Summary of papers published in this month's research quarterly, I S E C Product Research and Development
HYDROLYTIC DEGRADATION OF SODIUM TRIPOLYPHOSPHATE IN CONCENTRATED SOLUTIONS AND I N PRESENCE OF FOREIGN IONS
The degradation rate of tripolyphosphate in concentrated solutions follows first-order kinetics and increases exponentially with concentration of solids or sodium ion. T h e reaction product, which contains a higher a'nount Of pyrophosphate at higher 'Oncentrations, may be explained by the slow formation of a n acwhich undergoes various faster tivated tripolyphosphate reactions. Traces of multivalent cations have only a small effect on the degradation rate in concentrated solutions.
C. Y . Shen and D . R. D y r o f , Monsanto Co., St. Louis, M o . IND. ENG.CHEM. PROD.RES.DEVELOP. 5,97-100 (1966)
Cellulose propionate valerate containing about 8yo propionyl exhibits properties similar to those of cellulose trivalerate. This ester, prepa;ed from water-activated, propionic acid-dehydrated cellulose, was selected as representative of this class of esters for a study of properties. T h e properties of cellulose propionate valerate are more like those of the higher fatty acid esters of cellulose than those of the lower ( Cz to C,) esters. I t shows a low melting point, high moisture resistance, good heat stability, and compatibility with a wide variety of resins and plasticizers, forms flexible compositions with several waxes, and has good adhesion to glass, metal, and paper. T h e ester is soluble in a wider variety of organic solvents than any other aliphatic ester of cellulose.
J . W. Mench, Brazelton Fulkerson, and G. D. Hiatt, Eastman Kodak Co., Rochester, N. Y . IND.ENC.CHEM. PROD.RES.DEVELOP. 5,110-115 (1966)
LIQUID AMMONIA-SOLVENT COMBINATIONS IN WOOD PLASTICIZATION. CHEMICAL TREATMENTS
Wood plasticized by anhydrous ammonia becomes a deformable material without elastic return and with permanent set. Liquid ammonia is more effective than gaseous ammonia. Deformation in the absence of ammonia, however, is always followed by recovery of shape if the restraining force is immediately relaxed. There is little chemical change in the wood, but physical changes include relaxation of the crystal lattice and hydrogen bonding. Swelling and warping during treatment and shrinkage and checking during drying can be controlled by rapid even penetration, slow evaporation, and addition of nonhydroxylic additives to the ammonia. High concentrations of additive sometimes maintain flexibility i n the wood after removal of the ammonia or make it susceptible to rapid softening with cold water. Hydroxylic solvents, including water, compete with the cellulose for the ammonia and must be kept to a minimum. Factors influencing the rate of ammonia penetration by diffusion and convection are described.
Conrad Schuerch, M a r y P. Burdick, and Miroslau Mahdalik, State University College of Forestry, Syracuse, N . Y .
DIRECT PROCESS FOR PREPARATION OF SMALL PARTICLE CELLULOSE NITRATE
Small particle cellulose nitrate was prepared by a direct process starting with microcrystalline cellulose. Nitrations were performed in a high solids reactor using low weight ratios of nitrating acid mixtures. Nitrating acid mixtures were added to the cellulose raw material. Some other conventional steps were eliminated: nitrating acid recovery, kiering viscosity control, and the solvent emulsion technique for preparing densified particles from fibrous cellulose nitrate. T h e small particle cellulose nitrate product had an average particle size of 2.4 microns, a high bulk density, and a homogeneous molecular weight distribution.
A . M . Belfort atrd R. B . Wortz, FMC Gorp., Marcus Hook, Pa.
IND.ENG.CHEWPROD.RES.DEVELOP. 5, 115-118 (1966)
IND.ENG.CHEM.PROD.RES.DEVELOP. 5, 101-105 (1966) A MODEL FOR MOLECULAR WEIGHT DISTRIBUTIONS
LIQUID AMMONIA-SOLVENT COMBINATIONS I N WOOD PLASTICIZATION, PROPERTIES OF TREATED WOOD
Wood treated with anhydrous ammonia and dried is denser and more flexible than dry untreated wood. Tensile strength is increased but compressive strength is decreased by treatment and the dielectric constant increases proportionally with the increase of density. T h e treated wood is more hygroscopic and swells more than untreated wood. Density increases caused by treatment can be reduced by adding solvents to the ammonia.
R. E. Pentoney, State University College of Forestry, Syracuse, N. Y , IND.ENG.CHEM.PROD.RES.DEVELOP. 5, 105-110 (1966)
A model is proposed for the distribution of cumulative weight fraction, W , of polymer u p to molecular weight M . The model is a triangle when d W / d log M is plotted against log M with M equal to M L and M H a t the ends of the base and M , a t the apex. T h e ordinate can be k ' d W / d log M where k' is any arbitrary proportionality constant. Mathematically we have: k ' d W / d log M = log M/ML/log M , / M L when M L < M < M,; k ' d W / d l o g M = log M H / M / l o g M H / M , when M , < M < M H ; and d W / d log M = 0 when M x < or M < M L . T h e experimental distributions resulting from gel permeation chromatography often resemble this model. Aids for the analytical and graphical solutions for the Bw, and as a function of the average molecular weights three parameters M L , M,, a n d M x are presented.
an,
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Ferdinand Rodriguez and 0. K. Clark, Union Carbide Corp., Tonawanda, N. Y. VALERIC ACID ESTERS OF CELLULOSE
Cellulose valerate as well as the mixed cellulose acetate, propionate, and butyrate valerate esters have been prepared economically by the conventional acid-anhydride-sulfuric acid catalyst procedure.
IND.ENG.CHEM.PROD.RES.DEVELOP. 5,118-121
(1966)
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BRIEFS CHARACTERIZATION OF SILICONES BY GEL PERMEATION CHROMATOGRAPHY
After calibration by fractions from the same polymer species to be analyzed, gel permeation chromatography is a rapid method for measuring molecular weight distributions. When applicable, infrared absorbance is a convenient and specific measure of concentration. I n the case of silicones, a single chromatograph measures all molecular weights present without losing volatile portions. T h e column system can be changed to give very high resolution over a small molecular weight range, if desirable. Ferdinand Rodriguez, R. A. Kulakowski, and 0. K . Clark, Union Carbide Corp., Tonawanda, N . Y.
peroxide, and in the presence of a polyfunctional coagent yield pleasantly mild, and in some cases nearly odorless, vulcanizates. O n the basis of active oxygen content, they are less efficient than dicumyl peroxide but are competitive with it when compared on a weight basis. T h e ketal peroxides possess a superior cure cycle, requiring only 9.5 minutes at 300" F., whereas dicumyl peroxide requires 19 minutes at 320' F. for an equivalent cure. Dicumyl peroxide, however, has an advantage in scorch safety.
L. P.Lenas, Enjay Polymer Laboratories, Linden, N . J. IND. ENG.CHEM.PROD.RES.DEVELOP. 5,138-144 (1966)
IND.ENG.CHEM.PROD.RES. DEVELOP. 5,121-125 (1966) OXIDATIVE DEGRADATION OF THE POLYPHENYL ETHERS
GEL PERMEATION CHROMATOGRAPHY OF POLYBUTADIENE
T h e use of gel permeation chromatography (GPC) to determine the molecular weight distribution of polybutadiene polymers was investigated. Calibration with a series of anionically polymerized polymers of narrow distributions established a linear relationship between the elution volume of GPC and the logarithm of the molecular weight. Molecular weight distribution data obtained from GPC for two polybutadienes, one having a narrow and the other a broader distribution, were compaled with fractional precipitation data. Molecular weight averages, on a weight and number basis, were calculated from GPC distribution curves and compared with values obtained experimentally by independent means. GPC consistently indicates greater polydispersity than the other methods. Data are presented to show that flow rates slower than 1.O cc. per minute are preferred to improve the resolution for the polybutadiene-tetrahydrofuran system.
H. E. Adams, Kelly Farhat, and B. L. Johnson, The Firestone Tire @ Rubber Co., Akron, Ohio
IND. END.CHEM.PROD.RES.DEVELOP. 5,126-133 (1966)
PROPERTIES AND APPLICATIONS OF TRANS-l,4-POLYISOPRENE
Synthetic trans-l,4-polyisoprene, a stereospecific rubber, is almost identical with naturally occurring trans-l,4-polyisoprene ( a polymer found in natural balata). It is similar to natural rubber and most synthetic rubbers in that it is vulcanizable with sulfur, but differs from most rubbers in that it is relatively crystalline at room temperature. T h e crystals, however, melt at 130' F. (54.5' C.), so that trans-l,4-polyisoprene exhibits thermoplastic characteristics. These characteristics, combined with high tensile strength and cut abrasion and scuff resistance, make trans-1,4-polyisoprene ideal for use as the base polymer in golf ball cover stock. Natural balata is suitable for a variety of other applications, but use has been limited by uncertainty of supply and unpredictable price fluctuations. With the advent of uniformly high-quality synthetic trans-l,4-polyisoprene at a stable price, trans-polyisoprene can now be considered for many new applications in addition to those traditionally served by balata.
E. G. Kent and F. B. Swinney, Polymer Corp., Ltd., Sarnia, Ont., Canada
IND. ENG.CHEM.PROD.RES.DEVELOP. 5,134-138 (1966)
Polyphenyl ethers which are thermally stable at temperatures in excess of 800" F. undergo significant oxidative degradation at 600" F. in the presence of air. This paper discusses the isolation and identification of these oxidation products and presents a systematic series of equations proposing a mode of oxidative degradation consistent with the experimental results. A significant difference in the oxidative stability of the meta and para isomers has been noted and is also accounted for in the proposed mechanism.
W. L. Archer and K. B. Bozer, The Dow Chemical Co., Midland, Mich. IND.ENC.CHEM.PROD.RES.DEVELOP. 5,145-149 (1966)
COMPRESSIVE STRENGTH OF POLYMER-MODIFIED HYDRAULIC CEMENTS
The principal variables determining compressive strength of polymer-modified hydraulic cements are the "gel-space'' ratio and the degree of air entrainment. Secondary variables, of significance under particular conditions, are rate of evaporative water loss during the hardening period and degree of wetness. Polymer type can influence rate of evaporative water loss and also the magnitude of the compressive strength decrease due to wetting. A quantitative correlation of compressive strength is made with the two principal variables. Herman B. Wagner, Drexel Institute of Technology, Philadelphia, Pa.
IND. ENC.CHEM.PROD.RES.DEVELOP. 5,149-152 (1966)
RELATIONSHIPBETWEEN CHEMICAL STRUCTURES AND WEATHERABILITY OF COATING ASPHALT AS SHOWN BY INFRARED ABSORPTION SPECTROSCOPY
Application of precise quantitative infrared spectroscopic techniques to coating asphalts shows that the nature of the hydrocarbon structure of a n asphalt has a major influence on its weatherability. Weatherability predictions can be useful from the infrared spectrum of an asphalt of unknown origin, and very close if the origin is known. Hydrocarbon structures established as of major significance are: Noncrystalline methylene chains constitute a principal factor for good weathering performance; crystalline methylene chains are detrimental to weathering performance; an absorption peak exhibited in differential spectra at 13.3 microns, after cancellation of highly aromatic structures, correlates as a component detrimental to weathering performance. The rate of oxidative change during in-the-dark heating and ultraviolet irradiation is not as reliable an indication of weatherability as the nature of the hydrocarbon structure present.
NEW LOW-ODOR ETHYLENE-PROPYLENE COPOLYMER CROSSLINKING SYSTEMS
Clara D.Smith, Clara D. Smith Laboratory, Cranbury, N . J.,and C. C. Schuetr, and R. S. Hodgson, U. S. Gypsum Go., Des Plaines, Ill.
Several peroxides containing more than one peroxide group were evaluated as curing agents for ethylene-propylene rubber. These aliphatic and cycloaliphatic ketal peroxides yield vulcanizates possessing much lower odor than those resulting from dicumyl
IND.ENC. CHEM.PROD.RES. DEVELOP.5 , 153-161 (1966) (Continued on page 703) VOL. 5 8
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I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
BRIEFS
SEPARATION AND RECOVERY OF TRIETHYLALUMINUM FROM NORMAL ALPHA-OLEFINS
ALKYLATION OF ISOBUTANE WITH 1-BUTENE USING SULFURIC ACID AS CATALYST AT HIGH RATES OF AGITATION
Ziegler’s method for separating and recovering triethylaluminum (AIEta) from high molecular weight normal alpha-olefins, using alkali metal fluorides as complexing agents, has been investigated and somewhat modified. Thermal decomposition data for bis(triethyla1umine)alkali metal fluoride (MAltEteF) complexes of NaF, KF, RbF, and CsF indicated that the ease in removing 1 mole of AlEt3 from the MA1,EteF (1 to 2) complex followed the order Na>K>Rb>Cs. High molecular weight normal alphaolefins could be distilled in the presence of AlEta, potassium triethylfluoroalumane (KAIEtaF), or bis(triethyla1umine)potassium fluoride (KAltEteF), without olefin degradation, at temperatures sufficiently low to prevent decomposition of the KA1,EteF complex. Olefin degradation studies, in the presence of high AlEta concentrations, indicated that a 1-dodecene : I-tetradecene: AlEta fraction could be vacuum-distilled from higher molecular weight normal alpha-olefins without significant isomerization to cis-trans olefins or dimerization to vinylidene-type olefins. A modification of Ziegler’s method by complexing with K F or KAlEtaF is described.
Isobutane was alkalyated with 1-butene in the presence of sulfuric acid in a small (24-ml.) stirred autoclave at various rates of agitation, IOo to 40’ C., isobutane-1-buteneratios of 2.5 to 1 and 5 to 1, average residence time in the reactor of 15 to 60 seconds, and volumetric acid-hydrocarbon ratios of 0.5 :1 to 2 :l. T h e sulfuric acid used as feed varied from 88 to 99% acid containing 1 to 2% water and the remainder organic materials formed in the alkylation reaction. T h e hydrocarbon product was analyzed using a gas chromatographic procedure for all major compounds through the C g range. Several Cl0 and higher peaks were noted but not identified. Numerous runs were made to determine quantitatively the effect of operating variables on the product quality, yields, and drop in acid strength. In all runs, the I-butene reacted completely by polymerization, esterification, or alkylation reactions. Reasons for certain phenomena are postulated.
James F. Mosby and Lyle F. Albright, Purdue Uniuersity, Lajayette, Ind. IND.ENG.CHEM.PROD.RES.DEVELOP. 5,183-190 (1966)
E. R. Tucci, Gulf Research &? Development Co., Pittsburgh, Pa. IND.ENC.CHEM.PROD.RES. DEVELOP. 5,161-165 (1966) DIFFERENTIAL THERMAL ANALYSIS FOR ESTIMATION OF THE RELATIVE THERMAL STABILITY OF LUBRICANTS PREPARATION AND CHEMISTRY OF EPOXY ALCOHOLS
A new reaction has been discovered in which allylic hydroperoxides formed by olefin autoxidation are catalytically rearranged to epoxy alcohols. Epoxy alcohol-forming catalysts are transition elements of Groups 4, 5, and 6 of the Periodic Table and their compounds, excluding chromium. Vanadium, molybdenum, and tungsten compounds are especially active. The epoxy alcohols can be produced either by a two-step process in which the hydroperoxides are formed and rearranged in separate steps, or in a single step by olefin autoxidation in the presence of a n epoxy alcohol-forming catalyst. A range of olefins has been investigated. High yields (90 to 100 weight yo) of a mixture of two epoxy alcohols-2-methyl-3,4-epoxypentan-2-ol ( I ) and 4-methyl-3,4epoxy pentan-2-01 (11)-have been realized with 4-methyl-2pentene, and a wide range of derivatives of potential commercial utility has been prepared from I and I1 by reaction a t both the epoxide and hydroxyl groups.
Kenneth Alfison, Peter Johnson, Gordon Foster, and M . B. Sparke, British Petroleum Co., Ltd., Sunbury-on- Thames, Middlesex, England IND.ENG. CHEM.PROD.RES. DEVELOP. 5 , 166-173 (1966)
PORE STRUCTURE OF CRACKING CATALYSTS
T h e pcre size distributions of typical fluid cracking catalysts have been determined by nitrogen desorptiun measurements. Data are reported on thermal and steam-deactivated silica-alumina and silica-magnesia catalysts. With these systems pore size increases and distribution broadens as pore volume is raised. Thermal treatment of silica-alumina has little effect on pore size, whereas steam treatment enlarges pores and widens their distribution. T h e pore structure of equilibrium silica-alumina can be closely matched by steam-treating fresh catalyst at 1540’ F. DTA measurements reflect pore structure to a limited extent and provide a measure of “reactive alumina” from the mullite exotherm intensity. Silica-magnesia catalysts exhibit a bimodal distribution, the frequency of the modes varying with pore volume. Fluoride markedly promotes pore widening on heating, retards crystallization, and produces a more stable structure. DTA illustrates this effect by a sharply reduced enstatite exotherm.
R. M . Dobres, Leo Rheaume, and F. G. Ciapetta, W . R. Grace 63 Co.,
Experimental studies of samples representative of several distinctly different classes of materials have established the applicability of the techniques of differential thermal analysis to the study of the thermal de-omposition of organic lubricant systems. The data illustrate effectiveness of differential thermal analysis measurements made at ambient and at elevated pressures as a screening tool for evaluation of the thermal stability of lubricating fluids.
A . A . Krawetz and Theodore Tovrog, Phoenix Chemical Laboratory, Inc., Chicago, Ill. IND.END.CHEM.PROD.RES. DEVELOP. 5 , 191-198 (1966)
DEPENDENCE OF LITHIUM GREASE DROPPING POINTS ON THE SOLUBILITY PARAMETER OF THE OIL COMPONENT
T h e use of the solubility parameter concept as an index of oil character in metal soap-oil systems is briefly reviewed. T h e ASTM dropping points of greases made from a commercial lithium stearate have been shown to be a function of the solubility parameter of the oil used in the grease formulation. A new method for estimating the solubility parameter of an oil is suggested.
R. N . Bolster and R. C. Little, U. S.Naual Research Laboratory, Washington, D. C. IND.ENC. CHEM.PROD.RES. DEVELOP.5,198-202 (1966)
ARYLAMINO POLYFLUOROALKOXY PHOSPHONITRILES. A NEW CLASS OF POTENTIAL FIRE-RESISTANT HYDRAULIC FLUIDS AND LUBRICANTS
Several trimeric and tetrameric arylamino polyfluoroalkoxy phosphonitriles were synthesized. Preliminary evaluations indicated that this novel class of compounds possesses considerable potential for use as fire-resistant hydraulic fluids and lubricants. Some of these fluids had autogenous ignition temperatures between 1100 ’ and 1175 O F. A purified model product passed the hydrolytic stability test, showed good wear properties in the Falex test, and exhibited good thermal stability.
Clarksville, M d .
Gerhard Ottmann, Henry Lederle, and Ehrenfried Kober, Olin Mathieson Chemical Corp., N e w Haven, Conn.
IND.END.CHEM.PROD.RES.DEVELOP. 5,174-182 (1966)
IND.ENC.CHEM.PROD.RES.DEVELOP. 5,202-204 (1966) VOL. 5 8
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