Anal. Chem. 1983. 55. 8 7 R - 9 3 R (52G) Verma, K. K.; Gulati, A. K. Anal. Chem. 1980, 52, 2336, TECHNIQUES Chromatography (1H) Baker, John K.; Flfer, E. Kim J . Pharm. Sci. 1980, 69 (5), 590. (2H) Buegtr, A.; Pelnhardt, G. Pharmazle 1980, 35 (7), 443. (3H) Carteir, G. T.; Schlesswohl, R. E.; Burke, H.; Yang, R. J . Pharm. Scl. 1082, 77, (3), 317. (4H) Davydlov, V. Ya.; Oonzalez, M. E.; Klselev, A. V.; Lenda, K. Chromatographla 1981, 74 (l), 13. (5H) Eall, Robert A.; Mueller, Hannes; Tanner, Susanne fresenius' Z. Anal. Cheh. 1981. 305 (4), 267. (6H) Ellert, Udo; Ehmke, Adelheld; Wolters, Bruno Dtsch. Apoth .-Ztg. 1980,
-
120(3Q\ \--,. 1815 -
7H)-Ernl, F. J . Chromatogr. 1982, 257 (2), 141. 8H) Falrbrother, J. E. Pharm. J. 1980, 224, 352. 9H) Greig, D. G. T. Dev. Chromatogr. 1080, 2, 147. IOH) Hermansson, J. Chromatographla 1980, 73 (12), 741. 11H) Klng, Leslie A. J . Chromatogr. 1981, 208(1),113. 12H) Kllne, Berry J.: Solne, Wllllam H. Drum Pharm. Sci. 1981, 7 7 (Pharm. . Anal., pt. A), i. (13H) Krummen. K. J. Liq. Chromafogr. 1980, 3 (e), 1243. (14H) Kucera, Paul J. Chromatogr. 1980, 7919(2), 93. (ISH) Lindbergh, Walter; Johansson, Erik; Johansson, Kenneth J . Chroma toor. IgBI. 2 7 7 (21.201. ( 1 6 Lyman,'&ry W.' Johnson, ; Raymond N.; Kho, Boen T. J. Assoc. Off. Anal. Chem. 1981. 64 11). 177. (17H) Meakln, Glory; Allingion, Robert Am. Lab. (Fairfleld, Conn.) 1980, 72 (a), 65. (18H) Ng, L.lnda L. Anal. Chem. 1081, 53(7), 1142. (19H) Oelrich, E.; Preusch, H.; Wllhelm, E. HRC CC, J . Hlgh Resolut. Chromatogr. Chromatogr. Commun. 1080, 3 (6),269. (20H) Rabel, Fredrlc M. J . Assoc. Off. Anal. Chem. 1981, 64 (5). 1258. (21H) Roggla, S.;Gallo, G. G. Anal. Chem. Symp. Ser. 1980, 3 (Recent Dev. Chromatogr. Electrophor.), 47. (22H) Sternson, Larry A. Chem. Derlv. Anal. Chem. 1981. 7, 127. (23H) Stulik, Karel; Pacakova, Ver J . Chromatogr. 1980, 192 (l), 135. (24H) Subert, J. Cesk. Farm. 1980, 29 (6),212. (25H) Traveset, J.; Such, V.; Gonzalo, R.; Gelpl, E. J . Chromafogr. 1981, 204, 51. (26H) Vlnk, Jan; Van Hal, Henk J. M.; Koppens, Paul C. J. M. Adv. Mass Specfron?. 1980, 8B, 1251. (27H) Wollmann, H.; Patrunky, M. Pharmazle 1981, 313(7), 453. (28H) Zhou, L.; Poole, C. F.; Trlsca, J.; Zlatkls, A. HRC CC, J . H/ghResolut. Chromatogr. Chromatogr. Commun. 1080, 3 (9), 440.
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Spectroscopy (29H) Arnaud, P.; Metayer, C.; Le Gall, N. Labo-Pharma-Probl. Tech. 1980, 28 (298), 380. (30H) Bailev, Glen F.: Moore. Herbert A.. Jr. J . Parenter. Drua. Assoc. 1980, 34 (2), 127. (31H) Elsayed, M. Abdel-Hady; Elsayed, Yousry M.; Abdlne, Hassan Anakst (London) 1980, 705 (1248), 222.(32H) Falrbrother, John E. Pharm. J. 1979, 223 (6053), 651. (33H) Guebitz, G.; Wlntersteiger, R.; Hartinger, A. J . Chromafogr. 1981, 278. 51. (34H) Hellbnrg, Hans; Holmqulst, Per; Vallen. Staffan Acta Pharm. Suec. 1981, 78 (5), 315, (35H) Moss, W. Wayne; Posey, F. T.; Peterson, P. C. J. Forensic Sci. 1980, 25 (2), 304. Electrochemlcal Analysls (36H) Alary, J.; Cantin, D. Labo-fharma-Probl. Tech. 1979, 2 7 (293), 937. (37H) Davldson, Ian E.; Smyth, W. Franklln Anal. Chem. 1979, 51 (13), 2127.
(38H) Jacobsen, E. Anal. Chem. Symp. Ser. 1980, 2 (electroanal. tiyg., Environ., Clin. Pharm. Chem.), 227. (39H) Messner, Janet l..; Engstrom, Royce C. Anal. Chem. 1981, 53 (l), 128. (40H) Patriarche, 0. J.; Chateau-Gosselln, M.; Vandenbalck, J. L.; Zurnan, Petr Electroanel. Chem. 1979, f l , 141. 141H) Punaor. E.: Feher, 2.: Naav. ' -. 0.: Llndner, E.: Toth. K. Anal. Proc. b n don), 1582, 79 (2), 79. (42H) Schaar, Jerome Charles Diss. Abstr. Int. 6 . 1981, 42 (5),1877. (43H) Sharma, L. R.; Bnnsal, P. C.; Kalla, R. K.; Manchanda, A. K. Analyst (London) 1980, 105 (1253), 779. (44H) Smyth, W. Franklin; Ivaska, A.; Burmlcz, J. S.; Davidson, I. E., Vaneesorn, Y. Bloelectrochem. Bloenerg. 1981, 8 (4), 459. (45H) Vlre, 3. C.; Chateau-Gosselln, M.; Patrlarche, G. J. Mikrochlm. Acta 1981, I (3-4), 227. Thermal Analysis (46H) Gustln, Grant M. Thermochlm. Acta 1980, 39 (2), 81. (47H) Radeckl, A.; Wesolowski, M. J . Therm. Anal. 1979, 77(1), 73. (48H) Wesolowski, Marak Mlcrochem. J. 1981, 26 (l),105. Mlscellaneous (49H) Beaublen, L. J.; Vanderwielen, A. J. J . Pharm. Sci. 1980, 69(6), €61. (50H) Cantwell, Frederick F.; Murray, Carmlchael Anal. Chem. 1982, 54 (4), 697. (51H) Castellano, Thomas; Medwick, Thomas; Shlnkal, John H.; Bailey, Leonard J . Pharm. Sci. 1981, 70 (I), 104. (52H) Chaplin, H.; Hoffmann, N. L. Transfusion (fhiladelphla) 1982, 22 (l), 6. MISCELLANEOUS (11) Fed. Reglst. 1981, 46 (79) (24 Apr), 23224. (21) Arbin, A.; Ostelius J . Chromatogr. 1980, 793 (3), 405. (31) Bontinck, A. M.; Herbots, H.; Klnget, R. Acta. fharm. Technol. 1980, 26 (2), 117. (41) Boudreau, C. F.; Harrison, D.J. Drug Dev. I n d . Pharm. 1980, 6 (6), 539. (51) Cloux, J. L.; Laplere, C. L.; Bonnard J.; Bosly, J. J . Pharm. Belg. 1982, 37 (I), 27. (81) Dlprose, K. V.; Epsteln, H. 0.;Redman, L. R. Br. J . Anaesth. 1980, 52 (11). 1155. (71) Dokladalova, J.; Barton, A. Y.; Mackenzie, E. A. J. Assoc. Off. Anal. Chem. 1980, 63 (3), 864. (81) Eiden, F.; Tittel, C. Dtsch. Apoth-Ztg. 1981, 7 2 7 (g), 431. (91) Fell, A. F.; Allan, J. Q.Anal. Proc. (London) 1981, 78(7), 291. (101) Gonnet, C.; Marichy, M. Anal. Chem. Symp. Ser. 1980, 3 (reoent Dev. Chromatogr. Electrophor.), 11. (111) Jaques, B. Pharm. J . 1981, 227(6140), 261. (121) Mablleau, N. Scl. Tech. Pharm. 1981, 70 (5), 195. (131) Mascoll, C. C.; Weary, M. E. frog. Ciin. Biol. Res. 1979, 29 (Biomod, Appl. Horseshoe Crab [Limulidae]), 387. (141) Mattson, L. N.; Gaebler, R. N.; Biebe, K. E.; Peppers, R. E. J . Parenbw, Drug Assoc. 1080, 34 (6),436. (151) Moren, F.; Jacobsson, S. E. Int. J . fharm. 1080, 5(4), 287. (161) Novitsky, T. J.; Ryther, S.S.; Case, M. J.; Watson, S. W. J . Parenter. Sci. Technol. 1082, 36 (l), 11. (171) Rudischer, S.;Bauer, H. J. Pharmazie 1981, 36 (7), 477. (181) Sampson, E. J.; Culbreth, P. H. Clin. Chem. (Winston-Salem, N . C . ) 1981, 27 (lo), 1773. (191) Stahl, E.; Tugrul, L. Dtsch. A p o t h J t g . 1981. 727 (27), 1409. (201) Van de Vaart, F. J. Pharm. Weekbl. 1981, 176(36), 1098. (211) Van de Vaart, F. J.; Hulshoff, A.; Indemans, A. W. M. fharm. WeekiW. 1980, 775 (44), 1429. (221) Waaler, T.; Gundersen, H.; Kvaleid, I.; Torud, Y.; Muller, H.; Hasler, C. Pharm. Acta Helv. 1080, 55 (7-8), 203. (231) Wesolowski, M. Mlkrochim. Acta 1980, 7 (3-4), 199.
Rubber Anoop Krlshen Fiber & Polymer R&D Division, The Goodyear Tire & Rubber Company,' Akron, Ohio 443 16
This review covers methods for the identification, characterization, and determination of rubber and materials in rubber. Literature which became available to the author between November 1980, the end of the period covered by the last Contribution No. 632 from T h e Goodyear T i r e Research Laboratory, Akron, OH 44316.
& Rubber CO.,
review in the series (94), and November 1982 is reviewed. Abbreviations recommended in ANSI/ASTM Designation D1418-81 have been used (2). These are listed in Table [.
GENERAL INFORMATION The American Society for Testing and Materials published the annual edition of test methods for rubber (2). The work of the International Technical Committee TC/45, which deals
0003-2700/83/0355-87R$01.50~0 0 1983 Amsrlcan Chemical Society
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RUBBER
Table I. Abbreviations Recommended by ASTM ( 2 ) EP DM terpolymer of ethylene, propylene, and a diene with the residual unsaturated portion of the diene in the side chain BR butadiene rubber CR chloroprene rubber IIR isobutene-isoprene rubber IR isoprene synthetic rubber NBR nitrile-butadiene rubber NR natural rubber SBR styrene-butadiene rubber with the standardization of rubber and rubber products, was the subject of a review (70). The International Organization for Standardization issued International Standard 5478-1980 for determination of styrene content by nitration (81)while DIN 53747 for the analysis of polystyrene and styrene copolymers was issued by Deutscher Normenausschuss (43). Reviews dealing with (i) chromatographic tecniques for analysis of rubber (951,(ii) as chromatographic applications to analysis of rubber ( l o g ) , Eii) analysis of rubber and plastics chemicals by liquid chromatography/spectroscopy (135),(iv) application of radiothermoluminescence methods to the analysis of polymers and polymer composites (127),(v) recent developmentsin pyrolysis gas chromatographyfor application to analysis of rubber ( 1 8 3 , (vi) separation techniques for polymers (62),(vii) physiochemical characterization of composites and raw materials (137), (viii) recent developments in test procedures for natural and synthetic latexes (23),(ix) morphological and structural characterization of ultra-oriented polymers (24),(x) chemical methods in polymer physics (134), (xi) analysis of high polymers (34), (xii) spectroscopic and chromatographicdata required for the identification of fillers, pigments, antioxidants, UV stabilizers, flame retardants, accelerators, and blowing agents (154),(xiii) physicochemical methods of analysis of rubber used to monitor the production of synthetic rubbers (12), (xiv) development of polymer characterization from the time-averaged to time-developed molecular transport properties (129), (xv) use of thermal analysis, liquid and gas chromatography,dynamic mechanical analysis, IR spectroscopy, and advanced rheological measurements in quality control (5),and (xvi) analysis in rubber technology (156) were published during the period under review.
POLYMER IDENTIFICATION A thin-layer chromatographicmethod was described for the identification of natural polyisoprene and synthetic polyisoprene in model compounds and in uncompounded gum stocks (142). FuUy deuterated polystyrene (PS)and standard PS samples were found to be separable by phase separation thin-layer chromatography and adsorption thin-layer chromatography (176). Gradient adsorption thin-layer chromatography was used to detect inhomogeneity in polymers (53) and the use of TLC was examined for P S and styrene copolymers (56). The potential of pyrolysis gas chromatography was investigated, and innovative techniques for processing and interpreting chromatographic patterns to enhance the information displayed in pyrograms were discussed (122). Applications of pyrolysis gas chromatographyin polymer identification were discussed along with comparison of different types of pyrolyzers (20). Some aspects of the pyrolysis method for rubbers were discussed to bring out the utility of the molecular thermometer concept as a standardization method (108). A discussion on the use of an adaptation of pyrolysis gas chromatography for the rapid identification of NR, CR, and NBR was presented (79). This technique was used to evaluate the degree of cross-linking in chloromethylated postcured PSdivinylbenzene (138). Pyrolysis glass capillary gas chromatography was described for microstructural characterization of copolymers (182). High-resolution pyrolysis hydrogenation glass capillary chromatography was used to determine the stereoregularity and the degree of chemical inversion for monomer units along polymer chains of polypropylene (167). Diad sequence distribution in styrene copolymers was determined by pyrolysis 88R
ANALYTICAL CHEMISTRY, VOL. 55,
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gas chromatography by analyzing the dimer and codimer fractions (96). Light beam and Curie point pyrolysis gas chromatography (PGC) were found to be useful for characterization of crosslinked PBD containing fillers (64). This technique was suitable for both sulfur cross-linked PBD and diisocyanate cross-linked hydroxylated PBD (60). Head to head and head to tail PS were characterized by using pyrolysis gas chromatography with a high-resolution glass capillary column (166). Peak assignment was carried out by combining PGC mass spectrometry retentiorr data for the products and pyrolysis hydrogenation gas chromatographic results. Microstructural characterization of various copolymers was obtained by the use of pyrolysis glass capillary chromatography (183). Applications of pyrolysis gas chromatography to the analysis of NBR, SBR, CR, and IR were presented (190). Results were presented of a pyrolysis gas chromatographic investigation of the effect of sample weight, microstructure, and temperature of pyrolysis on the relative concentrations of the various pyrolyzates from cis-l,CPBD, trans-1,4-PBD, and 1,2-PBD (140).
By use of pyrolysis as chromatography with a Curie point pyrolyzer, it was founcfthat the blended ratio of a vulcanizate containing two kinds of rubber-blends of SBR with PBD, NBR, or NR-could be determined with a precision of f 3 % . In the case of ternary blends-SBR, PBD, NR-the precision was k5% (74). A study was made of the pyrolysis conditions to establish a satisfactory analysis method for vulcanized rubbers. Precise control of the pyrolysis temperature was found to be most critical for obtaining reproducible data. Three pyrolyzers commercially available in Japan were compared for this purpose (75). Pyrolysis GC equipment and methods were described for the microstructural characterization of polyolefins including EPDM (184). Pyrolysis of cis-1,4-IR was examined with respect to volume, temperature, and temperature rise of the probes when coupled with a GC mass spectrometer. Pye Unicam and Varian CDS pyrolyzers were used in this study (126). A 13CNMR method was described for the rapid quantitative determination of the rubber content in guayule bushes (186). This method permits 0.3- pieces from selected portions of the bush to be analyzed i o t h before and after solvent extraction, The 13CNMR relaxation time ( T I )in natural rubber latex was used for determining the rubber content from the integrated intensities without gated decoupling or paramagnetic relaxation agents (3). The structure of IIR copolymers was investigated by IH and 13C NMR spectroscopy (36). Monomer unit sequence distribution was determined by proton decoupled I3C NMR spectroscopy in partially epoxidized cis-l,l-PBD (68) and in partially epoxidized trans-1,4-IR (69). NR and IR blends were characterized by differential scanning calorimetry at 400-500 K. In oxygen atmosphere IR was characterized by a broad and shallow oxidation exotherm with a peak at 440 K while NR showed a sharp oxidation exotherm at 494 K. The blend showed a single oxidation exotherm positioned between 440 and 494 K depending on the composition. Addition of small amounts of NR to IR produced a significant effect on the shape and position of the oxidation exotherm,while the DSC curve of the NR-IR blends was essentially the same as that of NR except that the exotherm appeared at a slightly lower temperature. IR was also characterized by a lower oxidation exotherm peak temperature, activation energy of oxidation, and heat of oxidation as compared with N R presumably due to lower oxidative stability of IR. The parameters were increased to higher values by blending NR into IR (57, 58). DTA, TG, and related techniques were used in research on morphology of polymers, in determination of first- and second-order transition points, and in analysis to identify polymers (114). The use of thermogravimetry in conjunction with microprocessors and electronic storage systems in the qualitative analysis of the main components of rubber blends was discussed (191). The blends studied were NR/EPDM, NR/SBR, and NR/BR. Analysis of cured compounds by thermogravimetry was investigated for (i) the comparison of TGA results with formulas as mixed and also as analyzed by
RUBBER
me
AmOp K h k . n received Ph.D. degree horn me Unkarsny of Pmabugh and mS M.Sc. (Honours School) and the B.Sc. (Hoc-
School) W r e e s horn me Unkarsny of Punlab. He her been wlth me Research DC vlsion of the Godyear Tire and Rubber Company In Akron. OH, slnnce 1963. where he is a Senkx Research Chemlpt In the Sep aratms and Idenlincatbns Section of the Analytical Sclence and Technoloay Department. Hls publications cover the areas of GPC. GC. pyrolysis-Gc. and Sotvent extramn. He 15 a membet of the American Chernlcal Sociev and its Analflical and Rubber Dkisbns. OUIS
.
(refractometer/viscometer) when calculating average molecular weights. Particular attention was paid to axial dispersion in columns, dependence of elution volumes on solution concentration, and application of the hydrodynamic volume concept (107). Short and long term-up to 3 years-reproducibility was studied on PS and polyethylene (PE) standards of different molecular weights in two instruments-one with trichlorobenzene 88 solvent at 130 'C and the other with THF at room temperature (149). Operational Parameters and Corrections. Some of the sources of error in determination of molecular weight distributions hy GPC were examined and methods for increasing precision, particularly between laboratories were considered (172).
ASTM D-297 on a series of different compounds, (ii) identification of type of polymers present and pceaibly their ratio, and (iii) identification of c a r h n hlack type in hoth NR and SBR cured stocks (147).
GEL PERMEATION AND SIZE EXCLUSION CHROMATOGRAPHY (GPC-SEC) Recent advances in GPC were reviewed, the major areas covered being data acquisition and processing, high-pressure chromatography, and detectors (131). A hrief discussion on GPC included a mathematical description of the separation process. and a highly efficient experimental layout which enahled GPC data to he evaluated without computing machinery (164). A real-time computer system WBS applied to reduce the total analysis time in GPC by automatically acquiring the data, performing the necessary calculations, and displaying molecular weight distributions and molecular weight averages for linear homopolymers. An auxiliary program run in parallel was used for on-line parameter changes ( 1 18). Methods of measuring average molecular masjw. molar mas9 distrihutions, and miscellaneous methods for characterization of synthetic polymers were reviewed (151. Data handling in GPC for routine operatims was described (221. Calibration. For PS and poly(ethy1ene oxide) (PEO) it was shown that for molecular weights up to 2000, linear calibration dependencies could be plotted for retention volume VI. molerulnr weight without using standard samples. Absolute molecular weights were calculated hy taking into acmum instrument broadening and the dependene of refractive index on molecular weight ( 9 9 ) . A GI'C study of the molecular indices of solution-polymerieed I S H I ) was reported (91 ). Simple, single-valued equations were d e v e l o d for iterative evaluation of calibration parnmetem of both direct and universal calibration relationships by application of the formalism of averaged elution vulumes curresponding to average molecular weights or intrinsic visrosities of polydisperse standards. These evaluation procedures are claimed to be simpler and to converge faster than other corresponding methods (170). Kvaluation of a trial and error GPC ralihration method which assumes a polynomial mathematical model for true calihration relationship hetween log molecular weight and retention vdume was presented 1171). A method was developed to measure hydrodvnamic dimensions directly at finite concentrations hy differential GPC ( 1 1 ) . A process was described for broad-standard calibration of GPC without interference by column dispersion. Potential applications for nonlinear calibration curves were discussed ,"~~
~~~~~~~~~~
1/11.
A method involving a combination of GPC and intrinsic viscosity measurements was used to determine Mark-Houwink-Sakurada constants. The method requires that the samples should differ in molecular weight hy as large a margin as possible and that their chromatograms should exhibit Gaussian or near-Gaussian distribution (193). A GPC calibration procedure based on the Benoit universal calibration dependence was developed (173). A rapid method w a proposed ~ for determining molecular weight and molecular weight distribution utilizing the GPC data and universal calibration. The molecular weight determined was close to the M, (168). An examination was made of some problems which can lead to incorrect values in GPC with dual detection
The feasibility of utilizing two gel permeation chromatographs coupled together to effect a type of cross-fractionation before detection by dual UV detectors was investigated (7). Two methods for developing GPC calibration parameters for any polymer were described and compared for PS, BR, poly(methy1methacrylate) (PMMA), and poly(viny1chloride) (PVC) (27). Various theories on the concentration effects in GPC were outlined (85). Plate height data for GPC separations of PS with macroporous silica microspheres were reported. The chromatographic broadening term arising from mass transfer in the stationary phase was evaluated (39). The molecular weight averages were calculated and these were used in the Fox-Flory relationship to calculate number-average and z-average dimensions (8). Changes were noted in the elution volume of some polymers by adsorption onto porous glass columns (124). Viscosities of solutions of IR having narrow molecular weight distributions in toluene were measured in the concentration range of 0.04-0.20 g mL It was found that when and molecular wei ht (M) the product of concentration was less than lo' the relative viscosity varied as C1.s;M and above lo' it varied as C'MJ" (136). Correlation between the average network size with the maximum size of the polymer molecule which can permeate the gels was attempted (73).It was shown that concentration effects in solutions of moderately high molecular weight polymers can substantially alter the apparent molecular weight distribution calculated from GPC traces (47). When the peak spreading is a delta function, a unique and stable solution to Tung's equation for correction of experimental chromatograms was obtained (192). Two methods for correcting instrumental spreading in GPC were presented (143). The reliability of the method for determining spreading factor in Tung's integral equation was verified on model chromatograms and tested experimentally (188). Solvent dependence of GPC retention of low molecular weight compounds on PS-DVB gels was studied by use of benzene, toluene, chlorobenzene,o-dichlorobenzeneand THF as solvents (148). Applications. Long chain branching of polymer chains was determined by GPC (15). Low molecular weight materials were isolated hy extraction and these were then fractionated on a combination of steric exclusion columns (55). A novel technique was described to determine the composition of two-component resin hlends using GPC in conjunction with an iterative curve-fitting computer program (46). Determination of cyclic dimers and other low molecular weight compounds in polymers was reported (21). The use of chromatographic methods in monitoring the molecular weight and functional distribution of synthetic rubbers was discussed (158). The results of a study on the compatibility of PS/PBD/ tetralin systems using a GPC technique and a modified turbidimetric titration technique were compared (111). The pore properties of microporoua styrene-divinylbenzene copolymer gels were investigated by inverse GPC (51). Fractionation by GPC of PS oligomers with propyl end groups was described (151).
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ANALYTICAL CHEMISTRY, VOL. 55. NO. 5. APRIL 1983
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Some examples of the use of GPC to study polymer related problems were presented. These included defective powder coatings, selection of appropriate adhesives, fabricating a composite, injection molding problems, evaluation of P E additives, and quality control of an epoxy laminate printed circuit board (49). The use of high-performance GPC with column packings of pstyragel for the analysis of oligomers and polymers in environmental1 acceptable powder coatings, high solids coatings. water gorne.coatings, - . and UV curable coatings - was discussed (98). The effect of the polymerization conditions on the molecular characteristics of IR was studied bv GPC (13). A method that uses a combination bf GPC and radioisotopic labeling was proposed for investigation of ionic polymerization mechanisms (174). The de ree of graftin of PS onto PBD was determined by selective 6iissolution and the molecular weight and molecular weight distribution of homopolystyrene were measured by GPC (48). Centrifu ation and chromatogra hic techniques were described to 6ietermine particle size Jstribution in NR, SBR, Hevea, and guayule latexes (159). Results were presented of measurements of microgel in uncured EPDM and EPM carried out by using GPC combined with on-line small angle laser light scattering (LALLS) or dynamic mechanical techniques (155). An analysis was made of the branching characteristics of Hevea fractions of different molecular weight obtained from the soluble fractions of rubber coagulated from freshly tapped latex (4). A report was presented on the use of molecular weight distribution measurements carried out on a high-temperature GPC to follow the aging of cable insulation for underground service (287). Problems associated with the characterization by SEC of complex polymers were considered (63). The examination of the molecular weight distribution of eDoxv resins by GPC was discussed (100). -GPC was used td examine the effect of grafting styrene-acrylonitrile (SAN) onto ethylenepropylene (EP) polymer (41). GPC data were utilized for elucidation of polymer degradation kinetics (1). A “mixed solution exclusion” method for the porous structure analysis of gel substances was described (97). Separations of PS standards by GPC were performed with columns containing silica microspheres having a particle diameter of 8 bm (40).
LIGHT SCATTERING A review of recent developments in classical light scattering in polymer solutions included (i) light scattering photometers, (ii) characterization of important polymers, (iii) combination of light scattering with other methods, (iv) characterization of the degree of branching, (v) particle shape, (vi) microgels, (vii) aggregates, (viii) copolymers, (ix) polyelectrolytes, (x) DNA, (xi) thermodynamics of concentrated solutions, (xii) solutions of polymer mixtures, (xiii) kinetic measurements, and (xiv) depolarization of scattered light (93). Monte Carlo techniques were used to study chain statistics in dilute solution and to probe the properties of short sequences within a polymer chain of 300 units. Structure factor was obtained from these calculations. Dilute solutions of PS in cyclopentane were studied by low-angle X-ray scattering as a function of temperature (152). Small angle X-ray scattering as a function of molecular weight was utilized to measure sizes of microdomain structures in a series of A-B type styrene-isoprene block copolymers (65). Results of X-ray diffraction, bifringence, and scattered light depolarization of lyoprotic mesomorphous systems of diblock butadiene-styrene and isoprene-a-methylstyrene copolymers were presented (187). PS samdes with molecular mass of the order of lo’ where characterfzed by light scattering in toluene, viscometry in toluene and decalin, and GPC in MEK-methanol mixtures (165).
Polymer samples were characterized by an instrument developed for measuring pulse-induced critical scattering intensities. PS solutions in cyclohexane were studied to demonstrate the sensitivity of spinodal curves and cloud point curves (52). 90R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
An apparatus was described for high-speed measurements of small angle X-ray scattering (SAXS). This apparatus uses a 12-kW rotating anode X-ray generator, a linear position sensitive proportional counter, and a two-parameter multichannel pulse height analyzer with 12K memory area for SAXS intensity data as function of position and time scale. Results of studies on phase separation in styrene-isoprene block polymers and on kinetics of crystallization of PBD were given (67). The effect of transforming phase separated block copolymers or polymer blends into homogeneous mixtures by a sudden temperature increase on changes in X-ray, light, and neutron elastic scattering intensity distributions with time was studied (66). Variable contrast small angle neutron scattering was used to study the molecular conformation of styrene-isoprene block copolymers in dilute solutions (82).
MISCELLANEOUS TECHNIQUES Thermal analysis in the rubber industry was the subject of a number of reviews (17, 18, 130). The efficiency of antioxidants in rubbers-guayule, Hevea, IR, PBD, and SBR-was evaluated by DSC analysis (59). The use of various thermal techniques, e.g., DSC, TGA, TMA, and DTA, for production and quality control as well as material property characterization was discussed (116). A study was made of the glass transition behavior of two sets of PS/IR triblock polymers and it was found that in some case three Tis were present (120). Developments in thermal analysis were discussed with particular reference to microprocessor-controlled analyzers (25).
The thermodynamic interaction parameters for blends of cis- and trans-polyisoprenes were examined by thermal analysis and by analysis of the melting point depression curves (32).
An investigation of styrene-isoprene block copolymers by means of pyrolysis GC and TGA revealed that the microstructure influence the thermal behavior (153). DSC was used to determine the enthalpy changes accompanying the thermal homolysis and subsequent radical reactions (19). Data were given for the geometric and physical free volumes which are indices for the looseness of packing and for the intensity of thermal oscillation of the molecule, for filled and unfilled vulcanizates (133). The principles involved in the determination of Tgand melting temperatures by gas chromatography were discussed (106). Thermally decomposed and undecomposed polymers were studied by means of GPC for molecular weight distribution and by DSC for changes in the polymer T (113). Calorimetry was used to study the effects of mechanical stress and deformation on chemical reactions occurring during oxidation (16). The kinetics of thermal oxidation of auavule rubber both with and without antioxidants were dkermined from the infrared spectra (CO and OH bands) ‘(26). Applications of computerized NMR and IR techniques to rubber analyses were described (76). Techniques such as IR, lH NMR spectroscopy, and viscosity measurements were used to study the properties of SBR latexes (37). The dispersion homogeneity of a filler in an elastomer composition was determined by an NMR test method (190). A deconvolution approach to the analysis of NMR relaxation decay functions was evaluated. The Roesler approach was found to be important for processing the NMR decay data
i
(33).
Pulsed NMR techniques were utilized in the evaluation of radiation effects in polymers (28). Pulsed NMR results were presented for a very high molecular weight polydisperse Natsyn 2200, a gel prepared from this polymer and two mono disperse samples of molecular weight 7200 and 80 000 (29). The direct I3C NMR method for measuring long chain branching was compared with the indirect intrinsic viscosity-universal calibration methods (50). Pulsed NMR was used to measure the spin-spin relaxation for NR and NRlcis-polyisopreneblend vulcanizates time (Tz) (128).
NMR analysis of stereoregular vinyl polymers was described (64).
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HPLC and 13C NMR were used to study the chemical composition and molecular configuration of PS oligomers (45). Simulated model bonding studies were conducted by using column chromatography, NMR, and IR spectroscopy (6). Deuterium NMR was used to investigate molecular orientation within swollen rubber networks under simple uniaxial tension (42). Changes occurring in PS on thermal degradation were analyzed by GPC, reverse-phase LC and gas chromatography (38).
IR spectroscopy was used to follow thermoxidative degradation of various PBD's (84). Inverse gas chromatography was used to investigate solubility parameters of CR, PBD, and nitrile rubber (110). Applications of gas chromatography for the analysis of solvents, water content, plasticizers, and monomers were discussed (9). The use of pyrolysis gas chromatography/mass spectrometry was described (119). The polymer surface structure of PEO-PS blends was investigated by inverse gas chromatography and scanning electron microscopy (169). This technique was also used for characterizing cross-linked PBD (61). A quality control method using pyrolysis-mass spectrometry was described for rapid characterization of polymers (31). A combined pyrolysis-gas chromatography-SEC method was described for determining copolymer composition (86). Cross-link density of vulcanized IR was determined by pyrolysis-GC-MS (123). The method and equipment for pyrolysis-IR of polymers were described (112). Characterizationof copolymers by TLC, GPC, and light scattering was reported (80). A method was described and results were presented for determination of long and short chain sequences in SBR by ozonolysis-GPC ( I 77). Application of chemiluminescence to the characterization of olymeric materials was reported (125). Wpplication of Fourier transform infrared spectroscopy for analysis of microtomed, sulfur-cured, carbon black reinforced sam les of SBR was reported (44). This technique was also usefto follow the reversion process during vulcanization of NR (30). The surfaces of PBD and SBR subjected to different degrees of abrasion were studied by SEM (14). The results of SEM, energy dispersive X-ray analysis, transmission electron microscopy, and optical microsco y on worn tire tread surfaces and tread rubber debris were Ascribed (163). ESR was used to monitor and quantitate the stability of oxygenated and hydrocarbon radicals formed during and after tensile deformation (117). The adhesion of smooth surfaced rubber rolling and sliding on polisheid ice was investigated by an optical study of the contact interface (141). A diffusion cell was developed for determining the coefficients of vapor and liquid transfer through polymer f i s using gas Chromatography (88). Molecular characteristics of polyisobutylene were determined by IX combined with a double bond analyzer (139).
EXTRACTION Thiol antioxidants and stabilizers were found to react chemically with acrylonitrile-butadiene-styrene polymer (ABS) in substantial amounts when subjected to high temperatures and high shear during processing. These materials showed a high resistance to removal by solvent extraction (54).
CUR1:NG AGENTS AND AGE RESISTERS Recent work undertaken at RAPRA was described. It examined the capabilities and limitations of HPLC for the analysis of plasticizers, antioxidants, cross-linking agents, isocyanates, and polycyclic aromatic hydrocarbons (160). Analysis of antioxidants by LC was described and applications of this technique along with analysis conditions were summarized (189). TLC and LC techniques were utilized to determine changes in the composition of amine AO's during thermal oxidation, photooxidation, and ozonation (144). The mechanism of amine AO's in rubber was studied in model compounds by extraction with acetone and analysis by
TLC with 95:5:0.1 C6H6:acetone:NH,0H or 50:60:0.1 ligroin:diethyl ether:triethylamine (145). Reverse-phase chromatography and LC with macroporous gel sorbent Separon SE (a 1:l styreneethylene dimethacrylate copolymer) was used to characterize the retention behavior and to determine several commercial antioxidants in NR and PS (162). Determination of o-nitrophenol, tert-butylpyrocatechol, and wood resin derived inhibitors in is0 rene was carried out by treating isoprene with ethanolic K 8 H followed by photocolorimetric analysis of the colored phenoxides (101). Polar groups in IR vulcanized with sulfur and accelerators were determined by the frequency dependence of dielectric absorption. Their concentration was directly proportional to the logarithm of the tangent to the dielectric loss angle for MBT derived systems and it was proportional to the area under the absorption curve for TMTD based systems (78). Santoflex IP and PBNA were determined in NR, SBR, PBD, SMR20, and IR by reverse-phase chromatography on Separon SE (161). N,N'-Diphenyl-p-phenylenediamine and the products formed from it on atmospheric aging were studied by TIL! and LC. The color reactions of the individual compounds with sulfuric acid and with aqueous ammonia were also examined (146).
ADDITIVES AND MONOMERS Maleic anhydride a t less than 1% levels was determinled in maleated IR by infrared spectroscopy of CS2solutions by the 1781.5-cm-l peak (179, 180). An equation was derived for calculating the free soiap content in SBR latex from the amount of soap dialyzing over two different intervals (103). TLC was described for estimating small amounts of chlorine in copolymers of l-chloro-1,3-butadiene and styrene (92). Several phenolic resins were analyzed by using field desorption MS, LC, and ATR infrared spectroscopy (104). The concentration of resorcinol-urotropine complex was determined thermogravimetrically at 90-110 "C (115). An automated turbidimetric method for the determination of sulfur was found to be comparable to the colorimetric method using potassium chromate (102). The compounding ingredients blooming out on the surface of rubber vulcanizates were extracted with acetone, chlorloform. or toluene for 5 s and then identified bv comtmtcsr assisted MS (185). Pyrolysis at 220 "C for 20 s followed by GC on a columln of 15% poly(ethy1ene glycol) on Celite 545 at 100 "C was used to determine styrene down to 1ppm levels in SBR latex (175;). A GC/MS system which uses electron impact and a auadruDole mass filter were described for the analvsis of residual trace organics in raw and vulcanized SBR (PO).
ANALYSIS RELATED TO SAFETY AND HEALTH Adsorption on activated charcoal, extraction of the charcoal with heptane, and GC were used to determine styrene in air (35). A method was detailed for quantitation of polymer bound p-nitrosodiphenylamine in chloroform solution of modified diene rubber (89). N-Nitrosodialkylamines were quantitated in cured CR, EPDM, and NR by water extraction (83). Quantitation of N-nitrosoamines in amines was accomplished directly with a combination of GC and a thermal energy analyzer (132). Various Chromosorbs and Tenax-GC were compared for use as adsorbents of volatile odorous compounds in air (101. Toluene was found to be better than benzene for the extraction of polycyclic aromatic hydrocarbons from rubber-grade oil furnace blacks (178). Gas chromatographic methods for the determination of acetylene and butadiene in wastewater were presented (157). The toxicity of gas evolved on heating PS and SBR from 200 to 800 "C was examined (71). Carbon monoxide evolved 011 thermal degradation of PE, ABS, PS copolymers, PVC, polycarbonates, and polyamides was quantitated by GC on i% molecular sieve column (121, 72). Normal-phase HPLC with UV detection and reverse-phase HPLC with polarographic detection were used to detect ethylenethiourea and related compounds in the urine of rats fed ethylenethiourea (105). ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
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ACKNOWLEDGMENT The permission of The Goodyear Tire & Rubber Company to prepare and publish this review is greatly appreciated. LITERATURE CITED (1) Abbas, K. B. Llquid Chromatography of Polymers and Related Materials. 4th InternationalLiquid Chromatography Symposlum, Strassbourg, 1979, (2) American Society for Testlng and Materials “1982 Annual Book of ASTM Standards, Parts 37 and 38”; ASTM: Phlladelphla, PA, 1982. (3) Ang, T. T.; Roberts, J. D. Rest. Rubber Mater. Appl. 4, 138-139 (1979). (4) . . Anaulo-Sanchez. J. L.: Caballero-Mata, P. Rubb. Chem. Technol. 54, 34-41 (1981). (5) “Anonymous”, flasf. Technol. 27, 75-80 (1981). (8) Ashida, M.; Oono, S.; Kan, S. Nlppon Gomu Kyokaishl, 53, 738-44 (1980). (7) Balke, S. T.; Patel, R. D. J. folym. Sci., folym. Lett. 18, 453-56 (1980). (8) Bareiss, R. E. Makromol. Chem. 182, 1761-64 (1981). (9) Barla, F. Muanyag es &mi 18, 171-9 (1981). ( I O ) Barnes, R. D.; Law, L. M.; MacLeod, A. J. Analyst (London) 108, 412-18 (1981). (11) Bartlck, E. 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Surfactants Ramon A. Llenado"' Packaged Soap & Detergent Product Development, The Procter & Gamble Company, Ivorydale Technical Center, Cincinnati, Ohio 452 17
Thomas A. Neubecker Environmental Safety Department, The Procter & Gamble Company, Ivorydale Technical Center, Cincinnati, Ohio 452 17
This is a selective literature review of the analysis of surfactants. It includes books, symposia, patents, and journal articles published during the period 1981-1982. Following the format of an earlier review ( I A ) ,we have summarized
recent developments illustrative of trends from an extensive number of publications. Not all publications could be cited due to space limitations.
Present address: H e a l t h a n d Personal Care Division, T h e Procter a n d Gamble Co., Sharon Woods Technical Center, Cincinnati, O H 45241.
Surfactant is a contraction for surface active agent. The term is used to describe organic chemicals that, when added to a liquid, change the interfacial properties of that liquid.
BACKGROUND
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