PREPARATION OF BITUMINOUS COATING COMPOSITIONS AND ASSEMBLY OF CONSTITUENTS REQUIRED FOR THE PREPARATION

Abstract: A method is disclosed of preparing a bituminous compo­ sition from an anionic bituminous (bitumen or bitumen plus a rubber) emulsion, which composition is suitable for coatings for sealing, water-proofing and insulating purposes. The composition has a controlled and known pot-life, acceptable drying time and good resistance to re-emulsification. The me­ thod is characterised by intimately mixing the emulsion with an amount of an emulsion-breaking accelerator, the compo­ sition and quantity of which are such as initially to delay re­ lease of cations and thereafter release cations in a controlled, uniform, rate for reaction with the anionic emulsifier(s) of the emulsion. Further essential properties of the accelerator em­ ployed are that it neither materially alters the pH value of the emulsion nor binds any substantial quantity of water. Calcium sulphate dihydrate in a water-insoluble hydrocarbon fraction, and employed at 1 to 2% treat rate, is a preferred accelerator. An assembly of units containing various constituents re­ quired to produce the bituminous coating composition is also described.

Description: Preparation of Bituminous Coating Composition This invention relates to bituminous coating and sealing compositions and to their preparation and use. The compositions are based on bituminous emulsions, more especially those suitable for water-proofing, sealing, insulation, and similar purposes in, for example, building and construction industries and in mining. As employed herein the term bituminous emulsion includes an emulsion of any one or more of: naturally occuring asphalt, petroleum derived asphalt, and bitumen derived from coal, for example pitches and tars. The term is also used to include the simple type of emulsions of bitumen and water and the type additionally containing a natural or synthetic rubber. This latter type is of especial interest in the building and the like industries. The emulsions are anionic emulsions, almost invariably of the oil-in-water type. One method of using such an emulsion is for it to be applied to the surface to be treated and the coating thus formed is left to dry by evaporation of the water component of the emulsion. This method of application suffers from a number of difficulties and disadvantages. Two major ones are (a) the time taken for the coating to dry; during the drying period the coating is very vulnerable to damage, particularly by water, for example rainfall; and (b) after formation of a continuous film the emulsifiers present in the emulsion tend to be concentrated in the outer surface. Persistent contact with water, for example during rainfall, tends to lead to a degree 'of re-emulsification with consequent loss of sealing quality or the water repellent quality of the coating. One type of solution to the problem which has been attempted is to spray a bitumen emulsion, or a bitumen-latex emulsion, onto a surface whilst at the same time separately spraying an emulsionbreaking/latex-breaking chemical onto the surface in such a way that the two sprays impinge at the moment the emulsion contacts the surface (as disclosed in British Patent 941,656). In another proposal of this type, the spray of the chemical intersects the other spray before the surface is reached so that the emulsion and latex are broken before contact with the surface (as disclosed in British Patent 1,383,463). In yet another proposal the emulsion is first coated on the surface and immediately after, while it is still wet, a coating of an aqueous solution of a salt such as calcium chloride is sprayed onto the surface as a protective layer (as disclosed in British Patents Nos 353,702 and 1,443,173). The above type of proposal essentially requires the use of very accurate spraying. However, when a wind is blowing then, often, atomized material cannot be directed accurately and consistently. Material is wasted and environmental pollution cannot be avoided. A second type of attempted solution to the problem is concerned with reducing drying time by adding to the emulsion, before use, an accelerator of such composition and quantity that it binds all the water of the emulsion after the latter has broken (as disclosed in East German Patent 66,128). Although this is a useful approach to overcoming the problem nevertheless, in practice, it does give rise to considerable difficulties. Thus, it is found that pot-life of the resultant mix is too variable and uncontrollable; often being so short as to give rise to gelling in the container. Additionally, often a non-uniform coating is observed due to lumpiness caused by the uncontrollable action of the accelerator. This is particularly to be observed if cement is used as accelerator. IVhen cement, either dry or as an aqueous slurry is added to an anionic emulsion of bitumen, or bitumen/rubber, the calcium ions rapidly react with the anionic emulsifiers, and this leads to a very rapid and uneven breaking of the emulsion. The initial concentration of calcium ions is so high that immediate emulsion-breaking in the vicinity of a cement particle occurs, which leads to formation of lumps. The rapid supply of calcium ions also leads to an unacceptably short pot-life. A proposal for extending pot-life is disclosed in German Auslegeschrift 2,447,791, wherein a cement/oil dispersion is employed in a manner which is required to break the emulsion and bind all the water present. The pot-life can be extended to some extent in this way, but the problem of lump formation will still arise due to uneven take-up of water by the substantial quantity of cement employed. It is an object of the present invention to provide a method of preparing a bituminous composition suitable for sealing, coating, etc., which composition has an acceptably long pot-life, is substantially or completely free from lumps, and from which a seal or coating of good resistance against re-emulsification can be obtained. According to one aspect of the present invention there is provided a method of preparing a bituminous composition suitable for coating onto a substrate as a sealant, insulating or waterproofing compound, comprising the steps of initimately mixing together an aqueous anionic emulsion of bitumen or of bitumen and a rubber (preferably in latex form), and an amount of an emulsionbreaking accelerator; which method is characterised in that the composition of, and the quantity of, the accelerator employed are such as to cause the accelerator initially to delay release of cations for a period of time and then release cations at a substantially controlled and uniform rate for reaction with anionic emulsifier(s) of the emulsion without materially altering the pH value of the emulsion and without binding any substantial quantity of the water of the emulsion. The applicants have found that, surprisingly and contrary to the tenor of the prior proposals, it is not essential to bind all the water of the emulsion when breaking the emulsion. Applicants have found unexpectedly good results are obtained when, in accordance with their invention, the emulsion-breaking accelerator is such as will neither bind any substantial quantity of the water, nor materially alter the pH value of the emulsion (which is normally a value in the range 7 to 12, suitably about 10). In all cases it is preferred that the accelerator contains a compound of a metal of Group 2 or Group 3, or a heav .y metal, of the Periodic Table of Elements. Thus, for example, an aluminium compound (if pH is about 7 or 8) or an iron compound can be employed, but most preferably a calcium compound is used. In accordance with one preferred embodiment of the invention the accelerator comprises a solution, dispersion, suspension or slurry in a substantially water-insoluble hydrocarbon fraction of a said metal compound which has a water-solubility at 20 C in the range 0.02 to 0.60, expressed as concentration Ca in grams per ml water (C.H. Hodgeman - "Handbook of Chemistry & Physics", 3rd Edition, 1955. Chemical Rubber Publishing Co., Cleveland, Ohio). Thus, for example, suitable calcium compounds include the fumarate, lactate, benzoate, salicylate, citrate, succinate, cinnamate, tungstate and sulphate. Calcium sulphate dihydrate is a preferred compound. Unsuitable compounds are calcium chloride and calcium selenate (solubility too high) and calcium oxalate and calcium fluoride (solubility too low). The water-insoluble hydrocarbon fraction in which the calcium or other compound is dissolved, dispersed, slurried or suspended, must, of course, be substantially compatible with the bitumen/latex system and have a relatively high initial boiling point (preferably at least 1500C). Examples are mineral oils (paraffinic; naphthenic; aromatic; mixed); alkylated aromatic fractions; tar oils; fractions from steam-cracker tars; naphthenic fractions; and chlorinated aliphatic hydrocarbons. Generally an aromatic type oil is preferred. A stabilizing agent will normally be included to prevent any substantial settling out of the compound which might otherwise occur. The stabilizing agent(s) employed will normally be thixotropic agents. Clay minerals are suitable, including organic derivatives thereof. Compounds sold under the trade mark Bentone, are preferred. The following table shows normal, preferred and most preferred quantities (% by wt.) of the preferred components of an accelerator in accordance with this feature of the invention: Normal Preferred Most Preferred Ca salt 20 - 40 25 - 35 30 - 33 Stabilizer 5 - 10 7 - 9 7 - 3 Hydrocarbon fraction 75 - 50 68 - 56 63 - 59 Normally, slurry of a paste-like consistency will be employed; and normally will be employed in an amount up to 5 wt.% (as active ingredients), very preferably 1 to 2 wt.%, by wt. of the bituminous emulsion. In accordance with another embodiment of the invention the accelerator comprises a mixture, slurry, dispersion or suspension of a compound of Group 2 or Group 3 metal or of a heavy metal, and a masking agent which regulates the rate of and/or quantity of cations delivered for reaction with the emulsifiers of the anionic emulsion. Again, calcium compounds are preferred and finely divided hydraulic cement may conveniently be employed; being preferably sodium aluminate, but can be any other suitable compound reacting with calcium ions. Other examples are phosphates and oxalates. Suitably, as active ingredients, from 90 to 98 wt.% of cement and 10 to 2 wt.% of masking agent will be employed, preferably 94 to 96 wt.% cement and 6 to 4% accelerator, most preferably 95 and 5 wt.% respectively. In all embodiments of the invention the accelerator can contain, if desired, non-active ingredients, for -example a pigment. A pigment is useful in indicating the degree of homogeneity achieved during mixing the accelerator with the emulsion. Preferably, the accelerator and masking agent are employed as a slurry, dispersion or suspension in water or one or more of the aforesaid hydrocarbon fractions. Preferably, too, the ratio total solids to total liquids is approximately 1:1. Normally, in practice of the invention, upto 5 wt.%, more often upto 3 wt.%; preferably 0.+ to 2 wt.%, especially 1 to 2 wt.%, of active ingredients (accelerator plus masking agent) is employed, based on wt. of bituminous emulsion. In all cases the bitumen emulsion employed is anionic and is most preferably a bitumen/rubber emulsion, very suitably one which is paste-like, and solvent - and plasticizer-free. These are known products, the bitumen being of suitable penetration for the purposes of emulsification and subsequent coating. The rubber is preferably employed in latex form. The rubber can be natural or synthetic, such as butyl rubber, butadiene-styrene copolymers, polychloroprenes, polychlorobutadienes, and polyisoprenes. Normally, the total solids content of the emulsions will lie between 50 and 70 wt.%, more especially from 55 to 65 wt. %. The method of making such emulsions is known. It has been discovered in connection with the use of a masked accelerator that the hardness of the water used for the manufacture of the bituminous emulsion may influence the release of cations from the accelerator. Water is often softened, for example by means of known chemical agents such as phosphate or polyphosphate (trisodium phosphate being commonly used). Accordingly, water hardness, or quantity of softener present, should be taken into account to enable best results to be achieved. This is illustrated hereinafter. In accordance with another aspect of the invention, there is provided an assembly of constituents required for preparing a sealing etc., composition by the method of the invention; which assembly is characterised by having the constituents contained in individual but associated, units, one unit comprising a quantity of the said aqueous anionic emulsion of bitumen or of bitumen and rubber, and at least one other unit containing the corresponding quantity of the said emulsion-breaking accelerator as individual solids, or as a mixture of solids, or as a solution, slurry, dispersion of suspension of said solids in water or the said hydrocarbon fraction. In a modification, said second unit contains only the required quantity of solid constituent(s) for forming the said slurry, etc. of the emulsion-breaking accelerator. In a further modification, where there are two or more such solid constituents then these may be contained in two or more separate units. In all cases the emulsion-breaking accelerator quantities are preferably such that on adding and intimately mixing with the emulsion a pot-life (time available for using the resultant composition) is approximately 30 to 40 minutes. Hence, as a direct result of this aspect of the invention, all that need be done at the work site is for the accelerator components to be mixed, or slurried, etc., or for pre-mixed slurry to be taken, and then added to the bituminous emulsion and thoroughly stirred. No calculation of amounts is required because the quantity of solids or slurry provided is the calculated quantity for the associated emulsion. Thus, unskilled labour can undertake the mixing and obtain a composition having a consistently standard pot-life of say, thirty to thirty-five or forty minutes. The composition is easily brushable and can be readily coated onto most substrates, which may be at any angle to the horizontal. The coating is of consistent thickness and has very good resistance to re-emulsification and thus retains its water-proofing properties. The essence of the invention lies in the controlled attack of the accelerator on the emulsifier(s) of the anionic bituminous emulsion, in a manner which forms water-insoluble metal soaps; without materially altering the pH value of the emulsion, or without binding any substantial quantity of the emulsion water. In effect, in the present invention the accelerator is one which acts in two stages. For example, assuming a calcium compound (as hereinbefore defined) is selected as a component of the accelerator. In the first stage Ca++ ions are prevented from release from the accelerator by other components of the accelerator, for example the masking agent and/or the water-insoluble hydrocarbon fraction. This permits the accelerator to be intimately mixed with the emulsion before breaking commences. In the second stage Ca ions are released in regulated manner to bring about controlled breaking of the emulsion and formation of water-insoluble soap(s) of the emulsifier(s) of the emulsion. The calcium salt of the accelerator is of lower solubility product than the calcium soap(s) formed. Stage 1 can extend over about 10 mins and stage 2 from 20 to 30 further minutes. By means of the accelerator, and quantity thereof employed, no water-binding occurs, no pH change of the system occurs, and the composition is readily spreadable or brushable, having no lumpiness caused by non-homogeneous action and effects of the accelerator. There is, furthermore, no emulsion-inversion brought about and therefore, no trapping of water, such as would give rise to unwanted bubble effects to a surface coated with such a composition. The following examples illustrate the invention further: Example 1 Four samples of a bitumen/latex emulsion of approximately 65 wt.% total solids content were taken and each was treated with a different one of four accelerator compositions, only the first being in accordance with invention. The compositions involved and results observed are shown in Table 1. It will be seen that only the first composition gave a combination of (a) acceptable pot-life (which in practice is not less than 20 mins or above 60 mins; desirably 20 to 40 mins. and preferably approximately 30 mins.) and (b) low tendency of the composition to re-emulsify. Example 2 Four further samples of the same bitumen/latex emulsion were taken and each treated with a different one of four accelerator compositions having the same calcium salt but having differing proportions of it, the organic liquid and the stabilizing agent. The compositions involved and results observed are shown in Table 2. It will be seen that at least 20 wt.% of calcium salt in the accelerator (0.4 wt.% based on wt. of emulsion) is necessary for acceptable pot-life and acceptable resistance to re-emulsification; very preferably the amount used is of the order of 30 wt.%. (0.6 wt% based on wt.% of emulsion). Example 3 The same bitumen/latex emulsion was taken and the accelerator employed was the third one of those set out in Table 2. The pot-life of mixtures was measured at temperatures from 10 C to 60 C. The attached graph shows the results obtained. It will be seen that over the temperature range 100C to 25 0C the pot-life is sufficient to enable easy application of the composition. The pot-life is predictable and repeatable over that range, emphasizing the usefulness of the invention in practice, particularly where un-skilled labour is involved. Example 4 The same bitumen/latex emulsion was taken. The emulsionbreaking accelerator employed was in intimate mix of finely divided cement and finely divided sodium aluminate. Table 3 shows that on occasions with such an accelerator it may be desir able -to add an amount of a softening agent to the water employed in forming the bituminous emulsion, in order to keep pot-life to the preferred thirty minutes and to minimise any tendency of a coating to re-emulsify (for example during rainfall). TABLE 1 Pot life and re-emulsification tendency when employing various calcium accelerator systems when added to a latex/bitumen emulsion. Accelerator 60 wt% tar oil 60 wt% oil 60 wt% tar oil 60 wt% tar oil System 7 wt% BENTONE 34 7 wt% BENTONE 34 7 wt% BENTONE 34 7 wt% BENTONE 34 (a paste) 33 wt% CaSO4.2 H2O 30 wt% CaCl2 33 wt% CaF2 33 wt% Ca (OH)2 Finished 100 g bitumen/latex emulsion (EUBIT-PLAST) Composition EMI10.1 plus 2 g paste EMI10.2 Pot-life 30 minutes 15 minutes 24 hours 24 hours Tendency to low low high high re-emulsify TABLE 2 Pot life and re-emulsification tendency when employing a hydrated calcium sulfate accelerator system added in varying concentrations to a bitumen/latex emulsion. Accelerator 75 wt% tar oil 69 wt% oil 60 wt% tar oil System 8 wt% BENTONE 34 8 wt% BENTONE 34 7 wt% BENTONE 34 (a paste) 17 wt% CaSO4 x 2 H2O 23 wt% CaSO4 x 2 H2O 33 wt% CaSO4 x 2 H2O Finished 100 g bitumen/latex emulsion (EUBIT-PLAST) Composition EMI11.1 plus 2 g paste EMI11.2 Pot-life 150 minutes 45 minutes 30 minutes Tendency to Medium low low re-emulsify Table 3 Pot Life vs. Degree of hardness of water in emulsion. Degree of hardness wt % TSP +) Composition of Pot - Life Tendency to of water for latex/ added to accelerator added Re-emulsify bitumen emulsion water phase at a 1 wt% level hours DGH ++) 7 0 none undefined high 7 0 100 % Cement 0.25 low (but non-homogeneous, lumpy) 3 0 95 % Cement 0.5 low 5 % Na-Aluminate 7 0.1 - " - 0.5 low 15 0.2 - " - 0.5 low 30 0.3 - " - 0.5 low +) TSP = Trisodium phosphate ++) DGH = Degree German Hardness. 1 German Hardness is the hardness equivalent to 1 mg CaO in 100 cc H2O; (which is 10 ppm CaO).

Claims: WHAT E CLAD'I IS: 1. A method of preparing a bituminous composition suitable for coating onto a substrate as a sealant, or insulating or waterproofing agent, comprising the steps of intimately mixing together an aqueous anionic emulsion of bitumen or of bitumen and a rubber, and an amount of an emulsion-breaking accelerator; characterised in that the composition of, and the quantity of the accelerator employed are such as to cause the accelerator initially to delay release of cations for a period of time and then release cations at a substantially controlled and uniform rate for reaction with anionic emulsifier(s) of the emulsion without materially altering the pH value of the emulsion and without binding any substantial quantity of the water of the emulsion. 2. A method as claimed in claim 1, characterised in that the accelerator includes at least one compound of a metal of Group 2 or Group 3 of the Periodic Table of Elements. 3. A method as claimed in claim 2, characterised in that the accelerator comprises a solution, dispersion, suspension or slurry in a substantially water-insoluble hydrocarbon fraction, preferably a mineral oil or a steam-cracker tar, of a said metal compound which has a water-solubility at 200C in the range 0.02 to 0.60, when expressed as Ca gram per ml water. 4. A method as claimed in claim 3, characterised in that the compound is calcium compound, preferably calcium sulphate dihydrate. 5. A method as claimed in claim 1 or claim 2, characterised in that the accelerator comprises a mixture, slurry, dispersion or suspension, preferably in water or a substantially water-insoluble hydrocarbon fraction, of the metal compound and a masking agent for regulating delivery of cations for reaction with the said emulsifier(s). 6. A method as claimed in claim 5, wherein a calcium compound is employed, preferably an hydraulic cement is employed. 7. A method as claimed in claim 5 or claim 6, characterised in that the masking agent is sodium aluminate. 8. A method as claimed in any one of the preceding claims, characterised in that the accelerator is employed in amount up to 5 wt.% (calculated as active constituent) by wt. of the emulsion, preferably from 0.4 to 2 wt.%. 9. An assembly of constituents required for the preparation of a bituminous composition by the method defined in any preceding claim; the assembly being characterised by having the constituents contained in individual but associated units, one unit comprising a quantity of the said aqueous anionic emulsion of bitumen or of bitumen and rubber, and at least one other unit containing the corresponding quantity of the said emulsionbreaking accelerator as individual solids, or as a mixture of solids, or as a solution, slurry, dispersion of suspension of said solids in water or the said hydrocarbon fraction.

Inventors: GLET, WALTHER
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1979
Main classification: C09D3
IPC codes: C08L95, E04B1, C09K3