由（双氯代酞酰亚胺）与双酚盐的亲核取代缩聚合成聚酰亚胺的研究

利用邻苯二甲酸酐中苯环上的取代基由于受到两个羰基的吸电子作用有较好的活性，进行亲核取代反应合成聚酰亚胺近年来才引起人们的注意。根据这个反应可以从邻苯二甲酸酐出发，与双酚缩合先合成二酐单体，再与二胺反应合成易加工而性能良好的聚酰亚胺，而且已实现了工业生产。同时也可以从双取代酞酰亚胺出发直接与双酚进行亲核取代缩聚合成相同结构的聚酰亚胺。后者较前者具有合成路线短的优点，又无前者由于多种会反应所引起复杂分子链结构等缺点。文献上对双（硝基酞酰亚胺）与双酚的亲核取代缩聚反应合成聚酰亚胺的研究工作，有一些报导，而对双（氯代酞酰亚胺）与双酚A的亲核取代缩聚亦有专利，从文献报导来看，亲核取代缩聚法合成聚酰亚胺因反应条件要求苛刻，利用此法还不易合成出分子量高的聚合物。如何克服上述缺点，解决合成上的问题，是很有意义的。我们以双酚A与双（4－氯代酞亚胺）二苯醚的亲核取代缩聚反应为重点，采用NaOH溶液成盐的方法进行双（氯代酞酰亚胺）与双酚的亲核取代缩聚合成聚酰亚胺的研究。对影响反应的各种参数，如碱量，温度、固含量，溶剂，代水剂以及水份等对反应的影响，作了比较详细的探索，提出了从双（氯代酞酰亚胺）与双酚出发，用NaOH溶液成盐，通过亲核取代缩聚反应合成聚酰亚胺的比较合适的条件。研究了几种具有代表性的不同结构的双酚分别与双（4－氯代酞酰亚胺）二苯醚和双（3－氯代酞酰亚胺）二苯醚的亲核取代缩聚反应，所得结果表明，在相同的反应条件下，反应的难易一般取决于苯氧负离子的电子密度，和反应中心上正电荷对电子的吸引力，以及聚合物的溶解性。双酚A不仅其氧负离子有很强的亲核性，而且所得聚合的溶解性能也很好，照理应能很好地进行反应，但无论从我们的工作或文献上报导的结果来看，用惯常方法，以NaOH溶液成盐，从双酚A很难得比浓对数粘度较高的聚合物（美国专利从双（氯代酞酰亚胺）出发，合成的双酚A型聚酰亚胺的比浓对数粘度为0.21分升／克，美国General Electric Compang从双（硝茎酞酰亚胺）二苯醚与双酚A缩聚反应所得聚合物的比浓对数粘度是0.23分升／克）。我们从电子密度大的苯氧基虽有较强的亲核能力，但也同时具有较强的与反体系中微量水份形成氢键的能力出发考虑，认为解决问题的关键在于如何使体系中微量水份排除尽，为此我们采用两次代水方法，效果较为明显，使双酚A与双（4－氯代酞酰亚胺）二苯醚缩聚所得聚合物的比浓对数粘度达到0.4分升／克（DMAC，30℃），在此条件下，研究了不同结构的单体的构聚和共聚反应，所合成的一系列均聚和共聚物比浓和粘度在0.4～0.7分升／克范围，且通过共聚可以改善聚合物的溶解性，改进反应情况。在此基础上，我们又对双酚A与双（4－氯代酞酰亚胺）二苯醚的缩聚反应，用NaOH溶值成盐进行了五次代水实险，所得聚合物的分子量又得到进一步提高，其比浓对数粘度达到0.59分升／克。这些研究结果说明我们上述分析是正确的，同时也说明，双氯单体的活是不及双硝基单体，但在我们提出的实验条件下，反应也能很好的进行，而且此种方法没有双硝基单体与酚盐取代反应后所释放的亚硝酸盐所易引起的会反应。我们对所合成的各种不同结构的聚酰亚胺分别利用红外，核磁，X－射线，裂解色谱等进行了结构上的初步分析和探讨。不同结构的聚酰亚胺的红外光谱的显示出所合的聚合物特征峰，结合元素分析结果，并参照合成反应的基本原理证实了所合成的聚酰亚胺的化学结构与所予期的相符。在红外光谱上也初步鉴别了3们异构体聚酰亚胺和4位异构体聚酰亚胺。用~(13)C-NMR对本法所合成的溶解性较好的4种不同结构的聚酰亚胺进行表征，进一步证实了所得聚合物的化学结构，其中两种聚酰胺的~(13)C-NMR谱图与最近文献报导的从双（硝基酞酰亚胺）二苯醚与双酚A进行亲核取代缩聚所得相同结构的聚酰亚胺的~(13)C-NMR表征结果一致。~(13)C-NMR，~1C-NMR鉴定结果还表明利用双(酞酰亚胺)一醚虽需较高温度条件下进行取代缩聚反应，而聚合物的化学结构没有受到破坏。~(13)C-NMR也证明了从双（3－氯代酞酰亚胺）二苯醚出发所合成的聚合物的化学结构。用X－射线对不同结构的聚酰亚胺均聚物和共聚物进行结晶性的初步鉴定，其中由双酚醚和联苯双酚分别与双（4－氯代酞酰亚胺）二苯醚的缩聚产物具有一定程度的结晶，并通过DSC析测发现结晶熔融吸热峰予以进一步证实。普通X－射线鉴定结果对3位和4位异构聚酰亚胺的溶解性能上的差异作出解释。对不同结构的聚酰亚胺用居里点裂解器进行裂解色谱的初步研究和探讨，通过主要裂解产物进一步证明所合成的聚合物的化学结构，并讨论了裂解过程和机理。对各种不同结构的均聚和共聚聚酰亚胺进行溶解性及热稳定性的研究，并与从二胺和二酐出发合成的聚酰亚胺进行比较。亲核取代缩聚法所合成的聚酰胺不仅均有较明显的玻璃化转变，而且也有较好的溶解性能。从二酐与二胺所得相同结构的聚酰亚胺溶解性能不好，可能是由于在热处理环化过程中不易掌握容易产生交联所致。在溶解性能方面还表明3位异构体聚酰亚胺普遍处于4位异构体，由双酚A参与共聚的聚酰亚胺其溶解性能却不同程度地得到改善。热性能研究表明4位异构体聚酰亚胺较3位异构体聚酰亚胺稍稳定，由二酐与二胺缩聚和通过某核取代缩聚所得的相同结构的聚亚胺经DTA和DSC测试，其热稳定性基本相同。

Electric and magnetic losses and gains in determining the sign of refractive index

Within the framework of classic electromagnetic theories, we have studied the sign of refractive index of optical medias with the emphases on the roles of the electric and magnetic losses and gains. Starting from the Maxwell equations for an isotropic and homogeneous media, we have derived the general form of the complex refractive index and its relation with the complex electric permittivity and magnetic permeability, i.e. n = root epsilon mu, in which the intrinsic electric and magnetic losses and gains are included as the imaginary parts of the complex permittivity and permeability, respectively, as epsilon = epsilon(r) + i(epsilon i) and mu = mu(r) + i mu(i). The electric and magnetic losses are present in all passive materials, which correspond, respectively, to the positive imaginary permittivity and permeability epsilon(i) > 0 and mu(i) > 0. The electric and magnetic gains are present in materials where external pumping sources enable the light to be amplified instead of attenuated, which correspond, respectively, to the negative imaginary permittivity and permeability epsilon(i) < 0 and mu(i) < 0. We have analyzed and determined uniquely the sign of the refractive index, for all possible combinations of the four parameters epsilon(r), mu(r), epsilon(i), and mu(i), in light of the relativistic causality. A causal solution requires that the wave impedance be positive Re {Z} > 0. We illustrate the results for all cases in tables of the sign of refractive index. One of the most important messages from the sign tables is that, apart from the well-known case where simultaneously epsilon < 0 and mu < 0, there are other possibilities for the refractive index to be negative n < 0, for example, for epsilon(r) < 0, mu(r) > 0, epsilon(i) > 0, and mu(i) > 0, the refractive index is negative n < 0 provided mu(i)/epsilon(i) > mu(r)/vertical bar epsilon(r)vertical bar. (c) 2006 Elsevier B.V. All rights reserved.

Static and dynamic electric field domain formation in a doped GaAs/AlAs superlattice

We have observed the transition from static to dynamic electric field domain formation induced by a transverse magnetic field and the sample temperature in a doped GaAs/AlAs superlattice. The observations can be very well explained by a general analysis of instabilities and oscillations of the sequential tunnelling current in superlattices based solely on the magnitude of the negative differential resistance region in the tunnelling characteristic of a single barrier. Both increasing magnetic field and sample temperature change the negative differential resistance and cause the transition between static and dynamic electric field domain formation. (C) 2000 Elsevier Science B.V. All rights reserved.

Dynamic dc voltage band observed within each current branch in the transition from static to dynamic electric-field domain formation in a doped GaAs/AlAs superlattice

A dynamic dc voltage band was found emerging from each sawtooth-like branch of the current-voltage characteristics of a doped GaAs/AlAs superlattice in the transition process from static to dynamic electric-field domain formation caused by increasing the sample temperature. As the temperature increases, these dynamic dc voltage bands expand within each sawtooth-like branch, squeeze out the static regions, and join up together to turn the whole plateau into dynamic electric-field domain formation. These results are well explained by a general analysis of stability of the sequential tunneling current in superlattices. (C) 1999 American Institute of Physics. [S0003-6951(99)04443-5].

Optical response in a quantum dot superlattice nanoring under a lateral electric field

The optical absorption of a GaAs/AlGaAs quantum dot superlattice nanoring (QDSLNR) under a lateral dc electric field and with magnetic flux threading the ring is investigated. This structure and configuration provides a unique opportunity to study the optical response of a superlattice under an inhomogeneous electric field, which is not easily realized for general quantum well superlattices (QWSLs) but naturally realized for QDSLNRs under a homogeneous lateral electric field. It has been shown that a lateral dc electric field gives rise to a substantial change of the optical absorption spectra. Under a low field, the excitonic optical absorption is dominated by a 1s exciton. And with the electric field increasing, the optical absorption undergoes a transition from 1s excitonic absorption to 0 excitronic WSL absorption. (The number of 0, and -1 and +1 below are WSLs index.) The -1 and the +1 WSLs corresponding to the maximum effective field can also be identified. Due to the inhomogeneity of the electric field, the peaks of the -1 and the +1 WSLs are diminished and between them there exist rich and complicated structures. This is in contrast to the general QWSLs under a homogenous electric field. The complicated structures can be understood by considering the inhomogeneity of the electric field along the ring, which results in the nearest-neighbor transition, the next-nearest-neighbor transition, etc., have a different value repectively, at different sites along the ring. This may give rise to multiple WSLs. We have also shown that the line shape of the optical absorption is not sensitive to the threading magnetic flux. The threading magnetic flux only gives rise to a slight diamagnetic shift. Thus the enhancement of the sensitivity to the flux allowing for observation of the excitonic Aharanov-Bohm effect in the plain nanoring is not expected in QDSLNRs.

Static and dynamic electric field domain formation in a doped GaAs/AlAs superlattice

We have observed the transition from static to dynamic electric field domain formation induced by a transverse magnetic field and the sample temperature in a doped GaAs/AlAs superlattice. The observations can be very well explained by a general analysis of instabilities and oscillations of the sequential tunnelling current in superlattices based solely on the magnitude of the negative differential resistance region in the tunnelling characteristic of a single barrier. Both increasing magnetic field and sample temperature change the negative differential resistance and cause the transition between static and dynamic electric field domain formation. (C) 2000 Elsevier Science B.V. All rights reserved.

General SU(2)(L) x SU(2)(R) x U(1)(EM) sigma model with external sources, dynamical breaking and spontaneous vacuum symmetry breaking

We give a general SU(2)(L) x SU(2)(R) x U(1)(EM) sigma model with external sources, dynamical breaking and spontaneous vacuum symmetry breaking, and present the general formulation of the model. It is found that sigma and pi(0) without electric charges have electromagnetic interaction effects coming front the internal structures. A general Lorentz transformation relative to external sources J(gauge) - (J(A mu) J(A mu)(kappa)) derived, using the general Lorentz transformation and the four-dimensional current of nuclear matter of the ground si ate with J(gauge) = 0, we give the four-dimensional general relations between the different currents of nuclear matter systems with J(gauge) not equal 0 and those with J(gauge) = 0. The relation of the density's coupling with external magnetic field is derived, which conforms well to dense nuclear matter in a strong magnetic field. We show different condensed effects in strong interaction about fermions and antifermions, and give the concrete scalar and pseudoscalar condensed expressions of sigma(0) and pi(0) bosons. About different dynamical breaking and spontaneous vacuum symmetry breaking, the concrete expressions of different mass spectra are obtained in field theory. This paper acquires the running spontaneous vacuum breaking value sigma'(0), and obtains the spontaneous vacuum breaking in tenus of the running sigma'(0), which make nucleon, sigma, and pi particles gain effective masses. We achieve both the effect of external sources and nonvanishing value of the condensed scalar and pseudoscalar paticles. It is deduced that the masses of nucleons, sigma and pi generally depend on different external sources.

Dielectric response of graded composites having general power-law-graded cylindrical inclusions

The dielectric response of graded composites having general power-law-graded cylindrical inclusions under a uniform applied electric field is investigated. The dielectric profile of the cylindrical inclusions is modeled by the equation epsilon(i)(r)=c(b+r)(k) (where r is the radius of the cylindrical inclusions and c, b and k are parameters). Analytical solutions for the local electrical potentials are derived in terms of hypergeometric functions and the effective dielectric response of the graded composites is predicted in the dilute limit. Moreover, for a simple power-law dielectric profile epsilon(i)(r) = cr(k) and a linear dielectric profile epsilon(i)(r) = c(b + r), analytical expressions of the electrical potentials and the effective dielectric response are derived exactly from our results by taking the limits b -> 0 and k -> 1, respectively. For a higher concentration of inclusions, the effective dielectric response is estimated by an effective-medium approximation. In addition, we have discussed the effective response of graded cylindrical composites with a more complex dielectric profile of inclusion, epsilon(i)(r)=c(b+r)(k)e(beta r). (c) 2005 American Institute of Physics.

Effective dielectric responses of graded composites of the particles with a general power-law gradation profile

The effective dielectric response of graded spherical composites having general power-law gradient inclusions is investigated under a uniform applied electric field, where the dielectric gradation profile of the spherical inclusions is modeled by the equation epsilon(i) (r) = c(b+r)(k). Analytical solutions of the local electrical potentials are derived in terms of hyper-geometric function and the effective dielectric response of the graded composites is predicted in the dilute limit. From our result, the local potentials of graded spherical composites having both simple power-law dielectric profile epsilon(i)(r) = cr(k) and linear dielectric profile epsilon(i) (r) = c(b+r) are derived exactly by taking the limits b --> 0 and k --> 1, respectively. In the dilute limit, our exact result is used to test the validity of differential effective dipole approximation (DEDA) for estimating the effective response of graded spherical composites, and it is shown that the DEDA is in excellent agreement with exact result. (C) 2005 Elsevier B.V. All rights reserved.

Effective dielectric response of nonlinear composites with external ac and dc electric field

The perturbation method is developed to investigate the effective nonlinear dielectric response of Kerr composites when the external ac and dc electric field is applied. Under the external ac and dc electric field E-app=E-a(1+sin omegat), the effective coupling nonlinear response can be induced by the cubic nonlinearity of Kerr nonlinear materials at the zero frequency, the finite basic frequency omega, the second and the third harmonics, 2omega and 3omega, and so on. As an example, we have investigated the cylindrical inclusions randomly embedded in a host and derived the formulas of the effective nonlinear dielectric response at harmonics in dilute limit. For a higher concentration of inclusions, we have proposed a nonlinear effective-medium approximation by introducing the general effective nonlinear response. With the relationships between the effective nonlinear response at harmonics and the general effective nonlinear response, we have derived a set of formulas of the effective nonlinear dielectric responses at harmonics for a larger volume fraction. (C) 2004 American Institute of Physics.

Higher order response of nonlinear composite in external AC electric field

The fifth-order effective nonlinear responses at fundament frequency and higher-order harmonics are given for nonlinear composites, which obey a current-field relation of the form J = sigmaE + x\E\(2) E, if a sinusoidal alternating current (AC) external field with finite frequency omega is applied. As two examples, we have investigated the cylinder and spherical inclusion embedded in a host and, for larger volume fraction, also derived the formulae of effective nonlinear responses at higher-order harmonics by the aid of the general effective response definition. Furthermore, the relationships between effective nonlinear responses at harmonics are given. (C) 2003 Elsevier Science B.V. All rights reserved.

Effective response of a non-linear composite in external AC electric field

A general effective response is proposed for nonlinear composite media, which obey a current field relation of the form J = sigmaE + chi\E\(2) E when an external alternating current (AC) electrical field is applied. For a sinusoidal applied field with finite frequency omega, the effective constitutive relation between the current density and electric field can be defined as, = sigma(e) + chi(e) <\E(x, omega, t)\(2) E(x, omega, t)> + (. . .), where sigma(e) and chi(e) are the general effective linear and nonlinear conductive responses, respectively. The angled brackets <(. . .)> denotes the ensemble average. As two examples, we have investigated the cylindrical and spherical inclusions embedded in a host and also derived the formulae of the general effective linear and nonlinear conductive responses in dilute limit. For higher volume fraction of inclusions, we have proposed a nonlinear effective medium approximation (EMA) method to estimate the general effective response of nonlinear composites in external AC field. Furthermore, the effective nonlinear responses at harmonics are predicted by using the general effective response. (C) 2002 Elsevier Science B.V. All rights reserved.