RU2492386C1 - Polymer-containing adhesive primer - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: primer contains butadiene-nitrile rubber as thermoplastic, chlorinated polyvinyl chloride as a modifier, phenol-formaldehyde resin or epoxy-diane resin as an adhesive additive, ethyl acetate, toluene, isopropyl alcohol and acetone as solvents, as well as polyethylene polyamine and can contain EDOS plasticiser, bitumen and technical carbon. Components are in the following ratio, wt %: butadiene-nitrile rubber - 5.0-15.0; technical carbon - 0.0-0.5; ethyl acetate - 25.0-50.0; toluene - 5.0-25.0; polyethylene polyamine - 0.1-0.5; isopropyl alcohol -5.0-15.0; chlorinated polyvinyl chloride - 0.5-5.0; phenol-formaldehyde resin or epoxy-diane resin - 5.0-20.0; EDOS plasticiser - 0.0-5.0; acetone - 2.0-10.0; bitumen - 0.0-50.0.

EFFECT: improved protective properties of the primer due to high adhesion to the coated surface of the pipe, reliability of the coating due to high resistance to cathodic disbonding during use.

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Description

The invention relates to materials for protection against underground and atmospheric corrosion of the outer surface of trunk pipelines, pipes and pipe systems, in particular to polymer-containing compositions intended for use as primers in structures with insulating tape (film) and other materials.

Polymer-bitumen compositions in the form of mastics or primers are widely used in the above technical field.

Known mastic for protecting pipelines against corrosion, containing bitumen, cement, sand and granular material [US Patent 4196922, IPC F16L 58/12, 04/08/1980]. From the same patent, a method for making mastic is known, which consists in mixing bitumen and filler. Known mastic and the method of its manufacture allow to obtain mastic, which can be used only in the summer or in conditions where there is no decrease in temperature below 0 ° C. Thus, the scope of this kind of mastic is limited.

Known bitumen-polymer mastic for corrosion protection, which contains bitumen, thermoplastic elastomer and filler [Application UK 1538267, IPC F16L 58/12, 01/17/1979]. However, this mastic has insufficient adhesion to steel - the material from which various kinds of pipelines are most often made. In addition, this mastic does not provide the required reliability of protecting the pipeline from corrosion in conditions of significant temperature drops, including at negative ambient temperatures. As for the method of making mastic, it is quite laborious.

Patent RU 2300542 describes bitumen-polymer mastic, comprising: BNI-4 insulating bitumen - 51.0%, BN-70/30 construction bitumen - 40.7%, DST-30R-01 divinyl-styrene thermoplastic elastomer - 2.5%, plasticizer - Petroleum oil PN-6Sh - 3.5%, stearic acid T-18 - 0.8% and emulsifying surfactant auxiliary substance OP-10 - 1.5%.

Polymer-bitumen compositions are known including, among other components, styrene butadiene rubber, butyl rubber and low molecular weight polybutadiene rubber. For example, such compositions are described in patents RU 2307142, RU 2160293 and RU 2325586.

Primer - a type of primer used for preliminary surface preparation before applying any coating.

Known adhesive primer P-001, used for insulating adhesive tapes and made by dissolving butyl rubber with soot additives in solvents - gasoline and toluene ["Temporary process schedule for the production of primer P-001", Moscow, VNIIST, 1989.] The specified primer contains the following components : primer solid (butyl rubber and soot), rosin, white zinc, aluminum hydroxide, escort resin, Kalosha gasoline, toluene, phenosan, dialkyl phosphate and distilled amine. The production of adhesive primer P-001 includes the following steps. Production of rosin-based resin-33 intermediate, manufacture of an inhibitor and stabilizer, manufacture of a primer in a mixer and spill, and storage of finished products.

The disadvantages of the known adhesive primer are the multi-stage manufacturing process, insufficiently high adhesion to an insulated steel surface, low resistance to cathodic peeling of the coating over time.

Known adhesive primer PM-001BK, containing the following ingredients, parts by weight: butyl rubber 76-82; carbon black 20-26; rosin 68-72; zinc white 6-8; aluminum hydroxide 2.0-2.5; resin 20-70; Kalosh gasoline 550-570; toluene 210-220; phenosan 0.07-1.20; dialkyl phosphate 1.04-1.08; distilled amine 1.04-1.08; paraquinondioxime 0.5-3.0; isopropylene benzene hydroperoxide 0.5-5.0; ferrocene or diethylferrocene 0.02-0.20.

A method of manufacturing a primer - polymer primer PM-001 VK - consists in loading gasoline and toluene into the mixer for 15 minutes, feeding resin based on rosin, zinc oxide and aluminum hydroxide for 60 minutes at a temperature of 220 ° C while cooling with stirring, then, the loading of gasoline, stirred for 60 minutes, toluene for 50 minutes, and Escoret or Octofor-10F resin, or Edenkumaronova or styrolindenova, or phenol-formaldehyde, or aminophenol, or a mixture thereof, stirred for 60 mi, is repeated Simultaneously with the resin loaded solid substance coats in succession to the resin for 45 minutes, then loading solid repeated again for 80 minutes, followed by stirring for 150 minutes while cooling the mixture to a temperature not higher than 45 ° C. A separately prepared inhibitor from toluene, dialkyl phosphate, distilled amine, and phenosan is introduced into the mixer by stirring after loading the resin and stirred for 10 minutes, then modifying additives are introduced into the resulting mass, and a 10% solution of ferrocene or diethylferrocene in toluene obtained the mass is stirred for 15 minutes, then, with continued stirring, paraquinone dioxime is added, adding it in small portions with further mixing of the mixture for 60 minutes. In addition, it is possible to additionally introduce copper dihydride chloride in the form of a 10% solution in isopropanol into the obtained primer, after which the mixture is stirred for 60 minutes. As a solvent for the preparation of the primer, a solution of gasoline and toluene is used in an amount, parts by weight: gasoline 500-550; toluene 240-280; the volatile phase of gasoline 1500-1700 [RF Patent 2085802, 07.27.1997].

A disadvantage of the known invention is the relatively low adhesion to an insulated steel surface, low resistance to cathodic peeling of the coating over time.

The closest to the claimed invention in technical essence and the achieved result is insulating bitumen-polymer mastic for anti-corrosion protective coatings of underground pipelines, including bitumen, divinyl styrene thermoplastic elastomer, plasticizer, filler, petroleum resin, adhesive additive, modifier having the following component composition, wt.% : bitumen BND-60/90 8.5-90, bitumen BNI-4 1-20 or bitumen BN-70/30 1-90, divinyl styrene thermoplastic elastomer 1.5-5, plasticizer 1-5, filler 1-8, oil-polymer cm ol 2-8, adhesive additive 0.3-1.5, modifier 1-6 [RF Patent 2241897, publ. December 10, 2004].

A method of manufacturing a bitumen-polymer mastic according to the prototype includes mixing bitumen, thermoplastic elastomer, plasticizer and filler. The components are mixed as follows: first, a mixture of road and insulating bitumen or building bitumen is prepared, then this mixture is dehydrated by heating to a temperature of 160-170 ° C, a mixture of bitumen is fed into the mixer and plasticizer is added. The resulting mixture is stirred at a temperature of 165-175 ° C for 3.5 hours until the plasticizer is completely dissolved. Then a filler, for example rubber crumb, is added, and the resulting mixture is stirred for 35-35 minutes, an oil-polymer resin, a modifier, an adhesive additive and thermoplastic elastomer are added.

The authors of the claimed invention for the prototype was obtained and tested mastic. However, it was experimentally established that its adhesion properties and the indicator "coating peeling area at cathodic polarization" are relatively low. The adhesion of the tape to primed steel at 20 ° C according to the test results was 4.7 N / cm, the area of peeling of the coating at cathodic polarization at T 20 ° C - 6.1 cm ² .

The objective of the proposed technical solution is to develop a polymer adhesive adhesive primer that works in a construction with a PVC adhesive tape with high performance properties, improve the quality of corrosion protection of underground pipelines and increase the trouble-free service life of underground oil and gas pipelines.

The technical result when using the invention is to improve the protective properties of the primer by increasing adhesion to the coated surface of the pipeline, the reliability of the coating by increasing the resistance to cathodic peeling during operation.

The above technical result is achieved by using an adhesive polymer-containing primer, including thermoplastic elastomer, a modifier, an adhesive additive, namely, its feature is that it contains nitrile butadiene rubber as a thermoplastic elastomer, chlorinated polyvinyl chloride as a modifier, additives - phenol-formaldehyde or epoxy-resin, as solvents - ethyl acetate, toluene, isopropyl alcohol, acetone, in addition, contains um polyethylene polyamines and may contain a plasticizer EDOS, bitumen, technical carbon in the following ratio, wt.%:

Nitrile butadiene rubber 5.0-15.0 Technical carbon 0,0-0,5 Ethyl acetate 25.0-50.0 Toluene 5.0-25.0 Polyethylene polyamines 0.1-0.5 Isopropyl alcohol 5.0-15.0 Chlorinated Polyvinyl Chloride 0.5-5.0 Phenol formaldehyde or Epoxy resin 5.0-20.0 Plasticizer EDOS 0,0-5,0 Acetone 2.0-10.0 Bitumen 0,0-50,0

In the composition of the primer use:

- butadiene-nitrile rubber BNKS 33AMN according to TU 38.30313-2006,

- polyethylene polyamines according to TU 2413-214-00203312-2002;

- epoxy-diane resin ED-20 according to GOST 10587-84;

- EDOS plasticizer according to TU 2493-003-13004749-93;

- ethyl acetate according to GOST 8981-78;

- petroleum toluene in accordance with GOST 14710-78;

- technical isopropyl alcohol in accordance with GOST 9805-84;

- technical acetone in accordance with GOST 276884.

In addition to the listed components, the proposed adhesive coating may contain viscous road bitumen BND-60/90 in accordance with GOST 22245-90, construction bitumen BN-70/30 in accordance with GOST 6617-76, insulating bitumen BNI-4 or their mixtures in accordance with GOST 9812-74.

In the composition of the primer can be used and other brands of components that are not inferior in quality characteristics to the above.

The adhesive polymer-containing primer is prepared as follows. The calculated amount of solvents is loaded into the reactor with a stirring device according to the recipe format: ethyl acetate, toluene, isopropyl alcohol, acetone, EDOS plasticizer, and then the rest of the primer ingredients - PSX-LS resin, BNKS 33AMN rubber, polyethylene polyamines, technical epoxydianine resin ED-20, technical (song numbers 1-10 table 1). The mixture is stirred for 3-6 hours until all components are completely dissolved at room temperature. Bitumen, if necessary, is introduced until a viscosity is obtained within 20-60 s according to VZ-246 with a nozzle diameter of 4 mm.

The area of peeling of the coating at cathodic polarization at a temperature of 20 ° C and the adhesion of the tape to the primed steel is determined according to TU 2245-001-00203312-2003 and GOST R 51164-98 (Polyvinyl chloride adhesive tape).

The composition and test results of the primer are presented in table 1. Tests of the primer according to the claimed formulation showed good results, expressed in increased adhesion to the coated surface of the pipeline and in high resistance to cathodic peeling during operation. Examples of the composition and test results are shown in table 1.

Table 1 Name of components Patent Example Prototype one 2 3 four 5 6 7 8 9 10 Nitrile butadiene rubber, wt.% fifteen 5 10,4 6 12 9 17 10 7 5 Technical carbon mass.% 0.2 0.3 0 0.5 0.25 0.5 0 0.4 0.5 0 Ethyl acetate, wt.% 40 35 60 35 35 fifty 55 45 40 fifteen Toluene, wt.% fifteen 17 5 25 twenty 7 5 21 22 5 Polyethylene polyamines wt.% 0.5 0.1 - 0.25 - 0.3 0.2 0.5 - Urotropin, wt.% 0.3 - - 0.4 - 0.5 - 0.1 - 0.2

Isopropyl alcohol, wt.% 10 12 5 fifteen 12 5 7 9 10 5 Resin PSX-LS, wt.% 1,5 3 0.5 3,1 5 one 0.7 4.4 four 0.8 Phenol-formaldehyde resin, wt.% 10 twenty - - 5 - 12 - 10 ED-20, wt.% - - 9 5 - twenty - 5 12 - Plasticizer EDOS, wt.% 2 2.2 5 0 2,5 four one one 1,5 5 Acetone, wt.% 6 5 5 10 5 3 2 four 2,5 four Oil bitumen, wt.% - - - - - - - 10 25 fifty Name of indicator Analysis results Adhesion of the tape to steel during peeling at a temperature of 20 ± 3) ° C, N / cm 5 5,6 5.8 6.0 5,6 6.4 5.9 6.4 5.7 5.5 4.7 Peeling area of the coating at cathodic polarization at a temperature of 20 ° C, cm ² , no more 0.3 0.5 0.8 1,1 0.8 0.4 0.9 0.7 0.85 1,2 6.1

The quality indicators of the protective coating in the design with the tape PVC sticky with a primer, according to example composition No. 8 in table 1, are shown in Table 2.

table 2 Name of indicator Norm according to requirements Test result GOST R51164 TU 2245-00100203312-2003 1. Ribbon color - Blue black the black 2. The thickness of the tape, mm - 0.4 ± 0.05 0.43-0.45 3. The width of the tape, mm - 450 ± 2 450

4. Strength of the tape at break at a temperature of (20 ± 3) ° C, N / cm, not less fifty fifty 87 5. The relative elongation of the tape at break at a temperature of (20 ± 3) ° C,%, not less 80 80 85 6. Adhesion of the tape to steel during peeling at a temperature of (20 ± 3) ° C, N / cm, not less than 5,0 5,0 5,6 7. Stickiness, s, not less - 25 103 8. Fragility temperature ° C, not higher minus 20 minus 30 minus 30 9. Water absorption of the tape for 1000 hours at a temperature of (20 ± 3) ° C,%, not more than 0.5 0.5 0.38 10. The transition resistance of the coating in a 3% NaCl solution at a temperature of (20 ± 3) ° C, Ohm, not less - source 5 × 10 ⁶ 5 × 10 ⁶ 8.1 × 10 ¹⁰ -after 5 × 10 ⁵ 5 × 10 ⁵ 7.5 × 10 ¹⁰ 11. The area of peeling of the coating at cathodic polarization, cm ² , no more than temperature: 20 ± 3) ° C 10.0 10.0 0.8 40 ± 3) ° C, 10.0 - 1,2 12. Dielectric continuity. No breakdown at electric voltage, kV / mm, not less 5 - lack of breakdown 13. Mushroom resistance, score, no more 2 2 2

Claims (1)

Adhesive polymer-containing primer, including thermoplastic elastomer, modifier, adhesive additive, characterized in that it contains nitrile butadiene rubber as a thermoplastic elastomer, chlorinated polyvinyl chloride as a modifier, phenol-formaldehyde resin or epoxy solvent as an adhesive additive; ethyl acetate, toluene, isopropyl alcohol, acetone, in addition, contains polyethylene polyamines and may contain EDOS plasticizer, bitumen, technical carbon in the wake present component ratio, wt.%:
nitrile butadiene rubber 5.0-15.0 carbon technical 0,0-0,5 ethyl acetate 25.0-50.0 toluene 5.0-25.0 polyethylene polyamines 0.1-0.5 isopropyl alcohol 5.0-15.0 chlorinated polyvinyl chloride 0.5-5.0 phenol formaldehyde or epoxy resin 5.0-20.0 plasticizer EDOS 0,0-5,0 acetone 2.0-10.0 bitumen 0,0-50,0