Diffusion-limited hyperbranched polymers with substitution effect

Highly branched structure has the essential influence on macromolecular property and functionality in physics and chemistry. In this work, we proposed a diffusion-limited reaction model with the consideration of macromolecular unit relaxations and substitution effect of monomers to study the structure of hyperbranched polymers prepared by slow monomer addition to a core molecule. The exponential relationship (R(g) ～ N(λ)) between the radius of gyration R(g) and the degree of polymerization N, was systematically analyzed at various branching degrees. It is shown that the effective exponent λ(eff) decreases at lower N and but increases toward that of diffusion-limited aggregation (DLA) clusters (λ(DLA) = 0.4) with the degree of polymerization increasing. The substitution effect of monomers in reaction strongly influences the evolution pathway of λ(eff). With the static light scattering technique, the fractal property of internal chains was further calculated. A general law about the radial distribution of the units of diffusion-limited hyperbranched polymers was found that, at smaller reactivity ratio k(12), the radial density of all monomer units D(A) declines from the center region to the peripheral layer revealing the dense core structure; however, at larger k(12), the density distribution shows a loose-dense-loose structure. These structural characteristics are helpful to deeply understand the property of hyperbranched polymers.     

Modification of polymers via electrophilic aromatic substitution

Three vinyl monomers, 2,4,6-trimethoxystyrene, 4-(N,N-dimethylamino)styrene, and N-methyl-2-vinylpyrrole, were synthesized via the Wittig reaction from the corresponding aldehyes. These monomers were homopolymerized by radical polymerization using α,α′-azoisobutyronitrile (AIBN) as initiator at 60°C. The reaction of these polymers with 4-phenyl-1,2,4-triazoline-3,5-dione (phTD) and 4-methyl-1,2,4-triazoline-3,5-dione (MeTD) was investigated. Although polytrimethoxystyrene reacts slowly with PhTD at room temperature, the other two polymers react fast and lead to the incorporation of the triazolinedione unit into the side chain of the polymer via electrophilic aromatic substitution. The reaction of bistriazolinediones (BTD) with these polymers was performed in dimethylformamide using 10–20% molar concentration of the BTD. The resulting crosslinked polymers are insoluble in polar as well as nonpolar solvents. Some physical properties of the unmodified and modified polymers were studied.     

Selective metal substitution for the preparation of heterobimetallic microporous coordination polymers

The designed synthesis of heterobimetallic microporous coordination polymers (MCPs) is reported by a strategy employing the selective replacement of a single metal in homometallic MCPs with two unique metal coordination environments: octahedral and tetrahedral. This strategy is successful in the preparation of six mixed-metal MCPs, where Co/Zn and Ni/Zn versions of MOF-4, MOF-39, and a Zn-BTEC MCP are reported.     

Impact of lipid substitution on assembly and delivery of siRNA by cationic polymers

Characterization of a polymer library engineered to enhance their ability to protect and deliver their nucleotide cargo to the cells is reported. The ζ-potential continuously increased with higher polymer:siRNA weight ratio, and the ζ-potential of lipid-modified polymers:siRNA complexes were higher than PEI2 at all ratios. At polymer:siRNA ratio of 1:1, all lipid-substituted polymers showed complete protection against degradation. Lipid-modified polymers significantly increased the cellular uptake of siRNA complexes and down-regulation of GAPDH and P-gp (max. 66% and 67%, respectively). The results indicate that hydrophobic modification of low molecular PEI could render this otherwise ineffective polymer to a safe effective delivery system for intracellular siRNA delivery and protein silencing.     

Synthesis of well‐defined comb‐like graft (co)polymers by nucleophilic substitution reaction between living polymers and polyhalohydrocarbon

A series of graft (co)polymers were synthesized by nucleophilic substitution reaction between iodinated 1,2‐polybutadiene (PB‐I, backbone) and living polymer lithium (side chains). The coupling reaction between PB‐I and living polymers can finish within minutes at room temperature, and high conversion (up to 92%) could be obtained by effectively avoiding side reaction of dimerization when living polymers were capped with 1,1‐diphenylethylene. By virtue of living anionic polymerization, backbone length, side chain length, and side chain composition, as well as graft density, were well controlled. Tunable molecular weight of graft (co)polymers with narrow molecular weight distribution can be obtained by changing either the lengths of side chain and backbone, or the graft density. Graft copolymers could also be synthesized with side chains of multicomponent polymers, such as block polymer (polystyrene‐b‐polybutadiene) and even mixed polymers (polystyrene and polybutadiene) as hetero chains. Thus, based on living anionic polymerization, this work provides a facile way for modular synthesis of graft (co)polymers via nucleophilic substitution reaction between living polymers and polyhalohydrocarbon (PB‐I). © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Syntheses of homopolymer and water-soluble polymers containing tetraphenylporphinatomanganese(III) complex,and ligand substitution reaction for anionic ligand

A vinyl monomer containing the pendant tetraphenylporphyrin (TPP) group, 4-vinyltetraphenylporphyrin (VTPP), was synthesized. A homopolymer (PVTPP) which is insoluble in water, and three water-soluble polymers were obtained by radical polymerization. The water-soluble polymers are two anionic polymers (PVPTSPP and PVTPP-StSO₃) and a cationic polymer (PVTPP-VPyM). PVPTSPP has sulfonic acid groups in a TPP group and very high charge density. PVTPP-StSO₃ was obtained by copolymerization of VTPP and sodium 4-styrenesulfonate. PVTPP-VPyM was obtained by quarternarization of a copolymer of VTPP and 4-vinylpyridine. Polymeric manganese(III) complexes (PMn-VTPP, PMnVPTSPP, PMnVTPP-StSO₃, and PMnVTPP-VPyM) were prepared from the polymers and manganese acetate. The acetate ligand in PMnVTPP can be easily substituted by another ligand such as Cl^?, AcO^?, OH^?, and SCN^?. The substitution reaction occurs in the interface between water and chloroform. The sulfonated homopolymer, PMnVPTSPP, cannot incorporate with anionic ligands because of the strong electrostatic repulsion. In the anionic copolymer, PMnVTPP-StSO₃, the ligand substitution reaction with SCN ligand needs activation energy of 53 kJ/mol. In the cationic polymer complex, PMnVTPP-VPyM, the OH ligand can be easily substituted with the SCN ligand and the equilibrium constant of the reaction was estimated at 1.38 × 10^?3. © 1994 John Wiley & Sons, Inc.     

Degree of branching of the hyperbranched polymers resulted from ab<Subscript>2</Subscript> polycondensation with substitution effect

The analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from AB₂ polycondensation with substitution effect were derived by the kinetic mechanism.The reactivity difference between the B group in linear unit and that in terminal group has great effect on the molecular parameters of the products obtained.The concentration of terminal units has a maximum with the increase of the conversion of A groups（x）.The higher the reactivity ratio（r） of linear B group to branched one is,the later the maximum appears and the larger it is.The degree of branching of the hyperbranched polymers obtained is controllable by adjusting the parameters of r and x,which increases with increasing both x and r.     

Aromatic substitution

It is demonstrated that a previously developed topological expression for the total π-electron energy of aromatic molecules provides a good qualitative account of localization energies. The logarithm of the ratio of the algebraic structure counts for the ground state and the localized reaction intermediate is the principle energy determining factor. This expression fails for hydrocarbons with unusually small HOMO-LUMO separations. An alternative topological expression that includes a correction for this situation provides an excellent non-empirical explanation for the successful empirical use of Dewar reactivity numbers in correlating exact localization energies. The present analysis provides an explanation for the success of the traditional resonance structure counting technique in predicting relative rates of aromatic substitution. The analysis develop applied only to alternant hydrocarbons.     

Reaction of chlorine-containing polymers with living polymers

A graft polymer was prepared by means of the coupling reaction of chlorinated ethylene–propylene terpolymer with living polystyrene, obtained with a sodium–naphthalene complex as initiator, under various conditions; the grafting efficiency and the percentage of grafting are discussed. Poly(chloroprene), chlorinated butyl rubber, poly(vinyl chloride), poly(epichlorohydrin), and epichlorohydrin–ethylene oxide copolymer were also used as chlorine-containing polymers. The grafting efficiencies were found to be in the following order: chlorinated butyl rubber > poly(epichlorohydrin) > epichlorohydrin-ethylene oxide copolymer > chlorinated ethylene-propylene terpolymer > poly(chloroprene) > poly(vinyl chloride). A graft polymer was obtained from the reaction between chlorinated ethylene–propylene terpolymer and living poly(isoprene), with butyllithium in benzene. The undesirable metal–halogen interchange reaction was considerable.     

Statistics of aggregates

Aggregation phenomena of elementary particles into clusters has received considerable attention during the past few decades. We adopt here a stochastic approach for the modeling of these phenomena. More precisely, we formulate the problem in the following dynamical setup: given a population of n discernible atoms partitioned into p discernible (model 1) or indiscernible (model 2) groups, how does a new atom eventually connect to any of these p groups forming up a new partition of n+1 atoms into a certain amount of clusters? Nucleation is said to occur when the inserted atom does not connect (it nucleates), whereas aggregation takes place if it does (clusters coalesce). Depending on this local “logic” of pattern formation, the asymptotic structure of groups can be quite different, in the thermodynamic limit N→∞. These studies are the main purpose of this work. Understanding these aggregation phenomena requires first to derive the fragment size distributions (that is, the number P of fragments, or clusters, and the number n_m of size-m fragments with m fragments with constitutive atoms), as a function of the control parameter which is chosen here to be the average number of atoms 〈N〉. As 〈N〉 approaches infinity, we derive the study of these variables in the thermodynamic limit n → ∞. It is shown, making extensive use of combinatorics, that two regimes are to be distinguished: the one of weakly connected aggregates where nucleation dominates aggregation and the one of strongly connected aggregates where aggregation dominates nucleation. In the first (“diluted”) regime, the number of clusters P(n) always diverges as n → ∞, the asymptotic equivalent of which being under control in most cases. Large deviation results are shown to be available. Concerning N _m(n), distinct behaviours are observed in models 1 and 2. In the second (“condensed”) regime, the number of groups P(n) and size-m groups N _m(n) may converge in the thermodynamic limit, with a special role played by the geometric and Poisson distributions. The asymptotic variables become observable macroscopically. This work is therefore aimed toward a better understanding of the fundamentals involved in clusters' formation processes.     

Calculation of the effect of substitution on the yield and topological parameters of hyperbranched polymers synthesized by the cyclotrimerization of mono- and bifunctional monomers

A kinetic model allowing for the effect of substitution has been developed for the synthesis of hyperbranched polymers through the cocyclotrimerization of mono- and bifunctional monomers. The calculation has been performed by means of a mathematical apparatus for generating functions. New theoretical relationships have been obtained that enable one to predict critical conversion and variations in the structural and molecular-mass parameters of hyperbranched polymers during reaction in relation to the initial monomer ratio, relative reactivities of functional groups, and variations in the reactivities during the process.     

Electroactive polymers including non-linear optical polymers

Recent advances in design, synthesis, and processing of electroactive polymers promise important commercial applications ranging from improved performance flat panel displays to critical components of the next generation information superhighway. Electroactive polymer research is also providing fundamental new insight into the role of long range electrostatic interactions with consequences for condensed matter theory and the development of nanostructured materials.     

Selenoketene substitution structure

Microwave studies (26.5–40 GHz) of further isotopic species of selenoketene formed by pyrolysis of 1,2,3-selenodiazole (¹²CH₂¹²C^76,77,82Se, ¹²CH₂¹³C⁸⁰Se and ¹³CH₂¹²C⁸⁰Se) and by pyrolysis of 5-deuterio-1,2,3-selenodiazole (¹²CHD¹²C^78,80Se) are reported. In conjunction with earlier results for ¹²CH¹²C^78,80Se an r_s structure has been derived with distances SeC (1.706 Å), CC (1.303 Å), CH (1.0908 A) and a HCH bond angle of 119.7°. The geometry of the CH₂C moiety of selenoketene is closer to allene, CH₂CCH₂, than to ketene, CH₂CO.     

羟丙基瓜尔胶中羟丙基摩尔取代度以及取代位置的表征

本文探索了表征羟丙基瓜尔胶(HPG)中羟丙基摩尔取代度(MS)以及取代位置的化学方法.当反应温度为110℃、反应时间为14h以及HPG中羟基与对甲苯磺酸-乙酸酐摩尔比为1:3.5时,用对甲苯磺酸-乙酸酐化学法和气相色谱法可准确测定HPG的羟丙基MS,与1H-NMR测定结果相对误差小于10%.在pH=10.30和0℃的条件下,瓜尔胶的伯羟基被2,2,6,6-四甲基哌啶氮--氧化物(TEMPO)-NaClO-NaBr体系选择性氧化成羧基,由此可表征羟丙基链段的取代位置.     

羟乙基瓜尔胶中羟乙基摩尔取代度以及取代位置的表征

本文探索了表征羟乙基瓜尔胶(HEG)中羟乙基摩尔取代度(MS)以及取代位置的化学方法。当反应温度为110℃,时间为14hr,HEG中羟基与混酐比例为1:2.5时,用混酐化学法可准确测定HEG的羟乙基MS,测定结果与计算值的相对误差小于10%。在pH=10.30和0℃的条件下,瓜尔胶的伯羟基被2,2,6,6-四甲基哌啶氮氧化物(TEMPO)-NaClO-NaBr体系选择性氧化成羧基,由此可表征羟乙基链段的取代位置。在瓜尔胶醚化生成羟乙基瓜尔胶的过程中,醚化反应并不是完全发生在伯羟基上。伯羟基的反应活性是仲羟基的6-10倍。随着MS的增大,连接在仲羟基上羟乙基链段占所有羟乙基链段的比例逐渐增大,当MS=0.4时该比例基本不再变化,为40%左右。