RU2233298C1 - Method for producing adhesive bitumen additive - Google Patents

Abstract

FIELD: building materials production, particularly for producing materials used in road-building, road pavement building and in road repairing.

SUBSTANCE: method involved combining acidic component, namely fatty acids or flotation tar with main component, namely polyethylene polyamine under 140^oC - 180^oC temperature up to obtaining acid number of reaction products of not more than 25 mg of KOH per 1 gram; cooling mixture up to 60^oC - 45^oC and adding dibutylphosphoric acid in amount of 3% - 10% by weight.

EFFECT: increased additive efficiency due to enhanced adhesive properties thereof.

1 tbl, 8 ex

Description

FIELD OF THE INVENTION

The invention relates to the field of technology of building materials, and more particularly to methods for producing surface-active (adhesive) substances used as additives to bitumen to improve the adhesion of bitumen to mineral materials.

State of the art

Amidoamines, imidazolines and / or their mixtures formed in the synthesis process are used as an adhesive additive to bitumen. The methods for producing adhesive additives largely determine the quality of a marketable product and the achievement of the main goal of its introduction into building materials - improving the adhesion of bitumen and mineral materials in real-world applications, for example, in road construction.

A known method of producing an adhesive additive for bitumen polyfunctional action [1]. The method includes combining in the reactor a mixture of polyethylene polyamines with piperazines and a mixture of saturated and unsaturated fatty acids with a length of hydrocarbon radical C ₈ -C ₂₆ , mixing the reaction mass with self-heating due to an exothermic reaction for 2-30 minutes, supplying an inert gas (nitrogen), gradual heating the reaction mass to 200 ° C for 3-4 hours, to 240-260 ° C for 1 h and thermostating the reaction mass at 240-260 ° C for 3-4 hours, followed by distillation of excess amines at a pressure of 20-50 mmHg. The method involves the use of a mixture of polyethylene polyamines with piperazines of the following composition, wt.%:

Diethylenetriamine, (DETA) 25-35

Triethylene Pentamine (THETA) 15-25

Tetraethylene pentamine (TEPA) 15-25

β-aminopiperazine (β-AP) 8-12

di β-aminopiperazine (di β-AP) 5-10

The combination of the reaction mixtures of polyethylene polyamines with piperazines and saturated and unsaturated fatty acids is carried out in a ratio of 1: (1.1-1.3).

As a result of the implementation of the method, an adhesive additive of the following composition is formed:

1. Amidoimidazolines 40 + 50, n = 1, 2

2. Bisimidazolines 10-20

3. Aminoethylimidazolines 15-25, m = 1, 2

4. Amidopiperazines 5-25, x = 0, 1

where R is the hydrocarbon radical of C _15-55 saturated and unsaturated acids or mixtures thereof.

After the completion of the cyclocondensation reaction, the adhesive additive is characterized by an acid number of 2-85 mg KOH / g and has a melting point of 45-85 ° C.

The closest in technical essence and the effectiveness of adhesion is a method of obtaining a cationic adhesive additive to bitumen, including combining in the reactor acid and basic components and mixing for 1-2 hours when heated to 100-180 ° C. As the main components, according to the invention, solutions of amino-containing resins are used, and as acidic components are mixtures of synthetic fatty acids of a fraction of C ₂₀ and above [2]. The initial characteristics of mixtures of synthetic fatty acids in the known method (acid number) - 70-100 mg KOH / g The synthesis mode of the adhesive additive in the parameters of the acid number in the description of the invention is not disclosed. The stability of the adhesive additive according to the invention to heat treatment at 160-220 ° C is shown.

The effectiveness of known additives, evaluated by the adhesion index of reference bitumen (by dye adsorption), with an amount of adhesive additive in bitumen of at least 1%, is 91-92% with sand, 92-94% with marble (table).

The disadvantage of this method is the high consumption of additives and insufficient adhesion of bitumen to marble and sand when used in amounts of less than 1 wt.%

SUMMARY OF THE INVENTION

The objective of the invention is to increase the effectiveness of the additive mainly by increasing the adhesion of bitumen to sand and reducing its consumption.

This problem is solved by the fact that the reaction of fatty acids with an amino compound is carried out at a temperature of 140-180 ° C until the acid number (Cp) reaches not more than 25 mg KOH / g (more than 85% conversion of fatty acids to amido amines and imidazolines), then the mixture is cooled to 60-45 ° C and dibutyl phosphoric acid is added to it.

As a result of the reaction at 140-180 ° C, a predominantly mixture of amidoamines and imidazolines is formed, which at 60-45 ° C react with dibutylphosphoric acid to form the corresponding salts. The latter provide a high adhesion of bitumen to mineral materials.

As polyethylene polyamine, triethylene pentamine and tetraethylene pentamine, as well as a mixture thereof, can be used. As fatty acids - oleic acid, stearic acid, synthetic fatty acids of fraction C _14-18 , as well as flotogudron.

Information confirming the possibility of carrying out the invention

Example 1. In a reactor with a stirrer and heating, 700 g of oleic acid with Cp = 196 mg KOH / g and 300 g of polyethylene polyamine with an alkalinity of 149 ml of 0.1 N are charged. Hcl and heated to 160 ° C. When fatty acids interact with polyethylene polyamine (PEPA), salt formation reactions occur:

RCOO ^- NH ₃ [(CH ₂ ) ₂ NH] _n CH ₂ CH ₂ NH ₂ ,

which, as a result of further transformations, form amidoamines:

and imidazoline:

the lubin of the process at the 1st stage is characterized by an acid number (Cp). Cf is determined by potentiometric titration of a portion of the reaction products with a solution of potassium hydroxide and is expressed in mg KOH per 1 g of product. Cch characterizes the amount of unreacted fatty acids in a free state or in the form of salts with PEPA.

With stirring for 90 min, the Cc of the reaction mass reaches 7.5 mg KOH / g, i.e. the degree of conversion of fatty acids to amidomines and imidazolines is 96.2%. The mass is cooled to 45 ° C and 100 g (10 wt.%) Of dibutyl phosphoric acid are introduced.

Get 1060 g of a product containing mainly (more than 85%) salts of amido amines and imidazolines with dibutyl phosphoric acid, 5% salts of fatty acids, excess polyethylene polyamine free or in the form of salts - the rest.

Example 2 (control)

Under the conditions of example 1, the reaction mixture is heated to 100 ° C. After 9 hours, Cz is 60 mg KOH / g. Mass 3 was cooled and 106 g of dibutyl phosphoric acid was added. Received 1092 g of a product containing about 60% salt of amido amines and imidazolines with dibutyl phosphoric acid, 20% salt of fatty acids, excess polyethylene polyamine free or in the form of salts - the rest

Example 3

In a reactor with a stirrer and heating load 500 g of flotation asphalt Kch = 70 mg / g KOH and 200 g of polyethylene polyamine. The reaction mass is heated to 160 ° C. After 30 minutes, Cc reaches 14 mg KOH / g. The reaction mass is cooled to 60 ° C and 35.5 g of dibutylphosphoric acid (5 wt.%) Is added and 726 g of salt are obtained.

Example 4

500 g of sunflower oil fatty acids with 172.5 mg KOH / g and 357 g of polyethylene polyamine are loaded into a heated and stirred reactor. The reaction mass is heated to 150 ° C, after 180 minutes CKh reaches 24.3 mg KOH / g. Cool the reaction mass to 60 ° C and add 82.0 g (about 10 wt.%) Of dibutyl phosphoric acid. 919 g of salt is obtained.

Example 5 (control)

In the experiment of Example 4, instead of dibutylphosphoric acid, 92.0 g of orthophosphoric acid are added. A vitreous mass forms in the reaction medium, which cannot be unloaded from the reactor.

Example 6

In the experiment of Example 4, 25.6 g (about 3% by weight) of dibutyl phosphoric acid are added. 852.6 g of salt are obtained.

Example 7

In the experiment of Example 4, 16.9 g (about 2% by weight) of dibutyl phosphoric acid were added. 843.9 g of salt are obtained.

Example 8 (control).

In the experiment of Example 5, 112.8 (12.0%) of dibutylphosphoric acid was added. 939.8 g of salt are obtained.

The test results of the adhesive properties of additives in comparison with the prototype are shown in the table.

As can be seen from the examples, the reaction at temperatures below 140 ° C leads to a significant increase in reaction time (example 2). The main reaction product are salts of polyethylene polyamine and fatty acids.

In this case, dibutylphosphoric acid as a stronger one displaces fatty acids from their salts with polyethylene polyamine.

The resulting salts of polyethylene polyamine and dibutyl phosphoric acid are not surface-active substances and will not work as an adhesive additive, and the released fatty acids will be ballast.

When the mass fraction of dibutylphosphoric acid is less than 3%, the effectiveness of the additive decreases (example 7), while the mass fraction of more than 10% does not increase (example 8).

Thus, the proposed method provides an adhesive additive with greater adhesion at a lower consumption than the analogue.

Used sources

1. RF patent 2130954, cl. C 08 L 95/00, publ. 1999, bull. 15.

2. RF patent 2185401, cl. From 04 to 26/26, publ. 2002, bull. 20 - prototype.

3. RF patent 2099370, cl. C 08 L 95/00, publ. 1997, bull. 35.

Claims (1)

A method of obtaining an adhesive additive to bitumen, including combining acid and basic components in a reactor, mixing them under heating, characterized in that fatty acids or flotogudron are used as the acid component, polyethylene polyamines are used as the main component, heating is carried out at a temperature of 140- 180 ° C until the acid number of the reaction products reaches not more than 25 mg KOH / g, then the mixture is cooled to 60-45 ° C and dibutyl phosphoric acid in an amount of 3-10 wt. .%.