Polymer stabilisers for temperature-induced dispersion gelation: versatility and control

In this study the temperature-induced gelation of butadiene-acrylonitrile latex containing the added temperature-responsive polymer surfactant, poly(NIPAM-co-PEGMa) is investigated for the first time. (NIPAM and PEGMa are N-isopropylacrylamide and poly(ethylene glycol)methacrylate, respectively.) The results are compared with temperature-induced gelation of oil-in-water emulsions containing 1-bromohexadecane. The effect of added anionic surfactant, NaDBS (sodium dodecylbenzene sulfonate) on the temperature-induced gelation process and mechanism is considered. It was found that the gelation temperature (T(gel)) for the latex occurs at the cloud point temperature (T(cpt)) of the polymer and that T(gel) is much less affected by added NaDBS than is the case for emulsion gelation. The mathematical predictive theory recently derived for temperature-induced emulsion gelation was applied to the latex data and gave a good fit (i.e., T(gel) approximately 1/C(p), where C(p) is the concentration of added poly(NIPAM-co-PEGMa)). However, the causes for the variation of T(gel) with C(p) for temperature-induced latex and emulsion gelation are different. The variation of T(gel) for latex gelation in the presence of added NaDBS originates from surfactant association with poly(NIPAM-co-PEGMa) which increased T(cpt). In the case of emulsion gelation there are electrostatic interactions above T(cpt) which control T(gel). The subtle difference in the temperature-induced latex gelation mechanism is a consequence of the very high latex surface area (cf. emulsion), small inter-particle separation and the presence of electrolyte. The reason that T(gel) follows 1/C(p) for the latex is due to a fortuitous T(cpt) approximately 1/C(p) relationship that applies for poly(NIPAM-co-PEGMa) solution in the presence of NaDBS. The work presented here shows that addition of poly(NIPAM-co-PEGMa) to dispersions gives a versatile method for temperature-triggered gelation. Furthermore, the theory presented provides a framework for predicting their gelation temperatures.     

Efficient formation of multicompartment hydrogels by stepwise self-assembly of thermoresponsive ABC triblock terpolymers

The gelation behavior of a poly(ethylene-alt-propylene)-b-poly(ethylene oxide)-b-poly(N-isopropylacrylamide) (PON) triblock terpolymer and a poly(N-isopropylacrylamide)-b-poly(ethylene oxide)-b-poly(N-isopropylacrylamide) (NON) triblock copolymer was studied by rheology over the concentration range 1-5 wt %. In comparison to the NON copolymer, gelation of the PON terpolymer was achieved at a much lower concentration, with a much sharper sol-gel transition. This is due to a stepwise gelation of PON terpolymers involving micellization at room temperature and gelation at elevated temperatures. The separation of micellization and gelation leads to the formation of a two-compartment network as observed by cryoTEM. The results highlight the intricate and tunable nanostructures and new properties accessible from ABC terpolymer hydrogels.     

Thermoreversible gelation of blend of poly(vinylidene fluoride) and poly(vinylidene fluoride-trifluoroethylene) in γ-butyrolactone solution

Thermoreversible gelation behavior of blend of poly(vinylidene fluoride) and poly(vinylidene fluoride-trifluoroethylene) in γ-butyrolactone solution was studied. Sol-gel transition temperature increased with the increase of polymer concentration, but was independent of the blend ratio of two polymers. An equation for gelation rate was derived, assuming that the gelation is a first-order reaction and that the gelation rate obeys an Arrhenius type. According to the equation, the growth index of gelation and supercooling temperature had a dominant effect on gelation rate. The growth index of gelation, which was calculated from the dependence of activation energy on the supercooling temperature in the isothermal gelation, varied with the blend ratio of two polymers. Growth index of gelation larger than 2 was obtained for the blend gels studied in this experiment. It may suggest that the multidimensional growth of gels occurs in such polymer blend solutions. X-ray diffraction and differential scanning calorimetry measurements showed existence of separate crystals due to each component of polymer in the blend gels. © 1996 John Wiley & Sons, Inc.     

To gel or not to gel: A prior prediction of gelation in solvent mixtures

The gelation behaviours of low molecular weight gelators 1,3:2,5:4,6-tris(3,4-dichlorobenzylidene)-D-mannitol(G1)and 2,4-(3,4-dichlorobenzylidene)-N-(3-aminopropyl)-D-gluconamide(G2)in 34 solvents have been studied.We found that sample dissolved at low concentrations may become a gel or precipitate at higher concentrations.The Hansen solubility parameters(HSPs)and a Teas plot were employed to correlate the gelation behaviours with solvent properties,but with no success if the concentration of the tests was not maintained constant.Instead,on the basis of the gelation results obtained for the G1 and G2 in single solvents,we studied the gelation behaviours of G1 and G2 in 23 solvent mixtures and found that the tendency of a gelator to form a gel in mixed solvents is strongly correlated with its gelation behaviours in good solvents.If the gelation occurs in a good solvent at higher concentrations,it will take place as well in a mixed solvent(the good solvent plus a poor solvent)at a certain volume ratio.In contrast,if the gelator forms a precipitate in a good solvent at higher concentrations,no gelation is to be observed in the mixed solvents.A gelation rule for mixed solvents is thus proposed,which may facilitate decision making with regard to solvent selection for gel formation in the solvent mixtures in practical applications.     

Effect of pharmaceuticals on thermoreversible gelation of PEO-PPO-PEO copolymers

Pluronic F127, a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), has generated considerable interest as a drug delivery vehicle due to its ability to gel at physiological temperatures. This work examines the gelation behavior of Pluronic F127 in the presence of a series of hydrophobic pharmaceuticals, to determine whether there is any correlation between gelation and physicochemical parameters of drug solutes. The study includes the local anesthetics dibucaine, lidocaine, and tetracaine; the pharmaceutical additives methyl paraben, ethyl paraben, and propyl paraben; the anti-cancer agents paclitaxel and baccatin III; and the anti-inflammatory agent sulindac. The results indicate that the presence of local anesthetics and pharmaceutical additives allows F127 solutions to form gels at lower copolymer concentrations; local anesthetics and pharmaceutical additives also shift gelation down to a lower gelation temperature. This behavior is strongly dependent on drug solubility; poorly soluble drugs (paclitaxel, baccatin III, sulindac) do not change the lower gelation temperature or minimum F127 concentration for gelation. An equation relating the decrease in gelation temperature to drug solubility is presented, and the equation fits the data well. The results have significant positive implications on the toxicity and economic issues related to use of Pluronic F127 in drug delivery.     

The role of protecting groups in the formation of organogels through a nano-fibrillar network formed by self-assembling terminally protected tripeptides

A series of eight synthetic self-assembling terminally blocked tripeptides have been studied for gelation. Some of them form gels in various aromatic solvents including benzene, toluene, xylene, and chlorobenzene. It has been found that the protecting groups play an important role in the formation of organogels. It has been observed that, if the C-terminal has been changed from methyl ester to ethyl ester the gelation property does not change significantly (keeping the N-terminal protecting group same), while the change of the protecting group from ethyl ester to isopropyl ester completely abolishes the gelation property. Similarly, keeping the identical C-terminal protecting group (methyl ester) the results of the gelation study indicate that the substitution of N-terminal protection Boc- (tert-butyloxycarbonyl) to Cbz- (benzyloxycarbonyl) does change the gelation property insignificantly, while the change from Boc- to pivaloyl (Piv-) or acetyl (Ac-) group completely eliminates the gelation property. Morphological studies of the dried gels of two of the peptides indicate the presence of an entangled nano-fibrillar network that might be responsible for gelation. FTIR studies of the gels demonstrate that an intermolecular hydrogen bonding network is formed during gelation. Results of X-ray powder diffraction studies for these gelator peptides in different states (dried gels, gel, and bulk solids) reflected that the structure in the wet gel is distinctly different from the dried gel and solid state structures. Single crystal X-ray diffraction studies of a non-gelator peptide, which is structurally similar to the gelator molecules reveal that the peptide forms an antiparallel β-sheet structure in crystals.     

Investigation of the gelation process by in‐situ interferometry

An in‐situ interferometric technique was established to investigate the gelation process of poly(acrylic acid) (PAA) gel. The basic principles of the in‐situ interferometric technique is illustrated. It can provide sufficient information for a non‐destructive and successful investigation throughout the whole gelation process. Moreover, the effect of the photoinitiator concentration on the gelation process was studied. The polymerization rate of AA increases with increasing the concentration of the photoinitiator. The error caused by thermal effects during the gelation process can be neglected.     

On the gelation rate of thermoreversible poly(vinylidene fluoride) gels in glyceryl tributyrate

The gelation rate of poly(vinylidene fluoride) (PVF₂)/glyceryl tributyrate (GTB) system has been measured. It has been analysed with the help of an equation which contains φⁿ and f(T) term where φ is a reduced overlapping concentration and n is analogous to the percolation exponent β in a three-dimensional lattice. f(T) is related to the temperature function of the coil-to-helix transition. Analysis of the gelation rates supports that the three-dimensional percolation is a suitable mechanism in this gelation process and it also indicates that the gelation is caused by coil-to-helix transition followed by their association.     

流变学法研究部分水解聚丙烯酰胺/Cr(III)交联反应I.浓度的影响

采用流变学法系统地考察了部分水解聚丙烯酰胺（HPAM）/Cr(III)交联体系的 反应动力学。HPAM溶液的粘性模量G”大于弹性模量G’,且其数值随时间不发生变 化,体系为粘性溶液。而HPAM/Cr(III)体系的G’和G”的数值都随时间变化,G” 在反应开始阶段大于G’,当反应进行一段时间后,G’超过G”占据主要地位,体 系成为弹性体系。交联过程可分为三个阶段：第一上升阶段,平缓上升阶段和第二 上升阶段。利用G’～ t曲线可以推测反应机理。实验发现成胶速率随反应物HPAM 和Cr(III)的浓度的增加而增加,而成胶时间缩短。在羧基浓度过量的情况下,交 联反应对Cr(III)浓度的反应级数是1。凝胶的有效弹性交联密度随聚合物浓度的增 加而增,且随凝胶反应的进行而增加。凝胶的交联点间的平均分子量随Cr(III)浓 度的增加和交联反应的进行而下降。     

Topology evolution and gelation mechanism of agarose gel

Kinetics as well as the evolution of the agarose gel topology is discussed, and the agarose gelation mechanism is identified. Aqueous high melting (HM) agarose solution (0.5% w/v) is used as the model system. It is found that the gelation process can be clearly divided into three stages: induction stage, gelation stage, and pseudoequilibrium stage. The induction stage of the gelation mechanism is identified using an advanced rheological expansion system (ARES, Rheometric Scientific). When a quench rate as large as 30 deg C/min is applied, gelation seems to occur through a nucleation and growth mechanism with a well-defined induction time (time required for the formation of the critical nuclei which enable further growth). The relationship between the induction time and the driving force which is determined by the final setting temperature follows the 3D nucleation model. A schematic representation of the three stages of the gelation mechanism is given based on turbidity and rheological measurements. Aggregation of agarose chains is promoted in the polymer-rich phase and this effect is evident from the increasing mass/length ratio of the fiber bundles upon gelation. Continuously increasing pore size during gelation may be attributed to the coagulation of the local polymer-rich phase in order to achieve the global minimum of the free energy of the gelling system. The gel pore size determined using turbidity measurements has been verified by electrophoretic mobility measurements.     

聚丙烯腈溶液的凝胶化研究

聚丙烯腈是用途最广泛的聚合物之一,其溶于适当溶剂中形成的聚丙烯腈溶液是制备聚丙烯腈纤维、渗透膜等高分子材料的原料。聚丙烯腈溶液的物理化学性质对所制备材料的性能有很大的影响。本文对高分子溶液的凝胶化和高分子凝胶的特点做了简要介绍,并介绍了聚丙烯腈及其凝胶的特点。根据高分子浓溶液体系的特点提出用于表征聚丙烯腈溶液凝胶化的主要方法。从浓度和温度对聚丙烯腈溶液凝胶化行为的影响、熟化和非溶剂对聚丙烯腈溶液凝胶化行为的影响、聚丙烯腈溶液凝胶化的热可逆性、聚丙烯腈溶液凝胶化的分形特征以及聚丙烯腈凝胶的交联机理这几个方面对已有聚丙烯腈溶液的凝胶化研究成果和最新进展进行了综述。最后对聚丙烯腈溶液凝胶化和聚丙烯腈凝胶的研究前景做了展望。     

PEO-PPO-PEO水溶液体系胶束化及凝胶化行为的耗散粒子动力学模拟

采用耗散粒子动力学(Dissipative particle dynamics, DPD)模拟方法研究了三嵌段共聚物聚氧乙烯-聚氧丙烯-聚氧乙烯(PEO-PPO-PEO)的胶束化和凝胶化行为. 通过模拟得到了F127(EO₉₉PO₆₅EO₉₉)水溶液的临界胶束浓度和临界凝胶浓度. 结果发现, 在298 K、 质量分数低于40%时, F127水溶液中形成的胶束形状均为球形. 此外,进一步研究了亲水嵌段长度对胶束结构及凝胶形成浓度的影响, 结果发现, 亲水嵌段越短, 越有利于长椭球状胶束的形成, 而临界凝胶浓度随着亲水嵌段PEO长度的增加而降低.     

Interplay between gelation and phase separation in aqueous solutions of methylcellulose and hydroxypropylmethylcellulose

Thermally induced gelation in aqueous solutions of methylcellulose (MC) and hydroxypropylmethylcellulose (HPMC) has been studied by rheological, optical microscopy, and turbidimetry measurements. The structural and mechanical properties of these hydrogels are dominated by the interplay between phase separation and gelation. In MC solutions, phase separation takes place almost simultaneously with gelation. An increase in the storage modulus is coupled to the appearance of a bicontinuous structure upon heating. However, a thermal gap exists between phase separation and gelation in the case of HPMC solutions. The storage modulus shows a dramatic decrease during phase separation and then rises in the subsequent gelation. A macroporous structure forms in the gels via "viscoelastic phase separation" linked to "double phase separation".     

IN SITU INTERFEROMETRIC STUDY ON THE GELATION PROCESS OF POLYACRYLIC ACID GELS*

In situ interferometry was used to investigate the gelation process of polyacrylic acid (PAA) gels. The basicprinciple of the in situ interferometry technique is illustrated. It can give sufficient information for non-destructive andsuccessful investigation of the whole gelation process. The effect of initiator concentration on the gelation process wasstudied. The polymerization rate of AA increases with increasing initiator concentration. The error arising from the thermaleffect in the gelation process can be neglected.     

Rate equation of gelation of chromium(III)-polyacrylamide sol

During gelation, the time dependence of the apparent viscosity has been used to analyze the kinetics of the gelation of polyacrylamide (PA) sol with chromium (III) ions. The investigations have stablished the following facts: Before gelation the relation between the viscosity, η, of Cr(III)-PA sol and the PA concentration is η = f([PA]) = 2.36×10¹⁵ [PA]^3.15 and the rate equation of gelation in the steady-state stage during gelation is expressed as V_n = k_s f([PA]) [PA]² [Cr(III)]².     

凝胶化反应中标度行为及凝胶化点关系

在苯乙烯(St)-二乙烯苯(DVB)自由基聚合的凝胶化反应过程中,定时取样,得到凝胶化点前后及直至反应终点的一系列溶胶样品,利用光散射技术研究了溶胶相的重均分子量M_w、尺寸均方旋转半径R_g的变化过程,建立了M_w、R_g和反应时间t的标度关系,并在此基础上提出一神新的准确求取凝胶化时间t_gel的方法.     

超分子凝胶性质与溶剂参数关系的研究进展

为了能有效地开发功能性凝胶,人们对超分子凝胶机理做了大量研究.但目前的研究还局限于凝胶因子结构和外界环境等影响因素,而有关溶剂对超分子凝胶体系的影响规律还不十分清楚.本文将结合最新研究进展详细地讨论凝胶性质(如凝胶-溶胶转变温度(Tgel)、临界凝胶浓度(CGC)、凝胶流变学性质等)与溶剂参数(如ε、ET(30)、χ、δ、δd、δp、δh等)的关系,揭示溶剂影响凝胶性质的规律;在此基础上,进一步介绍了超分子凝胶行为预测模型:一维模型、Teas图模型和Hansen空间模型,并讨论了各模型的优缺点,以期为新型超分子凝胶体系的设计提供参考.     

Temperature-Concentration Phase Diagrams in The Study of Thermoreversible Gelation

The contribution of thermal analysis, and particularly of temperature-concentration phase diagrams to the understanding of the phenomenon of thermoreversible gelation is illustrated for two different cases. The important role played by the solvent in the thermoreversible gelation of syndiotactic poly(methyl methacrylate) is emphasized. The heterogeneous nucleation of the gelation of isotactic polystyrene by a self-assembling bicopper complex is presented.     

Rheological and thermal properties of agarose aqueous solutions and hydrogels

In this article, we report on the rheological properties of agarose aqueous solutions and gels. Viscosity curves were determined for homogeneous agarose aqueous solutions at different temperatures (from 68 to 38 °C) to study the viscosity behavior as the systems undergo gelation. The gelation phenomenon of agarose solutions was also investigated by shear oscillation experiments and differential scanning calorimetry. The gelation and melting temperature as a function of agarose concentration were determined together with the gelation and melting enthalpies. The results obtained were interpreted using the two‐step model describing the gelation of agarose in water. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 322–328, 2008     

酚酞基聚芳醚砜非对称超滤膜凝胶动力学研究

采用耐高温工程塑料——含酚酞侧基的聚芳醚砜(PES-C)为膜材料,草酸和聚乙二醇为添加剂,N,N-二甲基乙酰胺为溶剂,并利用改进的凝胶动力学实验装置和方法,使之能真实地再现不同膜孔结构生长及发展演化的过程,借助相关软件对图像进行处理,考察了添加剂、聚合物浓度对铸膜液凝胶速度的影响,对酚酞基聚芳醚砜非对称膜的凝胶过程的动力学进行研究.结果表明,动力学图像与最终膜结构有很好的一致性,凝胶动力学方面得到了与Strathman等不同的研究结果,发现凝胶前锋位移的平方与时间不是线性关系,凝胶动力学过程不能简单地用Fick扩散定律来描述.