PAS-Formaldehyde Polymer as a Polymeric Ligand

p-Aminosalicylic acid (PAS) was condensed with formaldehyde in the presence of aqueous oxalic acid and aqueous sodium hydroxide. The polymer sample (PAS-F,1) obtained withacid catalyst was characterized by IR spectral study, by its M_n determined by nonaqueous conductometric titration both against standard acid and alkali, by viscometric study in formic acid, and by DTA. The IR spectral and general characteristics of a polymer sample (PAS-F,2) prepared in the presence of aqueous alkali resemble those of a polymer sample (AP-F) prepared similarly from m-aminophenol and formaldehyde, indicating decarboxylation of PAS during the base-catalyzed polymerization of PAS with formaldehyde. Polymeric metal chelates of Fe(III), Cu(II), Zn(II), and Mn(II) ions with the PAS-F,1 polymer sample have been prepared and characterized by elemental analyses, IR spectral study, measurements of magnetic moments, and thermal analyses. Chelation ion-exchanging properties of the PAS-F,1 polymer sample have also been studied employing the batch equilibration method.     

Accelerated Curing Speed of Ethyl α‐Cyanoacrylate by Polymer with Catecholamine Groups

Four kinds of poly(ethylene glycol) (PEG) derivatives with the similar backbone and different side groups have been synthesized successfully. When both catecholamine and double bond are tethered to polymer backbone, i.e., the PEG backbone, simultaneously, the polymer can accelerate the curing speed of ethyl α‐cyanoacrylate (commercially available as 502) greatly under the same conditions (the curing time of such system is no more than 5 s). Probably this is due to the autoxidation of catecholamines. Through the redox‐cycling, catecholamines can produce, collect free radicals, and thus initiate the free radical polymerization. Due to the fast‐curing of such material when mixed with α‐cyanoacrylate, we could design and develop a new bicomponent super bioglue used in the dentistry or other bioenvironment requiring super fast settlement for further surgical operations.     

Novel sub-ceiling temperature rapid depolymerization-repolymerization reactions of cyanoacrylate polymers

Dilute solutions of unimodal high-molecular-weight poly(butyl cyanoacrylate) (“parent” polymer) in tetrahydrofuran (THF) at 21°C underwent rapid depolymerization accompanied by simultaneous repolymerization of the unzipped monomer to yield lower-molecular-weight “daughter” polymer following addition of tetrabutylammonium hydroxide (TBAOH), a slow initiator of butyl cyanoacrylate (BCA) monomer. The rate-determining step for the reaction was tentatively identified as abstraction of the terminal chain proton. Similarly, addition of TBAOH to a THF solution of BCA monomer resulted in initial formation of high-molecular-weight (MW) polymer that subsequently rapidly depolymerized with simultaneous formation of TBAOH initiated, low-MW daughter polymer. The depolymerization-repolymerization reaction is the relaxation process that occurs following perturbation of the monomer/high-MW parent polymer equilibrium by low-MW daughter polymer and proceeds at least 100°C below the ceiling temperature of the parent polymer.     

Kinetic studies of photopolymerization using real time FT-IR spectroscopy

The real time FT-IR (RT/FT-IR) technique has been recognized as a very vital tool to quantitatively study the curing parameters such as the effects of initiator (or catalyst) type and concentration, accelerator, stabilizer, irradiation wavelength, temperature, and curing environments. Herein, our results in studies of photoinduced polymerizations for adhesive and coating applications are reported. The photoinduced polymerizations studied included anionic and hydrosilation (a polyaddition polymerization) reactions. In photoinduced anionic polymerization our studies for ethyl cyanoacrylate polymerization are described. The effect of the concentration of photoinitiator and inhibitor on the ethyl cyanoacrylate polymerization kinetic rate will be discussed. In photoinduced catalytic hydrosilation reaction studies, the effects of the catalyst concentration and staging irradiation are disclosed. The hydrosilation reaction was monitored using a Si? H silicone hydride stretching band located at 2169 cm^?1. The cyanoacrylate polymerization was monitored using the C?C stretching band occurring at 1617 cm^?1. The hydrosilation conversion was completed with an appropriate formulation. For monofunctional cyanoacrylate monomer, the photoinduced conversion to straight chain polymer was approximately 85% for a 60 s period. The intrinsic rates of the reactions were calculated for kinetic comparisons. For very fast cyanoacrylate polymerization studies, new FT-IR kinetic software was used to collect 204 spectra/min. Some detailed experimental techniques and polymerization reaction mechanisms are also discussed. © 1993 John Wiley & Sons, Inc.     

Synthesis and degradation behavior of poly(ethyl cyanoacrylate)

Poly(ethyl cyanoacrylate) was synthesized using N,N′-dimethyl-p-toluidine as an initiator through an anionic/zwitterionic pathway. The degradability and the degradation mechanism of the prepared polymer were examined from various viewpoints. A combination of TGA and GPC analysis allowed us to confirm that the thermal degradation of this polymer was predominantly due to an unzipping depolymerization process initiated from the polymer chain terminus. The polymer was inherently unstable and exhibited interesting degradation behavior in solution with basic reagents. The degradation in solution was also found to be attributed to the unzipping of the monomer from the chain end. However, the degradation behavior of the polymer could be controlled by changing solvents, temperatures, and additives. These findings give an insight into the degradation behavior of poly(alkyl cyanoacrylate)s, which is a crucial point in utilizing these polymer homologues for various applications.     

Development of an Advanced Process for Manufacturing Polyacetal Resin

Abstract

An advanced process for manufacturing polyacetal resin has been developed. First, a new technology for the production of highly concentrated aqueous formaldehyde was developed by oxidizing methylal. Whereas the oxidation of methanol yields 1 mol water per mole formaldehyde, methylal oxidation produces only 1 mol water for every 3 mol formaldehyde. Thus, the output from methylal oxidation is more than 70% formaldehyde, compared with 55% from methanol oxidation. Second, a new extraction distillation process for formaldehyde purification was developed in order to get highly purified formaldehyde directly from formalin. By using highly purified formaldehyde, an end-capped polymer was obtained in the presence of acetic anhydride as a chain transfer or end-capping agent during polymerization. Third, the relatively high formaldehyde concentration enhances the formation of trioxane. Purified trioxane is copolymerized with ethylene oxide in the presence of an end-capping agent to get an end-capped polymer with high thermal stability. Two new intermediates from the initiation reaction of the copolymerization, 1,3,5,7-tetraoxacyclononane (TOCN) and 1,3,5,7,10-pentaoxacyclododecane (POCD), were isolated, and a new initiation mechanism was proposed. Fourth, the world's first acetal block copolymer was commercialized by the polymerization of formaldehyde in the presence of a lubricant functional polymer having an active hydrogen atom. This acetal block copolymer exhibits super lubrication properties.     

The mechanism of polymerisation of butyl cyanoacrylate in aqueous dispersions

Butyl cyanoacrylate has been polymerised by dispersion in acidified water to yield nanoparticles. Reactions have been carried out at various temperatures and the molecular weight of the growing polymer measured. In all cases polymerisation proceeds by generation of discrete populations of oligomers, which are then re‐initiated and undergo further growth. The peak molecular weight is around 1300 g/mol and it is considered that a stepwise initiation, termination and re‐initiation process continues until diffusionally limited by the internal viscosity within the nanoparticle.     

新型可用于荧光标记的α-氰基丙烯酸酯单体的合成及在小鼠活体成像中的应用

设计合成了新型含有荧光基团的α-氰基丙烯酸酯单体,并与其它α-氰基丙烯酸酯单体共聚,得到产生荧光的聚氰基丙烯酸酯材料.将其包埋在小鼠背部肌肉层,可获得良好的荧光成像效果.通过对荧光强度的监测,初步研究了聚氰基丙烯酸酯材料中的侧链酯基在小鼠体内的降解情况.单体合成是以蒽合氰基丙烯酸和4,4'-二甲氧基三苯基-氨基己醇为原料,得到蒽合氰基丙烯酸(4,4'-二甲氧基三苯基-氨基己醇)酯,脱保护后再将异硫氰酸荧光素以化学键合的方式标记在末端氨基上,脱蒽还原烯双键后,得到可用于荧光标记的α-氰基丙烯酸(异硫氰酸荧光素-氨基己醇)酯单体.反应中间体及单体结构采用核磁共振氢谱和质谱进行表征.该单体及其高聚物均可在激发光(488 nm)和发射光(525 nm)条件下观察到明显荧光.     

Revisions to the microstructural assignments of poly(ethyl cyanoacrylate)

The tacticity assignments from the literature for the ¹³C-NMR signals of the side-chain methylene group of poly(ethyl cyanoacrylate) are reversed, and new assignments of the main-chain methylene group are proposed. The assignments were made possible by a combination of DEPT and HETCOR NMR experiments on samples of varying microstructure distributions. The polymer tends toward syndiotacticity, not isotacticity as previously reported. The distribution of stereoisomers fits well to a Bernoulian statistical model. The stereochemical assignments were corroborated by similar analyses of a model compound for two cyanoacrylate repeat units. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2219–2224, 1999     

The detection of drugs of abuse in fingerprints using Raman spectroscopy II: cyanoacrylate-fumed fingerprints

This paper describes the application of Raman spectroscopy to the detection of exogenous substances in cyanoacrylate-fumed fingerprints. The scenario considered was that of an individual handling a substance and subsequently depositing a contaminated fingerprint. These fingerprints were enhanced by cyanoacrylate fuming, a process in which a layer of white cyanoacrylate polymer is deposited on the fingerprint material, enabling visual detection. Five drugs of abuse (codeine phosphate, cocaine hydrochloride, amphetamine sulphate, barbital and nitrazepam) and five non-controlled substances of similar appearance, which may be used in the adulteration of drugs of abuse (caffeine, aspirin, paracetamol, starch and talc), were used. The substances studied could be clearly distinguished using their Raman spectra and were all successfully detected in cyanoacrylate-fumed fingerprints. Photobleaching was necessary to reduce the fluorescence background in the spectra of some substances. Raman spectra obtained from the substances in cyanoacrylate-fumed fingerprints were of a similar quality to spectra obtained from the substances under normal sampling conditions, however, interfering Raman bands arising from the cyanoacrylate polymer were present in the spectra. In most cases the only interfering band was the C triple bond N stretching mode of the polymer, and there were no cases where the interfering bands prevented identification of the substances. If necessary, the interfering bands could be successfully removed by spectral subtraction. The most difficult aspect of the detection of these substances in cyanoacrylate-fumed fingerprints was visually locating the substance in the fingerprint beneath the polymer layer in order to obtain a Raman spectrum.     

Synthesis and characterization of four alkyl 2‐cyanoacrylate monomers and their precursors for use in latent fingerprint detection

Four novel cyanoacrylates, 2‐cyanoethyl 2‐cyanoacrylate, 1‐cyanoethyl 2‐cyanoacrylate, trideuteromethyl 2‐cyanoacrylate and pentadeuteroethyl 2‐cyanoacrylate have been synthesized using a Diels‐Alder protection/deprotection route involving anthracene. The common route for the synthesis of alkyl 2‐cyanoacrylates was found to be unsatisfactory for the production of small quantities of the targeted cyanoacrylates, which have potential as reagents for the mid‐infrared spectral imaging of fingerprints on difficult surfaces. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

高分子复合材料中残余甲醛的萃取及高效液相色谱分析

 依据顶空 /气 液平衡原理 ,较为系统地研究了高分子复合材料中残余甲醛的萃取及高效液相色谱定量分析方法 ,探讨了影响萃取率的主要因素 ,进行了萃取及色谱分离条件的优化 ,并实现了复合材料中微量残余甲醛的准确定量测定。方法检测限为 0 1mg/kg ;相对标准偏差小于 5 % ,加标回收率为 96 %～ 10 3%。     

Grafting of Oligomers on Phenolic Polymer Chains and its Influence on Their Titration Curves in Nonaqueous Media

A linear phenolic polymer has been prepared by condensing p-bromophenol with formaldehyde in the presence of a catalyst. The linear polymer was dehalogenated completely by a standard procedure. Some oligomers of uniform structure and molecular weight were grafted on the dehalogenated polymer. Electrometric titration curves of the grafted copolymers have been studied, and the shape of the titration curves has been interpreted in terms of the length of the grafted chain and the intramolecular H-bonding between neighbouring OH groups.     

Well-Defined Poly(butyl cyanoacrylate) Nanoparticles via Miniemulsion Polymerization

Summary: Despite the high reactivity of the monomer, nanoparticles with a hydrophobic core based on poly(butyl cyanoacrylate) and a hydrophilic shell based on poly(ethylene oxide) PEO were synthesized in one step by miniemulsion polymerization. Colloidal properties of the nanoparticles were controlled by the structure and the amount of amphiphilic polymer in the aqueous phase, while the molecular weight of core depended on pH of the continuous phase and the polymerization mechanism (anionic or radical). The evolution of the molecular weight of the synthesized poly(butyl cyanoacrylate) was followed as a function of time at pH 7.4 by size exclusion chromatography. As expected, the degradation kinetics depended on the polymerization mechanism. Finally, a model compound, pyrene, was encapsulated in the synthesized nanoparticles. Its release was found to depend on the conditions of nanoparticles synthesis, especially on the polymerization mechanism.     

Titration curves of p-aminobenzoic acid–formaldehyde polymer in relation to its structure

p-Aminobenzoic acid and formaldehyde were condensed in the presence of acid catalyst. The linear condensation polymer thus obtained was then separated into four fractions by a fractional precipitation method. Conductometric titrations were carried out on these four polymer fractions and the conglomerate in nonaqueous solvents with acid as well as base. The titration curves indicated a large number of additional breaks before the complete neutralization of COOH or NH₂ groups. These observations have been interpreted in terms of degree of polymerization and the structure of the polymer.     

基于一维分子线的甲醛分子探针研究

甲醛为公认的致癌物质,本文针对目前甲醛分析需使用专用仪器和试剂盒的不便现状,合成了分子探针(km2bn),通过晶体结构分析发现其苯并二氮杂卓基团与水自组装为一维分子线材料(km2bn·H2O),可与甲醛分子发生固-气相Hantzsch反应,生成具有更大共轭体系二氢吡啶杂环结构,双官能团反应使其生成一维伸展的线性聚合物,共轭体系得到更大的拓展,具有深色与光谱红移效应,其颜色坐标与甲醛浓度具有线性关系,兼具检测选择性,因而可通过该可视显色反应检测甲醛,并可制成试纸,方便普通家庭使用。     

Improved measurement of formaldehyde in water-soluble polymers by high-performance liquid chromatography coupled with post-column reaction detection

An improved methodology for the analysis of free formaldehyde in water-soluble polymers used for industrial water treatment is reported. Previously, derivatization prior to HPLC or colorimetric techniques has been used. The data generated by these approaches are suspect in that the derivatizing agent can react with the polymer or other sample components to produce high results. Post-column reaction derivatization is applied after separation of the free formaldehyde from the product interferences. The type of polymer product analyzed influences the choice of column(s). The degree of high bias of the commonly used 2,4-dinitrophenylhydrazine pre-column derivatization is reported and the results are compared to those with the post-column reaction for two polymer products. This method, being more selective, should be applicable to any polymer containing formaldehyde.     

Preparation and Chelating Properties of 4-Bromosalicylic Acid-Formaldehyde Polymers. Part II

4-Bromosalicylic acid (BS) was condensed with various proportions of formaldehyde using different acid catalysts. The polymer samples have been characterized by IR spectral studies, by their number-average molecular weight (M _n), and by TGA. Viscosity measurements of selected polymer samples in DMF showed that their solutions exhibited polyelectrolyte behavior. The intrinsic viscosity [η] of the polymer samples were measured in 80:20 (v/v) DMF/water containing 1% KBr, a medium in which the polymers exhibited normal behavior. Metal chelates of one polymer sample are characterized. Ion-exchanging properties of the same sample are studied by application of the batch equilibrium method     

甲醛分子印迹聚合物的制备、性能及水产品测定

以甲醛为模板分子,α-甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,用氯仿做溶剂,制备了甲醛分子印迹聚合物,并优化了此制备方法,在模板分子、功能单体和交联剂的摩尔比为1:2:20,预聚合时间为4 h,聚合时间为8 h的条件下制备的聚合物对甲醛的特异性吸附能力最好,当甲醛溶液的浓度为2 mmol/L时聚合物对甲醛的吸附量达到了12.40×10^-2 mmol/g。 对市售鱿鱼处理后用高效液相色谱法测定得样品中甲醛的浓度是5.92 mg/Kg,将该样稀释100倍以后甲醛已无法检出,经MIP柱富集后检测计算样品中甲醛浓度为5.76 mg/Kg,表明该聚合物用于样品前处理高效且结果无显著性差异。     

Preparation of Water-Soluble Polymers via the Mannich Reaction

The Mannich reaction, defined as the condensation of ammonia or a primary or secondary amine with formaldehyde and a compound containing at least one hydrogen atom of pronounced activity, was first shown to yield polymers from suitably selected reactants as early as 1946 [l]. Surprisingly, very few further attempts to utilize this interesting reaction in polymer formation have been reported in the literature.