Acrylic acid Analytical method

Brandt [200] has extracted tri(nonylphenyl) phosphite (TNPP) from a styrene-butadiene polymer using iso-octane. Brown [211] has reported US extraction of acrylic acid monomer from polyacrylates. Ultrasonication was also shown to be a fast and efficient extraction method for organophosphate ester flame retardants and plasticisers [212]. Greenpeace [213] has recently reported the concentration of phthalate esters in 72 toys (mostly made in China) using shaking and sonication extraction methods. Extraction and analytical procedures were carefully quality controlled. QC procedures and acceptance criteria were based on USEPA method 606 for the analysis of phthalates in water samples [214]. Extraction efficiency was tested by spiking blank matrix and by standard addition to phthalate-containing samples. For removal of fatty acids from the surface of EVA pellets a lmin ultrasonic bath treatment in isopropanol is sufficient [215]. It has been noticed that the experimental ultrasonic extraction conditions are often ill defined and do not allow independent verification. 

Analysis for Poly(Ethylene Oxide). Another special analytical method takes advantage of the fact that poly (ethylene oxide) forms a water-insoluble association compound with poly (acrylic acid). This reaction can be used in the analysis of the concentration of poly(ethylene oxide) in a dilute aqueous solution. Freshly prepared poly (acrylic acid) is added to a solution of unknown poly(ethylene oxide) concentration. A precipitate forms, and its concentration can be measured turbidimetrically. Using appropriate calibration standards, the precipitate concentration can then be converted to concentration of poly(ethylene oxide). The optimum resin concentration in the unknown sample is 0.2—0.4 ppm. Therefore, it is necessary to dilute more concentrated solutions to this range before analysis (97). Low concentrations of poly(ethylene oxide) in water may also be determined by viscometry (98) or by complexation with KI3 and then titration with Na2S203 (99). 

There are two possibilities for converting polymer-bound 3-hydroxy-2-methylidene propionic acids into 2-diethoxy-phosphorylmethyl acrylic acids. One is the treatment of these substrates with diethyl chlorophosphite and Et3N followed by an Arbuzow rearrangement. The other method, which resulted in higher purities [28], is the reaction of acetylated 3-hydroxy-2-methylidene propionic acids with triethylphosphite in DMF for 5 h at 60°C (Fig. 6.12). Table 6.6 shows the variation of the aldehydes in this reaction. All compounds were analyzed by ES-MS and analytical HPLC. 

From an environmental point of view, a substantial decrease in CO2 emissions would follow the replacement of propylene with a propane feedstock, considering the overall process ca. five times higher in the propylene process than for propane). In this way, a recent study on the evaluation of the environmental impact by a systematic analytical method comparing the current commercial process from propylene with a hypothetical propane process (assuming in both a yield to acrylic acid close to 90%, currently obtained with the propene process) concluded that the propane process implied a decrease of 20% in the environmental impact of the industrial process. Moreover, a yield to acrylic acid higher than 61% was calculated to be enough for the propane process to be more enviromnentally benign. 

In order to obtain quantitative results by HS-GC, the system must be calibrated. Absolute quantitation is not possible. Quantification can be done by the conventional external calibration method with liquids containing the analytes concerned in known concentrations or by means of standard addition. Pausch et al. [958] have developed an internal standard method for solid headspace analysis of residuals in polymers in order to overcome the limitations of external standardisation cfr. Chp. 4.2.2 of ref. [213a]). Use of an internal standard works quite well, as shown in case of the determination of residual hydrocarbon solvent in poly(acrylic acid) using the solid HS-GC-FID approach [959]. In the comparison made by Lattimer et al. [959] the concentrations determined by solid HS-GC exceeded those from either solution GC or extraction UV methods. Solid HS-GC-FID allows sub-ppm detection. For quantitative analysis, both in equilibrium and non-equilibrium conditions, cfr. ref. [960]. Multiple headspace extraction (MHE) has the advantage that by extracting the whole amount of the analyte, any effect of the sample matrix is eliminated the technique is normally used only for method development and validation. 

Analytical A proc is described for the quant titrimetric analysis of TeNMe in nitric acid (Ref 35)s and a spectrophotometric method is described in Ref 41 for the detn of small amts of TeNMe in air and w Critical Diameter. The crit diam for deton propagation of TeNMe thickened with poly-(methyl acrylate) and loaded with up to 75% inert solids was detd and found to decrease with increasing solids loading. It was postulated that the solids acted as reaction foci ahead of the deton front (Ref 45)... 

Another successful example is the separation of a series of steroids listed in Fig. 6.11 using a monolithic capillary column prepared by redox initiated polymerization of a solution of acrylamide 4, methylene bisacrylamide 5, vinylsulfonic acid 12, and dodecyl acrylate 18 in N-methylformamide/TRIS-boric acid buffer (pH 8.2) to which polyethylene glycol) (MW 10,000) was added (overall composition 5% T, 60% C, 10% vinylsulfonic acid, 15% lauryl acrylate, 3% polyethylene glycol)). The capillary tube was first vinylized and its part beyond the detection window was coated with linear polyacrylamide to avoid band broadening. Since laser induced fluorescence was used to decrease the detection limit of the method to about 100 attomoles for neutral steroids, all of the analytes were first tagged with dansylhydrazine. Fig. 6.12 shows an... 

The free-radical copolymerization of acrylamide with three common cationic comonomers diallyldimethylammonium chloride, dimethyl-aminoethyl methacrylate, and dimethylaminoethyl acrylate, has been investigated. Polymerizations were carried out in solution and inverse microsuspension with azocyanovaleric acid, potassium persulfate, and azobisisobutyronitrile over the temperature range 45 to 60 C. The copolymer reactivity ratios were determined with the error-in-variables method by using residual monomer concentrations measured by high-performance liquid chromatography. This combination of estimation procedure and analytical technique has been found to be superior to any methods previously used for the estimation of reactivity ratios for cationic acrylamide copolymers. A preliminary kinetic investigation of inverse microsuspension copolymerization at high monomer concentrations is also discussed. 

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