RU2185402C2 - Polymer-bitumen composition and polymer-modifier production process - Google Patents

Abstract

FIELD: manufacture of building and road-building materials. SUBSTANCE: invention relates to improved bitumen-based materials for use in manufacture of road pavement and roofing waterproofing coatings. Composition is prepared from bitumen with softening temperature 60-110 C, %: lube fraction selective treatment extract, 19-40; and polymer-modifier, 1-12; prepared by thermal copolymerization of C8-C9 fraction and synthetic butadiene rubber (weight ratio from 80:20 to 95:5) or C8-C9 fraction, synthetic butadiene rubber, and sulfur (weight ratio from 83.5 : 15 : 1.5 to 94.5 : 5 : 0.5). Thermal copolymerization is conducted at 240-260 C for 5-10 h. Components are mixed at 150-200 C. EFFECT: improved consumer's properties. 4 cl, 4 tbl, 16 ex

Description

 The invention relates to the processing of heavy oil residues, namely, to obtain improved materials on a bitumen basis, and can be used in the manufacture of road, roofing, waterproofing coatings.

 To improve the operational properties of the latter, polymer bitumen compositions (PBC) are used on a bitumen basis with various polymer modifiers, as well as plasticizers, stabilizers and the like additives. The introduction of polymer additives into bitumen makes it possible to directionally control the structural and mechanical properties of the material. At the same time, PBC combines the qualities inherent in polymers (high elasticity, heat resistance, strength, frost resistance) and bitumen. The properties and structure of PBC are determined largely by the type of polymer and the dispersed structure of bitumen. The introduction of a plasticizer into the PBC (various hydrocarbon fractions) can improve the ductility and frost resistance of PBC, as well as the compatibility of polymers and bitumen.

 In (L. M. Gokhman, S. L. Gershkogen. The effect of multiple stretching on the properties of organic binders. KhTTM, 1999, 1, p. 36-39) there is information about the creation of PBC, consisting of road bitumen (grades BND-40 / 60, 60/90, 90/130), solvent-plasticizer (industrial oils), polymer-modifier (divinyl-styrene thermoplastic elastomer).

The disadvantages of the technical solution are:
the high cost of the polymer additive and the plasticizer solvent;
increased energy consumption in the manufacture of PBC;
the tendency of PBC to delaminate during storage.

 From (D. A. Rozental, L. S. Tabolin, V. A. Fedosova. Modification of the properties of bitumen with polymer additives. Thematic review. TsNIITEneftekhim, 1988, 6, p. 17, 18) there is a known method for producing PBC used for roofing road surfaces and consisting of bitumen and linear polymers (polyethylene, polypropylene).

The disadvantages of this technical solution include:
low indicators of PBC elongation;
poor elasticity of PBC.

 The closest in technical essence is the technical solution in which PBCs are proposed to be made from bitumen and a modifier polymer (oil-polymer resins obtained from unsaturated liquid products of hydrocarbon pyrolysis), described in (V.V. Leonenko, L.Yu. Novoselova, T .V. Petrenko, G. A. Safonov. Polymer Modifiers for Petroleum Bitumen from Liquid Pyrolysis Products. Oil Refining and Petrochemicals, 1997, 11, pp. 27-29).

Its disadvantages are:
low modifying ability of petroleum polymer resins;
low indicators of plasticity and elasticity of PBC;
low frost resistance of PBC.

 The objective of the invention is the development of a method for producing PBC with high performance properties using more affordable reagents (by-products), and the synthesis of an inexpensive polymer modifier for the manufacture of PBC.

The task is achieved by introducing into the peroxidized bitumen (softening temperature 60-110 ^o C) a plasticizer solvent (selective purification extract of residual oil fractions) and a modifier polymer based on the C ₈ -C ₉₊ fraction. The reagents used are most appropriate to use in the following ratio,% (mass.):
Polymer modifier - - 1-12;
Plasticizer solvent - - 19-40;
Bitumen - - Else
The main difference from the prototype is the following:
bitumen oxidized to a softening point of 60-110 ^o C is used as the main component;
the plasticizer solvent is an extract for the selective purification of residual oil fractions;
the modifier polymer is obtained by thermal copolymerization at a temperature of 240-260 ^{° C.} for 5-10 hours of the C ₈ -C ₉₊ fraction and synthetic butadiene rubber, or the C ₈ -C ₉₊ fraction, synthetic butadiene rubber and sulfur. The optimal ratios of the reagents are,% (mass.): 80-95: 5-20, or 83.5-94.5: 5-15: 0.5-1.5, respectively;
the mixing of the components of the PBC is carried out at a temperature of 150-200 ^o C.

The possibility of implementing the proposed technical solution is shown in the following examples:
Example 1
Synthesis of a polymer modifier
The feedstock for the polymer modifier is fr. C ₈ -C ₉₊ liquid products of pyrolysis of gasoline fractions in plants of the EP type (production of ethylene and propylene) without any additional processing (fractionation, etc.). Physico-chemical characteristics of the raw materials are presented in table 1. The specified fraction contains valuable monomers (styrene, α, β-methylstyrene, vinyl toluene, indene, dicyclopentadiene), which are the raw material for the polymer modifier.

The synthesis of the polymer modifier was carried out by thermal polymerization. A sample of Fr. was poured into the autoclave. C ₈ -C ₉₊ in an amount of 120-150 cm ³ , if necessary, calculated volumes of other additives were added. The mixture was well mixed, the autoclave was sealed, placed in a thermostat, heated to a temperature of 250 ± 2 ^o C, and kept for 5-20 hours. At the end of the thermostating process, the autoclave was cooled, the polymer solution in the hydrocarbons fr was quantitatively unloaded. C ₈ -C ₉₊ . Synthetic butadiene rubber of the SKD-PS brand (according to TU 38-103248-84, which is the product of the polymerization of butadiene in solution in the presence of complex catalysts and is a polymer with a mass fraction of cis-1, 4 units 87, was chosen as additives in the synthesis of polymer modifiers. -93% and iron not more than 0.004%) and sulfur. The composition of the raw materials and the synthesis conditions are given in table.2.

At the end of the synthesis, the reaction mixture was cooled, transferred to a flask and subjected to distillation in an oil bath heated to a temperature of 250 ^o C, under vacuum using an oil pump to a residual pressure of 20 mm RT. Art. to remove unreacted components of the original composition and solvent (if used). Xylene was used as a solvent for preliminary swelling and dissolution of rubber. In experiments without the introduction of rubber, the solvent was not used. The distillation under the indicated conditions was carried out to the last drop, after which the flask was cooled and the resin yield was determined.

 The obtained modifier polymers were used to prepare PBC.

Example 2
The method of obtaining PBC
PBC was obtained by mixing the components at a temperature of 150-200 ^o C to a homogeneous state for 1-4 hours. In the experiments used: road bitumen BND-90/130; bitumen, peroxidized to a softening temperature of 70-100 ^o C; plasticizer solvent (extract of selective purification of residual oil fractions); polymer modifier (samples of table 2).

 The characteristics of the solvent plasticizer are presented in table.3.

 The obtained PBCs were analyzed according to the following indicators: needle penetration depth (penetration) according to GOST 11501, softening temperature on the ring and ball according to GOST 11506, elongation according to GOST 11505, brittleness temperature according to GOST 11507 and elasticity according to clause 7.2.2 OST 218.010-98. The composition of the obtained PBC and their properties are given in table 4.

Analysis of the data given in table 4 shows:
1. PBC obtained by compounding (mixing) of road bitumen BND-90/130 and polymer modifier (samples 1-3 of table 2) according to the prototype (experiments 2-8 of table 4) have rather low heat resistance and ductility (at the softening temperature of 43-45 ^o C penetration was at 0 ^o C 34-44 • 0.1 mm and at 25 ^o C - 113-121 • 0.1 mm, ductility interval 64-69 ^o C), frost resistance (brittle temperature minus 20 - minus 25 ^o C) and elasticity (17-19%).

2. PBC, obtained on the basis of peroxidized bitumen, solvent-plasticizer and polymer-modifier (sample 7 of Table 2), in their properties significantly exceed the prototype (experiments 12, 13, 15 of Table 4). PBCs have higher ductility indicators (at a softening temperature of 44-48 ^o С, penetration at 0 ^o С is 56-74 • 0.1 mm and at 25 ^o С - 120-208 • 0.1 mm, the ductility interval 72-77 ^o C), frost resistance (brittle temperature minus 31 - minus 33 ^o C), elasticity (30-36%) and elasticity at 0 ^o C (10-18 versus 7.1-12 cm).

3. PBC, consisting of peroxidized bitumen, a plasticizer solvent and a polymer modifier (sample 5 of Table 2), also significantly surpass the prototype in their properties (experiment 11 of Table 4) and are similar to previous PBC (it differs only in much higher extensibility at 0 ^o C - 29 cm). PBC data can be used in the manufacture of improved road surfaces.

 4. PBC obtained by compounding peroxidized bitumen, solvent-plasticizer and polymer-modifier (samples 4, 8 of Table 2) surpass the prototype in terms of heat resistance, ductility, frost resistance and elasticity, but are inferior to it and the above-mentioned PBC in terms of extensibility (experiments 9, 10, 16 table 4). The obtained PBC can be used in the manufacture of improved roofing and waterproofing materials.

 Thus, a method for producing PBC with improved operational properties, as well as the composition of the raw materials and the conditions for the synthesis of the polymer modifier, were selected.

Claims (3)

1. A method of obtaining a polymer-bitumen composition based on bitumen, an extract for the selective purification of residual oil fractions, a polymer modifier, characterized in that the polymer obtained by thermal copolymerization of the C ₈ -C ₉ fraction and synthetic butadiene rubber in the ratio wt. %: (80-95): (5-20), or C ₈ -C ₉ fractions, synthetic butadiene rubber and sulfur in the ratio, wt. %: (83.5-94.5): (5-15): (0.5-1.5), bitumen with a softening point of 60-110 ^o C is used as bitumen in the following ratio of components, wt. %:
The above polymer modifier - 1 - 12
Extract of selective purification of residual oil fractions - 19 - 40
Above Bitumen - Else
2. The method according to p. 1, characterized in that the mixing of the components is carried out at a temperature of 150-200 ^o C. 3. A method of producing a polymer modifier by thermal copolymerization of the components specified in paragraph 1, at a temperature of 240-260 ^o C.  4. The method according to p. 3, characterized in that the thermal copolymerization is carried out for 5-10 hours

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