US2115306A - Asphaltic material and process for producing the same - Google Patents

Description

April 26, 1938. w.-I-I. IIAMI=T0N ET AI. 2,115,306

' ASPHALTIC MATERIAL AND PROCESS FOR PRODUCING THE SAME Filed Aug. 11, 1934 2 SheeIs-Shet 1 IIs Iso IL- \v, I` I25 9 I` \9 f /1/ I \00y 75 MERS E o 4 e 5X 2 e o a?? Q@ ODU Aj/PHALIS oIso zoo o soo 350 MELTING POINT F. Fig; l

Io.o

u.' ao

3, @4 l @QWLPO E 40 W%\L% I- La) D I MELTING POINT F. .Figi 2 SPECIFIC GRAVITY April 26, 1938. H. HAMPTON ET AL. 2,115,305

ASPHALTIC MATERIAL AND PROCESS FOR PRODUCING THE SAME- 'Filed Aug. lll, 1954 sheets-sheet 2 loo 90 P0 4f o eo 9 d) 2: 70 n0 3 5o 5? 4o zoo 25o soo MELTING POINT F.

fk 4 I6 I4 lz lo u 4 D a Lu E 5 h. 4 MR B OWN MELTING POINT F.

FL' 5 12o g HJ d m 4o D. z ,:1

PENETRATION fig'. 6

Patented Apr. 26, 1938 UNITED vSTATES PATENT oFFleE ASPHALTIC MATERIAL AND PROCESS FOR PRODUCING THE SAME William H. Hampton, Orville E. ushman, and

Joseph E. Fratis, Berkeley, Calif., assignors to Standard Oil Company of California,

San

Francisco, Calif., a corporation of Delaware v'Application .August 1l, 1934, Serial No. '739,448

` 1o claims. (el. 26o-'2) This invention relates to a new composition of matter and more particularly to a synthetic plastic material, which for convenience in identication by comparison and contrast with petro- 5 leum and natural asphalts may be called a synthetic asphalt, and toa method for preparing y thesame. Y

It has long been known that the gaseous olens and dioleiines containing from two to about ve carbon atoms can be caused, by appropriate means, to polymerize into various liquid and solid materials. It hasv more recently been learned that-by proper choice of the gaseous raw mamolecular weight olens low boiling compounds in the range of motor fuels, intermediate boiling fractions such as transformer oils, cosmetic oils, etc, and high boiling stocks in the boiling range of lubricating oils and cylinder oilsare now being produced on a considerable scale.v As was to have been expected these synthetic products differ markedly in many respects from the similar boiling distillates from petroleum.

We have now discoveredthat by still further of oxidation an entirely new group of materials may be produced, which we have chosen to call synthetic asphalts. .These materials may be produced with varying degrees of hardness arid with melting or softening points variable throughout a considerable range depending upon the nature of the olene polymer material oxi- 45 dized and the extent to which oxidation is carried. They are apparently supercooled liquids as distinguished from true solids and hence may be subjected to and identified 'by the same set of physical tests as are customarily applied to 50 natural and petroleum asphalts. l

It is the broad object of this invention to produce a synthetic plastic of desirable characteristics from gaseous olens.

It is a further object of this invention to pro- 55 duce a synthetic asphalt-like material from gasetreating certain of these heavier olen 'polymers' by subjecting them to what is broadly a process dation' proceeds.

ous olens through the successive reactions of Apolymerization and oxidation.

Another object of .our invention is to produce a synthetic asphalt-like material whose physical characteristics may Vbe predetermined within 5 rather wide limits.

Still another object of our linvention is to produce an asphalt-like material Whosev physical properties change but little with changes in temperature. l0 A further object of our invention is to produce` a synthetic asphalt-like material which isv extremely'resistant to subsequent attack either by chemical agencies or by the atmospheric agencies which contribute to weathering: 15 Still other, objects will become apparent fromk the description and discussion of our process and product which follow.

nal source.' Oxidation is continued until a sample of the product drawnfrom the apparatus shows the desired characteristics. Oxidation nee-ai not necessarily be conned to a single oxidizing agent. Air and sulfur used together may often yield a product which is more desirable than that l produced by either alone.

The temperature of oxidation with air will vary between about 300 F. and 500 F. and may advantageously be started somewhere near the lower limit and progressively raised vas the oxi- 40 Operation with sulfur as the oxidizing agent is very similar while when chlorine is employed the conditions may have to be varied somewhat in order to secure lthe proper absorption of chlorine and its re-emission as hydrogen chloride.

Usual precautions should be observed to prevent excessive local or skin temperatures at any time during the reactionk since the inclusion of even small amounts of cracked Vproducts would in most cases confer upon the synthetic asphalt properties which would be highly undesirable and v in no sense characteristic of the synthetic product itself.

^ polymer liquid with a viscosity of about 1000 seconds Saybolt universal at 210 F. and freed it from any residual catalyst we next charge it to a still equipped for the introduction oi' air -and similar in general to the stills employed inthe preparation of air-blown petroleum asphalts. Having raisedthe temperature of the liquid v polymers to about 300 F. a current of air is admitted 'and the temperature is increased at a rate of about 1 F. per hour so that at the end of 150-170 hours the temperature of the still contents will have reached about 450; F. II

oxidation is discontinued at this point a material giving the tests recorded in column 3 of .Table 1, which follows,'will 'have been produced.

The materials of columns 1 and 2 of this table.

resulted from'somewhat less oxidation while column 4 contains results on a sulfur oxidized matei-iai.

yond the limits that have ever been realized in materials prepared directly from petroleum inlgredients as to clearly set it apart as a new composition of matter.

With regard to Figure 2 it should be noted that petroleum asphalts of melting point greater than 275 F. having an appreciable ductility are en tirely unknown while our materials of F. higher melting point still have very appreciable and highly useful ductilities. In connection with this same chart it should be pointed out that, as

is well .known inthe industry, ductilities greater with the penetrations at these two temperatures of our #3 sample of air oxidized polymers;

Still another reason for the choice of air-blown asphalt #lis apparent from Figure 3. This particular product is a commercial preparation designed especially for sealing storage batteries and is made by air-blowing a petroleum distillate in- I stead of a residuum and since it is'tlius not strict- Table 1 w l 70 pen. Air-blown asphalt 175 100 n. 70 pen. air-b own air-b own air-blown polymers polymersv polymers polymers 1 2 3 specific gravity o. am .951 .seo 1.005 1. 1.050 Pen. 77 F.:

100 grasrznos g 175 104 74 69 75 30 14 Pen.

m0 l 60" 181 125 99 86 16 18 12 Pen. o 115 F.:

50 grams 5" 210 124 74 80 230 72 22 M. P. ball and ring, F 175 255 3H) 320 178 176 238 Flash 5w 480 510 435 420 S01. C014 99.9 99.9 92.6 98.6 99.9 99.9

. S01. 86 gas 99. 9 91. 7 7l. 7 67. 8 61. 2 58. 0 Percent ilxed carbon. 3. 6 5. 4 5. 0 l2. 9, 13. 1 12. 6 Loss by evaporation, 100 hours 325 F-- 0. 0 0. 0 0. 0 0. 10 0. 63 0. 30 Penetration alter heating 169 101 72 72 28 14 Ductlity 77 7. 5 3. 5 2. 5 3. 0 2. 75 5. 0 1. 0 Ductiiity 32 9. 5 4. 5 v I -Since our oxidizedA polymers resemblesomewhat air-blown petroleum asphalts we have included 'A in this same table for comparison the results of tests on three air-blown petroleum products. However, except for illustrating some specific point or points of similarity or ditierence, such tables of figures are of little value. In order thereforethat the novelcharacteristics of our new synthetic material may be more easily appreciated and visualized the attached drawings are presented. I n Figures 1 to 5 various funcv tions, penetration, ductility. specific gravity, solubility in 86 naphtha and ilxed carbon are plotted against the melting point as determined by the have been able to compile them, ifor air-blown petrolem products from crude oils of a suiliciently wide range oi.' characteristics as to include substantially all air-blown 'asphalts In" each instance the physical properties of our synthetic material fall so far outside of and bely an air-blown asphalt it might be expected to show as wide a departure in physical properties from a true air-blown asphalt as it would be possible to prepare from the ingredients of a natural petroleum. It, however, falls without the shaded area of air-blown asphalts on only this one chart, specific gravity vs. melting point, falling well within this area on all the other charts. u

While we have been unable to find any such it appears entirely possible that still other petroleum derivatives may have been or might be specially -prepared which would have properties that would fall without the shaded area of some one or other of the charts. It would however seem highly improbable thatany such material has been or could ever be obtained from the components` of a natural petroleum which would fall substantially without the shaded areas -of two or lol y perature above300 F. until a that we consider the material of our invention to be entitled to a reasonable range of equivalents of which the lines drawn may be taken as the average. i

Other than the physical properties of Aour synthetic asphalts which set them apart from the closest 2hitherto known preparations are certain .of their chemical characteristics chief among which is probably their striking unreactivity.

The very fact that it takes 150 to 170 hours of siderable decomposition at the end of three complete cycles while paintsprepared from' our synthetic product showed no deterioration whatever after fifty complete cycles" which is the equivalent of a year or more of exposure to ordinary atmospheric weathering. This same unreactivity coupled with a low dielectric constant, high dielectric strength and a low susceptibility to temperature changes all. combine to give a product which is highly desirable for many uses as an electrical insulating material.

' We have further foundthat the several characteristics of our synthetic asphalts are so pr.

nounced that when they are blended in even minor proportions with petroleum asphalts, products of very superior properties for certain spe-- cific uses are obtained. lFor instance a blend of 25% of our product with an ordinary air-blown petroleum asphalt will produce a base for an asphaltic paint which is far superior in its ability to withstand weathering to any'asphaltic paint prepared wholly from petroleum asphalt or petroleum asphalt i'n admixture with natural asphalts or asphaltites.

Still other desirable uses to which our product 'may be put will be readily apparent to those skilled in the arts from the novel properties which have been given.

The term olen" is used herein in its strict chemical sense to mean solely an aliphatic hydrocarbon. having one carbon to carbon double bond per molecule.

Having now described our new product and the methods by which it may be prepared what we claim is: l 1. The method of .producing a synthetic as phalt-like hydrocarbon plastic which comprises polymerizing normally gaseous olens by means of anhydrous'aluminum chloride followed by subjecting the"heavy liquid oleiln polymers so produced to oxidation by blowing with air at a temuct is produced.

2. The method of producing a synthetic asphalt-like hydrocarbon plastic which comprises polymerizing normally gaseous olefns by means of anhydrous aluminum chloride, separating a fraction of the polymerization product having a viscosity above about 500 seconds Saybolt universal at 210 F., subjecting such fraction to oxidation at a temperature above about 300 but belowa temperature at which appreciable therplastic solid prodmal cracking would occur and continuing such oxidation until a plastic having a melting point above ordinary atmospheric temperatures is obtained.

3. The method of producing a synthetic asphalt-like hydrocarbon plastic which comprises polymerizing normally gaseous oleiins by means of a polymerization catalyst selected from the group consisting of strong sulfuric acid and aluminum chloride, followed by subjecting the heavy liquid olen polymers so produced to oxidation by blowing with air at a temperature above 300 F. until a plastic solid product is produced. 1

4. The method of producing a synthetic asphalt-like hydrocarbon plastic which comprises polymerizing normally gaseous olelns by means of strong sulfuric acid followed by subjecting the heavy liquid olenpolymers so produced to oxidation byblowing with air at a temperature above 300 F. until a plastic solid product is produced. y

5. The method of producing a synthetic asphalt-like hydrocarbon plastic which comprises polymerizing normally gaseous olefins by means of a polymerization catalyst selected from the group consisting of strong sulfuric acid and aluminum. chloride, separating a fraction of the polymerization product having a viscosity above about 500 seconds Saybolt universal at 210 F.,

v subjecting such fraction to oxidation at a temperature above about 300 F., but below a temperature at which appreciable thermal cracking would occur and continuing such oxidation until a plastic having a melting point above ordinary atmospheric temperatures is obtained.

6. The method of producing a lsynthetic asphalt-like hydrocarbon plastic which comprisesA polymerizing normally gaseous olens by means of strong sulfuric acid, separating a fraction of the polymerization product having a viscosity above about 500 seconds Saybolt universal at 210 F., subjecting such fraction to oxidation at a temperature above about 300 F., but below a temperature at which appreciable thermal cracking would occur and continuing such oxidation until a plastic having a melting point above ordinary atmospheric temperatures 'is obtained.

7. The method of producing a synthetic asphalt-.like hydrocarbon plastic which comprises polymerizing normally gaseous oleiins by sub-- jecting them to the action of a polymerization.

continuingsuch oxidation until a plastic having a melting point above ordinary atmospheric temperatures is obtained.

8. A synthetic asphalt-like hydrocarbon plastic as prepared by the process of claim l2 which has a ductilit'y greater than 1.0 at a melting point of 320 F. and having ductilities progressively greater than 1.0 at melting points below 320 F. being 6.5 or above at a melting point of 175 F., which has a penetration at '77 F. of 50 or above for a melting point of 320 F.' and having penetrations progressively greater than 50 for melting points below 320 F. being 140 or above at a melting point .of 175" F., which has a fixed carbon content of less than 9 for all melting points up to and including 320 F., and which has a. specic gravity less than 0.98 for all melting points up to and including 320 F., and which has a solubility in 86 naphtha greater than' 70% for a melting point of l320" F. and progressively greater at lower melting pointsapproaching :100% at a melting point o! 175 F.

, ing points below 320 F. being 140 or above at a melting point of 175 F., which has a iixed carbon content 4oi' less than 9 for all melting points up to and including 320 F., and which has a speciflc gravity less than 0.98 for all melting points up to and including 320 F.. and which has a solubility in 86 naphtha greater than 70% for almelting point of 320 F. and progressively greater at lower melting points approaching `,100% at a melting point of 175 F.

10. A synthetic asphalt-like hydrocarbon plastic as prepared by the process of4 claim 7 which has a ductility greater than 1.0 at a melting point of 320 F. and having ductilities progressively greater than 1.0 at melting points below 320 F. being 6.5 or above at a melting point of 175 F., which has a penetration at 77 F. of 50 or above for a melting point of 320 F. and having penetrations progressively greater Athan for melting points below 320 F. being 140 or above at a melting point of 175 F., which has a ilxed carbon content of less than 9 for all melt-v in g points up to and including 320 F., andwhich has a specic gravity lessthan 0.98 for all melting points up to and including 320 F., and which has 'a solubility in 86 naphtha greater than 70% for a melting point of 320 F. and progressively greater at lower f melting points approaching at a melting point of 175 F.

g WILLIAM H. HAMPTON.

ORVILLE E. CUSHMAN.l JOSEPH E. FRATIS.

Images