Chlorination Of Poly Research Articles

Poly(Alkyloxyethylene-Lactate Phosphate) for Delivery of Doxorubicin: Synthesis and Characterization.

Serious side effects are associated with the use of doxorubicin. Nanoparticles as carriers for anticancer drugs are useful for reducing side effects and improving therapeutic effects. In this study, a polymer for preparing doxorubicin-containing nanoparticles was developed. Using a novel strategy, a biodegradable poly(oxyethylene glycol lactate H-phosphonate) based on dimethyl H-phosphonate and poly(ethylene glycol)-lactate (PEG-lactate) was synthesized. Poly(hexadecanyloxyethylene - lactate phosphate) was obtained via chlorination of poly(oxyethylene glycol - lactate H-phosphonate) with trichloroisocyanuric acid and the addition of 1-hexadecanol. The polymer was characterized by 1H NMR and 31P NMR. The results of 1H NMR and 31P NMR showed that the polymer was successfully synthesized, and the yield was 46.9%. Poly(hexadecanyloxyethylene - lactate phosphate) has potential as a drug carrier.

Preparation of PolyHIPE monolithic materials functionalization by tris(2-aminoethyl)amine

The developments of monolithic materials rapidly in nowadays hold an impressively strong position in separation science as well as in other areas of chemistry. In this research are presented functionalization of PolyHIPE monolithic materials by tris(2-aminoethyl) amine. Monolithic polymer supports and scavengers were synthesized via nucleophilic displacement of chlorine in poly(4-vinyl benzyl chloride-co-divinylbenzene) as PolyHIPE materials. Porous copolymers of DVB/DVB were prepared by emulsion templating using high internal phase emulsions (HIPEs) as precursors for monoliths. The properties of the final products synthesized were functionalized with an amino group, at a different ratio of amine/chloromethyl groups, in different time refluxed were explored. PolyHIPE functionalized with tris(2-aminoethyl)amine to yield a product with high degrees of conversion. The extent of the functionalization reactions was investigated by a range of qualitative and quantitative techniques: FTIR, CHN analysis, potentiometric measurements, and (BET) measurements have been performed.

Poly(vinyl chloride) reactions with sodium and potassium derivatives of heteroaromatic and aromatic NH- and SH-acids in aprotic solvents

The observed featured and regularities of nucleophilic substitution of chlorine in poly(vinyl chloride) upon its reaction with sodium and potassium derivatives of pyrazole, 3,5-dimethylpyrazole, and 2-thiobenzimidazole, and with sodium thiophenolate have been understood in the frame of hard and soft acids and bases theory.

Preparation and crystallization behavior of poly(vinylidene fluoride‐ter‐chlorotrifluoroethylene‐ ter‐trifluoroethylene)

AbstractSeveral poly(vinylidene fluoride‐ter‐chlorotrifluoroethylene‐ter‐trifluoroethylene) terpolymers, including 68 mol % vinylidene fluoride, were prepared by the partial reduction of chlorine in poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) copolymers. The terpolymers were then allowed to crystallize under two sets of conditions: (1) crystallized from solution (in N,N‐dimethylformamide) at 35°C for 108 h and (2) annealed at temperatures 5°C below their respective melting points for 11 h. The effect of the chlorotrifluoroethylene (CTFE) content and crystallization conditions on the crystallization behavior of the terpolymers was investigated by X‐ray diffraction, Fourier transform infrared spectroscopy, and differential scanning calorimetry. The results show that with increasing CTFE content, the terpolymers contained less of the β phase (it even disappeared), which had an all‐trans chain conformation, and more of the γ phase was found, which became prominent with the trans–trans–trans–gauche conformation. The crystallinity, crystal size, fusion enthalpy, and melting temperatures of the terpolymers decreased with increasing CTFE content. Compared with annealed terpolymers, the terpolymers crystallized from the solution at 35°C included more polar components that contained more trans conformations but had lower crystallinities, melting temperatures, and fusion enthalpies and smaller crystal sizes. These results suggest that crystallization from the solution may be helpful in forming polar crystals, whereas an annealing process at a high temperature is beneficial in perfecting the crystal structure. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Oligomerization of 1-decene under the action of catalytic systems based on Al-aluminum activator-RCl and Al-RCl

Novel catalytic systems for the cationic oligomerization of 1-decene into synthetic poly(α-olefin) oils have been worked out; these systems include a highly disperse (0.1–40 μm) aluminum, an aluminum activator [I2, Mg, (C2H5)nAlCl3 − n, (CH3)3CCl and some other RX, HCl, benzene, and toluene], and a cocatalyst based on organic halide compounds RX (R is primary, secondary, or tertiary alkyl, allyl, or benzyl; X is Cl, Br, or I). We study the effect of various factors (characteristics of Al, nature of aluminum activator, RCl: Al molar ratio in the catalyst, concentration of Al, temperature, benzene additives, reaction duration) on the conversion of 1-decene into poly(α-olefins), the fractional composition of oligomerization products, the content of chlorine in poly(α-olefins), and the structure and physicochemical characteristics of fractions.

Novel Refreshable N-Halamine Polymeric Biocides: N-Chlorination of Aromatic Polyamides

Chlorination of poly(m-phenyleneisophthalamide) (Nomex) and poly(p-phenyleneterephthalamide) (Kevlar) fabrics by sodium hypochlorite aqueous solution was investigated. Results indicated that stable N-halamine structures could be readily formed in Nomex, which provided potent, durable, and refreshable antibacterial functions against both Gram-negative and Gram-positive bacteria. However, similar chlorination treatment of Kevlar led to serious hydrolysis of the polymer. The treated fabrics were fully characterized by Fourier trasnform infrared, thermal, and X-ray diffraction studies. Possible mechanisms of this effect were discussed.

Water-soluble and nonionic polyphosphoester: synthesis, degradation, biocompatibility and enhancement of gene expression in mouse muscle.

A nonionic and water-soluble polyphosphoester, poly(2-hydroxyethyl propylene phosphate) (PPE3), was synthesized by chlorination of poly(4-methyl-2-oxo-2-hydro-1,3,2-dioxaphospholane), followed by esterification with 2-benzyloxyethanol and deprotection of the hydroxyl group by catalytic hydrogenation in the presence of Pd-C. PPE3 degraded rapidly in PBS 7.4 at 37 degrees C. The cytotoxicity and tissue compatibility assays suggested good biocompatibility of PPE3 in vitro and in vivo. The expression of pVR1255 Luc plasmid in mouse muscle after intramuscular (i.m.) injection of DNA formulated with PPE3 solution in saline was enhanced up to 4-fold compared with that of naked DNA. These results suggest the potential of this polyphosphoester for naked DNA-based gene therapy. The advantages of this polymer design include the biodegradability of the polyphosphoester and its structural versatility, which allows the fine-tuning of the physicochemical properties to optimize the enhancement of gene expression in muscle.

Monolithic scavenger resins by amine functionalizations of poly(4-vinylbenzyl chloride-co-divinylbenzene) PolyHIPE materials.

[reaction: see text] Monolithic polymer supports and scavengers were prepared via nucleophilic displacement of chlorine in poly(4-vinylbenzyl chloride-co-divinylbenzene) PolyHIPE materials. Reactions of monolithic PolyHIPE with tris(2-aminoethyl)amine, 4-aminobutanol, tris(hydroxymethyl)aminomethane, morpholine, and hexamethylenetetramine led to functionalized polymers with amino and hydroxy functionalities with high degrees of conversion. 4-Chlorobenzoyl chloride was efficiently and rapidly scavenged from solution by the tris(2-aminoethyl)amine derivative of monolithic poly(4-vinylbenzyl chloride-co-divinylbenzene) PolyHIPE at ambient temperature.

Chlorination of Poly-(3-hydroxy alkanoates) Containing Unsaturated Side Chains. Volume 33, Number 9, May 2, 2000, pp 3219−3223.

Chlorination of Poly-(3-hydroxy alkanoates) Containing Unsaturated Side Chains. Volume 33, Number 9, May 2, 2000, pp 3219−3223.

Chlorination of Poly(3-hydroxy alkanoates) Containing Unsaturated Side Chains

Unsaturated biopolyesters, (PHA−DB), obtained from pure anchovy (hamci), hazelnut, soybean oily acids and the mixtures of octanoic acid (in weight ratios of 50/50 and 70/30) were chlorinated up to 54 wt % Cl content. The molecular weights (MW) of the chlorinated biopolyesters were between 1.3 × 104 and 3.0 × 104 and decreased with the increase in chlorine content in PHA−DB. Melting transitions of the chlorinated biopolyesters were between 62 and 125 °C depending on the chlorine content when compared with those of the original PHAs, 44−55 °C.

In situ chlorination of poly(vinyl chloride) in aqueous hydrochloric acid

Based on environmental, safety, corrosion and technological considerations a new method has been developed for chlorination of PVC in aqueous hydrochloric acid solvent by controlled electrolytic in situ generation of chlorine using graphite and chlorine-selective Ti-RuO2 electrodes. The byproduct, HCl gas, is dissolved at the moment of its formation and acts as starting material of further chlorination. This way, the application of corrosive chlorine gas is avoided. The chlorination conditions have been optimized. The highest chlorine content was found at 5.5 h reaction time using a graphite electrode. The obtained chlorinated PVC did not contain any CCl2 units. Aufgrund von Uberlegungen zu Umweltschutz, Sicherheit, Korrosion und Verfahrenstechnik wurde eine neue Methode zur Chlorierung von PVC entwickelt, wobei Chlor mit Graphit- und chlorselektiven Ti-RuO2-Elektroden in wasseriger Salzsaure elektrolytisch in situ erzeugt wird. Als Nebenprodukt entsteht Chlorwasserstoff, der im Moment der Entstehung gelost wird und als Ausgangsmaterial fur weitere Chlorierung dient. Dadurch wird die Verwendung von korrosivem Chlorgas vermieden. Die Bedingungen der Chlorierung wurden optimiert. Der hochste Chlorgehalt wurde bei einer Reaktionszeit von 5,5 h mit einer Graphitelektrode erhalten. Das chlorierte PVC enthielt keine CCl2-Einheiten.

Studies on Poly(Dialkoxyphosphazenes) for the Medical Applications

Abstract The presence of trace of chlorine in poly(diorganophosphazenes) [-N=P(OR)2-]., where R = C2H5, CH2CF3, C2F5, C4H5, C6H13, C8H17, C12H25, CH2C6H5 in many cases leads to the substantial changes of their physicochemical properties and limits application possibilities of this class of polymers especial for the medical materials. Despite the optimization of reaction conditions for each nucleophilic alkoxy substituent, the obtained poly(dia1koxyphosphaenes) exhibited some physicochemical anomalies.

Spectroscopic studies on poly(diorgano)phosphazenes, a new class of medical polymers

Poly(diorgano)phosphazenes belong to a relatively new class of polymeric materials. Generally, poly(dichloro)phosphazene is used as a starting material in the reactions involving the chlorine atom replacement by different nucleophilic organic substituents.Such a reaction scheme is accepted also for the synthesis of poly(dialkoxy)phosphazenes.▪R = C2H5; C4H9; C6H13; C8H17; C12H25; CH2C6H5The presence of trace of chlorine in poly(diorgano)phosphazenes in many cases leads to the substantial changes of their physico-chemical properties and limits application possibilities of this class of polymers.The influence of the substitution rate of chlorine atoms in poly(dichloro)phosphazenes on physicochemical properties of these polymers is shown for poly(dialkoxy)phosphazenes samples and of poly(dibutoxy)phosphazene fractions having similar molecular weights and obtained in two different synthesis.

A comparison of the phase-transfer-catalysed chlorinations of various polymethylstyrenes by hypochlorite

The phase-transfer-catalysed chlorinations of poly (2-methylstyrene), poly(3-methylstyrene), poly(2,4-dimethylstyrene) and poly(2,5-dimethylstyrene) using sodium hypochlorite in chloroform/dichloromethane mixtures are compared with that for poly(4-methylstyrene). Over the range of conditions employed, the chlorination of poly(2-methylstyrene) is barely detectable and the polymers with methyl substituents in the meta position show a lesser tendency to undergo chlorination than those with methyl substituents in the para position. In all cases concomitant modification of the molecular weight distributions of the polymers are minimal when the reactions are carried out at an aqueous phase pH of 8.5 and with a chloroform-rich organic phase. With a dichloromethane-rich organic phase, polymer chain scission is marked. The experimental observations are discussed both in terms of a compatible mechanism and of inductive effects involving the phenyl ring substituents.

Phase-transfer-catalysed chlorination of poly(4-methylstyrene) by hypochlorite

The effects of variation of the conditions of phase-transfer-catalysed chlorination of poly(4-methylstyrene) using sodium hypochlorite in chloroform/dichloromethane mixtures are investigated. When the reaction is carried out at an aqueous phase pH of 8.5 and using a chloroform-rich organic phase, chlorination is predominantly at the 4-methyl substituent and di-/trichlorination and concomitant modification of the molecular-weight distribution of the polymer are minimal. Kinetic mechanisms compatible with the experimental observations are proposed.

Conversion distribution in diffusion‐governed chlorination of poly(vinyl chloride)

AbstractConversion distribution in particles of chlorinated poly(vinyl chloride) (CPVC) is conceptually described based on balance equations involving mass transfer and chemical reaction. In the physical sorption of chlorine in poly(vinyl chloride) (PVC) as measured by the constant volume cell method, equilibrium concentration and diffusion rate obeyed Henry's law and Fick's law. The rate process of photo chlorination of PVC, which was investigated by the gravimetric method, could be well predicted by theoretical calculation of chlorine diffusion in PVC accompanying the infinitely fast chemical reaction. In a free grain of PVC synthesized by suspension polymerization, the chlorination rate was governed by the polymer‐phase diffusion within agglomerates of coalesced primary particles.To produce homogeneously chlorinated PVC, a periodic photo‐irradiation method was theoretically proposed and experimentally demonstrated. The effect of the periodic operation on the thermal property of CPVC was evaluated by DSC.

Further chlorination of poly(vinyl chloride): effects on flammability and smoke production tendency

Studies have been carried out of the flammability (by the limiting oxygen index, LOI), of the level of smoke production (by two different procedures) and of the amount of char remaining after combustion, for a variety of chlorinated polymers. The chlorine level of the samples ranged between that in ordinary poly(vinyl chloride) (PVC) and 70 wt%. The intrinsic viscosity of the PVC from which these resins were produced ranged between 0.6 and 1.1. The investigation involved both mass-polymerized and suspension-polymerized based materials. It is clear that the further chlorination of PVC leads to the production of materials which have exceptionally good fire properties. The LOI increases from a level of 45–49 (for PVC) to over 70 (for 67 wt% Cl) and to pure oxygen (for sustained flaming combustion at 70 wt% CI). A flammability property (LOI(F)] was defined which corresponds to sustained flaming combustion; some of the highly chlorinated samples require pure oxygen atmospheres to achieve an LOI(F) of 100. The amount of smoke evolved also decreases drastically with increasing chlorination, while there is a substantial increase in the char remaining after combustion. Fitting of the experimental results generated systems of equations which give very good predictions of the properties to be measured. There does not seem to be any major effect of the molecular weight or of the polymerization process of the base polymer on the flammability or smoke properties of the chlorinated polymers.

Phase-transfer-catalyzed chlorination of poly(p-methylstyrene)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPhase-transfer-catalyzed chlorination of poly(p-methylstyrene)S. Mohanraj and Warren T. FordCite this: Macromolecules 1986, 19, 10, 2470–2472Publication Date (Print):October 1, 1986Publication History Published online1 May 2002Published inissue 1 October 1986https://doi.org/10.1021/ma00164a001RIGHTS & PERMISSIONSArticle Views233Altmetric-Citations32LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (393 KB) Get e-Alerts Get e-Alerts

Studies on reactivity of polymers—I. Chlorination of poly(vinyl chloride) using sulphuryl chloride in solution in the presence of radical initiators

The chlorination of poly(vinyl chloride) with sulphuryl chloride in solution in the presence of azobisisobutyronitrile has been studied. The microstructure of the product is similar to that of the products of chlorination by gaseous chlorine. The rate constant and the activation energy of chlorination of the methylene group in the grouping -CHCl-CH 2-CHCl- have been determined.

Chlorination of Poly(vinyltoluene) by Electrolysis in an Organic/Water Suspension System

Abstract Chlorinated poly(vinyltoluene) was synthesized by controlled-current electrolysis of poly(vinyltoluene) in a suspension system consisting of aqueous and organic solutions. A high Cl-content polymer, in which Cl was introduced to the methyl group and the main chain, was obtained without changes in the molecular-weight distribution of the polymer.