首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
A variety of composites comprising complexes between macromolecules and growing species such as macromolecules or particles may be prepared using matrix or pseudo-matrix processes. Matrix polycondensation of silica acid in the presence of poly(ethylene glycol) and other polymers in benzene resulting in formation of interpolymer complex (IPC) poly(silica acid)-matrix or composites including the IPC is regarded as an example of matrix processes providing the possibility to synthesize an IPC or composite which cannot be (or hardly may be) obtained by other ways: Theoretical aspects of pseudo-matrix processes in which pseudo-matrix macromolecule recognizes (i.e., forms a complex with) a particle of forming new phase and terminates its subsequent growth are discussed. Experimental data dealing with reduction of Ni(II) in polymer solutions and formation of nano-composites ‘polymer - metallic nickel’ including small particles (3–5 nm in diameter) with narrow size distribution are presented.  相似文献   

2.
Bis(imidazolylporphyrinatozinc) molecules linked through a 1,3-butadiynylene moiety respond to the solvents they are dissolved in to afford exclusively extended (E) or stacked (S) supramolecular polymers. This system is expected to be a solvation/desolvation indicator. However, the principles underlying the solvent-dependent formation of the two types of polymers and the mechanism of the transformation between them are unclear. The formation of the polymers is considered to depend on the two types of complementary coordination bonds that can be formed and the π–π interactions between the porphyrins. In this study, the contributions and solvent dependence of both the coordination bonds and the π–π interactions have been investigated. The results clearly indicate that the coordination bonds are weakly or little solvent-dependent, and that the π–π interactions function effectively only in the inner porphyrins of the S-polymer and are strongly solvent-dependent. Thermodynamic analysis revealed that the formation of the E- or S-polymer in solution is determined by the total energies and the type of solvent used. The transformation of the E- to S-polymer was investigated by gel permeation chromatography. The kinetics of the transformation were also determined. The role of the terminal imidazolylporphyrinatozinc moieties was also investigated: The results indicate that the transformation from the E- to S-polymer occurs by an exchange mechanism between the polymers, induced by attack of terminal free imidazolyl groups on a polymer to zinc porphyrins on other polymers.  相似文献   

3.
Metal sols composed of metal nanoparticles (1 - 10 nm in diameter) protected with polymer molecules may be regarded as dispersions of polymer-metal complexes formed due to cooperative non-covalent (e.g., hydrophobic, coulombic) interaction of polymer chains with the surface of metal nanoparticles. The sols are commonly prepared by reducing of metal ions in solutions of appropriate polymers. The interactions between macromolecules and nanoparticles are reversible. In the case of long polymer chains and minute particles, the equilibrium constant of the reaction exponentially depends on the surface area of the particle. The probability of mutual “recognition” (complex formation) of growing particle and a macromolecule rapidly increases from practically zero to practically unity in narrow interval of the particle's diameters. The recognition is followed with the shadowing of the particles and the stop of their growths. Such kind of processes was termed “pseudo-template”. In frame of the concept of pseudo-template processes can be estimated: (1) the conditions at which sol particles of desirable size can be prepared, (2) the influence of temperature, polymer concentration, nanoparticles size, and other conditions on the stability of polymer - particle complex having been prepared, and (3) the conditions at which stable sol does not exist and can not be prepared at all. The interactions between metal nanoparticles and macromolecules are highly selective regard to the structure of polymer chains. The property can be effectively used for the control the size characteristics of metal nanoparticles (in course of their formation) and the stability of metal sols. The selectivity provides high conversions in catalytic chemical modification reactions in which a macromolecule is the substrate and a component of the catalyst in the same time. As an example, the hydrolysis of lactame groups in monomer unites of poly(N-vinyl pyrrolidone) catalyzed with copper sols is discussed.  相似文献   

4.
The matrix synthesis of polyaniline in the presence of water-soluble aromatic polyamides containing sulfo acid groups has been studied. It has been shown that the nature of polyacid and the concentration of reagents affect the shape and dynamics of a change in absorption spectra. The S-shaped profile of kinetic curves for spectra variation and the experiments on the seed polymerization provide evidence for the autocatalytic character of polymerization. It has been concluded that, depending on the nature of polyacid, polymer complexes form in which polyaniline macromolecules are situated along main chains of polyacid macromolecules (the two-stream structure) or appear as side chains of polyacid macromolecules (the comb-shape structure). In the latter case, polyaniline macromolecules serve as ionic bridges crosslinking polyacid macromolecules, as is confirmed by the viscometric study of solutions in the course of polymerization.  相似文献   

5.
Stable polyacrylamide (polyAA)–montmorillonite adducts were prepared by two distinct processes: (1) free radical copolymerization of AA with alkaline clay previously treated with 2-(N-methyl-N,N-diethyl ammonium iodide)ethylacrylate (QD1) and (2) direct interactions of alkaline montmorillonite with various preformed copolymers of AA with QD1. The structure of the adducts as determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction was shown to consist of AA macromolecules inserted between lamellar layers whose spacing was larger than in the polymer-free clay. The polymer was strongly attached to the inorganic surfaces, probably due to cooperative formation of electrostatic bonding. The thermal stability of the organic polymers in the resulting complexes was substantially enhanced while the mobility of macromolecules decreased.  相似文献   

6.
On the basis of previous concepts concerning the molecular nature of pressure-sensitive adhesion, a simple method of preparing new adhesives with the desired mechanical and adhesive behavior and water-absorbability via mixing of nonadhesive polymers has been developed. Pressure-sensitive adhesion is related to the combination of a high energy of cohesion and a large free volume, which leads to a high molecular mobility. This method is based on the formation of interpolymer or polymer-oligomer complexes during mixing of macromolecules capable of hydrogen, electrostatic, or ionic bonding. In interpolymer complexes, a high cohesion results from the formation of bonds between macromolecules carrying complementary groups in main chains, whereas free volume is related to defectiveness of the resulting network and formation of loops. In complexes formed by a high-molecular-mass polymer and an oligomer carrying complementary reactive groups at ends of short chains, a high energy of cohesion is related to their interaction with mainchain functional groups of the polymer, whereas a relatively large free volume is associated with the length and flexibility of intermacromolecular crosslinks via oligomer chains. The adhesive and viscoelastic properties of adhesives and their water absorbability are regulated by changes in the composition of mixtures of a film-forming polymer with a polymer or oligomer crosslinker and a plasticizer. In this case, an increase in cohesive strength is achieved owing to an increase in the crosslinker concentration, while the enhancement of free volume is ensured by the increasing plasticizer content in the blend. Adhesive materials capable of adherence to wet substrates, hydroactivated adhesives, and adhesion moisture sorbents have been prepared for the first time.  相似文献   

7.
The process of formation and structural organization of interpolymer complexes formed by macromolecules of poly(N-vinylpyrrolidone) and poly(methacrylic acid) chains grafted onto polyimide in solution is investigated via the method of polarized luminescence. A luminescent label of anthracene structure is covalently bound to both polymers. Relaxation times characterizing intramolecular mobility of each of the components in their interpolymer complex are measured in relation to the composition of the system.  相似文献   

8.
The poly(carboxylic acid) bound phenosafranine and thionine dyes show that, the fluorescence intensity and lifetime increases first and starts to decrease after reaching a maximum at pH 4.0. The fluorescence decay curve of the fluorophore bound polymers follow the biexponential decay fit independent of pH, while poly(MAA-Th) follows single exponential function above pH 4.0. At low pH, a more compact environment of the fluorophore exerts a more hydrophobic environment. In the subnanosecond time domain the solvation process is found to be incomplete while in the nanosecond time scale the solvation of the macromolecular chains is found to be over. The time resolved fluorescence spectra of the polymer bound fluorophores at different pH indicate distinct hydrophobic and hydrophilic environments due to the dynamics of the macromolecules in dilute aqueous solutions. For the first time structural transitions involving solvent are observed in the nanosecond and picosecond time domains for the same macromolecule.  相似文献   

9.
The influence of salt additives on structural transformations in macromolecules of synthetic polymers free of ionogenic groups and DNA molecules has been determined with the use of the nanosecond dynamics luminescent method. When polyvalent metal salts are added, a coil-globule transition is observed in macromolecules of poly(N-n-propylmethacrylamide), while structural transformations occur in DNA macromolecules in aqueous solutions, processes that are accompanied by the passage of low-molecular-mass organic cations intercalated into DNA into solution. These transformations make themselves evident when polyvalent metal ions are added in an amount of one Mt3+ ion per ten phosphate groups of DNA. The same effect takes place when salts of polycations are added to solutions of DNA-polycation interpolyelectrolyte complexes.  相似文献   

10.
The results of molecular dynamics simulation of solutions of highly charged rigid-chain polymers in the presence of multivalent counterions are presented. The processes of self-assembly of macromolecules that occur during the condensation of counterions and depend on temperature, the dielectric permittivity of the medium, and the charge of counterions were studied. Various conformational rearrangements induced by changing the parameters of the medium were examined. The conditions that lead to the formation of network superstructures composed of aggregating polymer chains were found. Size distribution functions for free-volume holes were constructed and the average dimensions of voids in the network structures formed were calculated.  相似文献   

11.
Solutions of surfactant-polymer mixtures often exhibit different foaming properties, compared to the solutions of the individual components, due to the strong tendency for formation of polymer-surfactant complexes in the bulk and on the surface of the mixed solutions. A generally shared view in the literature is that electrostatic interactions govern the formation of these complexes, for example between anionic surfactants and cationic polymers. In this study we combine foam tests with model experiments to evaluate and explain the effect of several polymer-surfactant mixtures on the foaminess and foam stability of the respective solutions. Anionic, cationic, and nonionic surfactants (SDS, C(12)TAB, and C(12)EO(23)) were studied to clarify the role of surfactant charge. Highly hydrophilic cationic and nonionic polymers (polyvinylamine and polyvinylformamide, respectivey) were chosen to eliminate the (more trivial) effect of direct hydrophobic interactions between the surfactant tails and the hydrophobic regions on the polymer chains. Our experiments showed clearly that the presence of opposite charges is not a necessary condition for boosting the foaminess and foam stability in the surfactant-polymer mixtures studied. Clear foam boosting (synergistic) effects were observed in the mixtures of cationic surfactant and cationic polymer, cationic surfactant and nonionic polymer, and anionic surfactant and nonionic polymer. The mixtures of anionic surfactant and cationic polymer showed improved foam stability, however, the foaminess was strongly reduced, as compared to the surfactant solutions without polymer. No significant synergistic or antagonistic effects were observed for the mixture of nonionic surfactant (with low critical micelle concentration) and nonionic polymer. The results from the model experiments allowed us to explain the observed trends by the different adsorption dynamics and complex formation pattern in the systems studied.  相似文献   

12.
In this study, a copolymer of N,N-dimethylacrylamide and hydroxyethyl-methacrylate was synthesized and hydrophobically modified with about 2 mole % of adamantyl groups. The mixing of this modified copolymer with water-soluble β-cyclodextrin polymers reveals thickening properties. Inclusion complexes formation between adamantyl groups and β-cyclodextrin cavities are responsible of intermolecular associations. Above a given total polymer concentration a phase separation occurs, giving a gel phase topped by a liquid phase. We have stated the phase diagram by analysis of the two phases in equilibrium. It has been observed that the two polymers are present in both phases and that the gel phase is more concentrated than the other one. This phase behavior is an original complex coacervation phenomenom which is due to the specific attractive interactions of the two different macromolecules: inclusion complexes formed between the two neutral polymers.  相似文献   

13.
The causes of a high total conversion and the S-shaped pattern of the time dependence of conversion for copper sol-catalyzed hydrolysis of the lactam rings of poly(N-vinylpyrrolidone) have been studied. The high conversion of the hydrolusis is achieved via replacement of modified macromolecules in shields of catalyst particles with less modified macromolecules from the dispersion medium of a sol in the course of reaction owing to a decline in the stability of copper nanoparticle complexes with macromolecules with an increase in the degree of hydrolysis. A reduction in the complex stability leads to an increase in the lability of bonding of shielding polymer chains with the catalyst surface and to the growth of the rate of rearrangement and the overall rate of reaction after the induction period. This situation is also responsible for the enlargement of nanosized catalyst particles in the course of reaction and the destruction of the sol after a limiting conversion of units of ~40–50% is attained.  相似文献   

14.
一种梳状高分子固体电解质的分子运动和离子导电性   总被引:6,自引:3,他引:6  
用交流复阻抗谱和动态粘弹谱等对交替马来酸酐共聚物多缩乙二醇酯衍生物及其LiClO4盐复合物进行了研究.结果表明,在Li/EO=0.07—0.042范围内,从173K到373K,本聚合物一高氯酸锂复合体系的动态粘弹谱存在着两个明显的转变,其中β转变归属于PEO的侧链玻璃化转变,转变温度随LiClO4盐浓度的增加而增加。α转变归属于主链玻璃化转变,在Li/EO=0.028时有极大值。盐浓度与电导率的关系与通常不一样,在所研究盐浓度范围内观察到两个峰,其一在Li/EO<0.014,另一峰在Li/EO=0.028.电导率与温度的依赖关系不符合Arrhenius行为;以lgσ对1/T-T0作图,用侧链玻璃化转变温度Tβ作T0时,呈典型的VTF行为。该体系室温电导率最高可达6×10-6s/cm.  相似文献   

15.
Hyperbranched macromolecules have been first synthesized by the three-dimensional free-radical polymerization of vinyl monomers in the presence of oxygen, which is known to be a strong inhibitor of freeradical chain processes. The inhibition of free-radical polymerization by molecular oxygen results in the shortening of primary polymer chains with pendant double bonds. As a consequence, the formation of insoluble gel, which develops at conversions of less than 1%, when the crosslinking free-radical polymerization is carried out under ordinary conditions, may be avoided up to a conversion of 100%. In terms of the kinetic scheme, including nearly 100 elementary reactions, the effects of temperature and concentration of reagents on the kinetic parameters of the process and the structural parameters of hyperbranched polymers based on methacrylate and styrene-like monomers have been studied. Optimal conditions that make it possible to synthesize hyperbranched polymers of the desired architecture and functionality at a sufficiently high yield, which are specified by the occurrence of oxygen-containing groups in primary polymer chains and at its ends, have been estimated.  相似文献   

16.
17.
The nanosecond mobility of polymer micelles in aqueous solution of poly(N-propylmethacrylamide) and that of reversed micelles of a surfactant in organic solvents were studied by polarized luminescence. The factors affecting the polymer micelles formation and the effect of polymers solubilized in systems of reversed micelles of a surfactant on their relaxation properties were established.  相似文献   

18.
Capability of NMR technique to study fracture and elementary destruction acts in polymers is discussed. Tensile stress influences macromolecular mobility As a rule mobility of macromolecules decreases under deformation. So far deformation remains reversible, this effect is reversible, too. As a result of chain micro-Brownian motion hindering under stress the amorphous layers can pass from high-elastic to solid state even at temperatures rather higher than Tg measured under initial conditions. It is mechanical vitrification (not structure changes) that is regarded as the general causes of draw process interruption (destruction of polymer). Deformation-induced electron emission was detected. It is caused by ionization of stressed chains and tunnel transitions of electrons into deep traps. Influence of molecular mobility on the traps and their destroying under stress are considered.  相似文献   

19.
Structure and dynamics of complex macromolecules in computer simulated systems is analyzed. The algorithm based on cooperative molecular rearrangements is applied to various macromolecular structures represented in a simplified form on the lattice. Various macromolecular architectures such as linear chains, stars, dendrimers, bottle‐brush polymers as well as cyclic chains and catenane are considered both as single molecules and as dense systems corresponding to polymer melts. A broad range of structural parameters characteristic for each system is taken into account. In some cases, the simulation results are compared with the behavior of real systems in which the structure and dynamics has been studied by X‐ray scattering and mechanical spectroscopy, respectively.  相似文献   

20.
Cyclodextrins are cyclic oligosaccharides, capable of forming inclusion complexes with many active substances. This way, the aqueous solubility and rate of dissolution of active substances can be changed. For this research we have selected celecoxib as the model active substance, due to its low water solubility, high lipophilicity, and high intestinal permeability. Usually, the amount of cyclodextrin complex that can be incorporated into a pharmaceutical dosage form is limited. The usage of hydrophilic polymers can overcome this problem. In this study, we wanted to point out the potential of various types of hydrophilic polymers for enhancing the complex formation efficiencies, and to highlight the possible use of alginate as a solubility stabilizer/enhancer and as a microsphere matrix polymer. The phase solubility investigation showed greater stability constants (> 250 M?1) in ternary complexes than in the binary complex, which is a good indicator of the complex formation enhancer properties of these hydrophilic polymers. The relative solubilizing efficiency decreased in the next order: PVP K25 (6.49) > Sodium alginate (6.26) > PEG 6000 (5.72) > without polymer (4.81). The DSC curves showed that all samples that were prepared with β-cyclodextrin (both complexes and physical mixtures) had lower melting endotherms at 160 °C than pure celecoxib. XRD confirmed the complex formation by partial celecoxib amorphisation. The dissolution studies of the prepared microspheres revealed that all samples had different release rates (shown by the similarity factor f2, which was 36.37, 42.46 and 38.11 % respectively) and that the use of β-cyclodextrin increased the dissolution rate of celecoxib from alginate microspheres in a controlled manner. We concluded that sodium alginate could act as a complex stabilizing/enhancing agent and as a microsphere matrix polymer, at the same time.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号