MXPA98007088A

MXPA98007088A - Liquid amine composition for be emulsifiers

Info

Publication number: MXPA98007088A
Application number: MXPA/A/1998/007088A
Authority: MX
Inventors: Asamori Katsuhiko; Tamaki Ryoichi; Taniguchi Takao; Nagao Shigeru; Tomioka Keiichiro; Koyanagi Kouji
Original assignee: Kao Corp
Priority date: 1997-09-01
Filing date: 1998-08-31
Publication date: 1999-12-10

Abstract

The present invention provides a liquid amine composition for an emulsifier or emulsifier for bitumen which can impart, to a bitumen emulsion, more excellent emulsifier stability and adhesive properties to aggregates than conventional products. The liquid amine composition for the bitumen emulsifier of the present invention comprises (1) from 5 to 70% by weight of a monoamine having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms, (2) from 20 to 80% by weight. weight of a polyamine having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms and (3) of 10 to 75% by weight of organic acid of 4 to 18 carbon atoms

Description

i.

LIQUID COMPOSITION OF AMINE FOR EMULSIFIERS OF BITUMEN BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to an amine composition for emulsifier or emulsifier for bitumen that can be easily handled and that is liquid at ordinary room temperature. More specifically, the present invention relates to a liquid amine composition that is a precursor of an emulsifier for emulsifying bituminous materials such as asphalt and which is excellent in the handling properties and which can impart, to a finally emulsified bituminous material, a more excellent emulsifying stability and adhesive properties to aggregates than conventional products. 20 Previous Technique The amine compounds each having a hydrocarbon group of at least 8 carbon atoms carbon have been widely used in several REF .: 28197 industrial applications, because the active cationic agents on the surface derived from the amine compounds, can exert excellent properties. For example, these amine compounds are useful as aqueous emulsifying agents for bituminous materials, i.e. viscous solids such as oils called petroleum asphalts, bitumens and the like, in road fragment material applications, waterproof material for a sea pier , and a material for the roof. Furthermore, it is also known that these amine compounds are useful as a flotation separation agent for minerals, as an antistatic agent for polymers, fibers and the like, as a corrosion inhibitor for metals, and as an anticoagulant for fertilizers. In order to exert the excellent properties of the amine compounds in these applications, high absorbent properties are required of an object, and thus, the amine compounds each having a long chain hydrocarbyl group have been used in a manner preferential. However, most of these amine compounds are solid at room temperature, and thus, are inconvenient to handle them. Therefore, for the liquefaction of these amine compounds, several investigations have been carried out to date. This handling problem is particularly noticeable in the winter and in different cold. For example, in US-A-4496474 and US-A-5098604, for the purpose of lowering the melting point, it has been described to use alkyl ether amine, branched alkyl amine, or an oxyalkylated amine having a poor property of crystallization. In this case, however, there is a disadvantage that the cationic activity of the surface is deteriorated, and even if the amount of the amine is increased, the excellent characteristics that the solid amine has can not be exerted on the occasion. Additionally, in JP-A-59-123523, a liquid amine composition containing an aliphatic amine and a specific carboxylic acid has been described. This liquid amine composition is liquid even at a low temperature, and in the case that the liquid amine composition is used as an active cationic agent on the surface, an amine hydrochloride is formed by adding a strong acid such as a hydrochloric acid. , so that it is possible to obtain almost the same performance as the original solid amine. It is not known in the state of the art what relationship took place between an amine composition, the stability of the emulsion and the bituminous materials and the performance of the adhesion of bituminous materials. With the enlargement of the weight of the trolleys and the speed of the trolleys in recent years, high adhesive properties to aggregates have been strongly demanded. This is the reason why hard asphalts that have little penetration have been widely used. However, these conventional products do not always meet the required performance.

BRIEF DESCRIPTION OF THE INVENTION Under these circumstances, the present invention has been developed to further improve emulsifying stability and handling properties, and in this manner, an object of the present invention is to provide an amine composition which is liquid at ordinary temperature and which allows the formation of an emulsion which has a high performance. The present inventors have intensively investigated a relationship between an amine composition and the emulsifying stability of bituminous materials and a relationship between the amine composition and the adhesive properties of the bituminous materials after the decomposition of an emulsion for the purpose of elucidating the optimum amine composition. As a result, liquid amine compositions have been found for an emulsifier for bituminous materials that can split this high emulsifying stability and these adhesive properties to the aggregates as has not been reported to date. Additionally, among these new liquid amine compositions, a composition having a low viscosity and therefore more excellent handling properties has been found. That is, an object of the present invention is to provide a liquid amine composition for an emulsifier for bituminous materials comprising (1) from 5 to 70% by weight of a monoamine having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms , (2) from 20 to 80% by weight of a polyamine having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms and (3) of from 1.0 to 75% by weight of organic acid of 4 to 18 carbon atoms .

DETAILED DESCRIPTION OF THE INVENTION A monoamine (1) having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms that can be used in the present invention is an aliphatic amine compound represented by the formula R? R2R3N wherein Ri is a straight chain hydrocarbyl group 8 to 22 carbon atoms, R2 and R3 are each a hydrogen atom or a straight chain hydrocarbyl group having from 8 to 22 carbon atoms. Typical examples of the monoamine include alkylamines such as decylamine, lauryl ina, myristyl ina, cetylamine, stearylamine behenylamine, seboa ina and hydrogenated seboamine. A polyamine (2) having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms which can be used in the present invention is an aliphatic amine represented by the formula R? R2N (ANH) FH wherein Ri, R2 and 3 are as they are defined above, A is an ethylene group or a propylene group, and P is a value from 1 to 4. Typical examples of the polyamine include diamines obtained by reacting the monoamine (1) mentioned above with acrylonitrile and then hydrogenating the product of reaction and examples of these diamines include N-aminopropylalkylamines such as N-aminopropylcylamine, N-aminopropylarnurylamine, N-aminopropylmyristylamine, N-aminopropylcetylamine, N-aminopropylstearylamine, N-aminopropylbehenylamine, N-aminopropyl-tallowamine and hydrogenated N-aminopropyl-tallowamine . In addition, additional examples of the polyamine include triamines and tetramines obtained by repeating the same process. Examples of the triamines include N-alkyldipropylenetriamines such as N-decyldipropylenetriamine, N-lauryldipropylenetriamine, N-myristyldipropylenetriamine, N-cetyldipropylenetriamine, N-stearyldipropylenetriamine, N-behenyldipropylenetriamine, N-sebodipropylenetriamine; Y Hydrogenated N-sebodipropylenetriamine, examples of the tetramines include N-alkyltripropylenetetramine such as N-decyltripropylenetetramine, N-lauryltripropylenetetramine, N-iristyltripropylentetrantran, N-cetyltripropylenetetramine, N-stearyltripropylenetetramine, N-behenyltripropylenetetramine, N-sebotripropylentetran and hydrogenated N-sebotripropylenetetramine. . In addition, examples of the tetramines include diamines and triamines obtained by the reaction of a halogenated hydrocarbon with each of the ethylenediamine and diethylene diamine. In the present invention, the liquid amine composition may contain an alkylene oxide adduct such as an ethylene oxide adduct or a propylene oxide adduct of the aforementioned monoamine or polyamine having the aliphatic hydrocarbyl group of 8 to 22 carbon atoms in an amount of 10 to 300 parts by weight, preferably 40 to 150 parts by weight based on 100 parts by weight of the total of the monoamine (1) and the polyamine (2). From both viewpoints of an improvement in liquid property and an emulsifying performance, the above interval is preferable. When used together, the mixed amount of the organic acid having 4 to 18 carbon atoms that is required to obtain the liquid amine composition can be reduced. That is, the simultaneous use of the alkylene oxide adduct can improve the liquid properties. Of the aforementioned monoamines and polyamines, it is a preferable embodiment that the aliphatic hydrocarbyl group having 8 to 22 carbon atoms is derived from the tallow or hydrogenated tallow. Examples of an organic acid (3) having 4 to 18 carbon atoms that can be used in the present invention include carboxylic acids having 4 to 18 carbon atoms, phosphoric acid esters having 4 to 18 carbon atoms. of carbon, and sulfuric acid compounds having from 4 to 18 carbon atoms. Examples of the carboxylic acids having 4 to 18 carbon atoms include aliphatic carboxylic acids and naphthenic carboxylic acids, and examples of the aliphatic carboxylic acids include straight chain saturated fatty acids such as butyric acid, valeric acid, capric acid, hetanoic acid, caprylic acid and capric acid, saturated, branched fatty acids, such as isobutyric acid, 2-methylbutyric acid, 3-methylbutyric acid, 2-methylvaleric acid, 3-methylvaleric acid, 4- fatty acid methylvaleric acid, 2-ethylhexanoic acid, isononaenoic acid, isodecanoic acid, isotriadecanoic acid, isotetradecanoic acid, palmitic acid and isostearic acid, and unsaturated fatty acids such as decanoic acid, undeceneic acid, dodecenic acid, myristoleic acid, paclylitolic acid, oleic acid, acid linoleic, and linolenic acid. The tertiary carboxylic acids obtained by the Koch reaction of olefins and carbon monoxide can also be used. As the naphthenic carboxylic acids, the naphthenic acids obtained from a crude oil can be used by the alkaline extraction. Above all, aliphatic, branched carboxylic acids having from 4 to 10 carbon atoms can be used preferentially. In addition, examples of the acid esters of phosphoric acid having from 4 to 18 carbon atoms include butyl phosphate, pentyl phosphate, hexyl phosphate, octyl phosphate, 2-ethylhexyl phosphate, nonyl phosphate, decyl phosphate. , undecyl phosphate, dodecyl phosphate and isotridecyl phosphate. Examples of the sulfuric acid compounds having 4 to 18 carbon atoms include sulfonic acid compounds of the sulfonic compounds of α-olefins having 4 to 18 carbon atoms, sulfonic compounds of alkylbenzenes having a hydrocarbyl group of 4 to 12 carbon atoms and sulfonic compounds of alkylphenols having a hydrocarbyl group of 4 to 12 carbon atoms, and the acid esters of sulfuric acid of alcohols having from 4 to 18 carbon atoms. According to the present invention, the content of the monoamine (1) having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms is in the range of 5 to 70% by weight, the content of the polyamine (2) having the aliphatic hydrocarbon group of 8 to 22 carbon atoms is in the range of 20 to 80% by weight, the content of organic acid (3) of 4 to 18 carbon atoms is in the range of 10 to 75% by weight. More preferably, the content of component (1) is in the range of 10 to 40% by weight, the content of component (2) is in the range of 15 to 50% by weight, component (3) is in the range of 20 to 50% by weight. These amounts are suitably adjustable according to the classes of the monoamine and polyamine to be used, but from the point of view of obtaining excellent adhesive properties to aggregates and emulsifying stability, the weight ratio of the monoamine content ( 1) to the polyamine (2) is preferably in the range of 5/95 to 30/70, preferably 5/95 to 50/50. In accordance with the present invention, the liquid amine composition may contain water (4) in an amount such that the system is not separated. In the case that the water is contained, the viscosity of the liquid amine composition decreases, whereby the properties and handling can be further improved. The amount of water is such that the viscosity of the composition becomes preferably 4000 Pa.s or less, preferably 2000 mPa.s or less. This effect of viscosity decrease depends on the kind of amine in the raw material and the fatty acid in the raw material to be used, and particularly in the case where the branched fatty acid is used, for example, an aliphatic carboxylic acid branched having 4 to 10 carbon atoms, the effect of decreasing viscosity is greater. In the case of fatty acid, straight chain, a liquid crystal is formed depending on the composition, so that a highly dimensional structure is formed and thus the effect of viscosity reduction can not be obtained sufficiently on occasion. . When water is added in an excessive amount, turbidity occurs on the occasion, and during a long-term period, a precipitate is sometimes formed. The ease of this precipitate formation is affected by the kind of amine in raw material to be used as well as the kind and amount of the acid. Therefore, the amount of water to be used is required to be adjusted so that the system is not separated by the formation of the precipitate. More completely, water can be added in an amount of 2 to 50 parts by weight based on 100 parts by weight of the total amount of monoamine (1), polyamine (2) and organic acid (3) . Even a small amount of water can be exerted to the effect of viscosity reduction, but if the amount of water is smaller than 2 parts by weight, the effect is insufficient, and even if the amount of water is more than 50 parts by weight , the effect of the reduction and viscosity can be poorly improved and the precipitate is formed, so that the system inconveniently tends to separate. According to the present invention, the liquid amine composition may additionally contain at least one of the monovalent or polyvalent alcohols (5) in an amount of 2 to 50 parts based on 100 parts by weight of the total monoamine ( 1), the polyamine (2) and the organic acid (3). The alcohol also contributes to the decrease in the viscosity of the liquid amine composition, and examples of the alcohol include monovalent alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, raetylpentanol, octanol, 2-ethylhexanol, isodecyl alcohol, isotridecyl alcohol and oleyl alcohol, and polyvalent alcohols such as ethylene glycol, propylene glycol, glycerin, polyglycerin, diethylene glycol, polyethylene glycol, and polypropylene glycol. Incidentally, in water or alcohol that can be mixed with the liquid amine composition, a water-soluble first or phenol compound can be dissolved. According to the present invention, the liquid amine composition further contains at least one acid (6) selected from the group consisting of mineral acids, acetic acid and propionic acid in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the total monoamine (1), polyamine (2) and organic acid (3). Examples of the mineral acids include hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and may be used in a combination of two or more thereof. When this acid is added to the liquid amine composition to which water has been added to lower the viscosity and improve the handling properties, the problems of the occurrence of turbidity and formation of precipitate during long-term storage are minimized. In this case, if the amount of the acid is less than 0.05 parts by weight, the turbidity improving effect is insufficient, if there is more than 10 parts by weight, the viscosity of the liquid amine composition inconveniently tends to increase again. Preferably, the amount of the acid (6) is in the range of 0.5 to 5 parts by weight. No particular restriction is placed on the method to obtain a bituminous emulsion of an asphalt or the like using the liquid amine composition of the present invention as the emulsifier or emulsifier for bituminous materials. However, an example comprises preparing an aqueous solution of the liquid amine composition of the present invention having a pH of about 1 to 5 with a monobasic acid, raising the temperature of the solution from about 30 to 50 ° C, mixing it with a molten asphalt heated to 120-180 ° C and then, if necessary, stir and cut the mixture to form an emulsion. The amount of the liquid amine composition of the present invention is in the range of 0.5 to 10% by weight, preferably 0.1 to 3% by weight based on the emulsified asphalt, and the amount of a bituminous amount such as Asphalt is in the range of 50 to 80% by weight, more generally 60 to 75% by weight in emulsion. Examples of the useful monobasic acid include hydrochloric acid, nitric acid, formic acid, acetic acid and monochloroacetic acid, and their amount is more than one neutral equivalent of the liquid amine composition to be used, and more generally, is in the range of approximately 1.2 to 1.8 times as much as the neutral equivalent.

Eg emplos Next, the present invention will be described with reference to the examples, but the scope of the present invention should not be "limited to these examples throughout.

Preparation of asphalt emulsion and performance evaluation The amine compositions shown in Tables 1 to 4 the aqueous solutions were changed in the form of an amine hydrochloride. The amount of hydrochloric acid was adjusted so that the pH of the aqueous solution can be 2. 415 g of this aqueous solution was heated to 45 ° C, and passed through a harrel-type homogenizer together with 600 g of a straight asphalt having a penetration of 80 to 100, which has been heated to 145 ° C until melting. The asphalt emulsion was obtained. In this case, the amount of the amine hydrochloride to be added is adjusted so that 0.15% by weight of the total asphalt emulsion is made. For this asphalt emulsion, the emulsifying stability and the adhesive properties to an aggregate are measured, by the following procedures. The results are shown in Tables 1 to 4, and the chemical structures of the amines used are shown in Table 5. The values that show the values in the tables are in% by weight, unless stated otherwise. In addition, the solidification temperature of the amine composition was measured by carrying out a fluidity evaluation every 1 ° C according to JIS K2269, and the viscosity was measured by the use of a rotary type B viscometer made by Tokyo Keiki Co . , Ltd.

[Emulsifying stability test] Approximately 250 ml of a sample of prepared asphalt emulsion was transferred to a cylindrical vessel according to ASTM D244-86, and then allowed to stand at room temperature of about 20 ° C for one day. 50 g of the emulsion of the upper portion and the upper portion of the cylinder were shown, respectively, and the percent of the evaporation residues were measured. A difference between the percent of the evaporation residues of the upper portion and the lower portion indicates stability of the emulsion. It can be considered that the smaller the value of the difference, the better the stability of the emulsion. The percent measurement of evaporation residues was made by the following procedure, that is, a sample of asphalt emulsion, taken, was weighed into a container stipulated by ASTM D244-86, and then heated for 30 minutes to the use of an electric heater, while stirring. After it was observed that no water was present, the heating was further carried out at 160 ° C for 1 minute. Subsequently, the sample was allowed to stand at room temperature, and the weight (g) of the resulting residue was measured. A percent of the residue in the mixture was considered as the percent of the evaporation residue.

[Test of adhesive properties to aggregates] Pieces of ground limestone having a size of 10 to 15 mm were immersed in water for one minute, and then removed, immersed immediately in an emulsion of asphalt for a few minutes, then, these limestones were removed from the emulsion, then they were placed side by side in a No. 14 sieve (1.4 mm), and then allowed to stand at room temperature for 5 hours. Subsequently, they were immersed in hot water at 80 ° C for one hour, and the state of detachment of the asphalt was observed. A ratio of an area on the surface of the limestone covered with an asphalt film was measured visually, and (%) of adhesion area was then calculated. This was represented as the adhesive properties to the aggregates (%). The higher this value, the stronger the adhesive properties, which is preferable. However, the number of milled limestones that was measured in this test was 10, and an average value of 10 milled limestones was considered as the adhesive properties to the aggregates.

Table 1 • Table 2 * 1: Sebomonoamine / sebodia ina / sebotriamine mixture in a weight ratio of 30/40/30.

Table 3 F polyamine and organic acid Table 4 F * 1: Parts by weight for 100 parts by weight of total monoamine, polyamine and organic acid + Table 5 As apparent from the results of the tables, the liquid amine composition according to the present invention can impart, to a bituminous emulsion, such as an asphalt emulsion, an emulsifying stability more excellent adhesive properties to aggregates than the products conventional In addition, the liquid amine composition according to the present invention can also exert an excellent additional effect at the point of handling properties.

It is noted that in relation to this date, the best method known by the applicant to carry out the present invention, is the conventional one for the manufacture of the objects to which it refers. Having described the invention as above, the content of the following is claimed as property:

Claims

1. A liquid amine composition for an emulsifier or emulsifier for bitumen, characterized in that it comprises: (1) from 5 to 70% by weight of a monoamine having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms, (2) of 20 to 80% by weight of a polyamine Having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms and (3) of 10 to 75% by weight of organic acid of 4 to 18 carbon atoms.

2. The amine composition according to claim 1, characterized in that the organic acid (3) is an aliphatic carboxylic acid or a naphthenic carboxylic acid, having from 4 to 18 carbon atoms.

3. The amine composition according to claim 1, characterized in that a weight ratio of the monoamine (1) to the polyamine (2) is in the range of 5/95 to 50/50. 25

4. The amine composition according to claim 1, characterized in that it contains an alkylene oxide adduct (7) of a monoamine or a polyamine having an aliphatic hydrocarbyl group of 8 to 22 carbon atoms in an amount of 10 to 300 parts. by weight with respect to 100 parts by weight of the total of the monoamine (1) and the polyamine (2).

5. The amine composition according to claim 1 or 4, characterized in that the aliphatic hydrocarbyl group having from 8 to 22 carbon atoms in component (1), (2) and / or (7) is -derived from sebum or hydrogenated tallow.

6. The amine composition according to claim 1, characterized in that the organic acid (3) having from 4 to 18 carbon atoms is a branched, aliphatic, carboxylic acid having from 4 to 10 carbon atoms.