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ALKOXYPHOSPHAZENES AS FLAME RETARDANTS FOR RAYON
h new approach t o the problem of flameproofing cellulosic textiles has been demonstrated. Rayon fibers with excellcnt flame retardancy were produced by mixing a liquid flame retardant with viscose dope before spinning. T h e norlnal propyl ester of a mixture of polymeric phosphoiiitriiic chlorides \vas particularly suitable for this application. Fibcrs have been spun containing over 307c by weight of this additive. T h e flame retardant, uniformly dispersed throughout the fibcr in small pockets, is retained after extensive laundering or dry cleaning. Fabrics wovcn from fibers containing 20c0 by dry weight of the mixed propoxyphosphazenes have passed the N. Y .City Board of Standards aiid .\ppeals Test Calendar No. 294-40 SR, a s e x r e test of flame retardancy.
Leunard E . A . G o d f i e j , F.WC Curl,., Princeton, .l‘, J . , 085.10, and Joseph LV. Scliafifiel, Aine~icaii Viscose lliuision> I;aUC Cor)., :\larcus IIook, P a . 7 9 0 6 7
All Others
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5.00.. . . . $ 5.50.. , , . $ 6.00 10.00, . . . 10.50.. . . . 11.00 I
discussed. There are ar least two gciieral mechanisms whereby colloid stability is imparted : electrostatic stabilization and steric stabilization. T h e Deryagin-Laiidau-Verwey-Overbeck theory provides a quantitative explanation of many phenomena involving electrostatic stabilization. No comparablc theory for steric stabilization exists, although some general principles which appear to govern this type of stabilization have bcen delineated. Thesc give considerable insight into the venerable phenomenon of the protective action of certain adsorbed polymers. .\n understanding of the general principles that govcrn colloid stability also permits conclusions as to the best procedures by which stable dispersions may be induced to flocculate.
11. H. n’apper, Uniuersib of Sjdnv, Sydng .l-.S.TV.: 2006, Australia
IND.E N G .CIIEM.PROD. RES.DEVELOP. 9, 467-477 (1970)
IND.ENG.CIIEM.PKOD.R E S .DEVELOP. 9, 426-436 (1970) REACTIVE FLAME RETARDANTS FOR POLYURETHANE FOAMS REVIEW OF RECENT LITERATURE O N THE ZIEGLER-TYPE CATALYST
This review describes a potclitidi unified model to explain t h r isotactic- and syndiotactic-typc propagations and strrcosclectionisotatic propagation, and gives a progrcss report o n recent iuvestigations of morphologies of polymer chains forgrd a t Zieglrr-rypr sites and morpholoSirr of polyinrr partirlcs and the catalyst parric.les from which they arc formed.
foliii Boor, Jr., Shell Iler~eiopnienlGo., h e y ? ~ i , !Gal$. / t , 94008 I N D ENG. . CHEM.PROD.KES.DEVCLOP. 9, 437 -456 (1970)
ASPECTS OF THE MECHANISM OF COORDINATION POLYMERIZATION OF CONJUGATED DIENES
T h c recent chemistry of coordination polymcriLaiioii of conjugated dienes is rxamincd. T h e structure of the catalyst is considered from thc viewpoint that the propagatiiip chain is a T allylic complcx of the transition mctal, formcd by rcactioii of inoiiomer with a n intcrmediatc alkyl or aryl complcs from a inetnl salt and a n orSaiiomctallic compound, a preformed organic complcx of thc metal, or i n the casc of Group VI11 metals, particularly the second scrics, formed by direct reaction of t h e monomer With the metal salt. T h e cffeets of ligands on catalyst acii\-ity and the rclationship bctkveen catalyst structurr and inonomrr coordination are discussed. .Ittempts to detrrminc the nature of the propagating chain from tcrmiiiatioii rcacrioiis bvith labclcd ;ilcohols and similar reagents arc reviewed. Only limited information has been gained oii propagation, transfer, and termination reactions from kinetic studies aiid the factors influenciiig molecular weight control \carrant further detailcd in\-estigation.
WilJrid CGO~C?-: Ilunlop Reseai ch Cmtw, Birminghain: England I N D .E N G .C I I I ? ~PROD. . RES. DEVELOP. 9, 457-466 (1970)
COLLOID STABILITY
T h e principles that govern colloid stability are of manifold importance to many different technologies. T h e origin of the London dispcrsiori forces, which cause naked, uncharged colloidal partides to flocculate, and how this flocculation may be prevented are 156
INDUSTRIAL A N D ENGINEERING CHEMISTRY
This article presents an up-to-date review of chcinical compositions, particularly those bearing the elements of halogen and phosphorus, and structural features of flame retardants which have been chcmirally incorporated in poiyurerhanc foams. Particular emphasis is g i x n to flame retardant efficiency and synthetic proccdurcs for conipositions of commcrcial signihcancc. T h c rcagcnts are catcgorized according to reactive functionalities for polyurethane foriliatioil. This section is preceded by a bricf discussion of the many aspects of flame-proofing polyurethane foams and the current thinking in this area. No effort was made to critically evaluate this field. Kecent trends in devcloping low-flammability polyurethane-based copolymers containing heat-resistant groups, such as isocyanurate and cyclic imide, are also prcsented. An extensive bibliography is given of the scientific work surveyed. A forecast of trends of flame retarding polyurethane foams is given.
A . J . P a p a , Union Carbide Cor$., South Charleston, JV. Va. 25303 IND.E K G .CHEM.PROD.RES.DEVELOP. 9, 478-496 (1970)
QUANTITATIVE EFFICIENCY EVALUATIONS OF COMPLEX OXIDATION REACTIONS
.\I1 compounds of carbon, hydrogen, and oxygcn can be placed on an arbitrary “oxidation stale” scale. Methane has a valuc of zero; carbon dioxide has a value of 100. Differcnces in oxidation state values permit direct calculation of the number of oxidation (or reduction) equivalents required to convert one compound to another (whether or not the reaction is practical or possible). Usiiig this approach it is possible to make a quantitative evaluation of any oxidation reaction aiid to deal conveniently with reactions utilizing multiple oxidation agents a n d / o r multiple feeds producing multiple products. .1 redox balance can be made around a system. This is a valuable supplement and check on a mass balance. I n some cases, such as l o w conversion oxidations, ir is possible to make a definitive redox balance even when mass balance d a t a are inconclusive. C. C. Hobbs, Technical Center: Celanese Chemical Co., Corpus Christi, T e x . 78408
IND.EXG.CHEM. PROD.RES.DEVELOP. 9, 497-503 (1970)
CATALYST SYSTEM FOR LOW TEMPERATURE POLYMERIZATION OF VINYL CHLORIDE
Organic hydroperoxides react with SO2 i n the presence of nucleophilic agents, giving R O . and SOS. radicals that are efficient initiators of vinyl chloride polymerization i n bulk a t subzero temperatures. When cumyl or tert-butyl hydroperoxides and SO2 are used together with ethers, ketones, or alcohols, sulfone groups are incorporated i n the polymer chain because of the copolymerization of S o n . When the hydroperoxides and SOZare used with M e O - or E t O - (from N a or M g alkoxides), SO2 copolymerization is completely suppressed, provided the ratio (MeO-) or (EtO-)/ (SOZ) is a t least 1 When the feed rate of hydroperoxide is constant, maximum monomer conversion in continuous bulk polymerization is reached when the ratio (SOz)/(hydroperoxide) is 1.5 or higher. T h e n the dependence of monomer conversion (c) o n hydroperoxide concentration (C,) and dwell time ( Q ) is expressed as c / ( l - c)i‘2 = (K,/K~.”2)f11z(C,)1/zQ1~z, where Kp is the rate constant for propagation, K , is the rate constant for combination, and f is the radical efficiency. Polymerization examples are given for vinyl acetate, vinyl formate, acrylonitrile, acrylamide, and 2-hydroxy-ethyl acrylate a t -30’ and - 6 O O C . Corrado Mazzolznz, Luigi Patron, Alberta Morettz, and Marcello Camanellz, Chatillon, Milan, Itah
9, 504-511 (1970) IND.ENG.CHEM.PROD.R E S .DEVELOP.
SELECTIVE METHANATION
OF CARBON MONOXIDE
T h e selective methanation of carbon monoxide in a gas mixture containing hydrogen, carbon dioxide, and carbon monoxide (-3000 p p m ) was investigated within a temperature range of 125’ to 300’C using several catalysts. T h e object was to decrease the concentration of carbon monoxide to about 50 to 100 p p m without considerably affecting the concentration of other components. Ruthenium was the most effective carbon monoxide methanation catalyst, followed closely by the Kaney nickel-type catalyst. Catalysts prepared by precipitating nickel on the supports were unsatisfactory. Amirali Rehmat and S. S. Randhaua, Institute of Gas Technology, Chicago, lll. 606 76 I N D .ENG.CHEM.PROD.RES.DEVELOP. 9, 512-515 (1970)
TEREPHTHALIC ACID FROM p-XYLENE
T h e cobalt acetate-catalyzed autoxidation of p-xylene to terephthalic acid was promoted by certain carboxylic acids, alcohols, and epoxides. T h e reactions were r u n under pressure, from 50 to 150 psig, a t temperatures from 100’ to 150°C. Of the carboxylic acids studied, 2-methylbutyric acid stands out i n augmenting the p-xylene autoxidation. For secondary alcohols, 2-butanol was most effective. For tertiary alcohols, the requirement for a successful promoter seems to be the presence of two alkyl groups which are larger than ethyl. Of the epoxides studied, only 2,3epoxybutane proved to b e beneficial. T h e success of these promoters c a n i n general be rationalized o n the basis of the oxidation products expected from cobaltic ion oxidations.
James W . Patton and Ned F. Seppz, Marathon Ozl Co., Littleton, Colo. 80 720 IND.ENG.CHEM.PROD.RES.DEVELOP. 9, 521-524 (1970) POLYMER-THICKENED LUBRICATING OILS. PREDICT MECHANICAL SHEAR STABILITY
LABORATORY TEST TO
T h e mechanical shear stability of polymer-thickened lubricating oils in relation to laboratory bench-scale tcchniques was investigated. I n subsequent studies using standard laboratory-type paint blending-mixing devices, a kinetic dispersion mill (Model L ) provided a mechanical shear environment demonstrating a directional trend of degradation for polymer thickeners. Further refinement of this technique led t o the establishing of a correlation with single and multicylinder engine tests.
M . E. Le Peru and Jules Pqliacampz, US.Arm9 Aberdeen Research 61 Development Center, Aberdeen Prouzng Grounds, Md. 27005 I N D .END.CHEM.PROD.RES.DEVELOP. 9, 525-529 (1970)
SOLID LUBRICATING FILMS. FRICTION-WEAR IMPROVEMENT WITH POLY (BENZOTHIAZOLE) BINDERS
Selection of organic resins as binder materials is based on their thermal and oxidative stability, toughness, adhesive properties, and ease of handling. Poly (benzothiazole) (PBT) was chosen from among several candidates for investigation as a binder for solid film lubricant formulations. T h e polymer, its structure, and properties are described. Procedures for formulating solid lubricants and wear behavior obtained are presented. Several formulations have potential for improved performance. O n e formulation, MoSz S b Z O 3 PBT, was selected for detailed study. Evaluation of friction and wear properties in several test devices is discussed. I m proved performance is demonstrated a t 500’F and higher, compared to the performance exhibited by other available films.
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HYDROFORMYLATING TERMINAL OLEFINS. INFLUENCE OF ORGANOPHOSPHINE LIGAND
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T h c hydroforniylation of 1-1icxcnc \$.as invcsriuarztl i i i cobalt hydrocarbonyl-tertiary organophosphine s)’stenis to dercrini nc the cffecrs of orqanophosphinc Imsicir). 011 rcacrion rates, srcrcosclccrivit), in formiiiz linear products, and hydroqencirio!l characrerisrics. .A lincar frce-cnergy corrclarion bet\\.ccn hydroformylation raws and liqand basicit). is observed a r 160°C: liqands of lo\%. basic char;icrer--c,.q.. I’Ph;-fa\.or fasrcr reacrion rates. Karc diffcwnces \\.irhin this rclared lieantl scrics are atrribured I O a-donor effects rarhcr than steric effects. T h e srercospeciiic addition of rhc cobalr hytlrocarbons~complex to thc olefin is scnsiti\.e to IiSancl ~ y p c . Generally, liaantis of Ion basicity and larxc bulky sizcs are Icss fa\.ornble for high product Iiiieai-ity and favor a h l a r k n o ~ n i k o \ . additioii. I.ack of stcrrospcciflcity is atrributed mainly I O caialystcomplex dissociation resulrinp in frcc cobalt hydrocarbonyl, or undesirable steric intrracrions between thc caralysr complex :Ind r e x i a n t olefin. EIydrogenarion of olehns to parafin.; iiridcr hydroform).l;ition conditions is not sipnificnnrly affecwd by changitiy the type of orgaiiophosphine ligand, tvherens aldehyde hydroqcnation to alcohol qreatly irnpro\.rs i n p i n g from PPh: to n-RiP systems. Diffcrcnccs in :ildehyde hydrorenation rharactcrisrics bct\\.ecn PRr and PPh; svirems are attributed to greater sreric iiitc~ractionsand more favorablr formation of free cobalt hydrocarbonyl in t h e larrer sysrcm.
B. D. McConnell, Air Force Materials Laboratory, W7ipht Patterson AFB, Ohio 45433 IND. ENG.CHEM.PROD. RES.DEVELOP. 9,529-534 (1970) EXPLANATION OF SOME LUBRICATING OIL HYDROCRACKING RESULTS I N TERMS OF THE STRUCTURE OF THE VISCOSITY INDEX SCALE
Viscosity index (VI ) measurements on hydrocracked lubricating oils exhibit two anomalies: As hydrocracking severity is increased, viscosity index of the product oil increases t o a maximum and then decreases, and fractions distilled from a hydrocracked oil exhibit a wide range of VI’S; the lower-boiling fractions always are significantly lower i n V I than the full range oil. Both of these unexpected results have been traced to a discontinuity i n the VI system. Alternative systems for rating the viscosity-temperature characteristics of lube oils have been examined, b u t none is completely satisfactory. A modified system has been outlined which would remove molecular weight effects, and therefore present a somewhat more fundamental basis for the viscosity-temperature rating system.
E. R. Tucci, Gulf RrjParrh 3 Ue:dofinmt Co., Pi/t>Lurg!i. Pa. 75230
Bernard Gillespie and F. A . Smith, Mobzl Research and Development Corp., Paulsboro, N. J . 08066
I K D . EsG. CticM. PROD.R E S .DEVELOP. 9, 516- 521 I 1970 I
IND. ENG.CHEM.PROD.RES.DEVELOP.9, 535-540 (1970) VOL. 6 2
NO. 12
DECEMBER 1970
157
BRIEFS
ASSOCIATION COLLOIDS IN NONAQUEOUS FLUIDS. VISCOSITY AND DRAG REDUCTION CHARACTERISTICS
Soaps that form association colloids are effective drag-reducing agents in nonaqueous fluids, while simultaneously building the desired viscosity characteristics of the fluid. Such agents, while effective in a drag-reduction sense, are sensitive to trace amounts of water and catalyze the oxidative degradation of oils a t elevated temperatures.
H . R. Baker, R. .IT.Bolster, P. B. Leach, and R. C. Little, ;Choal Research L a b o r a t o v , Washington, D . C. 20390 I N D .ENG.CHEY.PROD.RES.DEVELOP. 9, 541-548 (1970)
DILUTE SOLUTION PROPERTIES OF DRAG-REDUCING POLYMERS
Experimenral data on the dilute solution viscosity behavior of two effective drag-reducing polymers [poly(ethylene oxide)-Polyox and Separan, a partially hydrolyzed polyacrylamide] in various solvents (distilled water, salt water, and simulated sea water) are presented and discussed. T h e unusual viscosity behavior observed for both polymers in the simulated sea water for concentrations less than 30 ppm is explained by postulating a n interchain ionic bonding effect for the Separan solutions and ion-dipole, saltpolyether complex formation in thc Polyox solutions. Tentative conclusions are offered concerning the effectiveness of the polymers as drag reducers in the solvents and concentrations tested.
JV.D . S9lvester and J . S. Tyler, U n i c e r s i b of N o t r e D a m e , iVot7e f l a m e , I n d . 46556 IKD.ENG.CHEM.PROD.RES.DEVELOP. 9,548-553 (1970)
CHARACTERIZATION OF OIL SLICKS IN SURFACE WATERS
h-umerous unidentified oil samples collected from the surface waters of the United States were analyzed by the method of ratios of infrared absorbance using six wavenumbers. Two key ratios, 810 cm-'/1375 cm-I and 810 cm-'/720 cm-' were useful for the initial classification of the oil spill samples of unknown and uncharacterized origin, while confirmation requires the use of the other ratios. For rapid field evaluation, the graphic method is useful for classifying petroleum pollutants in water. Ratio values from unidentified petroleum pollutants are compared with those from industrial asphalts and residual fuel oils. Classical analyses.\PI gravity, solubility, boiling points, etc.-supplement the findings of the R I A method. Asphalts, No. 6 fuel oils, Yo. 5 fuel oils, and a lubricating oil were characterized.
F. K . Kawahara and D . G. Ballinger, Federal W a t e r Pollution Control Administration, Cincinnati, Ohio 45202 IKD.
ENG.CHEM. PROD. RES.DEVELOP. 9, 553-558 (1970)
LEAD DIOXIDE-GRAPHITE ELECTRODE
T h e lead dioxide electrode is used as a substitute for the conventional graphite and platinum electrodes in cells for the preparation of chlorates, perchlorates, chloroalkali, hypochlorite, etc. Stationary or flowing electrolytes are used with or without addition agent, the mode being stationary or rotating for the electrodeposition from a n aqueous bath of a suitable lead salt, of lead dioxide on graphite, carbon; or other metallic substrate. PbOz was deposited onto a substrate like graphite and carbon rods and plates of different sizes, from an electrolyte containing lead nitrate and copper nitrate in a fluidized bed of a n inert material. T h e substrate material is the anode; the cathode is copper. T h e lead dioxide obtained is smooth, dense, hard, uniform, and free from pinholes and adheres to the surface of the substrate material.
R a m a s w a m y Thangappan, S u b r a m a v a m Nachiappan, and SriniLasa Sampath, Central Electrochemical Research Institute, Karaikudi-3, T a m i l Nadu: India
IND.E N G .CHEM.PROD.RES.DEVELOP. 9, 563-567 (1970)
STATISTICAL CONCEPTS IN TESTING OF DISPERSANTS
Effectiveness of various surfactants for use as hydrocarbon process antifoulants was investigated by measuring their ability to disperse carbon black particles in kerosine. Stability of the dispersions could be measured reproducibly for materials that were very effective or very ineffective. Systems of intermediate stability gave poorly reproducible d a t a ; however, the scatter a€the data can be calculated and follows the statistical relations reported previously for adsorption-type corrosion inhibitors. T h e standard deviation, U , of the dispersant efficiency, E , is expressed by the equation c = 1.33 ~ ( -l E ) . This is the relationship reported for reproducibility of corrosion inhibition data where e represented the efficiency of inhibition. C. C. A'athan and C. L . Ilulaney, Bet2 Laboratories, Ins., Treuose, Pa.
19407 IND.EXG.CHEM.PROD.RES.DEVELOP. 9, 567-569 (1970)
ADSORPTION OF WATER ON BORON PHOSPHATE AT 25OC
T h e adsorption ofwater at 25.0' zk 0.1 "C was examined on samples of boron phosphate preheated to loo", 200", or 300°C. T h e BET (nitrogen) surface areas and the total amount of water absorbed increase with preheat temperature. T h e quantity of water physically adsorbed and that chemisorbed are both much greater than would be expected from the nitrogen surface areas. However, the amount of water chemisorbed may be accounted for on the basis of a single layer of water molecules.
J . B . M a f f a t and K. F. Tang, UnioersiQ of Waterloo, Waterloo, Ontario, Canada
IND.EKG.CHEM. PROD.RES.DEVELOP. 9, 570-573 (1970) FIRE-RETARDANT UNSATURATED POLYESTERS. COMPARISONS OF ANALOGOUS BROMINATED AND CHLORINATED REACTIVE INTERMEDIATES
METAL-IMPREGNATED CARBONS
T h e effectiveness of bromine us. chlorine has been determined for the fire-retardant unsaturated polyester intermediates : dihalomaleic anhydrides, dihaloneopentyl glycols, tetrahalophthalic anhydrides, and tetrahalobisphenol A-ethylene oxide derivative. New polyesters were prepared from 1,4,5,6.7,7-hexabromo[2.2,1] 5-heptene-2,3-dicarboxylicanhydride, and 1,4,5,6-tetrabromo-7oxo-5-norbornene-2,3-dicarboxylicanhydride dimethyl acetal.
Metal compounds have been incorporated into a rayon-based Reinforced Pyrolytic Graphite and subsequently reduced to the metal or converted the carbide to increase oxidation resistance. T h e impregnants used were H Z r O 3 H 2 0 , TaC14, HfC14, ZrHZ, boron, and silicon. None reduced flexural strength significantly. T h e first four impregnants increased resistance to burning, whereas the last five retarded weight loss in static oxidation tests at 1850'F.
J . A. Schneider, R. G. Pews, and J . D . Herring, T h e Do& Chemical Co., Mzdland, Mach. 48640
D . H . LePds, E d Kelly, and J u l i a n Heicklen, Super-TemP GO.,Santa Fe Springs, Calzf. 90670
I N D .ENG.CHEM.PROD.RES.DEVELOP. 9, 559-563 (1970)
IND.ENG.CHEM.PROD.RES.DEVELOP. 9 , 573-576 (1970)
158
INDUSTRIAL AND ENGINEERING CHEMISTRY
