DE2642926C3 - Use of imidazoline derivatives to influence the rheological properties of bitumen and bituminous compounds - Google Patents

Description

25th

Bitumen is understood to be the semi-solid to that obtained from the gentle processing of crude oils Spring-hard fusible, high-molecular carbon / hydrogen mixtures and the parts of natural asphalt that are soluble in carbon disulfide (Römpp, »Chemielexikon«, 5th edition, page 541).

This definition, which is based on the production and extraction of bitumen, says nothing about the internal structure of the bitumen. This is understandable insofar as, depending on how the Bitumen, be it from distillation residues from the gentle processing of crude oil, be it from petrochemically treated mineral oil products, bitumen, the internal structure of which depends on the process Bitumen is a colloidal disperse system. Put simply, it consists of an outer oily phase, in which micelles or micelle associations are embedded, which essentially consist of asphaltenes exist, on which petroleum resins are adsorbed. In the gentle processing of crude oil arise distillation residues, in which the bitumen in a - colloid-chemical seen - relative there is a little disturbed condition. Are distillation residues processed petrochemically, for example fed to the blowing process, arise through dehydration and polymerization reactions (radical mechanisms) Bitumen, the colloid chemical structure of which is more or less disturbed. Such Bitumen can tend to segregation (oil excretion) and accelerated aging, which for example due to the catalytically active components and radical formers contained in the bitumen is Nonetheless, all these different types of bitumen almost always comply with the norm and are called such, z. B. in road construction, civil engineering and many other purposes.

However, the colloidal structure of bitumen determines its application properties. One goes based on the idea that the micelles or the micelle associations form framework-like structures. The type, size and properties of these structures are determined by many parameters, such as: B. the chemical and physical properties of the oil and resin phases, temperature, mechanical Stress and time

The elastic behavior of bitumen is essentially determined by the ability that this Can form structures quickly after mechanical stress. A more or less far-reaching one Disruption of this framework promotes the plastic behavior of the bitumen. It must be taken into account that the formation of the micellar structure in the bitumen is not only dependent on the composition of the bitumen, but also depends on the temperature of the bitumen. If bitumen is heated, reduce it As the temperature rises, the elastic properties of the bitumen change due to the degradation of the load-bearing Micellar framework with the formation of structures with a low degree of order, so that at higher temperatures a sol condition is reached in which the viscosity behavior of the bitumen is a Newtonian Liquid corresponds to When the bitumen cools down, the framework structure is formed again, but can the formation of the micellar framework by the action of mechanical forces such. B. by high Shear forces are influenced. By cooling down quickly, certain instantaneous states of the Colloid system are frozen, whereby the setting of the state of equilibrium corresponding to the temperature can then only take place very slowly and barely measurable. With the formation of scaffold-like structures, bitumen takes more and more more gel-like character to it. It acquires elastic properties, which increase with further cooling pass into a brittle state.

If you use bitumen z. B. in road construction, it is initially desirable that the hot bitumen the rock easily enveloped and as a result of low viscosity in connection with the mix to a road surface can be processed. The cold bitumen in the road surface should then be absorbed by the traffic load show predominantly elastic, but strongly repressed plastic behavior. Means colloid chemical that the deformed or collapsed framework of the bitumen under the traffic load regresses as quickly as possible. At the same time, the tendency to embrittlement should be low, since bitumen too must meet the demands of traffic at low temperatures. As a result of the use of Bitumen types of various origins and quality do not always meet these requirements Man therefore often observes damage to road surfaces at the points of increased stress, which among other things. on unfavorable colloid-chemical conditions can be attributed to (plastic deformation, crack formation).

It is known from the prior art to influence the theological properties of bitumen or bituminous masses. One possibility is the addition of solvents or fluxing agents. This shifts the viscosity-temperature curve as a whole and generally lowers it. In terms of application, this means that z. B. in road construction, the viscosity of the bitumen at the mixed temperature, about 180 to 240 ⁰ C, is lowered. The lowering of the viscosity also facilitates the installation of the mix at around 100 to 160 ° C. However, the disadvantage of adding solvents and / or fluxing agents is that the plastic-elastic properties of the bitumen or the mixed material are impaired at the temperature of use. The road surface is subject to seasonal fluctuations in temperature of

about -30 to + 60 ° C. If you influence the theological Properties of bitumen or bituminous masses with flux agents, such as tar oils, remain the flux agents in the bitumen or the mass. They increase plasticity under dynamic loading, while the elastic restoring forces are reduced. In practice, this leads z. B. in heavy traffic, in particular in the area of slow travel routes, such as crawl tracks, to ruts, ruts and the like. But if you use solvents that evaporate from the laid layer and thus escape, _ you can only lay very thin layers because of the diffusion. This can result in cavities in the road surface occur that can lead to delamination and erosion. In addition, after evaporation, the Solvents the risk of embrittlement at low temperatures.

The theological properties of bitumen can also be influenced by adding plastics. Even small amounts of plastics have a considerable influence on the viscosity of the bitumen. Of the Because of the increased viscosity, the temperature in the mixing and processing area must be increased. This leads to thermal stress on the bitumen and promotes its degradation and increases its brittleness Usage temperature. In addition, the oily components contained in the bitumen tend to get into the Plastic particles migrate. As a result, sponge-like structures form with relatively low-oil, brittle bitumen as a matrix with an oil-rich plastic phase distributed therein, whereby under load, e.g. are squeezed out by axle loads, oily parts or sweat out in sunlight.

As literature on the prior art, E.]. Barth, "Asphalt, Science and Technology", 1962, Verlag Gordon and Breach, New York / London, and A. HoIl, "Bituminous roads, technology and construction methods", 1971, Bauverlag GmbH, Wiesbaden / Berlin.

There was thus a need for agents which the theological properties of bitumen and bituminous Influence masses without including the aforementioned disadvantages. The connections you are looking for should be effective in small amounts and as targeted as possible in the micellar structure of the bitumen intervene and improve the processability while maintaining the usage properties. It is clear that compounds which intervene in the micellar structure cause concentration-dependent effects have to.

It has surprisingly been found that the properties can be achieved with selected compounds can specifically influence this colloidal system.

The invention therefore relates to the use of compounds of the general formula

R ¹ -R ² -C-N-R ³

Il I

N- (CH ₂ J ₂

to influence the theological properties of bitumen or bituminous masses.

In this general formula, R ^{1 is} hydrogen or an aliphatic hydrocarbon radical with up to 8 carbon atoms or the radical —NH ₂ . The aliphatic hydrocarbon radical can be straight-chain or branched. The lower hydrocarbon radicals with up to 4 carbon atoms are particularly preferred.

R ² is an aromatic or cycloaliphatic hydrocarbon radical with 6 carbon atoms.

The radical R ³ is a lower aliphatic hydrocarbon radical with preferably 2 to 4 carbon atoms with a terminal OH or NH 2 group or hydrogen.

Examples of selected compounds to be used according to the invention are:

1. 2-Phenyl-P-imidazoline

55

65

2. 2-m-tolyk P-imidazoline
H ₃ C

3. 2-p-Tolyl -.- l ² -imidazoline

H ₃ C

4. 2-CyclohexyI- l ² -imidazoline

5. 2-p-aminophenyl-l ² -imidazoline

6. 2-p-tert-butylphenyl-l ² -imidazoline

(CH ₃ ) ₃ C

7. 2-Cydohexyl-.I ² -arninoethylimidazoline
-C N-CH ₂ CH ₂ NH ₂

CH ₂
8. 2-p-tert-butylphenyl- ^ l ² -oxyethylimidazoline

(CH ₃ J ₃ C

N-CH ₂ CH ₂ OH
CH ₂

The compounds to be used according to the invention are added to the bitumen in an amount of 0.1 to 5 % By weight, preferably 0.2 to 3% by weight, added. Since the compounds are soluble in the bitumen, they can be used in pure form are added. However, it is also possible to use a stock solution of these compounds and mix the solution with the bitumen.

As already indicated, these compounds intervene in the colloid-chemical behavior of bitumen. The state of pepfization of the micelle-forming asphaltenes is changed in terms of application technology this has the following consequences:

In the case of bitumen, an effective amount of the compounds to be used according to the invention contains changes the viscosity temperature behavior. By influencing the micellar framework, a homogenization and stabilization is achieved. In addition to theological measurements, this can be also by determining the so-called thread-pulling length (ductility). These properties are for a binder of great importance.

If bitumen is used in conjunction with minerals of different grain sizes, e.g. B. together with Chippings and rock flour, for road construction, reduce the mixing effort in the production of the mix. The bitumen is distributed more evenly; the wetting of the mineral surface and thus the mechanical adhesion is improved. The concept of wetting here is uniform Understand rock coverage. The term should not be confused with chemisorption am Rock, which cause certain so-called adhesives.

The hot mix shows improved ease of installation and compaction. For mastic-like structures Mass, the viscosity temperature dependence is reduced. In practice this means essential improved flow and leveling properties.

An additional advantage of the invention is shown in the colloid-chemical stabilization of thermally overstressed bitumen. Such overuse can occur in a number of ways. In modern mixing plants, for example, ^{bitumen heated to 160 to 180 °} C. is sprayed onto hot rock. The bitumen is therefore at high temperature with a large surface in an oxygen-containing atmosphere. This significantly accelerates the oxidation, ie aging, and thus embrittlement. In addition, silicates or minerals containing silicate, which are catalytically active, are often used as rocks

and accelerate chemical reactions in the bitumen. Overall, these aging reactions often affect the performance properties of the bitumen degrading uncontrollable induration observed this form of aging and thus one However, the agents to be used according to the invention counteract unintentional embrittlement.

The compounds to be used according to the invention are in part, for. B. from H ο f m a η η, »Imidazole and its Derivatives ”(1953), page 217, known The compounds can be eliminated in a manner known per se Produce easily accessible raw materials.

The following examples show the properties of commercially available types of bitumen compared with products which are to be used according to the invention Connections included. This shows the superior effect of those to be used according to the invention Connections in a special way.

Sample preparation and implementation

of theological measurements

I. Sample preparation

a) Preparation of the mixtures

des ^ u investigating, one according to the invention

Compound containing bitumen to be used

In each case about 50 g of liquefied bitumen are to be used according to the invention with an accuracy of ± 0.01 g Products weighed in, mixed homogeneously using a paddle stirrer and then with further stirring 10 Simultaneously heated to 160 ± 2 ° C for minutes Set the measuring cup and rotating body of the rotary viscometer to 145 ± 1 ° C, the thermostat to + 25.00 + 0.0PC pre-tempered.

After placing the bitumen mixture in the measuring cup and slowly inserting the measuring cup The sample is left in the thermostat for 5 hours to establish a state of equilibrium at a temperature of + 25.00 ° C.

b) Preparation of the mastic samples

The mastic samples are made according to the following recipe:

49.5 g bitumen

46.7 g of limestone flour
178.8 grams of quartz sand

275.0 g total

The components are brought to a mixing temperature of 170 to 180 ° C in the heating cabinet, the Bitumen poured into tinplate cans 7 cm high and 6 cm in diameter, the appropriate amount Product added and homogeneously distributed using a paddle stirrer. Then the Limestone powder and then the quartz sand are added.

The mixture obtained is then mixed as homogeneously as possible ^{at 170 to 180 ° C. for 15 minutes.}

With the samples obtained according to a) or b), the theological measurements (cooling curves) carried out.

II. Carrying out the theological measurements
(Hysteresis method) '

a) Measurements of the bitumen samples

The measurements were carried out with a rotary viscometer. The prepared bitumen samples

are gradually subjected to a defined shear gradient D (see- ¹ ) by means of the rotating body. The shear stress r (dyn · cm- ') associated with each shear gradient D gives the viscosity η in (cP) ^{via the relationship - ^ - · 10 2.} A registering meter was used.

When the highest shear gradient D _{mBX is} reached, the shear stress on the sample is maintained for 240 seconds, the measured value is recorded and then the shear gradient D is reduced again in stages. In this way, a curve for viscosity with increasing and decreasing shear rate is obtained.

b) Measurements of the mastic samples

The rotating body is introduced into the mastic sample after it has been brought to the mixing temperature and has the desired shear rate. The temperature corresponding to the respective viscosity is measured by means of a temperature sensor located 5 mm from the center of the lateral surface of the rotating body. At the same time, the viscosity changes are measured, which set by cooling the hot mastic at an ambient temperature of 20 ⁰ C.

example 1

In order to influence the theological properties, the samples were prepared as follows Compound mixed

NH

35

a) Bitumen I was a bitumen of type B 80, a penetration number 81 with a softening

10

15th

20th

25 point, determined with the ring and ball method, of 44 ° C used. The flow curves were determined at 25 ° C. The measurement was carried out with the bitumen I without additives and with the bitumen which contains 0.5 or 1% by weight of the aforementioned compound to be used according to the invention. The resulting shear stress as a function of the shear rate and the viscosity calculated from this can be found in Table I.

b) The mastic cooling curve was made with a bitumen I of type B 80, a penetration number 81 with a softening point, determined with the ring and ball method, of 44 ° C. A mastic sample was obtained without the addition or with 0.8, 1.0 and 1.2% by weight of the aforementioned according to the invention to be used compound measured. The measured values are given in Table II remove.

c) Bitumen II was a bitumen of type B 65, a penetration number 57 with a softening point, determined by the ring and ball method, used from 51 ° C. The flow curves were at 25 ° C determined. The measurement was made with the bitumen II additive-free as well as with the bitumen, which is 1.0, 1.5 or 2.0% by weight of the aforementioned compound to be used according to the invention contains, carried out. The shear stress and the The viscosity calculated from this can be found in Table III.

d) The mastic cooling curve was made with a bitumen II of type B 65, a penetration number 57 with a softening point, determined by the ring and ball method, of 51 ° C. A mastic sample was obtained without the addition or with 0.8, 1.0 and 1.2% by weight of the aforementioned according to the invention to be used compound measured. The measured values are given in Table IV remove.

Table I.

Shear trap D
[see " ¹ ] ■ 10" ²

Shear stress τ in [dyn - cm '] - 10 ⁴ without addition + 0.5% by weight + 1% by weight viscosity ι, in [cP] · 10 ⁸

without additive + 0.5% by weight + 1% by weight

4.0735

8.1850

12.2966

23.8699

34.1869

240 "

2.9695

5.5582

8.4515

16.7508

23.6034

240 "

3.3121

6.2054

9.2510

17.6260

25.6592

240 "

32.8163 20.7101 22.4613 22.4613 14.3905 14.8473 11.4971 7.3856 7.5378 7.7282 5.0633 5.1394 3.9593 2.4745 2.7410

1.4963 1.0907 1.2166 1.5033 1.0208 1.1397 1.5056 1.0348 1.1327 1.4613 1.0255 1.0791 1.3953 0.9633 1.0472

1.3393 0.8452 0.9167 1.3751 0.8810 0.9089 1.4077 0.9043 0.9229 1.4193 0.9299 0.9439 1.4543 0.9089 030 208/332

ίο

Table II

Dynamic viscosities in [cP]

C. Mastic sample t 10 ⁵ without + 1 + 0.8% by weight • 10 ⁵ + 1% by weight · 10 ⁵ // in [cP] · 10 ⁸ + 1.2 % By weight ■ 10 ⁵ without addition · additive Wt% 0.91 _ + i 0.27 180 0.32 1.1000 0.7804 1.06 - Wt% 0.33 175 0.38 2.2195 1.5494 1.28 0.51 2.8666 0.41 170 0.46 3.2245 2.2347 1.52 0.65 2.8457 0.50 165 0.54 - - 1.78 0.80 2.7362 0.62 160 0.62 240 " 240 " 2.08 η nc
U, 7Y - 0.77 155 υ, ι £. - - 2.40 1.15 0.95 150 0.85 3.0913 1.8578 2.75 1.33 - 1.17 145 1.02 2.0367 1.1916 3.30 1.60 2.2747 1.45 140 1.22 1.0393 0.5901 3.55 1.90 2.1745 1.77 135 1.50 4.00 2.32 2.1675 2.20 130 1.85 Viscosities in [cP] 4.60 2.82 2.67 125 2.30 ■ Mastic sample 5.10 3.50 3.30 120 2.90 without addition · 10 ^s - 4.40 4.10 115 3.65 - - 5.50 + 1% by weight - 10 ⁵ 5.00 110 4.70 0.45 Table III Shear rate D shear stress r in [dyn 0.69 ■ cm ¹ ] ■ 10 ^s viscosity 0.24 [see " ¹ ] - 10" ² 1.05 + 1.5 + 2 without 0.39 + 1.5 + 2 1.60 Wt% Wt% additive 0.63 Wt% Wt% 2.72 2.42 0.6015 0.6243 4.0413 1.00 2.2099 2.2933 5.44 5.80 1.1421 1.1992 4.0763 1.60 2.0975 2.2024 8.16 6.00 1.6484 1.7284 3.9481 2.60 2.0183 2.1161 16.33 9.00 - - - 4.50 - - D _max 240 " 240 " 8.10 16.33 2.9999 3.1903 - 1.8365 1.9531 8.16 1.5038 1.5913 3.7849 1.8412 1.9484 5.44 1.0469 1.0659 3.7407 1.9228 1.9577 2.72 0.5254 0.5596 3.8176 1.9297 2.0556 Table IV Dynamic "C +0.8% by weight ■ 10 ⁵ + 1.2 Ow .-% - 10 ^sec 180 0.27 170 - 0.43 160 0.34 0.69 150 0.46 1.08 140 0.71 1.70 130 1.03 2.70 120 1.87 4.25 110 3.22 6.70 100 5.40 9.50

Example 2

In order to influence the theological properties, the samples were prepared as follows Compound mixed

CH ₃

IO

a) Bitumen I was a bitumen of type B 80, a penetration number 81 with a softening point, determined by the ring and ball method, used from 44 ° C. The flow curves were used at 25 ° C determined The measurement was made with bitumen I without additives as well as with the bitumen, which is 0.5, 1.0 or 1.5% by weight of the aforementioned Contains compound to be used according to the invention, carried out depending on the Shear stress resulting in the shear rate and the

Table V

15th

20 thereof calculated viscosity of Table V can be removed.

b) Bitumen II was a bitumen of type B 65, a penetration number 57 with a softening point, determined by the ring and ball method, used from 51 ° C. The flow curves were at 25 ° C determined. The measurement was made with the bitumen II additive-free as well as with the bitumen, which is 1.0, 1.5 or 2.0% by weight of the aforementioned compound to be used according to the invention contains, carried out. The shear stress and the The viscosity calculated from this can be found in Table VI.

c) The mastic cooling curve was made with a bitumen II of type B 65, a penetration number 57 with a softening point, determined by the ring and ball method, of 51 ° C. A mastic sample was obtained without the addition or with 0.8, 1.0 and 1.2% by weight of the aforementioned according to the invention to be used compound measured. The measured values are given in Table VII remove.

Shear rate D Shear stress r in [dyn + 0.5 + 1 ■ cm " ¹ ] ■ 10 ⁴ + 1.5 viscosity ,, [cP] x 10 ⁸ + 1 + 1.5 [see " ¹ ] x 10 ~ ² without Wt% Wt% + 1 Wt% without + 0.5 Weight% Wt% additive 3.3502 Wt% 3.5024 additive Wt% 1.2306 1.2865 2.72 4.0735 6.7384 3.3502 6.5861 1.4963 1.2306 1.1676 1.2096 5.44 8.1850 9.9743 6.3577 9.8601 1.5033 1.2375 1.1745 1.2073 8.16 12.2966 19.1492 9.2510 19.0350 1.5056 1.2212 1.1350 1.1653 16.33 23.8699 26.4586 18.5400 27.9814 1.4613 1.1723 1.0829 1.1420 24.50 34.1869 - 26.5348 - 1.3953 1.0798 - - 49.00 - 240 " - 240 " - - D _max 240 " - 240 " - - - 49.00 - 22.7658 - 26.0399 - - 1.0053 1.0628 24.50 32.8163 15.3803 24.6313 16.9031 1.3393 0.9291 1.0115 1.0348 16.33 22.4613 7.7282 16.5224 8.4896 1.3751 0.9416 1.0876 1.0395 8.16 11.4911 5.5201 8.5675 5.7105 1.4077 0.9462 1.0278 1.0487 5.44 7.7282 2.9695 5.5963 3.0456 1.4193 1.0138 1.0488 1.1187 2.72 3.9593 2.8552 1.4543 1.0907 Table VI Shear stress r in [dyn Shear vessels D without • cm " ¹ ] x 10 ^sec + 2 viscosity ij in [cP] ■ 10 ⁸ + 1.5 + 2 [see " ¹ ] - 10 ~ ² additive + 1.5 Wt% without + 1 Wt% Wt% Wt% additive Wt%

16.33
8.16
5.44
2.72

1.1000
2.2195
3.2245

240 "

3.0913
2.0367
1.0393

0.8679 1.6598 2.3527

240 "

2.0253 1.3248 0.6548

0.8679 1.6674 2.3108

240 "

2.0443 1.3819 0.6929

0.7576 1.4505 1.9873

3.5976 1.8197 1.2563 0.6281 4.0413
4.0763
3.9481

3.7849
3.7407
3.8176

3.1883
3.0485
2.8807

2.4798
2.4332
2.4052

3.1883
3.0617
2.8294

2.5031
2.5381
2.5451

2.7831
2.6639
2.4332

2.2024
2.2281
2.3073
2.3073

13th

Table VII

Dynamic viscosities in [cP]

Mastic sample without additives

+ 0.8% by weight · + 1% by weight ■ ICI ⁵

1.2% by weight · 10 ⁵

175
170
165
160
155
150
145
140
135
130
125
120
115
110
105

0.37 0.45 0.56 0.69 0.85 1.05 1.30 1.60 1.95 2.47 3.00 3.65 4.70 6.00 8.00

0.24 0.27 0.32 0.38 0.45 0.55 0.68 0.84 1.03 1.30 1.65 2.10 2.70 3.50 4.65 0.35
0.41
0.50
0.52
0.76
0.93
1.14
1.40
1.74
2.35
2.76
3.50
4.60
6.00
8.40

0.38 0.47 0.57 0.70 0.86 1.06 1.31 1.62 2.00 2.50 3.30 4.00 5.10 6.50 8.00

Example 3

To influence the rheological properties, the samples were prepared as follows Compound mixed

30th

-NH

CH ₂

35

40

a) Bitumen I was a bitumen of type B 80, a penetration number 81 with a softening point, determined by the ring and ball method, used from 44 ° C. The flow curves were at 25 ° C determined The measurement was made with bitumen I without additives and with bitumen, which is 0.5, 1.0 or 1.5% by weight of the aforementioned compound to be used according to the invention contains, carried out. Which depends on the The shear stress resulting from the shear gradient and the viscosity calculated from this can be found in Table VIII can be removed.

b) The mastic cooling curve was made with a bitumen I of type B 80, a penetration number with a softening point, determined by the ring and ball method, of 44 ° C. A mastic sample was obtained without the addition or with 0.8, 1.0 and 1.2% by weight of the aforementioned according to the invention to be used compound measured. The measured values are given in Table IX remove.

c) As a bitumen II a bitumen of the type B was 65, a penetration number of 57 with a softening point, as determined by the ring and ball method, of 51 ⁰ C was used The flow curves were at 25 ° C determined The measurement was thereby with the bitumen II added free and with the bitumen which contains 1.0, 1.5 or 2.0% by weight of the aforementioned compound to be used according to the invention. The shear stress and the viscosity calculated from this can be found in Table X. can be removed.

d) The mastic cooling curve was made with a bitumen II of type B 65, a penetration number 57 with a softening point, determined by the ring and ball method, of 51 ° C A Mastixprofae without addition or rnil 0.8, 1.0 and 1.2% by weight of the aforementioned compound to be used according to the invention measured. The measured values can be found in Table XI.

Table VIH

Schergeßlle D [see " ¹ ] x 10" ²

Shear stress τ in [dyn without + 0.5

additive

Wt%

■ cm ']

+ 1% by weight

10 "

+ 1.5% by weight viscosity in / m [cP] -10 ⁸

without
additive

+ 0.5
Wt%

+ 1
Wt%

+ 1.5% by weight

2.72 4.0735 2,4365 3.1598 2.7791 1.4963 0.8949 1.1606 1.0208 5.44 "8.1850 4.8349 6.0531 5.4821 1.5033 0.8879 1.1117 1.0068 8.16 12.2966 6.5861 8.9464 8.1089 1.5056 0.8064 1.0954 0.9928 16.33 23.8699 12.1824 16.9411 15.7229 1.4613 0.7580 1.0371 0.9625

15th

16

continuation

Shear flanges D Shear stress τ in [dyn + 0.5 + 1 - cm "'] - 10 ⁴ + 1.5 Viscosity ι / in [cP] -10 ⁸ '/ [cP] x 10 ⁸ + 1 + 1.5 [sec "'] · ΙΟ" ² without Wt% Wt% + 1 Wt% without + 0.5 + 1 Wt% Wt% additive 17.2838 Wt% 23.0323 additive Wt% Wt% 0.9555 0.9400 24.50 34.1869 27,9053 23.4130 - 1.3953 0.7054 - - 49.00 - 240 " - 240 " - 0.5694 Απ « 240 " 27.6769 240 " - - - 49.00 - 14.0478 - 22.1948 - 0.5648 0.8079 0.9058 24.50 32.8163 9.2510 19.7964 14.0098 1.3393 0.5733 0.8227 0.8577 16.33 22.4613 5.5201 13.4387 7.11191 1.3751 0.5663 0.8483 0.8716 8.16 11.4971 3.5024 6.9287 4.7587 1.4077 0.6759 0.8949 0.8740 5.44 7.7282 1.9416 4.8729 2,4365 1.4193 0.6852 0.9509 0.8949 2.72 3.9593 2.5888 1.4543 0.7132 Table IX in [cP] Dynamic Viscosities X Mastic sample 10 ⁵ ■ 10 ^s + 1.2 Weight - · 10 ⁵ without addition ■ + 0.8% by weight + 1% by weight ■ 10 ⁵ 0.22 175 0.39 0.34 0.16 0.26 170 0.46 0.41 0.21 0.27 165 0.54 0.50 0.31 0.37 160 0.62 0.61 0.34 0.45 155 0.74 0.75 0.43 0.55 150 0.86 0.92 0.55 0.68 145 1.02 1.23 0.71 0.86 140 1.21 1.40 0.90 1.10 135 1.47 1.70 1.16 1.37 130 1.80 2.10 1.50 1.75 125 2.25 2.55 1.90 2.30 120 2.80 3.15 2.40 3.10 115 3.60 3.85 3.10 4.10 110 4.80 4.80 4.00 5.50 105 6.00 5.80 5.00 Table X ) Shear stress r in [dyn Shear Rate I without • cm "'] · 10 ⁵ + 2 Viscosity ι + 1.5 + 2 [sec "'] · ΙΟ" ² additive + 1.5 Wt% without Wt% Wt% Wt% additive

2.72 5.44 8.17 16.33 An « 16.33 8.17 5.44 2.72

1.1000 2.2195 3.2245

240 "

3.0913 2.0367 1.0393

0.9822 1.9036 2.7106

240 "

2.6523 1.8007 0.9213

0.6776
1.3629
1.9764

240 "

3.4758

1.8083

1.2449

0.6243

0.6015 1.1840 1.7055

240 "

3.0837

1.5228

1.0127

0.4949

4.0413 4.0763 3.9481

3.7849 3.7407 3.8176

3.6078
3.4959
3.3188

3.2536
3.3072
3.3841

2.4891
2.5031
2.4238

2.1278
2.2141
2.2863
2.2933

2.2094 2.1745 2.0882

1.8878 1.8645 1.8598 1.8179

17th

Table XI

Dynamic viscosities in [cP]

Mastic sample
without addition 10 ⁵

+ 0.8% by weight + 1% by weight - 10 ⁵

+ 1.2% by weight - 10 ⁵

175 0.37 170 0.45 165 0.56 160 0.69 155 0.85 150 1.05 145 1.30 140 1.60 135 1.95 130 2.47 125 3.00 120 3.65 115 4.70 110 6.00 105 8.00

0.33 0.40 0.50 0.63 0.77 0.96 1.20 1.50 1.90 2.40 3.00 3.80 4.90 6.20 8.00 0.30
0.37
0.46
0.57
0.70
0.86
1.06
1.30
1.60
2.00
2.60
3.50

0.32 0.40 0.50 0.63 0.70 1.00 1.25 1.57 2.00 2.50 3.10 4.10 5.40

Example 4

To influence the rheological properties, the samples were prepared as follows Compound mixed

NH ₂ -

-NH
CH ₂

CH ₂

a) Bitumen I was a bitumen of type B 80, a penetration number 81 with a softening point, determined by the ring and ball method, used from 44 ° C. The flow curves were used at 25 ° C determined The measurement was made with bitumen I without additives and with bitumen, which is 1.0 or 1.5% by weight of the aforementioned compound to be used according to the invention contains, carried out The shear stress resulting from the shear rate and the The viscosity calculated from this can be found in Table XII.

b) A bitumen of type B 65, a penetration number 57 with a softening point, determined by the ring and ball method, of 51 ° C. was used as bitumen H. The flow curves were determined at 25 ° C. The measurement was carried out with the bitumen II without additives and with the bitumen with a softening point, determined using the ring and ball method, of 51 ° C. A mastic sample was measured with no addition or with 0.8, 1.0 and 1.2% by weight of the aforementioned compound to be used according to the invention. The measured values can be found in Table XIV,
which contains 1 or 2% by weight of the aforementioned compound to be used according to the invention, carried out. The resulting shear stress as a function of the shear rate and the viscosity calculated from this can be found in Table XIII.

see above c) The mastic cooling curve with a bitumen II of type B 65, a penetration number 57

Table XII

Shear rate D
[see "'] · 10 ~ ²

Shear stress rin [dyn · cm " ¹ ] ·

without the addition of + 1 wt .-% + 1.5 wt ⁰ / I ₁ in viscosity [cP] 10 · ⁸

without additive + 1% by weight + 1.5% by weight

2.72 4.0735 3.4263 3.9593 1.4963 1.2585 1.4543 5.44 8.1850 6.3196 7.7282 , 5033 1.1606 1.4193 8.16 12.2966 9.2129 11.4210 1.5056 1.1280 1.3984 16.33 23.8699 17.6264 21.7760 1.4613 1.0791 1.3331 24.50 34.1869 24.8216 30.5702 , 3953 1.0130 1.2477 49.00 - _ _ _ _

20th

continuation Shear stress τ in [dyn · cm - '] - 10 ⁴ Viscosity tj in [cP] ■ 10 ⁸ + 1.5% by weight Shear trap D without addition + 1% by weight + 1.5% by weight without addition + 1% by weight [sec " ¹ ] - ΙΟ"" ² 240 " 240 " 240 " - D _max - - - - - 1.0565 49.00 32.8163 22.1567 25.8876 1.3393 0.9043 1.0814 24.50 22.4613 14.7712 17.6645 1.3751 0.9043 1.1094 16.33 11.4971 7.6521 9.0607 1.4077 0.9369 1.1327 8.16 7.7282 5.1775 6.1673 1.4193 0.9509 1.1886 5.44 3.9593 2.5887 3.2359 1.4543 0.9509 2.72

Table XIH

Shear gradient D Shear stress rin [dyn ■ cm " ¹ ] - 10 ⁵ + 2% by weight Viscosity // In [cP] ■ 10 ⁸ + 2% by weight tsec-'j-10 " ² without addition + 1% by weight 0.9479 without addition + 1% by weight 3.4820 2.72 1.1000 1.3819 1.8997 4.0413 5.0761 3.4889 5.44 2.2195 2.5469 2.7677 4.0763 4.6776 3.3747 8.16 3.2245 3.4644 - 3.9481 4.2417 - 16.33 - - 240 " - - D _max 240 " 240 ' - - 16.33 - - 2.6649 - - 3.2628 8.16 3.0913 3.0722 1.8312 3.7849 3.7616 3.3631 5.44 2.0367 2.0824 0.9251 3.7407 3.8246 3.3981 2.72 1.0393 1.0812 3.8176 3.9714 Table XIV Dynamic Viscosities in [cP] "C Mastic robe Wt% x 10 ^sec Gev /.-% · 10 ⁵ without addition · I0 ^s + 0.8 + 1% by weight · 10 ⁵ + 1.2

175 170 165 160 155 150 145 140 135 130 125 120 115 110 105 100

0.38 0.46 0.56 0.68 0.84 1.02 1.27 1.60 1.95 2.45 3.10 3.75 4.80 6.00 7.50

0.25
0.30
0.38
0.47
0.59
0.74
0.91
1.12
1.40
1.75
2.17
2.70
3.40
4.20

0.38 0.46 0.54 0.65 0.79 0.95 1.17 1.50 1.85 2.30 2.90 3.75 4.65 5.90 7.50

0.25 0.31 0.39 0.49 0.52 0.78 0.97 1.25 1.60 2.10 2.70 3.50 4.60 6.00

Example 5

In order to influence the rheological properties of the samples, the following was used during preparation Compound mixed

(CH ₃ J ₃ C

-NH

CH ₂

10

CH ₂

a) Bitumen I was a bitumen of type B 80, a penetration number 81 with a softening point, determined by the ring and ball method, used from 44 "C. The flow curves were used at 25 ° C determined The measurement was made with bitumen I without additives and with bitumen, which 1 or 2 wt .-% of the aforementioned compound to be used according to the invention contains carried out The resulting shear stress and the The viscosity calculated from this can be found in Table XV.

b) The mastic cooling curve was made with a bitumen I of type B 80, a penetration number 81

Table XV

with a softening point, determined by the ring and ball method, of 44 ° C A mastic sample was obtained without the addition or with 0.8, 1.0 and 1.2% by weight of the aforementioned according to the invention to be used compound measured. The measured values are to be found in Table XVI remove.

c) Bitumen II was a bitumen of type B 65, a penetration number 57 with a softening point, determined by the ring and ball method, used at 51 ° C. The flow curves were used at 25 ° C determined The measurement was made with the bitumen II additive-free as well as with the bitumen, which is 1.0 or 1.5% by weight of the aforementioned compound to be used according to the invention contains carried out The resulting shear stress and the The viscosity calculated from this can be found in Table XVIII.

d) The cooling curve was mastic with a bitumen II type B 65, a penetration number of 57 with a softening point, as determined by the ring and ball method, carried out by 51 ⁰ C. A mastic sample was measured with no addition or with 0.8, 1.0 and 1.2% by weight of the aforementioned compound to be used according to the invention. The measured values can be found in Table XVIII.

Shear rate D Shear stress rinfdyn · cm " ¹ ] ■ 10 ⁴ + 2% by weight Viscosity 1; in [cP] - 10 ⁸ + 2% by weight [see " ¹ ] ■ 10" ² without addition + 1% by weight 3.6166 without addition + 1% by weight 1.3285 2.72 4.0735 3.5786 7.0429 1.4963 1.3145 1.2935 5.44 8.1850 6.9287 10.5454 1.5033 1.2725 1.2912 8.16 12.2966 10.3931 20.1010 1.5056 1.2725 1.2306 16.33 23.8699 19.7964 27.9814 1.4613 1.2119 1.1420 24.50 34.1869 28.6286 - 1.3953 1.1684 - 49.00 - - 240 " - - D _max 240 " 240 " - - 49.00 - - 23.9460 - - 0.9773 24.50 32.8163 23.2227 15.9894 1.3393 0.9478 0.9789 16.33 22.4613 15.7229 8.1470 1.3751 0.9625 0.9789 8.16 11.4971 8.0708 5.5963 1.4077 0.9882 1.0278 5.44 7.7282 5.7105 2.8932 1.4193 1.0488 1.0628 2.72 3.9593 3.1217 1.4543 1.1467 Table XVI Dynamic Viscosities in [cP] ° C Mastic sample Wt% x 10 ^sec Wt% x 10 ⁵ without addition 10 ⁵ + 0.8 + 1 wt% x 10 ^sec + 1.2

175 0.38 170 0.46 165 0.54 160 0.63 155 0.73 150 0.86

0.23 0.29 0.36 0.46 0.57 0.73

0.20
0.25
0.34
0.40
0.51
0.64

0.29
0.35
0.45
0.55

23

24

continuation

Mastic sample XVII 10 ² without addition XVIII Mastic sample + 0.8% by weight · 10 ⁵ cm " ¹ ] x 10 ⁵ + 1 wt% x 10 ^sec Viscosity // in + 1.2 Wt% x 10 ⁵ I. . ι ϋ without addition 10 ⁵ Shear all D shear stress 1.1000 Dynamic viscosities in [cP] without addition ■ 10 ^s 0.92 / o +1.5% by weight 0.82 without addition 0.69 L. I. j 145 1.00 [sec " ¹ ] · 2.2195 ° C 1.17 0.9822 1.02 4.0413 0.86 P.
I. j I. 140 1.20 2.72 3.2245 1.47 1.8845 1.30 4.0763 1.07 ί 2.9459 ί 135 1.47 5.44 - 1.85 2.6154 1.63 3.9481 1.35 ί j 2.9715 ί 130 1.80 8.16 240 " 2.35 - 2.05 - 1.70 + 1.5% by weight of I. 3.0485 \ 125 2.25 16.33 - 2.95 240 " 2.60 2.20 i
3.6078 I. x.
ί
I. 120 2.85 A ** 3.0913 3.70 - 3.25 - 2.80 3.4610 I. I. 115 3.60 16.33 2.0367 4.75 2.4060 4.10 3.7849 3.60 3.2023 110 4.75 8.16 1.0393 6.00 1.6179 5.20 3.7407 4.50 + 1.2% by weight · 10 ⁵ 1
$ 105 6.20 5.44 0.8299 3.8176 Tabel 2.72 τ in [dyn [cP] x 10 ⁸ Tabel + 1 wt. " + 1% by weight 1.0583 3.8875 2.0596 Wt% x 10 ⁵ + 1% by weight · 10 ⁵ 3.7826 2.8552 3.4959 - - 240 " - - 2.5887 3.1697 1.7741 3.2582 0.9099 3.3421 + 0.8

175
170
165
160
155
150
145
140
135
130
125
120
115
110

0.40 0.46 0.56 0.70 0.85 1.05 1.30 1.62 2.00 2.40 3.00 3.70 4.70 6.00

0.70 0.85 1.00 1.17 1.35 1.50 1.75 2.00 2.40 2.90 3.50 4.30 5.30 6.60

0.29 0.39 0.50 0.63 0.80 0.96 1.20 1.45 1.85 2.30 2.80 3.50 4.30 5.40

0.27 0.41 0.56 0.70 0.90 1.15 1.45 1.85 2.40 3.10 4.00 5.00 6.30

030 208/332

25th

26th

Table XIX

Comparison of the graphically corrected start and end values from hysteresis measurements on test products activated bitumen samples with the same pretreatment and test temperature

Bitumen product additional amount of Schergelalle
[% By weight] D [see " ¹ ]

Shear stress

rf [dyn

Shear stress viscosity

citT ¹ ] 4 [dyn

cm"']

ξ. , O ²

viscosity

'/ 1 = egg. ίο ²

(cP) ^D.

I. - - I. A. 0.5 1.0 I. B. 0.5 1.0 1.5 I. C. 0.5 1.0 1.5 ! D. 1.0 1.5 I. E. 1.0 2.0 II - - II A. 1.0 1.5 2.0 II B. 1.0 1.5 2.0 II C. 1.0 1.5 2.0 II D. 1.0 2.0 II E. 1.0 1.5

2.72
2.72
2.72
2.72
2.72
2.72
2.72
2.72
2.72
2.72
2.72
2.72
2.72

2.72-

2.72
2.72
2.72-2.72-
2.72
2.72-2.722.72 2.72-
2.72 ■
2.72-2.72 ■
2.72-

10 " ²
10 " ²
HT ²
10 " ²

ίο- ² ίο- ²

ΙΟ " ²
KT ²
KT ²

ίο- ²

10 " ²
ΙΟ " ²
ΙΟ " ²

IO ²

ΙΟ " ²
ΙΟ ' ²

ίο- ²

IO ²
10 ²
ΙΟ " ²
10 " ²
ΙΟ " ²

ίο- ² ίο- ²

10 ²
10 " ²
10 " ²

4.0735

2.9695 3.3121 3.3502 3.3502 3.5024 2.4365 3.1598 2.7791 3.4263 3.9593 3.5786 3.6166

11.0020 7.8043 6.0151 6.2435 8.6799 8.6799 7.5759 9.822! 6.7764 6.0151

13.8194 9.4794

10.5830 9.8221

10 ⁴ 10 ⁴ 10 ⁴ 10 ⁴

10 "3,9593

10 ⁴ 2.4745 · 10 ⁴ 2.7410 · I0 ⁴ 2.7550 · 10 "2.8552 ■ 10" 3.0456 · 10 "1.9416 · 10" 2.5888 · 2.4365 · 2.5087 · 3.2359 3.1217 10 ⁴ 2.8932

10 ⁴ 10.3930

10 "5.9008 10" 5.2537 10 ⁴ 5.5963 x 10 "6.5480 10" 6.9287 x 10 "6.2815 x 10 ⁴ 9.2129 ■ 10 ⁴ 6.2435 x 10" 4.9491 10 "10.8119-10 ⁴ 9.2510 x 10 ⁴ 9.0987 x 10 ⁴ 8.2992 1.4976

10 "1.0917
1.2176
10 "1.2317
1.2317
1.2876
0.8957
10 "1.1617
1.0217
1.2597
1.4556
1.3157
1.3296

4.0448

2.8692
10 "2.2114
2.2954
3.1911
3.1911
2.7852
10 "3.6110
10 "2.4913
2.2114

10 ⁴ 10 ⁴ 10 ⁴ 10 ⁴ 10 ⁴

10 ⁴ 10 ⁴ 10 ⁴ 10 ⁴

10 ⁴

■ 10 ^s 100

• 10 * 73

• 10 * 81

• ΙΟ ⁸ 82

• ΙΟ ⁸ 82

• ΙΟ ⁸ 86

• 10 * 60

• 10 * 77

• 10 * 68

• 10 * 84

ΙΟ ⁸
ΙΟ ⁸
ΙΟ ⁸

97
88
89

5.0807
3.4851

3.8908
2.6110

ΙΟ ⁸ 100-

10 * 71

10 * 55

ΙΟ ⁸ 57

10 * 72

ΙΟ * 79

10 * 69

ΙΟ ⁸ 89

ΙΟ ⁸ 62

ΙΟ ⁸ 55

ΙΟ ⁸ 126

10 * 86

ΙΟ ⁸ 96

10 * 89

1.4556 0.9097 1.0077 1.0128 1.0497 1.1197 0.7138 0.9517 0.8958 0.9517 1.1897 1.1477 1.0637 3.8209

2.1694

1.9315

2.0574

2.4073

2.5473

2.3094

3.3871

2.2954

1.8195

3.9749

3.4011

3.3451 ■

3.0512

10 *.

10 *

ΙΟ ⁸ ΙΟ ⁸ ΙΟ ⁸ ΙΟ ⁸

ΙΟ ⁸

10 *

10 *

10 *

10 *

10 *

10 *

ΙΟ ⁸

ΙΟ ⁸

ΙΟ ⁸

10 *

10 *

10 *

10 *

10 *

10 *

10 *

ΙΟ ⁸

10 *

10 *

10 *

* "" ^ VtWiViI t vv «vu« -t iriuaauiig UCI aiclgcllUCIIl OCIICrgCIUllC, UiIS Z.CfCncn 4- DCUCUlCl AICSSUUg OCI

The shear stress i] and τ \ or // T and r / j are to be understood analogously.

Example 6

In order to influence the theological properties, the samples were prepared as follows Compound mixed

N-CH ₂ CH ₂ NH ₂

The bitumen used was a bitumen of type B 65, a penetration number 51 with a softening point, determined using the ring and ball method, of 51 ° C. The flow curves were determined at 25 ° C. The measurement was made with the bitumen without additives and with the bitumen , which contains 0.5, 1.0 or 2.0% by weight of the aforementioned compound to be used according to the invention. The shear stress resulting as a function of the shear gradient and the viscosity calculated from this can be found in Table XX.

Table XX

27

Shear rate D [sec " ¹ ] · ΙΟ" ²

Shear stress r in [dyn without + 0.5

additive

Weight- »/

cm '] + wt%

10 ⁵

+% By weight viscosity a [cP] · 10 ⁸

without

additive

+ 0.5
Wt%

+ 1
Wt%

+ 2
Wt%

1.1000 2.2195 3.2245

240 "

0.9422 1.8751 2.7114

240 "

0.8014 1.6230 2.3892

240 "

0.6265 1.2773 1.8696

240 "4.0413
4.0763
3.9481

3.4639
3.4468
3.3187

2.4663
2.9834
2.9224

2.3033
2.3480
2.2883

3.0913 2.5143 2.1693 1.6787 3.7849 3.0775 2.6552 2.0547 2.0367 1.7281 1.4208 1.1042 3.7407 3.1766 2.6117 2.0298 1.0393 0.8678 0.7161 0.5356 3.8176 3.1904 2.6327 1.9691

example

In order to influence the theological properties, the samples were prepared as follows Compound mixed

Table XXI

-N-CH ₂ CH ₂ OH

CH ₂ The bitumen used was a bitumen of type B 80, a penetration number 81 with a softening point, determined using the ring and ball method, of 44 ° C. The flow curves were determined at 25 ° C. The measurement was carried out with the bitumen additive-ei and with the bitumen which contains 0.5 or 1% by weight of the aforementioned compound to be used according to the invention can be taken from Table XXl.

Shear rate D ^{Isec "1} ] ·

-2

Shear stress r in [dyn · cm " ¹ ] without addition + 0.5% by weight + 1% by weight viscosity i / in [cP] · 10 ⁸

without additive + 0.5% by weight + 1% by weight

4.0735

8.1850

12.2966

23.8699

34.1869

240 "

2.7231

5,4002

7.6233

15.0014

22.1416

240 "

2.9014

5.7232

8.2651

16.4742

24.5883

240 "

32.8163 19.2218 20.3633 22.4613 12.6827 13.7417 11.4971 6.3545 6.9022 7.7282 4.2001 4.6595 3.9593 2.1131 2.4107

1.4963 1.0011 1.0667 1.5033 0.9927 1.0521 1.5056 0.9342 1.0129 1.4613 0.9186 1.0088 1.3953 0.9037 1.0040

U393 0.7845 0.8311 1.3751 0.7766 0.8415 1.4077 0.7787 0.8458 1.4193 fl, 7721 0.8565 1.4543 0.7769 0.8863

The following results from the measurement results: The theological behavior of bitumen is a Mirror of his inner qualities. It is determined by the reversible structure build-up and breakdown. All External disruptive factors affect the respective state. It is therefore possible to get out Isothermally recorded flow curves make statements about the properties, in particular the properties in use of bitumen.

The influence of the products A to E used according to the invention on the bitumen I and II is dependent on the chemical structure of the products, the amount added, the bitumen type, the test temperature and sample pretreatment.

It should be noted that, in some cases, the initial viscosity is changed only slightly by additives However, the final viscosity is greatly reduced. In these cases, the additives cause an increase in Shear sensitivity. In other cases, the initial and final viscosity are significantly lowered, what on a stabilization of the colloid chemical state. There are also increases in both the

Observe initial and final viscosities. As a result of the many variables that have a determining effect on the properties, it is therefore necessary to go through a preliminary experiment to determine in which a certain connection is made to the theological properties has an effect in order to then select the additional product for the desired application, which affects the properties in the desired direction

If bitumen is in physical and / or chemical interaction with mineral surfaces, so Due to their polar properties, the latter have an orienting effect on the likewise polar asphaltene micelles the neighboring bitumen phase and are thus indirectly structure-forming (short-range order). About these The increase in viscosity, the extent of which is determined by the mineral-bitumen interaction, is explained i.a. the stiffening effect of rock flour as fillers.

However, the increase in viscosity can also have a negative effect on preparation and processing operations (increased expenditure of energy in the mixing and processing steps).

As can be seen from the cooling curves of mastic, by adding the according to the invention products used the behavior of hot masses, especially in the temperature range from 200 to Targeted influence of 100 ° C. The slope of the viscosity temperature curve changes. Due to the liquefaction effect, the bitumen requirement for an easily workable mastic. The pronounced concentration dependence of the Effects: Depending on the added amount of the compound used according to the invention, a viscosity minimum can occur adjusted, the viscosity being increased at other concentrations of the same substance and the mastic mixture thus stiffens. Here too, in the case of technical use, the invention is closed using substances to clarify by means of a preliminary test which concentration of the compound to be added according to the invention is optimal in application terms results in the desired effect.

Claims (1)

Claim: Use of compounds of the general formula R ^{1 - R 2} - C - N - R ³ N- (CH ₂ J ₂ IO whereby Ri is hydrogen or an aliphatic hydrocarbon radical with up to 8 carbon atoms or the radical -NH ₂ , R ^{2 is} an aromatic or cycloaliphatic hydrocarbon radical with 6 carbon atoms, R ^{3 is} a lower aliphatic hydrocarbon radical with a terminal OH or NH ₂ group or hydrogen, to influence the theological properties of bitumen and bituminous compounds.