Graft copolymers of para-hydroxybenzoic acid (PHB). I. A general method for grafting mesogenic oligo-PHB to oligomers

A method for grafting oligo-(p-hydroxybenzoic acid) to carboxyl-functional oligomers or polymers to give copolymers having mesogenic side chains was developed. The method employs dicyclohexylcarbodiimide (DCC) to promote esterification of PHB at mild temperatures and to remove water. Pyridine is used as solvent, and catalytic amounts of p-TSA are added to suppress side reactions. Grafting efficiencies are estimated to range from 74 to 90%. Ungrafted oligo-PHB and other by-products are readily removed. Structure assignments were supported by IR,¹H-NMR, GPC, DSC and model compound studies. The method appears capable of grafting oligo-PHB side chains to any pyridine soluble oligomer or polymer having carboxyl groups and no other reactive groups that could interfere.     

Poly[(4-N-ethylene-N-ethylamino)-α-cyanocinnamate]: A nonlinear optical polymer with a chromophoric mainchain. I. Synthesis and spectral characterization

Poly[(4-N-ethylene-N-ethylamino)-α-cyanocinnamate] was prepared by solution esterification of (4-N-ethyl-N-(2-hydroxyethyl) amino)-α-Cyanocinnamic acid and by melt transesterification of ethyl (4-N-ethyl-N-(2-hydroxyethyl) amino)-α-cyanocinnamate. The melt transesterification generally yielded polymer with a number-average molecular weight of about 10,200 by gel permeation chromatography (GPC) versus polystyrene standards. The polymer was found to be amorphous with a glass transition temperature of about 103°C by differential scanning calorimetry (DSC). The solution esterification generally gave a polymer with a number-average molecular weight of about 2200 by GPC versus polystyrene standards. This polymer was found to have a glass transition temperature varying between 60 and 90°C by DSC. The infrared (IR) spectrum of the polymer made from both methods were analyzed in detail. The ¹H- and ¹³C-NMR spectra of the meltsynthesized ethyl cinnamate derivative polymer are consistent with the reported structure.     

Synthesis of crosslinked poly(α-amino acids) with various functional groups

The esterification of the carboxyl group in copoly(γ-benzyl-L -glutamyl-L -glutamic acid) was carried out using N-hydroxysuccinimide and dicyclohexylcarbodimide to yield the activated site for the coupling reaction with amino compounds. The α-helix stability of the reactive copolymer thus obtained is remarkably affected in the presence of succinimide ring. This copolymer was proved to react nearly completely with amino alcohols such as 2-aminoethanol, 3-aminopropanol, and diethanolamine. The copoly(N⁵-hydroxyalkyl-L -glutamine) thus prepared is insoluble in water, since the benzyl ester remains in this copolymer. The copoly(α-amino acids) having another functional group were also prepared using aminoalkylsilane. Crosslinked poly(α-amino acids) were prepared by the reaction of the reactive copolymer with a low-molecular-weight polymer of PBLG having one amino group on each end of its main chain which was obtained from the corresponding NCA using p-diaminobenzene as an initiator. Another crosslinked polymer was prepared using an alkyl diamine such as 1,6-diaminohexane or 1,12-diaminododecane as a crosslinking reagent. The crosslinked copoly(α-amino acids) bearing the activated site are able to further react with various compounds having amino groups.     

Regio-and Stereo-selective Synthesis of Peracetylated Carbohydrate Esters of Aromatic Fatty Acid Using p-Toluenesulfonic Acid as Catalyst

This paper describes an efficient synthesis of carbohydrate fatty acid esters based on a highly stereo‐ and regio‐selective esterification. The suitably protected glycosyl was esterified with stearic acid to give mainly the β‐anomer in good yield using p‐toluenesulfonic acid as catalyst. The structures of these compounds were fully confirmed by ¹H, ¹³C NMR, mass spectra and HRMS.     

Conducting polymers. I. Electrical conductivity of poly(bis-p-phenylenediaminosulphoxide)

Poly(bis-p-phenylenediaminosulphoxide) was prepared by Michael addition of p-bis-N-sulphinylphenylenediamine with p-phenylenediamine at 150°C. Thermal and electrical behaviors of the polymer have been studied. The polymer is found to have increased conductivity possibly due to the participation of lone pairs of electrons on nitrogen and sulphur atoms with σ bond of the macrochain. Thermogravimetric analysis indicates that the polymer is fairly stable than other conducting polymers up to 200°C. The activation energy of the polymer was measured and found to be 13 kcal mol^?1.     

Horseradish peroxidase-catalyzed polymerization of<Emphasis Type="Italic"> p</Emphasis>-hydroxycinnamic acid for synthesis of reactive microspheres

In this article, we report the experimental synthesis of reactive polymer microspheres of poly(p-hydroxycinnamic acid). Enzyme-catalyzed polymerization of poly(p-hydroxycinnamic acid) using horseradish peroxidase as a catalyst and hydrogen peroxide as an oxidant took place in a mixture solution of methanol and phosphate buffer solution; it was found that the fraction of methanol in the mixture solution strongly affected the yield of powdery polymer materials. The chemical structure of the polymers was characterized by ¹H-NMR and FT-IR spectroscopies, and the molecular weight was measured by gel permeation chromatography. The ¹H-NMR chart of the obtained polymer was almost the same as that of the monomer; FT-IR spectra indicated the existence of carboxyl groups. The weight-average molecular weight of the soluble part in tetrahydrofuran was found to be 1,451. Dispersion polymerization of p-hydroxycinnamic acid was carried out in a mixture solution of methanol and phosphate buffer solution by adding a dispersion stabilizer. Of the several such polymers tested, poly(vinyl alcohol) was found to be the most effective in producing reactive poly(p-hydroxycinnamic acid) microspheres.     

Novel synthesis of polyimide with pendant 1-phenylethyl ester using DBU and its thermal acid-catalyzed deesterification

A model reaction of o-(N-phenylcarbamoyl)benzoic acid (amic acid) with threefold amounts of 1-phenylethyl bromide (PEB) and 1,8-diazabicyclo-[5,4,0]-7-undecene (DBU) was carried out in NMP. The reaction gave N-[m-(1-phenylethoxycarbonyl)phenyl]phthalimide in almost quantitative yield at room temperature for 2 h. Polyimide containing pendant 1-phenylethyl ester (P-1a) was also prepared from polyamic acid with PEB using DBU according to the model reaction. The obtained polymer was exactly consistent with P-1a synthesized stepwise from the esterification of the corresponding polyimide containing pendant carboxylic acid with PEB. Therefore, the reaction of polyamic acid bearing pendant carboxylic acid with alkyl bromide proceeded quantitatively to give polyimide containing pendant ester in the presence of DBU. Also, this method was applied to the synthesis of polyimide containing 1-phenylethyl ether. However, the polyimide with quantitative etherification was not synthesized. The acid-catalyzed deesterification of P-1a film was carried out by heating the irradiated polymer film containing 10 wt % of p-nitrobenzyl 9,10-diethoxyanthracene-2-sulfonate, which produced sulfonic acid by irradiation, at various temperatures. Although thermal deesterification of P-1a started at 220°C without any acid catalyst, the deesterification occurred when the irradiated film was heated at the lower temperature. The degree of esterification can be determined from the disappearance of absorption at 700 cm⁻¹. The deesterification obeyed first-order kinetics. © 1996 John Wiley & Sons, Inc.     

Magnetic molecularly imprinted composite for the selective solid‐phase extraction of p‐aminosalicylic acid followed by high‐performance liquid chromatography with ultraviolet detection

A new method for the selective extraction of p‐aminosalicylic acid from aqueous and urine samples has been developed using magnetic molecularly imprinted polymer nanoparticles before determination by high‐performance liquid chromatography. The Fe₃O₄ nanoparticles were first prepared through the chemical coprecipitation of Fe²⁺ and Fe³⁺ and then coated with a vinyl shell. Subsequently, a layer of molecularly imprinted polymers was grafted onto the vinyl‐modified magnetic nanoparticles by precipitation polymerization. FTIR spectroscopy, scanning electron microscopy, vibrating sample magnetometry, and thermogravimetric analysis were applied to characterize the sorbent properties. Moreover, the predominant parameters affecting the magnetic solid phase extraction such as sample pH, sorption and elution times, the amount of sorbent, and composition and volume of eluent were investigated thoroughly. The maximum sorption capacity of the imprinted polymer toward p‐aminosalicylic acid was 70.9 mg/g, which is 4.5 times higher than that of the magnetic nonimprinted polymer. The magnetic molecularly imprinted polymer nanoparticles were applied for the selective extraction of p‐aminosalicylic acid from aqueous and urine samples and satisfactory results were achieved. The results illustrate that magnetic molecularly imprinted polymer nanoparticles have a great potential in the extraction of p‐aminosalicylic acid from environmental and biological matrices.     

A (1→4)-β-D-Glucuronan Excreted by a Mutant of the Rhizobium Meliloti M5N1 Strain

Abstract

A mutant of the R. meliloti M5N1 strain has been selected. This strain, R. meliloti M5N1 CS (NCIMB 40472), excretes an extracellular material composed of 2-O-Ac-β-GlcpA, 3-O-Ac-β-GlcpA, 2,3-di-O-Ac-β-GlcpA and three species of β-GlcpA residues 1→4 linked. For the culture conditions used, the weight average molecular weight of the polymer varied in the range of 6 × 10⁴ < Mw < 4 × 10⁵. High molecular weight glucuronate forms thermoreversible gels at 5 g L^?l. In the presence of divalent cation such as Ca²⁺ or trivalent cations such as Cr³⁺ or Fe^{3 +}, cross linking of the polymer occurs. This polysaccharide is the first exocellular (1→4)-β-D-glucuronan produced by a R. meliloti strain.     

Rotational diffusivity of rodlike molecules in amorphous polymeric matrices

In this note, scaling laws for rotational diffusivity of dilute monodisperse rigid-rod molecules (guest rods) in semidilute amorphous polymer solutions (host molecules) are derived. The coillike matrix molecules are modeled as a collection of flexibly connected rigid subunits. This allows an analogy with the Doi-Edwards theory for monodisperse rigid rods in semidilute solutions to be used in the analysis. Very strong dependencies are predicted for the rotational diffusivity of the rods on host polymer volume fraction and rod length. In semidilute polymer solutions the coils dramatically hinder the rotational freedom of the rods for r² ? ψ_p^?1, r being the rod aspect ratio and ψ_p the polymer volume fraction.     

Graft polymers: Chain transfer and branching

The vinyl monomers, methyl methacrylate, ethyl methacrylate, and methyl acrylate were polymerized in the presence of chlorinated rubber or poly(vinyl chloride) in homogeneous solution with benzoyl peroxide as catalyst. A graft polymer was formed by a chain-transfer reaction involving the growing polymer radicals to the backbone of chlorinated rubber or poly(vinyl chloride), in addition to homopolymer from the monomer. The homopolymer was isolated from the polymer mixture by fractional precipitation from methyl ethyl ketone solution with methanol as precipitant. The chain-transfer constants for the branching reactions were evaluated. The ratios k_p/(k_t)^1/2 for the grafting reactions were obtained by a correlation of chain-transfer constants with the extent of branching. The chain-transfer data were correlated on the basis of an extension of the Q–e scheme of Alfrey and Price to polymer–polymer transfer reactions. Specific effects due to the backbone are found to have considerable influence on the course of the chaintransfer reactions and k_p/(k_t)^1/2 of the grafting reactions.     

Intramolecular cyclization of styrene–p-divinylbenzene copolymers

Styrene has been copolymerized at low conversion with minor quantities of p-divinyl-benzene (p-DVB) in (10–15%) solution in toluene and cyclohexane. Under these conditions the molecular weight of the polystyrene formed in the absence of p-DVB was controlled by chain transfer, and the copolymerization coefficients of the styrene and the p-DVB agreed with previous work. Polymer molecular weights were studied as a function of conversion. At very low conversions the number-average (2.2 × 10⁵) and the weight-average (4.4 × 10⁵) molecular weights were unaffected by substituting some of the styrene by p-DVB, but as the reaction continued M?_n increased slowly and M?_w much faster. On the other hand, even at the lowest conversions the intrinsic viscosity was drastically reduced by the introduction of p-DVB, and the radius of gyration, as measured by light scattering, fell. Infrared studies on the polymer show that the concentration of pendent double bonds in low-conversion copolymers is about half of the doubly substituted phenyl groups. It is concluded that the first polymer chains formed are extensively cyclized with the formation of a relatively large number of small rings.     

Emulsifier-free emulsion polymerization of tetrafluoroethylene by radiation. II. Effects of reaction conditions on polymer particle size and number

The size, distribution, and number of PTFE particles formed by radiation-induced emulsifier-free polymerization were measured by electron microscope and automatic particle analyzer (centrifugation method). From the electron micrographs we found that the particles are formed within 5 min. The change in the number of polymer particles (n_p) with reaction time (t) depends on the relative concentration of growing polymer chains to stabilizing species produced by the radiolysis of water and monomer; that is, it was governed by TFE pressure/dose rate ratio and classified into three cases: case I, dn_p/dt = 0 (e.g., at 3 × 10⁴ rad/hr and 20 kg/cm²); case II, dn_p/dt < 0 (e.g., at dose rate below 1.9 × 10⁴ rad/hr and 20 kg/cm²); case III, dn_p/dt > 0 (e.g., at 3 × 10⁴ rad/hr and 2 kg/cm²). The polymer molecular weight above 10⁶ is almost independent of the particle size. The polymerization loci are mainly on the surface of polymer particles dispersed in the aqueous phase in cases I and II except in the initial stage. In case III new particles are formed successively during polymerization. Therefore the polymerization loci are mainly in the aqueous phase. Especially in case I, we concluded that after the generation of particles the propagation proceeds mainly on the surface of polymer particles like the core shell model proposed by Granico and Williams.     

Poly(P-phenylene sulfide) hexafluoroarsenate: A novel conducting polymer

Poly(p-phenylene sulfide) (PPS) is a melt- and solution-processible polymer which on treatment with AsF₅ forms a blue-black material with a conductivity of 1–10 Ω^?1 cm^?1. Thermopower measurements indicate that the resulting polymer is p type, consistent with partial oxidation of the PPS by the AsF₅. The rate and extent of this doping process prove to be particularly sensitive to the degree of crystallinity of the starting polymer. There is also evidence of crosslinking of the polymer chains during the reaction with AsF₅. The details of both the chemistry and physics of the doping of PPS and several of its derivatives are presented.     

Conjugated and Non-conjugated Polymers Containing Two-Electron Redox Dihydrophenazines for Lithium-Organic Batteries

Organic p-type cathode materials have recently attracted increasing attention due to their higher redox potentials and rate capabilities in comparison to n-type cathodes. However, most of the p-type cathodes based on one-electron redox still suffer from limited stability and low specific capacity (<150 mAh g⁻¹). Herein, two polymers, conjugated poly(diethyldihydrophenazine vinylene) ( CPP ) and non-conjugated poly(diethyldihydrophenazine ethylidene) ( NCPP ) containing two-electron redox dihydrophenazine, have been developed as p-type cathode materials. It is experimentally and theoretically found that the conjugated linkage among the redox centers in polymer CPP is more favorable for the effective charge delocalization on the conjugated polymer backbone and the sufficient oxidation in the higher potential region (3.3–4.2 V vs. Li/Li⁺). Consequently, the CPP cathode displays a higher reversible specific capacity of 184 mAh g⁻¹ with excellent cycling stability.     

乙酰水杨酰对羟基桂皮酸与呋咱氮氧化物和硝酸酯偶联物的合成及其抗血栓作用

对羟基桂皮酸酚羟基经保护后与相应的羟基呋咱氮氧化物酯化, 酯化物脱保护, 再与阿司匹林缩合得II₁～II₃; 对羟基桂皮酸与相应二溴烷烃作用, 再经阿司匹林酯化, 得到的溴代烷基酯与硝酸银反应得II₄～II₇; 酚羟基保护的对羟基桂皮酸与异山梨醇单硝酸酯酯化, 脱保护后与阿司匹林缩合得II₈. 目标物II₁～II₈均经MS, IR, ¹H NMR和元素分析确证, 并通过大小鼠体内外抗血栓活性初筛, 结果表明, 多数目标物显示与阿司匹林相当的抗血栓活性, II₆活性优于阿司匹林.     

Long branching in poly(vinyl acetate) and poly(vinyl alcohol). III. Kinetic study of the branching reaction in the radical polymerization of vinyl acetate

The branching reaction in the radical polymerization of vinyl acetate was studied kinetically. Branching occurs by polymer transfer as well as terminal double-bond copolymerization. The chain-transfer constants to the main chain (C_p,2) and to the acetoxy methyl group (C_p,1) on the polymer were calculated on the basis of the experimental data described in the preceding paper giving C_p,2 = 3.03 × 10^?4, C_p,1 = 1.27 × 10^?4 at 60°C, and C_p,2 = 2.48 × 10^?4, C_p,1 = 0.52 × 10^?4 at 0°C. Chain transfer to monomer is important with respect to the formation of the terminal double bond. The total values of transfer constants to the α- or β-position in the vinyl group and the acetoxymethyl group in vinyl acetate was determined to be 2.15 × 10^?4 at 60°C. The transfer constant to the acetyl group in the monomer (C_m,1) was also evaluated to be 2.26 × 10^?4 at 60°C from the quantitative determination of the carboxyl terminals in PVA. These facts suggest that the chain-transfer constant to the α- or β-position in the monomer (C_m,2) is nearly equal to zero within experimental error. Copolymerization reactivity parameters of the terminal double bond were also estimated. In conclusion, it has become clear that the formation of nonhydrolyzable branching by the terminal double-bond reaction can be almost neglected, and hence that the long branching in PVA is formed only by the polymer transfer mechanism. On the other hand, a large number of hydrolyzable branches in PVAc are prepared by the terminal double-bond reaction rather than by polymer transfer.     

Propagation Kinetics of Isoprene Radical Homopolymerization Derived from Pulsed Laser Initiated Polymerizations

The propagation kinetics of isoprene radical polymerizations in bulk and in solution are investigated via pulsed laser initiated polymerizations and subsequent polymer analyses via size‐exclusion chromatography, the PLP‐SEC method. Because of low polymerization rate and high volatility of isoprene, the polymerizations are carried out at elevated pressure ranging from 134 to 1320 bar. The temperatures are varied between 55 and 105 °C. PLP‐SEC yields activation parameters of k_p (Arrhenius parameters and activation volume) over a wide temperature and pressure range that allow for the calculation of k_p at technically relevant ambient pressure conditions. The k_p values determined are very low, e.g., 99 L mol^?1 s^?1 at 50 °C, which is even lower than the corresponding value for styrene polymerizations. The presence of a polar solvent results in a slight increase of k_p compared to the bulk system. The k_p values reported are important for determining rate coefficients of other elemental reactions from coupled parameters as well as for modeling isoprene free‐radical polymerizations and reversible deactivation radical polymerization with respect to tailored polymer properties and optimizing the polymerization processes.     

Grafting Efficiency of Hydroxy‐Terminated Poly(methyl methacrylate) with Multiwalled Carbon Nanotubes

Summary: Poly(methyl methacrylate)s (PMMAs) containing a terminal hydroxy group or multiple hydroxy groups as pendants were grafted to multiwalled carbon nanotubes (MWNTs) by esterification in toluene at 100 °C. The recovered polymer with a low level of MWNTs and the PMMA‐g‐MWNTs with up to 12 wt.‐% grafted polymer were characterized using spectroscopic, microscopic, and thermogravimetric analyses. The percentage of polymer present in the PMMA‐g‐MWNT samples is very low based upon the concentration of the acid groups in the tubes.

The grafting of hydroxy‐terminated PMMA to MWNTs by esterification.     

Reaction of polyamine polymer with molecular iodine via charge-transfer complex formation

The reaction of a Mannich base type-polyamine polymer with iodine (I₂) was studied kinetically and thermodynamically in order to clarify the polymer effects in the formation of triiodide ions (I₃^?). N,N-Dimethyl-p-(4-methylpiperazinomethyl) aniline and 1,4-dimethylpiperazine were used as low molecular weight donor model compounds. Triiodide ions are produced from the polyamine–I₂ system immediately after mixing the two-component solutions, while in the systems with I₂ and N,N-dimethyl-p-(4-methyl-piperazinomethyl)aniline and 1,4-dimethylpiperazine they are obtained only when relatively high concentrations of both donor and acceptor solutions were mixed. This is explained by the entropic contributions of the polymer chain such as the stacking effect of donor nitrogen atoms, i.e., the increment of local donor concentration around I₂ in the reaction field. The relation between the solution behavior of the reaction systems and the rate of formation of I₃^? ions also supports this kind of polymer effect. The effects of neighboring groups and dielectric constant on the reaction are also discussed.