紫外光同步固化合成互穿聚合物网络研究

互穿聚合物网络是研制高阻尼材料的理想结构,但从目前国内外文献报道的同步法互穿网络体系来看,由于在制备中采用了两种不同的聚合方法,实际上在形成网络结构的过程中都不是十分理想的同步反应,其反应速度均存在着一定程度的差别。     

POLYIMIDE/INORGANIC INTERPENETRATING POLYMER NETWORKS FOR STABLE SECOND-ORDER NONLINEAR OPTICS

Thermally stable NLO interpenetrating polymer networks (IPNs) based on an organosoluble polyimides functionalized with methacryloyl groups (PIB), and an alkoxysilane dye (ASD) have been developed. IPNs were formed through the free radical polymerization of methacryloyl group containing PIB, and sol-gel process of ASD. Optically clear samples exhibit large second-order optical nonlinearity (d₃₃ = 6.9-39.6 pm/V at 1064 nm) after poling and curing at 180°C for 2 hours. The temporal stability of the PIB/ASD IPN samples was much better than the inter-chain crosslinking polyimide/inorganic samples. The high rigidity of the polymer backbone and the interpenetrating structure of the polymer networks prevent the randomization of the aligned NLO chromophores     

SYNTHESIS AND PROPERTIES OF POLYURETHANE ACRYLATE/EPOXY RESIN INTERPENETRATING POLYMER NETWORKS

In this paper, a series of interpenetrating polymer networks (IPNs) based on polyurethane acrylate and epoxy resin was prepared by simultaneous photoinitiating by both free-radical and cationic polymerization. The effects of the polyurethane acrylate prepolymer's molecular weight, various components ratio and polymerization methods on IPN's dynamic mechanical and mechanical properties were investigated.     

INTERPENETRATING POLYMER NETWORKS BASED ON OIL MODIFIED CASTOR OIL URETHANE AND POLY(METHYL METHACRYLATE)

Castor oil was initially subjected to an interesterification reaction with linseed and tung oils and the resulting intermediate was used for the preparation of polyurethanes and their IPNs with poly(methyl methacrylate). They were characterized for their physico-mechanical, swelling, and thermal properties. The morphologies of IPNs were studied with the aid of scanning electron microscopy and differential scanning calorimetry. On comparing the mechanical properties of castor oil polyurethane (CU) and their IPNs (C-IPNs) with those of the castor oil modified with linseed and tung oil (L-IPN and T-IPN, respectively) it was found that L-IPNs showed higher tensile strength, hardness, and better compatibility than C-IPNs. All IPNs showed synergistic effect in elongation and exhibited similar thermal behavior with no significant change with respect to their composition. However, the castor oil polyurethane and their IPNs showed relatively higher elongation and better resistance to solvents.     

SPECTRAL CHARACTERISTICS OF FREE AND LINKED PYRENE-TYPE CHROMOPHORES IN SOLUTION,POLYMER MATRICES,AND INTERPENETRATING NETWORKS

Monomers, 1-pyrenylmethyl methacrylate (PyMMA), 1-pyrenylbutyl methacrylate (PyBMA), 4-(1-pyrenyl)methoxymethyl styrene (PyMMS) and allyl-(1-pyrenylmehtyl) ether (PyMAE), with pyrene as chromophore, were prepared. Their spectral properties (absorption, emission and emission decay) in solution, and doped or bonded in polymer matrices and complex polymer systems as interpenetrating polymer networks (IPN), were investigated. Spectral properties of pyrene-containing monomers doped in polystyrene (PS), polymethylmethacrylate (PMMA), polyvinylchloride (PVC), polyethylene (PE) and grafted on PE as well as copolymerized in buthylmethacrylate-co-styrene copolymer (BMA-co-S) have been compared. Absorption and emission spectra of pyrene type probes in solution and in IPN matrices exhibit typical absorption of the pyrene moiety. For IPN with grafted probes on PE, the absorption is slightly shifted to red wavelength. For monomers, PyMMA, PyBMA and PyMAE grafted to PE, the shape of the emission spectrum depends on the wavelength of excitation. The ratio of intensity of the vibrational band, I₁/I₃, (I₁ peak at 377 nm and I₃ peak at 388 nm) has been a quite useful indicator of polarity of IPN. The relative quantum yields of fluorescence in IPN matrices are lower in comparison to polymer matrices of PE, PS, PMMA for all probes under study. The fluorescence life-times for bound and free probes have been in the range 100–200 ns, which is substiantialy shorter than for the parent pyrene chromophore under the same or similar condition. Grafted probes on PE alone, or as a part of IPN, exhibit substantially shorter life-time around 10 ns and decay is rather complex.     

聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究——1.聚合条件对体系相容性的影响

用分步法合成了聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物(PVAc/PMA-IPN),PVAc和PMA的交联剂分别是丁二酸二烯丙酯(DAS),和二乙烯基苯(DVB)。当DAS用量较小时,VAc聚合时的接枝反应较明显,PVAc网络的交联密度高于化学当量的计算值。动态力学的实验结果表明,丙烯酸甲酯的聚合温度和聚合过程中的溶胶-凝胶转变对PVAc/PMA-IPN体系的相容性有很大影响。     

聚醋酸乙烯酯/聚丙烯酸甲酯互穿网络聚合物的研究——4.橡胶态模量和网络间的互穿缠结

用动态粘弹谱仪测定了分步法互穿网络聚合物,聚醋酸乙烯酯/聚丙烯酸甲酯(PVAc/PMA-IPN)的橡胶态模量。实验值与从方程E_R=φ_Ⅰ~1/3·E_(R,Ⅰ)~0+φ_(Ⅱ)E_(R,Ⅱ)~0所得理论值的比较,表明网络问有明显的互穿缠结,网络Ⅰ交联程度对其的影响大于网络Ⅱ。并结合实验结果对Binder-Frisch理论中,ΔS_(ent)∝N_(c,Ⅰ)~(-1)·N_(c,Ⅱ)~(-1/2)关系的合理性进行了讨论。     

TWO INTERPENETRATING COBALT COORDINATION POLYMERS CONSTRUCTED BY DICARBOXYLATE AND V-SHAPED N-DONOR LIGANDS

Journal of Structural Chemistry - Two novel cobalt coordination polymers {[L1Co(ipa)]·0.25(DMF)}n (1) and {[L2Co(cis-1,3-chdc)]·3(H2O)}n (2)...     

REINFORCEMENT OF POLYDIMETHYLSILOXANE NETWORKS BY NANOCALCIUM CARBONATE

Although a number of investigations have been devoted to the analysis of silica or carbon black filled elastomer networks, little work has been done on the reinforcement of CaCO3 filled elastomer network. In this work, the reinforcement of polydimethylsiloxane (PDMS) network by using CaCO3 nano-particles was investigated. We have found a simultaneous increase of tensile strength, modulus and elongation with the increase in nano-CaCO3 content, which suggests that nano-CaCO3 particles can indeed be used as a reinforcing agent, just like silica or carbon black. Interestingly, the tensile strength, modulus and elongation were seen to leave off for the first time when the content of nano-CaCO3 particles reaches to 80%. PDMS also showed an enhanced elastic modulus and storage modulus with the increase in nano-CaCO3 content, particularly for samples with high nano-CaCO3 content. SEM was used to investigate the dispersion of the filler in PDMS matrix. A better dispersion was found for samples with high nano-CaCO3 content. A great increase of viscosity was found for samples with higher filler content, which is considered to be the reason for the good dispersion thus the reinforcement, because high viscosity will be helpful for breaking the agglomerates of fillers into small size particles under effect of shear. Our work provides a new way for the reinforcement of elastomer by using an adequate amount of nano-CaCO3 particles instead of a small quantity of silica, which is not only economically cheap but also very effective.     

采用重复互贯聚合用废弃白球末合成凝胶型阳离子交换树脂的研究

采用重复互贯聚合工艺将废弃白球末加入单体－交联剂－引发剂体系中充分溶胀,再按照常规悬浮聚合和磺化反应工艺合成凝胶型阳离子交换树脂,结果显示,细粒度白球的交联度在4％－7％,单体吸收比为100％,采用盐水滴加工艺保证单体在白球中的均匀扩散和吸收,所合成的阳树脂的各项性能指标均国家标准,这种重复互贯聚合白球与相同交联度的普通白球比较,具有较高的磺化反应活性,较高的交联度,湿真密度,湿视密度和较高的交换容量。     

MOLECULAR DESIGN OF NEW KINDS OF AUXETIC POLYMERS AND NETWORKS

Three new kinds of molecular networks are designed and predicted to exhibit negative Poisson ratios. Molecular mechanics calculations on these networks show that the magnitude of Poisson ratios depends on the relative flexibility of beam and arm structures. Several new kinds of auxetic polymers, whose successful synthesis should be easier than that of the corresponding auxetic networks, are then proposed. It is found that the kabob-like polymers with auxegens lying vertically on the main chain can acquire auxeticity while those with auxegens lying horizontally on the main chain cannot. Besides, a half kabob-like or pseudo-ladder polymer with auxegens linked at the intersection of the beam and the arm does show auxeticity when adopting constrictive conformers. It is, however, worthwhile noting that the origins of auxeticity still await and strongly deserve further experimental and theoretical investigations.     

人工神经网络解析紫外光度法同时测定复方制剂

在ANN－BP网络中,分别用Sigmoid函数和双典正切函数作为传递函数,建立ANNBP算法两个模型,对复方制剂中碘胺甲恶唑和甲氧苄啶的我谱进行解析,两个函数作为传递函数 的方法各有优点,但分析结果均很满意,每种算法模型的传递函数由δi^k^=f^1(s）（Tik^-Yi^k）均分别改进用δi^k=[f^1(s) 0.1](Ti^k-Yi^k) 和δi^k=arcth(Ti^k-Yi^k)/2的作为误差传递函数,使传递函数的导数在学习过程中自行调节,不致趋近于0,从而避免麻痹现象,方法也可用其他样品多组分同时测定。     

人工神经网络吸光光度法同时测定钛和铌

确立了钛 4,5-二溴邻硝基苯基荧光酮 - CTMAB显色体系 ,在此基础上确立了钛和铌同时测定的显色体系 ,应用三层 ANN- BP网络解析钛和铌吸收光谱 ,吸光光度法同时测定铌和钛。方法选择性好 ,表观摩尔吸光系数 εTi557=1 .2 4× 1 0 5L· mol-1· cm-1,εNb54 0 =1 .63× 1 0 5L· mol-1·cm-1。对合金钢中铌和钛进行了同时测定 ,钛和铌的平均相对误差分别为 1 .30 %和 1 .0 8%。使用改进的 BP算法 ,避免了可能产生的麻痹现象。提出了便于网络参数选择的收敛评价函数。     

人工神经网络方法用于PC/ABS材料定量分析

采用人工神经网络(ANN)算法建立了不同共混比的ABS/PC样品的近红外光谱数据与共混比的定量校正模型,并对校正模型的准确性进行了验证。实验分析结果表明,该方法适合于高分子材料共混比的测定。     

人工神经网络用于预测脂肪醇沸点

本文利用误差反向传播（ＢＰ）的人工神经网络（ＡＮＮ）模型研脂肪醇的结构与沸点的定量关系。提出一组分子描述码（Ｎ，Ｃ，Ｔ＿ｍ，Ｔ＿３，Ｔ＿ｄ）作为输入的结构参数，取隐含节点数为３的三层网络用于脂肪醇沸点预测，预测结果与实验结果符合良好，优于多元回归分析的方法所得结果。     

人工神经网络吸光光度法同时测定钛锆

在钛,锆-二溴羟基苯基荧光酮-CTMAB显色体系中,应用三层ANN—BP网络解析钛和锆的吸收光谱,不经分离吸光光度法同时测定钛和锆。钛和锆的表观摩尔吸光系数分别为ε_(547)=9.66×10~4,ε_(533)=1.80×10~5。同时测定合金钢中钛和锆,结果满意。使用改进的BP算法,避免了神经网络学习过程中可能产生的麻痹现象。提出了目标向量的简单变换方法及便于网络参数选择的收敛评价函数。     

互贯型螯合树脂的研究．Ⅱ．IPN型含偕胺肟基螯合树脂的合成与性能研究

以交联聚苯乙烯－聚丙烯腈树脂为骨架，经功能基化反应制备出含偕胺肟基团的互贯型螯合树脂。对功能基化反应条件和螯合树脂对金的吸着性能，吸着选择性和吸着机理进行了研究。互贯型螯合树脂的吸着性能与互贯树脂的结构有关，而螯合树脂的选择吸着性则与互贯网络无关．     

SWELLING DYNAMICS OF A TERNARY INTERPENETRATING POLYMER NETWORK (IPN) AND CONTROLLED RELEASE OF POTASSIUM NITRATE AS A MODEL AGROCHEMICAL

ABSTRACT

An interpenetrating polymer network (IPN) of carboxymethyl cellulose (CMC), polyethylene glycol (PEG) and crosslinked polyacrylamide (PAM) has been prepared and dynamic water sorption properties have been investigated as a function of chemical architecture of the IPN, pH and temperature of the swelling medium and presence of salt ions in the bathing medium. Based on the Fick's law the swelling exponent (n) and diffusion constant (D) were evaluated suggesting possible modes of water transport through the IPN's. The IPN's synthesized were loaded with KNO₃ as a representative agrochemical and its release dynamics was studied conductometrically. The influences of percent loading and chemical composition of the IPN were also observed on the release rate and released amounts of KNO₃.     

神经网络法用于多元混酸同时测定

利用多层神经网络误差反向传播算法处理酸碱电位滴定数据，求得出多元混合酸各组分的浓度，优化了神经网络的结构和参数，测定了三组分有机酸混合样品，结果良好，平均相对偏差ＲＳＤ≤４％。