RU2226203C2 - Bitumen composition - Google Patents

Abstract

FIELD: petroleum product-based materials. SUBSTANCE: bitumen composition appropriate for use in road building, manufacture of roofing, waterproofing, and sealing materials contains, wt %: bitumen 81.0-97.5, butadiene/styrene copolymer 1.0-14.0, adhesion additive 0.5-5.0, and optionally triethanolamine or polyethylenepolyamine, 0.25-2.0 wt parts per 1 wt part adhesion additive. The latter is maleic anhydridemodified low-molecular polybutadiene with bound maleic anhydride content 12-21% and having dynamic viscosity 10-100 Pa.s (25 C). EFFECT: preserved high adhesion properties of bitumen composition at insignificant dosages of adhesion additive, improved physico-mechanical characteristics, and enlarged assortment of adhesion additives. 2 cl, 2 tbl, 7 ex

Description

The invention relates to the field of producing bitumen compositions containing polymer additives, in particular block copolymers (thermoplastic elastomers) used in road construction, for the manufacture of roofing, waterproofing materials and sealants.

A known composition for roofing and waterproofing materials, comprising as a polymer additive a mixture of 0.5-10.0 wt.% Linear block copolymer AB, 2.0-5.0 wt.% Linear block copolymer ABA, 65.0- 95.0 wt.% Star-shaped block copolymer (AB) ₄ X, where A is a polystyrene block with a molecular weight of 10000-30000, B is a polybutadiene block with a molecular weight, X is a multifunctional crosslinking agent, and 2.0-20.0 wt.% polystyrene with a molecular weight of 10000-30000, unoxidized bitumen, filler and tire regenerate or polybutadiene in the ratio of components in the comp itsii, wt.%:

The specified mixture of block copolymers and polystyrene 7-12

Unoxidized Bitumen 58-73

Filler 10-12

Tire regenerate or polybutadiene 5-15

Moreover, to prepare the composition, the specified polymer additive, tire regenerate and filler (talc) are loaded into a mixer with heating and a stirrer at a temperature of 130 ± 20 ° С, mixing is carried out for 15 minutes, after which unoxidized bitumen is heated in parts, heated to a temperature of 150-170 ° C, and stirring for 45-75 minutes until a homogeneous mass is obtained (USSR Patent No. 1807999, IPC C 08 L 95/00, C 08 K 7/00 // C 08 L 95/00, 9:00, 25 : 06, 53:00, priority 11/29/90, publ. 04/07/93, BI No. 13)

The known technical solution allows to increase the relative elongation at break and the strength of the fastening to the metal material based on the composition, as well as reduce the temperature of its preparation.

A disadvantage of the known invention is the multicomponent polymer base of the composition, the multi-stage method for its preparation, the complexity of its preparation due to the need to preheat the polymer additive and bitumen to fairly high temperatures, and the need to use it in the molten state.

Known bitumen composition containing 80-99 parts by weight of bitumen, 1-20 parts by weight rubber (homopolymers of conjugated dienes, random copolymers of the styrene-conjugated diene type and linear or branched block copolymers of the styrene-conjugated diene type, preferably a linear or branched block copolymer of the styrene-butadiene type), 1-20 parts by weight a mixture of sulfur and a sulfur-containing compound in a mass ratio of 20-60: 40-80, respectively, which is obtained by mixing at a temperature of 150-170 ° C for 1.5-2.0 hours of bitumen and rubber (mainly a block copolymer of styrene-conjugated diene) , then a mixture of sulfur and a sulfur-containing compound is introduced and, optionally, an amino-containing additive soluble in bitumen (triethanolamine), and mixing is carried out for 1.5-4.0 hours (RF patent No. 2011166, IPC C 08 L 95/00, C 08 K 13/02, priority 07.12.90, published on 04.30.94, BI No. 8).

The combined use of the vulcanizing system used in the known bituminous composition and the amine-containing additive significantly increases the resistance of the bitumen binder to cracking.

A disadvantage of the known composition is the duration of its preparation, the need to use a sulfur vulcanizing group, which is a mixture of elemental sulfur and a sulfur-containing compound, the preparation of which is separated into a separate stage, the possibility of an uncontrolled increase in the viscosity of the bitumen composition during storage due to the course of vulcanization processes over time.

Also known is a bitumen composition for waterproofing and sealing, including 70-79 wt.% Bitumen, 9.5-15 wt.% Butadiene-styrene thermoplastic elastomer DST-30 or rubber crumb (waste from the production of synthetic rubbers and styrene-butadiene latexes), 1.0-3, 0 wt.% Low molecular weight copolymer of butadiene with piperylene or acrylonitrile, 8.0-10.0 wt.% Plasticizer (naphthenoaromatic hydrocarbons), 0.5-1.0 wt.% Stearic acid, 1.5-3.0 wt. % surfactant (OP-7 or OP-10), which is obtained by mixing for 1.5-2.0 hours components o in the mixer, where bitumen heated to 160-170 ° C is fed, and then thermoplastic elastomer (or crumb rubber) and stearic acid are introduced into it in portions, mixed until a homogeneous mass, after which a low molecular weight copolymer, a plasticizer and a surfactant are introduced, or in two stages: in the first stage, a concentrate is obtained by mixing in a vacuum mixer for 1 h at a temperature of 70 ° C part of bitumen with all other components, in the second stage, the remaining part of bitumen heated to 160-170 ° C is introduced into the mixer, the concentrate obtained in the first stage, and stirring at a temperature of 150-170 ° C for 1.5-2.0 hours, and the ratio of bitumen introduced in the first and second stages is 1: 1.41-2.95, respectively (RF patent No. 2011667, IPC C 08 L 95/00, C 08 K 5/00, priority 09/01/91, publ. 04/30/94, Bull. No. 8).

Known bitumen composition has increased frost resistance, strength, reduced elongation at break at positive temperatures.

Its disadvantage is the multicomponent nature, the use of a low molecular weight copolymer of butadiene with acrylic acid nitrile (NAC), which is unsafe from an environmental point of view, since prolonged exposure to high temperatures during dissolution of the copolymer in bitumen may release residual unpolymerized monomer (NAC) into the environment.

Known bitumen-polymer waterproofing mastic, including 72-85 wt.% Low-grade bitumen, 5-8 wt.% Butadiene-styrene thermoplastic elastomer DST-30 and 10-20 wt.% Fine filler - phosphogypsum hemihydrate, which is obtained as follows: bitumen is fed into the turbo mixer , it is heated to a temperature of 160-180 ° C, part of the filler is introduced with constant stirring in the ratio bitumen filler 1: 0.028 and stirred for 10-20 minutes, then the first portion of DST-30 thermoplastic elastomer is introduced into the mixture to obtain a mixture with the corresponding By applying bitumen: thermoplastic elastomer: filler 1: 0.002: 0.028, after which the rest of thermoplastic elastomer is charged in equal parts for 5-10 minutes to obtain a mixture with the ratio bitumen: thermoplastic elastomer: filler 1: 0.058-0.110: 0.028, the mixture is stirred for 40- 60 minutes, after which the remaining amount of filler is introduced for 4-8 minutes, then the final mixing is carried out for 10-30 minutes until the composition is completely homogenized (RF patent No. 2016019, IPC C 08 L 95/00, C 08 K 3/24 // С 08 L 95/00, 53:02, priority January 31, 1992, publ. July 15, 94).

The disadvantages of the known technical solution is the multi-stage and duration of the process, as well as the discharge form, which is inconvenient for transportation, storage and subsequent use - at ambient temperature, the composition is an unbricked mass.

The closest in technical essence and the achieved result to the proposed one is a bitumen composition comprising bitumen, styrene-butadiene thermoplastic elastomer and an adhesive additive, which is used as tall oil or the product of the interaction of tall oil and triethanolamine with a weight ratio of tall oil: triethanolamine (66-68) :( 32-34), in the following ratio of the components in the composition, wt.%: Bitumen 97.3-77, styrene-butadiene thermoplastic elastomer 2-16, the specified adhesive additive 0.7-7.0 (RF patent No. 2119513; C 08 L 95 / 00, publ. 09/27/98, BI No. 27).

The disadvantages of the known composition are:

the indeterminate composition of tall oil, depending on the type of natural raw materials (coniferous or deciduous species of wood) and production technology, the content of resin acids changes significantly, which determine mainly the adhesion properties of tall oil;

insufficiently effective mixture of tall oil or the product of the interaction of tall oil and triethanolamine with thermoplastic elastomers, which can lead to a violation of the dosages of the components when obtaining the polymer-bitumen composition;

the need for the introduction of the pre-heating stage of the used adhesive additives, which leads to additional consumption of steam or electricity.

The technical task of the invention is to reduce the dosage of the adhesive additive while maintaining the high adhesive properties of the bitumen composition, increasing its physico-mechanical characteristics, expanding the range of adhesive additives used.

The low molecular weight maleinized polybutadiene used in the present invention is similar in chemical nature to the polybutadiene block of thermoplastic elastomer, which contributes to the effective combination of these polymers and the introduction of maleic groups directly into the polymer chain of thermoplastic elastomer, enhancing the effect of the latter as a bitumen modifier.

The stated technical problem is solved in that the bitumen composition includes bitumen, a styrene-butadiene block copolymer and an adhesive additive - low molecular weight maleized polybutadiene with a content of bound maleic acid hydride 12-21 wt.%, Having a dynamic viscosity of 10-100 Pa · s at a temperature of 25 ° C, in the following ratio of components, wt.%

Bitumen 97.5-81.0

Styrene butadiene block copolymer 2.0-14.0

Specified adhesive additive 0.5-5.0

The stated technical problem is also solved by the fact that the bitumen composition additionally contains an organic nitrogen-containing compound with a tertiary nitrogen atom selected from the group: triethanolamine, polyethylene polyamine in a weight ratio of the specified adhesive additive: nitrogen-containing compound 1.0: 0.25-2.0.

It is known to use maleic anhydride to modify an unsaturated petroleum polymer resin, which is used as an emulsifier in the manufacture of an aqueous dispersion of tire rubber, which is part of the asphalt mix (AS USSR No. 975646, MKI C 04 V 13/30, publ. 23.11.82 g ., BI No. 43), but the use of maleic anhydride or maleized polymers as adhesive additives of polymer-bitumen mixtures is unknown from the literature.

The invention is supported by specific examples. When carrying out the invention, use is made of: as a styrene-butadiene block copolymer - butadiene-styrene thermoplastic elastomer of linear structure DST-30-01 according to TU 38.103267-99, butadiene-styrene thermoplastic elastomer of branched structure DST-30R-01 according to TU 38.40327-98; triethanolamine according to TU 6-04-573445-90; polyethylene polyamine according to TU 6-02-594-85.

Used as an adhesive additive, low molecular weight maleated polybutadiene PBNM obtained by the method described in RF patent No. 2153508.

Physico-mechanical properties of polymer-bitumen compositions are determined by the following methods:

Determination of the penetration depth of the needle - according to GOST 11501-78;

Determination of the softening temperature of the ring and ball according to GOST 11506-73;

Determination of the fragility temperature according to Fraas - according to GOST 11507-78;

Determination of elongation - according to GOST 11505-75;

Determination of elasticity - according to OST 218.010-98;

Determination of adhesive properties by adhesion to marble or sand according to GOST 11508-74.

Data on the composition of polymer-bitumen compositions are presented in table 1, by properties - in table 2.

Example 1. The rubber mixer is loaded with thermoelastoplast of linear structure DST-30R-01 in the form of crumbs in an amount of 2.0 kg, low molecular weight maleated polybutadiene in an amount of 0.5 kg, containing 12 wt.% Bound maleic anhydride and having a dynamic viscosity of 10 Pa · s . Polymers are mixed for 15-20 minutes at ambient temperature.

The resulting mixture in the form of loose crumb in the amount of 2.5 kg is fed into a container equipped with a paddle mixer and a circulation pump, from 97.5 kg of oil bitumen, heated to a temperature of 140-160 ° C, and mixing is carried out at a temperature of 150-160 ° C within 60 minutes until the polymer is completely dissolved. A sample of the obtained bitumen composition is subjected to standard tests.

Example 2. In a tank equipped with a paddle mixer and a circulation pump, 81.0 kg of petroleum road bitumen are loaded, heated to 140-160 ° C, 14 kg of branched thermoplastic elastomer DST-30R-01 are sequentially loaded in the form of a loose powder with a particle size of less than 2.5 mm and 5 kg of low molecular weight maleinized polybutadiene PBN-M with a content of bound maleic anhydride of 21%, having a dynamic viscosity at 25 ° C of 100 Pa · s. Stirring is carried out for 60 minutes at a temperature of 150-160 ° C until the polymer is completely dissolved. A sample of the obtained bitumen composition is tested according to standard methods.

Example 3. In a mixer equipped with a paddle mixer, load 17.5 kg of a 20% solution of thermoplastic elastomer linear structure DST-30-01 in a mixed solvent (ratio cyclohexane: nefras = 70:30 wt.%) And 1.5 kg of low molecular weight maleated polybutadiene PBN-M containing 17 wt.% Bound maleic anhydride and having a dynamic viscosity of 50 Pa · s. Stirring is carried out for 20-30 minutes at ambient temperature. Then, the resulting polymer mixture is isolated by water degassing and dried in an air dryer.

The resulting polymer mixture in the form of loose powder in an amount of 5 kg is fed into a container with 95 kg of oil bitumen, heated to a temperature of 140-160 ° C, and stirred at a temperature of 150-160 ° C for 60 minutes until completely dissolved. A sample of the composition is tested according to standard methods.

Example 4. The bitumen composition is obtained as in example 1, but 1 kg of triethanolamine (TEA) is additionally introduced into bitumen. The mass ratio of PBN-M: TEA = 1: 2.

Example 5. The bitumen composition is obtained as in example 2, but additionally introduced into bitumen polyethylene polyamine (PEPA) in an amount of 1.25 kg. The mass ratio of PBN-M: PEPA = 1: 0.25.

Example 6. The bitumen composition is obtained as in example 3, but additionally, triethanolamine is added to bitumen in an amount of 1.5 kg. The mass ratio of PBN-M: TEA = 1: 1.

Example 7. (According to the prototype).

In a mixer equipped with a paddle mixer, load 2 kg of branched DST-30R-01 thermoplastic elastomer in the form of a powder with a particle size of less than 2.3 mm and 0.7 kg of the TMT product heated to a temperature of 40-50 ° C obtained by reaction tall oil with triethanolamine. Mixing lead 15 minutes The obtained filled TEP DST-30R-01 TM in the form of bulk powder is fed into a container with oil road bitumen, taken in an amount of 97.3 kg and heated to a temperature of 140-160 ° C. Stirring is carried out for 20 minutes until the polymer is completely dissolved. A sample of the bitumen composition is analyzed by standard methods.

As the data of table 2 show, samples of polymer-bitumen compositions have high adhesion properties - the bitumen film is preserved on 100% of the surface of the mineral filler at lower dosages of the adhesive additive lower than in the prototype. The indicators of extensibility and elasticity of the softening temperature of the ring and ball of polymer-bitumen compositions obtained by the claimed technical solution is higher than similar indicators for compositions obtained by the known method. The highest values of these indicators are polymer-bitumen compositions containing maleated polybutadiene and a nitrogen-containing compound. The reaction between the latter provides increased elasticity and temperature resistance of the mixture.

Thus, the proposed technical solution expands the range of adhesive additives for polymer-bitumen compositions, allows you to slightly reduce the dosage of adhesive additives and obtain polymer-bitumen compositions with high physical and mechanical characteristics, and the technology for preparing the composition is simple and suggests any manufacturer-friendly options for mixing components without deterioration of the properties of the composition.

Claims (2)

1. A bituminous composition comprising bitumen, a block copolymer of butadiene with styrene and an adhesive additive, characterized in that the adhesive additive contains maleized low molecular weight polybutadiene with a content of bound maleated anhydride of 12-21 wt.% Having a dynamic viscosity at 25 ° C 10-100 Pa · s, in the following ratio of components, parts by weight: Bitumen 81.0 - 97.5 Block copolymer of butadiene with styrene 2.0 - 14.0 Specified adhesive additive 0.5 - 5.0 2. The bituminous composition according to claim 1, characterized in that it additionally contains an organic nitrogen-containing compound with a tertiary nitrogen atom selected from the group of triethanolamine, polyethylene polyamine, in a weight ratio of the specified adhesive additive: nitrogen-containing compound 1: 0.25 - 2.00, respectively .