A MODEL FOR THE RELEASE BEHAVIOR OF DRUGS FROM HYDROGEL NANOPARTICLE

A model to correlate and predict the release behavior of drugs from hydrogel nanoparticles is presented in this paper. The nanoparticle is considered as a combination of a shell of an elastic semipermeable membrane and a core of a fluid phase (After swelling equilibrium). The fluid core consists of network building materials and other components that are able to partition in hydrogel nanoparticle phase and surrounding coexisting liquid phase, and is enveloped by the membrane shell. The excess Gibbs energies of the hydrogel nanoparticle phase and the surrounding coexisting fiuid phase are expressed e.g. using UNIQUAC equation with "free-volume" contribution for non-ionic solution and VERS-model for ionic one. The elastic properties of polymer network could be described, for example, by the "phantom network" theory.     

直链型与支链型疏水缔合水凝胶的机械性能与溶胀行为

以丙烯酰胺(AM)为亲水单体,脂肪醇聚氧乙烯醚丙烯酸酯(AEO-AC-n-m,n为疏水端烷基链碳的数目,m为亲水端PEG链的长度,n,m=13,5;10,5;13,10)为疏水单体,十二烷基硫酸钠(SDS)为表面活性剂,过硫酸钾(KPS)为引发剂,通过胶束聚合制备了3种聚丙烯酰胺-co-脂肪醇聚氧乙烯醚丙烯酸酯(AM-co-AEO-AC)疏水缔合水凝胶.以疏水烷基链为直链的疏水单体AEO-AC-13-5合成的直链型水凝胶的网络结构均匀且强度高,其形态在水中可维持180 d.而以疏水烷基链为支链的疏水单体AEO-AC-10-5与AEO-AC-13-10合成的支链型水凝胶的机械性能较弱,60 d内即溶解于水中.在相同条件下,直链型水凝胶断裂时的最大应力是支链型水凝胶的4~5倍.利用弹性橡胶理论中的新胡克方程计算了直链型和支链型水凝胶的有效交联密度ν0和有效交联点间的分子量Mc.     

An experimental and analytical study of the elasticity of model polyurethane networks crosslinked by tri- and quadriisocyanate

Polyurethane networks have been prepared from a mix of tri- and quadriisocyanate and from two types of diols, polyether-based (with molar masses of 1,000, 2,000, and 4,000 g/mol) and polyester-based (1,035 g/mol). The weight fraction of sol has been measured, as well as the elastic shear modulus of the gels. It has been found that the statistical theory of network formation predicts a weight fraction of sol in agreement with the experimental results, but its standard combination with the theory of rubber elasticity disagrees significantly with the elastic modulus measured. This suggests a discrepancy between theory and experiment in terms of elastically active chains. In contrast, the assumption that all nodes in the gel, or even in the system, are elastically active gives much better predictions for the system considered.     

辐射交联顺-1,4-聚丁二烯的网络结构特性和力学性能

本文根据Flory的溶胀理论和橡胶弹性理论,考察了顺-1 4-聚丁二烯辐射交联产物的化学网络和物理缠结网络结构特性及其对固体力学性能的影响。结果表明,交联产物的物理缠结网络密度远远大于化学交联网络密度。随着辐照剂量的增大,化学交联密度增高,物理缠结数下降。探讨了交联、缠结密度与Mooney-Rivlin方程的常数项C_1和C_2的关系。C_1来自化学交联网络的贡献;C_2来自物理缠结的贡献。物理缠结网络主要贡献于交联物体在小形变下的起始弹性模量G_0;化学交联网络则主要贡献于交联物体在大形变下的非线性弹性,即断裂强度(?)_B。     

Computer design,synthesis and investigation of gradient-modulus polymers

Gradient-modulus polymeric materials have been prepared, which show a continuous transition, within the same sample, from rubber to plastic without any junctions, joints, etc. These materials are elastic and have a modulus ranging from 4.5 to 2000 MPa. The properties of the materials were calculated before their synthesis. It was shown that a prerequisite of such materials is a network structure comprising rigid bulky crosslinked points and short flexible linking chains. Another prerequisite of such materials is the occurrence of microphase separation.     

Polydomains in liquid-crystal elastomers

In liquid-crystal elastomers, the simultaneous presence of rubber elasticity due to the crosslinked backbone chains and of optical birefringence due to the mesogens in the side chains lead to exceptional physical properties. An elastic deformation of the network influences the order of the mesogens and, therefore, the optical properties. A theory based on a Landau-de Gennes expansion of the free energy is proposed. In the opaque polydomain phase, the local orientation is given by a compromise between the external mechanical field and a local anchoring interaction. As the field is increased, it becomes energetically favorable for the mesogens to align parallel to the mechanical field, and a transition to a transparent monodomain structure occurs. Results for the average orientation, the stress and the chain conformation are given.     

Measurements of freezing‐point depression to evaluate rubber network structure. Crosslinking of natural rubber with dicumyl peroxide

An experimental approach based on the freezing‐point depression of a solvent in a swollen gel has been developed to characterize the structure of rubber networks. This property depends on the conditions required for the formation of crystalline nuclei, which are limited by the elastomer network restrictions. Information about the functionality, spatial distribution, and number of crosslinks can be obtained by the use of this easy and ready experimental method. Application of the tube model of rubber elasticity in the uniaxial stress–strain experiments of natural rubber samples vulcanized with dicumyl peroxide yields the characteristic parameters of the rubber networks, which are in concordance with the network structures predicted by the freezing point method. Finally influence of vulcanization conditions in network structure and its relationship with the mechanical properties was evaluated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 544–556, 2007     

The effect of the nature of cross-links on stress-relaxation and elastic deformations of α-methyl styrene-butadiene vulcanizates

Six systems were employed to vulcanize α-methyl styrene-butadiene rubber SKMS-30, viz. sulphur-MBTS + DPG, sulphur-DEBTSA, sulphur-Zn dimethyl dithiocarbamate, sulphur-MBT, TMTD. and p-tert-butylphenol-formaldehyde resin-chlorosulphonated polyethylene. The resulting vulcanizates had good physicomechanical properties.The natures of the network structures formed by these vulcanizing systems were evaluated by stress-relaxation experiments at 130 in air. TMTD and phenolic resin form the most rigid networks. while sulphur-MBTS + DPG forms the most flexible one.Rubber samples vulcanized with different systems were subjected to a compression of 20% of the initial sample height for fixed periods at 100 and 130°. The instantaneous and retarded elastic recoveries were determined. The relation between the nature of the network structure and elastic recoveries of the rubber vulcanizate are discussed.     

Alteration of matrix curing characteristics and its role in extension of hydrodynamic equation for predicting viscoelastic properties of nitrile rubber/silica nanocomposites

Neglecting the alteration of matrix curing characteristics in a filled rubber nanocomposite, as a result of possible interactions between the nano filler and curing agent ingredients, leads to inaccurate properties prediction using conventional hydrodynamic equations. In the current work, we present a new empirical extended version of hydrodynamic equation and examine its capability in predicting the viscoelastic properties of NBR/nanosilica system in which the negative influence of the filler on the curing process of the NBR matrix was confirmed through various analyses such as tensile test, rheometry, swelling experiments, and dynamic mechanical analysis. The results showed that the proposed empirical extended model is able to account the contribution of alteration of matrix curing characteristics in changing the composite properties below the filler percolation threshold. It was demonstrated that the extended model provides more accurate prediction of viscoelastic properties of silica‐filled cured NBR nanocomposites above glass transition temperature.     

Transient Changes in Topology and Energy on Extension of Polybutadiene Networks

The theory of elasticity of polymer networks has been developed along two lines. The phenomenological approach leads to the Mooney-Rivlin relation between stress and extension ratio for uniaxial extension. The statistical theory of elasticity, based on a model for polymer molecules, predicts a similar relation with one of the constants zero. Actual elastic properties of rubbers do not agree fully with either theory.

Experimental results are reported obtained with quantitatively cured polybutadiene and polyisoprene vulcanizates. These data are near-equilibrium results through the use of a cyclic stress sequence which largely eliminates the influence of long-time creep. The dependence of the initial modulus and the parameters of the Mooney-Rivlin relation on the chemical nature and the degree of branching of the polymer, the type of cross-links, and temperature has been investigated. A possible relation between the energy component of the elastic force and one of the parameters is discussed.

These results as well as those in the literature refer to irreversible processes. It is proposed that this irreversibility results from friction accompanying slippage of chain entanglements. This mechanism is compatible with the observed dependences. It is concluded that the variation of elastic properties with elongation is due to changes in network topography.

Some observations are made on the topological changes of vulcanizate networks at very high elongations. Similarities are pointed out between reinforcement by stress crystallization and by addition of carbon black. The effect of blacks is attributed mainly to preferential adsorption on the carbon particles of short network chains which become overstressed at high deformation. On adsorption the kinetic energy of these particular chains will be dissipated in the form of heat of adsorption.

Examples are given of the applicability of F. Bueche's relation between extension of the sample and that of the elastomer matrix in a filled vulcanizate. This equation differs from that based on Einstein's relation for the viscosity of suspensions, which has been shown to be applicable in other filled rubbers. The difference between the two relations may be associated with the absence or presence of chemical bonding of elastomer to filler.

Network topography has an influence on the ultimate properties of vulcanizates. Polybutadiene samples in which the cross-links are single bonds break at lower elongation than those with equal concentrations of cross-links consisting of 18-atom chains.     

Pulse dynamics in an excitable reaction – diffusion system

We formulate a theory for pulse dynamics in an excitable reaction‐diffusion system not only in one dimension but also in higher dimensions. In the singular limit where the width of pulse boundaries is infinitesimally thin we derive the equation of motion for a pair of interacting pulses. This equation contains the bifurcation that a motionless pulse loses stability and begins to propagate. The theory predicts the following remarkable properties. When the system is far away from the bifurcation threshold, two propagating pulses merge each other upon head‐on collision. However when the system is close to the threshold the pulses behave as if they are elastic objects. These results are consistent with recent computer simulations.     

Properties of ultrahighly filled composites based on polymers and ground rubber

The stress-strain and strength properties of ultrahighly filled composites based on thermoplastic polymers and ground rubber wastes are studied. The content of the elastic filler is higher than 70 wt%. As is shown, introduction of minor amounts of the plastic polymer, which serves as the binder for the filler particles, makes it possible to improve the strength properties of ultrahighly filled composites and to prepare materials of a desired thickness. A correlation between the stress-strain properties of the plastic polymer-rubber systems and the effective viscosity of the matrix polymer is established. When a polymer with homogeneous deformation and good adhesion to the elastic filler is used as the matrix, the resultant composites are characterized by properties close to those of vulcanized rubbers. A new method is proposed for processing of ground rubber wastes and preparation of materials that are similar to hard rubbers.     

The effect of low-temperature crystallization on the mechanical behavior of rubber

In cold climates the correct performance of rubber components such as seismic isolators depends on them maintaining their elastic properties when exposed to prolonged periods at low temperatures. The high damping compounds developed for seismic isolation are normally especially prone to crystallization when exposed to subzero temperatures for periods of a few weeks. The effect of low-temperature crystallization on the mechanical stiffening of natural rubber is evaluated. The relationship between the shear modulus and amount of crystallization is measured using a technique in which the dimensional change and stiffness are monitored simultaneously. The relationship is found to be approximately independent of the crosslink density and the temperature of crystallization. It appears not to be realistically modeled by considering the crystals to behave as rigid filler particles but good qualitative agreement with experiment was obtained by modeling the crystals as a network of threads. Partially crystalline rubbers are found to yield under the application of a large stress like other partially crystalline polymers. Mechanisms for suppressing crystallization in rubber are discussed and the low-temperature stiffening of specially formulated rubber compounds for seismic isolation is presented. These results show that carefully formulated high damping natural rubber compounds can give adequate performance at low temperatures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2181–2190, 2004     

Experimental analysis of the molecular theory of rubber elasticity

Stress-strain and birefringence-strain experiments, on polybutadiene and poly(methyl-3,3,3, trifluoropropyl siloxane) elastomeric networks of various degrees of crosslinking have been carried out in order to evaluate the recent molecular theory of rubber elasticity of Erman and Flory, which is based on the idea of constraints imposed by entangled network chains on crosslink fluctuations. Previously published results on polyoxypylene and poly(dimethylsiloxane) networks have also been analyzed. In general, the theory describes the elastic behavior of all these systems satisfactorily. Stress-strain and birefringence data can be interpreted using the same set of parameters. The most important theoretical parameter κ, which is a measure of the severity of constraints, varies with the elastic modulus as predicted by theory. However, the relationship is not a universal one, as was originally suggested.     

Stress–strain behavior of swollen polymeric networks

The network parameters of swollen, solution-crosslinked polymer filaments can be collected from deswelling measurements in solutions of nonpermeating polymer or, as shown in this paper, from the stress–strain relation when in equilibrium with the surrounding solvent. The degree of swelling, at which the partial molar free energy of elasticity equals zero, is found to vary with solvent power in agreement with earlier findings on other systems. Comparison with results of studies on rubber networks crosslinked in the absence of diluent show that previously observed discrepancies between theory and experiment can be attributed to the deficiency of the single term involving the one-third power of the volume fraction of polymer in the swollen network to describe the contribution of the partial elastic free energy.     

The Reinforcing Effect of Rubber Modification with Nitroso Derivatives

The use of nitroso derivatives in rubber compounds leads to a reinforcing effect with important practical implications. The mechanism of action of these promoters is explained on the basis of the theory according to which the reinforcing effect is due to the strain-crystallization process. This process is dependent on various factors, one of them being the presence of a network based on weak “rubber…carbon black” bonds. The properties of crude and cured blends on natural rubber, polyisoprene, and modified polyisoprene are compared. When nitroso derivatives are used, the active sites on the polymer chain are probably the nitroxyl radicals formed during the modification process. According to the mechanism proposed by the authors in previous papers, the formation of nitroxyl radicals is accompanied by changes of macromolecular characteristics which permit us to explain the reinforcement as well as the modification of viscoelastic and physical-mechanical properties of crude and cured compounds. On the basis of assumptions made on the whole set of reactions regaxding both polymer modification with nitroso derivatives and that of rubber compounds, one can explain not only some of the properties but also the conditions in which modification should be made in order to obtain an optimal reinforcing effect.     

Influence of the crosslink network structure on stress‐relaxation behavior: Viscoelastic modeling of the compression set experiment

A viscoelastic approach of the compression set test is addressed in this work. This test measures the ability of rubber compounds to retain elastic properties after prolonged action of compressive stresses. Elastic properties were tested by recording the normal stress under a constant deformation of 25% with a laboratory rheometer. Considering the Boltzmann superposition principle, compression set data were modeled from the relaxation of Young's modulus, described by a Maxwell spectrum plus a constant E_∞ defining the elastic properties at the long times. This approach was developed with the copolymer of ethylene and vinyl acetate (EVA) networks crosslinked by radical chemistry and by an exchange reaction between acetate groups and silane compounds as crosslinking agents. Regarding the recovery of the elastic properties, radical chemistry provided better results than the exchange reaction for the identical crosslinking density of the network. Then, the Curro–Pincus molecular approach was developed to understand the influence of the microstructure of the EVA network on the elastic properties. The difference of the elastic properties between the two networks crosslinked by two different chemistry means was accounted for by considering the probability of having a dangling end of n units for a random crosslinking process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1779–1790, 2003     

A Note on “Modified Chain Displacement Function of Gaussian Networks” by A. H. Crossland

Crossland claims that the development of the conventional Gaussian theory of rubber elasticity does not take into account the requirement that the polymer chain end-to-end vector must be equal in direction to the network junction-to-junction vector. Reintroducing the directional probability, he develops a novel Gaussian strain-energy function. H correct, Crossland's work is a significant contribution, resulting in notable improvements in important models in rubber elasticity and polymer rheology. Unfortunately, there is an error in Crossland's analysis. Correction of the error reduces Crossland's results to those of the conventional Gaussian theory and shows that the conventional theory does correctly account for the directional probability. The “improved” strain-energy function, therefore, has no theoretical basis and, at best, must be considered purely empirical.     

Bond Scrambling and Network Elasticity

Dynamic networks (DNs) recently reported in the literature are based on cross‐linked supramolecular chains or on covalent chains with reversible bonds. As originally pointed out by Lehn, these networks should be regarded as dynamic materials exhibiting adaptive features due to continuous scrambling of their bonds and sequences. Results in the recent literature reveal that these networks undergo reversible long‐range deformation resembling that of rubber networks. The present analysis of this process in terms of the theory of composite networks is based on the expectation that the scrambling process should allow rupture of bonds in the undeformed state and their reformation in the stretched state. Accordingly, a permanent set of the resting length of DNs should generally be expected and set materials should retain long‐range elasticity relative to the set state. However, only a limited set is shown by DNs, implying that a strong memory of the initial network topology assists elastic recovery of the original dimensions. The analysis of reported experimental data further reveals that the stress‐strain dependence of dynamic networks accurately follows the classical rubber elasticity theory. In this respect, DNs show better rubber behavior than typical covalent networks. Consistently with theoretical predictions, this surprising finding suggests that bond scrambling relieves local strain constraints on the fluctuations of networks junctions and favors the recovery of the initial network topology. Scrambling therefore allows compliance under stress and enhanced recovery when stress is released. Unprecedented applications of these advanced materials thus become foreseeable.