CZ24193A3 - Bituminous emulsion and the use thereof - Google Patents

Abstract

Cationic type bitumen emulsion contains associative nonionic type thickener (I). Pref. (I) comprises hydrophobically modified urethane ethoxylates. Breaking additive may be supplied to the emulsion as a water-in-oil emulsion in which aq. soln. of neutralising substance (II) is dispersed in an oil continuous phase (III).

Description

The invention relates to a cationic bitumen emulsion containing a thickener, the use of this bitumen emulsion in road construction, roofing and waterproofing and the use of certain groups of substances as a thickener in the bitumen emulsion.

BACKGROUND OF THE INVENTION

A common problem when preparing a cold asphalt mixture of aggregate (gravel) and a cationic bitumen emulsion is that the emulsion flows off the aggregate, resulting in a very thin bituminous binder layer on the aggregate surface. This problem is particularly worrying when working with the so-called open-graded mixtures, that is mixtures based on aggregates, which have open grading. A thin binder layer leads to poor stability of the composition and the composition becomes aging sensitive.

Various consistent ways have been tried to solve this problem. The most common method involves mixing a small amount of fine aggregate with a bitumen emulsion to thicken the emulsion. The disadvantage of this technology, however, is that this emulsion breaks into the aggregate, which results in the resulting mixture being very stiff and difficult to spread on the road.

Other methods of thickening the emulsion include concentrating the aqueous phase with additives such as carboxymethylcellulose, polyvinylpyrrolidone, methoxycellulose, etc. However, all of these methods have the disadvantage that the additive will absorb water and / or have a negative effect on the emulsion breakdown. .

The basic requirement of a cationic agent operating in acidic cationic emulsions of this type, which is the most common type for bitumen, is that they are nonionic or optionally cationic.

Another method that has been used for a long time in the past is to use anionic emulsions which can be made of very high viscosity by suitable selection of emulsifiers. This type of emulsion is called 'high-emulsion emulsion'. The disadvantage of this type is that it reflects very slowly and is therefore unsuitable in areas where there is a significant risk of rain (eg Sweden).

SUMMARY OF THE INVENTION

According to the present invention there is provided a method in which a type of thickener is used which interferes with the emulsifier on the surface of the bituminous droplets and forms forces, causing a high pseudo-viscosity of the emulsion. However, this network is not stable enough to prevent the emulsion from flooding across the aggregate surface to form thick layers. Such a thickener belongs to a group commonly referred to as "associative thickeners". Such thickeners have the general hydrophobic hydrophilic-hydrophobic structure. For information about this group of thickeners, see, for example, "Associative Thickeners and Their Rheological Effect on Commercial Sales Formulations by J. E. Glasse et al., Org. Coat. Appl. Polym. Sci. Proc., 47, 1982, p.

498-502.

Thus, the cationic bitumen emulsion containing the thickener of the present invention is characterized in that the thickener comprises at least one substance selected from the group consisting of non-ionic associative thickeners.

According to an embodiment of the bitumen emulsion of the present invention, the nonionic type associative thickeners are hydrophobically modified urethanethoxylates, preferably urethanethoxylates, having the general formula I:

° Γ ° - ° Ί Π

RNC- (CH CH 0) | -CN-RMJ -S- (CH., CH ₉ o) -CN-R / 1 / lxu | | 2 ** ** I

Η Η Η H in which

R and R 'are the same or different and each represents a straight or branched alkyl group having 12 to 18 carbon atoms,

R 'is a saturated or unsaturated hydrocarbon chain of up to 36 carbon atoms, part of which can be closed to form a ring,

X is a number of 90 to 500 and n is an integer of 1 to 4.

The concentration of the quencher in the bitumen emulsion depends on the specific thickener used on one side and the specific bitumen emulsion on the other side. Generally, the concentration of the thickener is in the range of 0.05 to 1% by weight based on the weight of the bitumen emulsion. The appropriate concentration in each individual case is preferably determined by a series of simple tests using variable concentrations of the thickening agent.

The bitumen emulsion of the invention can be prepared by mixing a thickener and a standard cation-type bitumen emulsion using conventional mixing methods for bituminous products.

The standard cation-type bitumen emulsions to be used as starting materials for the preparation of the bituminous emulsions of the invention both contain a bituminous balance of 50 to 70% by weight, based on the total weight of the emulsion (starting material).

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

According to a preferred embodiment of the bitumen emulsion of the present invention, the emulsion has a precipitating agent added in the form of a water-in-oil emulsion, wherein the aqueous neutralizing agent solution is dispersed in an oil continuous phase.

The term "neutralizing agent" is used herein to refer to a substance that has a neutralizing effect on a cationic type bitumen emulsion when added thereto.

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

Examples of such substances are organic bases such as low molecular weight amines, for example monoethanolamine, diethanolamine, triethanolamine and aminopropanol; basic salts of organic acids such as trisodium citrate; basic inorganic acid salts 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 dispersed in a mineral oil or petroleum naphtha solvent.

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

Appropriate amounts and compositions of precipitants for various purposes and effects are readily determined by a series of experiments. However, in general, the amount of this additive is 1 to 10%, preferably 1.5 to 6% and especially 2 to 4% by weight, based on the total weight of the final bitumen emulsion.

According to a further aspect of the invention, the invention also relates to the use of a non-ionic associative thickener as a thickener in a cationic type bitumen emulsion.

The associative thickener of the nonionic type may be a hydrophobically modified methanethoxylate, preferably a modified urethanethoxylate of the aforementioned formula I, wherein R, R ', R, x and n are as previously defined.

According to yet another aspect of the invention, the invention relates to the use of the bitumen emulsion of the invention in road construction, road maintenance, or construction work such as roofing, coating and waterproofing.

According to a preferred embodiment of this aspect of the invention, a water-in-oil emulsion comprising an aqueous solution of a neutralizing agent dispersed in an oil continuous phase is mixed into the bitumen emulsion before or in conjunction with the use of the bitumen emulsion.

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DETAILED DESCRIPTION OF THE INVENTION

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

Example 1

A. An average cation-type precipitating bitumen emulsion containing 60% by weight based on the total weight of the emulsion, distilled bitumen / commercial product of the trade name BE60M from Nynfls Bitumen AB, Johanneshov, Sweden /, was placed in a vessel equipped with a stirrer. Hydrophobically modified urethanethoxylate (Collacral PU 75 from BASF, Ludwigshafen, Germany) was then added under stirring.

The viscosity of the additive-containing emulsion was measured with a Brookfield viscometer equipped with spindle No. 4. The sample was tested at a speed of 5 rpm.

Three different additive concentrations were used, namely 0.1, 0.2 and 0.4% by weight based on the total weight of the emulsion. For comparison, the viscosity of the emulsion without additive was also tested.

B. The procedure of Part A was repeated but using another hydrophobically modified urethanethoxylate (Collacral PU 85 from BASF, Ludwigshafen, Germany) as an additive.

The results of the viscosity tests are given in Table I below.

Example 2

Example 1 was repeated, but using an average cationic type precipitating bitumen emulsion containing 67% by weight based on the total weight of the emulsion, distilled bitumen / commercial product of the trade name BE65M from Nynás Bitumen AB, Johanneshov, Sweden / instead of the emulsion of Example 1 and using of the following hydrophobically modified urethanethoxylates in various amounts 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 DS 6049 from BASF, Ludwigshafen, Germany.

The results are shown in Table I below.

Example 3

Example 1 was repeated, but using a fast-cationic type emulsion bitumen emulsion containing 67% by weight based on the total weight of the emulsion, polymer modified resin / commercial product, trade name PME 89 from NynSs Bitumen AB, Johanneshov, Sweden / instead of the emulsion of Example 1 .

The same ingredients were used as in Example 1, that is

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

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

The results are shown in Table I below.

L

Example 4

Example 1 was repeated, but using a rapidly precipitating cationic type bitumen emulsion containing 67% by weight based on the total weight of the emulsion, distilled bitumen / commercial product, trade name BE65R from Nynfis Bitumen AB, Johanneshov, Sweden / instead of the emulsion of Example 1. They were used the same ingredients as in Example 1, that is

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

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

The results are shown in Table I below.

Table I additive viscosity (p.s.i.) for emulsion according to the amount of type no.

/% (w / w) / 1 2 3 4 none 0.6 1.6 0.6 1,8 0.05 AND 13.2 0.05 (B) 12.4 OJ AND 2.6 14.4 8.0 4.0 0.1 (B) 2.8 14.8 10.4 5.2 0.2 AND 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 AND 4.8 15.4 12.0 4.8 0.4 (B) 6.8 17.2 16.8 6.0 0.4 C 3.4 0.4 D 17.2 0.4 E 23.8

Additive Notes (see Examples 1-4):

A: Collacral PU 75

B: Collacral PU 85

C: Acrysol EM 8

C: Bermodol PUR 2100

E: Collacral DS 6049

Example 5

Using the procedure of Example 1, a blend was prepared from the starting bitumen emulsion of Example 2 (BE65M from Nynás Bitumen AB, Johanneshov, Sweden) and each of the additives A to E specified in Example 2, added in an amount of 0.2% by weight emulsion.

The mixture between the mineral gravel and each of the bituminous emulsions containing the additive was prepared using 500 grams of gravel / Farsta granite 0-16 mm meeting the requirements for asphalt emulsion concrete with a 0-16 mm open curve aggregate as determined by the Road Administration, Sweden och allmanna rad // Construction engineering guidelines and general counters // moistened with 1% water by weight. 7% w / w gravel / bitumen emulsion was added and mixed manually for 72 seconds. The mixture was then poured into a funnel having a sieve at the bottom for effluent and leach tests.

The effluent is the amount of material that is collected in the weighed aluminum container under the funnel over 30 minutes. The vessel is dried in an oven at 110 ° C. The amount of effluent is given as a percentage of binder lost based on the weight of the ballast.

τ 10The remaining sample in the funnel is then used for the leachate test, which is carried out as follows.

After 1 hour pour 200 ml of water onto the sample in the funnel and collect the extract in a weighed aluminum container. Dry the contents in an oven at 110 ° C and weigh. The amount of leachate is reported as a lost binder in percent by weight in the same way as the effluent. The procedure is described in the Asphalt Institute Gollege Park, Maryland, USA.

The results of the above tests and comparative tests using emulsion without additive are given in Table II below.

Table II

Ingredient discharge /% (w / w) / leach /% (w / w) / none 0.56 0.64 Collacral PU 75 none 0.40 Collacral PU 85 none 0.42 Acrysol RM8 0.04 0.82 Bermodol PUR 2100 0.17 0.55 Collacral DS 6049 0.30 0.59 The results can be derived ingredients prevent or

they reduce the effluent but have no detrimental effect on the emulsion breaking.

The results show that by using the emulsion of the invention higher bituminous binder concentrations in the cold asphalt mixture can be used and thus cold mixing technology can be used to prepare asphalt mixtures for roads with higher traffic intensity and longer durability than hitherto possible.

Example 6

To the average cation-type precipitating bitumen emulsion containing 67% by weight based on the total weight of the emulsion, distilled bitumen / commercial product, trade name BE 65 M from Nynas Bitumen AB, Johanneshov, Sweden / was added 2.1% by weight of bitumen emulsion, bleaching agent mixture and hydrophobically modified urethanethoxylate (Collacral PU 75 from BASF, Ludwigshafen, Germany) in a 20: 1 weight ratio.

The precipitant was in the form of a water-in-oil emulsion consisting of an oil phase of Hypermer A60 solution (a commercial product from ICI Europe Ltd., Kortenberg, Belgium) at a concentration

6.6% by weight, Diamin BG (commercial product from Scanroad AB, Nacka, Sweden) at a concentration of 0.33% by weight and ViscoII plex BA9-7OO (commercial product from Rohm GmbH, Darmstadt, Germany) at a concentration of 0.66% / wt / wt / in hydrotreated naphthenic tt oil (Nytex 800 standard quality from Nynas Naphthenics AB, Nynashamn, Sweden), and an aqueous phase consisting of an aqueous solution containing 8% (wt / wt) sodium carbonate and 16% (wt / wt) citrate The water-in-oil emulsion contains 70% by weight of water.

The mixture of precipitating agent and thickener was mixed with the bitumen emulsion by stirring with a glass rod immediately before adding 50 g of the emulsion to 500 g of aggregate with the so-called open dimensional distribution.

The gravel / emulsion mixture was mixed for 60 seconds with a steel shovel and poured into a plastic funnel with a sieve at its bottom for discharge and leach tests.

In this case, no effluent was detected within 30 minutes (a few drops of pure water were detected but there were no bitumen).

After 1 hour the mixture was tested for leach by pouring 200 ml of water onto the mixture. No leach was detected (clear water flowing out of the funnel).

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Claims (10)

AND Cation-type bitumen emulsion comprising a thickener, characterized in that the thickener comprises at least one substance selected from the group consisting of non-ionic associative thickeners. 2. The bitumen emulsion of claim 1, wherein the non-ionic associative thickener is hydrophobically modified urethanethoxylates. 3. A bituminous emulsion according to claim 2, characterized in that the hydrophobically modified urethanethoxylates have the general formula: O 0 0 O RNC- (CH ₂ CH ₂ O) 4 CNRNC- (CH ₂ CH ₂ O) / _n -CN-R ' Η Η Η H in which R and R jsou are the same or different and each represents an unbranched or branched alkyl group having 12 to 18 carbon atoms, R ^M is a saturated or unsaturated hydrocarbon chain of 7 to 36 carbon atoms, part of which can be closed to form a ring, x is a number of 90 to 500 and n is an integer of 1 to 4. 4. A bituminous emulsion according to any one of Claims 1 to 3 comprising an added precipitant in the form of a water-in-oil emulsion in which the aqueous neutralizing agent solution is dispersed in an oil continuous phase. - 14 5. A bituminous emulsion according to claim 4, wherein the neutralizing agent is selected from the group consisting of organic bases, basic salts of organic or inorganic acids and alkali metal hydroxides, which bases, salts and hydroxides are soluble in water but sparingly or insoluble in oil. . 6. The bituminous emulsion of any one of items 4 and 5, wherein the neutralizing agent is dispersed in a mineral oil or a petroleum naphtha solvent. Use of a non-ionic associative thickener as a thickener in a cationic bitumen emulsion. 8. The use according to item 7, wherein the associative thickener of the nonionic type is a hydrophobically modified urethanethoxylate. 9. The use according to item 8, wherein the hydrophobically modified urethanethoxylate is a compound of the general formula 0 0 0 0 μ μι »n RNC- (GH ₂ CH ₂ O) _x / '- GNRNC- (CH CHO) / _n -CN-R' Η Η Η H in which R and B jsou are the same or different and each represents an unbranched or branched alkyl group having 12 to 18 carbon atoms, R is a saturated or unsaturated hydrocarbon chain of 7 to 36 carbon atoms, part of which chain may be closed to form a ring, x is a number of 90 to 500 and n is an integer of 1 to 4. 10. Use of the bitumen emulsion as set forth in any one of items 1 to 3 in road construction, road maintenance and construction work. 11. Use according to item 10, wherein the water-in-oil emulsion comprising an aqueous solution of a neutralizing agent dispersed in an oil continuous phase is mixed into the bitumen emulsion before or in conjunction with the use of the bituminous emulsion. Represented by: JUDr. Ing. Milap Hořejš