Effect of chemical cross-linking under elongation on shape restoring of poly(vinyl alcohol) hydrogel

An anisotropically swollen hydrogel of poly(vinyl alcohol) (PVA) was found to be able to restore an isotropic physical shape by restoring isotropic physical cross-links induced by anisotropically distributed chemical cross-links. The anisotropic chemical cross-links were introduced in the isotropic physical gel by cross-linking with glutaraldehyde under elongation. The physical gel was made from the PVA aqueous solution by repetitive freezing and thawing. The chemically cross-linked gel had kept its original shape and physical properties despite the chemical treatment under strain. However, by the heat treatment in boiling water, the gel changed its form anisotropically depending on the strain applied in the chemical treatment. The anisotropically swollen gel was deswollen in methanol and then reswollen in water. The reswollen gel took back its original isotropic shape, suggesting that the anisotropic chemical cross-links thus introduced in the gel have a memory effect on the restoration of isotropic physical cross-links. © 1992 John Wiley & Sons, Inc.     

PH-induced structure change of poly(vinyl alcohol) hydrogel crosslinked with poly(acrylic acid)

The structure of the hydrogel of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) was investigated by small angle X-ray scattering (SAXS) of synchrotron radiation. A physically crosslinked blend gel, which was prepared by repetitive freezing and thawing of an aqueous solution of PVA and PAA, could be chemically crosslinked by esterfication of PVA with PAA even in the hydrogel state. The chemical crosslinking induced the destruction of physical crosslinks into a folded structure, indicating that the chemical crosslinking proceeds at the sites around the physical crosslinks that contain PVA and PAA in much higher concentration than other portion of the gel. The pH-induced structure changes of the PVA hydrogels, chemically crosslinked with poly(acrylic acid) (PAA) were investigated by SAXS on the samples of various chemical crosslinking time. The gels were shrunk at pH4, and swollen at pH8. The results of SAXS showed, that the Porod slope changed with chemical crosslinking time from -3.5 to ?2.9 at pH4, and from ?2.9 to ?2.4 at pH8. The results suggest that a folded structure as a structural domain, which is characterized by fractally rough interface, tends to change into the structure that corresponds to percolation cluster, particularly at pH8. The gels immersed in pH8 showed a remarkable structure change accompanying swelling. The results revealed that a conformational change of PAA chains, induced by the pH change, can be explained by the presence of a structural domain in the gel network, where both PVA chains and PAA chains get entangled and partially form a interpenetrating polymer network(IPN).     

A comparative study of swelling properties of hydrogels based on poly(acrylamide‐co‐methyl methacrylate) containing physical and chemical crosslinks

Poly (acrylamide‐co‐methyl methacrylate) hydrogels of different ratios were prepared by using chemical and physical crosslinks to study the effect of nature of crosslinks on swelling behavior of hydrogels. The chemically crosslinked gels were prepared by using NN′‐methylene bis acrylamide, while physically crosslinked hydrogels were prepared by precipitation polymerization method, using dioxane as solvent. Detailed swelling kinetics such as swelling ratio, transport exponent n, diffusion coefficient D and the effect of pH on equilibrium swelling studies. The study revealed that the nature of crosslinks alter the swelling characteristics of the hydrogel. In chemically crosslinked hydrogels the water transport is Fickian in nature, while in the case of the physically crosslinked hydrogels the water transport mechanism is anomalous indicating major change in relaxation mechanism due to nature of crosslinks. The results also indicate that with increasing acrylamide content the swelling ratio of the hydrogels were also increased, but the transport exponent n remains nearly constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 779–786, 2003     

Swelling behavior of physical and chemical DNA hydrogels

DNA hydrogels were prepared from aqueous solutions of double‐stranded DNA (about 2000 base pairs long) by physical and chemical means. Physical gels were obtained via denaturation–renaturation cycle of 5% aqueous DNA solutions between 25 and 90°C. Although physical DNA gels exhibit a high modulus of elasticity, the crosslinks holding the DNA network together are destroyed during the expansion of gels in water or in dilute salt solutions. It was shown that these gels can be used for the controlled release of DNA in aqueous media. Chemical DNA gels formed using ethylene glycol diglycidyl ether crosslinker are stable in water with a wide range of swelling ratios that could be adjusted by the amount of DNA at the gel preparation. Swelling behavior of chemical DNA gels in acetone/water mixtures as well as in aqueous salt solutions is very similar to that of synthetic polyelectrolyte hydrogels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crosslinking structures of gelatin hydrogels crosslinked with genipin or a water‐soluble carbodiimide

It was suggested in our previous studies that carbodiimide‐ and genipin‐crosslinked gelatin hydrogels could be used as bioadhesives to overcome the cytotoxicity problem associated with formaldehyde‐crosslinked gelatin hydrogels. In this study, we investigated the crosslinking structures of carbodiimide‐ and genipin‐crosslinked gelatin hydrogels. We found that crosslinking gelatin hydrogels with carbodiimide or genipin could produce distinct crosslinking structures because of the differences in their crosslinking types. Carbodiimide could form intramolecular crosslinks within a gelatin molecule or short‐range intermolecular crosslinks between two adjacent gelatin molecules. On the basis of gel permeation chromatography, we found that the polymerization of genipin molecules could occur under the conditions used in crosslinking gelatin hydrogels via a possible aldol condensation. Therefore, besides intramolecular and short‐range intermolecular crosslinks, additional long‐range intermolecular crosslinks could be introduced into genipin‐crosslinked gelatin hydrogels. Crosslinking a gelatin hydrogel with carbodiimide was more rapid than crosslinking with genipin. Therefore, the gelation time for the carbodiimide‐crosslinked gelatin hydrogels was significantly shorter than that of the genipin‐crosslinked gelatin hydrogels. However, the cohesive (interconnected) structure of the carbodiimide‐crosslinked gelatin hydrogels was readily broken because, unlike the genipin‐crosslinked gelatin hydrogels, there were simply intramolecular and short‐range intermolecular crosslinks present in the carbodiimide‐crosslinked hydrogel. In the cytotoxicity study, the carbodiimide‐crosslinked gelatin hydrogels were dissolved into small fragments in the cultural medium within 10 min. In contrast, the genipin‐crosslinked gelatin hydrogels remained intact in the medium throughout the entire course of the study. Again, this may be attributed to the differences in their crosslinking structures. The genipin‐crosslinked gelatin hydrogels were less cytotoxic than the carbodiimide‐crosslinked gelatin hydrogels. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4017–4026, 2004     

Peroxide crosslinking of a styrene‐free unsaturated polyester

Thermoset unsaturated polyesters are usually obtained by the crosslinking of unsaturated polyester chains dissolved in an unsaturated, reactive, monomeric diluent, which is usually styrene. This article describes a new approach in which styrene‐free unsaturated polyester chains are intrinsically cured into a crosslinked matrix. The gel time, gel content, swelling degree, glass‐transition temperature, dynamic mechanical properties, tensile properties, and molecular weight between crosslinks (calculated according to both the Flory–Rehner equation and the theory of rubber elasticity) of the crosslinked polymer are studied as a function of the peroxide concentration. All properties change considerably upon the addition of small amounts of peroxide (between 1 and 2 wt %) and change to a lesser extent with higher peroxide concentrations (up to 6 wt %). The thermal properties of the isolated gel fraction are studied as a function of the peroxide concentration. The sol fraction demonstrates a plasticizing effect on the crosslinked network, affecting the glass‐transition temperature and stress–strain behavior of the crosslinked polymer. In light of the crosslink densities derived from swelling experiments, a molecular structure and crosslinking mechanism are suggested for the gel fractions of 1 and 6 wt % peroxide crosslinked unsaturated polyester chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Pure shear deformation of physical and chemical gels of poly(vinyl alcohol)

Pure shear deformation reveals the significant differences in elastic properties of the poly(vinyl alcohol) (PVA) gels with almost identical initial modulus, but with different types of crosslinks, physical crosslinks formed by microcrystallites and chemical crosslinks made of covalent bonds. The ratio of the two principal stresses steeply increases with elongation in the physical gels, while that remains almost constant independently of stretching in the chemical gels. The marked growth of the stress ratio with elongation in the physical gels leads to the negative values of the derivative of the elastic free energy (W₂) with respect to the second invariant of the deformation tensor in the whole range of deformation, which is firstly observed for elastomeric materials. By contrast, the chemical gels exhibit the positive values of W₂ like most chemically crosslinked rubbers. Among the existing theories of rubber elasticity, the classical non-Gaussian three-chain model considering the effect of finite chain-length is qualitatively successful in accounting for the steep increase of the stress ratio and the negative values of W₂ in the physical gels, although it fails to reproduce the large difference in the stress-strain behavior among uniaxial, pure shear and equi-biaxial deformations. These features of the physical gels are expected to stem from the structural characteristics such as fewer amounts of slippery-trapped entanglement along network strands compared to the chemical PVA gels.     

化学微交联聚氯乙烯的结构和性能

通过氯乙烯/邻苯二甲酸二烯丙酯(VC/DAP)悬浮共聚,合成了含部分凝胶结构的化学微交联PVC树脂,对微交联PVC的玻璃化转变行为、加工性能、消光性能、加热-形变行为和力学性能进行了研究。当DAP用量在0.25%mol以下时,PVC的玻璃化温度变动不大。凝胶含量的增加将导致交联PVC_d~T的光泽度下降,消光性能提高;塑化时间和加工扭矩均增加,加工性能急剧变差;加热变形值下降,最高使用温度提高。凝胶对PVC拉伸性能的影响较为复杂,但压缩永久变形则随凝胶含量的增加而下降,材料的弹性性能逐渐提高。     

Structure–property relationships of lightly chemical crosslinked poly(vinyl chloride) thermoplastic elastomer

Chemical crosslinked poly(vinyl chloride) (C‐PVC) was synthesized by vinyl chloride suspension polymerization in the presence of diallyl phthalate (DAP) and plasticized to prepare poly(vinyl chloride) (PVC) thermoplastic elastomer (TPE) materials. The chemical crosslinking and physical crosslinking structure in chemical crosslinked PVC‐TPE were investigated. It showed that the gel fraction and the crosslinking density of gel increased as the feed concentration of DAP increased. C‐PVC prepared by VC/DAP copolymerization was lightly crosslinked as compared with irradiation crosslinked PVC. Physical entanglements would greatly influence the crosslinking density of gel when the gel fraction was high. Chemical crosslinking had little influence on the recrystallization behavior of PVC. A structure model of chemical crosslinked PVC‐TPE was proposed, in which chemical networks acted with physical networks cooperatively. It also showed that chemical crosslinking and physical crosslinking influenced the processability and mechanical properties of chemical crosslinked PVC‐TPE cooperatively. Although the processability of PVC‐TPE deteriorated with chemical crosslinking, the dimension stability and elasticity of PVC‐TPE were improved as the permanent chemical networks were introduced. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 868–874, 2000     

Formation and destruction of physical crosslinks by mild treatments in chemically crosslinked poly(vinyl alcohol) gels

We report the formation, destruction, and re-formation of the microcrystallites in a chemical PVA gel, crosslinked slightly by glutaraldehyde. The dried gel, in which the microcrystallites were formed, was immersed in a poor solvent of a mixture of DMSO and water at 8 °C, where the gel stayed in its collapsed state. The gels swelled on heating to 50 °C, but did not return to the initial state on cooling to 8 °C. After washing the gel completely in water, a drying process caused the microcrystallites to be re-formed and the gel could return to the initial dried state at 8 °C. By using XRD and FT-IR measurements, it was concluded that the formation and destruction of microcrystallites in chemically crosslinked PVA gels could be controlled by the mild treatments of initial drying, temperature change, and washing and drying.     

Zum kautschukelastischen verhalten von polyurethan-ionomeren

Dispersions of cationic and anionic ionomers of polyurethanes were prepared by the acetone method. Characteristic changes of the viscosity were observed during the addition of water. This change was studied with a cationic ionomer. The ionomers are mainly associated dimeric species in solution of acetone. During the addition of water the ions are solvated while the hydrophobic segments are increasingly associated. At the maximum of the observed viscosity the apparent molecular weight M_max ≈ 3 M_min. In the absence of solvents the ionomers behave like crosslinked materials even if no covalent crosslinks are present. The modulus at small elongations is a linear function of the square of the concentration of the cations. It is concluded that two ionic centers are required per crosslink. The anionic ionomers were also chemically crosslinked since an excess of isocyanate was used. A linear increase of the modulus was observed with increasing amount of chemical crosslinks, while the concentration of ions and hydrogen bonds was constant. The crosslinks formed by ions can be suspended by swelling with water. The portion of the modulus caused by ionic crosslinking can be computed from the difference of the moduli in the dry and swollen state.     

Exchange reactions as a basis of thermopiastic behaviour in crosslinked polymers

An attempt has been made to achieve thermoplastic behaviour in a chemically crosslinked elastomer by arranging that the crosslinks should undergo rapid exchange at high temperatures. Natural rubber was chemically modified to give pendent hydroxyl groups which were then used as crosslinking sites to form β-keto-ester or malonate crosslinks. The resultant vulcanisates showed high stress relaxation rates in the temperature range 120 to 160°C and some degree of remouldability at 180°C. The incursion of permanent crosslinking prevented quantitative correlation between stress relaxation rates and chemical exchange rates of the crosslinking systems.     

The role of entanglements in network formation in unsaturated low density polyethylene

In this study the network formation in a new poly(ethylene-co-1,9-decadiene) polymer was compared with that formed in an ‘ordinary’ low density polyethylene after being crosslinked with a peroxide. The crosslink density was determined by swelling measurements and by strain measurements at different stresses. Above the melting point, physical crosslinking points, in the form of ‘trapped entanglements’, constitute around 60% of the total number of crosslinking points. The chemical crosslinks, which originate from peroxide and from reacted vinyl groups, are in minority. However, although the chemical crosslinks are fewer, they are indeed very important for making the large fraction of physical crosslinks permanent, i.e. that they do not slip under load.     

Dynamic light scattering from polymer gels: spring-rotor model

Dynamic light scattering behaviour in the form of periodic oscillating correlation functions has been found from measurements on both physically and chemically crosslinked hydrogels. The former were aqueous methyl cellulose at the thermal gelation temperature and the latter were poly(N,N-dimethylacrylamide-co-methyl methacrylate-co-ethylene dimethacrylate) at swelling equilibrium in water. In order to explain the oscillating behaviour, a spring-rotor model is proposed in which the molecular motions inside a gel are modelled as vibrations of springs having various frequencies. These frequencies are equivalent to the rotational frequencies when the free rotor theory was used to process the oscillating correlation functions by a modified CONTIN computer program. The validity of this model is supported by experimental data in three ways. (1) The model fits the experimental data almost perfectly. (2) The main peak positions of the obtained frequency distribution are not affected by the scattering angle. (3) For the chemically crosslinked hydrogels differing only in content of ethylene dimethacrylate, the mean vibrational frequency of the gel spring is higher the shorter the spring, i.e. the lower the average molecular mass between crosslinks. © 1998 SCI     

pH‐reversible magnetic gel with a biodegradable polymer

Polymer gels that react to external stimuli, such as pH, temperature, and electromagnetic fields, are an important class of materials. Such materials have pharmaceutical, industrial, and biomedical applications. Our intention in this study was to synthesize a stimuli‐responsive polymer gel with a biodegradable polymer. However, the chemical crosslinker, divinyl sulfone, which is most widely used for the crosslinking of this type of material, is highly toxic in nature. To overcome this problem, a reversible magnetic gel was synthesized with hydroxy propyl cellulose (HPC) and maghemite at pH 13 without with a chemical crosslinker. With a decrease in pH from 13 to 9, the gel formed a homogeneous dispersion of HPC particles with maghemite in it. This process was a reversible physical gelation where the crosslinks of the network had a physical origin (in this case, hydrogen bonding) and, therefore, were sensitive to variations in pH. When this physically prepared gel was compared with the chemically crosslinked one, no significant differences in structural properties were noted. At higher pH values, the gel was formed due to weak intermolecular hydrogen bonding, as observed by the broadening of the IR band in both the magnetic and nonmagnetic gels. Transmission electron micrographs also showed no significant difference in the gel morphology. Differential scanning calorimetry showed an increase in melting temperature for the gel sample compared to that of pure HPC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3337–3341, 2004     

硅烷接枝ABS树脂及其水解交联的研究

在Haake密炼机中进行硅烷和ABS树脂的接枝反应,接枝产物在沸水中进行水解交联。研究了硅烷种类和用量、引发剂种类和用量对接枝率和凝胶率的影响,同时考察了反应条件对凝胶率的影响。结果表明,在本研究范围内,对于ABS树脂,只有使用3－甲基丙烯酰氧基三甲氧基硅烷（VMMS）作为接枝单体和丙烯酰胺作为引发剂才能得到一定的凝胶率。接枝率随单体用量增加而增加,凝胶率则先升高后趋于一定值。接枝率和疑胶率还随引发剂用量的增加先迅速增加后趋于一定值。温度和转速较低时,对凝胶率没有明显影响,但温度和转速很高时,凝胶率有所下降。     

Polyurethane elastomers made from linear polybutadiene diols

Segmented polyurethane elastomers made from linear polybutadiene diols terminated with primary (Krasol LBH‐P) or secondary (Krasol LBH) hydroxy groups, alicyclic diisocyanate, and aliphatic chain extender were prepared and tested. The system was chemically crosslinked either through isocyanurate, that is, hexahydro‐1,3,5‐triazine‐2,4,6‐trione groups (formed by catalyzed cyclotrimerization of isocyanate groups), or by low molecular weight triols. The best balance of stress‐strain properties and reasonable thermal stability was obtained for systems in which only a small amount of chemical crosslinks was present in predominantly physically crosslinked networks. The influence of the type of polymer diol, chemical crosslinking, diisocyanate, and technique of preparation on mechanical, thermal, and swelling properties is discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 84–91, 2002     

Improvement of flame-retardant properties of insulated wires by radiation crosslinking

Electric wires coated with polyethylene insulation crosslinked by a chemical method (gel fraction = 80%) and a jacket of self-extinguishing resin were produced. The jacket was crosslinked by irradiation with γ rays or accelerated electrons. Flame retardant properties of the wire improved by γ-ray induced crosslinking up to ～60% gel fraction in the jacket. Beyond this point, however, the flame resistance rapidly decreased with increasing gel fraction. The flame resistance was also improved by irradiation with electrons, but the extent of the improvement was strongly dependent on the energy of incident electrons. This fact was attributed to the difference in the distribution of energy dissipation, i.e., crosslinks formed in the jacket. By introducing a double layer structure to the jacket, in which the inner layer adjacent to the polyethylene insulation was crosslinked more densely than the outer layer, the wires were markedly improved in resistance to flame and heat deformation.     

Dodecyl methacrylate as a crosslinker in the preparation of tough polyacrylamide hydrogels

Copolymerization of acrylamide with dodecyl methacrylate (C12) solubilized in aqueous micelles of sodium dodecyl sulfate produces tough hydrogels exhibiting moduli of elasticity around 1 kPa. Swelling and gel fraction measurements show that the hydrophobic associations acting as temporary crosslinks are too strong to be destroyed in water during the expansion of the gel network. An order of magnitude larger value of loss factor tan δ of the hydrogels formed using the hydrophobe C12 as compared to the conventional hydrogels indicates the dynamic nature of their crosslink zones. The hydrogels are more homogeneous than the corresponding gels prepared by a chemical crosslinker, as determined by the static light scattering measurements. Mechanical tests indicate that, in addition to the dodecyl domains, permanent crosslinks are also needed to obtain hydrogels that are mechanically stable up to 250% elongation ratios.     

From topological gels to slide‐ring materials

A novel type of gel, called a topological gel, has been recently developed with a supramolecular architecture with topological characteristics. In the topological gel, polymer chains with bulky end groups are neither covalently crosslinked as in chemical gels nor attractively interacting as in physical gels but are topologically interlocked by figure‐eight shaped crosslinks. Hence, these crosslinks can pass along the polymer chains freely to equalize the tension of the threading polymer chains similarly to pulleys; this is called the pulley effect. This concept can be applied not only to gels but also to a wide variety of polymeric materials without solvents. Then, polymeric materials with movable crosslinks are referred to as slide‐ring materials (SRMs) in a wider sense. Here, we review the synthesis, structure, physical properties, and applications of topological gels and SRMs. In particular, slide‐ring elastomers show remarkable scratch‐proof properties for application to coating materials for automobiles, cell phones, mobile computers, golf clubs, and so on. © 2014 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40509.