Identification of polymer building blocks by Py–GC/MS and MALDI-TOF MS

The main goal of this work is to identify polyurethane (PU) building blocks by pyrolysis gas chromatography/mass spectrometry (Py–GC/MS) and matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS). Toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are widely used polymer building blocks. Py–GC/MS and MALDI-TOF MS were proved to be powerful methods to distinguish TDI-PU and MDI-PU according to the characteristic pyrolysis products and the different repeated units, respectively. In Py–GC/MS, the specific pyrolyzates are TDI for TDI-PU and MDI for MDI-PU. In MALDI-TOF MS, the weights of repeated units are 264?g/mol for TDI-PU and 340?g/mol for MDI-PU.     

Photochemical degradation study of polyvinyl acetate paints used in artworks by Py–GC/MS

Photochemical degradation of commercial polyvinyl acetate (PVAc) homopolymer and PVAc paints mixed with burnt umber, cobalt blue, cadmium red dark, nickel azo yellow and titanium white commonly used for artworks were studied by pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR). Py–GC/MS with single-shot technique was used for the characterization of the thermal degradation of PVAc at different temperatures, while the double-shot technique of Py–GC/MS was used to reveal the differences in the specimens before and after UV ageing, including the changes of detectable amounts of deacetylation product – acetic acid and plasticizers such as diethyl phthalate (DEP). Furthermore, the relative concentration of the pyrolysis products of the paint samples could be measured and compared in the second step of the double-shot Py–GC/MS, which are highly dependent on the presence of pigments and the ageing status of PVAc paints.     

Composition of non-woody plant lignins and cinnamic acids by Py-GC/MS,Py/TMAH and FT-IR

Lignins from different non-woody plants such as hemp (Cannabis sativa), flax (Linum usitatissimum), jute (Corchorus capsularis), sisal (Agave sisalana) and abaca (Musa textilis), commonly used for manufacturing specialty papers, were analyzed by pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) in the absence and in the presence of tetramethylammonium hydroxide (TMAH) and by Fourier-transform infrared (FTIR) spectroscopy, after alkaline isolation. Hemp and flax lignins showed a predominance of guaiacyl (1-hydroxy-2-methoxyphenyl) units, while jute, sisal and abaca lignins contained predominantly syringyl (1-hydroxy-2,6-dimethoxyphenyl) units. p-Hydroxycinnamic acids, namely p-coumaric and ferulic acids, were also found in the isolated lignins, linked by alkali-resistant ether bonds, especially in abaca and sisal lignins. The presence of the latter compounds in the isolated lignins, as well as in their respective whole fibers, was shown by pyrolysis in the presence of tetramethylammonium hydroxide (Py/TMAH), p-coumaric acid being especially abundant in abaca.     

Synthesis and characterization of saturated and unsaturated polysulfide polymers and their thermal degradation processes investigated by flash pyrolysis–gas chromatography/mass spectrometry

The synthesis of polysulfide polymers with unsaturated and saturated units in the backbone and their characterization by Fourier transform infrared, NMR, gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry are reported. This is the first report on an analysis of the thermal degradation of an unsaturated polysulfide polymer [poly(2‐butene sulfide)] carried out by pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS). A unique phenomenon of exothermic degradation has been detected by differential thermal analysis and has been attributed to the energetics of the unsaturated polysulfide linkage during degradation. The thermal degradation products studied by Py–GC/MS indicate that the formation of sulfur‐containing products is more favored than the formation of non‐sulfur‐containing products. Furthermore, a comparative study of the thermal degradation of unsaturated and saturated polysulfide polymers has been conducted with thermogravimetry and Py–GC/MS analyses. These analyses have shown that the mechanisms of degradation of these polymers are different, and the lower number of pyrolysis products indicates a selective cleavage of the polymer during degradation in the saturated polysulfide polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 638–649, 2005     

Mass spectrometric techniques for characterizing low-molecular-weight resins used as paint varnishes

The molecular structure of three low-molecular-weight resins used as paint varnishes has been characterized by use of an approach based on three different mass spectrometric techniques. We investigated the ketone resin MS2A, the aldehyde resin Laropal A81, and the hydrocarbon resin Regalrez 1094, now commonly used in restoration. To date, the molecular structures of these resins have not been completely elucidated. To improve current knowledge of the chemical composition of these materials, information obtained by gas chromatography–mass spectrometry (GC/MS), pyrolysis–gas chromatography–mass spectrometry (Py/GC/MS), and electrospray ionization mass spectrometry (ESI–Q–ToF) was combined. Analysis, in solution, of the whole polymeric fraction of the resins by flow-injection ESI–Q–ToF, and of the non-polymeric fraction by GC–MS, enabled us to identify previously unreported features of the polymer structures. In addition, the Py–GC/MS profiles that we obtained will help to enhance the databases currently available in the literature. The proposed approach can be extended to other low-molecular-weight resins used as varnishes in conservation.     

Orientation Dependent FT Raman Microspectroscopy on Hemp Fibers

Summary: FT Raman microspectroscopy was used for polarization experiments on strained hemp fibre cells. The cellulosic plant fibers were macerated with alkaline and enzymatic solutions. Those cleaned and refined single fiber cells were subjected to micro tensile tests as well as to polarization measurements under the FT Raman microscope. Mechanical parameters of the fiber cells (e.g. E-modulus) were determined and changes in orientation of the  (C O C) structure units of the cellulose were considered with respect to fiber stress and molecular fiber structures. Intensity ratios R₁ and R₂ calculated on the polarized micro FT Raman spectra of the strained fibers describe the order parameter 〈P₂〉 and 〈P₄〉 allowing the quantitative determination of the orientation of the structure units  (C O C) of fiber cellulose with respect to the fiber cell axis.     

Direct analysis of alkylphenols in Ginkgo biloba leaves by thermochemolysis–gas chromatography/mass spectrometry in the presence of tetramethylammonium hydroxide

Thermochemolysis–gas chromatography/mass spectrometry (GC/MS) in the presence of tetramethylammonium hydroxide (TMAH) was applied to the determination of alkylphenols in Ginkgo biloba leaves directly using a vertical microfurnace pyrolyzer. TMAH thermochemolysis–GC enabled the highly sensitive determination of alkylphenols including ginkgolic acids and ginkgols in G. biloba leaves as their methyl derivatives on the resulted pyrograms. On the basis of their peak areas, the contents of the alkylphenols in G. biloba leaf sample were rapidly and precisely determined without using any tedious and time-consuming pretreatment.     

Ammonium Y zeolite applied as a thermochemolysis reagent for identification of polyethers and polyesters

A potential thermochemolysis reagent has been tested for the pyrolysis gas chromatographic identification of polyether, polyester and polyether- or polyester-based thermoplastic polyurethane. The main advantage of ammonium Y zeolite over liquid reagents is that it does not react prior to pyrolysis, and its reactions have no incomplete products. The procedure of the thermochemolysis is as simple as running a pyrolysis-GC/MS analysis sampling a powder mixture of roughly equal mass of polymer and ammonium Y zeolite. The GC/MS chromatograms obtained show that the products of thermochemolysis are specific to the diol and dicarboxylic units of the polymer. It was observed that ethanal or 1,4-dioxane forms from ethylene oxide components of polyethers and polyesters, tetrahydrofuran from butylene oxide units, hexanedinitrile from adipate groups, and benzodinitrile from terephthalate groups.     

Pyrolysis-gas chromatography/fourier-transform infrared spectrometry of poly(ester urethane) elastomers

Three types of industrial poly (ester urethane) elastomers were studied by Curie–point pyrolysis–gas chromatography/Fourier–Transform infrared spectrometry (Py–GC/FTIR) with a maximum pyrolysis temperature of 973 K. The samples chosen were the Urepans 600 and 641 from Bayer and Elastollan C 78 A from BASF/Elastogran. The poly(ester urethane) elastomers are composed of three units: a polyesterdiol, a short chain diol and a diisocyanate. Py–GC/FTIR allows a rapid and unambiguous identification of the polymer chains by key fragments.     

Thermal decomposition of bisphenol A-based polyetherurethanes blown with pentane: Part II—Influence of the novel NaH2PO4/NaHSO4 flame retardant system

The thermal degradation process of ethoxylated bisphenol A (BPA) and oxyalkylenated 2,6-toluylenediamine-based polyurethane (PU) foams blown with pentane and flame retarded by novel NaH₂PO₄ and NaHSO₄ intumescent system (5:3, w/w) was studied by thermogravimetry coupled with mass spectrometry (TG–MS), thermogravimetry coupled with Fourier transform infrared spectroscopy (TG–FTIR), pyrolysis–gas chromatography coupled with mass spectrometry (Py/GC–MS) and diffuse reflectance Fourier transform spectroscopy (DRIFTS) methods. It has been found that NaH₂PO₄/NaHSO₄ system is active both at the initiation stage of PU decomposition as well as it catalyses cross-linking reactions that lead to enhanced char formation during degradation; both effects contribute to the overall flame retardation effect.     

Characterization of the chemical differences between solvent extracts from Pu-erh tea and Dian Hong black tea by CP–Py–GC/MS

Solvent extracts from a type of Pu-erh tea and Dian Hong black tea were characterized by Curie-point pyrolysis–gas chromatography–mass spectroscopy (CP–Py–GC/MS). The ethyl-acetate extracts from both teas showed similar CP–Py–GC/MS results, with main pyrolytic products of carbon dioxide, caffeine, o-phenols, and phthalate esters. During pyrolysis, the n-butanol extract from Pu-erh tea formed carbon dioxide (38.92% of total pyrolytic products), alkaloids (49.7%), and nitrogen oxides (8.38%), as well as a small fraction of esters. The n-butanol extract from Dian Hong tea formed mainly alcohols, amines, esters, phenols, carboxylic acids, and alkaloids. The raw theabrownin extracts (ethanol precipitates) from the two teas produced substantially different CP–Py–GC/MS results. The raw theabrownin extract from Pu-erh tea formed mostly carbon dioxide during pyrolysis, whereas the counterpart extract from Dian Hong tea formed mainly carbon dioxide (48.23%) and nitrogen oxides (35.39%). The 3.5–100 kDa fractions separated from the theabrownin extracts of the two teas showed similar CP–Py–GC/MS results, whereas the fractions <3.5 kDa and >100 kDa formed substantially different pyrolytic products. These results showed that solvent extracts from Pu-erh tea and Dian Hong tea had substantially different chemical compositions and structures. The study suggested that CP–Py–GC/MS can be used to effectively identify chemical differences between tea extracts.     

FTIR及Py-GC/MS定性分析高聚物单体

红外光谱反应出的是特征化学基团的振动 ,对于高聚物的具体单体组成分析 ,只能借助于紫外光谱、核磁共振及质谱进行综合判断才能得到圆满的鉴定结果[1,2 ] 。本工作针对在红外光谱仪不能分辨的情况下通过气相色谱 质谱联用技术进行综合分析鉴定 ,结果可为其它高聚物分析研究提供实验依据。1　实验1 1　仪器及试验条件未知高聚物试样为白色颗粒状 (晨光化工二厂 )。ＳＹＳＴＥＭ2 0 0 0ＦＴＩＲ ,ＰＥ公司造ＩＲ谱仪 ;ＣＤＳ2 0 0 0铂金丝裂解器 ,裂解室温度 2 5 0℃ ,裂解温度 6 0 0℃ ,升温速率 1 40℃ ｍｓ;ＨＰ6 890型 ,Ｃｏｍｐｏｎｄ…     

Isolation and Identification of Residual Chromophores in Cellulosic Materials

A general procedure was developed for the isolation of residual chromophores in or on cellulosic material, which were hitherto inaccessible to structure elucidation due to their extremely low content in the ppb concentration scale. It is applicable to cellulosic pulp, cellulosic fibers (viscose, Lyocell) and cellulose derivatives (acetate, carbonyl-labeled cellulose) as well. The chromophore identification comprises treatment of the cellulosic material with boron trifluoride – acetic acid complex (BF₃*2HOAc) containing sulfite, chromatographic separation of the resulting chromophore-containing mixture, and structure determination of the main constituents by NMR / MS and comparison to authentic samples. Both adsorbed and covalently bound aromatic and quinoid compounds are selectively released by the treatment. Covalent ester, ether and secondary alkyl links between chromophore and cellulose are broken. Two cellulosic example substrates have been analyzed for their chromophore content: Lyocell fibers and non-bleached viscose fibers, and up to eleven chromophores per sample have been identified.     

The Effect of Hydrotalcite and Zinc Oxide on Smoke Suppression of Commercial Rigid PVC

To reduce the smoke release of poly(vinyl chloride) (PVC) during burning, layered double hydroxides (LDHs) and zinc oxide (ZnO) powders were used to modify the polymer. The results indicated that the addition of LDHs‐ZnO had a significant effect on smoke suppression. The limiting oxygen index (LOI) reached a maximum value and the smoke density rank (SDR) exhibited a minimum value when the weight percentages of LDHs and ZnO in PVC were 3% and 2%, respectively. Thermal stabilities of the modified PVC and degradation products were investigated by means of thermogravimetry and pyrolysis‐gas chromatography‐mass spectra (Py‐GC‐MS). The LDHs‐ZnO obviously accelerated the decomposition of PVC to release hydrogen chloride, and the decomposed PVC consequently produced the trans‐conjugated polyene sequences, which easily formed crosslinked structures. However, a cyclization reaction in PVC chain without the additives produced aromatic compounds such as benzene, toluene, and naphthalene at 350°C. Even though, an amount of aromatic compounds was released from the PVC modified with LDHs‐ZnO at the temperature of 600°C, the content of the decomposed products is relatively lower compared to unmodified PVC.     

Contribution of Thermal Analysis For Characterization of Asphaltenes From Brazilian Crude Oil

The thermal decomposition of asphaltenes is mainly responsible for the formation of coke in petroleum processing. Phenomena involved are not clearly understood, because of the difficulties to characterize such heavy components. This paper reports the application of thermal analysis techniques to study the thermal behavior of asphaltenes from Brazilian oil. The approach involves kinetic studies of the thermal decomposition of asphaltenes under controlled conditions by thermogravimetry (TG), characterization of volatile fractions by thermogravimetry and differential thermal analysis coupled with gas chromatography/mass spectrometry (TG-DTA/GC/MS) and by gas chromatography/mass spectrometry (GC/MS) in the volatile recovered. The coke formed was also studied after being decomposed into smaller molecules using selective oxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

The influence of nanodisperse iron(III) oxide on the morphology of microsized alumina fibers

The influence of fine-disperse iron oxide particles on the structure of alumina fibers prepared via the template synthesis has been studied. The template (fibers of bleached cotton cellulose) has been impregnated with mixed aqueous dispersions of aluminum and iron(III) hydroxides prepared via the sol–gel route. Thermal treatment of the precursor has afforded alumina ceramic fibers with average diameter of 3–10 µm containing uniformly distributed iron(III) oxide nanoparticles at the surface. Increase of the iron(III) oxide nanoparticles concentration has deteriorated the texture properties of the product.     

聚亚苯基苯并二噻唑与聚亚苯基苯并二噁唑的热分解

用高分辨裂解气相色谱 质谱（ＨＲＰｙＧＣ ＭＳ）研究了聚亚苯基苯并二噻唑、聚亚苯基苯并二唑的热分解行为,鉴定了相应裂解产物的组成、分布及其与高分子结构的关系,并用热重法（ＴＧ）测定了它们的热分解反应动力学参数,提出了其热分解反应机理     

Study of ageing of ketone resins used as picture varnishes by pyrolysis–silylation–gas chromatography–mass spectrometry

This contribution presents a research aimed at the study of the commercial products Laropal K80, Keton N and MS2A, ascribed to ketone resins prepared as thin films, in an attempt to reproduce the pictorial layers and protective finishes that are commonplace in contemporary paintings. For this purpose, a new method based on “online” silylation–pyrolysis using hexamethyldisilazane as a derivatisation reagent in pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) has been proposed. This procedure leads to the unambiguous identification of such varnishes and improves direct Py–GC–MS. Chemical changes due to the degradation effect of environmental agents have been especially considered. To that end, three different accelerated ageing processes were applied to a series of specimens prepared from the studied commercial products: thermal, UV light and ageing in an SO₂-polluted chamber. Chemical changes due to UV light ageing of Keton N resin are in good agreement with those previously reported in the literature.     

Thermal decomposition of bisphenol A-based polyetherurethanes blown with pentane: Part I—Thermal and pyrolytical studies

In this work thermal decomposition of ethoxylated 2,2-bis-(4-hydroxyphenyl)propane (BPA) and oxyalkylenated 2,6-toluyldiamine (TDA)-based rigid polyurethane (PU) foam, blown with pentane, is described. Thermogravimetry coupled with mass spectrometry (TG–MS) and thermogravimetry coupled with Fourier transform infrared spectroscopy (TG–FTIR) results of the evolution of volatile products during the degradation and gas chromatography coupled with mass spectrometry analysis of condensed products of PU foam pyrolysis (Py/GC–MS) are presented. Four temperature ranges of volatile products emission were detected under inert atmosphere—pentane used as blowing agent volatilizes in first range, the second one is dominated by dissociation reaction of urethane bonds by which first order amines, CO₂ and vinyl bonds, are formed, while complex reactions with formation of secondary amine and CO₂ occur in the third stage. Fourth stage is visible by further CO₂ evolution. Ethylene oxide and derivatives of dioxane, formed due to the presence of oxyalkylene chains, act as fuel during the burning of PU foam.     

溴化环氧树脂印刷线路板热分解机理实验研究

印刷线路板广泛应用于电子电器产品中,随着大量电子废弃物的产生,印刷线路板的回收处理得到了广泛关注.