Patented Aug. 10, 1943 2,326,610 UNITED STATES PATENT’ OFFICE - 2.326.610 EMULSIONS Joseph N. Borglin, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application March 26, 1941, Serial No. 385,312 7 Claims. (Cl. 252-3115) This invention relates to emulsions of the oil ms and adhesive compositions either with or in-water type and more particularly to emul without other materials. sions of this type wherein the dispersed phase While it is preferred to emulsify 0r disperse comprises a substantial amount of free poly free polymerized rosin alone, if desired emulsions merized rosin. may be prepared of polymerized rosin blended Emulsions of rosin have been heretofore pre with other water-insoluble organic materials pared by emulsifying or dispersing rosin in water which are preferably characterized by solu in any suitable manner. Such emulsions have, in bility in volatile organic solvents and which general, been unsatisfactory for many purposes generally exhibit binding properties, such as particularly because of the low melting point of 10 asphalt or other bituminous material, lin the rosin, the poor binding qualities of the emul seed oil, waxes, other resins such as gum sand sion, instability and deterioration due to the ob arac, copal, ordinary rosin, phenol formaldehyde jectionable tendency of the rosin to oxidize or resins, alkyd resins, shellac, hydrogenated rosin, otherwise deteriorate, improper consistency, and ester gum, cumarone resin, oil and resin modi?ed for various other reasons. 15 alkyd and phenol formaldehyde resins, etc. In It is an object of the present invention to pro general, it is desirable that the polymerized rosin vide an improved emulsion overcoming, to a large be present in substantial proportion say at least extent, the di?iculties with prior art emulsions. about 1% or more, and preferable that poly Another object is to prepare an emulsion of merized rosin constitute a preponderant portion, polymerized rosin in water. 20 of- the dispersed phase. An emulsion of bitumi Another object is to prepare an improved bitu nous material and of free poly-merized rosin may minous emulsion. advantageously be used as a binder for road as Another object is to prepare an improved resin gregate, soil stabilization, etc. emulsion or dispersion adapted to be used widely Instead of emulsifying or dispersing the solid in the arts. 25 polymerized rosin or blend thereof with one or Still other objects will more‘ fully hereinafter more of the foregoing materials, solutions there appear. of, either in a volatile organic solvent which is In accordance with the present invention, an preferably water-insoluble, or in a non-volatile emulsion of free or uncombined polymerized rosin solvent such as mineral oil, linseed oil or the like, in water is prepared. Polymerized rosin is char 30 may be emulsi?ed in water in accordance with acterized in general by properties similar to those the present invention. of rosin but with the difference that‘ it has a The polymerized rosin or blend thereof may be molecular weight within the range of 5% to 400% emulsi?ed in water in any of the conventional greater than ordinary rosin in its pure state, that methods, for example, by melting the polymerized it has a melting point as determined by the Her rosin and bringing it into contact with a hot cules Drop method above 85° C. and in general aqueous solution of a suitable alkali whereupon from about 5° C. to about 100° C. above that of there is formed an alkali soap of polymerized ordinary rosin in its pure stateythat it is sub rosin which acts as the emulsifying agent. Alter stantially free from hardening substances held in natively, the polymerized rosin may be melted and combination, and that it has an iodine value lower 40 commingled with a hot .aqueous solution of any than that of rosin. It is preferred to employ poly suitable emulsifying agent of the oil-in-water merized wood rosin having a melting point vary type such as ordinary fatty acid soap or poly ing from about'95° 0. up to about 170° C., the merized rosin alkali soap. In the case where melting point of the pure dimer. The dimer may casein is used as the emulsi?er, the polymerized be prepared by distilling the polymerized product rosin may be pulverized and admixed with the under reduced pressure to remove rosin oil, un-. casein, and this mixture added to the water with polymerized rosin and other materials of low vigorous agitation, ammonia being added to the melting point, leaving the dimer as a residue. mixture after thorough dispersion. Where a Methods of making polymerized rosin are well polymerized rosin soap and casein are used as known to the art and therefore need not be de 50 the emulsi?er, the polymerized rosin may be scribed here. The acid number of polymerized melted, and then partially neutralized with caus rosin may vary from that of rosin down to about tic alkali, followed by the addition of the casein 100. solution and then by the addition of the water. I have discovered that aqueous emulsions of If desired, the emulsion prepared thus or in some polymerized rosin offer numerous advantages for 55 other way may ?nally be passed through a colloid use in the arts, and are applicable in the manu mill to enhance its stability. facture of plastic and liquid coating compositions As the emulsifying agent, I may use any emulsi generally. Thus, the emulsions may be admixed fying agent of the oil-in-water type such as with any suitable aggregate such as stone, cork or polymerized rosin alkali soap, soaps of ordinary the like. The emulsions may also be used as coat 60 rosin, fatty acid alkali soap, such as the soap 2 2,826,610 of teaseed oil, corn oil, and other glyceride oils. Example 2 sodium oleate, etc., alkali caseinates. sulfonated fatty glycerides, mixtures of the foregoing, etc. Parts by Percent by Examples of suitable alkalies for preparation of weight weight the soaps or the alkali caseinates are sodium, 5 potassium, ammonium, or lithium hydroxides and Pol erlzed rosin__ 50 4.9 as“ ---- "1. ------s 2-: carbonates, triethanolamine, organic substituted man ______. ammonias or ammonium hydroxides such as “7??” 950 93.6 quaternary ammonium hydroxides, etc. The proportions of the ingredients of the emul The polymerized rosin was pulverized and ad sion may vary within wide limits depending upon mixed with the powdered casein. This mix was the emulsifying agent and upon other factors. added with vigorous agitation to the water and, ' Excellent emulsions have been prepared wherein when thoroughly dispersed, the ammonia was the proportions by weight comprise from about added. Stirring was continued for 30 minutes. 1% to about 70% of water-insoluble phase com 15 A stable gelatinous emulsion resulted. prising free polymerized ‘rosin, from about 1% to about 40% of emulsifying agent and from about Example 3 30% to about 98% of water or similar aqueous Parts by Per cent by phase. Where polymerized rosin soap is the sole weight weight emulsi?er, the amount thereof based on the 20 weight of water-insoluble phase may advanta Polymerized rosin ______-.__ 150 46. 2 geously range from about 35% to about 100% or Casein ______.. ____ l0 3. l 20% aqueous sodium hydroxide solution___ 10 3. 1 more. Ammonia (28%) ______. 4. 5 1. 4 In the case of emulsions of bituminous mate Water ______._ 150 46. 2 rial and polymerized rosin the proportions of the two phases and the emulsi?er may be as just The casein was stirred with‘ the ammonia and set forth. The proportions of bituminous ma- _ diluted with water to a 10 %‘ solution. The poly terial and polymerized rosin may vary from all merized rosin was melted and held at 105-110° C. _ polymerized rosin to about 1% polymerized rosin whereupon the caustic solution was added with and 99% bituminous material. A preferred vigorous stirring. Thereupon the casein solution amount of polymerized rosin is from about 1% was stirred in. The balance of the water was to about 20% on the weight of bituminous ma then added to give a pasty, White emulsion of terial, where the emulsion is to be used in road about 50% solids. paving, in the preparation of mastics, etc. Tl e amount of water present in the emulsion Example 4 will depend upon the nature of, amount of, and Per cent relative proportions of the other components and * by weight the use to which the emulsion is- to be put, pro Polymerized rosin___'______20.0 vided the emulsion is of the oil-in-water type. Asphalt (California 180-200 penetration)--- 39.6 If desired, there may be prepared an anhydrous 40 Polymerized rosin sodium soap ______4.2 or substantially anhydrous composition consist Water ______36.2 ing of the polymerized rosin or blend thereof The correct amount of polymerized rosin was ad with other organic material, and the emulsifying mixed with asphalt and the molten mixture run agent. This composition may be prepared in any into a warm solution of the correct amount of obvious manner and may be converted at the ' sodium hydroxide in water. Upon passing the place of use into an emulsion by the addition mixture through a colloid mill a stable emulsion of water followed, if desired, by passage of the was obtained. mixture through a colloid mill or the like. Example 5 It is preferred to use water which is free from Per cent objectionable amounts of dissolved substances, 50 by weight for example, distilled water, rain Water, softened Polymerized rosin ______32.3 hard water, etc. Asphalt (California 180-200 penetration) __ 21.6 Below are given several speci?c examples of Polymerized rosin sodium soap___~______1.7 emulsions and compositions adapted to yield Sodium o1eate_ _ 2.1 55 emulsions and prepared in accordance with the Water ______--'.\ 42.3 present invention. In these examples, the poly The correct amounts of polymerized rosin and of merized rosin employed had the following char oleic acid were fluxed with the asphalt and this acteristics: acid number 151, color 14-26 Amber, mixture commingled with the correct amount of grade X to WG, drop melting point 98-101° C., 61) sodium hydroxide dissolved in water. Upon color with 2% lead rosinate 25-40 Amber. passing the mixture through a colloid mill a stable emulsion was obtained. . Example 1 From the foregoing, it will be seen that the Per cent present invention enables the production of su by weight perior emulsions and compositions adapted to Mid-Continent asphalt (Arkansan, penetra yield such emulsions. Themarked resistance of tion 150-200) ______31.0 the resulting emulsions and solids deposited Polymerized rosin ______5.2 therefrom to chemical deterioration upon ex Sodium oleate ______. 1.8 posure to the air or upon ageing, and, the high Water ______62.0 70 melting point thereof is a particularly advanta The polymerized resin and asphalt were melted geous feature attendant upon the use of the pres together and the molten mixture and a solution ent invention. Numerous other advantages of of the sodium oleate in the water at 80° C. simul the present invention will be apparent to‘ those taneously passed through a colloid mill. A stable skilled in the art. emulsion resulted. 75 It will be understood that the details and ex 2,826,610 3 amples hereinbefore set forth are illustrative of water-insoluble phase comprising free poly only and that the invention as broadly described merized rosin, from about 1% to about 40% and claimed is in no way limited thereby. of an emulsifying agent capable of yielding an What I claim and desire to protect by Letters oil-in-water type emulsion, and from about 30% Patent is: to about 98% of an aqueous phase. 1. A composition of matter adapted to form an 5. A bituminous emulsion of the oil-in-water oil-in-water type emulsion upon addition of wa type comprising by weight from about 1% to ter comprising free polymerized rosin and an about 70% of water-insoluble phase comprising a emulsifying agent therefor. bituminous material and free polymerized rosin, _ 2. A substantially anhydrous composition of 10 from about 1% to about 40% of an emulsifying matter adapted to form an oil-in-water type agent capable of yielding an oil-in-water type emulsion upon addition of water comprising free emulsion, and from about 30% to about 98% polymerized rosin and an emulsifying agent of an aqueous phase. therefor. 6. An emulsion of the oil-in-water type com- ‘ 3. An emulsion comprising a, continuous aque prising free polymerized rosin, an alkali casein ous phase, a discontinuous dispersed phase com ate, and water. prising a solution of free polymerized rosin in a 7. An emulsion of the oil-in-water type ‘com volatile water-insoluble organic solvent therefor, prising free polymerized rosin, an alkali casein and an emulsifying agent adapted to maintain ate, an alkali soap of polymerized rosin, and said dispersed phase. 20 water. 4. An emulsion of the oil-in-water type com JOSEPH N. BORGLIN. prising by weight from about 1% to about r10%