RU2292369C2 - Polymeric composition - Google Patents

Abstract

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a polymeric composition designated for anti-corrosive protection of petroleum-gas-pipelines, metal constructions, equipment used in different techniques and as impregnating compositions, hermetic agents and others. The composition comprises the following content mas. p. p.: epoxy diane resin, 100; epoxy aliphatic resin. 24-60; oligoether cyclocarbonates with the mass part of cyclocarbonate groups from 18 to 29, 1-30; froth breaker, 0.5-2.5; coal resin, 0.75-2.0; ether epoxide "Penta-539", 0.5-8; filling agent, 1.5-8.5, and amine hardening agent, 40-85. As an epoxy aliphatic resin the invention uses oligoether epoxides with the content of epoxy group from 7.5% to 28%. As froth breaker the invention uses silicone froth breaker or siloxane resin, or an acrylic froth breaker. Ether epoxide "Penta-539" represents product of esterification of epoxy resin and saturated carboxylic acid. As amine hardening agent the invention uses a mixture of product (A) that is prepared by interaction of aromatic amine (B) with salicylic acid (C) and a plasticizing agent (D) representing an oxygen-containing compound from polyol group and taken in the ratio B:C:D = (73:2:25)-(42:8:50), respectively, and an organosilicon amine (E) in the ratio A:E = (99:1)-(1:99). The invention provides enhancing the rupture strength value, relative rupture elongation value, adhesion to steel, water resistance, to reduce water absorption being both in the parent and after prolonged effect of water state, and to reduce the viscosity value without using solvents also.

EFFECT: improved, enhanced and valuable properties of composition.

2 tbl, 9 ex

Description

The invention relates to polymer compositions based on epoxy resins and is intended for use mainly as anti-corrosion protection of oil and gas products, metal structures, equipment in various fields of technology, as well as as impregnating compositions, sealants, etc.

Polymer compositions for coatings of a new generation should have not only high protective properties for a long service life (at least 30 years), but also be technologically advanced and safe in preparation and use in both factory and route application conditions.

The most important indicators of the polymer composition, determining for each specific condition the operational parameters of the coating and its service life (durability) in accordance with GOST R 51164-98 "Steel main pipelines. General requirements for corrosion protection", are high physical and mechanical properties, before total tensile strength, elongation at break, adhesion to metal (steel), high water resistance and low water absorption of the film both in the initial state and after a long (1000 hour) effect Water Ia.

To calculate the durability of the anti-corrosion coating (AP), an indicator of water absorption for a different period of exposure to water is used as an evaluation criterion.

According to the three-point system of the reference manual by G. Ya. Vorobieva “Corrosion resistance of materials in aggressive environments of chemical industries” (p. 76-77), the period of time for which the film's water absorption reaches 8% is taken as the durability of the AP.

When developing the proposed polymer composition, the authors used more stringent requirements of the above GOST R 51164-98, according to which the durability of the AP is taken to be the period of time for which the water absorption of the film reaches 5%, and the predicted life of the AP in this case is 42 years.

Known polymer composition (AS RF No. 1719411, class C 08 L 63/00 of 03/15/92), including an epoxy resin, a modifying agent - epoxidized waste oxypropylene glycol, oligoester-epoxide, amine-containing hardener and λ-phenylnaphthalamine-1.

The disadvantages of this composition are the relatively low tensile strength, elongation, water resistance, high water absorption and significant instability of properties in connection with the use of raw waste in its manufacture.

Known composition for coatings (US Pat. RF No. 22219211, class C 09 D 163/2 dated 12/20/2003) containing an epoxy Dianova resin, a modifier is an epoxyurethane oligomer, a solvent, a polyethylsiloxane liquid, an amine hardener is a product of the interaction of γ-aminopropyltriethoxysilane and diphenylsilanediol .

The disadvantages of the composition are relatively low tensile strength at break, elongation, water resistance and high water absorption. In addition, the composition has an increased environmental hazard both in its manufacture and in use in connection with the use of toluene diisocyanate (hazard class 2) as a raw material and a solvent — a mixture of toluene and butyl cellosolve.

Known polymer composition is a sealant (AS RF No. 1199784, class C 09 K 3/10 dated 12/23/85), including an epoxy resin, a modifier - polyoxypropylenetriol tricyclic carbonate, carbon black, aerosil, an amine hardener - hydroxybenzyltriethylenetetramine.

The disadvantages of this technical solution are low tensile strength at break and adhesion to steel.

The closest technical solution to the proposed one is an epoxy composition (US Pat. RF No. 2186801, class C 08 L 63/00 dated 08/10/2002) containing the resin part — a mixture of epoxy diane and aliphatic resins, antifoam, modified urea-formaldehyde condensate, dye , filler and amine hardener - a mixture of reaction products based on aromatic and aliphatic di - or polyamines.

The disadvantages of this composition are the relatively low rates of tensile strength, elongation, water resistance and high rates of water absorption.

In addition, the composition is difficult to prepare (the hardener is prepared in parallel in two separate reactors under the strictest temperature conditions due to the high exothermicity of the processes for obtaining reaction products based on aromatic and especially aliphatic amines).

As for the use of the composition, it is difficult to apply it to the surface of the pipes in the most advanced way - by spraying - both in the factory and in the route conditions due to the increased viscosity due to the high filler content (up to 200 parts by weight).

The objective of the present invention is to provide a polymer composition that provides a long service life (~ 40 years) of protected metal structures, as well as the possibility of technologically and safely applying it to the surface of metal structures by all known methods, including the most advanced - spraying.

The technical result from the use of the invention is to increase the physicomechanical properties of the polymer composition: tensile strength, elongation at break, adhesion to steel, increased water resistance and reduced water absorption both in the initial state and after prolonged exposure to water, as well as in reducing viscosity without the use of solvents.

This result is achieved by the fact that the polymer composition for anticorrosion coating, comprising a mixture of epoxy diane and aliphatic resins, antifoam, filler and amine hardener, as an epoxy aliphatic resin, the composition contains oligoester epoxides with an epoxy content of 7.5 to 28%, as an antifoam silicone antifoam, or siloxane resin, or acrylic antifoam, as an amine hardener - a mixture of the product (A) obtained by reacting an aromatic amine (B), salicylo acid (C) and plasticizer (G), which is an oxygen-containing compound from the group of polyols, with a ratio of B: C: D from 73: 2: 25 to 42: 8: 50, and an organosilicon amine (D) with a ratio of A: D from 99: 1 to 1:99, and additionally contains oligoestercyclocarbonates with a mass fraction of cyclocarbonate groups from 18 to 29, coal tar, ether epoxide, which is the product of the esterification of epoxy resin and saturated carboxylic acid - Penta-539 - with the following components, wt. hours:

Epoxy Dianova Resin one hundred The above oligoester epoxides 24-60 The above oligoestercyclocarbonates 1-30 The above antifoam 0.5-2.5 Coal tar 0.75-2.0 Ether Pentoxide-539 0.5-8 Filler 1,5-8,5 The above amine hardener 40-85

The invention is illustrated by examples.

Example 1

In a reactor equipped with a mechanical stirrer, heating and cooling, 100 wt.h. preheated to 55-60 ° C epoxy dianovoy resin brand ED-20 (GOST 10587-90), 10 wt.h. diethylene glycol diglycidyl ether with an epoxy content of 28% (technical product DEG-1 TU 2225-027-002203306-97), 23 parts by weight polygropylene glycol diglycidyl ether with an epoxy content of 7.5 (technical product Laproxide-702 TU 2226-335-10488057-97) and 20 parts by weight tricyclic carbonate oligooxypropylene triol with a content of cyclocarbonate groups 18 (technical product Laprolat-803 TU 2226-303-10488057-94), 3 parts by weight octoxypropylene glycol monocyclocarbonate with a content of cyclocarbonate groups 29 (technical product Laprolat-301 TU 2226-303-10488057-94), 5.7 parts by weight preheated to 75 ° C ether epoxide (technical product Penta-539 TU 2225-003-40245042), 1.6 wt.h. BYK-A530 silicone defoamer (certificate B / EN 102043.IB), 1.2 parts by weight coal tar (TU 14-7-100-89) and 1.5 wt.h. Aerosil brand A-300 (GOST 14922-77).

The mixture of the introduced components is mixed for 25-30 minutes until a homogeneous dark color is obtained, after which the finished resin part of the polymer composition is poured into containers - buckets with an airtight lid and stored in storage conditions for 1 year.

In a similar reactor, a hardener is prepared: 60 parts by weight are charged with constant stirring. pre-molten aromatic amine brand Polyamine-B (TU 113-38-67-90) (B), 4 parts by weight salicylic acid (GOST 627-70) (B), previously dissolved at 70 ° C in 36 parts by weight plasticizer - a mixture of dioxane alcohols and their high boiling point esters of the EDOS Plasticizer brand (GOST 2493-003-13004749-93) (G) with a ratio of components B: C: D equal to 60: 4: 36, the temperature in the reactor is maintained at 70-80 ° C, the mixture is stirred for 15 min, then this finished reaction product (A) is cooled to a temperature of 40 ° C and mixed with an organosilicon amine - γ-aminopropyltriethoxysilane (technical product AGM-9, TU 6-02-724-77) ( D) in the ratio A: D, equal to 50:50, the mixture is stirred for 10-12 minutes, cooled to room temperature.

The hardener thus obtained is packaged in metal containers — buckets with a sealed lid, which are stored in storage conditions for 1 year.

The resin part of the polymer composition and hardener are supplied to the consumer as a whole.

The mixture of the resin part and the hardener is carried out immediately before use - as in example 1 - by mixing 170 parts by weight resin parts and 65 parts by weight hardener in a container with a stirrer for 5 min, followed by application on metal surfaces with a spray gun.

The use of the composition according to examples 2-9 is carried out analogously to example 1, but with the ratio of the components listed in table 1.

According to examples 2 and 4, the composition is applied with a roller and brush, respectively.

The properties of the polymer composition according to examples 1-9 in comparison with the known are presented in table 2.

As can be seen from table 2, the proposed polymer composition has significantly higher performance properties in comparison with the known, namely increased indicators:

Tensile strength 1.2-2 times Elongation at Break 1.4-3 times Adhesion to steel 12-37% Water resistant 2-5.6 times Water absorption (decrease) in the initial state 1.5-3 times after a long (1000 h) water exposure 1.8-3 times Viscosity reduction without application solvents 2.3 times

The set of achieved indicators of the proposed polymer composition according to properties that determine the quality and durability of the protective coating, allows you to ensure the service life of the coating, calculated according to the most stringent standards, of 42 years and above, which does not provide well-known technical solutions.

Claims (1)

A polymer composition for anticorrosion coating, comprising a mixture of epoxy diane and aliphatic resins, an antifoam, a filler and an amine hardener, characterized in that the composition contains oligoester epoxides with an epoxy content of 7.5 to 28% as an antifoam, and antifoam silicone or siloxane resin or acrylic antifoam, as an amine hardener - a mixture of the product (A) obtained by reacting an aromatic amine (B) with salicylic acid (C) and a plasticizer (G), which is an oxygen-containing compound from the group of polyols, with a ratio of B: C: G = 73: 2: 25 ÷ 42: 8: 50, and an organosilicon amine (D) with a ratio of A: D = 99 : 1 ÷ 1: 99, and additionally oligoestercyclocarbonates with a mass fraction of cyclocarbonate groups from 18 to 29, coal tar, ether epoxide, which is the product of the esterification of epoxy resin and saturated carboxylic acid - Penta-539, with the following components, wt.h .: Epoxy Dianova Resin one hundred The above oligoester epoxides 24-60 The above oligoestercyclocarbonates 1-30 The above antifoam 0.5-2.5 Coal tar 0.75-2.0 Ether Pentoxide-539 0.5-8 Filler 1,5-8,5 The above amine hardener 40-85