Sorption and swelling in ultra-thin polymer films

Different polymers were investigated with respect to the sorption of solvents and gases. Depending on the chemical nature of the polymers this sorption leads to polymer swelling. The degree of swelling D/D₀ was measured utilizing Small angle X-ray scattering (SAXS) as well as Surface plasmon resonance (SPR). From the change in film thickness after swelling in different solvents Hildebrand parameters of the polymers were determined. By crosslinking of the polymer films the degree of swelling can be controlled. In the case of ultra-thin polyimide films a higher degree of crosslinking led to a decreased selectivity of the transport of gases through the membrane. Reptation of macromolecules was also investigated and the influence of polymer swelling in different solvents has a great influence on the selectivity and diffusion coefficient.     

The Effects of Polymer Properties and Solution Composition on the Distribution,Properties, and Amount of Water in Swollen Ion Exchangers

The effects of the composition and concentration of an external solution on the swelling degree of polystyrene-based ion exchangers crosslinked with different amounts of divinylbenzene have been analyzed within the heterophase model of polymer gel structure. It has been confirmed experimentally that, upon variations in the composition of the external solution, the swelling degree of polymers is determined by the content of “sorbed” water alone. Therewith, the volume of the external solution incorporated into the swollen polymer remains constant; i.e., it depends neither on an ionic form of an ion exchanger nor the concentration and composition of the external solution, but rather depends linearly on the polymer crosslinking degree. An algorithm has been proposed for calculating the volume of water in a polymer gel and some quantitative estimates have been presented.     

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.     

Imidazole-containing chitosan derivative: a new synthetic approach and sorption properties

A novel method for the synthesis of a hetaryl-containing chelate amino polymer, namely, N-(4(5)-imidazolylmethyl)chitosan (IMC), with a degree of substitution up to 0.3 was proposed. The “synthesis in gel” approach involves direct substitution of the hydroxyl group in 4(5)-imidazolylmethanol. The structures of these polymers were confirmed by ¹H NMR data. For sorption studies, IMC samples were crosslinked with epichlorohydrin and diglycidyl ethers of ethylene glycol and diethylene glycol. The degrees of swelling and sorption properties of the polymers largely depend on the crosslinking agent and the degree of crosslinking. The sorption capacities of IMC for Au^III, Pt^IV, and Pd^II ions are higher than those of the nonmodified polymer. The extraction of noble metal ions from chloride solutions becomes more selective with increasing degree of crosslinking. The sorption capacity of IMC for Co^II and Ni^II ions is higher than those of chitosan and its known N-heterocyclic derivatives.     

Determination of the radiation yield of hydrogels crosslinking

The ability of polymer to crosslink or exposure to radiation is frequently represented by a G value, the number of crosslinks per 100 eV absorbed. Several methods are available for its determination, the most frequent being the dose D_g required to form an incipient network since (with many systems) this corresponds to one crosslinked unit per weight average molecular (δ = 1). Its determination therefore depends on a knowledge of the molecular weight of the starting polymer. An alternative method, far less frequently used, is to measure the degree of swelling of a crosslinked network. This involves a knowledge of the Flory-Huggins interaction parameter μ and of the initial number average M_n(0). However if the concentration V_e of effective chains (deduced from swelling) is plotted against dose D, the slope gives G(X) directly, independent of M_n(0). This applies only when the system is very largely crosslinked. It may also be used to determine G(X) even when starting from the monomer itself (i.e. combining polymerization and crosslinking). It is shown that, for a series of polymers, irradiated either as liquids or in solution, the theoretical relation between swelling and crosslink density is followed, and the G(X) values derived from swelling compare well with those given in the literature, and based on gel fraction.     

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.     

Transition in swollen polymer networks induced by intramolecular condensation

It is predicted that the net repulsion between the segments of a polymer network and a poor solvent can cause a phase transition marked by a sudden change in the degree of swelling. This is analogous to the “coil–globule” transition recently predicted by Ptitsyn to occur for a macromolecule in solution. The critical conditions for the transition. as well as phase diagrams, are calculated for the gel in free swelling and under uniaxial tension, which facilitates the transition. The transition depends on the gel being formed of chains crosslinked while greatly swollen by a diluent and also having a high degree of crosslinking. It is concluded that it would be difficult to attain the conditions necessary for the transition in the free-swelling case, but that it should be possible for gel under tension.     

Molecular weight distribution in random crosslinking of polymer chains

The molecular weight distribution (MWD) of crosslinked polymer molecules formed during polymeric network formation is the sum of the fractional MWDs containing 0, 1, 2, 3, … crosslinkages. The MWD for polymer molecules containing ?? crosslinkages is investigated for the random crosslinking of polymer chains whose initial MWD is given by the Schulz-Zimm distribution. For a very narrow initial MWD, each fractional MWD with ?? = 0, 1, 2, … is independent and a multimodal distribution is obtained for the whole distribution. When the initial MWD is uniform, the average crosslinking density within the polymer fraction whose degree of polymerization is r, ρ_r is simply given by ρ_r = ρ_gel,c – 2/r irrespective of the extent of crosslinking reaction where ρ_gel,c is the crosslinking density within gel fraction at the gel point. On the other hand, the MWDs with ?? crosslinkages overlap each other with different ?? values significantly for the broader initial distributions, and ρ_r increases with the progress of crosslinking reactions. The value of ρ_r increases with increasing r but levels off asymptotically at large r. The average crosslinking density of polymer molecules containing ?? crosslinkages ρ_?? is an increasing function of k but soon reaches a plateau; sooner for the broader initial MWDs. For ?? ≥ 1, ρ_?? is always larger than the average crosslinking density of the whole reaction system ρ in the pregelation period, i.e., in terms of the crosslinking density, the difference between polymer molecules with and without crosslinkage is most significant. In general, the average crosslinking density ρ, which is convenient to use in describing the nature of the whole reaction system, cannot be considered as a characteristic degree of crosslinking for polymer molecules containing at least one crosslinkage. Consideration of the bivariate distribution of r and k reveals important aspects of the polymeric network formation that have been obscured in the conventional theories in which the averages including linear polymers are solely considered. © 1995 John Wiley & Sons, Inc.     

乙丙三元胶的功能化研究

用马来酸二丁酯（ＤＢＭ）对乙丙三元胶（ＥＰＤＭ）进行了功能化，在烃链上导入极性基团，以改善ＥＰＤＭ与含极性基团聚合物的相容性．红外光谱表明功能化反应确已发生．用电子顺磁共振波谱仪（ＥＳＲ）研究了热引发的机理，产物的功能化率由皂化水解反应测定；产物交联程度由凝胶量间接表征；用凝胶渗透色谱法（ＧＰＣ）表征产物的分子量分布。研究了反应温度、反应时间、单体用量和引发剂用量等对产物功能化率和凝胶量的影响。     

Unusual mobility of hypercrosslinked polystyrene networks: Swelling and dilatometric studies

Hypercrosslinked polystyrene samples were prepared by an intensive postcrosslinking of highly swollen styrene–divinylbenzene copolymer beads to extremely high degrees of crosslinking that amounted to 100% or even higher. When in the dry state, the materials obtained represent transparent beads of reduced density. Despite the high degree of crosslinking, the materials manifest large increases in volume on swelling with any liquid media as well as large changes in volume on heating. The factors determining the unusual swelling ability of the hypercrosslinked polymers are briefly discussed. Thermodilatometric tests of the polymers with a moderate degree of crosslinking reveal a certain contraction of the beads at temperatures higher than 100 °C. When crosslinked far beyond 100%, the networks demonstrate unusual expansion in the 100–220 °C range; this is followed by a sharp shrinking at higher temperatures. The former is caused by an increased intensity of the vibration movements of the network and a partial relaxation of strong inner stresses; the latter is due to partial chemical oxidation, degradation of network units, or both. This degradation, however, is not accompanied by any loss in weight of the polymer but only results in a transformation into a more dense conventional nonporous material. The strained, rigid open‐work structure of the homogeneous expanded hypercrosslinked polystyrene networks is responsible for their unusual mobility. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1553–1563, 2000     

Determination of the swelling behavior of superabsorbent polymers by a tracer-assisted on-line spectroscopic measurement

This work reports on a method for the accurate determination of kinetic swelling behavior and properties of superabsorbent polymers by a tracer-assisted on-line spectroscopic measurement. Based on monitoring the spectral absorption of a tracer compound (blue dextran 2000) at 610 nm in a superabsorbent polymer containing solution, the swelling (water absorption) of the polymer during the process can be followed, from which the parameters in a kinetic equation can be obtained. The results showed that the data obtained by the present method has a good measurement precision and accuracy, in which the relative differences were less than 4.0% when comparing the data measured by a reference method (i.e., the tea bag method). Since the present method can perform an on-line measurement, it is much superior to the current tea bag method and therefore is very suitable to be used in the process related study for the swelling behavior of superabsorbent polymers in many applications.     

交联低密度聚乙烯交联程度表征方法的研究

硅烷交联法和过氧化物交联法是聚乙烯交联改性的两种重要方法［１］,以往的文献上通常都以凝胶含量来表征这两种方法制备的交联产物的交联程度［２～６］,但是在实践中我们发现,凝胶含量基本相同的硅烷交联聚乙烯和过氧化物交联聚乙烯的性能存在着很大的差异,例如在７０℃的二甲苯中凝胶含量为６２％的过氧化物交联低密度聚乙烯（ＬＤＰＥ）的平衡溶胀比是相同凝胶含量的硅烷交联ＬＤＰＥ的４倍,１５０℃时凝胶含量为７０％的硅烷交联聚乙烯的热延伸率比相同凝胶含量的过氧化物交联聚乙烯小三倍,而且二者的结晶行为和结晶度也有很大的…     

Preparation of amylose gel and probe diffusion through the gel membranes

Hydro‐swollen amylose gels were prepared by chemical crosslinking with a polyethylene glycol diglycidyl ether. The degree of swelling of the amylose gel (q_w) increases with increasing the amount of crosslinker in the preparation, which is a result contrary to other cases of chemically crosslinked polymer gels. The diffusion coefficient of a fluorescein and a fluorescein‐dextran conjugate in the gel membranes was determined by the time lag method and increases as q_w of the gels increases.     

聚氨酯的后交联研究进展

通过交联可以将线型聚合物连接成三维网状结构,适度交联后聚氨酯的拉伸强度、模量、耐溶剂性、耐高温性等许多性能都能得到大幅提高,而交联方法、交联的种类及交联密度的大小都是重要的影响因素,因此对交联方法、交联密度的测定、交联密度与聚氨酯性能之间的关系研究对于聚氨酯的质量控制非常重要。本文首先详细介绍了聚氨酯后交联的常用方法,然后对聚氨酯交联密度的测定方法进行了分析比较,在此基础上进一步介绍了国内外关于聚氨酯交联密度与其性能的关系方面的研究进展。     

Paradoxes of thermodynamics of aqua-vapor-polymer interface equilibrium

Schroeder’s paradox is the different equilibrium degree of swelling for a hydrophilic polymer in saturated aqueous vapor and in liquid water; it is experimentally verified by the registration of increasing volume of spherical polymer samples upon the processes of vapor and liquid water sorption. Specimens of three main classes of hydrophilic cross-linked polymers were tested. These had gel, hypercrosslinked, and macroporous structures that differed by the scale of the Schroeder effect. A similar effect is typical also for hydrophobic polymers upon swelling in liquid organic solvents and their saturated vapor. The paradox is explained by the lower activity of a sorbate in a saturated vapor compared to its activity in a liquid phase. The ability of many samples of cross-linked polymers with different degrees of saturation with a sorbate to be at equilibrium with the saturated vapor of a sorbate is explained by the differences in the inner structure of these samples, i.e., by differing in the swelling combinations and the intensity of the interchain interactions in a polymer network.     

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%。     

Crosslinking Index,Molecular Weight Distribution and Rubber Equilibrium Shear Modulus During Polyfunctional Crosslinking of Existing Polymer, 6. Primary Polymer with a Schulz–Zimm Distribution of Molecular Weights

A network model for the crosslinking of already existing polymer molecules with a so‐called Schulz–Zimm distribution of their molecular weights is presented. It is an extension of previously developed statistical network models applied to the crosslinking of primary polymers with several other molecular weight distributions and with crosslinks of any functionality. The model results in the possibility to obtain more insight into the structure of polymers, especially those with narrow distributions of the molecular weight. In more detail, the model can give a perspective on structural network parameters such as the weight fractions of ideal network, of dangling polymer ends, and of those molecules not connected to the network, i. e., the sol fraction, the number of crosslinks in which a polymer molecule is bound, the functionality of the crosslinks, or the average molar mass of the polymer molecules in between the crosslinks M̄_c. Results of calculations are shown for a hypothetical crosslinking process of polymers with various molecular weight distributions. Moreover, the dependency of the network parameters on the polydispersity index and the type of molecular weight distribution is shown. Finally the increase of the functionality of the crosslinks during the ageing process of a 9.9% poly(vinyl chloride) gel as a function of the polydispersity index of the molecular weight distribution is presented.     

Induced changes of polymer organization in a gel of poly(vinyl alcohol) crosslinked by Congo red

Different gel microstructures are induced at variable poly(vinyl alcohol) (PVA) and Congo red concentrations, as revealed by ultrarapid freezing and a replica technique for transmission electron microscopy. The polymer microstructures observed include random coils, rigid polymer rods, and long fibers. The development of the different polymer conformations is proposed to be dependent on the degree of intramolecular and intermolecular crosslinking and on the electrostatic interactions of the Congo red ions. The rigid‐rod conformation appears to be the most energetically stable form; it is disrupted by electrostatic effects around the polymer overlap concentration (C*_PVA). We propose that the gel microstructure influences the physical properties of the gel. Gels possessing the rigid‐rod microstructure have increased Young's storage modulus values. Two possible mechanisms of gelation are suggested. The first describes a one‐stage reaction when the polymer concentration approximates C*_PVA, where polymers in an extended random‐coil conformation undergo intermolecular crosslinking without any microstructural changes. The second describes a two‐stage reaction when the polymer concentration is less than or greater than C*, where a disorder–order transition results in the formation of rigid polymer rods and fibers followed by the formation of a macromolecular network. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1471–1483, 2001     

Pore size in one‐step swelling and polymerization of monodisperse polymer beads

Crosslinked polystyrene beads were prepared at low swelling ratios by one‐step swelling and polymerization method. Pore size of the beads was observed based on the GPC calibration curves. It is found that: (1) the pore size increases as the swelling ratio decreases; (2) when a good solvent is used as the porogen the pore size increases with the crosslinking monomer content; and (3) at high crosslinking monomer content the pore size does not depend on the porogen solubility. The effects are discussed in terms of polymer miscibility, including phase separation between the seed and bead polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3270–3277, 2000     

Synthesis and swelling behavior of thermosensitive hydrogels based on N-substituted acrylamides and sodium acrylate

A series of hydrogels based on N-isopropylacrylamide, sodium acrylate, and N-tert-butylacrylamide were synthesized by free radical polymerization in a mixture of dioxane and water with tetra(ethylene glycol) diacrylate as the crosslinker and benzoyl peroxide as the initiator. The swelling behavior including the swelling rate of the crosslinked gels in water was studied with gravimetric method. The swelling ratio of the gel (0.1 mol% crosslinking) can reach 420 g/g at 20 °C and such a gel can release 96% of the water absorbed at 40 °C. The lower critical swelling temperature (LCST) of the copolymers can be adjusted by changing the chemical composition of the polymers. Such crosslinked gels can be potentially used as thermosensitive superabsorbent because of their high water uptake and thermal sensitivity.