聚乙烯接枝马来酸酐极稀和稀溶液性质的研究

该文研究了聚乙烯接枝马来酸酐 (PE g MAH)在极稀和稀浓度范围内的溶液行为 .两个区间内的粘浓关系都呈直线关系 ,但极稀区间的斜率比稀浓度的大得多 .两者的交点C 为临界接触浓度 .随着接枝率的增大 ,比浓粘度逐渐增大 .温度升高也使比浓粘度增大 .     

氧和正丁基锂引发的阴离子活性聚合物的反应

对氧和正丁基锂引发的阴离子活性聚合物反应的研究发展,反应产物中有基础分子量两倍的大分子物,而且大分子产物的含量与正丁基锂用量成正向关系,提出了可能的反应机理。     

Topological polymer chemistry by programmed self-assembly and effective linking chemistry

Ongoing challenges in topological polymer chemistry are reviewed. In particular, we focus on recent developments in an “electrostatic self-assembly and covalent fixation (ESA–CF)” process in conjunction with effective linking/cleaving chemistry including a metathesis process and an alkyne–azide click reaction. A variety of novel cyclic polymers having specific functional groups and unprecedented multicyclic macromolecular topologies have been realized by combining intriguing synthetic protocols.     

Effect of chain compositions on interpolymer specific interaction in solutions

An interpolymer specific interaction of polymers with complementary proton donor units and proton acceptor units was studied with viscometry. In this study, poly(styrene-co-octyl acrylate-co-acrylic acid) as proton donating polymer (PDP) and poly(styrene-co-octyl acrylate-co-4-vinylpyridine) as proton accepting polymer (PAP) with different macromolecular chain compositions were prepared by emulsion copolymerization. Complexed solutions formed by PDP and PAP were studied with a novel interaction criterion k_a based on viscosity enhance factor. The effects of macromolecular chain compositions on the ability to interpolymer interaction and complex stoichiometry were discussed. The results showed that long chain alkyl acrylate units play an important role in the interpolymer specific interaction.     

α-photolabile amine semitelechelic polymers for light-induced macromolecular conjugation

The use of UV irradiation as a reaction stimulus provides a facile mean to obtain spatial and temporal control over polymer conjugation reactions. In this work, UV irradiation was used to induce an activated ester-amine conjugation of polymeric building blocks via photo-induced deprotection of an amine and subsequent reaction with an activated ester, resembling the first example of macromolecular conjugation using light-triggered activated ester-amine chemistry.     

Discrete macromolecular constructs via the Diels–Alder “Click” reaction

Functional polymeric materials with desired properties can be designed by precise control of macromolecular architectures. Over the recent years, click reactions have enabled efficient synthesis of a variety of polymers with different topologies via efficient polymer–polymer conjugations. While the copper catalyzed Huisgen type (3+2) dipolar cycloaddition between azide and alkyne has been widely used toward this goal, the Diels–Alder (DA) reaction offers an alternative click reaction that allow efficient macromolecular conjugations, oftentimes without the need of any additional reagent or catalyst. This article highlights, with illustrative examples, the power of the DA “click” reaction to efficiently synthesize a variety of different well‐defined macromolecular constructs in a modular fashion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthese anionique de polymeres comportant une fonction vinylsilane a l'une ou aux deux extremites de la chaine macromoleculaire

The reaction of vinyldimethylchlorosilane with a living polymer (ω or α,ω carbanionic) leads under certain conditions to the quantitative formation of a vinylsilane group to one or two ends of the macromolecular chain.     

A New Approach to C60-Containing Polyphosphazenes by Polymerization of Phosphonitrile Chloride Trimer in the Presence of C60

A novel synthetic strategy was developed to prepare polyphosphazenes containing C60 moieties. Thus, the phosphonitrile chloride trimer underwent thermal ring-opening polymerization （ROP） in the presence of C60 molecules to yield the reactive macromolecular intermediate, C60-containing poly（dichlorophosphazene）. And then, the other groups could be linked to the phosphazene backbone by nucleophilic substitution reaction of the chlorine atoms in this intermediate to produce a series of C60-containing polyphosphazene. The polymer exhibits good solubility in common organic solvents and is thermally stable.     

Boundary conditions for ionotropic gelation of polyuronides

The determination of reagent concentrations sufficient for gelation in the course of a crosslinking reaction in solution enables characterization of macromolecular coil dimensions as a function of solvent quality and calculation of the apparent equilibrium constant and the reaction order with respect to polymer. Interactions of polyuronides with polycoordinative metal ions are discussed.     

含偶氮苯基侧基聚硅氧烷的合成及光致变色性

含偶氮苯基侧基聚硅氧烷的合成及光致变色性张其震，张静智，王艳（山东大学化学系济南２５０１００）（山东大学环境科学中心济南２５０１００）关键词聚硅氧烷，光致变色，光异构化，量子产率将光致变色性和液晶性化合物结合可得到新的多功能高分子材料，Ｒｉｎｇｅｄｏ...     

Synthesis of a novel poly[2]-catenane containing rigid catenanes

A novel poly[2]-catenane containing rigid catenane subunits connected by semirigid spacers has been synthesized. This new macromolecular architecture is the second example of a polymer containing topological bonds in the main chain. The poly[2]-catenane structure was proved by spectroscopic methods, especially ¹H NMR, IR and MALDITOF. The polymer is thermally stable up to 380°C and shows a high glass transition temperature of ca. 265°C.     

A dynamic (reversible) covalent polymer: radical crossover behaviour of TEMPO-containing poly(alkoxyamine ester)s

A dynamic covalent polymer incorporating thermally alkoxyamine units in the main chain was synthesized. Due to a radical crossover reaction between the alkoxyamine units, an interchange of the main chains in poly(alkoxyamine ester) was observed on heating.     

Synthesis of a photoactive gemini surfactant and its use in AGET ATRP miniemulsion polymerisation and UV curing

A novel photoactive gemini surfactant was easily synthesised in high yields. The multi-functional molecule can be used as a gemini surfactant, a benzophenone type photoinitiator, and as an ATRP initiator. Poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate)-block-poly(allyl methacrylate) (PMMA-b-PAMA) were prepared using the photoactive gemini surfactant as an ATRP initiator under soap-free miniemulsion polymerisation conditions. Kinetic results of the miniemulsion polymerisation of methyl methacrylate (MMA) indicate that the reaction has controlled/living characteristics. UV curing was performed by irradiation of the linear PMMA-b-PAMA polymer, in which PMMA-b-PAMA containing a benzophenone moiety functioned as a macromolecular photoinitiator.     

Effect of microemulsion-like polysoap on the catalysed esterolysis of hydrophobic p-nitrophenyl esters

The esterolytic activity of metal ion complexes of n-alkyl-2-hydroxymethylbenzimidazoles/Zn²⁺ towards p-nitrophenyl esters (picolinates and alkanoates) was investigated in the presence of an amphiphilic polymer, poly(1-hexadecyl-3-vinylpyridinium bromide), as a macromolecular matrix. The reaction rate constants obtained for the polymer hydrophobic microdomains were compared with those observed for the new conventional surfactant, 3-ethyl-1-hexadecylpyridinium bromide, chosen as the model of the repeat unit of the homopolymer. In both cases, the kinetic analysis indicated that the esterolysis reaction proceeds through the formation of an initial binary complex Ligand–Zn²⁺, the stoichiometry of which is 2/1 type.     

Macromolecular reaction and interdiffusion in a compatible polymer blend, 2. The role of H‐bonding

A theory describing slow macromolecular reaction and interdiffusion in a compatible polymer blend is extended to consider H‐bonding. The known treatments of H‐bonding influence on the free energy of mixing and chains' mobilities are combined to calculate mutual diffusion coefficients in the framework of linear non‐equilibrium thermodynamics. Numerical calculations are performed for a blend of two random copolymers AC and BC to reveal the effect of H‐bonding (between A and B, B and B units) on the interdiffusion profiles. Then, the transformation of A units into B ones is included and the reaction‐diffusion equations are solved with the parameters corresponding to the blend of poly(tert‐butyl acrylate‐co‐styrene) with poly‐(acrylic acid‐co‐styrene) in which the thermal decomposition of tert‐butyl acrylate units takes place. The numerical calculations show that this system is suitable for the experimental verification of theoretical predictions concerning the interplay between macromolecular reaction and interdiffusion in polymer blends.     

Nonracemic dopant-mediated hierarchical amplification of macromolecular helicity in a charged polyacetylene leading to a cholesteric liquid crystal in water

Here we show the first example of a helical polyacetylene that forms a lyotropic liquid crystal (LC) through a hierarchical amplification of a macromolecular helicity process in water. The macromolecular helicity with an excess of one helical sense was first induced in the positively charged polyacetylene upon complexation with an extremely small oppositely charged nonracemic dopant through electrostatic interaction in water. Subsequently, the helicity was significantly amplified in the polymer backbone as an almost perfect single-handed helix through self-assembly into supramolecular helical arrays in a lyotropic cholesteric state. The present results will allow the detection of a tiny imbalance in chiral molecules and also provide new approaches for the design of novel water-soluble helical architectures and the construction of new chiral materials in areas such as biotechnology and materials science.     

Change of polymer reactivity in the course of macromolecular reaction

For a macromolecular reaction in polymer solution or melt, the reactivity of the transforming unit is supposed to depend upon its microenvironment, including both the nearest neighbours of the same chain and units belonging to the other chains or low molecular components of the reaction mixture. The microenvironment changes with conversion. Hence, the reactivity of polymer functional groups should change during the reaction. Such a reaction belongs to Markovian processes with locally interacting components and time-dependent transient probabilities. To describe the reaction kinetics, it is necessary: (1) to analyse statistical properties of an individual transforming chain, (2) to derive the kinetic equations using relations based on these properties, (3) to determine the dependence of the transient probabilities upon time or upon degree of conversion. For a general reaction model, equations are derived to describe the kinetic curve, distribution of units and composition heterogeneity of the products. The calculations reveal the influence of an interchain interaction on the reaction rate and also on the distribution of units for reaction in a polymer melt.     

My life with polymer science

This article describes the scientific investigations and accomplishments in the life of the author. After a dissertation on steroids, several years were spent on alkaloids and research on heterocyclic compounds. Much of the author's career was devoted to research on aldehyde polymerization, the discovery of the polymerization of higher aldehydes and their isotactic polymers, and haloaldehyde polymerization. The latter led to our work on the ceiling temperature of polymerization, on new polymerization techniques [involving the ceiling temperature and the concept of macromolecular asymmetry (polymer helicity)], and the genesis of chloral polymerization. Another important period was devoted to functional polymers, polymeric stabilizers, and polymeric drugs. Other research activities included studies of unusual polymers, head-to-head polymers, spacer groups in polymers, and oriental lacquers. Attention was also paid to the use of novel and unusual polymer intermediates, polymerization under extreme conditions and the preparation and behavior of uncommon polymer structures. Finally, it was recognized that macromolecules can be categorized with increasing frequency as polymers with broad and narrow molecular weight distributions and uniform polymers. The ultimate unity is isotopically pure uniform polymers, single macromolecular species. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 795–818, 2004     

Hydroxypropylcellulose-aceclofenac conjugates: high covalent loading design, structure characterization, nano-assemblies and thermal kinetics

This article presents synthesis of novel macromolecular prodrugs of aceclofenac (an anti-inflammatory drug) onto hydroxypropylcellulose (HPC). The HPC-aceclofenac conjugates were prepared using an acylating agent 1,1′-carbonyldiimidazole (CDI) under homogenous reaction conditions. Aceclofenac was first activated by using CDI to form its N-acylimidazole. The N-acylimidazole of aceclofenac was then reacted with HPC polymer at 80 °C for 24 h. Highly pure prodrugs of aceclofenac were synthesized with a wide range of moderate to high degree of substitution (DS 0.41–2.12) as calculated by ¹H NMR spectroscopy. The UV spectroscopic analysis has also revealed that the active drug aceclofenac was found in different conjugates from 28 to 67 mg/100 mg of HPC-aceclofenac conjugates which are in good agreement with DS calculated by ¹H NMR spectroscopy. The gel permeation chromatography showed unimodal absorption that indicates no significant degradation in polymer chains during the reaction. The macromolecular prodrugs of aceclofenac were characterized using different spectroscopic and chromatographic techniques. The thermal analysis has revealed that HPC-aceclofenac conjugates (prodrugs) are 92 and 96 °C more stable than pure aceclofenac regarding their initial (Tdi) and maximum degradation temperatures (Tdm), respectively. The activation energy (Ea) and frequency factor (Z) of the degradation reactions were evaluated using Friedman, Broido and Chang methods. Degradation followed first order (n) kinetics. Transmission electron microscopy has revealed the formation of sponge like nano aggregates with population size distribution of around 80–150 nm.     

Preparation and properties of novel hydrogels from oxidized konjac glucomannan cross-linked chitosan for in vitro drug delivery

In this paper, a novel composite hydrogel was prepared by the use of dialdehyde konjac glucomannan (DAK) as macromolecular cross-linking agent for chitosan (CS). This biocompatible material cross-links and gels in minutes. The structure and morphology were characterized by various analyses. The results indicate that the hydrogels formed through the Schiff-base reaction between the amino groups of CS chains and the aldehyde groups of DAK. The cross-link density (rho(x)) increases with the enhancement of DAK content in hydrogels, while equilibrium swelling ratio (SR) and the average molecular weight between cross-links (Mc) value decrease. Drug release was evaluated by varying the pH of the release medium, reversed dependence of release rate on the equilibrium SR of hydrogel indicated that drug release may be impeded by the association of drug with the polymer. Importantly, this process offers an entirely new window of materials preparation when compared with the traditional preparation of CS-based hydrogels with small molecules cross-linking agent.