Af型自由基均聚反应的固化理论(Ⅱ)——凝胶网络的结构参数

用高分子反应统计理论,给出A_f型自由基均聚反应在不同反应程度时的弹性有效链及悬吊链的链数、链节数和平均链长,也得到了体系的有效交联点数和弹性模量,进而给出弹性有效链的数量和重量分数,以此可进一步揭示该反应体系凝胶网络的粘弹性及相关的力学性质.     

Aluminum Alkyls as Highly Active Catalytic Chain Transfer Agents

During the production of free radical initiated low‐density polyethylene (LDPE), it was discovered that the addition of low levels of alkyl aluminum compounds caused the molecular weight of the LDPE to drop precipitously. Further investigation demonstrated that aluminum‐alkyl compounds are among the most effective chain transfer agents ever utilized. It was also shown that polymer chains, which transfer to Al alkyl species, contain almost exclusively vinyl terminated end groups. A catalytic chain transfer mechanism is proposed in which chain transfer occurs from a growing polymer chain to an aluminum center followed by beta hydride elimination to produce a vinyl terminated polymer chain and a new aluminum hydride bond. This new aluminum hydride bond can then undergo further chain transfer reactions. This is the first time such a catalytic chain transfer mechanism has been reported. As little as 10–20 mol ppm aluminum alkyl species decreased the degree of polymerization by a factor of 2 resulting in chain transfer constant (C_s) values as high as 1000–2000. Density functional theory (DFT) study elucidated the catalytic cycle of triethylaluminum (TEA). It is discovered that, depending on the reaction conditions, TEA can serve as a conventional as well as catalytic chain transfer agent.     

Steric and bridging interactions between two plates induced by grafted polyelectrolytes

If colloidal particles are grafted with a polymer, then the grafted chains can provide steric repulsion between them. If some of the grafted polymer chains are also adsorbed to a second particle, then a bridging force is generated as well. For uncharged plates and polymer, the following contributions to the free energy of the system have been taken into account in the calculation of the interaction force: (i) the Flory-Huggins expression for the mixing free energy of the grafted chains with the liquid; (ii) the entropy loss due to the connectivity of the polymeric segments; (iii) the van der Waals interactions between the segments and the plates; and (iv) the free energy of adsorption of the polymer segments of the grafted chains on the other plate. For charged plates, the electrostatic free energy as well as the free energy of the electrolyte are included in the total free energy of the system. By minimizing the free energy with respect to the segment concentration and, when it is the case, with respect to the electrical potential, equations for the segment number density distribution and for the electrical potential are obtained, on the basis of which the interactions between two plates grafted with polymer chains that can be also adsorbed on the other plate were calculated. The interaction thus obtained includes steric and bridging forces.     

High density cationic polymer brushes from combined “click chemistry” and RAFT‐mediated polymerization

A simple method for preparing cationic poly[(ar‐vinylbenzyl)trimethylammonium chloride)] [poly(VBTAC)] brushes was used by combined technology of “click chemistry” and reversible addition‐fragmentation chain transfer (RAFT) polymerization. Initially, silicon surfaces were modified with RAFT chain transfer agent by using a click reaction involving an azide‐modified silicon wafer and alkyne‐terminated 4‐cyanopentanoic acid dithiobenzoate (CPAD). A series of poly(VBTAC) brushes on silicon surface with different molecular weights, thicknesses, and grafting densities were then synthesized by RAFT‐mediated polymerization from the surface immobilized CPAD. The immobilization of CPAD on the silicon wafer and the subsequent polymer formation were characterized by X‐ray photoelectron spectroscopy, water contact angle measurements, grazing angle‐Fourier transform infrared spectroscopy, atomic force microscopy, and ellipsometry analysis. The addition of free CPAD was required for the formation of well‐defined polymer brushes, which subsequently resulted in the presence of free polymer chains in solution. The free polymer chains were isolated and used to estimate the molecular weights and polydispersity index of chains attached to the surface. In addition, by varying the polymerization time, we were able to obtain poly(VBTAC) brushes with grafting density up to 0.78 chains/nm² with homogeneous distributions of apparent needle‐like structures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Modified interfacial statistical associating fluid theory: application to tethered polymer chains

Modified interfacial statistical associating fluid theory density functional theory is extended to tethered polymer chains in the absence or presence of free polymer chains. The structures of the "dry" and "wet" polymer brushes have been calculated and compared with simulation results available in the literature. The comparisons show that the theory accurately predicts the structure of the tethered polymer brush. The average brush heights calculated from the theory agree with well-established scaling theories for tethered polymers. However, these scaling theories cannot predict the detailed structure, accurately. The effects of the segment-segment interactions of the tethered polymer and the free polymer have been effectively captured by the theory.     

Molecular weight distribution in emulsion polymerizations

A mathematical formulation is given which describes the evolution of the number distribution of the molecular weight (MWD) of linear polymer chains that grow in emulsion polymerization systems. The resulting set of coupled ordinary differential equations takes into account the microscopic events of free radical entry, exit, chain annihilation, bimolecular termination (by combination and disproportionation), and chain transfer in a mono- or polydisperse system. Simple analytic solutions are presented for systems in which the number of particles, as well as the average number of free radicals per particle, is constant and in which the rate coefficients are size independent. These solutions indicate that compartmentalization of the free radicals in the latex particles results in a significant increase in the polydispersity of the polymer produced by emulsion polymerization, compared with that in bulk systems. The theory shows that significant mechanistic information may be obtained from experimental MWDs and that, in principle, experimental conditions may be prescribed to grow a desired MWD. The MWDs are presented in a novel manner that facilitates the comparison of theory with experiment.     

Interactions between polymer brushes in solvents of variable quality: a density functional theory study

We present a density functional theory study of interactions between sterically stabilized colloidal particles in solvents of variable quality. Both flat and spherical polymer brushes are considered, as well as both monatomic and polymeric solvents. It is shown that the interaction between sterically stabilized particles can be tuned from repulsive to attractive by varying the solvent quality, the relative length of free and grafted chains, and by employing a mixed brush consisting of both well and poorly solvated chains.     

甲基丙烯酸甲酯/苯乙烯在硅片表面的RAFT接枝聚合

将3-(2-二硫代苯甲酸基丙酰氧基)丙基二甲基甲氧基硅烷化学键合于硅片表面.以甲基丙烯酸甲酯和苯乙烯为单体,在硅片表面进行可逆加成-断裂链转移(RAFT)接枝聚合.X-射线光电子能谱仪证实聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、苯乙烯/甲基丙烯酸甲酯的共聚物(poly(MMA-co-St))都接枝到硅片表面.但3个体系表现出不同的性质,甲基丙烯酸甲酯的RAFT聚合可控性差,分子量比设计分子量大得多,分子量分布指数宽,接枝密度仅为0·03chains/nm2;苯乙烯均聚合的活性/可控性好、分子量分布窄,接枝密度提高到0·21chains/nm2;共聚合体系综合了两个均聚体系的优点,分子量分布较窄,接枝密度最高为0·31chains/nm2,聚合物膜厚随转化率、数均分子量基本呈线性增长.     

Sterically stabilized lock and key colloids: a self-consistent field theory study

A self-consistent field theory study of lock and key type interactions between sterically stabilized colloids in polymer solution is performed. Both the key particle and the lock cavity are assumed to have cylindrical shape and their surfaces are uniformly grafted with polymer chains. The lock-key potential of mean force is computed for various model parameters, such as length of free and grafted chains, lock and key size matching, free chain volume fraction, grafting density, and various enthalpic interactions present in the system. The lock-key interaction is found to be highly tunable, which is important in the rapidly developing field of particle self-assembly.     

Investigating the Dynamic Viscoelasticity of Single Polymer Chains using Atomic Force Microscopy

In single‐molecule force spectroscopy (SMFS), many studies have focused on the elasticity and conformation of polymer chains, but little attention has been devoted to the dynamic properties of single polymer chains. In this study, we measured the energy dissipation and elastic properties of single polystyrene (PS) chains in toluene, methanol, and N,N‐dimethylformamide using a homemade piezo‐control and data acquisition system externally coupled to a commercial atomic force microscope (AFM), which provided more accurate information regarding the dynamic properties of the PS chains. We quantitatively measured the chain length‐dependent changes in the stiffness and viscosity of a single chain using a phenomenological model consistent with the theory of viscoelasticity for polymer chains in dilute solution. The effective viscosity of a polymer chain can be determined using the Kirkwood model, which is independent of the intrinsic viscosity of the solvent and dependent on the interaction between the polymer and solvent. The results indicated that the viscosity of a single PS chain is dominated by the interaction between the polymer and solvent. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1736–1743     

Taylor expansion of polymer chain dispersion relations and spectral densities to calculate thermodynamic functions

It is shown how to calculate exactly the derivatives of the dispersion relation and the spectral density for arbitrary regular polymer chains in harmonic approximation. The theory is based on a generalization of the characteristic polynomial. In the vibrational part of the free energy and other thermodynamic functions, the integral over normal modes is done approximately by Taylor expanding the density of states.Dedicated to Professor Dr. F. H. Müller.     

Density functional theory of homopolymer mixtures confined in a slit

A density functional theory (DFT) is developed for polymer mixtures with shorted-ranged attractive interparticle interactions confined in a slit. Different weighting functions are used separately for the repulsive part and the attractive part of the excess free energy functional by applying the weighted density approximation. The predicted results by DFT are in good agreement with the corresponding simulation data indicating the reliability of the theory. Furthermore, the center-of-mass profiles and the end-to-end distance distributions are obtained by the single chain simulation; the predictions also agree well with simulation data. The results reveal that both the attraction of the slit wall and the temperature has stronger effect on longer chains than on shorter ones because the intrasegment correlation of chains increases with increasing chain length.     

Curing theory of A_f-A_g type free radical polymerization (Ⅱ)——Characterization of network structural parameters

By means of the polymer statistical theory, the A_f-A_g type nonlinear free radical polymerization is investigated to give the number of effective elastic chains, the number of effective elastic mers and the average length for the elastic chains. The corresponding quantities for the dangling chains, the number of effective cross-linkage and the modulus are also obtained. Furthermore, the number- and weight-fractions of elastic chains are deduced.     

Molecular weight distribution in free radical polymerization with long-chain branching

A new theory to predict the molecular weight distribution in free radical polymerization that includes chain transfer to polymer is proposed. This theory is based on the branching density distribution of the primary polymer molecules. The branching density distribution provides the information on how each chain is connected to other chains, and therefore, a full molecular weight distribution can be calculated by application of the Monte Carlo simulation. The present theory accounts for the history of the generated branched structure and can be applied to various reaction systems that involve branching and crosslinking regardless of the reactor types used. The present simulation confirmed the validity of the method of moments in a batch polymerization proposed earlier. It was shown clearly why gelation never occurs by chain transfer to polymer without the assistance of other interlinking reaction such as bimolecular termination by combination. © 1993 John Wiley & Sons, Inc.     

Modeling the solid-like behavior of entangled polymer nanocomposites at low frequency regimes

A theory for the linear viscoelastic behavior of entangled polymeric liquids reinforced with non-aggregated colloidal nanoparticles is presented. Composites with low filler concentration and strong polymer-particle interaction are considered. A fraction of entangled chains is assumed to be reversibly adsorbed on the surface of fillers, due to the affinity between the polymer molecules in the matrix and dispersed filler particles. The relaxation of the system is analyzed by the combination of stress relaxation functions for free and adsorbed polymer chains. It is demonstrated that the emergence of solid-like behavior at low frequency regimes, is due to the significant slow down in relaxation of adsorbed chains. Fitting the model predictions with relevant experimental data indicates that while the effect of constraint release should be considered to obtain a reasonable estimation of neat polymer behavior, the linear combination of stress relaxation functions of free and adsorbed chains (i.e., no thermal constraint release) leads to a better agreement with experimental data of filled systems.     

Accelerated brush growth on nanoparticle surfaces by reversible addition‐fragmentation chain transfer polymerization

It is now well established that controlling the grafted chain lengths and densities on nanoparticle surfaces determines the effective interactions between particles, and their assembly. Here, we present unusual kinetic results for achieving grafted chain lengths longer than the free chains using reversible addition‐fragmentation chain transfer (RAFT) polymerization and discuss the limitations to obtaining polymer grafting density higher than ～0.06 chains/nm². We observe that surface initiated polymerization grows faster than the free chains in solution with high RAFT agent coverage (1.95 agents/nm²) on nanoparticles. The time‐dependence of graft density suggests that activation of the anchored chain transfer agent (CTA) is limited by the diffusion of macro‐radicals within growing grafts. Thus, radical transfer and exchange reactions become inefficient between grafts and free polymer, and convert the surface‐initiated RAFT mechanism to a free radical polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1700–1705     

Flexible polyelectrolyte simulations at the Poisson-Boltzmann level: a comparison of the kink-jump and multigrid configurational-bias Monte Carlo methods

We present a new approach for simulating the motions of flexible polyelectrolyte chains based on the continuous kink-jump Monte Carlo technique coupled to a lattice field theory based calculation of the Poisson-Boltzmann (PB) electrostatic free energy "on the fly." This approach is compared to the configurational-bias Monte Carlo technique, in which the chains are grown on a lattice and the PB equation is solved for each configuration with a linear scaling multigrid method to obtain the many-body free energy. The two approaches are used to calculate end-to-end distances of charged polymer chains in solutions with varying ionic strengths and give similar numerical results. The configurational-bias Monte Carlo/multigrid PB method is found to be more efficient, while the kink-jump Monte Carlo method shows potential utility for simulating nonequilibrium polyelectrolyte dynamics.     

螺旋型高分子链晶体结构所属空间群的演变规律性

本文利用有色对称的理论讨论了螺旋型高分子链晶体结构所属空间群的演变规律性。得出：（１）有序链结构的空间群是无序链结构空间群的有色空间群；（２）对称性较低的螺旋链所属空间群是高对称螺旋链所属空间群的有色空间群；（３）从而得出空间群演变的方向、途径和结果，总结出其演变的规律性。     

非线性Af—Bg型自由基交替共聚反应的凝胶网络结构参数

利用高分子反应统计理论,计算了非线性Ａｆ－Ｂｇ型自由基交替共聚反应凝胶网络中的弹性有效链和悬吊链的链数及相应的链节数,进而计算出弹性有效链的数量和质量分数、有效交联点数和弹性量等网络结构参数。