CN108219224B - Composite rubber and preparation method thereof - Google Patents
Composite rubber and preparation method thereof Download PDFInfo
- Publication number
- CN108219224B CN108219224B CN201810070358.XA CN201810070358A CN108219224B CN 108219224 B CN108219224 B CN 108219224B CN 201810070358 A CN201810070358 A CN 201810070358A CN 108219224 B CN108219224 B CN 108219224B
- Authority
- CN
- China
- Prior art keywords
- parts
- rubber
- polyurethane
- master batch
- roller spacing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the field of rubber materials, and provides a composite rubber and a preparation method thereof aiming at the problem of lack of ozone aging resistance, which can better improve the ozone aging resistance, and the technical scheme is as follows: the feed is prepared from the following raw materials in parts by mass: 20-50 parts of polyurethane, 50-80 parts of nitrile rubber, 4-8 parts of plasticizer, 20-50 parts of white carbon black, 0.5-3 parts of silane coupling agent, 40-60 parts of flame retardant, 1.5-4 parts of cross-linking agent and 6-10 parts of clay. A method for preparing the composite rubber comprises the following steps: (1) mixing master batch; (2) vulcanizing the master batch: the coagulation time of the master batch at the stage without adding the cross-linking agent is prolonged; (3) and (4) vulcanizing. The acrylonitrile in the nitrile rubber provides oil resistance, the flame retardant provides flame retardance, and the polyurethane provides good ozone aging resistance. The clay is better dispersed in the rubber compound by prolonging the mixing time of the master batch in the stage of not adding the cross-linking agent in the open mill, and the ozone aging resistance of the compound rubber is improved.
Description
Technical Field
The invention relates to the field of rubber materials, in particular to a composite rubber and a preparation method thereof.
Background
The composite rubber has the advantages of various materials, such as high strength, light weight, high and low temperature resistance, corrosion resistance, heat insulation, insulation and the like, and high polymer materials and other materials with special properties are selected according to application purposes to prepare the composite materials meeting the requirements.
The nitrile rubber is prepared from butadiene and acrylonitrile by an emulsion polymerization method, is mainly produced by a low-temperature emulsion polymerization method, and has the advantages of excellent oil resistance, higher wear resistance, better heat resistance and strong bonding force. The disadvantages are poor low temperature resistance, ozone resistance, poor insulation properties and slightly low elasticity. The nitrile rubber is mainly used for manufacturing oil-resistant rubber products.
The acrylonitrile-butadiene rubber contains five components of acrylonitrile by mass percentage of 42-46%, 36-41%, 31-35%, 25-30%, 18-24% and the like. The more the acrylonitrile content, the better the oil resistance, but the cold resistance is reduced accordingly, and it can be used in 120 ℃ air or 150 ℃ oil for a long time. In addition, it has excellent water resistance, air tightness and excellent adhesion performance. The rubber is widely used for manufacturing various oil-resistant rubber products, various oil-resistant gaskets, sleeves, flexible packages, flexible rubber tubes, printing and dyeing rubber rollers, cable rubber materials and the like, and becomes an indispensable elastic material in the industries of automobiles, aviation, petroleum, copying and the like.
However, the ozone resistance of nitrile rubber is poor, the application range of nitrile rubber is wide, and nitrile rubber is often used for oil-resistant products, and needs good flame retardance and long service life, and the poor ozone aging resistance becomes an important factor restricting the service life of nitrile rubber, and the improvement space is provided.
Disclosure of Invention
The first object of the present invention is to provide a compounded rubber which has advantages of good oil resistance and flame retardancy as well as excellent ozone aging resistance.
In order to achieve the purpose, the invention provides the following technical scheme:
the composite rubber is prepared from the following raw materials in parts by mass, wherein the contents of the components are represented by the parts by mass:
20-50 parts of polyurethane
50-80 parts of nitrile rubber
4-8 parts of plasticizer
20-50 parts of white carbon black
0.5-3 parts of silane coupling agent
40-60 parts of flame retardant
1.5-4 parts of a cross-linking agent.
By adopting the technical scheme, the acrylonitrile in the nitrile rubber provides oil resistance, the flame retardant provides flame retardance, the white carbon black is used for reinforcing so as to ensure the strength, and the polyurethane and the nitrile rubber form a matching system by adding the polyurethane, so that better ozone aging resistance is provided.
Preferably, the content of each component is as follows:
30-40 parts of polyurethane
60-70 parts of nitrile rubber
5-7 parts of plasticizer
30-40 parts of white carbon black
0.5-1.5 parts of silane coupling agent
45-55 parts of flame retardant
2-3 parts of a cross-linking agent.
By adopting the technical scheme, the acrylonitrile in the nitrile rubber provides oil resistance, the flame retardant provides flame retardance, the white carbon black is used for reinforcing so as to ensure the strength, and the polyurethane and the nitrile rubber form a matching system by adding the polyurethane, so that better ozone aging resistance is provided.
Preferably, the crosslinking agent is a peroxide crosslinking agent.
By adopting the technical scheme, the ozone aging resistance is further improved by adopting the peroxide crosslinking agent.
Preferably, the feed also comprises the following raw materials in parts by mass:
6-10 parts of clay.
By adopting the technical scheme, the clay is added, and is dispersed in the system to form the protective layer, so that ozone molecules are prevented from entering the composite rubber, the speed of the ozone molecules entering the composite rubber is slowed down, and the ozone aging resistance is further improved.
Preferably, the feed also comprises the following raw materials in parts by mass:
1-3 parts of antiozonant.
By adopting the technical scheme, the ozone aging resistance is further improved by adding the antiozonant.
Preferably, the feed also comprises the following raw materials in parts by mass:
1-2 parts of an anti-aging agent.
By adopting the technical scheme, the thermal oxidation and aging resistance is improved by adding the anti-aging agent.
Preferably, the polyurethane is a polyether polyurethane.
By adopting the technical scheme, the water resistance and the low-temperature performance of the whole composite rubber are improved by utilizing the hydrolysis resistance and the better low-temperature performance of the polyether polyurethane.
Preferably, the acrylonitrile-butadiene rubber contains 36-42% of acrylonitrile by mass.
By adopting the technical scheme, the acrylonitrile content of the nitrile rubber is 36-42%, so that the using amount of the nitrile rubber is reduced, and the sufficient oil resistance can be ensured, more polyurethane can be added into the composite rubber, and the better ozone aging resistance is further provided.
The second purpose of the invention is to provide a preparation method of the compounded rubber, which has the advantages of good oil resistance, good flame retardance and excellent ozone aging resistance.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing the composite rubber comprises the following steps:
(1) mixing master batch:
putting polyurethane and nitrile rubber into an internal mixer, pressing a top bolt for 10-30 seconds, then putting an anti-aging agent, an antiozonant and a flame retardant, pressing the top bolt for 10-30 seconds, then putting white carbon black, pressing the top bolt to 140-145 ℃, finally putting a silane coupling agent, a plasticizer and clay, and pressing the top bolt to 150-155 ℃ for rubber discharge;
(2) vulcanizing the master batch:
smashing the parked masterbatch on an open mill for 60-120 seconds at a roller spacing of 3-4mm, continuously smashing the masterbatch for 60-120 seconds at a roller spacing of 1-2mm for 6-12 times at a roller spacing of 0.5-1mm, adding a cross-linking agent at a roller spacing of 3-4mm for 3-5 times at a roller spacing of 1-2mm, and placing 6-8 pieces in a triangular bag at a roller spacing of 4-5 mm;
(3) and (3) vulcanization:
vulcanization conditions are as follows: the pressure is 6-14kg/cm2The temperature is 150-170 ℃, and the vulcanizing time is 10-30 minutes.
By adopting the technical scheme, the mixing time of the master batch in the stage without adding the cross-linking agent in the open mill is longer, so that the Mooney property of the master batch is reduced by utilizing the open mill, and the plastication step for reducing the Mooney property can be omitted, so that the process steps are reduced, the rubber material transportation is reduced, and the production efficiency is improved while the compound rubber obtains similar Mooney property; meanwhile, in the process of low roll gap and thin through, a stronger pulling effect is provided for rubber materials, the layered structure of the clay is better separated so as to be better dispersed in the rubber compound, the distribution area of a protective layer formed by the clay in the composite rubber is wider, ozone molecules are better prevented from entering the composite rubber, and the ozone aging resistance of the composite rubber is further improved.
Preferably, the roller spacing is 0.5mm when the thin passing is performed 6 to 12 times in the step 2.
By adopting the technical scheme, the roll distance is 0.5mm when the rubber is passed through the mill for 6-12 times, so that the pulling force of the master batch in the open mill is stronger, the effect of dispersing clay is further improved, and the ozone aging resistance of the composite rubber is further improved.
In conclusion, the invention has the following beneficial effects: the acrylonitrile in the nitrile rubber provides oil resistance, the flame retardant provides flame retardance, the white carbon black is used for reinforcing to ensure the strength, and the polyurethane and the nitrile rubber form a matching system by adding the polyurethane to provide better ozone aging resistance; the ozone aging resistance is improved by adopting a peroxide crosslinking agent, adding clay and adding an antiozonant; the thermal oxidation and aging resistance is improved by adding the anti-aging agent; because the master batch is mixed in the open mill for a long time in the stage without adding the cross-linking agent, the clay is better dispersed in the rubber compound in the process of low roll gap and thin passing, and the ozone aging resistance of the compound rubber is further improved.
Detailed Description
The present invention will be described in detail below by way of examples.
In the following specific examples, the following processing aids which do not substantially affect the product properties may also be added, specifically as follows: zinc oxide; polyethylene glycol; paraffin wax; titanium dioxide; and (4) color master batch.
In the following specific examples, the polyurethane is a pure polyurethane solid under the trademark urea 50EL06G, and belongs to polyether polyurethane; the nitrile rubber is under the brand name NBR3950F, and the acrylonitrile content is 39%; the flame retardant is FR516, belonging to halogen-containing flame retardants; the anti-aging agent is anti-aging agent RD; the antiozonant is NTU (antiozonant) and 6PPD (antiozonant); the plasticizer is a plasticizer which is conventional in the field, in particular to a plasticizer NB-4; the cross-linking agent is a cross-linking agent which is conventional in the field, and is dicumyl peroxide; the color master batches comprise three color master batches, namely color master batch MP-1005-1, color master batch MP-1002-1 and color master batch MP-100.
Example 1
The composite rubber is prepared from the following raw materials in parts by mass, wherein the contents of the components are represented by the parts by mass:
urea 50EL06G polyether urethane: 20 parts of (1); NBR3950F nitrile rubber: 50 parts of a mixture; white carbon black: 20 parts of (1); clay: 6 parts of (1); zinc oxide: 1 part; polyethylene glycol: 0.5 part; paraffin wax: 0.5 part; silane coupling agent: 0.5 part; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 1 part; flame retardant FR 516: 40 parts of a mixture; antiozonants NTU: 0.5 part; antiozonant 6 PPD: 0.5 part; and (3) a plasticizer NB-4: 4 parts of a mixture; dicumyl peroxide: 1.5 parts; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Example 2
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 30 parts of (1); NBR3950F nitrile rubber: 60 parts; white carbon black: 30 parts of (1); clay: 6 parts of (1); zinc oxide: 1 part; polyethylene glycol: 0.5 part; paraffin wax: 0.5 part; silane coupling agent: 0.5 part; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 1 part; flame retardant FR 516: 45 parts of (1); antiozonants NTU: 0.5 part; antiozonant 6 PPD: 0.5 part; and (3) a plasticizer NB-4: 4 parts of a mixture; dicumyl peroxide: 2 parts of (1); color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Example 3
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 40 parts of a mixture; NBR3950F nitrile rubber: 70 parts of (B); white carbon black: 40 parts of a mixture; clay: 10 parts of (A); zinc oxide: 3 parts of a mixture; polyethylene glycol: 1 part; paraffin wax: 1.5 parts; silane coupling agent: 1.5 parts; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 2 parts of (1); flame retardant FR 516: 55 parts of (1); antiozonants NTU: 2.5 parts; antiozonant 6 PPD: 0.5 part; and (3) a plasticizer NB-4: 7 parts; dicumyl peroxide: 3 parts of a mixture; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Example 4
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 50 parts of a mixture; NBR3950F nitrile rubber: 80 parts of a mixture; white carbon black: 50 parts of a mixture; clay: 10 parts of (A); zinc oxide: 3 parts of a mixture; polyethylene glycol: 1 part; paraffin wax: 1.5 parts; silane coupling agent: 3 parts of a mixture; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 2 parts of (1); flame retardant FR 516: 60 parts; antiozonants NTU: 2.5 parts; antiozonant 6 PPD: 0.5 part; and (3) a plasticizer NB-4: 8 parts of a mixture; dicumyl peroxide: 4 parts of a mixture; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Example 5
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 20 parts of (1); NBR3950F nitrile rubber: 80 parts of a mixture; white carbon black: 50 parts of a mixture; clay: 7 parts; zinc oxide: 2.5 parts; polyethylene glycol: 1 part; paraffin wax: 1 part; silane coupling agent: 1 part; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 1.5 parts; flame retardant FR 516: 48 parts of a mixture; antiozonants NTU: 1 part; antiozonant 6 PPD: 1 part; and (3) a plasticizer NB-4: 6.3 parts of a mixture; dicumyl peroxide: 2.2 parts of; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Example 6
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 50 parts of a mixture; NBR3950F nitrile rubber: 50 parts of a mixture; white carbon black: 50 parts of a mixture; clay: 7 parts; zinc oxide: 2.5 parts; polyethylene glycol: 1 part; paraffin wax: 1 part; silane coupling agent: 1 part; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 1.5 parts; flame retardant FR 516: 48 parts of a mixture; antiozonants NTU: 1 part; antiozonant 6 PPD: 1 part; and (3) a plasticizer NB-4: 6.3 parts of a mixture; dicumyl peroxide: 2.2 parts of; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Example 7
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 30 parts of (1); 70 parts of NBR3950F nitrile rubber; white carbon black: 40 parts of a mixture; clay: 7 parts; zinc oxide: 2.5 parts; polyethylene glycol: 1 part; paraffin wax: 1 part; silane coupling agent: 1 part; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 1.5 parts; flame retardant FR 516: 48 parts of a mixture; antiozonants NTU: 1 part; antiozonant 6 PPD: 1 part; and (3) a plasticizer NB-4: 6.3 parts of a mixture; dicumyl peroxide: 2.2 parts of; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Example 8
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 40 parts of a mixture; 60 parts of NBR3950F nitrile rubber; white carbon black: 40 parts of a mixture; clay: 7 parts; zinc oxide: 2.5 parts; polyethylene glycol: 1 part; paraffin wax: 1 part; silane coupling agent: 1 part; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 1.5 parts; flame retardant FR 516: 48 parts of a mixture; antiozonants NTU: 1 part; antiozonant 6 PPD: 1 part; and (3) a plasticizer NB-4: 6.3 parts of a mixture; dicumyl peroxide: 2.2 parts of; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Example 9
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 33 parts of (B); NBR3950F nitrile rubber: 67 parts; white carbon black: 37 parts of; clay: 7 parts; zinc oxide: 2.5 parts; polyethylene glycol: 1 part; paraffin wax: 1 part; silane coupling agent: 1 part; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 1.5 parts; flame retardant FR 516: 48 parts of a mixture; antiozonants NTU: 1 part; antiozonant 6 PPD: 1 part; and (3) a plasticizer NB-4: 6.3 parts of a mixture; dicumyl peroxide: 2.2 parts of; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
Examples 1-9A process for the preparation of the compounded rubber comprising the steps of:
(1) plasticating Urepan50EL06G polyether polyurethane and NBR3950F nitrile rubber through an open mill for 6 times, wherein the roll spacing is 0.5mm, and fully plasticating; then putting the mixture into an internal mixer at the temperature of 110 ℃ for pressing for 4 minutes again to obtain master batch;
(2) after the master batch is pressed, adding zinc oxide, paraffin, titanium dioxide, color master MP-1005-1, color master MP-1002-1 and color master MP-100, pressing for 2 minutes at the temperature of 100 ℃; adding an antioxidant RD, an antiozonant NTU, an antiozonant 6PPD and a flame retardant FR516, pressing at 115 ℃ for 2 minutes; then adding white carbon black and clay, pressing for 2 minutes at the temperature of 115 ℃; finally, adding a silane coupling agent, polyethylene glycol and a plasticizer NB-4, pressing for 3 minutes at the temperature of 115 ℃, conveying to a 22-inch open mill after molding, and tabletting for heat dissipation;
(3) smashing the master batch on an open mill for 2 minutes, wherein the roller spacing is 3 mm; adding dicumyl peroxide, and the roller spacing is 3 mm; the thin-pass is carried out for three times, and the roller spacing is 1 mm; packaging six rear lower pieces by a triangular bag, wherein the roller spacing is 5 mm; roll temperature: the front roller is less than or equal to 60 ℃, and the rear roller is less than or equal to 60 ℃; vulcanization conditions are as follows: pressure 6kg/cm2The temperature was 150 ℃ and the vulcanization time was 30 minutes.
Example 10
The composite rubber is prepared from the following raw materials in parts by mass, wherein the contents of the components are represented by the parts by mass:
urea 50EL06G polyether urethane: 20 parts of (1); NBR3950F nitrile rubber: 50 parts of a mixture; white carbon black: 20 parts of (1); clay: 6 parts of (1); silane coupling agent: 0.5 part; anti-aging agent RD: 1 part; flame retardant FR 516: 40 parts of a mixture; antiozonants NTU: 0.5 part; antiozonant 6 PPD: 0.5 part; and (3) a plasticizer NB-4: 4 parts of a mixture; dicumyl peroxide: 1.5 parts.
Example 11
The compound rubber has the following formula:
urea 50EL06G polyether urethane: 50 parts of a mixture; NBR3950F nitrile rubber: 80 parts of a mixture; white carbon black: 50 parts of a mixture; clay: 10 parts of (A); silane coupling agent: 3 parts of a mixture; anti-aging agent RD: 2 parts of (1); flame retardant FR 516: 60 parts; antiozonants NTU: 2.5 parts; antiozonant 6 PPD: 0.5 part; and (3) a plasticizer NB-4: 8 parts of a mixture; dicumyl peroxide: 4 parts.
Example 10-the process for the preparation of the compounded rubber of example 11, comprising the steps of:
(1) plasticating Urepan50EL06G polyether polyurethane and NBR3950F nitrile rubber through an open mill for 6 times, wherein the roll spacing is 0.5mm, and fully plasticating; then putting the mixture into an internal mixer at the temperature of 110 ℃ for pressing for 4 minutes again to obtain master batch;
(2) pressing the master batch at the temperature of 100 ℃ for 2 minutes; adding an antioxidant RD, an antiozonant NTU, an antiozonant 6PPD and a flame retardant FR516, pressing at 115 ℃ for 2 minutes; then adding white carbon black and clay, pressing for 2 minutes at the temperature of 115 ℃; finally, adding a silane coupling agent and a plasticizer NB-4, pressing for 3 minutes at the temperature of 115 ℃, conveying to a 22-inch open mill after molding, and tabletting for heat dissipation;
(3) smashing the master batch on an open mill for 2 minutes, wherein the roller spacing is 3 mm; adding dicumyl peroxide, and the roller spacing is 3 mm; the thin-pass is carried out for three times, and the roller spacing is 1 mm; packaging six rear lower pieces by a triangular bag, wherein the roller spacing is 5 mm; roll temperature: the front roller is less than or equal to 60 ℃, and the rear roller is less than or equal to 60 ℃; vulcanization conditions are as follows: pressure 6kg/cm2The temperature was 150 ℃ and the vulcanization time was 30 minutes.
Comparative example
The compound rubber has the following formula:
NBR3950F nitrile rubber: 100 parts of (A); white carbon black: 35 parts of (B); clay: 8 parts of a mixture; zinc oxide: 2 parts of (1); polyethylene glycol: 0.8 part; paraffin wax: 1 part; silane coupling agent: 1 part; titanium dioxide: 5 parts of a mixture; anti-aging agent RD: 1.5 parts; flame retardant FR 516: 50 parts of a mixture; antiozonants NTU: 1.5 parts; antiozonant 6 PPD: 0.5 part; and (3) a plasticizer NB-4: 6 parts of (1); dicumyl peroxide: 2.5 parts; color master MP-1005-1: 0.4 part; color master MP-1002-1: 1.6 parts; color master MP-100: and 3 parts.
The preparation method of the compounded rubber in the comparative example comprises the following steps:
(1) plasticating NBR3950F nitrile rubber through an open mill for 6 times, and fully plasticating with the roll spacing of 0.5 mm; then putting the mixture into an internal mixer at the temperature of 110 ℃ for pressing for 4 minutes again to obtain master batch;
(2) after the master batch is pressed, adding zinc oxide, paraffin, titanium dioxide, color master MP-1005-1, color master MP-1002-1 and color master MP-100, pressing for 2 minutes at the temperature of 100 ℃; adding an antioxidant RD, an antiozonant NTU, an antiozonant 6PPD and a flame retardant FR516, pressing at 115 ℃ for 2 minutes; then adding white carbon black and clay, pressing for 2 minutes at the temperature of 115 ℃; finally, adding a silane coupling agent, polyethylene glycol and a plasticizer NB-4, pressing for 3 minutes at the temperature of 115 ℃, conveying to a 22-inch open mill after molding, and tabletting for heat dissipation;
(3) smashing the master batch on an open mill for 2 minutes, wherein the roller spacing is 3 mm; adding dicumyl peroxide, and the roller spacing is 3 mm; the thin-pass is carried out for three times, and the roller spacing is 1 mm; packaging six rear lower pieces by a triangular bag, wherein the roller spacing is 5 mm; roll temperature: the front roller is less than or equal to 60 ℃, and the rear roller is less than or equal to 60 ℃; vulcanization conditions are as follows: 6kg/cm2The temperature was 150 ℃ and the vulcanization time was 30 minutes.
The specific properties are compared and the results are shown in tables 1 and 2
TABLE 1
TABLE 2
Wherein the ozone aging resistance test comprises the following steps: placing the sample at 100 ℃ for 70 hours, then placing the sample in an ozone environment with the temperature of 52 ℃ and the concentration of 600pphm for 6 hours, wherein the sample is qualified if no crack exists and unqualified if crack exists, and in order to reflect the difference of ozone aging resistance in different embodiments, the sample is placed under the conditions until the crack appears, and the test time is compared.
The data in table 1 show that the physical properties of the nitrile rubber partially replaced by polyurethane are not changed much, the ozone aging resistance is improved well, and the ozone aging resistance is improved greatly when the content of polyurethane is higher.
The data in table 2 show that the addition of the processing aid does not cause any actual influence, and that the higher the polyurethane content is, the greater the improvement of the ozone aging resistance is.
Example 12
A preparation method of composite rubber adopts the formula of example 9, and comprises the following specific steps:
(1) mixing master batch:
the preparation method comprises the steps of putting Urepan50EL06G and NBR3950F into an internal mixer, pressing a top bolt for 15 seconds, putting zinc oxide, paraffin, titanium dioxide, color master MP-1005-1, color master MP-1002-1, color master MP-100, antioxidant RD, antiozonant NTU, antiozonant 6PPD and flame retardant FR516 into the internal mixer, pressing the top bolt for 15 seconds, then putting white carbon black into the internal mixer, pressing the top bolt to 145 ℃, finally putting silane coupling agent, polyethylene glycol, plasticizer NB-4 and clay into the internal mixer, pressing the top bolt to 150 ℃, discharging glue, discharging the glue and obtaining master batch.
(2) Vulcanizing the master batch:
smashing the master batch on an open mill for 60 seconds, wherein the roller spacing is 3 mm; continuously ramming the rubber for 60 seconds, wherein the roller spacing is 1 mm; passing through the roller for 6 times with the roller spacing of 0.5 mm; adding dicumyl peroxide, and the roller spacing is 3 mm; passing through the roller for 3 times, wherein the roller spacing is 1 mm; packaging 6 pieces of back lower pieces in a triangular manner, wherein the roller spacing is 4 mm; roll temperature: the front roller is less than or equal to 60 ℃, and the rear roller is less than or equal to 60 ℃;
(3) and (3) vulcanization:
vulcanization conditions are as follows: pressure 6kg/cm2The temperature was 150 ℃ and the vulcanization time was 30 minutes.
Example 13
A preparation method of composite rubber adopts the formula of example 9, and comprises the following specific steps:
(1) mixing master batch:
the preparation method comprises the steps of putting Urepan50EL06G and NBR3950F into an internal mixer, pressing a top bolt for 15 seconds, putting zinc oxide, paraffin, titanium dioxide, color master MP-1005-1, color master MP-1002-1, color master MP-100, antioxidant RD, antiozonant NTU, antiozonant 6PPD and flame retardant FR516 into the internal mixer, pressing the top bolt for 15 seconds, then putting white carbon black into the internal mixer, pressing the top bolt to 145 ℃, finally putting silane coupling agent, polyethylene glycol, plasticizer NB-4 and clay into the internal mixer, pressing the top bolt to 150 ℃, discharging glue, discharging the glue and obtaining master batch.
(2) Vulcanizing the master batch:
smashing the master batch on an open mill for 90 seconds, wherein the roller spacing is 3 mm; continuously ramming the rubber for 90 seconds, wherein the roller spacing is 1 mm; passing through the roller for 8 times with the roller spacing of 0.5 mm; adding dicumyl peroxide, and the roller spacing is 3 mm; passing through the roller for 3 times, wherein the roller spacing is 1 mm; packaging 6 pieces of back lower pieces in a triangular manner, wherein the roller spacing is 4 mm; roll temperature: the front roller is less than or equal to 60 ℃, and the rear roller is less than or equal to 60 ℃;
(3) and (3) vulcanization:
vulcanization conditions are as follows: pressure 6kg/cm2The temperature was 150 ℃ and the vulcanization time was 30 minutes.
Example 14
A preparation method of composite rubber adopts the formula of example 9, and comprises the following specific steps:
(1) mixing master batch
The preparation method comprises the steps of putting Urepan50EL06G and NBR3950F into an internal mixer, pressing a top bolt for 15 seconds, putting zinc oxide, paraffin, titanium dioxide, color master MP-1005-1, color master MP-1002-1, color master MP-100, antioxidant RD, antiozonant NTU, antiozonant 6PPD and flame retardant FR516 into the internal mixer, pressing the top bolt for 15 seconds, then putting white carbon black into the internal mixer, pressing the top bolt to 145 ℃, finally putting silane coupling agent, polyethylene glycol, plasticizer NB-4 and clay into the internal mixer, pressing the top bolt to 150 ℃, discharging glue, discharging the glue and obtaining master batch.
(2) Vulcanizing the master batch:
smashing the master batch on an open mill for 120 seconds, wherein the roller spacing is 3 mm; continuously ramming the rubber for 120 seconds, wherein the roller spacing is 1 mm; passing through the roller for 12 times with the roller spacing of 0.5 mm; adding dicumyl peroxide, and the roller spacing is 3 mm; passing through the roller for 3 times, wherein the roller spacing is 1 mm; packaging 6 pieces of back lower pieces in a triangular manner, wherein the roller spacing is 4 mm; roll temperature: the front roller is less than or equal to 60 ℃, and the rear roller is less than or equal to 60 ℃;
(3) and (3) vulcanization:
vulcanization conditions are as follows: pressure 6kg/cm2The temperature was 150 ℃ and the vulcanization time was 30 minutes.
Specific performance comparisons are detailed in table 3.
TABLE 3
The data in table 3 show that the plastication step is eliminated, the mixing time of the master batch in the stage without adding the cross-linking agent in the open mill is prolonged, the mooney of the master batch is reduced by using the open mill, the process steps are reduced, the rubber transportation is reduced, and the production efficiency is improved while the compound rubber obtains similar mooney.
Meanwhile, as the clay forms a protection system in the composite rubber, the mixing time of the master batch in the stage of not adding the cross-linking agent in the open mill is prolonged, and in the process of low roll gap and thin passing, a stronger pulling effect is provided for rubber materials, so that the layered structure of the clay is better separated to be better dispersed in the mixed rubber, and further, the distribution area of a protection layer formed by the clay in the composite rubber is wider, ozone molecules are better prevented from entering the composite rubber, the ozone aging resistance of the composite rubber is better improved, and the longer the mixing time of the master batch in the stage of not adding the cross-linking agent in the open mill is, the better the ozone aging resistance is improved.
In examples 12 to 14, the mooney of the masterbatch was lowered by pyrolysis by banburying at a high temperature, the temperature of the masterbatch was lowered by adding the silane coupling agent, polyethylene glycol, and the plasticizer NB-4 at a high temperature of 145 ℃, the banburying time was prolonged, and the slip was prevented by adding clay together with the silane coupling agent, polyethylene glycol, and the plasticizer NB-4.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (7)
1. A preparation method of compounded rubber is characterized by comprising the following steps: the composite rubber is prepared from the following raw materials in parts by mass, wherein the contents of the components are represented by the parts by mass:
20-50 parts of polyurethane
50-80 parts of nitrile rubber
4-8 parts of plasticizer
20-50 parts of white carbon black
0.5-3 parts of silane coupling agent
40-60 parts of flame retardant
1.5-4 parts of a cross-linking agent;
6-10 parts of clay
The preparation method of the composite rubber comprises the following steps:
(1) mixing master batch:
putting polyurethane and nitrile rubber into an internal mixer, pressing a top bolt for 10-30 seconds, then putting an anti-aging agent, an antiozonant and a flame retardant, pressing the top bolt for 10-30 seconds, then putting white carbon black, pressing the top bolt to 140-145 ℃, finally putting a silane coupling agent, a plasticizer and clay, and pressing the top bolt to 150-155 ℃ for rubber discharge;
(2) vulcanizing the master batch:
smashing the parked masterbatch on an open mill for 60-120 seconds at a roller spacing of 3-4mm, continuously smashing the masterbatch for 60-120 seconds at a roller spacing of 1-2mm for 6-12 times at a roller spacing of 0.5mm, adding a cross-linking agent at a roller spacing of 3-4mm for 3-5 times at a roller spacing of 1-2mm, and making a triangular bag for 6-8 pieces and then discharging the pieces at a roller spacing of 4-5 mm;
(3) and (3) vulcanization:
vulcanization conditions are as follows: the pressure is 6-14kg/cm2The temperature is 150-170 ℃, and the vulcanizing time is 10-30 minutes.
2. The process for producing a compounded rubber according to claim 1, wherein: the contents of the components are as follows:
30-40 parts of polyurethane
60-70 parts of nitrile rubber
5-7 parts of plasticizer
30-40 parts of white carbon black
0.5-1.5 parts of silane coupling agent
45-55 parts of flame retardant
2-3 parts of a cross-linking agent.
3. The process for producing a compounded rubber according to claim 1 or 2, wherein: the crosslinking agent is a peroxide crosslinking agent.
4. The process for producing a compounded rubber according to claim 3, wherein: the material also comprises the following raw materials in parts by weight:
1-3 parts of antiozonant.
5. The process for producing a compounded rubber according to claim 4, wherein: the material also comprises the following raw materials in parts by weight:
1-2 parts of an anti-aging agent.
6. The process for producing a compounded rubber according to claim 1, wherein: the polyurethane is polyether polyurethane.
7. The process for producing a compounded rubber according to claim 1, wherein: the acrylonitrile-butadiene rubber contains 36-42% of acrylonitrile by mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810070358.XA CN108219224B (en) | 2018-01-24 | 2018-01-24 | Composite rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810070358.XA CN108219224B (en) | 2018-01-24 | 2018-01-24 | Composite rubber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108219224A CN108219224A (en) | 2018-06-29 |
| CN108219224B true CN108219224B (en) | 2020-05-19 |
Family
ID=62667610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810070358.XA Expired - Fee Related CN108219224B (en) | 2018-01-24 | 2018-01-24 | Composite rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108219224B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111696720B (en) * | 2020-04-24 | 2021-10-29 | 上海蓝昊电气股份有限公司 | Lightweight reel high-voltage cable and preparation method thereof |
| CN111777810A (en) * | 2020-07-21 | 2020-10-16 | 鞍山市宏图防腐工程有限公司 | PU resin type wear-resistant nitrile rubber and preparation method thereof |
| CN112831175B (en) * | 2021-01-08 | 2022-11-04 | 青岛科技大学 | Wear-resistant and slip-resistant thermoplastic elastomer and preparation method thereof |
| WO2023278572A1 (en) * | 2021-06-30 | 2023-01-05 | Avient Corporation | Thermoset articles comprising nitrile butadiene rubber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824217A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Polyurethane rubber composition and preparation process thereof |
| CN102863778A (en) * | 2012-09-24 | 2013-01-09 | 吴江市信许塑料鞋用配套有限公司 | Anti-puncturing sole material |
| CN104086980A (en) * | 2014-06-20 | 2014-10-08 | 广州机械科学研究院有限公司 | Oil-resistant low-temperature-resistant weather-proof rubber sealing material and preparation method and application thereof |
| CN106243422A (en) * | 2016-08-28 | 2016-12-21 | 肖丽燕 | A kind of oil resistant wear resistant nylon 66 chopped fiber modification strengthens nitrile rubber sealing plate material and preparation method thereof |
-
2018
- 2018-01-24 CN CN201810070358.XA patent/CN108219224B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824217A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Polyurethane rubber composition and preparation process thereof |
| CN102863778A (en) * | 2012-09-24 | 2013-01-09 | 吴江市信许塑料鞋用配套有限公司 | Anti-puncturing sole material |
| CN104086980A (en) * | 2014-06-20 | 2014-10-08 | 广州机械科学研究院有限公司 | Oil-resistant low-temperature-resistant weather-proof rubber sealing material and preparation method and application thereof |
| CN106243422A (en) * | 2016-08-28 | 2016-12-21 | 肖丽燕 | A kind of oil resistant wear resistant nylon 66 chopped fiber modification strengthens nitrile rubber sealing plate material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 聚醚型混炼型聚氨酯与丁腈橡胶的并用研究;刘建文;《橡胶工业》;20160411;第63卷(第3期);第138-141页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108219224A (en) | 2018-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108219224B (en) | Composite rubber and preparation method thereof | |
| US7414094B2 (en) | Rubber composition for inner liner | |
| CN103435858B (en) | Tyre inner liner rubber and preparation method thereof | |
| CN103804806A (en) | Rubber composite applicable to inside liner of tubeless tire | |
| WO2022041591A1 (en) | Polyoxymethylene composition, preparation method therefor and use thereof | |
| CN111849069A (en) | Composite rubber thermoplastic elastomer and preparation method thereof | |
| CN110372927A (en) | Ethanol petrol resistant fuel charger rubber hose internal layer rubber layer and preparation method thereof | |
| CN103804882A (en) | High-performance chlorohydrin rubber and preparation method thereof | |
| CN110591175B (en) | Non-filled rubber composition with high mechanical property and low hysteresis loss and preparation method thereof | |
| CN111040322A (en) | Airtight layer adhesive and preparation method thereof | |
| KR101000811B1 (en) | Rubber composition of tire tread base | |
| CN107540963B (en) | Tire inner liner composite material and preparation method thereof | |
| JP2001233997A (en) | Rubber composition and process for preparation thereof | |
| CN105348579A (en) | High-hardness rubber and preparation method and application thereof | |
| CN107337859A (en) | Oil-immersed pump electric power cable oil resistant EP rubbers sheath material and preparation method thereof | |
| CN105566702B (en) | A kind of agricultural tyre crown of high filling tyre reclaim | |
| CN111471290A (en) | Automobile oil delivery hose sizing material and preparation method and application thereof | |
| CN114181438B (en) | Aircraft tire shoulder rubber and preparation method and application thereof | |
| CN114456456B (en) | Low-temperature-resistant oil-resistant nitrile butadiene rubber composite material and preparation method thereof | |
| CN108659282B (en) | Wide-temperature-range high-damping oil-resistant damping rubber composite material and preparation method thereof | |
| CN113861529A (en) | Ethanol-resistant gasoline composite rubber material and preparation method thereof | |
| CN114149640A (en) | Oil-resistant ethylene propylene diene monomer hose and preparation method thereof | |
| CN112080081B (en) | Low-cost high-gas-barrier thermoplastic vulcanized rubber for bicycle tire and preparation method thereof | |
| CN106589498A (en) | EPDM and SBR roller modified sealing material and preparation method thereof | |
| CN110655690A (en) | High-hardness low-heat-generation low-rolling-resistance solid tire tread rubber material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200519 Termination date: 20220124 |