Bitumen compositions

Abstract: The invention provides bitumen compositions comprising bitumen and at least one polymerised fatty acid contained in the bitumen, processes for their preparation and their use in bitumen emulsions and surface dressings suitable for roads.

Description: This invention relates to bitumen compositions, their preparation, and their use in bitumen emulsions and surface dressings, e.g. for road surfacing. Venezuelan crude oils naturally contain naphthenic acids. Bitumens prepared from such crude oils (naphthenic bitumens) contain the napththenic acids and have improved properties relative to bitumens (non-napthenic bitumens) prepared from crude oils which do not contain naphthenic acids, e.g. Middle East oils. It is known to add (and incorporate) naphthenic acids to non-naphthenic bitumens in order to try to attain the quality of naphthenic bitumens. Australian Patent No. 557974 (Kao Corp.) discloses a liquid emulsifier composition suitable for preparing an asphalt (bitumen) emulsion which is dispersible in cold water and which comprises (1) at least one mono- or poly-amine containing a C₈₋₂₂ aliphatic group, and (2) at least one carboxylic acid that is (a) C₂₋₁₀ straight-chain saturated, (b) C₄₋₁₈ branched chain saturated, (c) C₁₂₋₁₈ straight-chain unsaturated, (d) C₅₋₁₈ saturated, containing a naphthenic ring, (e) C₇₋₁₈ aromatic, containing a benzene ring, or (f) a dimer acid, mainly a C₃₆ dicarboxylic acid. It has now surprisingly been found that bitumen compositions having surprisingly enhanced properties can be obtained by incorporating polymerised fatty acids into bitumens. According to the present invention therefore there is provided a bitumen composition comprising bitumen and at least one polymerised fatty acid contained (incorporated) in the bitumen, obtainable by a process which comprises incorporating the at least one polymerised fatty acid into the bitumen by mixing the acid or acids directly into molten bitumen. Polymerised fatty acids, particularly dimer and trimer acids, typically contain alkyl chains greater than 4 carbon atoms, preferably at least 7 carbon atoms, and may be obtained by polymerisation of unsaturated fatty acids such as tall oil fatty acids and linoleic acid. Dimer acids (fatty acids, C₁₈-unsaturated dimers) are known and are assigned Chemistry Abstracts Registry Number CAS/61788-89-4. Trimer acids (fatty acids, C₁₈-unsaturated trimers) are also known (CAS/68937-90-6). Such polymerised fatty acids are described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 7, pages 768 to 782, 3rd Ed. (1979), John Wiley & Sons Inc., USA, and examples are commercially available, e.g. under the trade mark "PRIPOL" (Unichema International, U.K.) and the trade mark "POLYMERGIN" (Harburger Fettchemie Brinckman & Mergell G.m.b.H., W. Germany). They can also be prepared by plasma polymerisation, e.g. by the method described in EP-A-346 999. Preferably, the at least one polymerised fatty acid comprises at least one acid selected from dimers and trimers of an unsaturated fatty acid, advantageously at least one acid selected from dimers and trimers of a C₁₈ unsaturated fatty acid. A particularly preferred polymerised fatty acid mixture comprises a blend containing 4 parts by weight C₃₆ dimer acid to 1 part by weight trimer acid, e.g. the dimer acid sold under the trade mark "PRIPOL 1017". The proportions of the at least one polymerised fatty acid relative to the bitumen are not critical. However the at least one polymerised fatty acid is preferably present in an amount of at least 0.1% w/w of the bitumen, e.g. an amount in the range 0.1% to 2% w/w of the bitumen, more preferably at least 0.5% w/w of the bitumen, e.g. an amount in the range 0.5% to 1% w/w of the bitumen. The invention also provides a process for preparing a bitumen composition of the invention which process comprises incorporating the at least one polymerised fatty acid into the bitumen, by mixing the acid component directly into molten bitumen. The bitumen may be any bitumen, but the advantages of the invention are most clearly attained when the bitumen is a non-naphthenic bitumen, as will readily be appreciated by those skilled in the art. Emulsions and surface dressings, e.g. for road surfacing may readily be prepared from bitumen compositions of the invention, in known manner. The invention thus further includes the use of bitumen compositions according to the invention in a bitumen emulsion or a surface dressing suitable for roads. The invention will be further understood from the following illustrative examples, in which parts and percentages are by weight unless otherwise indicated. EXAMPLES Various doped bitumens were prepared based on five 180/220 penetration bitumens, viz. an industrially produced bitumen (Bitumen A) and laboratory bitumens prepared by blending well defined short residues from crude oils of different geographical origins with wash oils from the same crude oils, i.e. Aral Heavy (Bitumen B), Maya Isthmus (Bitumen C), Ural (Bitumen D), or by including a vacuum flashed thermally cracked residue (Ural) (Bitumen E). The bitumens were doped by adding doping agents to the molten bitumens whilst stirring until homogeneous. Emulsions containing about 65% bitumen were prepared in conventional manner from the above bitumens, by introducing bitumen (at 140°C) into a turbine mill together with an aqueous phase containing hydrochloric acid and emulsifier ("DINORAM S"® cationic emulsifier ex CECA, France. (DNS)). Various properties of the bitumens (adhesivity) and of the emulsions (e.g. viscosity, breaking behaviour) were measured, and the results are given in Tables 1 to 6 following, in which the doping agent RCO (also known as NOR 90) is a naphthenic acid used for purposes of comparison, "PRIPOL 1013"® and "PRIPOL 1017"® are dimer acids (Unichema International, UK), "PRIPOL 1049"® is a trimer acid (Unichema International, UK), "POLYMERGIN D75"® is a mixture of polymerised fatty acids with a high trimer acid content (Harburger Fettchemie Brinckman & Mergell GmbH), and "P4" is a mixture obtained by plasma polymerisation by the method of EP-A-346 999 containing approximately 20% of dimer and 40% of trimer acids. Various properties of these dimer and trimer acids are given in Table A immediately following: The results of tests on the various emulsions given in Tables 1 to 6 above are illustrated in figures in the accompanying drawings, Figures 2 to 5 being concerned with the effect of doping on break performance. In the figures constituting the accompanying drawings: Figure 1 shows the effect of doping (% dimer and trimer acids on the X axis) on the pseudoviscosity of the emulsion (expressed in cSt (mm²/ s )) for various acid mixtures; Figure 2 records the SMS 210m test (%) on the X axis and the LCPC test (g/100g) on the Y axis for emulsions prepared from a bitumen A which is undoped or doped with different agents; Figure 3 is similar to Figure 2, but relates to different Bitumens, either undoped or doped with the same agent ("PRIPOL 1017"®); Figure 4 shows % of dimer and trimer acids on the X axis and percentage deposited on the Y axis, as recorded in the SMS 210m test; Figure 5 shows percentages of dimer and trimer acids on the X axis and filler (g/100g) on the Y axis, as recorded in the LCPC test; and Figure 6 shows the effect of "PRIPOL 1017"® on the mean adhesivity, pseudoviscosity and sedimentation of an emulsion, compared with an undoped bitumen. In the above Tables 1 to 6 and Figures 1 to 6, pseudoviscosity was measured in known manner using an Engler viscometer and using a standard tar viscometer (STV). The abbreviations under "Storage Stability" refer to upper layer ("U"), lower layer ("L") and the difference therebetween (Greek letter delta). Adhesivity of the bitumen and breaking rates of the emulsions were tested as follows: 1. ADHESIVITY (LCPC method) The purpose of this test is to assess the adhesivity, in the presence of water, of a hydrocarbon binder coated on aggregate, and in it the displacement of bitumen by water on the surface of the aggregate is measured. In the test, bitumen-coated aggregate is plunged into water while hot, and the percentage of the surface covered by the binder after 16 hours' immersion at 60°C is evaluated. The test is carried out with four types of reference aggregate, as indicated. 2. LCPC break index Reference fines (siliceous fines in the case of cationic emulsions) are poured continuously through a funnel at a rate of 0.3 to 0.5 g/s into a beaker containing 100g of emulsion. The mixture is agitated constantly, and the addition of fines halted when the aggregate-emulsion system takes on the appearance of a block. The quantity of fines added to the 100g of bitumen emulsion is called the break index. 3. SMS 210m break index 10g of aggregate (Corbigny porphyry, 2 to 4mm) are placed in contact with an excess of emulsion (about 10g) for 1 hour in an environment saturated with water in order to prevent any evaporation. The unbroken emulsion is removed with distilled water. After drying, the quantity of bitumen deposited is determined by weighing, and the result expressed in relation to 10g of emulsion. From the Tables and the Figures (particularly Figure 2) it is evident that all the dimer/trimer acids significantly improved the breaking performance of the emulsions. Overall, the dimer acid "PRIPOL 1017"® is the most preferred dimer/trimer acid for its combination of improvements in relation to adhesivity of the bitumens and sedimentation performance (Figure 6) and breaking behaviour (Figure 3) of the emulsions.

Claims: Claims for the following Contracting States : AT, CH, DE, DK, FR, GB, IT, LI, NL, SE A bitumen composition comprising bitumen and at least one polymerised fatty acid contained in the bitumen, obtainable by a process which comprises incorporating the at least one polymerised fatty acid into the bitumen by mixing the acid or acids directly into molten bitumen. A composition according to Claim 1 wherein the at least one polymerised fatty acid comprises at least one acid selected from dimers and trimers of an unsaturated fatty acid. A composition according to Claim 1 or 2 wherein the at least one polymerised fatty acid comprises at least one acid selected from dimers and trimers of a C₁₈ unsaturated fatty acid. A composition according to any one of Claims 1 to 3 wherein the at least one polymerised fatty acid is present in an amount of at least 0.1% w/w of the bitumen. A composition according to Claim 4 wherein the amount is in the range 0.1% to 2% w/w of the bitumen. A composition according to Claim 4 or 5 wherein the amount is at least 0.5% w/w of the bitumen. A composition according to Claim 6 wherein the amount is in the range 0.5% to 1% w/w of the bitumen. A process for preparing a bitumen composition according to any one of Claims 1 to 7 which comprises incorporating the at least one polymerised fatty acid into the bitumen by mixing the acid or acids directly into molten bitumen. Use of a composition according to any one of Claims 1 to 7 in a bitumen emulsion or a surface dressing suitable for roads. Claims for the following Contracting State : ES A process for preparing a bitumen composition comprising bitumen and at least one polymerised fatty acid contained in the bitumen, which comprises incorporating the at least one polymerised fatty acid into the bitumen by mixing the acid or acids directly into molten bitumen. A process according to Claim 1 wherein the at least one polymerised fatty acid comprises at least one acid selected from dimers and trimers of an unsaturated fatty acid. A process according to Claim 1 or 2 wherein the at least one polymerised fatty acid comprises at least one acid selected from dimers and trimers of a C₁₈ unsaturated fatty acid. A process according to any one of Claims 1 to 3 wherein the at least one polymerised fatty acid is present in an amount of at least 0.1% w/w of the bitumen. A process according to Claim 4 wherein the amount is in the range 0.1% to 2% w/w of the bitumen. A process according to Claim 4 or 5 wherein the amount is at least 0.5% w/w of the bitumen. A process according to Claim 6 wherein the amount is in the range 0.5% to 1% w/w of the bitumen. Use in a bitumen emulsion or a surface dressing suitable for roads of a bitumen composition comprising bitumen and at least one polymerised fatty acid contained in the bitumen, obtainable by a process which comprises incorporating the at least one polymerised fatty acid into the bitumen by mixing the acid or acids directly into molten bitumen.

Inventors: GERRITSEN ANTONIE HERMANUS, PAROIELLE PASCAL, RABIOT DENIS, GERRITSEN, ANTONIE HERMANUS, PAROIELLE, PASCAL, RABIOT, DENIS
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1990
Main classification: C08L95
IPC codes: C08K5