PL205142B1 - Emulsifier and method of obtaining an emulsifier - Google Patents

Description

Description of the invention

The subject of the invention is an emulsifier for the production of cationic bituminous emulsions and a method of its preparation. The invention relates to cationic, amine-containing bituminous emulsifiers which are used to prepare bituminous emulsions to be used as a substitute for hot asphalt in road pavement construction and renovation.

There is known from the patent FR 2071278 a method of obtaining cationic surface-active substances by condensation of tertiary amines with chlorobenzene (the amines are obtained on the basis of fatty alcohols and dimethylamine).

It is known from the RU 2124936 patent description of a method of obtaining an emulsifier for cationic bituminous emulsions by condensation of alkyldimethylamines with organic chlorides. The organic chlorides used are dichloropropanes and / or 1,2-dichloropropene-2. The molar ratio of alkyldimethylamine to dichloropropanes and / or 1.2-dichloropropene-2 is 1: 0.1-1. The resulting mixture is neutralized with hydrochloric acid to pH 7.

The patent specification GB 773 622 describes a cationic emulsifier for the production of bituminous emulsions, which are obtained by condensing mono- or polyaminoalkanes or their mixtures with the residues after distillation of lauric, palmitic, stearic, linoleic, tallow acids or their esters or lactones, or mixtures of these unions.

There is also known from US patent 5,085,704 a cationic emulsifier which is a reaction product of polyalkylene polyamines with polycarbonate acids and their anhydrides. This emulsifier ensures the formation of a homogeneous, stable, bituminous emulsion. However, the low content of free amino groups does not allow to ensure sufficient adhesion of asphalt to the stone material, and therefore its use requires additional introduction of an adhesive agent to the bitumen before preparing the emulsion, which in turn causes difficulties in the technological process of obtaining the emulsion and makes the finished production more expensive.

There is also known from the patent description RU 2241012 a cationic emulsifier KADEM-BT, with an amine number (mg HCl / g) of not less than 150 and an acid number of 0.6 mg KOH / g. The method of obtaining it is based on the reaction of acids of animal or vegetable origin (C16-C20) with polyethylene polyamines.

The most similar to the proposed invention is the known emulsifier for the production of cationic bituminous emulsions, obtained by the interaction of polyethylene polyamines with acids (in particular of vegetable origin) - known from the patent description RU 2230084. It is obtained by condensation of saturated and unsaturated C10-C20 acids with polyethylene polyamines, consisting of 90 to 100% of compounds with the number of nitrogen atoms not less than 4. Condensation is carried out at the temperature of 150 - 250 ° C with constant stirring. The lower limit of the synthesis temperature is determined by the fact that at lower temperatures no imidazoline groups are formed, which makes it impossible to obtain a product with an appropriate composition. The upper limit of the synthesis temperature is determined by the fact that at higher temperatures, thermal destruction of both the starting components and the reaction products begins. After condensation, the product, if necessary, is diluted with a diluent (up to 15 vol.%).

The disadvantage of the emulsifier, obtained by the above method, is insufficiently high operational properties, and in particular, low storage stability of EKB-1 class bituminous emulsions (quickly disintegrating).

The aim of the proposed invention is to obtain an emulsifier which makes it possible to increase the storage stability of bituminous emulsions and to improve their adhesion.

This technical result is achieved in the method of obtaining an emulsifier for the production of cationic bituminous emulsions through the action of polyethylene polyamine on fatty acids of vegetable origin, as polyethylene polyamine, diethylene triamine (DETA), and oils of vegetable origin - a mixture of coconut, palm and palm oils. rapeseed with their mass ratio respectively: (1-8): (1-8): (1-8). This process consists in mixing 1.1 - 1.5 parts. wt. DETA with 1 part wt. mixtures of vegetable oils at 120 - 130 ° C, heating the obtained mixture at the rate of 7.0 - 7.5 ° C / 10 min to the temperature of 210 - 215 ° C, maintaining this temperature while creating a vacuum at the speed of 0.07 - 0 , 09 atm./10 min to the final pressure of 0.14 - 0.16 atm. and distilling off the surplus DETA and then cooling the obtained product.

It is advisable to use up to 71 wt. recirculating DETA relative to the total amount of DETA used in the reaction.

PL 205 142 B1

It is preferable to purify the recirculating DETA by heating it in a stream of nitrogen at a temperature of 90-125 ° C in a vacuum at a pressure of 0.13-0.15 atm.

The technical result is also achieved because the emulsifier for the production of cationic bituminous emulsions based on alkylamidoamines obtained by the process described above is present as a mixture:

N- (2-alkylethylene) -N- (2-aminoethylene) -amines according to formula 1:

R-CONHC2H4NHC2H4NH2 (1) and N, N-di- (2-aminoethyl) -alkylamide according to formula 2:

R-CON (C2H4NH2) 2 (2) with their molar ratio of 2: 1, respectively, where R is the alkyl residue of higher fatty acids from the mixture of coconut, palm and rapeseed oils with their mass ratio respectively: (1-8): (1- 8): (1-8).

P r z k ł a d 1

A 1 l stainless steel reactor, equipped with a stirrer, thermometer, condenser, vacuum gauge, two 0.1 l and 0.5 l vacuum tanks, is loaded with 306 g (67% of the mass of the total amount charged DETA) of the recirculation DETA and 151 g 99% DETA. A nitrogen stream of 150 ml / h is started. The capacitor is connected to the vacuum tank with vol. 0.1 l. A vacuum is created in the reactor up to a pressure of 0.14 atm. At the same time, it is heated to 125 ° C for 1.5 hours. while distilling off about 31 g of the aqueous solution of the light amine fraction. After reaching the temperature of 125 ° C, the distillation is continued for 15 minutes, and then 368 g of the oil mixture is charged to the reactor in the ratio: coconut (ca): palm (op): rapeseed (orz) = 2.5: 5.0 : 2.5 (ratio of DETA weight to the mixture of oils 1.24: 1) and the content is heated to 210 ° C while stirring. After reaching the temperature of 210 ° C in the reactor, the condenser is switched on to the vacuum tank with the volume of 0.5 L and a vacuum is started to build over the reaction mass at 210 ° C. The vacuum generation process is continued to a final pressure of 0.15 atm. In the process of evacuation and holding the reaction mixture for 0.5 h. approximately 306 g of recirculating DETA is distilled off. After separating off the recirculating DETA, the reaction mass is cooled down to 70 ° C under a stream of nitrogen in vacuo. 508 g of a light brown viscous fluid are obtained which, according to the results of quantitative analysis with regard to functional groups, is a mixture of the alkylamidoamines of formula (1) and formula (2) with their molar ratio of 2: 1, respectively.

Functional group analysis:

The total content of titrated nitrogen - 7.51%

Primary nitrogen content - 6.19%

Secondary nitrogen content - 1.23%

The molar part of the compound of formula (1) in the mixture - 0.66

The molar part of the compound of formula (2) in the mixture - 0.33

The content of non-volatile substances - 96.7%

Density at 40 ° C - 0.9230 g / cm ³ .

The emulsifiers are prepared analogously on the basis of the other examples. The loading of the starting substances and the conditions for obtaining the emulsifier are shown in Table 1. Table 2 shows the properties of bituminous emulsions (examples 1-4) and using the emulsifier according to patent RU 2230084 (example 5). The composition of the bituminous emulsion: bitumen of the BND 90/130 brand - 50.00 wt.%, Emulsifier 0.25 wt.%, Hydrochloric acid (35%) - 0.25 wt.%, The rest - water.

T a b e l a 1

Conditions for obtaining emulsifiers Example no 1 2 3 4 1 2 3 4 5 Mass ratio ok: op: orz 2.5: 5: 2.5 1: 8: 1 8: 1: 1 1: 1: 8 DETA mass ratio: oil 1.24: 1 1.3: 1 1.5: 1 1.1: 1 Mixing temperature ° C 125 120 130 120

PL 205 142 B1 cont. table 1

1 2 3 4 5 Heating speed ° C / 10 min 7.0 7.5 7.0 7.5 Heating temperature ° C 210 215 215 210 Vacuuming rate, atm./min 0.08 0.07 0.08 0.09 Final pressure, atm. 0.15 0.16 0.15 0.14 Recirculation DETA quantity; wt.% from the total amount of DETA in the reaction 67 68 63 71

Signs:

ok - coconut oil op - palm oil orz - rapeseed oil

DETA - diethylenetriamine

T a b e l a 2

Properties of bituminous emulsions Example No. 1 2 3 4 5 Homogeneity (residue on the sieve 0.14 mm),% 0.07 0.08 0.09 0.09 0.2 Stability during storage for 7 days (residue on the sieve 0.14 mm),% 0.10 0.12 0.12 0.12 0.3 Stability during storage for 30 days (sieve residue 0.14 mm),% 0.19 0.19 0.20 0.21 0.45 Crushed stone adhesion (crushed stone surface coverage),% 99 100 99 100 98

Patent claims

Claims (4)

Patent claims 1. An emulsifier for the production of cationic bituminous emulsions based on alkylamidoamines, characterized in that it consists of N- (2-alkylethylene) -N- (2-aminoethylene) -amine of the formula 1: R-CONHC2H4NHC2H4NH2 (1) and N, N-di- (2-aminoethyl) -alkylamide of formula 2: R-CGN (C2H4NH2) 2 (2) with their molar ratio of 2: 1, respectively, where R is the alkyl residue of higher fatty acids from the mixture of coconut, palm and rapeseed oils with their mass ratio (1-8) respectively: (1-8 ): (1-8). 2. The method of obtaining an emulsifier for the production of cationic bituminous emulsions through the interaction of polyethylene polyamine with oils of vegetable origin at an elevated temperature, characterized in that the polyethylene polyamines are diethylene triamine (DETA) and the oil of vegetable origin is a mixture of coconut, palm and rapeseed oils in weight ratio, respectively: (1-8): (1-8): (1-8) and the process is carried out by mixing 1.1 - 1.5 parts by weight of diethylene triamine with 1 part by weight of a mixture of vegetable oils at a temperature of 120 - 130 ° C, then the mixture obtained is heated at the rate of 7.0 7.5 ° C / 10 minutes to the temperature of 210 - 215 ° C, kept at this temperature while creating a vacuum at the rate of 0.07 - 0.09 atm./10 min to a final pressure of 0.14 - 0.16 atm. and distils off the excess diethylene triamine while cooling the obtained product. 3. The method according to p. The process of claim 2, wherein diethylene triamine is used containing up to 71 wt.% Of the recirculating DETA to the total amount of DETA used for the reaction. 4. The method according to claim 3, characterized in that the purification of the recirculating diethylene triamine is carried out by heating it in a nitrogen stream at a temperature of 90 - 125 ° C in a vacuum with a final pressure of 0.13 - 0.15 atm.