CA1210551A

CA1210551A - Cationic bituminous emulsions

Info

Publication number: CA1210551A
Application number: CA000437018A
Authority: CA
Inventors: Hans G. Schreuders; Peter Schilling
Original assignee: Westvaco Corp
Current assignee: Westvaco Corp
Priority date: 1982-09-20
Filing date: 1983-09-19
Publication date: 1986-09-02
Also published as: JPS5978259A; FR2533225A1; US4450011A; JPH024623B2; GB2126919A; DE3333550A1; GB8324320D0; FR2533225B1; DE3333550C2; GB2126919B; AU1918383A; AU547960B2

Abstract

CATIONIC BITUMINOUS EMULSIONS

Abstract of the Disclosure Reaction products of polyamines with sulfonated oleic acid or sulfonated tall oil fatty acids are disclosed which give emulsions capable of producing cationic medium set mixing grade asphalt emulsions, as well as rapid set asphalt emulsions.
Solventless asphalts as well as asphalts containing up to 15% by volume of a hydrocarbon oil can be used for emulsification.

Description

12~QSS~

This invention relates to improved bituminous emulsions, specifically to cationic medium set mixing grade emulsions and to mixing-grade, quick setting and slow-setting cationic bituminous-aggregate paving slurry seal mixtures. ~Iore particularly, it relates to emulsifiers for solventless and solvent containing mixing grade, oil-in-water cationic bituminous emulsions, which emulsifiers are the reaction products of polyamines with certain sulfonated carboxylic acids.

In paving operations, three main practices are employed to achieve thorough mixing of bitumen and aggregate:
(1) mixing of free flowing heated asphalt (asphalt cement) with pre-dried aggregate;

(2) mixing pre-dried agg~egate with asphalt diluted with a hydrocarbon solvent (cutback asphalt, cutter stock) at ambient temperatures; and ~ 3) mixing a~gregate with asphalt emulsions, e.g., oil-in-water emulsions, obtained by vigorous agitation of asphalt and water in the presence of an emulsifying agent.
Because of increasing cost in energy and hydrocarbon solvents and because of environmental concerns, the use of emulsified asphalt is increasing. Dependent on the emulsi~ier used to achieve an emulsion, anionic or cationic emulsions are obtained. In anionic emulsions, asphalt droplets are negatively charged; in cationic emulsions, the asphalt droplets bear positive charges and migrate to the cathode when an electric field is applied. Experience in the field has shown that ~2~05S1 càtionic emulsions are easier to apply and obviate some of the disadvantages of anionic emulsions, such as unpredictable break and poor bonding of asphalt to the aggregate surface resulting in strîpping. Due to the electrostatic attraction of positively ~charged asphalt droplets and negatively charged aggregate surfaces, cationic bituminous emulsîons deposit more rapidly, and stronger bonds between bitu~en and aggregate are obtained.
Generally, depending on the characteristics of the type of mixing and rate of break, catîonic aqueous bîtuminous emulsions are classified as rapid setting (CRS), medium setting (CMS) and slow setting (CSS). The rate of set is determined by the type and ~he amount of emulsîfLer and the pH value of the cationic soap solution. In the case of rapid set~îng emulsions, mainly used for repair work of ald wearîng courses, the emulsion is applied on the existîng surface and aggregate is spread on top, and after compaction, the xoad can be opened to traffic shortly after the application of t~e new coat (chîp seal, etc.~.
Medium setting emulsions are mi~:ed~wîth aggregate prior to beîng used in road construction, and llow set emulsions can be mixed with aggregate and stored for a lo~ger period of tîme without breaking on the aggregate surface.
Cationic emulsions are o~tained by employing a variety `of nitrogen containîng organic c:ompounds, such as fatty amines, fatty dîamines, fatty triamines,~ fatty amidoamines, fatty imidazolines, fatty mono- and di~qu~ternary ammonîum salts, and reactîon products of all these compounds with ethylene oxide.
The fatty radical of these compounds can have a chain length of C12-C22 and comprise a varîety of ~hemical structures. The building blocks for the preparal:ion of these amines can b~
obtained from a variety of sources, such as petroleum refinates, animal fats, vegetable and fish oils, and tall oil. Amidoamines ;l Il - 2 -l2~assl suitable as emulsifiers are disclosed in U. S. Patent ~o.

3,230,10~ to Falkenberg and in U. S. Patent No. 3,097l174 to Mertens. Combinations of fatty monoamines and triamines are disclosed in U. S. Patent No. 3,738,852 to Doi; fatty diamines are disclosed in U. S. Patent ~lo, 3,728,278 to Tramelli and U. S.
Patent No. 3,5~1,101 to G~emski; fatty quaternary and diquaternary salts and modificcLtions thereof are disclosed in U. S. Patent No. 3,220,953 to E~orgfelt, U. S. Patent No.
3,867,162 to Elste, U. S. Patent ~o. 3,764,359 to Dybalski, U. S.
Patent No. 3,95~,524 to Doughty and U. S. Patent No. 3,466,247 to Ohtsuka, and fatty imidazolines are taught in U. S. Patent No.
3,445,258 to Ferm.
Generally, cationic emulsions prepared with fatty amines, fatty diamines, fatty amidoamines, etc., are unstable when mixed with a variety of siliceous or calcareous aggregates.
Rapid breaking on the aggregate surface is observed with an increase in stiffening. At this point, the mix becomes unworkable. To overcome this problem, it is common practice to use cutback asphalt instead of asphalt cement for medium se~
mixing grade asphalt emulsions. ~lthough cutback emulsions prepared with these emulsifiers also break when mixed with the aggregate, the solvent (a hydrocarbon oil, such as naphtha, kerosene, diesel oil, etc.) decreases the viscosity of the asphalt and increases the workability of the aggregate-asphalt mix. After placement of the mixes, the solvent evaporates and the final stiff aggregate-asphalt matrix is obtained~ Because of the dramatically increased cost of solvents in recent years and because of the effort to reduce pollution, suitable emulsifiers are sought for cationic mixing grade emulsions without using solvent. The use of tallow quaternary ammonium salts and tallow diquaternary dia~monium salts for making emulsions suitable for !
il ~.
Il lZ~()SSl slurry seal, a solventless application, is described in U. S.
Patent No. 3,764,359 to Dybalsk~, and the use of a quaternary amine obtained by reacting epichlorohydrin, trimethylamine and nonylphenol for solventless mixes is disclosed in U. S. Patent No. 3,95~,52~ to Doughty.
Slurry seal emulsions are special cases of a solventless mixing grade emulsion. Conventionally, emulsion slurry seals are formulated from (l) mineral aggregate which is a fine stone aggregate and/or mineral filler and (2) about 15Z to about 25% by weight thereof of a mixing-grade, s~ow-setting emulsion containing about 50% to about 75Z by weight of bituminous residue (usually asphalt), wi~h a further addition of about 10~ to about 15% of water, based on the weight of the dry aggregate, to att~in slurry consisjtency. Usually, difficult-to-coat, densely-graded aggregates, such as sand, pit-run, crushèr-run, etc., are combined with bituminous emulsions to produce slurry seal c~tmpositions. These aggregates range in size from anything passing all through a sieve of No. 4, and even ~o. lO mesh, with from 15X to 20Z passing through as fine a mesh as 200 mesh (U.S. Stan,dard).
The advent of slurry seal as a paving and road maintenance technique was first developed for use with anionic aqueous bituminous emulsions. A slurry seal is an intimate mixture of emulsified bituminous material and fine-grained `~
aggregate held in suitable suspension until applied to tha road surface. The slurry seal emulsion must be of an oil-in-water type. In such admixture with aggr~gate, the aqueous emulsion form of the bituminous materiaL has been generally preferred because it is less hazardous and more economical to use than molten or solvent solutions. ~urther, the aqueous emulsion form can be stored, transported and applied at much lower

- 4 -il ` I

12~(~551 temperatures, obviating the necessity of heating equipment to maintain a bitumen-aggregate s~rstem in a workable or usable form.
While these advances have been recognized, widespread acceptance has not been achieved due to d:Lsadvantages found in previous aqueous bituminous emulsions.
The aqueous cationic bituminous emulsions themselves are relatively stable, and the emulsion stability may be enhan~ed `
~y various additives well kno~ in the art. Most cationic bituminous emulsions, however, deposit on the surface of aggregate materials rapidly when aggregate is mi~ed with the emulsions, the emulsions applied to the aggregate, or aggregate applied to emulsions. Bitumen from an aqueous cationic bituminous emulsion is deposit,ed from the emulsion due to the charge attraction between the bituminous droplets and the aggregate materials. The rapid setting action of cationic bituminous emulsions is of considerable advantage in road building, such as seal coats, since the roads can be opened to traffic shortly after application of the coatin~. Although the rate of asphalt deposition, for example, from the emulsion can be controlled to some extent, the time required for co~plete deposition is never very long and it is therefore the practice to combine the cationic emulsion with the aggregate at the site of road construction, either on the surface of the road itself, or in a mobile mixer which penmits the emulsion aggregate mix to be `i rapidly spread. Due to the charge àttraction mechanism, the rapidity of deposition of bituminous materials from the cationic emulsion is closely related to the generally negatively charged surface area of the aggregate or filler material. ~hus, while a 'specific cationic bituminous emulsion might provide suitable properties for use in con~unction with some aggregates, the ssme cationic emulsion may not exhibit suitable properties when used Il -S

~2105Sl .
with very finely grou~d materials having vastly larger total surface area. The rapid deposition characteristics of the cationic bituminous emulsions frequently makes it impossible to use such emulsions with fine-grained aggregate in slurry form such as in gun application or spreader box application.
Therefore, since the slurry seal should mix well, pump well, lay down well, not stiffen while being applied, and, after setting, wear well under traffic, it is particularly desirable to be able to control the setting time of the slurry for various aggregates employed.
The general object of this invention is to provide ; versatile emulsifiers for solventless and solvent containing mixing grade, oil-in-water bituminous emulsions. ~nother object of this invention is to provide emulsifier formula~ions for mixing grade emulsions which give a variety of set times as expressed in percent initial washoff coating (the percent coat on , the aggregate surface after one minute mixing and immediate immersion in water) and percent one hour washoff coating. A
further object of this inventic,n is to provide a series of new amidoamines, imidazolines prepæred as the reaction product of ;sulfonated oleic acid or sulfonated tall oil fatty acids and polyamines, suitable as emulsifiers for cationic oil-in-water ; emulsions.
Accordingly, an object of this invention is to provide 2. novel mixture of aggregate and bituminous emulsion.
A further object is t:o provide a mixture of the above character which is workable.
~ Another object is to provide a mixture of cationic ;Ibituminous emulsion and aggregate whose setting time can be varied.

lZl(~5Sl A particular object is to provide a bituminous emul-sion, fine-grained aggregate slurry mixture which deposits at a fairly rapid rate after being applied to the surface to be treated, and is workable for a period of time long enough to enable application in slurry form.
It has been found that in contrast to amidoamines and imidazolines which are obtained by condensation of fatty acids, having a chain-lenth of C12-C22, with polyethylene amines, such as diethylene triamine, which give cationic rapid set emulsions, reaction products of polyamines with sulfonated oleic acid or sulfonated tall oil fatty acids give emulsions capable of producing cationic medium set mixing grade asphalt emulsions, as well as rapid set asphalt emulsions. Solvent-less asphalts as well as asphalts containing up to 15% by volume ~of a hydrocarbon oil can be used for emulsification.
According to one aspect of the present invention, there is provided a cationic bituminous emulsion comprising from about 30% to about 80% by weight of bitumen, from about 0.1% to about 10% by weight of an emulsifier selected from the group consisting of reaction products of polyamines react-ed with sulfonated carboxylic acids selected from the group consisting of sulfonated tall oil fatty acid and sulfonated oleic acid, and water to make up 100% by weight, the emulsion having a pH in the range of from 2-7.
Anotherlaspect of the invention provides a paving slurry seal mixture of a cationic aqueous bituminous emulsion and`mineral aggregate capable of being worked comprising: a densely graded mineral aggregate passing through No. 4 and at least 80% retained on 200 mesh screen; from about 8% to about 20% of an oil in water type emulsion, based on the weight ~2~55~

of the mineral aggregate, wherein the emulsion is comprised of from about 55% to about 65% bitumen, based on the weight of the emulsion, from about 0.5% to about 2% of a cation-active emulsifier based on the weight of the emulsion, wherein the emulsifier is the reaction product of one or more poly-amines reacted with a sulfonated carboxylic acid selected from the group consisting of sulfonated tall oil fatty acid and sulfonated oleic acid, and water to make up 100% by weight of the emulsion, the emulsion having a pH in the range of from 2-7; from about 4% to about 16% water, based on the "~
weight of the mineral aggregate, added to form a slurry of the aggregate and the emulsion; and up to 3% of an inorganic or organic additive to reduce the setting time of the mixture.
A further aspect of the invention provides an emul-sifier for cationic bituminous emulsions, which comprises the reaction product of a polyamine with a sulfonated carboxy-lic acid selected from the group consisting of sulfonated tall oil fatty acid and sulfonated oleic acid.
The sulfonated carboxylic acids used in the prepara-tion of the cationic emulsifiers of the invention are derived by sulfonation of tall oil fatty acids and oleic acid ad-vantageously of the following composition:

- 7a -1~

~2~ ;5i _ _ -Oleic Tall Oil Ac.id Fatty Acid Palmitic4.29 2.37 - 5.70 Acid .
Palmitoleic11.00 1.03 - 1,80 Acid Oleic 72.00 43.12 - 47.13 Acid Elaidic <1 <1 - 23.50 ~; Acid . I
Linoleic~.11 3.20 - 33.11 Acid Conjugated1l.4 5.30 - 9.10 Linoleic .
Acid _ The sulfonated produrts are characterized by an a~id number from about 220 to 330, sapo~ifica~ion number from about 300 to 360.
Sauls and Ruggenberg dis~lose the sulfonation of oleic acid with sulfur trioxide in liquid sulfur dioxide in U. S.
.. Patent 2,743,288.
Pugh and Chesworth disclose in British Patent 1,278,421 the sulfonation of oleic acid with gaseous sulfur trioxide diluted with an inert gas with a continuously formed liquid film of the unsaturated fatty acid.
The sulfonation of tall oil fatty acid is also disclosed in-the above men~ioned p~tents. Because of the complexity of the composition ~f t~ll oil fatty acids, no attempt to ~dentify the sulonated products was made.
Reaction mechanism and a~l aspects of sulfonation are reviewed in E. E. Gilbert, "Sulfonation and Related Reactions,"
R. E. Krieger Publishing Company, Hun~ington, New ~orkr 1977.

12~05Sl The'reaction products of these sulfonated fatty acids with polyamines, such as polyethylene amines or blend of suitable primary, secondary, tertiary amines and polyamines, give ammonium salts of sulfonated fa~ty acid ,~midoamines or, where applicable, imidazolines. The reaction products of sulfonated oils, fats, higher ~atty acids and higher fatty acid esters with organic amines and amides are disclosed in U. S. Patent 2,329,086 tO
Robinson and Webber for use as softeners for textile materials.
For example, when the major reaction product of sulfonated oleic acid is blended with two moles of diethylene triamine, the diammonium salt will be formed. Upon heating, one mole water is eliminated and the correspondent diethylene triammonium salt of the sulfonated oleic amidoamine is formed.
Further heating gives the corresponding diethylene triammonium salt of the sulfonated imidazoline. All these compounds are amphoteric in nature, thus soluble in both acidic and alkaline media. Based on the higher acidity of the sulfonic acid group, metal salts, such as the potassium salt, or ammonium salts, such as the triethanol ammonium salt, can be formed by addition of one mole of potassium hydroxide in methanol or triethanolamine; and by heating with an additional mole of a polyamine, the corresponding amidoamine is obt:ained.
In the course of sull.onation of double bonds, ~-sultone is considered as the primary sulfonation product. These sultones are very unstable and reactive. According to Gilbert, reaction with SO3 gives a sulfate-sulfonic anhydride.
By reacting a ~-sultone with an amine a ring opening reaction will occur forming a ~-amino sulfonic acid ammonium salt !
The anhydride will react with cm amine giving ammonium sulfate ; and ~-hydroxy-sul~onic acid a~onium salt.

'i _ 9 _ ~ I

121QSSl These amidoamines and imidazolines should serve as examples of the types of reaction products which one can expect.
Since, however, the reaction products of sulfonation of oleic acid and especially tall oil fatty acid are complex, an even more complex mix~ure of reaction products will result ~rom polyamine treatment.
The formation of imidazolines is limited to polyethylene amines and polyamines characterized by at least one ethylene diamine functional group with a~ least three hydrogens attached to the two nitrogens. Compounds of this group which are able to give both amidoamines and imidazolines are: ethylene diamine, diethylene triamine, t:riethylene tetramine, tetraethylene pentamine, penta~thylene hexamine, and higher homologues; N-aminoethyl propane diamine, N,N-diaminoethyl propane diamine and the N-aminoethyl or N,N-diaminoethyl substituted butane diamines, pentane diamines and hexane diamines, and N-hydroxy ethyl ethylene diamine. These compounds have the general formulae H2NCH2CH2NHR '~
~ = H-, CH3-, C2H5-- C3H7 ~
- CH2CH20H, - ~CH2CH2NH)XH
x = 1, 2, 3, 4, . . . . 1 or, RlR2N(CH2)yNHR3 Rl = H-, CH3-, C2H5~- C3H7-, NH2C~2 2 ' R2 H , CH3 , C2Hs , R3 - H-~ CH3-~ C2H5-- C3H7-, NH2cH2cH2 , y = 2, 3, 4, 5, 6 . `

Amines capable of forming amidoamines but not imida~olines are: 1,3-diaminopropane, 1,4-diaminobutane i! - 10 -1~ ..

lZ~0551 1,5-diaminopentane, 1~,6-diaminohexane, piperazine (1,4-diazacyclohexane), N-aminoethylpiperazine, N-hydroxyethyl piperazine, N-aminopropyl-propcme diamine-1,3, N-methyl-N-aminopropylpropane diamine-1,3, N,N-dimethylpropane diamine-1,3, N,N-diethyl propane diamine-1,3, N,N-dimethyl-ethylene diamine, N,N-diethyl ethylenediamine;
N-aminohexylhexane diamine-1,6.
Certain amidoamines or imidazolines with tertiary nitrogens, such as the reaction product of sulfonated oleic acid and N,N-dimethylpropane diamine-1,3 of the formula CH3(CH2)7CH = CHCH(C!~2)6ÇONHCH2CH2CH2N(CH3)2 S03~ $( CH3)2CH2CH2C~2NH2 t~ or H3NCH2CH2CH2N(CH3)2) may be modified by further reaction with one or two moles of an alkylating agent such as methyl-, ~thyl-, or benzyl halides, sulfates, phosphates, etc. The resulting compounds are classified as amphoteric quaternary ammonium salts. Their main characteristic is their solubility.in aqueous systems withou addition of acid, as is the case with amines, amidoamines, or imidazolines. An example of this ~ype of quaternary ammonium salt as prepared by reacting methyl sulfate to provide the following struc~ure:

!

i l I

~2~05Si CH3(CH2)7CH = CH-CH(CH2)2CONHCH2CH2CH2N(CH3)3 l3~) S04CH3 H3~CH2CH2cH2N(cH3)3 ~S04CH3 (~i ~
or LH2~l(cH3)cH2cH2cH2N(c~l3)3]
~ o4CH3)2 et~.

Further modifications of the above described mono-, di-, or polymeric amidoamines or imidazolines are the reaction products with reactive oxirane systems such as ethylene oxide, propylene oxide or butylene ox:ide. Reaction occurs preferentially on primary and ,econdary nitrogens, that is, a nitrogen to which one or two hydrogen atoms are covalently bound.
The reaction products belong to thl class of N-hydroxyethyl, N-2-hydroxypropyl- and N-2-hydroxy!butyl amidoamines or imidazolines. If excess oxirane isi reacted, polyethylene ether, polypropylene ether or polybutylene ether derivatives are obtained.
The examples which follow are illustrative of emulsifiers used to obtain cationi~ asphalt in water emulsions eminently useful for mixing under shear with a variety of siliceous and calcareous aggregates. After set~in~ ~evaporation of water), the asphalt films show ixcellent adhesion to the aggregate surface. ' i In preparing the bitumin~us emulsions of this ¦~
invention, an aqueous acidic solut~on of the eolulsifiers described below is intimately mixed under high shear in a colloid mill. The bitumen content can range from 30X to about 80% by !

~ 2 -'I I

~Z~0~5~

weight, pree~ably be~ween 6~% and 70Z. The dosage of the emul~ifier can range from 0.1~ by weight of the emulsion, pre~erably between 0.2-2.0~ by weight of the emulsion. Dependent on the emulsifier, a mixing grade emulsion is obtained in a pH
range of 2-7, with the optimum performance at a pH of about 2.5.
The "bitumen" used in the emulsion may be derived from ~omestic or foreign crude oil; it also includes bitumen, na~ural asphalt, petroleum oil, oil residue of paving grade, plastic residue from coal tar distillation, petroleum pitch, and asphalt cements diluted from solvents (cutback asphalts). Practically any vis osity or penetration graded asphalt cement for use in pavement construction as descri.bed in ASTM designation D-3381 and D-946 may be emulsified with the aid of the emulsifiers of this invention .
The cationic soap solutions are normally obtained by suspending the amidoamine or il~idazoline in water to which a sufficient amount of a suitable acid, for instance, hydrochloric, sulfuric, and phosphoric acid or the like is added until the desired pH value below 7 is re.lched and a clear emulsifier solution is obtained. Thereafter, the soap solution which is preheated to about 55C. and the fluid asphalt which is preheated I
to 120-125C. are mixed under high shear in a colloid mill for 30 seconds to give asphalt emulsions of brown color and creamy texture. Prior to testing according to ASTM D-244, the emulsions are stored at 70C. for 16 hours. Aggregate mixing tests are performed by placing a weighed amo~nt of aggregate in a mixing bowl, adding 5-10% by weight of thq emulsion on top of the aggregate and mixing for one minut~ to five minutes. The mix is divided into three equal parts and!placed in three dishes. The first sample is set aside; the second sample is washed with water ¦
immediately after mixing; and the third sample is washed with ~ 3 -water after it was get aside for one hour. The percent coating of the aggregate surface is estimated visually. From the first sample, the percent initial coating, from the second sample, the percent initial washoff coating, and from the third sample, the percent one-hour washoff coating are obtained. The construction industry coating requirements are generally set at 90-95%
minimum.
A typical cationic aqueous bituminous emulsion aggregate slurry is formulated in the laboratory with an amount of aggregate pre-wetted with water and admixed with a suitable cationic bituminous emulsion to a desired consistency. Suitable consistency is obtained by u-;ing mixed gradations of aggregates forming a smooth non-separat:ing uni~orm mixture of cationic aqueous bituminous emulsion-a~gregate which can be evenly spread onto an existing surface. The ultimate toughness of the applied slurry is obtained as the bitumen, such as asphalt, deposits on the aggregate particles and binds the newly applied coating to the pre-exi~sting surface as a mixture of asphalt cement and aggregate.
As a paving technique at the roadsite, a mobile self-propelled unit capable of uniformly metering the aggregate, water inorganic and organic additives emulsion components, may be used. A typical unit is equipped with separate tanks for aggregate, water, emulsion a:nd additives which are continually '~
metered into a mixing chamber at a,pre-determined ratio. The continually fed components are retained in the mixing chamber for approximately one minute and then fed into a spreader-box and applied to the surface to be coate~. Batch operated pneumatic ~evices can also be used for suitable placement of the cationic bituminous aggregate slurries of this invention.
, i I

12105S~

The emuls~fiers for the solventless emulsions of this invention perform very satisfl-~ctorily without auxiliary emulsifiers. However, occasi,~nally it may be necessary to alter the performance of the emulsion to obtain improved viscosity at a given asphalt content or improved stability to dust and fines on the aggregate and to lengthen or shorten setting time, etc. In these cases, one of two methods can be employed. Either a mixture of tall oil fatty acids, preferably tall oil pitch, can be added to the bitumen ~asphalt) prior to emulsification to improve break or improve the viscosity of the emulsion, or blends of the above described amidoa~ines and imidazolines with compatible cationic or nonionic emulsifiers may be used for the emulsification of the bitumen. Auxiliary emulsifiers~ which may constitute up to 90% of the total combined emulsifier formulation, are fatty amines, fatty propane diamines, fatty amidoamines, and fatty imidazolines. This class of compounds generally decreases setting time. Others are fatty monoquaternary ammonium salts and fatty diquaternary diammonium salts and nonionic emulsifiers, such as ethylene glycol polyethers of nonyl- or dodecyl phenol. Combinations of amidoamines and imidazolines, based on fatty monocarboxylic acids of various sources and the sul~onated oleic acid or sulfonated tall oil fatty acids disclosed in this invention, can also be obtained by reacting suitable polya~lines with a blend of fatty mono-, di- or tricarboxylic acids and sulfonated fatty acid.
Carboxylic acids suitable for this purpose are tall oil fatty acids, crude tall oil, resin acids, resin acids reacted with fumaric or maleic acid, tall oil pitch, tallow fatty acids, soya fatty acids and the like. Kraft lignin or Vinsol may also be co-reacted, 1 2~05~51 Dimer acids, ~hich are long chain C36-aliphatic carboxylic acids obtained by dimerization of fatty acids of various sources, may be also co-reacted. An example of this type of acid is produced by Emery Industries, Inc. under the trade name "Empol~ Dimer Acids".
Depending on the type of aggregate and its cleanliness, mixing is improved when aggregat,e i~ prewetted with 1-5% water by weight of the aggregate. The performance of the cationic asphalt emulsions in regard to mixing characteristics and setting (higher percentage of one-hour washoff coat) can, if nece~sary9 also be improved when, based on the weight of asphalt, 1-15% of a sol~ent such as diesel oil is added to the asphalt prior to emulsification. The emulsions prepared with the sulfonated carboxylic acid-polyamine condensates disclosed in this invention are stable and can be stored for a long period of time until required for use. Depending on the intended application, the emulsion may be mixed with the &ggregate at a central mixing plant in a large pug mill and the mix transported to the job site. Alternatively, the emulsion may be taken to the job site and mixed there, either with a mixing device, such as motorized mixing equipment, or manually.
In preparing the bituminous emulsions employed in the invention paving slurry seal mixtures, an aqueous acidic solution of the emulsifiers described below is intimately mixed under high shear in a colloid mill. The bitumen content can range from 30~ ¦
to about 80% by weight, preferably between 60Z and 70~. The dosage of the emulsifier can range from 0.1-10~ by weight of tha emulsion, preferably between 0.:7-2.0Z by weight of ehe emulsion.
Dependent on the emulsifier, a ~slurry grade emulsion is obtained in a pH range of 2-7, with the ~ptimum performance at a pH ~f about 2.S.
,, I
l~ - L6 - ¦

lZ~Q551 The aggrega~es of the invention paving slurry seal mixtures are conventional difficult to coat, densely graded aggregates such as sand, pit-r~n, crusher-run, etc., which ran2e in size from anything passing through a ~o. 4 sieve and at least 80% retained on 200 mesh (U. S. Standard Series).
Aggregate mixing tests are performed by mixing the ag~regate with water and aqueous bituminous emulsion. An inorganic additive-mineral filler, such as portland cement, hydrated lime, limestone dust and fly ash, may be added to accelerate set/break time and salts, such as ammo~ium sulfate, ~aluminum sulfate and other inorganic sulfates, or surfactants may be added to retard the se~/break o~ the slurry system. Mineral fillers shall comply with the requiremen~s of ASTM D242. These materials are mixed in a mixin~,bo~l until a homogeneous slurry mixture is obtained. The inability to form a stable slurry within 3 to 4 minutes of mixin~ time when proper proportions of each ingredient are used would ind~cate a mixture in which the materials are not compatible. This ~ix design is necessary to simulate field conditions. After ~he slurry is mixed, it is spread in a mold which is placed o~ an asphalt felt, and the~
set/break time is measured by blotting the exposed slurry surface with a paper towel. If no bro~m s~ain is transferred to the paper towel, the slurry is considered to be "set." The cure time could also be measured with a cohesion testing device. Many other tests such as described i-n ASTM D3910 are used to measure strength and other physical proper~ies of the slurry. The Performance Guide for Slurry Seal published by the Asphalt Emulsion Manufacturers Association,is used to measure the performance of the slurry seal.
,I The emulsion should be stable during mixing and should set within the designed time period following application. The ,l - 17 -il .

~ 1 2~ 05~S1 emulsifiers of this invention perform ~ery satisfactorily wi~hout auxiliary emulsifiers.
For instance, the setting times can be controlled with the concentration of emulsifier, ~he addition of lime, cement or an inorganic addi~ive, which would alter the break characteristics of the slurry system. An organic additive-polymer latex may also be employed to strengthen the matrix. The organic additive is preferably added to the emulsion-aggregate slurry.
A mixture of tall oil fatty acids, pre~erably tall oil pitch, can be added to the bit~en (asphalt) prior to emulsification to improve break or improve the viscosity of the emulsion. Alternatively, blencls of the above described amidoamines and imidazolines wi.th compatible cationic or nonionic emulsifiers may be used for the emulsification of the bitumen.
Auxiliary emulsifiers, which may constitute up to 90~ of the total combined emulsifier formulation, are fatty amines, fatty propane diamines, fatty amido~nines;, and fatty imidazolines.
Others are fatty monoquaternary ammpnium salts and fatty -diquaternary diammonium salts and nonionic emulsifiers, such as ethylene glycol polyethers of nonyl- or dodecyl phenol. I
The cationic bituminous e~ulsions employed in the invention slurries are slow-setting, mixing grade slurries under ASTM D-2397; however, the set time ~ay be shortened by adding lime or cement, providing an el~ulsi;on with quic~-setting characteristics.
The practice of this invention may be seen in the following examples wherein the prep'aration of various types of the emulsifiers of the invention is described and wherein the advantages of using these compounds`in a medium setting mixing I

~210551 grade cationic bitumi~ous emulsion and slurry seal applications are illustrated.

Exclmple 1 This example illustrates the variety of emulsifiers which can be obtained from sulionated oleic acid and polyamines under a variety of conditions.

Emulsifier 1 (Amidoamine type) One hundred fifty grams sulfonated oleic acid was placed in a three-necked flask of suitable size (500 mL) equipped with stirrer, thermometer and Dean-Stark trap to collect distillate. One hundred grams diethylene triamine was added slowly under stirring the temperature xose to 100C. The blend was heated to 210~C. When 18 ~ distillate was collected, the reaction was terminated.

Emulsifier 2 (Imidazoline type~
One hundred fifty grams sulfonated oleic acid and 100 grams diethylene triamine were blended as described under Emulsifier 1. The reaction mixture was heated to 260C. After 26 mL distillate was collected" the reaction was terminated.
!
Emulsifier 3 One hundred twenty grams sulfonated oleic acid and 100 grams aminoethylpiperazine were blended and heated to 240C.
After 12 mL distillate was collected the reaction was terminated.

Emulsif1er 4 1.
One hundred twenty g~ams sulfonated oleic acid and 100 grams triethylene tetramine were blended and heated to 230~.
A~ter 10 mL distillate was coll.ected, the reaction was terminated.

i 121û551 Emulsifier 5 One hundred grams sulfonated oleic acid and 100 grams tetraethylene pentamine were blended and heated to 240C. After 10 mL distillate was collected, the reaction was terminated.

Emulsifier 6 One hundred thirty grams sulfonated oleic acid and 100 grams N-aminoethylethanolamine were blended and heated to 240C~
After 20 mL distillate was col].ected, the reaction was terminated.

Emulsifier 7 One hundred twenty grams sulfonated oleic acid was blended with 50 grams triethanolamine and 40 grams diethylene triamine. It was heated to 250C. After 16 mL distillate was collected, the reaction was terminated.

Emulsifier 8 I
One hundred twenty grams~sulfona~ed oleic acid was blended with 60 grams aminoethylpiperazine and 40 grams triethylene tetramine. It wa5 hea~Pd to 240C. After 15 mL
distillate was collected, the reaction was terminated.

Example 2 This example illustrates a variety of emulsifiers prepared from polyamines and blends of sulfonated oleic acid and fatty acids of various sources, Vinsol or kraft lignin.`

Emulsifier 9 (Imidazoline) ! ` !
One hundred grams sulfon~ted oleic acid and 100 grams 1483 were blended at room temperature. To the blend 100 grams , _ ~ o _ , .1 ~

diethylene triamine ~as added and the mixture heated to 265C.
After 46 mL distillate was collected, the reaction was terminated.

Emulsifier 10 One hundred five gra~s sulfonated oleic acid and 1~5 grams Rosin S were heated to 100C. To this blend 85 grams diethylene triamine was added. The temperature rose to 150C.
It was further heated to 265C. After 35 mL distillate was collected, the reaction was terminated.

Emulsifier 11 One hundred grams sulfonated oleic acid and 100 grams tall oil pitch were blended and 100 grams diethylene triamine added. It was heated to 240~C. After 30 mL distillate was collected, the reaction was terminated.

Emulsifier 12 One hundred grams sulfonated oleic acid and 50 grams Industrene ~ (manufactured by Humko, now Witco) were blended and 80 grams diethylene triamine added. It was heated to 210C.
After 13 mL dis~illate was collected, the reaction was terminated.

Emulsifier 13 `i One hundred rams sulfonqted oleic acid and 100 grams C21 dicarboxylic acid (Diaci ~, man,ufactured by Westvaco) were blended and 100 grams diethylene triamine added. It was heated to 190C. After 14 mL distill.ate was collected, the reaction was .
terminated. , ,. !
!

!l ~210SSl Emulsifier 14 One hundred thirty-five grams sulfonated oleic ~cid and 135 grams C2l dicarboxylic acid (Diaci ~, manufactured by Westvaco) were blended and 120 grams DETA added. It was heated to 220C. After 28 mL distillate was collected, the reactinn was terminated.

Emulsifier 15 Ninety grams sulfonated oleic acid and 30 grams vinsol were blended and 80 grams diethylene triamine added. It was heated to 230C, After 20 mL distillate was collected, the reaction was terminated.

Emulsifier 16 One hundred grauls sulfonjated oleic acid and 100 grams diethylene triamine were blended a~ room temperature. The temperature rose to 80C. It was heated to 100C. and 40 grams Indulin A tkraft lignin acidified to pH 2.5) was added. A few drops of octanol prevented excessive foaming. It was heated to 200C. After 27 mL distillate was collected, it was cooled to 120C. and diluted with methyl celiosolve/isopropanol.
;
Emulsifier 17 - To 110 grams sulfonated oleic acid 13 grams potassium hydroxide in 80 mL methanol was adaed. The temperature rose to 65C. After 10 minutes 50 grams diethylene triamine was added through a dropping funnel and the reaction mixture heated to 200C. After 88 mL distillate was,collected, the reaction was terminated. It was cooled to 110Ç~ and diluted with diethylene glycollisopropanol.

,, I
1! - 22 _ `
il l lZ10551 Emulsifier 1%
Ninety grams sulfonated oleic acid and 90 grams DIAM llC (tallow propane diamine manufactured by General Mills Inc., now Henckel) were blende,1 and 30 grams diethylene triamine added. The temperature rose to 100C. It was further heated to 230C. After 7 mL of distillate was collected, the reaction was terminated.

Example 3 This example shows some emulsifiers prepared from sulfonated tall oil fatty acids and polyamines.

Emulsifier 19 One hundred fifty grsms sulfonated tall oil fatty acid was mixed with 100 grams diethylene triamine and heated to 210C.
After 14 mL distillate was collected, the reaction was terminated, Emulsifier 20 One hundred grams sulfonated tall oil fatty acid was mixed with 100 grams of a blen~ of,aminoethylpiperazine and tetraethylene triamine and heated to 210C. After 7 mL
distillate was collected, the reac~ion was terminated.

Emulsifier 21 One hundred grams sulfonated tall oil fatty acid was mixed with 100 grams of a blend oflaminoethylpipexazine and tetraethylene triamine and heated ~o 210C, After 7 mL
distillate was collected, the reaction was terminated.

1................................ ' i '11 Ex lmple 4 This example illustrates the properties of emulsions obtained when the above described emulsifiers were used for emulsification. To show the versatility of these emulsions, various siliceous and calcareous aggregates were used for the mixing experiments. Emulsions were prepared with Venezuelan based asphalt, having a penetration value of 120-150. Excellent emulsions were obtained when 0.3-1.5% emulsifier dosage was used.
Emulsions were prepared in the pH r,ange from 1.5-6.5 with pH 2.5 being the optimum pH value. The pH adjustments were made with dilute hydrochloric acid. The test data are given in Table I.
The aggregate test indica*es whether an emulsion is suitable for mixing operations. It was carried out with mixing bowl and spoon. Depending on the cleanlines,s of the aggregate, it was prewetted with 1-3~ water prior to addition of the emulsion.
After a 5-9 grams emulsion (per lOQ grams of aggregate) was mixed with aggregate for one-minute, init,ial coating, initial washoff coating, and one-hour washoff coating were determined visually.
From these data, the mixing efici~ncy and set time with a specific aggregate can be determin~d.

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This example shows the effectiveness of these types of emulsifiers for slurry seal application.
Table II illustrates t:he quick set times of the slurries prepared in Examples 1 - 3, as well as the ability to control the set times with addil:ion of a mineral filler tportland cement). The set ti~es are sho~ in the following table.

TAEILE II
SLURRY ST TIMES
(rLlin. ) _ .
Without With Emulsifier Cement Cement Emulsifier 1 198 4 Emulsifier 3 176 16 Emulsifier 4 247 7 Emulsifier 5 252 28 Emulsifier 6 180 10 Emulsifier 7 18~+ 35 Emulsifier 8 1~0+ 29 Emulsifier 9 brokebroke Emulsifier 10 1~0+broke Emulsifier 11 broke 5 Emulsifier 13 laO+ 4 Emulsifier 15 247 4 Emulsifier 16 176 15 Emulsifier 17 180+ 9 Emulsifier 19 120+
Emulsifier 20 19 E~ulsifier 21 broke 27 . ~
While the invention has been described and illustrated herein by references to various specific materials, procedures and examples, it is understood thaj the invention is not restricted to the particular materials, combinations of materials, and procedures selec:ted~fo~ that purpose. Numerous . ¦
variations of such details can be employed, as will be ;l,appreciated by those skilled in the art.

i~ .
Il - 33 -

Claims

What is claimed is

1. A cationic bituminous emulsion comprising from about 30% to about 80% by weight of bitumen, from about 0.1% to about 10% by weight of an emulsifier selected from the group consisting of reaction products of polyamines reacted with sulfonated carboxylic acids selected from the group consisting of sulfonated tall oil fatty acid and sulfonated oleic acid, and water to make up 100% by weight, the emulsion having a pH in the range of from 2-7.

2. The cationic bituminous emulsion of claim 1 wherein the emulsion is a mixing grade composition.

3. The cationic bituminous emulsion of claim 1 including up to 90% of the total emulsifier formulation of one or more auxiliary emulsifiers selected from the group consisting of fatty amines, fatty propane diamines, fatty amidoamines, fatty imidazolines, fatty monoquaternary ammonium salts, fatty diquaternary diammonium salts, and ethylene glycol polyethers of nonyl or dodecyl phenol.

4. The cationic bituminous emulsion of claim 1 including up to 90% of the total emulsifier formulation of one or more auxiliary emulsifiers selected from the group consisting of nitrogen derivatives of resin acids and nitrogen derivatives of kraft lignin.

5. The cationic bituminous emulsion of claim 1 wherein the emulsifier formulation,is prepared by reacting a polyamine with a blend of the sulfonated carboxylic acid of claim 1 and fatty carboxylic acids selected from the group consiting of fatty mono-, di- and tricarboxylic acids and mix-tures thereof.

6. The cationic bituminous emulsion wherein the emulsifier formulation is prepared by reacting a polyamine with a blend of resin acids and a sulfonated carboxylic acid of claim 1.

7. The cationic bituminous emulsion wherein the emulsifier formulation is prepared by reacting a polyamine with a blend of kraft lignin and a sulfonated carboxylic acid of claim 1.

8. The cationic bituminous emulsion of claim 1, 2, or 3, comprising from about 60% to 70% bitumen by weight of the emulsion, from about 0.2% to 2.0% emulsifier by weight of the emulsion, and water to make up 100% by weight, the emul-sion having a pH of about 2.5.

9. The cationic bituminous emulsion of claim 4, 5 or 6 comprising from about 60% to 70% bitumen by weight of the emulsion, from about 0.2% to 2.0% emulsifier by weight of the emulsion, and water to make up 100% by weight, the emul-sion having a pH of about 2.5.

10. The cationic bituminous emulsion of claim 7, comprising from about 60% to 70% bitumen by weight of the emul-sion, from about 0.2% to 2.0% emulsifier by weight of the emul-sion, and water to make up 100% by weight, the emulsion having a pH of about 2.5.

11. The cationic bituminous emulsion of claim 1 or 2 wherein the emulsion includes from 1% to 15% by volume of a hydrocarbon oil.

12. The cationic bituminous emulsion of claim 1 wherein a mixture of tall oil fatty acids is added to the bitumen prior to emulsification.

13. The cationic bituminous emulsion of claim 12 wherein the tall oil fatty acids mixture is tall oil pitch.

14. A paving slurry seal mixture of a cationic aqueous bituminous emulsion and mineral aggregate capable of being worked comprising: a densely graded mineral aggregate passing through No. 4 and at least 80% retained on 200 mesh screen;
from about 8% to about 20% of an oil in water type emulsion, based on the weight of the mineral aggregate, wherein the emul-sion is comprised of from about 55% to about 65% bitumen, based on the weight of the emulsion; from about 0.5% to about 2%
of a cation-active emulsifier based on the weight of the emul-sion, wherein the emulsifier is the reaction product of one or more polyamines reacted with a sulfonated carboxylic acid selected from the group consisting of sulfonated tall oil fatty acid and sulfonated oleic acid, and water to make up 100% by weight of the emulsion, the emulsion having a pH in the range of from 2-7; from about 4% to about 16% water, based on the weight of the mineral aggregate, added to form a slurry of the aggregate and the emulsion; and up to 3% of an inorganic or organic additive to reduce the setting time of the mixture.

15. The paving slurry seal mixture of claim 14 where-in the emulsion is a slow-setting, mixing grade composition.

16. The paving slurry seal mixture of claim 14 or 15 including up to 90% of the total emulsifier formulation of one or more auxiliary emulsifiers selected from the group consisting of fatty amines, fatty propane diamines, fatty amido-amines, fatty imidazolines, fatty monoquaternary ammonium salts, fatty diquaternary diammonium salts, and ethylene glycol polyethers of nonyl or dodecyl phenol.

17. The paving slurry seal mixture of claim 14 or 15 including up to 90% of the total emulsifier formulation of one of more auxiliary emulsifiers selected from the group consisting of nitrogen derivatives of resin acids and nitrogen derivatives of kraft lignin.

18. The paving slurry seal mixture of claim 14 or 15 wherein the emulsifier formulation is prepared by reacting the polyamine with a blend of the sulfonated carboxylic acid of claim 1 and fatty carboxylic acids selected from the group consisting of fatty mono-, di- and tricarboxylic acids and mixtures thereof.

19. The paving slurry seal mixture of claim 14 or 15 wherein the emulsifier formulation is prepared by reacting the polyamines with a blend of resin acids and the sulfonated carboxylic acid.

20. The paving slurry seal mixture of claim 14 or 15 wherein the emulsifier formulation is prepared by reacting the polyamines with a blend of kraft lignin and the sulfonated carboxylic acid.

21. The paving slurry seal mixture of claim 14 or 15 comprising from about 55% to 65% bitumen by weight of the emulsion, from about 0.2% to 2.0% emulsifier by weight of the emulsion, and water to make up 100% by weight, the emulsion having a pH of about 2.5.

22. The paving slurry seal mixture of claim 14 wherein a mixture of tall oil fatty acids is added to the bitumen prior to emulsification.

23. The paving slurry seal mixture of claim 22 wherein the tall oil fatty acids mixture is tall oil pitch.

24. The paving slurry seal mixture of claim 14 or 15 wherein the inorganic additive is selected from the group consisting of portland cement, hydrated lime, limestone dust, fly ash, ammonium sulfate and aluminum sulfate.