RU2501820C1 - Butadiene-nitrile rubber based rubber mixture - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to rubber industry, particularly production of rubber mixtures used to make articles for various purposes, including packer elements (rubber sealers in oil or gas wells), used in production of packer and anchor equipment. The rubber mixture contains the following ingredients, pts.wt (per 100.00 pts.wt rubber): paraffinate butadiene-nitrile rubber BNKS-40 AMN 100.00, with weight content of acrylonitrile of up to 41%, dicumyl peroxide (Perkadox BC-FF) - 3.0-4.0, vulcanisation coagent Deltagran HVA 2 70 GT - 1.0-3.0, zinc oxide - 3.0-5.0, antioxidant Irganox 1010 - 2.0-3.0, oligoester acrylates TGM-3 - 6.0-10.0, active technical carbon H-220 - 50.0-70.0, technical carbon T-900 - 10.0-30.0, dispersant zincolet BB 222 1.0-3.0, anti-scorch Santogard PVI - 0.3-0.5.

EFFECT: invention improves physical and mechanical properties of the rubber mixture, processability thereof by high-pressure casting, with improved elastic-strength properties, high aggressive heat resistance and low relative compression set, operating capacity under high loads.

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Description

The invention relates to the rubber industry, in particular to the production of rubber compounds used for the manufacture of products for various purposes, including packing elements (rubber seals in oil or gas wells) used in the production of packer-anchor equipment. The rubber mixture includes the following ingredients, parts by weight (per 100.00 parts by weight of rubber): butadiene-nitrile paraffinate rubber of the BNKS-40 AMN grade - 100.00, with a mass fraction of acrylic acid nitrile (NAC) up to 41 wt.%, dicumyl peroxide - 4.00, coagent vulcanization - 2.00, zinc oxide - 3.00, aging inhibitor - 3.00, three (oxyethylene) - α, ω-dimethacrylate - 6.00, active carbon black H-220 (H 245) - 60.00, T-900 - 20.00, a dispersant of fillers in a rubber matrix - 2.00, a moderator of premature vulcanization - 0.30.

The invention relates to the development of rubber compounding with high adaptability in the manufacture and processing. The developed formulation can be used in the preparation of vulcanizates with increased tensile strength, high resistance to aggressive media (oil, gas, hydrogen sulfide, weak acids and alkalis) at high temperatures (up to 125 ° C) and low relative residual compressive strain.

Known rubber mixture based on nitrile butadiene rubber comprising zinc oxide, rosin, chalk, carbon black, I-8A oil, dibutyl phthalate. It additionally contains tetramethylthiuram disulfide, N, N-dithiodimorpholine, N-cyclohexylbenzothiazole sulfenamide, N-phenylnaphthylamine, N-isopril N-phenylphenylenediamine in the following ratio of ingredients, parts by weight: butadiene-nitrile rubber 100.00, 5.00 oxide, oxide - 5.00, chalk - 25.00, carbon black P-701 - 75.00, I-8A oil - 5.00, dibutyl phthalate - 10.00 tetramethylthiuramdisulfide - 1.50, N, N-dithiodimorpholine - 2.00 , N-cyclohexylbenzothiazole sulfenamide - 2.20, N-phenylnaphthylamine - 21.50, N-isopril N-phenylphenylenediamine - 1.4-1.00, (RU 2232172 2002)

Also known is a rubber mixture based on nitrile butadiene rubber comprising zinc oxide, sulfur, carbon black, dibutyl phthalate. It additionally contains N, N′-diphenylguanidine, di- (2-benzothiazolyl) disulfide, aldol-α-naphthylamine, N- (4-hydroxyphenyl) naphthylamine-2, N- (1,3-dimethylbutyl) -N′-phenylenediamine -1.4, stearic acid, ultrafine diamond-containing powder in the following ratio of ingredients, parts by weight: butadiene-nitrile rubber - 100.00, zinc oxide - 7.40-7.60, sulfur - 2.45-2.65, carbon black P803-128-132, dibutyl phthalate 18.0-22.0, N, N′-diphenylguanidine 0.20-0.30, di- (2-benzothiazolyl) disulfide 2.60-2.80, aldol-α-naphthylamine - 3.80-4.20, N- (4-hydroxyphenyl) naphthylamine-2 - 0.90-1.10, N- (1,3-dimethylbutyl) -N '-Phenylenediamine-1.4 - 0.80-1.20, stearic acid - 0.80-0.20, dibutyl phthalate - 18.0-22.0, ultrafine diamond-containing powder - 0.1-1.0, described in patent RU 2129132 1996, which is selected by the number of matching features and technical nature as the closest analogue to the proposed composition.

When creating the invention, the task was to obtain a rubber mixture with improved physical and mechanical properties, technologically advanced during injection molding with increased elastic-strength properties, high heat-aggressive resistance and reduced relative residual deformation of compression, operable at high static loads in the temperature range from 100 to 130 ° C.

The task is achieved by selecting the appropriate ingredients in a certain ratio based on paraffinic nitrile butadiene rubber. The rubber mixture consists, parts by weight:

Butadiene-nitrile paraffinic rubber

brands BNKS-40 AMN - 100.00;

Dicumyl peroxide (Percadox BC-FF) - 3.5 ± 0.5;

Vulcanization coagent

Deltagran HVA 2 70 GT

(N, N-m-phenylene-bismaleimide) - 2.0 ± 1.0;

Zinc oxide - 4.0 ± 1.0;

Three (hydroxyethylene) - α, ω-dimethacrylate

(Oligoester acrylate TGM-3) - 8.0 ± 2.0;

Carbon black N 220 - 60.0 ± 10.0;

Carbon black T 900 - 20.0 ± 10.0;

Dispersant (Zinclet BB 222) - 2.0 ± 1.0

Antioxidant (Irganox 1010) - 2.5 ± 0.5

Anti-scorching (Santogard PVI) - 0.4 ± 0.1.

A new is the combination of well-known ingredients used in the rubber industry and their specific quantitative ratio, which allows to obtain a technical result: resistance to non-polar and polar solvents (oil, gas, water, inhibitors, alkali and acid solutions), heat resistance, since during operation aging of the packing element at high ambient temperatures during one cycle of the technological operation for testing the formation.

According to the applicant, this rubber compound is unknown and it can be concluded that the invention meets the condition of patentability for novelty.

Since the claimed combination of essential features exhibits new properties that make it possible to obtain a change in the quantitative measure of the result, namely, an improvement in the physico-mechanical properties of rubber compared to the known rubber, we can conclude that the invention meets the patentability condition "inventive step".

Obtaining the inventive rubber compound is carried out under industrial conditions on a mixing roller in two stages in the following sequence:

1. Make uterine rubber mixture for 100.00 parts by weight rubber: paraffinic butadiene-nitrile rubber brand BNKS-40 AMN - 100.00; Zinc oxide - 3.00; Ether of 3,5-di-tert-butyl-4-hydroxyphenyl-propinic acid and pentaerythritol (Irganox 1010) - 3.00; A mixture of high molecular weight aliphatic fatty acids and esters (Zinclet BB 222) 2,00; Oligoester acrylate TGM-3 (three (hydroxyethylene) -α, ω-dimethacrylate) - 6.00; anti-scorching Santogard PVI - 0.30.

The mode and sequence of input of ingredients into the rubber matrix:

1. Dissolution and plasticization of BNKS-40AMN with a gap between the rolls of not more than 2 mm for 5 minutes;

2. Input of zinc oxide, Irganox 1010 with a gap between the rolls of 3-4 mm for 4 minutes;

3. Enter ½ carbon black H 220, Santogard PVI with a gap between the rolls of 4-5 mm for 5 minutes;

4. Enter the rest of the carbon black N 220 and oligoester acrylate TGM-3 with a gap between the rolls of 4-5 mm for 5 minutes;

5. The introduction of zinc oxide BB 222 with a gap between the rolls of 4-5 mm for 3 minutes;

6. Increase the gap between the rolls to 6 mm and cut the rubber compound from the roll for 2 minutes.

2. Make a rubber mixture of the following composition (mass, hours): uterine rubber mixture 100.00; Percadox BC-FF -2.27; Carbon black T 900 - 11.34; Deltagran HVA 2 70 GT - 1.15.

The mode and sequence of introducing ingredients into the uterine rubber mixture:

1. Dissolution of the uterine rubber mixture with a gap between the rolls of up to 3 mm for 5 minutes;

2. Enter ½ carbon black T 900 with a gap between the rolls of 4-5 mm for 5 minutes;

3. Reducing the gap between the rollers up to 3 mm, removing the rubber compound on the roller tray and cooling for 8 minutes;

4. Loading the rubber mixture onto the rollers, planting it on the roll, introducing Percadox BC-FF and Deltagran HVA 270 GT with a gap between the rollers of 4-5 mm for 5 minutes;

5. A cut of the rubber mixture from the roll with a gap between the rolls of not more than 6 mm for 2 minutes

Cooling the masterbatch and rubber mixtures, after manufacture, in running water to room temperature.

Samples for determining the physical and mechanical properties of the rubber mixture were prepared according to the standards accepted for the rubber industry.

The main materials:

- Rubber butadiene-nitrile paraffinate brand BNKS-40 AMN (TU 38.30313-2006);

- Zinc oxide (GOST 202-84);

- Carbon black N 220 and T 900 (GOST 7885-86);

- Oligoester acrylate (TGM-3) (TU 2226-065-05761-643-2003);

- Percadox BC-FF (Akzo Nobel company);

- Irganox 1010 (company Ciba-Geigy, Switzerland)

- Deltagran HVA 2 70 GT (Deltagran HVA 2 70 GE - Dunlop company)

- Santogard PVI (Santgard PVI, Monsanto, USA);

- Zincolet BB 222 (Zincolet BB 222 - company DBH Osthandels Geselyiaft mbH).

Comparative technical characteristics of the rubber compound - prototype (patent RU 2129132 1996) and the new rubber compounding according to the application for the invention:

The name of indicators Famous rubber compound The rubber composition according to the invention Control methods Conditional tensile strength, MPa, not less 14.9-16.2 20,0 GOST 270-75 Elongation at break,%, not less than 257.0-280 one hundred GOST 270-75 Shore A hardness in units Shore a 79.0-82.0 85.0-95.0 GOST 263-75 Tear, N / mm, not less - 50,0 GOST 262-79 Change in indicators after exposure to standard liquid SZHR-3 (125 ° C × 24 hours),%, not more than - conditional strength - -10 GOST 270-75 - elongation -40 GOST 9.030-74 Mass change in I + T (7: 3),% no more +10 GOST 9.030-74 Relative residual deformation (ODS), (125 ° C × 24 h), no more 40.0-43.0 fifteen GOST 9.029-74

An analysis of the data in the table shows that the new rubber compounding has the best results for all important indicators: conditional tensile strength, change in parameters after exposure to aggressive media at elevated temperatures, weight change after exposure to a mixture of isoctane and toluene in a ratio of 7: 3 and SLM.

An activating system has been created that takes into account the interaction between the components of the composition from a combination of multi-purpose ingredients with multifunctional effects, which allows optimizing the technological and elastic-strength properties of vulcanizates. The vulcanization system, which includes the Percadox BC-FF group, the Deltagran HVA 2 70 GT vulcanization coagent and zinc oxide, has a high activating ability, the interaction of Percadox BC-FF with the polymerization oligoester acrylate TGM-3 contributes to the improvement of the vulcanization network. The use of Percadox BC-FF brand benzoyl peroxide and Deltagran HVA 270 GT vulcanization coagent in a 2: 1 ratio and temporary plasticizer (at the processing stage) of TGM-3 oligoester acrylate can purposefully improve the molding properties of the rubber compound. Highly active carbon black N 220 with high dispersion indices (particle size 20-25 nm) and structure improves elastic-strength indices, which give the rubber compound high wear resistance, tear and tear resistance. Low-active carbon black T 900 with a low dispersion index (particle size 08-13 nm) improves the processability of the rubber compound (formability, sprinkling, calendaring). A mixture of high molecular weight aliphatic and esters in a certain ratio contained in the product Zinclet BB 222 promotes a more uniform dispersion of fillers (Tekhuglerod N 220 and T 900), allows to increase the specific surface area of zinc oxide and reduce the energy consumption for mixing on rollers. Zincolet BB 222 is an ingredient of multifunctional action; it acts as a technological additive, dispersant of ingredients, and emollient. The use of phenolic antioxidant Irganox 1010 made it possible to increase the thermal aggressiveness of rubber and optimize Percadox BC-FF consumption. In view of the foregoing, in the applicant's opinion, the invention meets the patentability condition “industrial applicability”.

Claims (1)

A rubber mixture based on nitrile butadiene rubber, including zinc oxide, carbon black, vulcanizing agents and processing aids, characterized in that it contains BNX-40 AMN rubber as a base, carbon black of grades N 220 and T900 as a filler, as vulcanizing agents and technological additives percadox BC-FF, oligoester acrylate TGM-3, Irganox 1010, deltagran HVA 2 70 GT, zinc-oxide BB 222 and Santogard PVI in the following ratio of ingredients, parts by weight:
Rubber butadiene-nitrile brand BNKS - 40 AMN 100.0 Percadox BC-FF 3.0-4.0 Zinc oxide 3.0-5.0 Carbon black N 220 50.0-70.0 Carbon black T 900 10.0-30.0 Oligoester acrylate TGM-3 6.0-10.0 Irganox 1010 2.0-3.0 Zincolet BB 222 1.0-3.0 Santogard PVI 0.3-0.5