LT3233B - Bitumen emulsion and use them - Google Patents

Abstract

The discovered cationic-type bituminous emulsion consists of a graduation implement, which has at least one substance, selected from a group, consisting of non-ionic type of associative graduation implements. This invention is also designed for the usage of the type of the graduation implement mentioned above as the graduation implement in the cationic-type bituminous emulsion and as bituminous emulsion, which has the graduation implement inside, as described above, for use in civil engineering, roofing and creation of water resistance.

Description

The present invention relates to a cationic bitumen emulsion containing a thickener, to the use of this emulsion in road construction, roofing and waterproofing and to the use of a certain group of materials as thickeners in said bitumen emulsion.

A common problem when preparing a cold mix of aggregate and cationic bitumen emulsion is that the emulsion runs off the rocks, resulting in a very thin layer of bituminous binder on the rock surface.

This problem is particularly troublesome when working with so-called free sorting mixtures, i.e. mixtures based on rock material which has free sorting. Thin binder layers cause poor mix stability and make the mix susceptible to aging.

Several different ways have been tried to solve this problem. The most commonly used method consists of mixing a smaller amount of fine stone material in the bitumen emulsion to thicken this emulsion. However, the disadvantage of this method is that this emulsion breaks down in contact with rock material and results in a material which is very hard and very difficult to spread on the road.

Other methods of thickening the emulsion include thickening the aqueous phase with the addition of additives such as carboxymethylcellulose, polyvinylpyrrolidone, methoxycellulose and 1.1. However, all these methods have the disadvantage that the additive will absorb water and / or adversely affect the breakage of the emulsion.

It is a prerequisite that the thickeners present in acidic cationic emulsions, most common in those bitumens, are cationic.

flats non-ionic or maybe

Another method that has been used for a long time is to use anionic emulsions, which can be made with very high viscosity, with proper selection of emulsifiers. This type of emulsion is called High Buoyancy Emulsion. The reason for this is that they fracture very carna, which is essential in Sweden).

Lack of type emulsions is slow and therefore there is no risk of rain (e.g.

According to the present invention, we have found a method in which a type of thickener is used which mixes emulsifiers at the surface of bitumen drops and forms a network which gives the emulsion a high pseudo-viscosity. However, the mesh is not so stable as to prevent the emulsion from floating above the rocks and forming thick layers. These thickeners belong to a group commonly referred to as associative thickeners. Such thickeners have a common hydrophobic-hydrophilic-hydrophobic structure. The literature on this group of thickeners is extensive, e.g. J.E. Glass et al., Associative Thickeners and Their Rheological Influence on Trade-Sale Formulations, Org. Coat. Appl. Polym. Sci. Proc., 47, 1982, p. 498-502.

Thus, a cationic emulsion containing a thickener according to the present invention is characterized in that the thickener comprises at least one substance selected from the group consisting of associative nonionic thickeners.

According to an embodiment of the bitumen emulsion of the present invention, the associative nonionic thickeners are hydrophobically modified urethane ethoxylates, preferably urethane ethoxylates having the general formula (I):

O

II

RNC (CH ₂ CH ₂ O) _x

O O

II II

-CNRNC- (CH ₂ CH ₂ O)

H H

O

II

-C-N-R '(I),

I

I

H wherein R and R 'are each the same or different and represents a linear or branched alkyl group of 12 to 18 carbon atoms; R is a saturated or unsaturated hydrocarbon chain of 7 to 36 carbon atoms, which moiety may be closed to form a ring; x is a number 90-500; n is an integer from 1 to 4.

The concentration of the thickener in the bitumen emulsion depends on the specific thickener on the one hand and the specific bitumen emulsion on the other. Generally, the concentration of the thickener will range from 0.05 to 1% by weight of the bitumen emulsion. The appropriate concentration in each individual case is best determined by a series of simple experiments using varying concentrations of the thickening agent.

The bitumen emulsion of the present invention may be prepared by mixing a thickener and a standard cationic type bitumen emulsion using commonly accepted methods for mixing bitumen products.

Standard cationic bitumen emulsions used as starting materials for preparing bitumen emulsions of the present invention generally contain a residual bitumen content of 5070% by weight of the total emulsion (starting material).

The emulsifier used in the bitumen emulsions used as starting material in the emulsions of the present invention is not critical. Examples of emulsifiers used in cationic-type bitumen emulsions are, for example, fatty diamines, quaternary ammonium compounds, ethoxylated amines, amidoamines and imidazolines.

According to an embodiment of the bitumen emulsion of the present invention, which is preferred, said bitumen emulsion has a disintegrating additive in the form of a water-in-oil emulsion, wherein the aqueous solution of the neutralizing agent is distributed in the oil continuous phase.

The term neutralizing agent is used herein and in the definition of the invention to denote a substance which has a neutralizing effect on cationic bitumen emulsion when added thereto.

The neutralizing agent is preferably selected from the group consisting of organic bases and basic salts of organic and inorganic acids and an alkali metal hydroxide which (bases, salts and hydroxides) are water-soluble but slightly soluble or insoluble in oil.

Examples of such materials are organic bases such as low molecular weight amines such as monoethanolamine, diethanolamine, triethanolamine and aminopropanol; basic salts of organic acids such as trisodium citrate; basic salts of inorganic acids such as sodium carbonate, sodium borate, sodium silicate and trisodium phosphate; and alkali metal hydroxides such as sodium or potassium hydroxide.

The neutralizing agent is preferably distributed in mineral oil or in a naphtha-type solvent.

The emulsifier used to emulsify the neutralizing agent solution in the oil should be of nonionic type and have an HLB size (Hydrophilic Lipophilic Balance) within the range of 3-9, preferably 5-7.

Suitable amounts and mixtures of breakdown additives for various purposes and effects are in the series of experiments. However, the amount is 1-10, preferably the weight of the final bitumen emulsion.

the limits are usually set at 1.5-6, especially 2-6% of the said additive

According to another aspect of the present invention, the invention is also directed to the use of a non-ionic associative thickener in the form of thickened cationic bitumen emulsions.

The non-ionic associative thickener may be a hydrophobically modified methane ethoxylate, preferably a modified urethane ethoxylate of formula (I) wherein R, R ', R, x and n are as previously defined.

In yet another aspect of the present invention, the present invention is directed to the use of bitumen emulsion according to the present invention in road construction, road repair or construction such as roofing, paving, waterproofing.

According to an embodiment of this aspect, which should be preferred, the water-in-oil emulsion containing an aqueous solution of a neutralizing agent dispersed in the continuous oil phase is mixed into the bitumen emulsion before or in combination with the use of said emulsion.

The invention is illustrated by the following non-limiting examples.

'Example 1

A. Medium fracture cationic type bitumen emulsion containing 60% by weight of total distilled bitumen (commercial product, trade name BE60M from Nynas Bitumen AB, Johanneshov, Sweden) was loaded into a mixing vessel. Hydrophobically modified urethane ethoxylate (Collacral PU75 from BASF, Ludwigshafen, Germany) was added with stirring.

The viscosity of the emulsion containing the additive was measured with a Brookfield viscosity meter fitted with a spindle No 4. The sample was checked at 5 rpm. for speed.

Three different additive concentrations of 0.1, 0.2 and 0.4% of the total emulsion weight were used. The viscosity of the emulsion without additive was also checked for comparison.

B. The procedure in part A was repeated using another hydrophobically modified urethane ethoxylate (Collacral PU 85 from BASF, Ludwigshafen, Germany) as an additive.

The results of the viscosity test are shown in Table 1 below.

example

Example 1 was repeated, but using an average fracture cationic type bitumen emulsion containing 67% by weight of total distilled bitumen (commercial product, trade name BE65M from Nynas Bitumen AB, Johanneshov, Sweden) instead of Example 1 emulsion using such hydrophobically modified urethane ethoxylates. in various quantities as additives:

A. Collacral PU 75 from BASF, Ludwigshafen, Germany.

B. Collacral PU 85 from BASF, Ludwigshafen, Germany.

C. Acrysol RM 8 from Rohm and Haas, Philadelphia, USA.

D. Bermodol PUR2100 from Berol Nobel AB, Stockholm, Sweden.

E. Collacral DC 6049 from BASF, Ludwigshafen, Germany.

The results are shown in Table 1 below.

example

Example 1 was repeated but using a fast breaking cationic bitumen emulsion containing 67% by weight of the total polymer modified bitumen (commercial product, trade name PME 89 from Nynas Bitumen AB, Johanneshov, Sweden) instead of Example 1 emulsion. The same additives were used as in Example 1, i.e.

A. Collacral PU 75 from BASF, Ludwigshafen, Germany.

B. Collacral PU 85 from BASF, Ludwigshafen, Germany.

The results are shown in Table 1 below.

example

Example 1 was repeated, but using a fast disintegrating cationic bitumen emulsion containing 67% by weight of total distilled bitumen (commercial product, trade name BE65R from Nynas Bitumen AB, Johanneshov, Sweden) instead of Example 1 emulsion. The same additives were used as in Example 1, i.e.

A. Collacral PU 75 from BASF, Ludwigshafen, Germany.

B. Collacral PU 85 from BASF, Ludwigshafen, Germany.

The results are shown in Table 1 below.

table

Additive Viscosity [Pa.s] for Emulsion

Quantity Type according to eg. No.

[sv %] 1 2 3 4 - okay 0.6 1.6 0.6 1.8 0.05 A 13.2 0.05 B 12.4 0.1 A 2.6 14.4 8.0 4.0 0.1 B 2.8 14.8 10.4 5.2 0.2 A 6.4 14.0 12.8 4.8 0.2 B 4.0 12.8 14.0 6.0 0.2 C 3.6 0.2 D 5.4 0.2 E 5.2 0.4 A 4.8 15.4 12.0 4.8 0.4 B 6.8 17.2 16.8 6.0 0.4 C 8.4 0.4 D 17.2 0.4 E 23.8 Notes to the attachments (1-4 e.g.):

A: Collacral PU 75 B: Collacral PU 85 C: Acrysol RM 8 D: Bermodol PUR 2100 E: Collacral DS 6049.

example

Using the procedure of Example 1, a mixture of the initial bitumen emulsion of Example 2 (BE65M from Nynas Bitumen AB, Johanneshov, Sweden) and the additives of each of Example 2 A-E in 0.2% emulsion weight was prepared.

A mixture of mineral aggregates and each bitumen emulsion containing additives was made using 500 g aggregates [Farsta granite 0-16 mm, meeting the requirements for asphalt emulsion, specifically with the free-form stone size 0-16 mm set by the Road Administration, Sweden, and Byggnadstekniska foreskriffer och allmanna rad (Structural Techniques & General Tips)] dampened with 1% water. 7% by weight (based on aggregate weight) of bitumen emulsion was added and the mixture was stirred by hand for 72 seconds. The mixture was then poured into a funnel with a bottom mesh for Run and Wash tests.

Runoff is the amount of material collected in a packed aluminum container under a funnel within 30 minutes. The container is dried in a tile at 110 ° C. The amount of runoff is reported as a percentage of lost binder calculated from the weight of the loading assembly.

The remaining sample in the funnel is then used for the flushing test, which is performed as follows.

After 1 hour, place 200 ml of water on the sample funnel and collect the eluate in a packed aluminum container. The contents are dried in a tile at 110 ° C and weighed. The wash amount is reported as% binder weight loss in the same way as run off. The procedure is described in A Basic Asphalt Emulsion Manual from Asphalt Institute College Park, Manyland, USA.

The results of the above described tests and comparison tests using the emulsion without additives are shown in Table 2.

7th

Table J- v

Appendix  Run away, [sv %] Rinse sv % - 0.56 0.64 Collacral PU 75 - 0.40 Collacral PU 85 - 0.42 Acrysoi RM 8 0.40 0.82 Bermodol PUR 2100 0.17 0.55 Collacral DS 6049 0.30 0.59 From the results it is possible make a conclusion, that accessories with- interferes with or reduces run, but is not harmful

affecting the breakage of emulsions.

The results show that the emulsion according to the invention can be used in higher concentrations of bituminous binder in cold asphalt mix, and according to the cold mix method, this emulsion can be used for preparation of asphalt mixes for roads with high traffic volume and longer service life.

Example: An average disintegrating cationic bitumen emulsion containing 67% by weight of distilled bitumen (commercial product, trade name BE 65 M from Nynas Bitumen AB, Johanneshov, Sweden), 2.1% cleavage additive and hydrophobically modified urethane ethoxylate (Collacral PU 75). from BASF, Ludwigshafen, Germany) (20: 1 by weight) based on the weight of the bitumen emulsion.

The disintegrating additives were in the form of a water-in-oil emulsion containing an oil phase consisting of

Hypermer 60 solution (commercial product from ICI Europe

Ltd., Cortenberg, Belgium) 6.6% w / w Diamino BG (commercial product from Scanroad AB, Nacka, Sweden) 0.33 wt. % concentration and Viscoplex BA9-700 (commercial product from Rohm GmbH, Darmstadt, Germany) 0.6 wt. water-saturated naphthenic oil (standard quality Nytex 800 from Nynas Naphthenics AB, Nynashamn, Sweden), and an aqueous phase containing an aqueous solution of 8 wt. % sodium carbonate and 16 wt. % trisodium citrate, said water-in-oil emulsion containing 70% by weight of water.

The mixture of disintegrant and thickener was mixed in a bitumen emulsion by stirring with a glass stirrer immediately before adding 50 g of emulsion to 500 g of mineral aggregate with so-called free size distribution. The aggregate emulsion mixture is stirred for 60 seconds with a steel spatula and filled into a plastic bottom with a mesh bottom for run-off and flush tests.

In this case, there was no runoff for 30 minutes (a few drops of water could be seen but there was no bitumen).

After 1 hour, the mixture was checked by rinsing with 200 ml of water on the mixture. There was no flushing (clean water ran out of the funnel).

Claims (11)

DEFINITION OF INVENTION Cationic bitumen emulsion containing a thickener, characterized in that the thickener comprises at least one material selected from the group consisting of nonionic type associative thickeners. 2. Bitumen emulsion according to claim 1, characterized in that the non-ionic associative thickener is hydrophobically modified urethane ethoxylates. 3. Bitumen emulsion according to claim 2, characterized in that it is hydrophobically modified with urethane ethoxylates are present substance of general formula: 0 0 0 0 II r II II _Ί II RNC (CH ₂ CH ₂ O) _x i -CNRNC- (CH ₂ CH ₂ O) II n -C-N-R ', 1 1 H L 1 1 _ H H 1 H in which R and R 'is the same or different and each representing a straight or branched 12-18 an alkyl group of carbon atoms; R '' is present saturated or unsaturated hydrocarbon chain of 7 to 36 carbon atoms a piece, the part of which may be closed to form a ring in such a case; x is a number 90-500; n is an integer from 1 to 4. Bitumen emulsion according to any one of claims 1 to 3, characterized in that it contains a water-in-oil disintegrating additive, wherein the aqueous solution of the neutralizing agent is dispersed in the continuous oil phase. 5. Bitumen emulsion according to claim 4, characterized in that the neutralizing agent is selected from the group consisting of organic bases, basic salts of organic or inorganic acids and alkali metal hydroxides (bases, salts and hydroxides) which are water-soluble but slightly soluble or insoluble in oil. 6. Bitumen emulsion according to any one of claims 4 to 5, characterized in that the neutralizing agent is dispersed in a mineral oil or a naphtha-type solvent. Use of a non-ionic associative thickener in a cationic bitumen emulsion thickener. 8. Use according to claim 7, wherein the non-ionic associative condenser is hydrophobically modified urethane ethoxylate. Use according to claim 8, characterized in that the hydrophobically modified urethane ethoxylate is a substance of the general formula: O II RNC (CH ₂ CH ₂ O) _X H o o II II -CNRNC- (CH ₂ CH ₂ O) II HH _n -CNR ', I H wherein R and R 'are the same or different and each represents a straight or branched alkyl group of 12 to 18 carbon atoms; R '' is a saturated or unsaturated hydrocarbon chain of 7 to 36 carbon atoms, the moiety of which may be closed to form a ring; x is a number 90-500; n is an integer from 1 to 4. Use of bitumen emulsion according to any one of claims 1 to 3 in road construction, road repair and construction. Use according to claim 10, characterized in that the water-in-oil emulsion containing an aqueous solution of the neutralizing agent dispersed in the continuous oil phase is mixed with or combined with said bitumen emulsion before use.