121st NATIONAL ACS MEETING—MILWAUKEE
In instrumental analysis l a b at M a r q u e t t e J. R. Koch prepares to m e a s u r e expansion of commercial waxes in binary mixtures reactions observed with olefin oxides a n d organolithium c o m p o u n d s , Dr. Anderson observed. I n a related study, Charles C. Price of t h e University of Notre D a m e re ported that, using optically active 2 , 3 butylene oxide, t h e conversion of an epox ide to an episulfide has been shown to proceed with inversion of b o t h asym metric carbon atoms. These results cor roborate t h e mechanism previously sug gested by van T a m e l e n , Dr. Price ob served.
> N e w Compounds, Mew Approaches M e m b e r s of a new class of compounds, the ge???-dithiols, R a C ( S H ) » , h a v e been isolated for t h e first t i m e in work re ported by B. C. McKusick of D u Pont. In t h e p u r e form these compounds are quite stable, said Dr. McKusick. Their structure h a s been proved by physical measurements, as well as by reduction to the mercaptans, hydrolysis to t h e ketones, and alkylation t o t h e thioacetals. In the latter instance, structure was confirmed by independent direct synthesis, Dr. M c Kusick stated. G e m - D i h a l i d e s . T h e gem-dihalides, a related group of c o m p o u n d s , were de scribed b y Calvin L. Stevens of W a y n e University. T h e identification of a gemdihalide as major, p r o d u c t from the Hofmann hypobromite degradation of t h e achloroamide of methylethylacetic acid, said Dr. Stevens, led to the investigation of t h e reaction of several other a-haloamides w i t h this reagent. T h e results, he said, indicated that t h e formation of gemdibromides or gem-bromochlorides in the Hofmann degradation of α-haloamides is general in scope, a n d proceeds in yields sufficiently high to suggest its usefulness
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in many phases of synthetic organic- chem istry. Tetra spirohexadecane. A symthetic route for the preparation of tetraspiarohexadeeane and higher homologs of tînis u n usual c o m p o u n d was reported by Milton Macloff of Edsel B. F o r d Institute. T h e key step in the transfonnation, s a i d D r . Macloff, is t h e dimerization of a substituted cyclobutyl ketene, followed by reduction of t h e resulting k e t e n e dinner. H e t e r o c y c l i c Vinyl Ethers. Information regarding t h e electronic effects of sulfur and oxygen has been o b t a i n e d IDV t h e investigation of p-oxathiene, a 6-me3rnbered heterocycle containing b o t h an oxygen and a sulfur atom, separated by a vinyl group. T h e synthesis of 7?-oxathie:ne, according to W i l l i a m E. Parham of t h e University of Minnesota, involved ring closure by an acid-catalyzed interchange of an ω-hydroxy acetal, followed by deaDkoxylation of t h e resulting 2-alkoxy-p-oxathiane, using phosphorus pentoxide as catalyst. In a study of t h e behavior of the e t h e r , said Dr. Parham, the m o d e of addition of u n symmctrical reagents to t h e doublée bond indicated t h a t oxygen releases electrons more readily than sulfur, in t h e direction of its covalent b o n d s . Alkyl H y d r o p e r o x i d e s , hi the first of a series of t h r e e related p a p e r s o:n alkyl hydroperoxides, Joseph Hoffman of Mack-
lin Co. described a procedure for t h e preparation of the hydroperoxide from diisobutylene in 219& over-all yield, using h y d r o g e n peroxide a n d sulfuric acid at 25° C. E x p e r i e n c e gained in this s y n thesis i s applicable generally for tertiary olefins, Dr. Hoffman said, a n d was applied to triptene, 2 - m e t h y l - l - h e p t e n e , and 2 , 5 d i m ethyl- 1,5-hexadiene. A c i d catalyzed decomposition of t h e isooctyl hydroperoxide furnished a useful m e t h o d of synthesizing n e o p e n t y l alcohol. T h e thermal d e composition of triptyl hydroperoxide, said Dr. Hoffman, was shown t o b e kinetically first o r d e r , w i t h the formation of a 1 0 0 % yield of acetone. Antibiotic. T h e u n s t a b l e antibiotic my corny cin w a s isomerized i n sodium h y droxide solution to give a readily crystallizahle s o d i u m salt of a n organic acid, termed isomycomycin. Hydrogénation of this c o m p o u n d , described b y Walter D . Celnier of C h a s . Pfizer a n d Co., produces 7î-tridecanoic acid, with t h e consumption of 8 moles of hydrogen. Other physical a n d chemical evidence indicates a 13carbon linear c h a i n containing a terminal methyl, an unconjugated carboxyi group, 3 disubstituted conjugated acetylenic bonds, a n d a conjugated d i e n e . T h e struct u r e of isomycomycin d e d u c e d from t h i s work is 3,5-tridecadiene-7,9,l 1-triynoic acid, D r . Celnner c o n c l u d e d .
DIVISION OF PAINT. V A R N I S H . A N D P L A S T I C S C H E M I S T R Y
Isophthaiic A c i d Looms A s Source Of Paints, Plastics, a n d Fibers ^ Polystyrene-derived ion exchange resin holds promise as salting resin agent • M a n y test methods and analytical procedures for plastics inadequate • Breakdown in printing ink quality attributed to adsorption of drier J\. PREDICTION that isophthaiic a c i d will serve as the raw material for new or improved p a i n t s , plastics, a n d synthetic films and fibers w a s m a d e before t h e Division of Paint, Varnish, and Plastics Chiemistry by E. F. Carlston, California Research Corp. Dr. Carlston reported tHat oilmodified alkyd resins p r e p a r e d from isophthaiic acid are faster d r y i n g a n d more durable t h a n t h e corresponding: ortho phthalate resins. T h e iso acid a l s o has the advantages of greater reactivity, lower volatility, a n d greater thermal stability. Although isophthaiic acid is n o w being made only o n a pilot p l a n t scale, it may he prepared on a large scale fronii metaxylene, the largest c o m p o n e n t of natural xylene. T h e ortho acid i s generally p r e pared from naphthalene. Or. Carlston stated t h a t fibers m a d e
CHEMICAL
from p o l y a m i d e resins prepared from the iso acid and from terephthalic acid show excellent c o l d d r a w i n g properties a n d h a v e tensile a n d i m p a c t strengths similar to nylon polymers. T h e h i g h molecular w e i g h t polymer of e t h y l e n e glycol isophthalate prepared by Dr. Carlston a n d his associates proved to be a t o u g h resin which shows excellent adhesion to glass. A modification of the p o l y m e r , h e believes, s h o u l d yield n e w polyester products which will b e useful in fiber glass laminates, sandpaper adhesives, and other thermosetting resin applications.
• Sea w a f e r Deionizing Resin N e w anion exchange resins which show promise of u s e in desalting sea water, in
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PAINT, VARNISH, A N D
have no real value in helping to evaluate the product under consideration. The present symposium, he said, was designed to look into certain aspects of this question. Plasticizers în Vinyl Resins. Temple C. Patton of Baker Castor Oil brought out this point in his report on plasticizers used in vinyl resins. Dr. Patton stated that because plasticizers do not lose their chemical identity in* resins their properties must be considered in evaluating a resin. In evaluating the plasticizer itself, he said, the lack of color, odor, toxicity, flammability, volatility, solubility, and chemical reactivity are all pertinent factors. The contribution of the plasticizer to permanent film flexibility of the resin is also a major factor. Weathering Tests. An attempt to develop apparatus suitable for making accelerated tests of weathering damage in plastic specimens, was reported by J. W. Tamblyn, Tennessee Eastman Co. Dr. Tamblyn stated that conventional carbon arc machines do not give results which agree with outdoor exposure tests. He has been able to get much better results by incorporating sun lamps in the conventional apparatus. The sun lamps more nearly duplicate the short ultraviolet radiation of sunlight. Organic Acids Inactivate Ink Drier. One essential property of a printing ink, that of drying rapidly, is effected by use of a drying catalyst (drier). William C. Walker of Lehigh University reported that some driers, such as cobalt compounds, sometimes lose their drying effect as the ink ages. It has been determined that this phenomena is, associated with certain pigments such as alumina hydrate lakes. The effect is attributed to the reaction of the drier with oil-soluble organicacids or to the incorporation of the drier into the acidic water film surrounding the
The smallest known alkyd resin reaction kettle ( 100 grams ) is employed at the California Research Corp. for investigations on isophthalic acid alkyd resins decolorizing sugar, and in dye mordanting were described by Giffin D. Jones, Dow Chemical Co. The resins are obtained by the ehloromethylation of polystyrene in chloromethyi ether solution followed by animation with tertiary amines. In desalting sea water, the exchange resin would be suspended on a screen and the salt water forced through. The resin can b e regenerated by using an ion exchange resin of similar structure in. the hydroxide form. Phenolic Resins. One and two step phenolic resins which possess unusual properties such as oil solubility and acid reactivity have been prepared by Lloyd H. Brown, Quaker Oats Co., from various phenol-furfural combinations catalyzed by alkali metal hydroxides and carbonates. The products are similar to the Novolak resins prepared from phenol and formaldehyde. The new resins, stable under neutral or alkaline conditions, may b e thermoset on the acid side without addition of aldehyde. The lower molecular weight resins are soluble in drying oils and aromatic solvents. When cooked with drying oil products are obtained which are more useful in many respects than the formaldehyde-substituted phenol resins although they possess the drawback of having a red color.
PLASTICS CHEMISTRY
pigment particles. The solution to this problem, Dr. Walker stated, lies in avoidance of free sulfonic acids and excessive acidity in the lakes, keeping the lakes moisture free, and in avoiding the use of troublesome pigments as determined by moisture tests and by use of a recently d e veloped cobalt adsorption test. In some cases drying time stabilizers may also b e used. The behavior of printing inks during printing is dependent to a great extent on the particle size of the pigment and the interaction at the interface between the pigment and vehicle. A. C. Zettlemoyer of Lehigh University stated that the interaction is complex due to t h e heterogeneous nature of the pigment surface and the complex nature of the vehicles used. Dr. Zettlemoyer stated that he is trying to determine the effects of t h e different variables by studying simple inks made up from a simple vehicle and single pigments. Daniel Smith, Interchemical Corporation Research Laboratories, stated that t h e phenomena of bronzing, noted in paints, printing inks, and crystalline materials, may be classified as a special kind of gloss. Measurement of bronzing, like gloss, may be effected by means of an automaticrecording abridged spectrogoniophotometer of high resolution. Paper Chromatography. The use of the paper chromatography technique has been used by James H. Freeman, Westinghouse Research Laboratories, to help solve the long standing problem of deteranining which of the various possible mono- and poly-methylol phenols are formed when phenol reacts with formaldehyde. By comparing the spots made by known compounds with those obtained from the resin components, a qualitative analysis can be made.
A. L. Alexander (right) and Harold Segrave study chromate ion reading on polarograph at Naval Research Laboratory in connection with magnesium corrosion inhibitor studies
• Resin Test M e t h o d s Scrutinized Francis Scofield, National Paint, Varnish, and Lacquer Association, and chairman of the symposium on evaluation of test methods and analyses for plastic materials stated that in developing methods which give reproducible results, the ultimate goal of developing tests which are significant is sometimes overlooked. Similarly analytical methods may b e developed which V O L U M E
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1952
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121st NATIONAL ACS MEETING—MILWAUKEE a n d t h e composition of modifying fatty acids. Based o n his present paper, w h i c h deals with the effect of various oil-resin ratios, and his previous papers, Dr. M o o r e has developed a series of generalizations w h i c h make it possible to predict changes i n properties of alkyds as proportions of t h e various r a w materials are changed. F a c t o r s which may be predicted i n c l u d e d r y i n g time, ultimate hardness, and afteryellowing.
Low M o l e c u l a r W e i g h t Vinyl Polymers.
Polymers which offer promise as plasticizers, hydraulic fluids, and synthetic lubri cants h a v e b e e n prepared b y C. E . Rehberg, Eastern Regional Research Labora tory. T h e polymers are liquid alkyl polyacrylates prepared by polymerizing ethyl a n d b u t y l acrylates in various isopropyl benzenes. T h e molecular weights of the p r o d u c t s are estimated to b e in t h e one t h o u s a n d to t w o thousand range.
D I V I S I O N O F PETROLEUM CHEMISTRY
SSIort h y d r o c a r b o n Nuisances in Petroleum Pinned D o w n J. H . Freeman, Westinghouse Research Laboratories, applies indicator solution t o bring out spats o n a p a p e r chromatograrn Magnesium Corrosion Inhibitors, Allen L. Alexander, Naval Research Laboratory, stated that it would b e desirable t o u s e magnesium i n naval aircraft if the p r o b lem of corrosion in m a r i n e environments could be overcome. R e c e n t studies indicate that phenolic matrices in which, a r e incorporated calcium, barium, and s t r o n tium chromâtes, offer t h e best possibilities of preventing this corrosion. H e also n o t e d that magnesium salts, particularly t b e chromâtes, a p p e a r to have possibilities in this area. Hydrogen Bonds in Resins. The difference in acidity of hydroxyl groups ΟΩ cer tain phenolic resin intermediates a s d e termined by titrating i n various media, h a s led G. R. Sprengling of Westinghouse R e search Laboratories to conclude that there are strong intramolecular hydrogen b o n d s in some of these intermediates. C o n s e quently, these intermediates can not form as many intermolecular hydrogen b o n d s , and thus have a decreased intermolecular cohesion. This phenomena might explain w h y certain of the resins formed from these intermediates t e n d t o crack. Epon Resin Derivatives. J. W . McNabb, Brooklyn Polytechnic Institute, reported that esterification of Epon resins with fatty acids of dehydrated castor oil followed by styrenation, gave clear, h o m o geneous products. W h e n used as sur face coatings these resins showed good adhesion and flexibility qualities and b e t t e r resistance t o water and alkali than t h e E p o n resin esters. Roy W . Tess, Shell Chemical Co., p r e p a r e d Epon resin esters using linseed acids or a mixture of soya acids and dehydrated castor acids. T h e mixed acid esters, when styrenated, yielded products characterized b y rapid drying rates and mar resistance, alkali resistance, a n d flexibility greater t h a n styrenated alkyds. Alkyd Resin P r o p e r t i e s . Dudley T. Moore, E m e r y Industries, Inc., presented t h e third in his series of papers o n t h e correlation between properties of alkyds
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^ Presence of elemental definitely established
sulfur in crude
oil
• Oxygenated by-products of Hydrocol process include water-soluble and oil-soluble aromatics and aliphafics χ Ν OINHYIXROCARBON constituents of p e t r o leum can be divided into two groups— nuisances and major nuisances." This opening r e m a r k b y W . D. Seyfried., Humble O i l a n d Refining Co., chairman of t h e Symposium on Nonhydrocarbon Constituents, -would have b e e n funny if the p r o b l e m were not so serious. Presence of metallic compounds, Mr. Seyfried pointed o n t , h a s been emphasized in r e cent years because of poisoning effects o n cracking catalysts. Sulfur, whose ill ef fects seemed relatively simple a few years ago, now appears to be the source of serious difficulties. Oxygen a n d nitrogen offer a somewhat brighter picture to t h e refiner. Although presence of c o m p o u n d s containing them can b e «harmful, some of these same compounds, notably n a p h t h e nic acids and phenolic types, are becoming important by-product chemical raw m a t e rials. Metals in Distillates. How metals, p a r ticularly vanadium, get into distillates from c r u d e oil containing t h e metals, has b e e n a piizzle for some time. First proof t h a t this is caused by actual volatilization of m e t a l compounds in t h e crudes was p r e sented b y R. A. Woodle, The Texas C o . The importance of this proof lies in t h e indication that complete elimination of entrainment of metal compounds c a n still leave a minimum metal concentration i n the distillate. Mr. Woodle added t h e i n formation that although vanadium is p r o b ably present i n crude oil in a family of compounds covering a wide range of molecular weights, only those of l o w molecular weight distill over.
CHEMICAL
Ashing M e t h o d s C o m p a r e d . Losses in volved in ashing methods for determina tion of metals in crudes have led to care ful study of many variations in techniques. Use of a wet ashing method employing sulfuric acid, w i t h the sample h e a t e d by a n infrared lamp, was advocated b y J. P. Kirchner of Socony-Vacuum.* Spectrog r a p h i c or polarographic techniques on the ashed sample result in accurate determina tions. Studies at the Humble Refinery c o n d u c t e d by J. H. Karchmer have led to his conclusion that the direct emission spectrograph t e c h n i q u e offers definite ad vantages over any ashing methods, both in reducing time requirements and elim inating losses. T o strengthen his point, M r . Karchmer compared various ashing a n d other methods in detail. Surface-Active Constituents. Lively discussion showed t h e interest in work d o n e b y the surface chemistry laboratory of the U. S. Bureau of Mines on film-form i n g a n d surface-active constituents of petroleum. These materials are respon sible for m a n y production problems en countered and complicate core analyses. C . G. Dodd has used a water spray ex traction method on crude oil in a twisted glass column t o obtain more information about the nature of these compounds. Chromatography of both the benzenesoluble and benzene-insoluble portions of t h e extracts confirmed presence of zinc, c o p p e r , and titanium in t h e highly sur face-active fractions. Vanadium and iron, Mr. D o d d said, were not present in t h e surface-active fractions, b u t were concen trated to some extent into t h e film-forming
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