CS268560B1 - Admixture into bitumens and/or asphalt products - Google Patents

Abstract

The additive is applicable in an amount of 0.02 up to 2% hnot. into bitumens or asphalt products to a substantial increase their adhesion to aggregates, befcon, ceramics etc., consists of 50 to 80 wt. of at least one monoethanolamide and / or carboxylic acid diethanolamide From Cfi to C i, from 15 to 45% wt. the carboxylic acid ester C < with one to two hydroxyl groups triethanolamine or carboxylic acid triethanolamine. ZvySok do 100% are by-products (mono) triglycerides of carboxylic acids C --C ,, směsi mixtures of free carboxylic acids acids, mixtures of ethanolamine esters. Use it in construction and interesting is also a chemical industry

Description

The invention relates to an additive for blends and / or asphalt products, in particular for honorary asphalts, to increase the adhesion rates, respectively. adhesion to solid hydrophilic materials, in particular to aggregates, in particular to wet aggregates, saffron and ceramics based on technically readily available organic condensation products.

Bitumens, resp. Asphalts represent dark-colored plastic to solid sticky parts of coal carbonation tars, mainly of colloidal character, in which asphaltenes, petroleum resins and the heaviest hydrocarbon oils, among other minor components, are concentrated.

The usability of asphalt is largely determined by its rheological properties: it must not break at low temperatures and permanent deformations at higher temperatures have been small, so they should be at least minimally elastic, have a long service life, good adhesion to more hydrophilic aggregates, concrete and the like. Therefore, for practical applications, bitumens are generally modified with additives such as antioxidants, dispersants, anticorrosants, emulsifiers, rheological and other additives, and for many applications also adhesive additives. The 2 adhesive additives are the most important ones. Veselý, P. Kaš, V. Štěpina: Chemistry and Technology of Petroleum, p. 511-522, II. Slovak Publishing House of Technical Literature, Bratislava (1967) /, which increase the adhesion of asphalt to acidic or wet aggregates. Such are cationic surfactants, which are usually added to hot-processed asphalts, to dilute oils, to emulsions or to act directly on stone / face Kennell R.: Why. 2nd Intern. Congress Rheology, New York (1954), p. 350 /. However, asphaltogenic acids also increase the affinity of asphalt mainly for basic aggregates, e.g. to basalt and andesite aggregates, but it deteriorated: its affinity for acid aggregates, e.g. to quartz, granite and porphyry sand.

In the presence of water, Sále's conditions deteriorate, especially with regard to acidic aggregate, which acquires a negative charge. Because asphalt itself is generally alkaline in nature due to its aromaticity, and the anion of asphaltogenic acid gives it a negative charge, and asphalt has been expelled from the aggregate surface with water and the aggregate has been compacted. This adverse effect can not be eliminated on the one hand by adding lime to the acid aggregate, by hydrophobizing the aggregate, e.g. naphthenates or iron lignosulphonates or by means of cationic-active additives which accumulate on the asphalt surface and give it a positive charge.

Finally, it should be borne in mind that asphalts are always more hydrophobic in comparison with aggregates, concrete and other inorganic materials. Therefore, it is not surprising that good adhesives or adhesive additives generally belong to the group of surfactants. These hydrophilic parts of the molecules are oriented towards more hydrophilic aggregates and hydrophobic (lipophilic) parts towards asphalt, which also ensures good adhesion of asphalt to aggregates, concrete and the like. In addition to such surfactants used, a lot of salts of higher fatty amines or polyamines, quaternary pyridinium or long-chain ammonium salts, such as octadeelamine chloride. These admixtures are added to the asphalt or the aggregate is treated with it before treatment with the asphalt (Lee A.R., Nicholas J. H .: Petroleum 43, 255 (1957)). However, their disadvantages, in addition to technical and raw material demands, are also lower thermal stability, manifested in the application as an additive to asphalt. A special application on aggregate before adding asphalt is again laborious and more energy-intensive.

Effective adhesive additives for bitumens include aminoethylpiperazine (European Pat. No. 117,385), lipids, biolipids, glycerides, fatty acid phosphutides (GDR Pat. 200,742), siloxanes as well as organosilanes (NSR Pat. No. 3,236,381) and Hungarian U.S. Pat. No. 22,188) 1 'alkyl ether-1,3-propylenediamine. However, their disadvantage is the technical, energy and raw material complexity and lower efficiency for several aggregates. The same is true for additives, polyurethanes (NSR Pat. Application 3,028,365) to blumen. Lubricant additives are suitable for some additives (Lojko AI: Izv. Vuzov. Stroit. Archit. 10, 81 (1984), especially if they do not harm the lower hardness of the asphalt. The most commonly used, especially for honest asphalts and where there is no risk of corrosion of metals, are additives of naphthenic acids, naphthenates and especially iron naphthenates (GDR pat. 159 549; Woodhams RT, Varevorakul S.: Org. Coat. Appl. Polym.

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CS 26656ο 61

Sel. Proc. 46, J8O). .

On the other hand, it is an object of the present invention to add an admixture to alumina / or asphalt products in an amount of 0.0 to 2% by weight, in order to significantly increase the alumia of alumina, especially asphalt for aggregates, concrete and concrete. and mass. of at least one dono ethanolamine and / or diethanolamine of carboxylic acids C8 to C18, from 15 to 45%, of parenteral esters of at least one carboxylic acid C8 to C18, with a dehydric to tribal hydroxyl groups of triethanolamine and / or salts formed from at least one carboxylic acid. acid Cg 'to triethanolamine. In this case, _the IP zyyšok ° it is ncjmer.ej One of the byproducts of the border of the glycerides of carboxylic acids, Cg to C ^, a mixture of free carboxylic acids, the mixture of esters and raonoetanolamínu dletanolamínu the karbexylovýcí acid.

The advantage of the bitumen and asphalt additive according to the invention is the very good activity efficiency on the adhesion of asphalts to aggregates, concrete, ceramics, fired bricks, etc., good thermal stability and technical and raw material availability. Then, the fact that the mills, the additives do not have undesirable side effects, are not toxic, and moreover, together with the usual antioxidants applied to asphalts, also have a synergistic effect.

Both the individual amino alcohols, the monoethanolamine, diethanolamine and trlethanolamine and mixtures thereof, as well as the individual fatty acids C8 to C6, and mixtures of saturated and unsaturated carboxylic acids can be used for the production of the adhesive additives which can be used according to the invention. Carboxylic acids may additionally contain impurities of hydroxy acids, keto acids and lactones or glycerides. The condensation can be carried out at temperatures of 120 to 200 ° C, but it is most often carried out at 140 to 180 ° C, it being suitable to use an azeotrope-forming substance with water, so-called water extractors. The condensation is more preferably carried out in an inert atmosphere, at normal, reduced or elevated pressure. The condensation of the knives is carried out non-catalytically or in the presence of a catalyst, in particular in the form of ensolvoic acids, in particular in the form of oxides of manganese, lead, tin, zinc, titanium, antimony, nolybdenum. germanium. Aluminum or other compounds, especially salts, are most preferably used. ε · acids entering into condensation reactions, such as manganese laurate, oat stearate, zinc stearate and the like, or alcoholates with amino alcohols.

. A particularly important component of the additive is the presence in it of one narrow ester of one carboxylic acid of C8 to C18, with one to two hydroxyl groups of triethanolamine and / or a salt of a carboxylic acid with triethanolamine. is 0.01 to 2%, but most preferably 0.2 to 0.6%. A content lower than 0.2% no longer guarantees the good adhesion of asphalt to aggregates, concretes, etc. and higher than 0.6. cannot improve adhesion. Higher concentrations also require higher consumption of adhesive and, in some cases, knives to cause undesirable softening of the asphalt. However, higher concentrations may be justified in cases where it is necessary to achieve a synergistic effect with 3 rheological rubber additives.

Adhesives, resp. The adhesion cases according to the invention are also added to. bitumens in their production, or the formulation of asphalts together with other additives, in their refining, e.g. When it is more appropriate to add adhesion additives practically ... no termination. They can be added to asphalts just before application, e.g.

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together with thinner, whether in thinner, such as v ďechtóčM7úh6Thé tars-cp.-Prř.c-. best, but usable It is also possible to add the adhesives themselves to aggregates, concrete, etc. or in the form of solutions, penetrating coatings and only then add, resp. mix asphalt with pre-treated aggregate, clap, etc. According to the invention, the adhesive additives can be applied only to a part of the asphalt, which can also be diluted with a solvent, mixed with aggregates or other solid materials, and asphalt can be used even with a reduced content or even without an adhesive additive.

CS 26656ο B1

Adhesives to the bitumens ε / or asphalt products according to the invention can be applied in a single, portioned or continuous manner.

The specific results of the action and the composition of the adhesive additives according to the invention, as well as their further advantages, are apparent from the examples.

Example 1 '

To the dried aggregate (crushed dolomite limestone) changed by 10 to 16 mm, 4% by weight, based on weight, was added. aggregate, bitumen-asphalt component A-80, resp. honest petroleum asphalt Λ-80, both alone and with the addition of the product of the condensation of diethanolamine and triethanolamine with oleic acid at a temperature of 150 ° C (Additive A; acid number = 3 mg KOH / g; active substance content = 98% by weight; water content = 0.5% by weight) and additionally with the addition of 15% of addition product (salt) of oleic acid with triethanolamine (Additive A modified).

The starting honor petroleum asphalt A-80 has the following parameters: penetration at 25 ° C = 92; glass transition temperature KG = 45.5 ° C; volatility temperature = - Ί2 ° C and flash point = 248 ° C.

The adhesion of basic honorary petroleum asphalt A-80 to the mentioned aggregate, on the one hand added by Additive A, is tested. The evaluation of the adhesion of asphalts to the aggregate is performed according to ČSN 65 70 89.

The said dried aggregate in an amount of 300 g heated up to 150 ^c C for 30 I was added 12 g of bitumen pre-heated to 170 ° C for 30 min., Which wraps around the stone. The coated aggregate is then allowed to stand for 24 hours at room temperature. . After this time, the coated aggregate is covered with warm (60 ° C) distilled water and treated in a water bath at 60 ° C for 60 minutes. ,

The degree of coating is assessed visually as follows:

1st degree- · - adhesion good, aggregate is covered with asphalt 100%;

2nd degree - adhesion?., Satisfactory, in which the edges of the aggregate are exposed, covered only with a film of asphalt and water exposure of the aggregate is also possible;

3rd degree - adhesion unsatisfactory; Aggregates without oil film are exposed and the exposure of aggregates is more than point.

The evaluation of the adhesion of basic honorary petroleum asphalt A-80 as well as added by various amounts of Additive A is in Table 1.

Table 1

Bitumen - Added additive to 'bits' Evaluation of adhesion to aggregates kind of amount /% w / w Honorary petroleum asphalt A-80 Honorary petroleum asphalt A-80 Honorary petroleum asphalt A-80 Honorary petroleum asphalt A-80 without additive Additive A modified Additive A modified Additive A modified 0.2 0.5 1.0 3-unsatisfactory 1 - good 1 - good 2 - satisfactory

CS 26856ο B1

Furthermore, the softening effect of Additive A modified on said asphalt is determined. The results are shown in Table 2.

T a b u Γ k a 2

Parameter Amount of Ingredient Λ modified into dough. asphalt A-80 / wt. / 0 0.2 0.5 1.0 KG glass transition temperature in ° C Penetration at 25 ° 0 45.5 92 45 88 45 91 ^, 5 101 '

From the results in tab. It is clear that even Additive A, modified in an amount of 1.0% by weight, practically does not have a softening effect in the asphalt.

Next, the thermal stability of Additive A modified in an amount of 0.5 S by weight of additive honest petroleum asphalt A-80 at 160 ° C for 5 hours was tested. After thermal stressing of such additive asphalt, its adhesion is evaluated according to ČSN 65 70 89. The adhesion of this additive asphalt to aggregate did not deteriorate even after 5 hours at thermal stress at 160 ° C. This also demonstrates the suitability of using Additive A modified as an additive additive for honorary and concrete asphalts.

The thermal stability of Additive A modified, reps, doped with it in the amount of 0.5% by weight, of honorary petroleum asphalt A-80 was also evaluated by a standardized test in a thin layer, heating to 163 ° C for 5 hours according to ČSN 65 70 70.

Other properties of basic honor asphalt A-80 and additive with the addition of 0.5 wt. Additive A modified are listed in Table 3.

Table 3

Pointer ’ Flood sample of honor oil asphalt Additive sample with 0.5 wt. Ingredient A modified KG glass temperature in ° C 45.5 45.0 Penetration at 25 ° C 92 88 Breaking temperature in ° C - 12 - 12 ' Thermal stability: • weight loss at 163 ° C 5 h in% .. 0 0 KG glass temperature in ° C 50 50 penetration at 25 ° C / 5 h 73 69 penetration reduction in% 21 22 increase of KG glass temperature in ° C 4.5 5 breaking temperature in ° C - 8 - 8

Example 2.

The procedure is the same as in Example 1, except that 0.2% by weight of stearic acid ethanolamide (CH 2 Cl 2). ConHCl 2 Cl 2 OH, prepared by condensing ethanolamine with stearic acid at 160 ° C in the presence of xylene as condensate scavenger. After completion of the condensation, the remaining xylene is distilled off and 20% by weight of an equimolar mixture of triethanolamine and stearic acid are added. After documentary homogenization for 5 min. and the molten mixture with stearic acid ethanolamide is allowed to cool, solidifying and finally grinding to a fine powder.

The softening temperature of the honorary petroleum asphalt A-BO specified in Example 1 after the addition of 0.2 wt. this modified stearic acid ethanolamide is 46 ° C; penetration at 25 ° C is 92 and the breaking temperature -12 ° C. The asphalt added in this way has good adhesion (1st stage) to andesite aggregates with a grain size of 10 to 18 mm.

Example 3

0.1% by weight of lauric acid diethanolamine and 0.1% by weight of oleic acid triethanolamine ester are added to the honorary petroleum asphalt A-80. The softening temperature of the honor oil asphalt thus added is 45.5 ° C; penetration at 25 ° C reaches 91 and the breaking temperature -12 ° C. Its adhesion to andesite aggregates with a grain size of 1C to 18 mm is good.

Example 4

Condensation product of monoethanolamine, diethanolamine and triethanolamine with lauric acid, oleic acid, stearic acid and arachic acid, consisting of 36% by weight, monoethanolamide, oleic acid, 15% by weight, ethanolamide, lauric acid, 21% by weight, triethanolamine ester, lauric acid, 14 % by weight, triethanolamine ester of arachic acid and 10% by weight, a mixture of diethanolamine of stearic and oleic acid and 4% by weight, of the salt of triethanolamine with stearic acid, is added in an amount of 0.4% by weight to honest petroleum asphalt A-80. According to ČS’J 65 70 89, while honorary petroleum asphalt itself has unsatisfactory adhesion to andesite aggregates with a grain size of 10 to 18 mm, modified with 0.4% by weight, the additives already have a 1st degree adhesion, ie. good. Adhesive additives also have good temperature resistance and do not have a softening effect on asphalt.

Example 5 '

By condensing a mixture of aliphatic carboxylic acids C? to Ο- ^ θ, prepared by hydrocarboxylation of alkenes Cg to Cg, with a mixture of diethanolamine with monoisopropyl alcohol, with the catalytic action of zinc stearate and lead stearate, in a total amount of 0.5% by weight, and at a temperature of 180-190 ° C, purged with pure nitrogen and evacuation of the volatile products gives a condensation product to which 18% by weight of the triethanolamine salt with a mixture of ^C 20 ^{and S} 24 carboxylic acids are added in an amount of 0.5 5; mass, is added to the honor oil asphalt. Such asphalt has good adhesion (1st degree adhesion) to the aggregate. The softening temperature of the asphalt added in this way = 45 ° C and the breaking temperature »r12 ° C.

Example 6

Honorary andesite spruce grains 30 to 50 mm poured onto the stone substrate are, before rolling the sprayer, with a solution of the adhesive additives specified in Example 4 in hot coal pitch (145 ° C) at a concentration of 10% by weight. After solidification, it is rolled with an asphalt-spruce (7 to 15 mm grains) mixture in which 0.1% historical / honor asphalt has been used. Additive A modified from a new batch with a lower viscosity than that specified in Example 1 and modification with 15% by weight, oleic acid salt with triethanolamine (Additive A modified). While with the adhesive additive specified in Example 4, the adhesion level 1 is achieved (good), with Additive A unsatisfactory and with Additive A modified good again.

Example 7

Using the A-80 honest petroleum asphalt specified in Example 1, the effect of Siestich's potential asphalt adhesives was compared, the aggregate coating being visually assessed as similar to Example 1. The results obtained are summarized in Table 4.

Table 4

Bitumen Added additive to bitumen Evaluation of adhesion to aggregates kind of amount /% w / w / Honorary asphalt A-80 without additive -, 3 -n e vy h o vu j ú o a Honorary petroleum asphalt A-80 alkylbenzenesulfonate sodium (with alkyls 0.3 3-unsatisfactory Honorary petroleum asphalt A-80 Additive A modified 0.3 1-good Honorary petroleum asphalt A-80 Alkyl polyglycol (with alkyls C.q-C- ^ and with 6 moles of ethylene oxide 0.3 3-unsatisfactory Honorary petroleum asphalt A-80 Additive A modified 0.3 2-compliant Honorary petroleum asphalt A-80 48% hmot.etanolamidov mixture of saturated and unsaturated fatty acids, ^C -] 2 ^C 18 '23% hmot.zmesi dletanolamidov carboxylic acids, C ^ ₂ to 18.5% hnuot. salts of triethanolamine with a mixture of saturated carboxylic acids C 1 to 1, and additionally a hydroxy group esterified with these acids; 6.3% by weight, mixtures of monoglycerides of saturated and unsaturated ^C 12 ^{and C} 18 acids. 4.2% by weight, mixtures of triglycerides and free of saturated and unsaturated C ^ _o and C _o £ Honorary petroleum asphalt A-80 78% by weight, a mixture of stearic acid and oleic acid ethanolamide 4% by weight, oleic acid diethanolamide 16% by weight, of a mixture of the triethanolamine salt azealine and oil line 2% by weight of azelaic acid monoglyceride 0.3 l-good

CS. 268 560 Bl

Claims (1)

OBJECT OF THE INVENTION Additive to bitumens and / or asphalt products in an amount of 0.02 to 2% by weight to significantly increase the adhesion of bitumens, especially asphalts to aggregates, ceramics, boton, characterized in that it consists of 50 to 80% by weight, at least one monoethanolamide and / or or diethanolamide of C8 to _C24 carboxylic acids, from 15 to 45% by weight, of an ester of at least one C8 to _C24 carboxylic acid with one to divalent hydroxyl groups of triethanolamine and / or a salt formed from at least one C8 to _C24 carboxylic acid with triethanolamine, the remainder up to 100% is at least one of the by-products of the carboxylic acid glycerides C8 to _C24> mixtures of oleic carboxylic acids, mixtures of monoethanolamine and diethanolamine essents with carboxylic acids.