CN112094446A - Formula and preparation method of environment-friendly rubber layer sizing material for steel wire reinforced rubber hose - Google Patents

Abstract

The application discloses a formula of an environment-friendly steel wire reinforced rubber hose rubber layer rubber material and a preparation method of the rubber layer rubber material, wherein the formula of the rubber layer rubber material comprises the following components in parts by weight: 80-100 parts of nitrile butadiene rubber, 0-20 parts of solution-polymerized styrene butadiene rubber, 5-10 parts of zinc oxide, 5-10 parts of magnesium oxide, 1-2 parts of stearic acid, 3-5 parts of ferric oxide, 2-5 parts of an anti-aging agent, 20-40 parts of nano silicon dioxide, 2-4 parts of a sulfur carrying agent, 40-60 parts of fast extrusion carbon black, 40-60 parts of active nano calcium carbonate, 10-20 parts of a plasticizer, 6-10 parts of an adhesive, 1-2 parts of insoluble sulfur and 1-2 parts of an accelerator.

Description

Formula and preparation method of environment-friendly rubber layer sizing material for steel wire reinforced rubber hose

Technical Field

The application relates to a formula of an environment-friendly steel wire reinforced rubber hose rubber layer rubber material and a preparation method of the rubber layer rubber material, and belongs to the technical field of rubber manufacturing.

Background

At present, the steel wire reinforced rubber hose industry in China is developed rapidly, the yield accounts for 50 percent of the whole world, the annual output value is about 100 million yuan, and the steel wire reinforced rubber hose is a key system element of various engineering machinery. Wherein, the rubber material of the middle rubber layer plays a key role in the overall performance of the hose, while the research reports on the rubber material of the middle rubber layer in China are few, and most enterprises continue to produce the rubber hose by using old material compositions. That is, the raw rubber is mainly nitrile rubber with high acrylonitrile content, and a small amount of chloroprene rubber or styrene butadiene rubber, natural rubber, rubber-plastic alloy, high styrene and the like are used. And a high-sulfur low-acceleration vulcanization system, a metacresol system or a cobalt salt system and an inorganic filler or carbon black reinforcing filling system are adopted. And an anti-aging agent, tackifying resin, a plasticizer and the like are added. The vulcanization performance of the rubber compound is basically medium hardness (60A-70A), high elongation at break (more than 400%), high steel wire extraction (more than 100N/piece), low Mooney viscosity (ML1+ 4100 ℃ below 65%), 100% stress at definite elongation (less than 3 MPa), high compression set (more than 65%) and poor heat aging performance.

The rubber layer performance of the steel wire reinforced rubber hose is required to be improved, and the rubber hose has excellent adhesive performance with reinforced steel wires, good fluidity, higher stress at definite elongation (more than 4 MPa), lower compression set (less than 50%), and better heat resistance (tensile strength change rate +/-25%, elongation at break change rate 45%). Thereby ensuring that the steel wire reinforced rubber hose has good pressure resistance and higher pulse performance.

Therefore, the rubber layer sizing material of the steel wire reinforced rubber hose in China has the main problems that: low hardness, high productivity at break, low stress at 100% elongation, high permanent compression set and poor thermal ageing properties. The rigidity of the rubber material of the middle rubber layer is low, the fatigue deformation is large, the separation layer, the crack and the leakage of the hose are easily caused, and meanwhile, the powder is greatly raised in the production process, the smell is large, and the environmental protection requirement and the industrial discharge standard are not met.

Disclosure of Invention

According to a first aspect of the application, a formula of a glue layer sizing material for an environment-friendly steel wire reinforced rubber hose is provided, which is characterized in that the formula of the glue layer sizing material comprises the following components in parts by weight: 80-100 parts of nitrile butadiene rubber, 0-20 parts of solution-polymerized styrene butadiene rubber, 5-10 parts of zinc oxide, 5-10 parts of magnesium oxide, 1-2 parts of stearic acid, 3-5 parts of ferric oxide, 2-5 parts of an anti-aging agent, 20-40 parts of nano silicon dioxide, 2-4 parts of a sulfur carrying agent, 40-60 parts of fast extrusion carbon black, 40-60 parts of active nano calcium carbonate, 10-20 parts of a plasticizer, 6-10 parts of an adhesive, 1-2 parts of insoluble sulfur and 1-2 parts of an accelerator.

Optionally, the nitrile rubber is nitrile rubber NBR 1051.

Optionally, the solution-polymerized styrene-butadiene rubber is solution-polymerized styrene-butadiene rubber SSBR 1040.

Optionally, the fast extruding carbon black is fast extruding carbon black N550.

Optionally, the insoluble sulfur IS-60.

Optionally, the anti-aging agent is tmq (rd) and/or MB;

preferably, the formulation comprises 1-3 parts by weight of TMQ (RD); the formula comprises 1-2 parts of MB by weight.

Optionally, the sulfur carrier is CLD.

Optionally, the plasticizer is TP-95.

Optionally, the binder is binder LG-80.

Optionally, the accelerator is TBBS.

According to a second aspect of the present application, there is provided a method for preparing an environmentally friendly rubber hose rubber layer compound by using the formulation of the first aspect of the present application, wherein the method comprises the following steps:

step 1): plasticating in an internal mixer, adding nitrile rubber and solution polymerized butadiene styrene rubber into the internal mixer, controlling the rotating speed of the internal mixer to be 30-35 r/m, and carrying out internal mixing for 3-5 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 25-30 r/min, lifting a top bolt, adding zinc oxide, magnesium oxide, stearic acid, an anti-aging agent TMQ (RD), an anti-aging agent MB and 1/2 to quickly extrude carbon black, and internally mixing for 2-3 minutes;

step 3): adding the rest fast extrusion carbon black, plasticizer TP-95, active nano calcium carbonate and nano silicon dioxide, banburying for 4-5 minutes, then discharging rubber, discharging, cooling, standing for 10-12 hours for the next process, and controlling the temperature in the whole process at 90-110 ℃;

step 4): adjusting the rotating speed of an internal mixer to 25-30 r/min, adding the rubber material mixed in the step 3), insoluble sulfur, an accelerator TBBS, an adhesive LG-80, ferric oxide and a sulfur carrier CLD, carrying out internal mixing for 2-3 minutes, and discharging rubber at the temperature of 70-90 ℃;

step 5): adjusting the roll spacing of the open mill to 4-8 mm, pressing for 2-4 min, reciprocating the rubber on an upper rubber-ramming frame for 8-10 times, then cooling and placing the lower piece to obtain the rubber material of the rubber layer.

In the present application, "NBR 1051" refers to the kind of nitrile rubber;

in the present application, "SSBR 1040" refers to a kind of solution-polymerized styrene-butadiene rubber;

in this application, "tmq (rd)", refers to a 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer;

in this application, "MB" refers to 2-mercaptobenzimidazole;

as used herein, "CLD" refers to 1, 1' -dithiobiscaprolactam;

in the present application, "N550" refers to the type of fast extruding carbon black;

as used herein, "TP-95" refers to bis (butoxyethoxyethyl) adipate;

in the present application, "LG-80" refers to the kind of binder;

in the present application, "IS-60" refers to the species of insoluble sulfur;

as used herein, "TBBS" refers to N-tert-butyl-2-benzothiazoleinosine amide.

The beneficial effects that this application can produce include:

1) the formula of the application uses environment-friendly raw materials, reduces emissions in the processing process, and reduces flying of the raw materials;

2) the 100% stress at definite elongation of the rubber material is improved by selecting the environment-friendly accelerator, the vulcanizing agent and adjusting the vulcanizing system;

3) according to the preparation method, the nitrile rubber with high acrylonitrile content is mainly adopted, and a small amount of solution polymerized styrene butadiene rubber is used, so that the rubber material is ensured to have excellent mechanical property, medium resistance and aging resistance, and also has excellent flowing property and low heat buildup property;

4) the method adopts a vulcanization system combining sulfur and a sulfur carrier, wherein the sulfur adopts non-frosting insoluble sulfur, the accelerator adopts an environment-friendly accelerator TBBS and an environment-friendly sulfur carrier CLD for matching, and zinc oxide and magnesium oxide or iron oxide are added simultaneously;

5) the application selects the adhesive LG-80 and the ferric oxide adhesive system, so that the flying of powder in the production process is obviously reduced, the formaldehyde smell with obvious stimulation is avoided, and the production environment is obviously improved.

6) The plasticizer is environment-friendly TP-95.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the starting materials in the examples of the present application were all purchased commercially, wherein:

nitrile rubber NBR1051 was purchased from chemical Co., Ltd, Zhenjiangdi;

solution polymerized styrene butadiene rubber SSBR1040 is available from Chinese petroleum;

anti-aging agent TMQ (RD) available from Kogmai chemical Co., Ltd;

anti-aging agent MB was purchased from Henan Rongxin Xin science and technology Co., Ltd;

the sulfur carrying agent CLD was purchased from honoxin, science ltd, of south of the river;

the fast extrusion carbon black N550 is purchased from Kabot (chemical industry) Tianjin Co Ltd;

plasticizer TP-95 was purchased from Rohm and Haas, USA;

adhesive LG-80 was purchased from Heizhou eosin photo chemical factories;

insoluble sulfur IS-60 was purchased from Huangjiang yellow rock strength chemostat test, Inc.;

accelerator TBBS was purchased from Yongxin Xin science, Inc., Henan.

EXAMPLE 1 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 80 parts of nitrile-butadiene rubber NBR1051 and 20 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to 35 r/min, and carrying out internal mixing for 3 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 30 r/min, lifting a top plug, adding 5.0 parts of zinc oxide, 5.0 parts of magnesium oxide, 1.0 part of stearic acid, 1.0 part of an anti-aging agent TMQ (RD), 1.0 part of an anti-aging agent MB and 25 parts of fast extrusion carbon black, and internally mixing for 3 minutes;

step 3): adding 25 parts of fast extrusion carbon black, 10 parts of plasticizer TP-95, 40 parts of active nano calcium carbonate and 20 parts of nano silicon dioxide, banburying for 5 minutes, then discharging rubber, discharging sheets, cooling, standing for 12 hours for next process, and controlling the temperature in the whole process at 110 ℃;

step 4): adjusting the rotating speed of an internal mixer to 30 r/min, adding the mixed rubber material obtained in the step 3), 1.5 parts of insoluble sulfur IS-60, 1 part of accelerator TBBS, 8.0 parts of adhesive LG-80, 5.0 parts of ferric oxide and 2.0 parts of sulfur-carrying agent CLD, carrying out internal mixing for 3 minutes, and discharging rubber at the temperature of 90 ℃;

step 5): adjusting the roll spacing of the open mill to 8mm, pressing for 4min, reciprocating the rubber on the rubber-tamping frame for 10 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 2 preparation of rubber layer sizing material for steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 95 parts of nitrile-butadiene rubber NBR1051 and 5.0 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to be 30-35 r/min, and carrying out internal mixing for 5 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 25 r/min, lifting a top plug, adding 10 parts of zinc oxide, 10 parts of magnesium oxide, 2 parts of stearic acid, 3.0 parts of an anti-aging agent TMQ (RD), 2.0 parts of an anti-aging agent MB and 20 parts of fast extrusion carbon black, and internally mixing for 3 minutes;

step 3): adding 20 parts of fast extrusion carbon black, 20 parts of plasticizer TP-95, 60 parts of active nano calcium carbonate and 40 parts of nano silicon dioxide, banburying for 5 minutes, then discharging rubber, discharging sheets, cooling, standing for 10 hours for the next process, and controlling the temperature in the whole process at 90 ℃;

step 4): adjusting the rotating speed of an internal mixer to 25 r/min, adding the mixed rubber material obtained in the step 3), 1.5 parts of insoluble sulfur IS-60, 1 part of accelerator TBBS, 7.0 parts of adhesive LG-80, 3.0 parts of ferric oxide and 2.0 parts of sulfur-carrying agent CLD, carrying out internal mixing for 3 minutes, and discharging rubber at the temperature of 70-90 ℃;

step 5): adjusting the roll spacing of the open mill to 4mm, pressing for 2min, reciprocating the upper rubber-pounding frame for 8 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 3 preparation of rubber layer sizing Material for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 85 parts of nitrile-butadiene rubber NBR1051 and 15 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to be 33 r/min, and carrying out internal mixing for 4 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 28 r/min, lifting a top plug, adding 7.5 parts of zinc oxide, 7.5 parts of magnesium oxide, 1.5 parts of stearic acid, 2.0 parts of an anti-aging agent TMQ (RD), 1.5 parts of an anti-aging agent MB and 22.5 parts of fast extrusion carbon black, and internally mixing for 2-3 minutes;

step 3): adding 22.5 parts of fast extrusion carbon black, 15 parts of plasticizer TP-95, 50 parts of active nano calcium carbonate and 30 parts of nano silicon dioxide, banburying for 4 minutes, then discharging rubber, blanking, cooling, standing for 11 hours for next process, and controlling the temperature in the whole process at 100 ℃;

step 4): adjusting the rotating speed of an internal mixer to 28 r/min, adding the mixed rubber material obtained in the step 3), 2.0 parts of insoluble sulfur IS-60, 1.5 parts of promoter TBBS, 6.0 parts of adhesive LG-80, 4.0 parts of ferric oxide and 2.0 parts of sulfur-carrying agent CLD, carrying out internal mixing for 3 minutes, and discharging rubber at the temperature of 80 ℃;

step 5): adjusting the roll spacing of the open mill to 6mm, pressing for 3min, reciprocating the rubber on the rubber-tamping frame for 9 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 4 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): plasticating in an internal mixer, adding 100 parts of nitrile-butadiene rubber NBR1051 into the internal mixer, controlling the rotating speed of the internal mixer to be 32 r/m, and carrying out internal mixing for 3 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 27 r/min, lifting a top plug, adding 9.0 parts of zinc oxide, 9.0 parts of magnesium oxide, 1.8 parts of stearic acid, 2.5 parts of an anti-aging agent TMQ (RD), 1.8 parts of an anti-aging agent MB and 30 parts of fast extrusion carbon black, and internally mixing for 2 minutes;

step 3): adding 30 parts of fast extrusion carbon black, 18 parts of plasticizer TP-95, 55 parts of active nano calcium carbonate and 35 parts of nano silicon dioxide, banburying for 4 minutes, then discharging rubber, discharging sheets, cooling, standing for 12 hours for next process, and controlling the temperature in the whole process at 95 ℃;

step 4): adjusting the rotating speed of an internal mixer to 26 r/min, adding the mixed rubber material obtained in the step 3), 1.8 parts of insoluble sulfur IS-60, 1.8 parts of promoter TBBS, 10 parts of adhesive LG-80, 6.0 parts of ferric oxide and 4.0 parts of sulfur-carrying agent CLD, carrying out internal mixing for 2 minutes, and discharging rubber at the temperature of 75 ℃;

step 5): adjusting the roll spacing of the open mill to 7mm, pressing for 3min, reciprocating the rubber on the rubber-tamping frame for 10 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 5 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 90 parts of nitrile-butadiene rubber NBR1051 and 10 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to be 34 r/min, and carrying out internal mixing for 5 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 29 r/min, lifting a top plug, adding 6 parts of zinc oxide, 6 parts of magnesium oxide, 1.2 parts of stearic acid, 1.5 parts of antioxidant TMQ (RD), 1.2 parts of antioxidant MB and 20 parts of fast extrusion carbon black, and internally mixing for 2 minutes;

step 3): adding 20 parts of fast extrusion carbon black, 18 parts of plasticizer TP-95, 45 parts of active nano calcium carbonate and 25 parts of nano silicon dioxide, banburying for 4 minutes, then discharging rubber, discharging sheets, cooling, standing for 11 hours for next process, and controlling the temperature in the whole process at 105 ℃;

step 4): adjusting the rotating speed of an internal mixer to 28 r/min, adding the mixed rubber material obtained in the step 3), 2.0 parts of insoluble sulfur IS-60, 2.0 parts of promoter TBBS, 8.0 parts of adhesive LG-80, 5.0 parts of ferric oxide and 1.5 parts of sulfur-carrying agent CLD, carrying out internal mixing for 2 minutes, and discharging rubber at the temperature of 85 ℃;

step 5): adjusting the roll spacing of the open mill to 5mm, pressing for 4min, reciprocating the upper rubber-pounding frame for 9 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 6 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 80 parts of nitrile-butadiene rubber NBR1051 and 20 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to 35 r/min, and carrying out internal mixing for 3 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 30 r/min, lifting a top plug, adding 9.0 parts of zinc oxide, 9.0 parts of magnesium oxide, 2.0 parts of stearic acid, 2.5 parts of an anti-aging agent TMQ (RD), 1.5 parts of an anti-aging agent MB and 22.5 parts of fast extrusion carbon black, and internally mixing for 2 minutes;

step 3): adding 22.5 parts of fast extrusion carbon black, 20 parts of plasticizer TP-95, 50 parts of active nano calcium carbonate and 30 parts of nano silicon dioxide, banburying for 4 minutes, then discharging rubber, blanking, cooling, standing for 10 hours for next process, and controlling the temperature in the whole process at 110 ℃;

step 4): adjusting the rotating speed of an internal mixer to 30 r/min, adding the mixed rubber material obtained in the step 3), 2.0 parts of insoluble sulfur IS-60, 2.0 parts of promoter TBBS, 7.0 parts of adhesive LG-80, 3.0 parts of ferric oxide and 1.5 parts of sulfur-carrying agent CLD, carrying out internal mixing for 2 minutes, and discharging the rubber at 90 ℃;

step 5): adjusting the roll spacing of the open mill to 8mm, pressing for 2min, reciprocating the rubber on the rubber-tamping frame for 10 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 7 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 95 parts of nitrile-butadiene rubber NBR1051 and 5 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to 35 r/min, and carrying out internal mixing for 3 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 25 r/min, lifting a top plug, adding 5.0 parts of zinc oxide, 5.0 parts of magnesium oxide, 1.0 part of stearic acid, 1.0 part of an anti-aging agent TMQ (RD), 1.0 part of an anti-aging agent MB and 25 parts of fast extrusion carbon black, and internally mixing for 3 minutes;

step 3): adding 25 parts of fast extrusion carbon black, 10 parts of plasticizer TP-95, 40 parts of active nano calcium carbonate and 20 parts of nano silicon dioxide, banburying for 5 minutes, then discharging rubber, discharging sheets, cooling, standing for 12 hours for next process, and controlling the temperature in the whole process at 90 ℃;

step 4): adjusting the rotating speed of an internal mixer to 25 r/min, adding the mixed rubber material obtained in the step 3), 2.0 parts of insoluble sulfur IS-60, 2 parts of an accelerator TBBS, 6.0 parts of a binder LG-80, 4.0 parts of ferric oxide and 1.5 parts of a sulfur-carrying agent CLD, carrying out internal mixing for 2 minutes, and discharging rubber at the temperature of 70 ℃;

step 5): adjusting the roll spacing of the open mill to 6mm, pressing for 2min, reciprocating the upper rubber-pounding frame for 8 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 8 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 85 parts of nitrile-butadiene rubber NBR1051 and 15 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to be 30 r/min, and carrying out internal mixing for 5 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 30 r/min, lifting a top plug, adding 10 parts of zinc oxide, 10 parts of magnesium oxide, 2 parts of stearic acid, 3.0 parts of an anti-aging agent TMQ (RD), 2.0 parts of an anti-aging agent MB and 20 parts of fast extrusion carbon black, and internally mixing for 3 minutes;

step 3): adding 20 parts of fast extrusion carbon black, 20 parts of plasticizer TP-95, 60 parts of active nano calcium carbonate and 40 parts of nano silicon dioxide, banburying for 5 minutes, then discharging rubber, discharging sheets, cooling, standing for 12 hours for next process, and controlling the temperature in the whole process at 95 ℃;

step 4): adjusting the rotating speed of an internal mixer to 25 r/min, adding the mixed rubber material obtained in the step 3), 2.0 parts of insoluble sulfur IS-60, 2.0 parts of promoter TBBS, 8.0 parts of adhesive LG-80, 5.0 parts of ferric oxide and 1.5 parts of sulfur-carrying agent CLD, carrying out internal mixing for 2 minutes, and discharging rubber at the temperature of 80 ℃;

step 5): adjusting the roll spacing of the open mill to 5mm, pressing for 2min, reciprocating the rubber by an upper rubber-pounding frame for 10 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 9 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 95 parts of nitrile-butadiene rubber NBR1051 and 5.0 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to be 33 r/min, and carrying out internal mixing for 4 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 30 r/min, lifting a top plug, adding 7.5 parts of zinc oxide, 7.5 parts of magnesium oxide, 1.5 parts of stearic acid, 2.0 parts of an anti-aging agent TMQ (RD), 1.5 parts of an anti-aging agent MB and 25 parts of fast extrusion carbon black, and internally mixing for 3 minutes;

step 3): adding 25 parts of fast extrusion carbon black, 15 parts of plasticizer TP-95, 50 parts of active nano calcium carbonate and 30 parts of nano silicon dioxide, banburying for 5 minutes, then discharging rubber, discharging sheets, cooling, standing for 10 hours for the next process, and controlling the temperature in the whole process at 90 ℃;

step 4): adjusting the rotating speed of an internal mixer to 30 r/min, adding the mixed rubber material obtained in the step 3), 2.0 parts of insoluble sulfur IS-60, 1.5 parts of an accelerator TBBS, 6.0 parts of a binder LG-80, 4.0 parts of ferric oxide and 2.0 parts of a sulfur carrying agent CLD, carrying out internal mixing for 3 minutes, and discharging the rubber at the temperature of 90 ℃;

step 5): adjusting the roll spacing of the open mill to 4mm, pressing for 2min, reciprocating the upper rubber-pounding frame for 8 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 10 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 80 parts of nitrile-butadiene rubber NBR1051 and 20 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to be 30 r/min, and carrying out internal mixing for 3 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 25 r/min, lifting a top plug, adding 9.0 parts of zinc oxide, 9.0 parts of magnesium oxide, 1.8 parts of stearic acid, 2.5 parts of an anti-aging agent TMQ (RD), 1.8 parts of an anti-aging agent MB and 20 parts of fast extrusion carbon black, and internally mixing for 2 minutes;

step 3): adding 20 parts of fast extrusion carbon black, 18 parts of plasticizer TP-95, 55 parts of active nano calcium carbonate and 35 parts of nano silicon dioxide, banburying for 4 minutes, then discharging rubber, discharging sheets, cooling, standing for 10 hours for next process, and controlling the temperature in the whole process at 100 ℃;

step 4): adjusting the rotating speed of an internal mixer to 25 r/min, adding the mixed rubber material obtained in the step 3), 2.0 parts of insoluble sulfur IS-60, 1.5 parts of an accelerator TBBS, 7.0 parts of a binder LG-80, 3.0 parts of ferric oxide and 2.0 parts of a sulfur-carrying agent CLD, carrying out internal mixing for 3 minutes, and discharging rubber at the temperature of 80 ℃;

step 5): adjusting the roll spacing of the open mill to 6mm, pressing for 3min, reciprocating the rubber on the rubber-tamping frame for 9 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 11 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 85 parts of nitrile-butadiene rubber NBR1051 and 15 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to be 32 r/min, and carrying out internal mixing for 5 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 28 r/min, lifting a top plug, adding 6 parts of zinc oxide, 6 parts of magnesium oxide, 1.2 parts of stearic acid, 1.5 parts of an anti-aging agent TMQ (RD), 1.2 parts of an anti-aging agent MB and 22.5 parts of fast extrusion carbon black, and internally mixing for 3 minutes;

step 3): adding 22.5 parts of fast extrusion carbon black, 18 parts of plasticizer TP-95, 45 parts of active nano calcium carbonate and 25 parts of nano silicon dioxide, banburying for 5 minutes, then discharging rubber, blanking, cooling, standing for 11 hours for next process, and controlling the temperature in the whole process at 105 ℃;

step 4): adjusting the rotating speed of an internal mixer to 26 r/min, adding the mixed rubber material obtained in the step 3), 1.5 parts of insoluble sulfur IS-60, 1.0 part of promoter TBBS, 6.0 parts of adhesive LG-80, 4.0 parts of ferric oxide and 2.0 parts of sulfur-carrying agent CLD, carrying out internal mixing for 3 minutes, and discharging the rubber at 90 ℃;

step 5): adjusting the roll spacing of the open mill to 7mm, pressing for 3min, reciprocating the rubber on the rubber-tamping frame for 8 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 12 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and (3) plasticating by using an internal mixer, adding 80 parts of nitrile-butadiene rubber NBR1051 and 20 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to be 34 r/min, and carrying out internal mixing for 3 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 26 r/min, lifting a top plug, adding 9.0 parts of zinc oxide, 9.0 parts of magnesium oxide, 2.0 parts of stearic acid, 2.5 parts of an anti-aging agent TMQ (RD), 1.5 parts of an anti-aging agent MB and 25 parts of fast extrusion carbon black, and internally mixing for 2 minutes;

step 3): adding 25 parts of fast extrusion carbon black, 20 parts of plasticizer TP-95, 50 parts of active nano calcium carbonate and 30 parts of nano silicon dioxide, banburying for 4 minutes, then discharging rubber, discharging sheets, cooling, standing for 12 hours for next process, and controlling the temperature in the whole process at 110 ℃;

step 4): adjusting the rotating speed of an internal mixer to 26 r/min, adding the mixed rubber material obtained in the step 3), 2.0 parts of insoluble sulfur IS-60, 1.5 parts of an accelerator TBBS, 7.0 parts of a binder LG-80, 3.0 parts of ferric oxide and 2.0 parts of a sulfur-carrying agent CLD, carrying out internal mixing for 3 minutes, and discharging rubber at the temperature of 75 ℃;

step 5): adjusting the roll spacing of the open mill to 6mm, pressing for 4min, reciprocating the rubber on the rubber-tamping frame for 8 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 13 preparation of rubber layer stock for Steel wire reinforced rubber hose

Step 1): and plasticating by using an internal mixer, adding 85 parts of nitrile-butadiene rubber NBR1051 and 15 parts of solution-polymerized styrene-butadiene rubber SSBR1040 into the internal mixer, controlling the rotating speed of the internal mixer to 35 r/min, and carrying out internal mixing for 3 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 30 r/min, lifting a top plug, adding 9.0 parts of zinc oxide, 9.0 parts of magnesium oxide, 2.0 parts of stearic acid, 2.5 parts of an anti-aging agent TMQ (RD), 1.5 parts of an anti-aging agent MB and 22.5 parts of fast extrusion carbon black, and internally mixing for 3 minutes;

step 3): adding 22.5 parts of fast extrusion carbon black, 20 parts of plasticizer TP-95, 50 parts of active nano calcium carbonate and 30 parts of nano silicon dioxide, banburying for 5 minutes, then discharging rubber, blanking, cooling, standing for 12 hours for next process, and controlling the temperature in the whole process at 110 ℃;

step 4): adjusting the rotating speed of an internal mixer to 30 r/min, adding the mixed rubber material obtained in the step 3), 1.5 parts of insoluble sulfur IS-60, 1.0 part of accelerator TBBS, 6.0 parts of adhesive LG-80, 4.0 parts of ferric oxide and 2.0 parts of sulfur-carrying agent CLD, carrying out internal mixing for 3 minutes, and discharging the rubber at 90 ℃;

step 5): adjusting the roll spacing of the open mill to 8mm, pressing for 4min, reciprocating the rubber on the rubber-tamping frame for 10 times, cooling the lower piece, and standing to obtain rubber layer rubber material.

EXAMPLE 14 testing of the sizing

The tensile strength, elongation at break, hardness, 100% tensile strength, and single wire drawing performance of the above examples were measured by methods conventional in the art, and the results of some examples are shown in the following table:

although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (9)

1. The formula of the rubber layer rubber material for the environment-friendly steel wire reinforced rubber hose is characterized by comprising the following components in parts by weight: 80-100 parts of nitrile butadiene rubber, 0-20 parts of solution-polymerized styrene butadiene rubber, 5-10 parts of zinc oxide, 5-10 parts of magnesium oxide, 1-2 parts of stearic acid, 3-5 parts of ferric oxide, 2-5 parts of an anti-aging agent, 20-40 parts of nano silicon dioxide, 2-4 parts of a sulfur carrying agent, 40-60 parts of fast extrusion carbon black, 40-60 parts of active nano calcium carbonate, 10-20 parts of a plasticizer, 6-10 parts of an adhesive, 1-2 parts of insoluble sulfur and 1-2 parts of an accelerator.

2. The formulation of claim 1, wherein the nitrile rubber is nitrile rubber NBR 1051; the solution polymerized styrene-butadiene rubber is solution polymerized styrene-butadiene rubber SSBR 1040; the fast extrusion carbon black is fast extrusion carbon black N550; the insoluble sulfur IS insoluble sulfur IS-60.

3. The formulation according to claim 1, wherein the anti-aging agent is tmq (rd) and/or MB.

4. The formulation of claim 3, wherein the formulation comprises 1-3 parts by weight of TMQ (RD); the formula comprises 1-2 parts of MB by weight.

5. The formulation of claim 1, wherein the sulfur carrier is CLD.

6. The formulation of claim 1, wherein the plasticizer is TP-95.

7. The formulation of claim 1, wherein the binder is binder LG-80.

8. The formulation of claim 1, wherein the accelerator is TBBS.

9. The process for preparing an environmentally friendly rubber hose compound according to the formulation of any one of claims 1 to 7, wherein the process comprises the steps of:

step 1): plasticating in an internal mixer, adding nitrile rubber and solution polymerized butadiene styrene rubber into the internal mixer, controlling the rotating speed of the internal mixer to be 30-35 r/m, and carrying out internal mixing for 3-5 minutes.

Step 2): adjusting the rotating speed of an internal mixer to 25-30 r/min, lifting a top bolt, adding zinc oxide, magnesium oxide, stearic acid, an anti-aging agent TMQ (RD), an anti-aging agent MB and 1/2 to quickly extrude carbon black, and internally mixing for 2-3 minutes;

step 3): adding the rest fast extrusion carbon black, plasticizer TP-95, active nano calcium carbonate and nano silicon dioxide, banburying for 4-5 minutes, then discharging rubber, discharging, cooling, standing for 10-12 hours for the next process, and controlling the temperature in the whole process at 90-110 ℃;

step 4): adjusting the rotating speed of an internal mixer to 25-30 r/min, adding the rubber material mixed in the step 3), insoluble sulfur, an accelerator TBBS, an adhesive LG-80, ferric oxide and a sulfur carrier CLD, carrying out internal mixing for 2-3 minutes, and discharging rubber at the temperature of 70-90 ℃;

step 5): adjusting the roll spacing of the open mill to 4-8 mm, pressing for 2-4 min, reciprocating the rubber on an upper rubber-ramming frame for 8-10 times, then cooling and placing the lower piece to obtain the rubber material of the rubber layer.