RU2620120C1 - Stretching for colored asphalt concrete - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: stretching includes aromatic oil, glycerin rosin ester, coumarone-indene resin, styrene-butadiene-styrene block copolymer, antioxidant and surfactant-based surfactant containing amine groups at the following component ratio, wt %: aromatic oil - 25-50, glycerol ester of rosin - 30-60, coumarone-indene resin - 5-20, styrene-butadiene-styrene copolymer - 3-10, antioxidant - 0.1-0.5, adhesion additive - 0.1-1.0.

EFFECT: stretching has an increased plasticity at low ambient temperatures, increased resistance to shear deformations at elevated temperatures, adhesion to various types of stone material.

4 cl, 1 tbl

Description

The present invention relates to a colorless (transparent) synthetic polymer binder, which is a road-building material, and can be used for the production of colored asphalt concrete.

Colored asphalt mix consists of a grain mineral part (crushed stone, sand and mineral powder), a transparent polymer binder, pigments of organic or inorganic origin, taken in certain proportions and mixed in a heated state, used for the construction of asphalt concrete pavements of any types and brands.

Widespread bituminous binders based on petroleum bitumen, due to the presence of asphaltenes in them, are black and therefore difficult to stain. The field of application of colored road surfaces is growing all over the world, because, among other things, they help to improve the safety of road users by color identifying special traffic areas, such as pedestrian crossings, bicycle paths, dedicated road lanes for bus traffic, parking, etc. also apply for marking certain hazardous areas, such as entrances to the city center or dangerous bends. Colored surfaces contribute to visibility in low light conditions, such as at night or in some places, such as tunnels. With their help, the attractiveness of urban road and civilian facilities can be improved - they can be used for public squares, courtyards of buildings and schools, sidewalks, pedestrian walkways, paths in parks and gardens, parking and recreation areas. Therefore, for all of the above areas of application, it is preferable to use colorless synthetic polymer binders that do not contain asphaltenes and can be used in the manufacture of asphalt concrete of various colors.

Binders for colored asphalt should have good adhesion to mineral materials, provide the necessary strength, resistance to low temperatures, thermal stability, and durability. Work on the creation and use of colored asphalt concrete in road construction is being conducted in Russia to a lesser extent than abroad, therefore, in our country, colored road asphalt concrete has not yet been widely used. The widespread use of colored asphalt concrete is hindered by the shortage of materials used for their production, in particular imported binders, a narrow range of binders for colored asphalt concrete of Russian origin, the high cost and complexity of the technological process for their preparation.

Known astringent for road plastobeton (see patent RU 2418019, IPC C08L 95/00, С04В 26/26, published May 10, 2011), including light polymer components - oil solution in SKD synthetic polybutadiene rubber industrial oil (grade P), petroleum resin structuring polyolefin additives from recycled polyethylene and oxidized atactic polypropylene in the following ratio of components, wt.%:

petroleum resin 43-55 synthetic oil solution polybutadiene rubber SKD

with the ratio in the binder:

industrial oil 24-26 rubber 8-12 oxidized atactic polypropylene 7-10 recycled polyethylene 6-9

The known binder has a light color, it can be given various shades and create bright colored road surfaces, it has good adhesion to mineral materials of acidic and basic rocks, an acceptable softening temperature (62-67 ° C) and a low brittle temperature, however, the known binder requires the use of expensive components - synthetic rubber and oxidized atactic polypropylene, and also does not provide sufficient color brightness and durability of asphalt concrete pavement.

Known binder for colored asphalt concrete (patent RU 2537596, IPC C08L 95/00, C08J 11/04, С04В 26/26, published January 10, 2015), including petroleum resin, industrial oil, synthetic polybutadiene rubber and a secondary polymer, which is a mixture of polyethylene low density particles of aluminum foil and polyolefin with active functional groups, in the following ratio of components, wt.%:

petroleum resin 45-55 industrial oil 34-42 synthetic rubber 3.8-6 secondary polymer 7

Known binder is characterized by a small number of components, a low content of synthetic rubber, the use of packaging waste such as Tetra Pak. A disadvantage of the known binder is the use of a secondary polymer. Recycled products are always unstable in composition and quality, which leads to instability in the quality of the final binder.

Known astringent for colored asphalt concrete (see PCT application WO 200153409, IPC C08J 03/12, C08L 23/20, C08L 57/02, C08L 95/00, published July 26, 2001), including a plasticizer mixture based on aliphatic hydrocarbons with the number of atoms carbon of at least 20, a structuring component based on a cycloaliphatic hydrocarbon polymer and a compatible first polymer, taken in such a ratio that the softening temperature of this mixture lies in the range of 30-100 ° C, pigment and a second polymer, taken in an amount of 10-15 wt. .% and selected from the group: polyolefins, such as polyethylene or polypropylene and olefin copolymers, natural or synthetic rubbers such as ethylene-propylene-diene monomer, ethylene-propylene monomer, polyisobutylene, polynorbornene, chloroprene rubber. The plasticizer can be selected from the group: natural or synthetic aliphatic oils having an aniline point greater than or equal to 90 ° C, and selected from hydrogenated white oils, polymers with a low degree of polymerization, such as polyolefins. The plasticizer may be contained in an amount of 40-60 wt.% By weight of the binder, and the ratio of the weights of the structuring component and the plasticizer is 0.5-1.5.

A disadvantage of the known binder is a wide range of softening temperatures of the resulting binder, which, in turn, is determined by the variety of ingredients used.

Known as an adhesive for colored asphalt (see application CN 102558751, IPC C08K 03/22, C08K 05/11, C08K 05/12, C08K 13/02, C08L 09/06, C08L 53/02, C08L 57/02, C08L 95 / 00, Е01С 07/08, published July 11, 2012), including a plasticizer in the form of aromatic or naphthenic oil, resin thickeners, styrene-butadiene-styrene copolymer, styrene-butadiene rubber, plasticizer, pigment, pigment dispersion additive, ultraviolet absorber , antioxidant, crosslinking agent in the following ratio of components, wt.%:

aromatic or naphthenic oil 7-27 resin thickeners 36-71 styrene-butadiene-styrene copolymer 5-13 styrene butadiene rubber 5-15 pigment 4-9 pigment dispersant 1-5

The binder may contain a plasticizer (up to 16 wt.%), An ultraviolet absorber (up to 4 wt.%), An antioxidant (up to 4 wt.%), A crosslinking agent (up to 8 wt.%). As thickeners of the resin can be taken petroleum resins C5 / C9.

A disadvantage of the known binder is the high cost, determined by the price of the used polymers and petroleum resins, as well as the pigment introduced into the binder and the pigment dispersion additive, which significantly increase the viscosity of the binder and, therefore, worsen its technological characteristics (pumping, dosing, transportation storage).

Known astringent for colored asphalt concrete (see application CN 1475527, IPC C08L 53/02, published 02/18/2004), including inden-coumaron resin, polyurethane resin, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, Ti ₂ dioxane dioctyl phthalate and pigment in the following ratio of components, parts by weight:

dioctyl phthalate 70-80 styrene-butadiene-styrene block copolymer 10-20 titanium dioxide 2-12 styrene butadiene rubber 1-3 indene-coumarone resin 1-2 polyurethane resin 1-2 pigment 1-2

A disadvantage of the known binder is the high cost, determined by the high cost of polymers with a high content of the latter. Also, the low content of structural components (inden-coumaron and polyurethane resins) limits the scope of application of the binder in the composition of asphalt concrete for climatic zones with sharply continental climates. The titanium dioxide introduced into the binder without specialized additives for dispersing the pigment, firstly, significantly increases the viscosity of the binder and, therefore, worsens its technological characteristics (pumping, dosing, transportation, storage), and, secondly, leads the structure of the binder to heterogeneous state due to delamination of the latter.

Knitting cement for colored asphalt is known (see application CN 103013146, IPC C08L 53/02, C08L 57/02, C08L 91/00, C08L 95/00, published 04/03/2013), which coincides with this technical solution for the largest number of essential features and adopted as a prototype. The binder prototype includes an indene-coumarone resin, aromatic oil, styrene-butadiene tribloxopolymer, a viscosity reducing additive, an activating additive and a mixture of hydrocarbons in the following ratio, wt.%:

indene-coumarone resin 23-46 aromatic oil 25-44 styrene-butadiene tribloxopolymer 3-8 viscosity reducing agent 1-3 activating additive 0.05-1.5 hydrocarbon mixture 13-25

Known binder has insufficient ductility at low ambient temperatures, the activating additive, which is part of the binder, can settle during storage of the binder without stirring.

The present invention was the development of such a binder for colored asphalt, which would have increased ductility at low ambient temperatures, increased resistance to shear deformations at elevated temperatures, adhesion to various types of stone material.

The problem is solved in that the binder for colored asphalt concrete includes aromatic petroleum oil, rosin glycerin ester, indene-coumarone resin, styrene-butadiene-styrene block copolymer, antioxidant and an adhesive additive based on surface-active substances (surfactants) containing amine groups, the following ratio of components, wt.%:

aromatic oil 25-50 rosin glycerin ester 30-60 indene-coumarone resin 5-20 styrene-butadiene-styrene copolymer 3-10 antioxidant 0.1-0.5 surfactant-based adhesive additive, containing amine groups, 0.1-1.0

The binder may contain a crosslinking additive, contributing to the creation of a strong polymer network in the binder (crosslinking additive) in an amount of 0.1-5.0 wt. % by weight of the polymer in the binder.

New in this binder is the introduction into its composition of glycerol ether of rosin (HES) in the amount of (30-60) mass. %, antioxidant in the amount of (0.1-0.5) wt.% and additives based on surfactants containing amine groups, in the amount of (0.1-1.0) wt.%.

HES is a structure-forming component that gives the binder rigidity without deterioration of low-temperature characteristics (do not increase the brittle temperature), moisture resistance, high adhesion and cohesion. The introduction of an antioxidant allows the binder to maintain a range of performance indicators during long-term storage, transportation, reheating, as well as maintain an acceptable range of performance after preparation of asphalt concrete mixtures. In combination with antioxidants, the binder acquires resistance to oxidative aging of the binder and, accordingly, to an increase in the durability of colored asphalt concrete. The introduction of a surfactant-based additive changes the rheology of the asphalt mix at low technological temperatures and gives the binder high adhesion properties.

As aromatic petroleum oil (AM), which is a binder plasticizer, products obtained by purification of distillate or residual petroleum oil fractions can be used. It is preferable to use light products with a kinematic viscosity at 100 ° C of at least 18 cSt (GOST 33), and an aromatic hydrocarbon content of at least 60 (GOST 12329).

As structure-forming materials, glycerin rosin esters (HES) and indene-coumarone resins are introduced into the binder. HES - condensation products of polyhydric alcohols and modified rosin. It is preferable to use the lightest products with softening points of at least 75 ° C and an acid number of at least 15. Inden-coumarone resins (IR) are low molecular weight thermoplastic polymers obtained by polymerization of a large group of organic substances contained in crude benzene and phenolic fraction coal tar. IR are one of the varieties of aromatic hydrocarbon resins. It is preferable to use light-colored products with a softening point of at least 90 ° C.

As a polymer, a styrene-butadiene-styrene (SBS) copolymer of a linear structure consisting of butadiene monomer (69%) and styrene monomer (31%) at the ends of the blocks is introduced into the binder, which ensures quick distribution of oil and resins in the solution with the formation of a stable elastic dispersed system.

As an adhesive additive based on a surfactant containing amine groups, products containing at least one amine and / or modified amine surfactant or mixtures thereof can be used, for example, a product from amines, diamines, polyamines, ethoxylated can be selected amines, ethoxylated alkyl diamines, ethoxylated alkyl polyamines, amido amines, amidopolyamines, imidazolines and / or any corresponding organic and / or inorganic salts, and / or mixtures and / or combinations mentioned in societies.

The antioxidant may be a product containing 2,4-dinonyl-6-tert-butyl phenol or 4.4 methylene bis (2.6 ditretbutyl phenol).

The content of the above components of this binder is due to the following circumstances. When the content in the binder of aromatic oil is less than 25 wt. % it is difficult to obtain a binder with high decorative indicators in terms of elongation, and with a low brittle temperature, when the aromatic oil content in the binder is more than 50 wt.%, the binder will have reduced cohesion, a penetration rate higher than the standard value and a low softening temperature.

When the content in the binder of glycerol ether rosin is less than 30 wt. % the structure of the binder is unstable, adhesion and cohesion are also reduced, the binder has low softening points and high penetration and extensibility. If the glycerol ether content of rosin in the binder is more than 60 wt.%, The binder will have low penetration, stiffness, and low extensibility, which leads to a decrease in the performance of asphalt concrete.

When the binder content of indene-coumaron resin is less than 5 wt.%, The required softening temperature and viscosity are not achieved, when the binder contains kumaron-indene resin more than 20 wt.%, The binder has a very low elongation and brittleness (high brittle temperature).

When the content in the binder of styrene-butadiene-styrene copolymer is less than 3 wt. % it is not possible to create a polymer network in a binder, and to obtain a product that meets the regulatory requirements in terms of elasticity, when the styrene-butadiene-styrene copolymer contains more than 10 wt.% in the binder, the binder acquires a very high viscosity and low workability.

The content in the binder of an antioxidant of less than 0.1 wt.% Does not affect the reduction of oxidative aging, the introduction of a binder of an antioxidant of more than 0.5 wt.% Becomes economically impractical.

When the binder contains an adhesive additive based on a surfactant containing amine groups, less than 0.1 wt.% It does not affect the rheology of the binder and its adhesive properties, when the binder contains an additive based on a surfactant containing amine groups, more than 1.0 wt. % the effect of its administration does not increase.

The technology for preparing a binder for colored asphalt concrete is simple and consists in pre-mixing at a temperature of 155-175 ° С of aromatic oil with HES, IR and antioxidant, portioning them into the oil heated to 175 ° С with continuous stirring and a constant increase in temperature and maintaining it in the range from 155 to 175 ° C. After combining aromatic oil with resins (HES and IR) and an antioxidant, styrene-butadiene-styrene copolymer is introduced, a surfactant-based additive containing amine groups, an additive that helps to create a strong polymer network in a binder (crosslinking additive) (if necessary). Stirring is continued until all components are mixed uniformly and until the change in quality indicators (depth of penetration of the needle at 25 ° C, softening temperature, extensibility at 25 ° C) ceases.

Examples. 16 binder samples were prepared for colored asphalt. The content of the components of the prepared binder samples are shown in the drawing in table 1.

Symbols shown in table 1:

AM - aromatic petroleum oil, the Norman oil normalized by the content of polycyclic hydrocarbons was used (manufacturer of CJSC PO Orgkhim);

HES - rosin glycerin ether (CJSC PO Orgkhim, Russia);

IR - indene-coumarone resin with a softening point of 100 ° C (Dongguan Rayton Chemicals Co., Ltd. China);

SBS - styrene-butadiene-styrene copolymer brand LG 501 (manufactured by LG Chemical Ltd, South Korea);

ANT - antioxidant VS-30 AN (manufacturer of CJSC PO Orgkhim, Russia);

KD - surfactant-based additive containing amine groups, Amdor TS, (manufactured by Amdor CJSC, Russia);

SD - crosslinking additive (Rodoval S 199, Firm "Solvay" France);

P ₂₅ , mm ^-1 - the penetration depth of the needle at 25 ° C, mm ^-1 (penetration) in accordance with GOST 11501;

КИШ, ° С - softening temperature according to КИШ in accordance with GOST 11506;

D ₂₅ , cm - extensibility at 25 ° C, cm in accordance with GOST 11505;

Т _хр , ° С - fragility temperature, in accordance with GOST 11507;

E ₂₅ ,% - elasticity at 25 ° C, cm in accordance with GOST R 52056;

Coupling - points, in accordance with GOST 12801 p. 28.

As can be seen from the table, the compositions No. 5, 6, 7, 8, 12, 14, the values of the components of which fit into their intervals given in the claims, have increased elongation (ductility), low brittleness temperature, optimal viscosity, determined by the depth of penetration of the needle , and the highest score in terms of adhesion to granite stone material. Sample No. 1, containing an equal amount of AM and HES and a reduced amount of SBS, has a very low viscosity and softening temperature, and elasticity, which, if used as part of asphalt concrete, will lead to high shear deformations of the latter. Sample No. 2, containing 65 wt.% HES, has insufficient binder viscosity and low elasticity. Sample No. 3 contains an increased amount of IR, while there is a significant decrease in the depth of penetration of the needle and an increase in the temperature of brittleness, which will lead to a decrease in the low-temperature characteristics of asphalt concrete. In the case of sample No. 3, difficulties arise in the technological process of preparing the asphalt concrete mixture, requiring high mixing temperatures of the starting components, which is not provided for by the requirements for the working temperatures of the binder. Sample No. 9 has a low needle penetration depth and a high rate of brittleness. This composition can be used in some types of asphalt concrete, operated at elevated temperatures. Sample No. 11 has high softening points and elasticities. Such compositions will be much more expensive, but their use is advisable at facilities where there are various alternating loads. Sample No. 13 has a low score of the coefficient of adhesion to acidic stone material (granite), however, provided that stone materials of the main rocks are used, the coefficient of adhesion will be higher.

The real binder for colored asphalt was successfully used in the composition of dense asphalt mix type B grade 1, including, wt.%:

crushed granite fr. 5-10 mm 39.5 granite fractional screening 2-5 mm 9.9 granite screening 0-2 mm 34.0 granite fly ash 3.9 mineral powder 5.3 colorless polymer binder 5,4 pigment red pigment Iron Oxide Red HS -130 A, manufactured in China 2.0

Obtained with the use of a real asphalt concrete binder for colored asphalt concrete mix fully complies with the physical and mechanical requirements of GOST 9128-2013 for type 1 grade B asphalt concrete.

This binder has a light color (from a transparent mass to a translucent light brown or light greenish color), which allows, when used as part of asphalt mixes using various pigments of organic or inorganic origin, to obtain road surfaces of various colors and various purposes for any climatic zone. As the tests showed, the binder has high adhesive properties to various types of stone materials, high internal cohesion due to two types of structuring resins and styrene-butadiene-styrene polymer, has the ability to mix with stone material at temperatures below standard technological (20-30 ° C), due to the use of additives based on surfactants that improve the binder rheology. The introduction of the SBS type copolymer into the binder allows the asphalt-concrete mixture based on it to be resistant to shear deformations at high temperatures and resistant to low-temperature cracking at low temperatures.

Thus, a real binder for colored asphalt allows to produce asphalt mixes that meet the requirements of current regulatory documents, to be a replacement for standard oil road bitumen, not to change the technological processes for preparing, laying and compacting colored asphalt mixes.

Claims (5)

1. An astringent for colored asphalt concrete, including aromatic petroleum oil, rosin glycerin ester, coumarone-indene resin, styrene-butadiene-styrene block copolymer, antioxidant and an adhesive additive based on surfactants containing amine groups, in the following ratio, wt.%: aromatic oil 25-50 rosin glycerin ester 30-60 coumaron indene resin 5-20 styrene-butadiene-styrene copolymer 3-10 antioxidant 0.1-0.5 surfactant-based adhesive additive, containing amine groups 0.1-1.0 2. The binder according to claim 1, characterized in that it contains a crosslinking additive in an amount of 0.1-5.0 wt.% By weight of the polymer in the binder. 3. The binder according to claim 1, characterized in that it contains 2,4-dinonyl-6-tert-butyl-phenol as an antioxidant. 4. The binder according to claim 1, characterized in that it contains 4,4-methylene-bis (2,6-ditretbutyl-phenol) as an antioxidant.