DE3525882C2 - Emulsifiers for bituminous emulsions - Google Patents

Description

The invention relates to mixed grade asphalt emulsions of medium setting speed, fast setting Emulsions and quick setting mushy finishing or Sealing emulsions. This affects in particular Invention new emulsifiers for solvent free and Anionic and cationic solvents bituminous oil-in-water emulsions of mixed degree, where the emulsifiers from the reaction products of polyamines with certain polycarboxylic anhydrides and their modified products exist. Leave modifications do this by converting the nitrogen containing intermediates with formaldehyde and Sodium sulfite or bisulfite, chloroalkane sulfonic acid salt, γ-propane sultone, chloromethanephosphonic acid, Acrylic acid, fumaric acid, maleic acid and chloroalkanoic acids.

When making ceilings or coverings, three Main process applied to thorough mixing of bitumen and aggregates, namely:

• 1) Mixing free flowing heated asphalt (Asphalt cement with pre-dried aggregates;
• 2) Mixing pre-dried additives with Asphalt containing a hydrocarbon solution is diluted (waste asphalt, cutter material) at ambient temperatures and  
• 3) mixing the aggregates with asphalt emulsions, e.g. B. oil-in-water emulsions obtained by vigor stirring asphalt and water in the presence an emulsifier.

Due to rising energy and hydro costs solvent and with regard to environmental problems the use of emulsified asphalt is increasing. Each after that used to make an emulsion Anionic or cationic emulsions become emulsifiers receive. In the case of anionic emulsions Asphalt droplets negatively charged; in the case of kationi The asphalt droplets carry positive emulsions Charges and migrate to the cathode when an electrical Field is created.

In general, one differentiates according to the characters Risks of the mixed type and degree of disruption in the bituminous emulsions between quick setting or solidifying emulsions, emulsions of medium Setting or setting speed and slow setting or solidifying emulsions. In case of rapidly setting emulsions, mainly for Repair of old wear layers are applied, the emulsion is brought onto the existing surface, on which aggregates are distributed and on what after compression the road again for traffic can be released shortly after application of the new one Blanket (chip sealing and the like). Emulsions of medium setting speed with the surcharge substances mixed before use in road construction and slow setting emulsions can be added substances mixed and without for a longer period of time Keep open on the aggregate surface become.  

From US Pat. No. 3,062,829 it is known to be anionic to produce bituminous emulsions by using a Alkali emulsifier and polyamide additives where it are condensation products of dilinoleic acid and polyalkylene polyamines. From U.S. Patent 3,123,569 it is known to add lignin amines as anionic emulsifiers use. The US Pat. No. 3,956,002 is also used Formation of anionic emulsifiers from oxidized alkali Gnin, an ethylene oxide adduct of alkylphenols and bis known to 10 wt .-% sodium borate. In U.S. Patent 4,088,505 becomes an anionic emulsifier consisting of a Alkali metal salt of an alkali metal lignin, an ethylene oxide Adduct of an alkylphenol and water described.

Furthermore, US Pat. No. 3,344,082 is anionic Asphalt emulsifiers from alkali metal salts of complex known polynuclear aromatic polycarboxylic acids. Out U.S. Patent 3,006,860 also discloses alkali metal soaps from higher fatty acids, such as those found in tall oil occur to use.

From Chemical Abstracts, Vol. 71, 1969, Unit 61928w is the Reaction of oleic acid with maleic anhydride and the others Implementation with a polyamine as well as the surfactant Eigen known of the reaction product (surfactants).

From US-PS 3,740,344 the manufacture of fast is setting anionic bituminous sealing layers Application of a combination of anionic emulsifiers, e.g. B. arylalkyl sulfonates and condensation products of Ethylene oxide with alkylated phenols with fatty alcohols, with monoesters of fatty acids with glycerin or sorbitol or long chain fatty acids.

From US Pat. No. 3,615,796 the use of Petroleum sulfonates as fast setting anionic Sealing emulsifiers known. A combination of Sodium lignate or lignosulfonate and saponified colopho nium or tall oil is described in U.S. Patent No. 3,594,201.

Finally, the use is from US Pat. No. 3,350,321 of alkyl or alkoxyalkyl phosphoric acids as emulsifiers known for asphalt.  

Cationic emulsions can be prepared using a Variety of organic containing nitrogen Making connections, for example fatty amines, Fatty diamines, fatty triamines, fatty amidoamines, fatty imides zolines and reaction products from all of these Compound with ethylene oxide as well as mono- and diquaternary Fatty ammonium salts. The fat residues of these compounds can have a different chemical structure and the Units for the production of these amines can be of various origins, e.g. B. from petroleum refines, animal fats, vegetable oils and fish oils as well as tall oil. The suitability of amidoamines as Emulsifiers is known from U.S. Patent Nos. 3,230,104 and 3,097,174 known. Combinations of fat monoamines and fat tria mines are described in U.S. Patent No. 3,738,852; Fat diamines are also known from U.S. Patent Nos. 3,728,278 and 3,518,101 known. Quaternary and diquaternary fatty salts and Modifications thereof are also from U.S. Patent 3,220 953, 3 867 162, 3 764 359, 3 957 524 and 3 466 247 and fatty imidazolines are disclosed in U.S. Patent 3,445,258 described.

Generally, asphalt emulsions are used formation of fatty amines, fatty diamines, fatty amidoamines and Like. Are manufactured, unstable when they with the various silicas or calcareous aggregate substances are mixed. A quick break up the surface of the aggregate increases as the Stiffness observed. At this point the Mix cannot be edited. To overcome this problem it is common practice instead of asphalt cement Waste asphalt for the production of asphalt emulsions medium setting speed. Although Waste emulsions produced with these emulsifiers have been set up, even when they are with the Mixing aggregates reduces the solution medium (a hydrocarbon oil, e.g. naphtha, kerosene, Diesel oil and the like.) The viscosity of the asphalt and  increases the machinability of the aggregate asphalt mixture. This evaporates after using the mixture Solvent and it becomes a stiff or rigid Obtain aggregate asphalt matrix. Because of the dramatic increase in solvent costs in the past few years and because of the effort to prevent pollution exists Need for suitable emulsifiers for the production of mixed degree emulsions without using solvent teln. The use of quaternary lime ammonium salts and diquaternary ammonium salts for the production of Emulsions, suitable for porridge sealing, a solvent-free application, is from US Pat. No. 3,764,359 known and the use of a quaternary amine, obtained by reacting epichlorohydrin, trimethylamine and nonylphenol for solvent-free mixtures is made of U.S. Patent 3,957,524.

From US-PS 4,447,269 is an aqueous bituminous Emulsion made from a fine-grained aggregate the pasty mixture known to deal with moderate faster speed after your order to the settling treatment surface and that over a longer Period of time is usable and an application in Porridge enables. The cationic, quick-setting and solvent-free asphalt emulsion medium setting speed is used an emulsifier, which is the Reaction product of a polyamine with a polycarbon acid of the following general formula:

where x and y are integers from 3 to 9, x and y together are equal to 12 and at least one radical Z is one Is carboxylic acid group and any other remaining residue Z represents a hydrogen atom. The setting speed speed is determined by the emulsifier dose, the pH value, the aggregate gradation and the temperature.

The object of the present invention is to create new ones mutually usable emulsifiers for solvent-free and Bituminous oil-in-water containing solvents Rapid setting and medium emulsions Specify mixing degree of mixed degree type. Task of It is also an invention to use emulsifier mixtures degree emulsions indicate the different binding times, expressed as a percentage of the original Wash-off coating after one hour. It should furthermore new amidoamines, imidoamines or imidazolines and amphoteric derivatives, made by reacting Polycarboxylic anhydrides with polyamines and Modification of these products with a variety of  Reagents, e.g. B. formaldehyde and sodium sulfite or bisulfite, haloalkanesufonic acid sodium salts, γ- Propane sultone, chlorohydroxysulfonic acid sodium salt, Sodium vinyl sulfonic acid salt, haloalkanoic acids, e.g. B. Chloroacetic acid, α, β-unsaturated carboxylic acids, e.g. B. Acrylic, methacrylic, fumaric and maleic acid, epoxy carbon acids, haloalkane phosphoric acids, formaldehyde and phos phosphoric acid in the presence of hydrochloric acid, suitable as emulsifiers for both anionic and cationic oil-in-water emulsions are provided. It is known from the literature that these reagents with the active nitrogen atoms of amines in the case of Mannich-type reactions react through Michael- Additions or by nucleophilic substitution under Formation of aminoalkyl sulfonic acids and aminoalkyl carbon acids (amino acids). These products are amphoteric. she are soluble in both acidic and alkaline pH Values and at the isoelectric point where the number of positive charges is equal to the number of nega tive charges in the molecule, they do not move when an electric field is created. Furthermore show they have reduced solubility in water.

The invention is based on the finding that reak tion products of polyamines with certain tricarbon acid anhydrides and modified products thereof Emulsions lead to the production of anionic and cationic asphalt emulsions of mixed degree and medium setting speed as well as for the manufacture suitable for quickly setting asphalt emulsions are. For the emulsification, solutions can be used non-asphalt and asphalt with up to 15 Use volume% of a hydrocarbon oil.

The invention thus relates to bituminous emulsions and covering masses as they are known in the claims are drawn.  

The polycarbonates thus advantageously correspond acid anhydrides, which are used for the production of the invention anionic and cationic emulsifiers used the following formulas:

The C₂₂-tricarboxylic anhydrides I and II are and are obtained by reacting oleic acid or elaidin acid with maleic anhydride at temperatures of 180 ° C and above. Anhydride II is the monoadduct of Maleic anhydride and linoleic acid. Because of the two Double bonds can be inserted a second time acid anhydride, resulting in a pentacarboxylic acid Diahydrid leads. I, II and III are according to U.S. Patent 3,451,958 the main reaction products that come from tall oil fatty acid and derive maleic anhydride. The anhydride IV will obtained when linoleic acid is catalytically isomerized to conjugated linoleic acid before reaction with maleic acid anhydride. Using a Diels-Alder cycloaddition get a cyclohexene tricarboxylic anhydride. The Preparation of this type of cycloaliphatic acid anhydrides from conjugated linoleic acid and maleic acid anhydride is known from United Kingdom Patent 1,032,363 and U.S. Patent 3,412,056 known. Because tall oil fatty acid is about 50% from oleic acid and 50% linoleic acid, leads to a maleic acid anhydride addition in the presence of iodine to a mixture of cyclic (IV) and open (I, II) C₂₂ tricarbon acid anhydrides.

When 1 mole of the polycarboxylic anhydrides with 2 moles of one Polyamines is mixed, e.g. B. diethylene triamine neutralizes the carboxylic acid group and it forms Monoammonium salt (V). When heated to 80 to 90 ° C the very active anhydride group reacts to form an imidoamine ammonium salt (VI). By increasing the The temperature at 150 to 180 ° C reacts the terminal Carboxylic acid group to form an amido group a C₂₂-imidoamine-amidoamine (VII). Consists of the amine an amine of the class used to form imidazolines is capable, for example diethylenetriamine, so when heated to over 250 ° C an imidoamine imidazoline  (VIII) received. By increasing the weight ratio polymeric products (polymeric Amides).

Are three or more moles of amine per mole of polycarbonate acid anhydrides used, so a triamidoamine (X) and triamidazoline (XI) in a corresponding manner obtained the diammonium salt of monoamidoamine (IX).

The reaction sequence can be represented by implementation of (I) with diethylenetriamine:

The compounds VI to XI can also be obtained by reacting maleic anhydride adducts of natural oils (vetable oils) (triglycerides) with Polyamines. The interconnections VI and IX are amphoteric substances and show solubility in both Acids as well as alkali. The cycloaliphatic C₂₂- Tricarboxylic anhydride can have the same reaction sequence run through.

Amphoteric amido (imido) amines derived from Ethylenediamine, propylenediamine, the N-methyl, N-ethyl, Let N, N-dimethyl and N, N-diethyl derivatives of this can be made from an anhydride without difficulty, because they react below their boiling points. Amidoamines from these polyamines and fatty acids can usually be more difficult to manufacture because the amides from the reaction distill off the mixture before the reaction is complete, which leads to diamides insoluble in acid.  

However, these products described above will never obtained in a high-purity state because the tall oil fatty acids contain other reactive contaminants, for example wise small amounts of resin acid, which also with malein acid anhydride react, and saturated fatty acids. All of these are available in smaller quantities Components react with the amines to form Amidoamines, including smaller amounts of polymer Substances are created.

The formation of imidoamine imidazolines and imidazolines is limited to polyethylene amines and polyamines, characterized by at least one functional Ethylenediamine group with at least three hydrogen atoms on the two nitrogen atoms. Connections of this group, those for the formation of both amidoamines and imida zolinen are suitable: ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, Pentaethylene hexamine and higher homologues; Aminoethyl ethanolamine, N-aminoethylpropanediamine, N, N'-diaminoethyl propanediamine and the N-aminoethyl or N, N'-diaminoethyl substituted butanediamines, pentanediamines and hexane diamines and N-hydroxyethyl ethylenediamine. This verb The following formulas:

H₂NCH₂CH₂NHR

R = H-, CH₃-, C₂H₅-, C₃H₇-, -CH₂CH₂OH, - (CH₂CH₂NH) _x H
x = 1, 2, 3, 4,. . ., 10
or

R₁R₂N (CH₂) _y NHR₃ (XII)

R₁ = H-, CH₃-, C₂H₅-, C₃H₇-, NH₂CH₂CH₂-,
R₂ = H-, CH₃-, C₂H₅-,
R₃ = H-, CH₃-, C₂H₅-, C₃H₇-, NH₂CH₂CH₂-,
y = 2, 3, 4, 5, 6.

Amines which are used to form amidoamines but not Formation of imidazolines are suitable: 1,3- Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6- Diaminohexane, piperazine (1,4-diazacyclohexane), N- Aminoethylpiperazine, N-aminopropyl-propanediamine-1,3; N- Methyl N-aminopropylpropanediamine-1,3; N, N-dimethyl propane diamine-1,3; N, N-diethyl propanediamine-1,3; N, N-dimethyl ethylenediamine; N, N-diethylethylenediamine; N-aminohexyl hexanediamine-1,6.

Other modified compounds of the described Mono-di- or triamidoamines, imidoamines or imidazolines are the reaction products with reactive oxirane systems, e.g. B. ethylene oxide, propylene oxide or butylene oxide. The Reaction starts primarily on primary and secondary Nitrogen atoms, i. H. on a nitrogen atom the one or two hydrogen atoms covalently bound are. The reaction products belong to the class of N- Hydroxyethyl, N-2-hydroxypropyl and N-2-hydroxybutyl amidoamines or imidazolines. For production of Intermediates for further modification can the nitrogen atoms with active hydrogen atoms only partially implemented with these three-membered ring oxides become.

Combinations of amidoamines based on fat monocar bonic acids of various origins or resin acids and C₂₂-tricarboxylic anhydrides disclosed here can also be obtained by implementing suitable polyamines with a mixture of fatty monocar bon or tricarboxylic acid anhydrides. Monocarboxylic acids, suitable for this purpose are tall oil fat acids, crude tall oil, rosin, rosin, implemented with fumaric acid, maleic acid or maleic anhydride, Tall oil pitch or tall oil pitch, reacted with maleic acid anhydride, talc fatty acids, soy fatty acids and the like. These mixtures can also be partially Maleinization of tall oil or other fatty acids  receive. Mixtures of C₂₁-cyclohexenebicarboxylic acid and C₂₂-tricarboxylic anhydride can be obtained that first linoleic acid is reacted with acrylic acid, whereupon the remaining oleic acid and elaidic acid Maleic anhydride is implemented. Kraftlingnin or Vinsol can also be implemented together.

Dimer acids, which are long-chain C₃₆- aliphatic carboxylic acids is obtained by Dimerization of fatty acids of various origins, can also be implemented together. An example from this type of acid is commercially available under the Trade name "Empol® Dimer Acids", manufacturer: Emery Industries, Inc.

Depending on the number of active nitrogen atoms in them Derivatives containing nitrogen can be one, two or several moles of reagent per mole of amidoamine or imidazoline be implemented. To the new modifications of the above described amidoamines, imidoamines and imidazolines illustrate, the reaction products of two serve Moles of aminoethylpiperazine or diethylenetriamine with one Mol C₂₂-tricarboxylic anhydride as intermediates.

In the case of imidoamine-amidoamines (XIII, XIV)

can add one or two moles of reagent to the terminal NH- Groups are bound.

In the case of imidoamine imidazolines (VIII, XV)

one to five reagents react with the terminal NH₂ groups and the NH group.

The following structures can be obtained through implementation With:

• a) formaldehyde and sodium sulfite or bisulfite ⁻NH + CH₂O + NaHSO₃ → ⁻NCH₂SO₃Na
• b) sodium salts of haloalkanesulfonic acids ⁻NH + X (CH₂) _n SO₃Na → ⁻N (CH₂) _n SO₃NaX = Cl, Br, I
  n = 1, 2, 3, 4,. . .
• c) γ-propane sultone
• d) sodium salt of chlorohydroxypropanesulfonic acid
• e) Haloalkanoic acids (or sodium salts) ⁻NH + X (CH₂) _n COOH → ⁻N (CH₂) _n COOHX = Cl, Br, I
  n = 1, 2, 3, 4
• f) α, β-unsaturated carboxylic acids or dicarboxylic acids:
• g) Haloalkanephosphonic acids ⁻NH + X (CH₂) _n PO₃H₂ → ⁻N (CH₂) _n PO₃H₂
• h) formaldehyde and phosphoric acid in the presence of chlorine hydrochloric acids ⁻NH + CH₂O + H₃PO₃ → ⁻NCH₂PO₃H₂

The sulfomethylation of fatty monocarboxylic acid -polyamine- Condensation products with formaldehyde and bisulfite known from CH-PS 571 474. These products become Improvement of plastic materials, leather or Paper used. The patent also states by modifying these sulfonated products Post-alkylation with alkyl halides, chloroacetic acid, Acrylamide, acrylonitrile, ethylene oxide or propylene oxide and sulfomethylated quaternary nitrogen compounds described. These compounds have antistatic, bactericidal and dust-repellent properties. Out  Japanese publications Kokai 7765141 and 7758708 is the production of hydrolyzed reaction products of a lauric acid aminoethyl ethanol amine condensate Ethyl acrylate known as corrosion inhibitors or used in cleaning agents. From the japani The patent publication 77108915 is also the manufacturer treatment of carboxyethylated derivatives of condensation product of oleic acid and diethylenetriamine, which as stabilizers for ethylene oxide-propylene oxide copolymers are suitable.

In GB-PS 1 037 645 are also quaternary stick described compounds that can be obtained by reacting the condensation products of oleic acid with Aminoethylethanolamine or lauric acid with N, N-dimethyl propanediamine with sodium chlorohydroxypropanesulfonate. Reaction products of fatty acid polyamine condensates with Sodium chloroacetate used as an additive for heavy oils are also used in Japanese Patent publication Kokai 7342004. From the DE OS 25 37 289 is also the condensation of fatty acids with the reaction products of polyamines, implemented with Sodium hydroxyethanesulfonate known, products with surface-active properties can be obtained.

A preferred embodiment of the invention, which in The following is described in more detail, relates to emulsifiers, for the production of asphalt-in-water emulsion are suitable, which in turn are particularly suitable for Mix under shear with a variety of silicon or silicic acid containing as well calcareous or calcareous aggregates. After this The asphalt films show setting (evaporation of water) excellent adhesion to the surface of the Aggregates.  

In the production of the bituminous emulsions Invention is an aqueous soap solution from Emulga goals, which is described below, intimately under severe shear stress in a colloid mill mixes. The bitumen content can range from 30 to about 80% by weight, preferably between 60 and 70%. The dosage of the emulsifier can be 0.1 to 10 wt .-% of the emulsion, preferably between 0.25 to 2.5% by weight of the emulsion lie. Depending on the emulsifier used, a cationic emulsion of a degree of mixing in a pH Range from 1-7 obtained with optimal behavior at a pH of about 2.4 to 4. On the other hand a mixed degree type anionic emulsion in a pH Range from greater than 7 to 12 with the optimal Behavior at a pH of around 10 to 11.5 ten.

Use the to produce emulsions according to the invention dete "bitumen" can be from domestic or foreign crude oil come; this also includes bitumen, natural asphalt, Petroleum, oil residues of the degree of pavement or covering (paving grade), plastic residues from the coal tar style lation, petroleum tar and asphalt cements with solutions are diluted by a medium (so-called "cutback asphalt"). With help the emulsifiers used according to the invention can be practically all common asphalt cements for everyone usual degrees of viscosity or penetration for the Use of coverings and paving such as they are specified in ASTM D-3381 and D-946 are.

The acidic soap solutions are usually obtained by suspending the amidoamine in water, including a sufficient amount of a suitable acid, e.g. B. Chlorwas seric acid, sulfuric acid, phosphoric acid or the like. is added to the desired pH of 1-7 achieve, whereby a clear emulsifier solution is obtained. Alkaline soaps are made by adding sodium hydroxide  or another suitable base for aqueous suspension sion of the emulsifier obtained. Then the (acid or alkaline) soap solution, which is at approx. 55 ° C is heated and the liquid asphalt that to 120 to Is preheated to 125 ° C under high shear stress in a colloid mill for 30 seconds mixed, with asphalt emulsions of a brown color tones and a creamy consistency can be obtained. In front Carrying out the test procedure according to ASTM D-244 the emulsions are stored at 70 ° C for 16 hours. Aggregate admixture tests can be carried out leads that a weighed amount of the aggregate fes is placed in a mixing vessel, whereupon 5 to 10 % By weight of the emulsion applied to the aggregate and mix for one to five minutes. The Mix is then divided into three equal parts, the put in three bowls. The first sample will be set aside; the second sample is taken immediately after after mixing with water and the third sample comes with after a retention period of one hour Washed water. The percentage coating of the The aggregate surface is determined visually. From the first sample, the percentage initial Coating, percentage of the second sample initial washed coating and from the third Check the percentage of washed off coating one hour. The requirements of construction industry are generally at a minimum of 90 to 95% set.

A typical aqueous bituminous emulsion aggregate fabric slurry is determined in the laboratory under Use a lot of water dampened Aggregates with a suitable bituminous Mix the emulsion to the desired consistency. A suitable consistency is obtained through application different grades of aggregates under Generating a smooth, non-parting same  shaped mixture of aqueous bituminous emulsion and Aggregates that are even on an existing one Surface can be applied. The final Toughness of the applied slurry is obtained if the bitumen, e.g. B. asphalt, on the supplement separates particles of material and the newly applied Coating on the existing surface binds in Form of a mixture of asphalt cement and aggregate fabrics.

Can be used to create paving and road surfaces used a mobile, self-powered unit that allows the aggregate, water and inorganic and organic emulsion additives the same to be measured moderately. A typical unit is included equipped with a separate container for surcharge substances, water, emulsion and additives that are continuous in a mixing chamber in a predetermined ratio can be introduced. The continuously in the Components introduced into the mixing chamber are in the Mixing chamber retained for about 1 minute and then in a so-called. expansion vessel is fed in and then towards the coated surface applied. Batchwise Working pneumatic devices can also for the appropriate application of the bituminous aggregate fabric slurries used according to the invention become.

The emulsifiers for the solvent-free emulsions the invention can be satisfactorily use without auxiliary emulsifiers. Occasionally it can however, be necessary or appropriate, the Eigen to change the emulsion somewhat in order to improved viscosity for a given asphalt content or improved stability to dust and fines of the aggregates, and to to prolong or increase the setting or sitting time shorten. One of two methods can be used.  

In the case of a cationic slurry seal Liquid mass can either be a mixture of tall oil fat acids, preferably tall oil pitch to the bitumen (asphalt) added before emulsification to break up to improve or to increase the viscosity of the emulsion improve or mixtures of the above described benen imidoamine-amidoamines, imidoamine-imidazolines or their derivatives with compatible cationic or not ionogenic emulsifiers for emulsifying bitumen be used. Auxiliary emulsifiers or additionally used emulsifiers that make up 90% of the total combined emulsifier approach can be Fettamines, Fettpropandiamine, Fettamidoamine and Fettimi dazoline. This class of compounds diminishes in general the setting time. Other suitable auxiliary emul gators are monoquaternary fatty ammonium salts and diquaternary diammonium fatty salts (fatty monoquaternary ammonium salts and fatty diquaternary diammonium salts) and non-ionic emulsifiers, e.g. B. ethylene glycol poly ether of nonyl or dodecylphenol.

Modified emulsifier combinations can also be used get when blends of fatty amines, fatty diamines and amidoamines or imidazolines derived from C₁₉-, C₂₁-dicarboxylic acids, sulfonated oleic acid, sul formulated tall oil fatty acids, tall oil fatty acids and resin acids, the chemical process according to the invention Modifications are subjected. Amidoamines or Imidazolines of C₃₆ dicarboxylic acids (dimerized linole acid, etc.) can also be added to the mixtures become.

In the case of anionic emulsions, mixtures of the amphoteric compounds (type VI, IX or from modifi graced Type VII, XIII, XIV, XV derivatives) with emulsifiers, which are usually used for the production of anionic bituminous emulsions are used. Examples of such emulsifiers are fatty acids,  especially tall oil fatty acids, resin acids, lignin, the isolated from sulfite or kraft pulp lignins and sulfonic acid-containing surfactants Fabrics, e.g. B. aralkyl sulfonates, long chain alkyl sulfonates and petroleum sulfonates.

With the amphoteric compounds before adding Alkali also C₁₉-dicarboxylic acid, C₂₁-dicarboxylic acid, C₂₂- Tricarboxylic acid or sulfonated fatty acids mixed become.

Depending on the type of aggregate and its purity the mixing can be improved if the surcharge substance with 1 to 5 wt .-% water, based on the zu impact material that is pre-moistened. The behavior of the Asphalt emulsion with regard to the mixing characteristics and in terms of setting (higher percentage the 1 hour wash-off layer) can, if required Lich, also improve if, based on the weight of the Asphalt, 1 to 15% of a solvent, e.g. B. Diesel oil added to the asphalt before emulsification become. The using the ones described here Emulsifiers produced are stable and can be used over a longer period of time Save usage. Depending on the spac The emulsion can be used with the surcharge material are mixed in a central mixing plant, e.g. B. in a large pan mill, whereupon the obtained Mix can be transported to the place of use. Alternatively, the emulsion can also be sent to the processing site brought and mixed here, either in one Mixing device, e.g. B. a motorized mixing plant or manually.

The additives used to manufacture the invention suitable base mixtures can be used Seal common, difficult to coat additives Type, for example sand, pit sand, (pit-run) crushing  werk-Sand (crusher-run) and the like with a particle size in the range of particles that pass through a No. 4 sieve to particles of which at least 80% are on a 200- Mesh according to U.S. - Standard series held back become.

Aggregate mixed tests can be carried out Mixing the aggregate with water and one aqueous bituminous emulsion. An inorganic mineral filler, such as Portland cement, hydrated lime, limestone dust and Fly ash can be used to / Accelerate opening time and salts, e.g. B. ammonium sulfate, aluminum sulfate and other inorganic sulfates or surfactants can be added to the setting time of the slurry system delay. Mineral fillers are said to ASTM D-242 requirements meet. These substances are mixed in a blender until homogeneous Slurry mixture is obtained. The inability to a stable slurry within a mixing time of Generate 3 to 4 minutes if appropriate proportions of each ingredient would be used show that there is a mixture in which the use materials are not compatible. This Mix pattern is required to build conditions simulate. After the slurry is made, it becomes in a form that is placed on an asphalt felt (asphalt felt) is placed, whereupon the setting / opening time is measured by wiping the exposed porridge shaped surface with a paper towel. If no brown stains have been transferred to the paper towel are the slurry or slurry as "abge tied ". The curing time can also with a Cohesion test device can be determined. Furthermore can do many other tests, such as in the ASTM regulation D3910 described, can be used to about strength and other physical properties  of the slurry or slurry. The Guidelines "Performance Guide for Slurry Seal", published published by Asphalt Emulsion Manufacturers Associa tion, USA, can be used to control the property and the behavior of the slurry-shaped sealing or sealants to determine.

The emulsion should be stable during mixing and should be within the specified period of time after following their application. The invention The emulsifiers used have a very satisfactory effect without the use of auxiliary emulsifiers.

The setting times can be determined, for example, by the Concentration of emulsifier, the addition of lime, cement or another inorganic additive that the Change the opening characteristics of the pulpy system would control. An organic additive polymer latex can continue to be used to make the matrix reinforce. The organic additive is preferably the Emulsion additive porridge added.

The bituminous emulsions used in the invention Porridges (slurries) used are porridges from Mixed degree type. The setting time can be adjusted by adding Increase aluminum sulfate or by adding lime or Shorten cement quickly with the formation of an emulsion setting properties. The addition of small amounts of aluminum sulfate improves the mixing behavior. The The following examples are intended to illustrate the practice of the invention illustrate. The production is described different types of used according to the invention Emulsifiers. The advantages result from the examples the use of these compounds in a bituminous Medium-setting emulsion of mixed degree type. Of further the application of mushy seals or covering masses described.

example 1

This example illustrates the variety of emulga gates that can be obtained by modifying Reaction products of C₂₂-tricarboxylic anhydrides with Polyamines.

Manufacture of maleic anhydride adducts

50 to 100 were added to 280 parts of oleic or tall oil fatty acids Parts of maleic anhydride are added, after which the entire 3rd was heated to 180 to 220 ° C for 8 hours. in the For iodine-catalyzed reactions, 0.6 Parts of iodine added at ambient temperature. The Reak tions were carried out by gas chromatography and through Infrared spectroscopy followed. Unless otherwise is indicated, the crude reaction products for further condensation with the polyamines used.

Amphoteric substances (made from I-IV or their Mixtures)

100 parts of anhydride were mixed with 100 parts of a polyethylene enamines, for example ethylenediamine, propylenediamine, Diethylenetriamine and the like are mixed, whereupon the mixture was heated to 80 to 100 ° C with stirring until one 1% aqueous solution of the products obtained in dilute was soluble in acid and dilute alkali.

Imidoamine-amidoamines or polyamidoamines (made from I-IV or their mixtures)

100 parts of anhydride were mixed with 100 parts of diethylene triamine or a mixture of polyethylene amines from diethyl entriamine, triethylenetetramine, aminoethylpiperazine and Aminoethylethanol mixed, whereupon the mixture to 180 were heated up to 220 ° C. After all the distillate  was collected, it was cooled and with isopropanol diluted to the reaction products in liquid form hold.

Imidoamino-imidazolines, amidoamino-imidazolines (made from I to IV or their mixtures)

100 parts of anhydride were mixed with 100 parts of diethylene triamine mixed, whereupon the mixture was heated to 260 ° C. until all the condensation water and superfluous amine were caught. After cooling, the reaction product diluted with isopropanol.

Mixed C₂₁-dicarboxylic acid-C ₂₂-tricarboxylic acid anhydride- Polyamine reaction products

For Diacid 1525®, consisting of Diacid 1550® and one Mixture of oleic and elaidic acid became 1 mol malein acid anhydride per mole of unsaturated C₁₈ acid added. The mixture was heated to 180-220 ° C for 6 hours and then cooled. To 1 mole of the reaction product obtained At least 2 moles of the polyamine blend were used added, followed by heating to 240 ° C until all Water of reaction had been collected. Possibly can be diluted with isopropanol.

Mixed monoamidoamine-C₂₂-tricarboxylic acid Imidoamino amidoamines (or polyamidoamines)

These products can be obtained by heating unmodified fatty acids and fatty acid-maleic acid anhydride adducts with polyamines.

To 1 mole of the mixture was 1.5-2 moles of the polyamine S was added, followed by heating to 180-220 ° C until all water of reaction and excess amine had been caught.  

Manufacture of derivatives 1. Sulfomethylation

Based on the molecular weight and the number of active N-H bonds, were 0.1 to 1 mole of sodium sulfite or sodium bisulfite per active NH group in one adequate amount of water dissolved, whereupon the solutions the Polyamine condensates were added. The reaction is slightly exothermic. 1 up to 4 moles of formaldehyde in the form of paraformaldehyde or added as a 37% solution in water. The encore will accompanied by an exothermic reaction. Alternatively, you can Formaldehyde are added to the sulfite solution and that Reaction product made from the reagents used is generated, the nitrogen-containing verbin be added. By adding isopropanol and Leave water in a suitable ratio to the end product get clear solutions.

2. Carboxyalkylation

0.1 to 1 mole were reactive per active NH group Carboxylic acids, e.g. B. chloroacetic acid or correspond de Sodium salt or acrylic acid dissolved or in isopropanol or slurried water, and to 1 mole of the polyamine Condensation product added. The additions were made by accompanied by an increase in temperature. To complete The reaction was to ensure alkylations mixtures kept at 60 to 70 ° C for 1 to 2 hours.

Experiments with paste-like sealing compounds

Table I below shows the setting times of pasty emulsion aggregate masses specified, in Depending on the amount of C₂₂ tricarboxylic acid anhydride polyamine condensate in the emulsifier mixture. A high salary does not require opening  retarders such as B. aluminum sulfate; a little Receiving requires a delay to get mixing times from to achieve at least 1 minute. The emulsions were with Exxon asphalt (penetration 50/70) at one 64% residue produced. Camak aggregate (Granite, Georgia, USA) was used for the experiments.  

Table I

Setting times of cationic porridges

Tables II and III illustrate the setting times of cationic and anionic porridges made using Emulsions containing amphoteric emulsifiers were.  

Table II

Setting times of cationic slurries ^a)

Table III

Setting times of anionic slurries ^a)

Although the invention with reference to various special materials, processes and examples are described it is not limited to this. Rather, as is obvious to a person skilled in the art Variations in the details given are made.

Claims (20)

1. Bituminous emulsion, characterized by
contains about 30 to about 80% by weight of bitumen,
about 0.1 to about 10% by weight of an emulsifier consisting of the reaction product of polyamines with a polycarboxylic anhydride of the following formulas: and the balance (100% by weight) water, with a pH of 2 to 7. 2. Bituminous emulsion according to claim 1, characterized, that they also have one or more auxiliary emulsifiers, which up to 90% of the total emulsifier set can make up contains, this or this Auxiliary emulsifiers consist of: fatty amines, fat pro pandiamines, fatty amidamines, fatty imidazolines, monoquaternary fatty ammonium salts, diquaternary Fat diammonium salts and / or ethylene glycol polyethers of nonyl or dodecylphenol.   3. Bituminous emulsion according to claim 1, characterized, that they also have one or more auxiliary emulsifiers, which up to 90% of the total emulsifier batch can make up contains, this or this Auxiliary emulsifiers consist of nitrogen derivatives of resin (rosin) acids and / or nitrogen derivatives of Kraft lignin. 4. bituminous emulsion according to claim 1, characterized, that it contains an emulsifier approach that by Reaction of a polyamine with a mixture of the Polycarboxylic anhydride according to claim 1 and Fettcar bonic acids from the group of fatty mono-, fatty di- and Fatty tricarboxylic acids or mixtures thereof has been put. 5. bituminous emulsion according to claim 1, characterized, that it contains an emulsifier approach that by Reaction of a polyamine with a mixture of resin (Rosin) acids and the polycarboxylic anhydride has been manufactured. 6. bituminous emulsion according to claim 1, characterized, that it contains an emulsifier approach, the herge is by reacting a polyamine with a Mixture of Kraft lignin and the polycarboxylic acid anhydride. 7. Bituminous emulsion according to claims 1, 2, 3, 4, 5 or 6, marked by a content of about 60 to 70 wt .-% bitumen, about 0.2 to 2.0% by weight of emulsifier and water per 100 % By weight.   8. bituminous emulsion according to claim 1, characterized, that they have 1 to 15 vol .-% of a hydrocarbon oil contains. 9. bituminous emulsion according to claim 1, characterized that the bitumen has a mixture of Tall oil fatty acids is added. 10. bituminous emulsion according to claim 9, characterized, that the mixture of tall oil fatty acids from tall oil pitch consists.   11. Use of the aqueous bituminous emulsion according to one or more of claims 1 to 10 for the production in a slurry-like coating composition, which is characterized by a content of: a compact mineral aggregate, the particles of which pass through a mesh screen No. 4 and of which at least 80 % retained by a 200 mesh screen; about 8 to 20% of an oil-in-water emulsion, based on the weight of the mineral additive, the emulsion consisting of: about 55 to about 65% bitumen, based on the weight of the emulsion, about 0.5 to about 2% of a cation-active emulsifier, based on the weight of the emulsion, the emulsifier consisting of the reaction product of one or more polyamines and a polycarboxylic anhydride of the following formulas: and water to 100% by weight of the emulsion; from about 4 to about 16% water based on the weight of the mineral aggregates added to the emulsion to form a slurry from the aggregates; and up to 3% of an inorganic or organic additive to reduce the setting time of the mixture. 12. Aqueous bituminous emulsion for use in a slurry shaped covering compound according to claim 11, characterized, that they have one or more auxiliary emulsifiers that are up to Can make up 90% of the total emulsifier batch holds, this or these auxiliary emulsifiers exist from: fatty amines, fatty propane diamines, fatty amidoamines, fat imidazolines, monoquaternary fatty ammonium salts, diquater fat diammonium salts and / or ethylene glycol polyethers of nonyl or dodecylphenol. 13. Aqueous bituminous emulsion for use in a slurry shaped covering compound according to claim 11, characterized, that they have one or more auxiliary emulsifiers that are up to Can make up 90% of the total emulsifier batch holds, this or these auxiliary emulsifiers exist from: nitrogen derivatives of resin (rosin) acids and / or nitrogen derivatives of kraft lignin. 14. Aqueous bituminous emulsion for use in a slurry shaped covering compound according to claim 11, characterized, that it contains an emulsifier additive that by reaction a polyamine with a mixture of the polycarboxylic acid anhydride according to claim 1 and fatty carboxylic acids from the Group of fatty mono-, fatty di- and fatty tricarboxylic acids or Mixtures thereof have been made.   15. Aqueous bituminous emulsion for use in a slurry shaped covering compound according to claim 11, characterized, that it contains an emulsifier additive that by reaction a polyamine with a mixture of resin (rosin) acids and the polycarboxylic anhydride is. 16. Aqueous bituminous emulsion for use in a slurry shaped covering compound according to claim 11, characterized, that it contains an emulsifier batch that is made by reacting a polyamine with a mixture Kraft lignin and the polycarboxylic anhydride. 17. Aqueous bituminous emulsion for use in a slurry shaped lining mass according to claim 11, marked by about 55 to 65% bitumen, based on the weight of the Emulsion, about 0.2 to 2.0% emulsifier, based on the Weight of the emulsion and water to 100 wt .-%. 18. Aqueous emulsion for use in a slurry shaped covering compound according to claim 11, marked by Contains a mixture of tall oil fatty acids, the have been added to the bitumen before emulsification. 19. Aqueous bituminous emulsion for use in a slurry shaped covering compound according to claim 18, characterized, that they ent as tall oil pitch as a mixture of tall oil fatty acids holds. 20. Aqueous bituminous emulsion for use in a slurry  shaped covering compound according to claim 11, characterized, that it is an inorganic additive Portland cement, hydrati lime, limestone dust, fly ash, ammonium sulfate and / or contains aluminum sulfate.