塑料用膨胀型阻燃剂

本文叙述作者合成的两种单一化合物膨胀型阻燃剂的制法及应用，这两种阻燃剂是：２，４，８，１０－四氧－３，９－二磷螺环［５．５］十一烷－３，９－二氧－３，９－二三聚氰胺盐及双［２，６］－二氧－１－磷－双环［２，２，２］辛烷－１－氧甲基）磷酸酯三聚氰胺盐。此外，本文还讨论了Ｓｐｉｎｆｌａｍ膨胀型阻燃剂与聚磷酸铵混合物的阻燃效能。     

1，1─硫─双苯并咪唑与螺二邻二亚甲基噻吩和环二邻二亚甲基噻吩的合成

报道了螺二邻二亚甲基Ｋ塞吩和环二邻二亚甲基噻吩的硫转换法合成。硫转换试剂１，１′－硫－双苯并咪唑与２，３－二羟亚甲基噻吩作用生成活性中间体２，３－二亚甲基－２，３－二氢化噻吩７，后者在室温条件下通过双自由基聚合成螺二邻二亚甲基噻吩８和环二邻二亚甲基噻吩９。螺环化合物８和环状化合物９的结构由波谱分析给予确定。     

1,1—硫—双苯并咪唑与螺二邻二亚甲基噻吩和环二邻二亚甲基噻吩的合成

报道了螺二邻二亚甲基噻吩和环二邻二亚甲基噻吩的硫转换法合成。硫转换试剂１，１＇－硫－双苯并咪唑与２，３－二羟亚甲基噻吩作用生成活性中间体２，３－二甲甲基－２，３－二氢化噻吩７，后者在室温条件下通过双自由基聚合成螺二邻二亚甲基噻吩８和环二邻二亚甲基噻吩９。螺环化合物８和环状化合物９的结构由波谱分析给予确定。     

不饱和醇型檀香的合成与分析

在合成檀香化合物３－甲基－５－（２，２，３－三甲基环戊－３－烯－１－基）－戊－２－醇的过程中，对前体化合物３－甲基－５－（２，２，３－三甲基环戊－３－烯－１－基）－３－烯－２－酮采用化学还原方法，合成出不饱和醇型檀香化合物３－甲基－５－（２，２，３－三甲基环戊－３－烯－１－基）－３－烯－戊－２－醇，对其进行了物理常数、ＩＲ、￣１ＨＮＭＲ、ＧＣ－ＭＳ的分析测定。     

4—甲基—2—环戊基苯腈和1—氰基—4—甲基—1,4—二环戊基—2,5—环己二烯的合成

本文在进行甲基苯腈与溴化环戊烷的烷基化反应同时，发现有特殊的烷基加成反应发生，得到两种新化合物４－甲基－２－环戊基苯腈和１－氰基－４－甲基－１，４－二环戊基－２，５－环己二烯，并对其结构进行了鉴定。     

L—（＋）—2—氨基—1—对硝基苯基—1,3—丙二醇的硼化反应研究

研究了Ｌ－（＋）－２－氨基－１－对硝基苯基－１，３－丙二醇及其Ｎ－酰化产物在不同条件下的硼化反应，分别得到稀烃，三配位硼酸酯和四配位硼螺环化合物。     

一种新型螺环原碳酸酯共聚改性环氧树脂的研究

本文叙述了新螺环化合物3，9—二（对甲氧基苄基）－1，5，7，11—四氧杂螺环［5，5］十一烷对环氧树脂的共聚改性。通过示差扫描量热（DSC）、热解重量分析（TG）、差热分析（DTA）和粘接拉伸强度、粘接剪切强度的测定，对改性树脂的性能进行了研究。     

螺吡喃逆向变色光量子产率测定及其光致变色特性研究

研究了１’－十八烷基－３’，３’，－二甲基－６，８－二硝基螺「２Ｈ－１－苯并吡喃－２，２’－吲哚啉」的逆向光致变色特性，通过吸收光谱测定了其在不同溶剂中可见光照后无色体的开环生色速率常数及在甲醇中有色体光照关环的光量子产率，发现溶剂的极性对开环有色体的吸收光谱影响较大，但对无色体的开环速率常数的影响相对较小。利用＾１ＨＮＭＲ分析了ＳＰ和ＭＣ的结构，证实了ＭＣ处于反式构型。     

高分辨固体^13C—NMR和XPS技术表征碳的骨架结构

本文用高分辨固体＾１３Ｃ－ＮＭＲ和ＸＰＳ技术表征了抚顺老虎台气煤吡啶抽提残煤及其热解加氢产物中四氢呋喃不溶／吡啶可溶物和吡啶不溶物的碳骨架结构。固体＾１３Ｃ－ＮＭＲ谱的研究结果表明：三个样品的芳香组体积平均碳原子数分别是为１９，２２，２５个，芳香环数目依次是５．０，５．８，６．７个。随样品中碳元素百分含量（Ｃ％）的增加，芳香组体积的平均碳原子数目和芳环数目都增加。ＸＰＳ分析结果表明：碳元素主要以类     

螺环化合物改性紫外光固化胶黏剂的研究

合成了一种具有较高膨胀效率的螺环膨胀单体,采用FT-IR对其结构和光固化特性进行了表征,考察了该单体对光固化胶黏剂的体积收缩率和粘接强度的影响。结果表明:该螺环单体能在光辐照过程中与丙烯酸环氧酯同步固化,并能有效的降低混杂型光固化胶黏剂的体积收缩率,提高粘接强度。制备出混杂型阳离子光固化胶黏剂,剪切强度达14.2MPa,剥离强度达17.8N/cm。     

Control of pore generation and pore size in nanoparticles of poly(styrene‐methyl methacrylate‐acrylic acid)

Seeded emulsion polymerization of styrene‐methyl methacrylate‐acrylic acid onto seed latexes of monodisperse particles of poly(styrene‐methyl methacrylate) was conducted with or without divinyl benzene as a crosslinking agent. Experiments revealed that almost no new particles were formed during the second stage of polymerization, and that the seeded latex particles obtained were almost monodisperse. An alkali‐acid treatment was then applied to the seeded latex particles swollen in 2‐butanone. Experimental results indicated that: (1) for uncrosslinked particles, an optimum volume expansion of >50% is reached for a ratio of the swelling agent, 2‐butanone, to polymer (methyl‐ethyl‐ketone/polymer by weight) between 2.0 and 2.9; the volume expansion is much lower outside the above range. (2) For crosslinked particles, the particle volume expansion follows the same pattern, but with smaller values. (3) pH plays an important role in pore generation and volume expansion. Pore generation is optimized by decreasing pH to a value as low as 1.5 during acid treatment, and by keeping pH in the optimum range between 11.98 and 12.20 during alkali treatment. Based on the above observations, a discussion regarding the mechanism of pore generation and particle expansion is provided. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 419–426, 1999     

遇水膨胀型聚氨酯的制备与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇、二羟甲基丙酸(DMPA)、三羟甲基丙(烷TMP)等为原料,合成了遇水膨胀型聚氨酯。用FTIR对该聚氨酯进行了结构表征,并对其遇水体积膨胀率和力学性能进行了研究。结果表明:NCO/OH摩尔比(异氰酸酯指数)为1.3～1.4时试样遇水体积膨胀率较高;随着DMPA用量的增加,试样的遇水体积膨胀率增大,拉伸强度保持率降低;加入TMP后,聚氨酯形成化学交联,拉伸强度保持率得到改善但,是试样的体积膨胀率随着TMP用量的增加而降低。     

静态膨胀剂体积增长率的实验研究

研究了无约束状态下静态膨胀剂反应前后体积增长率随时间变化的规律。采用密度测量法,研究了不同水灰比条件下静态膨胀剂的体积膨胀率和温度在24 h内发生的变化。结果表明：水灰比越大,反应速度越快;反应开始和结束的时间随着水灰比的增大而提前,反应温度最高可达到152℃;在达到最高温度后将持续此温度7～9 h,等反应结束后再降至室温;反应过程中,体积膨胀率随着水灰比的增大而降低。静态膨胀剂反应后的体积能够达到原体积的2.2倍,但考虑到流动性要求,选择水灰比在0.25～0.35之间最合适。     

Resistivity–volume expansion characteristics of carbon black‐loaded polyethylene

The resistivity and volume expansion of carbon black (CB)/high‐density polyethylene (HDPE) composite with different CB volume fractions at different temperatures were measured simultaneously. A model based on Meyer's theory is proposed to explain the positive temperature coefficient resistance (PTCR) effect. The relationship between resistivity and volume expansion was determined. It was found that the phase change is the main cause of the PTC effect in the crystalline polymer PTC materials. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 53–58, 2000     

膨胀石墨膨胀机理的研究

在进行石墨膨胀实验的过程中，发现压片后的膨胀石墨不能再次膨胀很大倍数，通过XRD研究得出，膨胀石墨仍具有石墨的结构，并且还发现鳞片石墨中灰分的含量越少膨胀体积越大，这些实验结果证明传统的膨胀机理不完善，由此推断出一个新的膨胀机理，石墨的膨胀不仅发生在层间，还发生在鳞片石墨灰分挥发后留下的空位，并对这一结论作了论证。     

A multiscale modeling for predicting the thermal expansion behaviors of 3D C/SiC composites considering porosity and fiber volume fraction

Coefficients of thermal expansion (CTEs) are an essential design criterion of the three-dimensional carbon fiber reinforced SiC matrix composites (3D C/SiC). Representative volume element (RVE) models of microscale, void/matrix, and mesoscale developed in this work were used to investigate the CTEs of these composites. A coupled temp-displacement steady-state analysis step was created for assessing the thermal expansions behaviors of the composites by applying periodic displacement and temperature boundary conditions. Three RVE models of cuboid, hexagonal and fiber random distribution were respectively established to comparatively study the influence of fiber package pattern on the CTEs at microscale. Similarly, the effects of different void size, locations, and shapes on the CTEs of the matrix are comparatively analyzed by the void/matrix models. The prediction results at mesoscale corresponded closely to the experimental results. The effect of the porosities on the CTEs was studied by the void/matrix RVE models. The voids were effective in lowering the CTE of the 3D C/SiC composites. Furthermore, the effect of fiber volume fractions on the CTE were also taken into consideration. Equal in-plane and out-of-plane CTEs were realized by selecting appropriate fiber volume fractions for the different directions. The multiscale models developed in this work can be used to predict the thermal expansion behaviors of other complex structure composites.     

The effect of low‐filler volume fraction on the elastic modulus and thermal expansion coefficient of particulate composites simulated by a multiphase model

The aim of this investigation is to determine the effect of low‐filler volume fraction on the elastic modulus and the thermal expansion coefficient of particulate composites. In the theoretical part, theoretical model valid for low‐filler volume fractions is used to evaluate these two magnitudes. In the experimental part, low‐percentage filler contents of 3, 5, 7, and 10% are used. The density for these epoxy resin‐iron particle composites is also determined. At the same time, an attempt to explain some of the disagreements observed between theoretical values and experimental data on a qualitative basis is also made. This attempt is in part assisted by scanning electron microscopy (SEM) observations concerning structural inhomogeneities and fractographical data. The comparison of the theoretical values derived from the present model with experimental results and with theoretical values derived from other workers appears satisfactory in many cases, but in some others the discrepancies among them are considerable. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

螺环原碳酸酯类膨胀单体的合成

膨胀单体和膨胀聚合反应的特点是在聚合过程中能产生体积膨胀 ,可以用于环氧树脂粘合剂的改性研究。膨胀单体中很重要的一类是螺环原碳酸酯。本文综述此类单体的合成方法。     

Reaction Front Evolution during Electrochemical Lithiation of Crystalline Silicon Nanopillars

The high theoretical specific capacity of Si as an anode material is attractive in lithium-ion batteries, although the issues caused by large volume changes during cycling have been a major challenge. Efforts have been devoted to understanding how diffusion-induced stresses cause fracture, but recent observations of anisotropic volume expansion in single-crystalline Si nanostructures require new theoretical considerations of expansion behavior during lithiation. Further experimental investigation is also necessary to better understand the anisotropy of the lithiation process. Here, we present a method to reveal the crystalline core of partially lithiated Si nanopillars with three different crystallographic orientations by using methanol to dissolve the Li atoms from the amorphous Li-Si alloy. The exposed crystalline cores have flat {110} surfaces at the pillar sidewalls; these surfaces represent the position of the reaction front between the crystalline core and the amorphous Li-Si alloy. It was also found that an amorphous Si structure remained on the flat surfaces of the crystalline core after dissolution of the Li, which was presumed to be caused by the accumulation of Si atoms left over from the removal of Li from the Li-Si alloy.     

Free volume and dipole mobility in an epoxide oligomer before crosslinking

The free volume of a bisphenol‐A‐type epoxide oligomer (DGEBA) was studied using Williams–Landel–Ferry parameters and thermal expansion coefficients above and below the glass transition temperature (T_g). The values of the free‐volume fraction at the T_g are around 0.02 for the DGEBA oligomers having weight‐average molecular weights (M _w's) from 1396 to 2640. The dipole mobility, which was obtained from the analysis of the temperature dependence of the dielectric relaxation time, was compared with the segment mobility in terms of the critical volume for the transport of each moving unit. The critical volume for the segment transport increases with increase of the M _w of the oligomer. The critical volume for the dipole movement, on the other hand, is not different between the oligomers studied (1396 ≤ M _w ≤ 2640), which leads to that the dipole mobility in the epoxide oligomer is smaller than is the segment mobility. The low mobility of the dipole is considered to result from the molecular interaction restricting the dipole movement, especially in a smaller M _w oligomer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 207–214, 1999