The interaction parameter of crosslinked networks and star polymers

Recent results on blends containing star polymers have revived the interest on the interaction parameters of structures that contain junctions between chains, a matter which can be connected with the earlier studies on the influence of crosslinks on the interaction parameters of polymer networks and gels. Here, we review results on crosslinked networks and star polymer solutions together with the more recent work on star polymer blends. The review covers swelling and elastic deformation of gels, differential vapour sorption between crosslinked and uncrosslinked polymers, osmotic equilibrium of gels and of star polymer solutions, and neutron scattering of polymer blends containing star polymers. In the systems reviewed, the interaction parameters of stars and networks differ from those of linear chains, and the difference is attributed mainly to entropic effects.     

Interpolymer complex formation of some nonionogenic polymers with linear and crosslinked polyacrylic acid

The formation of interpolymer complexes on the surface of crosslinked poly (acrylic acid) with some nonionogenic polymers is compared with the complex formation in analogous linear polymer systems. The behavior of these systems is compared with that of complexes of two oppositely charged polyelectrolytes. The concentration redistribution of the linear polymer in the system polyelectrolyte network-polymer solution and the degree of swelling of this network in these solutions were determined. © 1994 John Wiley & Sons, Inc.     

Swelling and fractal heterogeneities in networks

In this paper we revisit old swelling data on polymer networks that have not been interpreted theoretically on a closed molecular basis. If the osmotic pressure of the swollen network is compared to the osmotic pressure of the corresponding uncrosslinked solution unsolved problems appear, when the relative osmotic pressure is plotted against the degree of swelling, i.e. the deformation due to swelling. A significant maximum appears which cannot be explained by any of the recently derived elastic models, such as junction constraint or other entanglement models. It is suggested in this paper that the maximum is a consequence of structural heterogeneities of fractal nature. If such fractal heterogeneities are assumed a strong maximum in the relative osmotic pressure can be reproduced. The physical reason is the different thermodynamic behavior of uncrosslinked linear chains and crosslinked self-similar (non-linear) polymers. The conclusion is supported by numerical (Monte Carlo) simulations.     

A generalized theory for the glass transition temperature of crosslinked and uncrosslinked polymers

A generalized theory for the glass transition temperature of crosslinked and uncrosslinked polymers has been developed, which takes into account the influences of end groups, branching, and crosslinking, and their functionality distribution. DiBenedetto's theory was found to correctly characterize the influence of crosslinks on the glass temperature. Normalized to constant crosslink functionality, the crosslink constant is a universal parameter suggesting that the entropic theory of glasses is applicable to crosslinked systems. Data on linear polymers and networks from the crosslinking of polymer chains, vinyl/divinyl-copolymers and step-growth polymers, such as polyurethanes, amine-cured epoxies, or inorganic glasses, are presented.     

Kinetics of solvent absorption and permeation through a highly swellable elastomeric network

To model a polymer gel or an elastomer undergoing a large change in volume under the action of a solvent diffusing in or out of it, a theoretical approach based on an elastohydrodynamic point of view is proposed. Drawing a parallel between the polymer network/solvent system of interest and a liquid flowing through a porous medium, the friction between the polymer and the solvent is described phenomenologically. An equation that couples the large elastic deformations undergone by the polymer network and the diffusion process is derived and then solved numerically in various cases. Special emphasis is placed on the influence of the shear elasticity during the diffusion process. During the swelling process, a nonzero shear modulus induces a nonisotropic swelling at the surface that is responsible for the “sigmoidal” shape of the mass uptake of solvent with the square root of time, as well as for the presence of a “front” in the concentration profile when the solvent advances inside the network. In a permeation process, the solvent flux deviates from its linear behavior as soon as a nonnegligible deformation of the membrane is present. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 166–182, 2003     

Modelling of water transport in ionic hydrophilic polymers

Water and ion transport in thin sheets of initially dry, ionic, hydrophilic crosslinked polymers was modelled throughout the dynamic swelling process. The water transport was expressed in terms of a non-Fickian equation with a diffusion term containing a Fujitatype concentration-dependent diffusion coefficient coupled with a pseudoconvective term arising from the reasonable assumption that the stress in ionic polymers is proportional to the total number of ionized pendant groups in the polymer. Ion transport was expressed in terms of generalized Fickian equations with water concentration-dependent diffusion coefficients. These equations were solved with appropriate boundary conditions to establish the water uptake as a function of time, pH and ionic strength in a citrate-phosphate-borate buffer solution. A new dimensionless number, the Stress Swelling number, A, was defined to quantify the relative importance of stress in the overall swelling process. Water uptake was a strong function of A. © 1994 John Wiley & Sons, Inc.     

Elastic properties of crosslinked poly(vinyl alcohol) gels: Network topology

Current network theory exhibits inconsistencies which show up particularly clearly in deformation of networks prepared by crosslinking a polymer in solution. A check of theory can be obtained if one knows precisely the number of crosslinks in the network and if a range of deformations is applied to the network. In an effort to explore this problem we have examined the relation of shear modulus to crosslink density, primary molecular weight, and polymer concentration for a series of poly(vinyl alcohol) gels at low to intermediate concentrations. Aqueous poly(vinyl alcohol) solutions were crosslinked to form infinite networks using terephthalaldehyde. We find a large discrepancy with these poly(vinyl alcohol) gels between measured shear modulus and that calculated from classical elasticity theory assuming quantitative reaction of crosslinking. The ratio of measured to calculated modulus is independent of crosslink density for a given primary molecular weight and concentration. It shows linear dependence on polymer concentration prior to crosslinking and extrapolates to a critical concentration which is consistent with the effective sizes of the polymer molecules.     

Determination of the degree of swelling and crosslinking of extremely small polymer gel quantities by analytical ultracentrifugation

The degree of crosslinking of very small amounts of polymer gel, encountered in the characterization of the molecular structure of rubber polymers or of polymers in powder form, cannot be determined satisfactorily by measurement of elasticity or conventional swelling. Therefore a method has been developed which enables us to determine the degree of crosslinking of such polymer systems reliably. This method is based on the measurement of equilibrium swelling by sedimentation in the analytical ultracentrifuge. The degree of swelling can either be used directly as a relative measure of the average degree of crosslinking or as basis for calculating the average degree of polymerization of the molecule chains between two crosslink sites according to the theory of Flory and Rehner. The efficiency of the method is demonstrated by several examples of application (differently crosslinked polybutadienes, gel portions of various polychloroprenes and polyurethane foams).Dedicated to Dr. Gerhard Fritz on the occasion of his 60th birthday.     

High-resolution NMR of crosslinked polymers: Effects of crosslinked density and solvent interaction

Measurements have been made of the dependence of nuclear magnetic resonance bandwidths of polymers on the degree of crosslinking. Poly(methyl methacrylates) and poly(hexadecyl acrylates) were studied. Three regions of behavior are apparent: (1) in lightly crosslinked materials, bandwidths are quite insensitive to the degree of crosslinking, and the networks behave almost as linear polymers in solution; (2) in moderately crosslinked material, bandwidths are significantly affected by the degree of crosslinking; and (3) in highly crosslinked materials, bandwidths are extremely sensitive to crosslink density, and the polymer peaks become so broad that they disappear almost completely. These results indicate that segmental motion of a polymer in solution is not a function solely of its molecular weight, and that a certain degree of crosslinking is required to restrict polymer motion at the segmental level. The solvent (benzene) peak is always a singlet in swollen poly(methyl methacrylate) systems with swelling ratios up to 6.4 (regions 1 and 2, above) but as the swelling ratio further decreases to 3.5 (region 3), the solvent peak splits into a doublet; this phenomenon may indicate the existence of two different arrangements of solvent molecules in the swollen network, for which interchange is not sufficiently rapid to produce a single line.     

Influence of physicochemical properties of solvents on swelling behavior of fluoropolymers

The experimental data are available on the swelling of carbon-black-filled fluorine-containing polymers (Viton) in a number of solvents. However, the quantitative relation between the physicochemical parameters of the solvents and the degree of swelling of the polymers is still unclear. It has been shown that this relation may be determined in terms of the linear free energy concept via solvation of linear equations with due regard for various characteristics of solvents. The polarizability and basicity of solvents are factors governing the degree of polymer swelling. This fact makes it possible to assume the existence of donor-acceptor interaction between fluorine atoms and donor solvents.     

Synthesis and characteristics of cryogels of chitosan crosslinked by glutaric aldehyde

The mechanism of cryotropic gelation in moderately frozen solutions of chitosan crosslinked by glutaric aldehyde is studied. Chitosan cryogels with large pores are synthesized at a low content of crosslinking agent in the reaction mixture or under conditions that do not lead to gelation at temperatures above 0°C. The dependences of the yield of gel fractions, the degree of swelling of the polymer phase of cryogels, and the hydrodynamic characteristics of cryogels on the temperature of synthesis are shown to be extremal. This result may be explained by the competition between the cryoconcentration of reagents in the nonfrozen liquid microphase, which assists the development of a crosslinked polymer network, and such factors as an increase in the viscosity of the reaction mixture and a reduced reagent mobility, which prevent gelation. The morphology of chitosan cryogels is studied, and the character of the macroporous structure of the samples prepared at different temperatures is shown to exert a stronger effect on the hydrodynamic characteristics of a cryogel than the degree of swelling of crosslinked polymers in the walls of its macropores.     

Solvent activity changes and phase separation during crosslinking of coating films

Changes in solvent activity and thermodynamic stability of a system undergoing crosslinking in the presence of a solvent are modeled by combination of branching theory with thermodynamics of polymer solutions and swelling of a crosslinked polymer. The system is considered as a quasiternary one in which the solvent, polydisperse soluble polymer (sol) and crosslinked network, respectively, represent the components. Crosslinking brings about growth of polymer structures but also changes in polymer-solvent interactions. The results are compared with onset of phase separation and changes in evaporation rates from films formed from a hydroxy-functional star oligomer and triisocyanate.     

Theory of nematic networks with finite extensibility

A statistical molecular model of polymer networks, which takes into account inter-molecular orientational interaction and constancy of the chain contour length, is proposed. A simple formula for the network free energy valid for any deformations is obtained. A system of equations which describes orientational-elastic interactions in polymer networks is derived. The influence of deformation and degree of cross linking on the conditions of network phase transition into the orientationally ordered state of the nematic type is studied. The deformation curves considerably deviate from those predicted by the classical elasticity theory. A comparison of the proposed theory with experimental data for natural rubbers is carried out.     

The role of the orientation tensor in the rheology of flexible polymers

The stress-strain relations for transversely isotropic deformations of linear and branched polymer melts as well as of (crosslinked) rubbers are discussed in terms of the orientation tensor. It is shown that orientation and network strand extension are decoupled, and that the relative tube diameter and its inverse, the molecular stress function f, can be extracted directly from experimental data, if the effect of network orientation is accounted for by the order parameter. The tension of the average network strand increases with increasing deformation. This is caused by an increasing restriction of lateral movement of polymer chains due to deformation. At small strains, f² is found to be linear in the average stretch for melts as well as for rubbers, which corresponds to a constant volume of the tube. At large strains, melts show maximum molecular tension, depending on the degree of longchain branching, while rubbers show maximum extensibility.     

Swelling studies of crosslinked poly(p-phenylene terephthalamide) copolymers in sulfuric acid

In an attempt to improve the mechanical properties of extended chain polymers such as poly(p-phenylene terephthalamide) (PPTA), a crosslinkable terephthalic acid derivative (XTA) has been developed which can be incorporated into copolymers in various concentrations and activated after polymerization. The crosslinking of PPTA-co-XTA copolymer particles was investigated through a series of swelling experiments in concentrated H₂SO₄. The data show a systematic decrease in equilibrium swelling with increasing XTA content, indicating the XTA units are in fact acting as crosslink sites. Values for crosslink density were calculated from the Flory-Rehner theory of polymer swelling and compared with previous findings on crosslinked rigid polymer network systems. The effective number of crosslinks per XTA unit (efficiency) predicted by the Flory-Rehner theory increases and then decreases with % XTA. The decrease in crosslinking efficiency at high XTA concentrations is consistent with differential scanning calorimetry data which show the enthalpy of XTA reaction decreasing slightly with % XTA. The deviations at low % XTA may represent a failure of the Flory-Rehner theory to properly describe the rubbery elasticity of extended chain polymers. © 1994 John Wiley & Sons, Inc.     

Poled amorphous polymers for second-order nonlinear optics

Recent advances in poled amorphous polymers for second-order nonlinear optics are discussed with emphasis on stabilizing the frozen-in nonlinearity via chemical crosslinking under electric fields. Specific examples of a linear polymer and a crosslinked polymer, both with nitroaniline-type chromophores covalently attached as side groups, are presented and compared in their glass transition behavior, linear optical properties, poling dynamics, and stability of frozen-in nonlinearity. It is demonstrated that by employing chemical crosslinking under electric fields one can prepare highly efficient and stable poled polymers that exhibit no decay in nonlinearity at ambient conditions and no apparent tendency of decay even at 85°C as well as excellent optical properties. The historical development of organic materials for second-order nonlinear optics and recent advances in device fabrication based on poled polymers are also discussed briefly.     

Some properties of networks produced by the Diels-Alder reaction between poly(styrene-co-furfuryl methacrylate) and bismaleimide

Poly (styrene-co-furfuryl methacrylate) networks were prepared by the Diels-Alder (D-A) reaction in solution at 25 °C between the linear copolymer and bismaleimide (BM). The resultant crosslinked polymers were swollen to equilibrium in toluene at 25 °C and swelling properties were studied by gravimetric and dimensional measurements. The swelling behaviour of these organogels depended on the composition of the copolymer and the concentration of BM used. Shear and Young’s moduli and the effective crosslinking densities (ν_e) were determined by compression (stress)-strain measurements. The theoretical crosslinking density was higher than the ν_e for all the crosslinked copolymers. An endothermic peak without T_g was observed on the DSC curve on heating the dry crosslinked polymer. On reheating a T_g at ≈98 °C was found, which is attributed to presence of linear copolymer produced by the retro D-A reaction in the first heating. The thermal stability of a crosslinked copolymer under nitrogen and air showed differences with the stability of the linear copolymer. The increase in viscosity of the solution during the D-A reaction was followed with time, for initial linear copolymers of different molecular weights. It was found that onset of gelation increased to longer reaction times the lower the molecular weight of copolymer.     

高分子熔体和浓溶液流变性能的研究

基于多重缠结网络结构模型和高分子链上缠结点在流动中可进行动态解缠和再缠结的多重蠕动机理,用统计力学和动力学相结合的方法,分别计算出了缠结链组的末端距分布函数;处于缠结状态下高分子链构象统计分布函数;受力下聚合物熔体粘弹性形变自由能和解除外力下高分子挤出体可回复性粘弹性形变自由能,提出了高分子挤出体可回复形变的粘弹性分子理论。推导出的高分子熔体的回忆函数、简单剪切流下的本构方程和物料函数,并采用一种新的方法测定出物料的四种参数： η0、 GN0、 n′和 a。对于高分子挤出体,可回复性粘弹性形变由快速弹性形变和慢速粘弹性形变两者组成,当把两种形变量的复合结构参数－分子链的反式构象分数引入两种形变自由能表达式后,就从理论上得到了可回复形变量同挤出胀大比间的定量表达式,从而建立起一个具有分子链结构参数的新的挤出胀大比方程,可回复形变量同挤出条件（温度、挤出速率和量以及口模长径比不同的挤出机）和树脂结构特征（分子量及分布）的关系式以及在特殊情形下的简化表达式,并用几种高分子熔融体系的挤出胀大比和可回复性形变量的实验数据对理论进行验证,理论方程同实验数据较好的符合。     

含羧基交联型质子交换膜的制备及其性能

合成了一种含酯基的磺化聚合物,利用后水解的方法得到了含有羧基侧基的聚合物;将磺化聚合物与聚乙烯醇通过溶液共混,热处理后得到交联型的共混膜材料。 研究结果表明,膜材料的玻璃化转变温度(Tg)有明显的上升,证明了交联反应的发生;同时,膜的吸水率和溶胀率有一定的下降,力学性能和热稳定性也有一定的提升。 通过共价交联的方法,制备了综合性能优异的磺化聚芳醚质子交换膜材料。 在100 ℃,交联膜的质子传导率为0.072~0.065 S/cm,吸水率为51%~89%,溶胀率为19%~30%。