgCl₂‐supported catalyst and the molecular weight distribution (MWD) of polyethylene (PE) markedly increased (from 10.8 to 47.9) with the increase of AlCl₃ content in catalysts. The changes in catalyst's active center distribution were studied based on nonlinear fitting of the polymer GPC curves by multiple Flory functions. It was found that increase of types of active centers by introducing AlCl₃ into the support should be responsible for the broadening of MWD of PE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1768–1772, 2006     

基于分布的中文词表示研究

针对基于分布的中文词表示构造过程中的参数选择问题进行了系统性的研究。选择了六种参数进行对比实验,在中文语义相似度任务上对不同参数设置下得到的中文词表示的质量进行了评估。实验结果表明,通过选择合适的参数,基于分布的词表示在中文语义相似度任务上能够得到较高的性能,而且,这种高维的词分布表示的质量甚至优于目前流行的基于神经网络（Skip-gram）或矩阵分解（GloVe）得到的低维的词表示。     

一种结合主题模型的推荐算法

针对传统协同过滤推荐算法存在的冷启动、数据稀疏以及相似度度量的准确性问题,基于LDA主题模型对文本隐式主题挖掘的有效性和KL散度在主题分布相似性度量的准确性,提出了结合LDA主题模型的矩阵分解推荐算法。首先,利用改进的LDA算法输出项目-主题分布,并用困惑度作为主题数设置的修正函数;然后分别基于余弦相似度和KL散度计算得到项目相似度矩阵,将得到的相似度矩阵结合原评分训练集输出预评分,再将预评分填充到训练集;最后将训练集输入ALS矩阵分解算法得到推荐结果。通过MovieLens数据集的实验结果表明,该算法在不同隐式参数设定下均能得到比ALS推荐算法以及更小的预测误差,并且最优预测误差小于传统推荐算法。该实验说明了通过集成LDA主题模型的ALS算法效果要优于其他推荐算法。     

基于排列熵和支持向量机的癫痫发作预测研究

针对癫痫发作给病人带来的巨大伤害,为临床治疗留下足够空余时间,提出一个可以预测癫痫发作的系统模型。对21名癫痫病人进行研究,提取具有较低算法复杂度的排列熵构成特征向量,将其输入支持向量机（support vector machine,SVM）训练出学习模型,用来识别发作期样本,利用投票机制充分考虑病人差异来判断所处状态,最终实现癫痫的实时预测。结果表明,其中81%的发作可以提前平均50多分钟预测到,且具有较低的误报率。为癫痫发作预测系统的理论研究打下坚实基础。     

Volume phase transition of polyelectrolyte gels in dimethyl sulfoxide/ tetrahydrofuran mixtures

Copolymer gels were prepared from 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS), N,N-dimethylacrylamide (DMAA, comonomer) and N,N′-methylenebis(acrylamide) (BIS). The mole fraction of AMPS were 0.2674 and 0.4318, respectively, with the same BIS mole fraction of 0.013. These gels with counterions H⁺, Na⁺, and K⁺ were swollen at 25°C in mixtures of dimethyl sulfoxide (DMSO) and tetrahydrofuran (THF). A volume phase transition was observed at the THF volume fraction of about 0.58, indicating that the volume phase transition in a polyelectrolyte gel occurs when the medium polarity decreases sufficiently for ion-pair formation. On changing the counterion, the fraction of DMSO in the solvent mixture which is required to initiate swelling decreases in the order Na⁺, H⁺, and K⁺, the same as for counterion condensation in identical gels.     

Synthesis of polystyrene end-capped with pyrene via reversible addition-fragmentation chain transfer polymerization

A novel benzodithioate compound with a pyrene structure in the R group, pyrenylmethyl benzodithioate (PMB) was synthesized. Using PMB as the chain transfer agent (CTA), the RAFT polymerizations of styrene with AIBN as an initiator were carried out in different reaction conditions. The results indicated that PMB was an effective CTA for the RAFT polymerizations of styrene with the “living”/controlled characteristics. The structures of the obtained polymers were characterized by ¹H NMR. The results showed that majority of the polymer chains contained the pyrene moiety in the chain end. The enhanced fluorescence property in CHCl₃ solution was observed. The chain-extension experiments of the obtained polystyrene (PS) with the monomers of styrene and methyl acrylate were successfully carried out.     

1,1,3-三甲基-3-苯基茚满的合成及表征

以α-甲基苯乙烯为原料，活性白土为催化剂，聚合成l，l，3-三甲基-3-苯基茚满并进行了表征，考察了催化剂用量、反应温度、反应时间对收率的影响。结果表明：在温度为150℃、催化剂用量为原料质量的7．5％、反应时间为5h的条件下，产品收率为89．06％。产品用适宜溶剂重结晶后，纯度可达99．9％。     

Preparation and characterization of calcium carbonate/low‐density‐polyethylene nanocomposites

Calcium carbonate/low‐density‐polyethylene (LDPE) nanocomposites have been prepared by melting blend with twin‐screw extruder. The mechanical properties of composites and the dispersion of the nanoparticles were studied. The reinforcement mechanism was discussed. The results show that not only the tensile property but also the flexural modulus of the system have been evidently increased by the addition of calcium carbonate. The calcium carbonate particles have been dispersed in the matrix in the nanometer scale. The reinforcement mechanism of the calcium carbonate lies on that the calcium carbonate particles, acting as hetero‐nuclei, can induce higher crystallinity at the matrix‐particle interface compared to regions away from the interface. Consequently, in the process of the tensile test, the nanocomposites have better tensile yield strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

超临界水中NaCl无限稀释扩散系数的研究

The molecular dynamics(MD) was employed to simulate the diffusion coefficient of sodium chloride at infinite dilution in supercritical water from 703.2K to 763.2K and from 30 MPa to 45 MPa ,Based on the simulated data and the Patel-Teja(PT) equation of state and the Liu-Ruckenstein equation,an equation for calculating the diffusion coefficient of NaCl at infinite dilution in supercritical water is proposed,Both the agreement between the simulated and correlated data,and that between the simulated and predicted data of diffusion coefficients for NaCl in supercritical water ranging from 703.2K to 803.2K and from 25 MPa to 50MPa show that this equation is applicable for calculation of diffusion coefficients.     

温度和氧浓度对PX氧化的影响

根据不同温度、氧浓度下实测的PX液相催化氧化各中间组分浓度 时间关系,采用双曲型的动力学模型拟合实验数据,得到了各步反应活化能数据和速率常数与氧浓度的关系式。结果说明,PT酸氧化为4 CBA这一步的活化能最大,是整个连串反应过程的速率控制步骤;反应有一个氧浓度门槛值,在此值以上,反应速率不再明显增大,在此值以下,反应速率随氧浓度增大而增大。工业尾氧体积分数一般在4%～5%,相应的反应速率在最大速率的90%左右。