DE1233770B - Light-colored road surface binder mixture that can be easily dyed with pigments or dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08h

German class: 80 b-25/01

Number: 1233 770

File number: S 80695IV c / 80 b

Filing date: July 31, 1962

Opened on: February 2, 1967

The invention relates to binder mixtures for road surfaces with improved color properties.

One of the classic materials that have been used for road surfaces is asphalt, which serves as a binder for mineral aggregates. While asphalt is satisfactory in most cases having chemical properties, there is a major disadvantage with regard to their use in their dark color, which almost all attempts to change the color of the road surface for the purpose of installation from traffic signs, colored areas and the like. Besides, it is for many purposes such as driveways, parking lots, pedestrian crossings and similar applications, such as tennis courts, for aesthetic reasons Often times it is desirable that a particular color of the coating material be selected and applied can be. This is almost impossible with asphalt, since the dark color of the same shows through, so that a colored coating results, which differs only slightly from the black asphalt. Even if many Types of hydrocarbons obtained from petroleum refineries are lighter in color than asphalt because they do not have the physical properties which are used as binders for road surfaces and the like are necessary.

Important properties that the binders should have in order to be used in the devices currently used for the production of road surfaces are as follows: The binder should have a viscosity of 50 to 250 SSF, a viscosity above, at mixing temperatures (120 to 180 ° C) 1000 poise at maximum road ^{temperature (approx. 6O 0} C) and a penetration greater than 20 tenths of a millimeter at 4 ° C. These criteria are important because of a number of interrelated reasons: The minimum viscosity at 6O ⁰ C, the viscosity is, which has been selected by experience after impressions (wells) had watched them and from tractors like on roads under.. hot temperature conditions. On the other hand, however, the same binder should be sufficiently plastic under normal cold weather conditions, i.e. it must not become brittle and tear, either as a result of shrinkage or as a result of physical influences such as traffic and the like, as long as the coating is cold. Further, from a practical point of view, it is very desirable to be able to use the equipment commonly used in road building which road builders are now using in paving and other types of paving. Such devices have been developed for treating light, lightly with pigments or dyes
dyeable road surface binder mixture

Applicant:

Shell Internationale Research Maatschappij N.V., The Hague

Representative:

Dr. E. Jung, patent attorney,

Munich 23, Siegesstr. 26th

Named as inventor:

Robert Lewis Dunning, Buena Park, Calif .;

Harry Junius Summers, Lafayette, Calif. (V. St. A.)

Claimed priority:

V. St. ν. America August 2, 1961 (128 678)

Ordinary asphalts, which have a low viscosity at a temperature of 120 to 280 ^{° C.} Consequently, with these considerations in mind, a single binder must be able to meet all three criteria discussed above.

Proposals for solving this problem are known, but none of them are satisfactory.

All of the materials proposed so far as a binder base are resins or at least have a high resin content. Resin binders based on calcium naphthenate are mentioned in particular. Such resin binders are but experience has shown that it is not suitable for road construction either by itself or with the use of phenolic resins, as they are both in terms of plasticity in cold weather and in terms of processability not satisfactory by means of the usual facilities in road construction.

Furthermore, the so-called sulphate pitch is a highly resinous distillation residue that occurs during wood processing has been recommended as a binder base. However, sulphate pitch has insufficient weather resistance and is also required with regard to the intended use only available in extremely limited quantities in large quantities. The preceding problem, a bright one Producing an easily dyed binder mixture for road surfaces cannot be done with sulphate pitch either be solved satisfactorily.

Furthermore, in the German patent 849 824, the use of selective extraction Resins obtained are described as binders.

709 507/377

3 4

These resins are not characterized as such - normally a specific gravity of 0.99 to

sated. You have the already mentioned 1.05 at 15.6 ° C, an ASTM color in 1% solution

shafts of these chemically not clearly determined between L 2 and L 5, a pour point of 20 to 46 ⁰ C,

Class of substance and are therefore used as a binder for roads - a refractive index at 20 ° C of about 1.59 or

covering masses unsuitable. In particular, those in Figure 5 are higher, with a volatility loss after 22 hours

German patent mentioned resins hydrophilic, 107 ° C of less than 0.5% and a viscosity

which can be seen on the one hand, that to produce gravitational constant between 0.96 and 0.99.

of the pavement masses and the colored binder are characterized as Next within the scope of the invention

Water-added mixture of filler and mine- suitable aromatic extracts by having them

ral mixture is added, and on the other hand, io normally an initial boiling point above 370 ⁰ C

that stone and a 90% distillate point above 480 ³ C are used as raw material for resin production,

Coal tar can be used so that the resins contain essentially no asphaltenes and resins

contain polar groups. have a content of saturated compounds below

Hydrophilic binders, however, make up about 20% of water. Even if it is preferred that the

washed out quickly, so that street aromatics content produced therefrom is at least 60 to 65%

covering compounds are not weather-resistant. but aromatic contents of over 55% are also permitted. the

It is an object of the invention, non-asphalt known selective solvents for recovery Table binders for road surfaces and the like to aromatic extracts from lubricating oils can also create that can be colored and used for the present purpose above. Beiais have desired specified properties. 2 ° furfural or edeleanu extracts are sometimes ge-Others Subjects of the invention are suitable from the. Typical fractions include lubricating oils as described below. fractions taken from the stills

According to the invention, a mixture is provided, and preferably those having viscosities

which contains a binder that is predominantly between 150 and 300 SSU at 98.9 ° C. These are

the proportion of certain lubricating oil aromatic extracts, d. H. 25 with selective solvents, e.g. B. Edeleanu Solution

92.5 to 99.5 percent by weight, and subordinate agents, or furfural, extracted to obtain the desired,

Amounts of rubbery hydrocarbon poly- useful in the present invention

meren, d. H. 0.5 to 7.5 percent by weight. To win aromatics. Lube extracts containing the

These aromatic extracts are said to have an aromatic desirable property to a high degree,

Hydrocarbon content of at least 55% by weight can also be achieved by mixing aromatic extracts

Percent and at 98.9 ° C a viscosity of 100 to can be obtained.

3000 SSU, preferably 350 to 2000 SSU, if extracts with a lower viscosity are examined for and in order to have the desired physical properties the present purposes will not only have to be practically free from that excessive amount of rubber or Asphalt, but should also be modified by the 35 of another rubbery hydrocarbon presence of 0.5 to 7.5 percent by weight of a polymer is required to bring the viscosity of rubbery hydrocarbon polymers with 60 ⁰ C to the desired minimum level, an average molecular weight from 5 · 10 * to 10 ⁷ . If this is achieved, however, it is determined that the

The invention in its preferred embodiment- desired viscosity within the mixed temperature form includes those aromatic extracts, which are exceeded with 40 ranges from 120 to 280 ° C, not vulcanized Rubbers are modified. As a result, these aromatic extracts are with Within the scope of the invention, the binder can not have a lower viscosity or a lower viscosity for the present purpose after adding a mineral aggregate with a suitable.

coloring material can be modified, which is a pigment The hydrocarbon polymers, which are

or can be a dye. Preferred road 45 conversion of the aromatic ex-

Coating compositions according to the invention therefore contain tracts with high viscosity in binders for road

3 to 10 percent by weight of a binder, which the ceiling mixes are suitable, include in particular

special aromatic extracts, with which the rubber types are modified, but do not include

Hydrocarbon polymers, 1 to 10 weight prophylactic hydrocarbon polymers, if

cent of a pigment or dye and at least 50 of these molecular weights above 50,000. Such substances

about 80 percent by weight of a mineral aggregate include z. B. ethylene-propylene copolymers, wel-

gates contains. before either rubbery or non-rubber

According to preferred embodiments contain the like characteristic properties,

the most suitable coating compounds 3 to 7G- The hydrocarbon copolymers including

weight percent of a pigment, 4 to 9 weight percent 55 borrowed their sulfur or chlorine analogues, which are

an essentially non-asphaltic lubricating oil has proven particularly suitable for this purpose

extracts, which have an aromatic hydrocarbon, are rubbers, among which a material

substance content of at least 65 percent by weight and a standing that is not fixed or reproducible

Viscosity from 600 to 1500 SSU at 98.9 ° C, 1 to softening point and that are vulcanized

3 percent by weight, calculated on the extract, of a 60 denier can. In the present case, however, the

Hydrocarbon rubber and at least 85 Ge rubbers from the selected polymers, preferably

contains weight percent of a mineral aggregate. wise not vulcanized. It is especially intended

The lubricating oil extracts from which the above elastomers - either natural or synthetic

Written mixtures can be made, table form - to use which vulcanized

are commercially available and well known. From 65 can be and used in the aromatic

Of the numerous available extracts, extracts are at least slightly soluble or at least

however, only a very limited part for use can exist in stable separate phases,

suitable in the present blends. These have to include synthetic or natural rubbers

Hevea, neoprene and especially styrene-butadiene copolymers and isobutylene-isoprene copolymers, Polyisoprene, polybutadienes, polychloroprenes, chlorosulfonated polyethylenes and the like. The styrene-butadiene copolymers are particularly desirable when they contain bound styrene on the order of 20 to 40 weight percent.

The polymers, including the rubbers, are preferably used in the form of their latexes. But they can also be used as solid particles or as solutions (cements). But when conventional equipment used in road construction technology to apply the ceilings, it is most expedient to use latexes of rubbers as they are particularly easy to incorporate can. Such latices preferably contain 50 to 70 percent by weight, particularly preferably 60 to 68 percent by weight, solids, although latexes with a lower solids content are also used can. They can contain dispersants such as soap and the like to stabilize the latex, if so is required. Mixtures of different polymers can be used to achieve special properties to achieve. Although for pavement purposes, any of the hydrocarbons listed above are suitable, the styrene-butadiene copolymers are preferred.

Useful pigments include the common organophilic or hydrophilic pigments. Organophiles Pigments include toluidine red, Hansa yellow, thiazolylamine blue, and phthalocyanine dyes as well Pigments made from organic dyes. Hydrophilic pigments include such of inorganic nature, usually oxides such as titanium dioxide, iron oxides and chrome green, and metal salts, such as lead chromate and the like. The earth colors in particular are effective colors.

It can be any of the well-known mineral aggregates commonly used for road surfaces be used. These can be of the acidic or basic type. The graduation and the particle size these are not essential aspects within the scope of the invention, but are intended to be the usual ones comply with recognized rules in road construction.

The pavement binder mixtures according to the invention have been specially developed with a view to their applicability with apparatus customary in the art. A preferred process therefore consists in adding the aromatic lubricating oil extract to a heated aggregate at a temperature of 120 to 280 ^° C., whereupon the polymer, preferably in the form of a latex, is added together with or after the pigments. Another way of working is to emulsify latex and extract (with or without pigment) with one another and apply them to the hot rock. The coating compound is then brought to the place of work and rolled at an elevated temperature, as is customary in road construction.

The amount of pigment used depends largely on the intensity of the color desired and their effectiveness as a paint in the mixtures according to the invention. The amount fluctuates within relatively low limits. 2 to 7 parts by weight of the pigment calculated on the aggregate usually suitable and effective.

Below is a list of properties of various typical aromatic extracts used in Application within the scope of the present invention are suitable.

TabeUeI Aromatic petroleum fractions

Specific gravity, 15.6 ° C

Paint, ASTM, diluted 1%

Flash point, COC, ⁰ C

Focus, ° C

Pour point, ⁰ C

Viscosity, SSU, 98.9 ⁰ C

Neutralization number, Mg, KOH / gm

Refractive index, 20 ⁰ C

Aniline point, ⁰ C,

Mixed aniline point, ° C

Loss of volatility, 22 hours, 107 ° C, weight percent

Viscosity-gravitational constant distillation, ⁰ C

Initial boiling point

5%

10%

50%

90%

Molecular type analysis, clay gel, weight percent

Asphaltenes

Resins

Aromatics

Saturated compounds

1.0443 0.9916 1.0489 L2.5 L3.5 L4.5 229 299 271 268 343 307 27 24 43 499 783 2443 0.3 0.05 0.2 1.5932 1.5624 1.5900 2.2 55.0 - · 33.9 53.3 36.7 0.01 0.1 0.1 0.988 0.912 0.974 393 434 416 432 483 463 443 491 477 488 527 538 523 - - Nile Nile Nile 26.0 22.5 30.5 68.5 62.6 65.6 5.5 14.9 3.9

Table I (continued)

Molecular type analysis, Rostler, weight percent

Asphaltenes

Nitrogen bases

Unsaturated compounds, group I.

Unsaturated compounds, group II

Saturated compounds

Carbon atom analysis,%

Approx

C _n

Cp

The following examples illustrate the limits and application of the present invention.

example 1

Mixtures of different aromatic extracts with a styrene-butadiene rubber, which contained 25 ± 2% bound styrene in the copolymer, produced and tested. For comparison were Paver mixes made from a road asphalt with a penetration of 85 to 100 at 25 ° C. This binder has a viscosity of 125 SSF

Nile Nile Nile 36.3 21.2 38.4 22.9 19.0 24.9 32.7 47.0 30.1 8.1 12.8 6.6 47 38 43 40 18th 36 13th 44 21

of the mixture of 725.7 at 135 ° C, a viscosity of 1500 poise at 6O ⁰ C and a penetration of 29 (ASTM method D5-59T) at 4 ° C, and a Marshall stability kg (ASTM D-1559).

First, a suitable aromatic extract was used which corresponds to the limits set forth in the general description of the invention above. This included an extract having a viscosity of 499 SSU at 98.9 ⁰ C. The results thus obtained are summarized in Table II.

Table II

% Rubber Viscosity at 135 ° C Viscosity at 6O ⁰ C Penetration at 4 ° C Marshall stability 0.0 SSF Poise dmm kg 12th 39 77 less than 1.0 227 2.5 49 280 86 553.4 186 1268 81 644.9

From the above data it can be seen that this extract provides binding agents for road surfaces, which have satisfactory properties.

Example 2

A second aromatic extract of high viscosity was tested and found to be useful with the exception of a somewhat low penetration at 4 ^° C. The advantage of this special extract, however, was that suitable viscosity corrections could be made by incorporating only 0.5 or 1% of the above-mentioned styrene-butadiene rubber. The extract used had a viscosity of 2218 SSU at 98.9 ⁰ C and contained about 55 weight percent aromatics. The unmodified aromatic extract and the extract containing 0.5% and 1% by weight of the rubber, respectively, had the following properties.

Table III

° / n rubber Viscosity at 135 ° C Viscosity at 6O ⁰ C Penetration at 4 ° C Marshall stability SSF Poise dmm kg 0.0 29 487 8th less than 227 0.5 51 790 8th 689.9 1.0 234 1457 9 734.8

Example 3 shafts, however, are achieved by the combination

of the latter aromatic extract with the

From Table III above it can be seen that 65 aromatic extract, which has a viscosity of the aromatic extract used for the pre-2218 SSU at 98.9 ° C, as in Example 1 was suitable, but at 4 ° C one was used. When using the same amounts had low penetration. The cheapest of these two aromatic extracts and modification

the mixture of the extracts with 2 percent by weight of styrene-butadiene rubber was an optimal composition obtained with the following properties:

Table IV

% Rubber Viscosity at 135 ° C
SSF Viscosity at 140 ^° C
Poise Penetration at 4 ° C
dmm Marshall stability
kg 2 167 1360 28 680.4

Example 4

Finally, an aromatic extract with a viscosity and boiling range below that specified for the present invention was tested. This extract contained 72.5% * 5 aromatics; however, it had a viscosity of 100 SSU at 98.9 ° C. It was recognized as necessary that more than 5 percent by weight of the synthetic rubber had to be used in order to thicken this extract sufficiently so that it had a viscosity of 1259 poise at 6O ⁰ C had. If this amount is added, however, resulted in a viscosity of 697 SSF (at 135 ⁰ C mixing temperature).

From the above it can be seen that it is necessary to use aromatic extracts or mixtures of extracts so that asphalt-like properties are obtained, both with respect to the mixed temperature than with regard to the road temperature and cold weather influences. It shows furthermore that these properties can be obtained by mixing the extracts, which on their own do not meet the requirements, but which when mixed with others do lead to favorable properties that meet the requirements.

For the Marshall stability test, road coatings were produced according to the standard methods, which can be found in the ASTM regulations, the binder from the described aromatic extract, modified by the specified amounts of synthetic rubber was. These binders were mixed with a standard aggregate that performed the following sieve analysis resulted in:

45

Sieve number Continuous amount in% 4th 100 8th 72 16 45 30th 34 50 24 100 11 200 5

Claims (7)

Patent claims: 1. Light, easily dyed with pigments or dyes road surface binder mixture which contains an essentially asphalt-free petroleum fraction, characterized in that the binder mixture of 92.5 to 99.5 percent by weight of an aromatic lubricating oil extract with an aromatic hydrocarbon content of at least 55 percent by weight and a viscosity at 98.9 ° C. for 100 to 3000 seconds Saybolt Universal and 0.5 to 7.5 percent by weight of a rubbery hydrocarbon polymer, in particular a styrene-butadiene rubber, with an average molecular weight of 5 · 10 ⁴ to 10 ⁷ . 2. Binder according to claim 1, characterized in that the polymer is an unvulcanized Rubber is. 3. Binder according to claim 1 or 2, characterized in that the polymer is a styrene-butadiene rubber is bound styrene with a content of 20 to 40 percent by weight. 4. A binder according to any one of claims 1 to 3, characterized in that the aromatic extract oil has a viscosity from 350 to 2000 SSU at 98.9 ⁰ C. 5. Binder according to one of claims 1 to 4, characterized in that the aromatic Extract has an aromatic content of at least 60 to 65 percent by weight. 6. Binder according to one of claims 1 to 5, characterized in that the lubricating oil extract by mixing aromatic extracts. 7. road surface binder mixture according to claim 1 to 6, consisting of 3 to 10 percent by weight of the binder mixture, 1 to 10 percent by weight of a pigment or a dye and at least 80 percent by weight of a mineral aggregate. The mixtures were also modified with, for example, 2 parts of iron oxide (red), 4 parts Chromium oxide (green) or 7 parts lead chromate (green) to 100 parts rock material. Considered publications:
German Patent Nos. 695138, 849 824, 852 883; German Auslegeschrift No. 1 065 317;
U.S. Patents Nos. 2,830,936, 2,921,105,
989 494; Roads and Civil Engineering, 1950, p. 105;
Abraham - Brühl, Asphalt and Related Materials, 1939, p. 348. 709 507/377 1.67 © Bundesdruckerei Berlin