CN115678129A - High-stiffness rubber material and production process thereof - Google Patents
High-stiffness rubber material and production process thereof Download PDFInfo
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Abstract
The invention provides a high-stiffness rubber material which comprises the following components in parts by mass: 75-95 parts of nitrile rubber, 5-25 parts of natural rubber, 1-5 parts of zinc oxide, 1-5 parts of sulfur, 2-7 parts of dispersant, 1-5 parts of stearic acid, 8-15 parts of plasticizer, 1-2 parts of paraffin and 30-60 parts of white carbon black. The high-stiffness rubber material. The high-stiffness rubber material specifically adopts calcium carbonate, oyster shell powder and shell powder which are combined to be used as a sulfur dispersing agent, the dispersing agent and sulfur are uniformly mixed, the mixture is used as a vulcanizing agent and then added into rubber, and the dispersing performance of the sulfur is effectively improved. Meanwhile, the invention provides a production process of the high-stiffness rubber material, which is simple, easy to operate and convenient for industrial production.
Description
Technical Field
The invention relates to the field of rubber, in particular to a high-stiffness rubber material and a production process thereof.
Background
With the rapid development of the rubber industry, particularly the continuous innovation of the rubber processing technology, the updating of rubber processing equipment and the continuous improvement of the quality requirement of rubber products, the requirements of the processing technologies such as extrusion, calendering and extrusion of rubber on the Mooney viscosity (ML (1+4) 100 ℃) of rubber materials in the rubber processing technology are increasingly finer and tighter, because the Mooney viscosity of the rubber materials determines the stiffness of the semi-finished rubber materials, and the stiffness of the semi-finished rubber materials determines the shape and the size quality of the semi-finished rubber products, the subsequent processing operation performance (process performance) and the quality of final vulcanized products.
For the high-stiffness rubber material, the components of the high-stiffness rubber material contain a large amount of reinforcing additives, in the rubber mixing production process, the contained compounding agents such as zinc oxide, sulfur and the like have low infiltration degree with rubber, the dispersion effect in the rubber is poor, and meanwhile, in the mixing process, the shearing force of rubber mixing equipment on the rubber material is large, so that the equipment load is large, the rubber material generates heat quickly, the temperature of the rubber mixing equipment and the rubber material is increased, when the temperature reaches a certain value (such as the nitrile butadiene rubber material is ultrahigh by 150 ℃), the rubber material can generate a large amount of gel, carbon black particles and even the rubber material is carbonized, and therefore, in the rubber mixing production process, when the temperature cannot meet the parameters in the production process, the production and processing can only be stopped.
Therefore, the traditional rubber mixing process can only adopt a two-stage method to process and produce the rubber with high Mooney viscosity. Firstly, rubber and compounding agents except a vulcanizing agent or an accelerating agent (and a bonding agent sometimes) are processed for a section to form master batch, and the temperature of equipment in the processing process is not over 140 ℃; secondly, after the master batch is fully cooled and placed, a vulcanizing agent or an accelerant (sometimes an adhesive) is added to the mixing equipment for secondary processing to form the final mixed batch, wherein the equipment temperature cannot exceed 120 ℃ in the production process. Therefore, the vulcanizing agent can only be added at the end of the two-stage processing for producing the high-stiffness rubber material, and the vulcanizing agent, particularly sulfur, zinc oxide and the like, has low solubility and poor divergence in rubber, so that the non-uniform dispersion in the rubber material is easily caused, the performance of the rubber material is influenced, and even the quality of a vulcanized product is influenced.
In order to solve the above problems, people are always seeking an ideal technical solution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a high-stiffness rubber material and a production process thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a high-stiffness rubber material comprises the following components in parts by mass: 75-95 parts of nitrile rubber, 5-25 parts of natural rubber, 1-5 parts of zinc oxide, 1-5 parts of sulfur, 2-7 parts of dispersing agent, 1-5 parts of stearic acid, 3-8 parts of silane coupling agent, 0.5-1 part of initiator, 8-15 parts of plasticizer, 1-2 parts of paraffin and 30-60 parts of white carbon black.
The Mooney viscosity ML (1+4) of the nitrile rubber is 100-130 at 100 ℃, and the content of acrylonitrile in the nitrile rubber is 31-35%; the polyisoprene content in the natural rubber is 91-94%.
The zinc oxide particle size range is 40-60 nm.
The silane coupling agent is selected from vinyl tri (2-methoxyethoxy) silane, vinyl triethoxysilane, and vinyl trimethoxysilane.
The dispersant comprises a dispersant with a volume ratio of 1: (2-4): (2-4) calcium carbonate, oyster shell powder, shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing. The organic matters of the oyster shells and the shells are decomposed by microorganisms through the decay, and a weakly acidic washing solution can be adopted in the cleaning process.
The particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm.
The decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 6-10 d.
A production process of the high-stiffness rubber material comprises the following steps:
dissolving a silane coupling agent in an ethanol water solution according to the proportion of 3-8 g/L, adjusting the pH, adding white carbon black and zinc oxide, mixing 1-3 h under the condition of 1000-1500 r/min, cooling, carrying out solid-liquid separation, and drying to obtain modified mixed powder;
mixing and ball-milling the sulfur and the dispersant for 5-20 min to obtain a vulcanizing agent;
firstly, plasticizing nitrile rubber and natural rubber for 1-2min, and then adding stearic acid, an initiator, a plasticizer, paraffin and modified mixed powder for continuously kneading to obtain a master batch; and adding a vulcanizing agent into the master batch, and continuously mixing to obtain the high-stiffness rubber material.
Compared with the prior art, the high-stiffness rubber material has outstanding substantive characteristics and remarkable progress, and particularly, the high-stiffness rubber material provided by the invention adopts calcium carbonate, oyster shell powder and shell powder which are combined to be used as a sulfur dispersing agent, the dispersing agent and sulfur are uniformly mixed, the mixture is used as a vulcanizing agent and then added into rubber, and the dispersing performance of the sulfur is effectively improved. In addition, the initiator and the silane coupling agent are added, so that on one hand, the silane coupling agent is used for modifying the white carbon black to improve the dispersibility of the white carbon black, and on the other hand, the initiator enables the silane coupling agent to react with double bonds in the rubber so as to improve the performance of the rubber product. Meanwhile, the invention provides a production process of the high-stiffness rubber material, which is simple, easy to operate and convenient for industrial production.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments.
Examples
A high-stiffness rubber material comprises the following components in parts by mass: 75-95 parts of nitrile rubber, 5-25 parts of natural rubber, 1-5 parts of zinc oxide, 1-5 parts of sulfur, 2-7 parts of dispersing agent, 1-5 parts of stearic acid, 3-8 parts of silane coupling agent, 0.5-1 part of initiator, 8-15 parts of plasticizer, 1-2 parts of paraffin and 30-60 parts of white carbon black.
Wherein the initiator is selected from a photoinitiator or a thermal initiator; the nitrile rubber is Krynac3311OF produced by Lanxess (Lanxess) OF Germany; the polyisoprene content in the natural rubber is 91-94%. The zinc oxide particle size range is 40-60 nm. The silane coupling agent is selected from one of vinyl tri (2-methoxyethoxy) silane, vinyl triethoxysilane and vinyl trimethoxysilane; the plasticizer is one or more of dipropylene glycol dibenzoate, alkyl polyether and adipic acid alkyl ether ester. The dispersant comprises a dispersant with a volume ratio of 1: (2-4): (2-4) calcium carbonate, oyster shell powder, shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing. The particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm. The decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 6-10 d.
A production process of the high-stiffness rubber compound comprises the following steps:
dissolving a silane coupling agent in an ethanol water solution according to the proportion of 3-8 g/L, adjusting the pH (citric acid and the like), adding white carbon black and zinc oxide, mixing 1-3 h under the condition of 1000-1500 r/min, cooling, carrying out solid-liquid separation, and drying to obtain modified mixed powder;
mixing and ball-milling the sulfur and the dispersing agent for 5-20 min to obtain a vulcanizing agent;
firstly, putting nitrile rubber and natural rubber into an internal mixer for plasticizing for 1-2min, then adding stearic acid, an initiator, a plasticizer, paraffin and modified mixed powder for continuous mixing, and mixing uniformly, wherein the rubber discharge temperature is 100-120 ℃, and the rotating speed of a rotor of the internal mixer is 20-50 revolutions; and cooling the masterbatch for a period of time, adding a vulcanizing agent into the open mill, continuously mixing, uniformly mixing and discharging to obtain the high-stiffness rubber material.
Taking the high-stiffness rubber material to perform sulfur transformation at 165 ℃ for 10 min, cooling the rubber material by 16 h, and testing the performance of the rubber material.
Example 1
A high-stiffness rubber material comprises the following components in parts by mass: 75 parts of nitrile rubber, 25 parts of natural rubber, 1 part of zinc oxide, 1 part of sulfur, 2 parts of a dispersing agent, 5 parts of stearic acid, 3 parts of a silane coupling agent, 0.5 part of an initiator, 8 parts of a plasticizer, 1 part of paraffin and 30 parts of white carbon black.
Wherein the initiator is thermal initiator Benzoyl Peroxide (BPO); the nitrile rubber is Krynac3311OF produced by Lanxess (Lanxess) OF Germany; the polyisoprene content in the natural rubber is 91-94%. The zinc oxide particle size range is 40-60 nm. The plasticizer is dipropylene glycol dibenzoate; the silane coupling agent is vinyl tri (2-methoxyethoxy) silane. The dispersant comprises a dispersant with a volume ratio of 1:2:2 calcium carbonate, oyster shell powder and shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing. The particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm. The decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 6 d.
A production process of the high-stiffness rubber compound comprises the following steps:
dissolving a silane coupling agent in an ethanol water solution according to the proportion of 3 g/L, adjusting the pH (citric acid and the like), adding white carbon black and zinc oxide, mixing 1 h under the condition of 1000-1500 r/min, cooling, carrying out solid-liquid separation, and drying to obtain modified mixed powder;
mixing and ball-milling the sulfur and the dispersing agent for 5 min to obtain a vulcanizing agent;
the rotation speed is 50 r/min, the initial temperature is 75 ℃, nitrile rubber and natural rubber are added into an internal mixer in 30 s, a ram is used for preheating and mixing 60 s, stearic acid, an initiator, a plasticizer, paraffin wax and modified mixed powder are added, ram is used for mixing 30 s, a ram is used for mixing 10 s, the operation is repeated for 3 times, a vulcanizing agent is added, the ram is used for mixing 30 s, the ram is used for mixing 10 s, rubber discharging is repeated for 3 times, and the rubber discharging temperature is 110 ℃; after rubber is discharged, the rubber material is added into an open mill, the roll gap of the open mill is 3mm, the roll temperature is 60 ℃, the roll wrapping is 30 s, the left and right cutting knives are 3/4 once, and the rubber material is taken out, cooled and placed.
Taking a high-stiffness sizing material to perform sulfur transformation at 165 ℃ for 10 min, cooling to 16 h, testing the hardness (Shore A type) to be 45 according to GB/T531.1-2008, testing the tensile strength to be 7.84 MPA according to GB/T528-2009, testing the elongation at break to be 670%, and testing the resilience to be 34% according to GB/T1681-2009.
Example 2
A high-stiffness rubber material comprises the following components in parts by mass: 80 parts of nitrile rubber, 20 parts of natural rubber, 5 parts of zinc oxide, 5 parts of sulfur, 7 parts of a dispersing agent, 5 parts of stearic acid, 8 parts of a silane coupling agent, 1 part of an initiator, 15 parts of a plasticizer, 2 parts of paraffin and 60 parts of white carbon black.
Wherein the initiator is thermal initiator Benzoyl Peroxide (BPO); the nitrile rubber is Krynac3311OF produced by Lanxess (Lanxess) OF Germany; the natural rubber contains 91-94% of polyisoprene. The zinc oxide particle size range is 40-60 nm. The plasticizer is dipropylene glycol dibenzoate; the silane coupling agent is vinyl triethoxysilane. The dispersant comprises a dispersant with a volume ratio of 1:4: 4 calcium carbonate, oyster shell powder and shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing. The particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm. The decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 10 d.
A production process of the high-stiffness rubber compound comprises the following steps:
dissolving a silane coupling agent in an ethanol water solution according to the proportion of 8 g/L, adjusting the pH (citric acid and the like), adding white carbon black and zinc oxide, mixing 3 h under the condition of 1000-1500 r/min, cooling, carrying out solid-liquid separation, and drying to obtain modified mixed powder;
mixing and ball-milling the sulfur and the dispersing agent for 20 min to obtain a vulcanizing agent;
the rotation speed is 50 r/min, the initial temperature is 75 ℃, nitrile rubber and natural rubber are added into an internal mixer in 30 s, a ram is used for preheating and mixing 60 s, stearic acid, an initiator, a plasticizer, paraffin wax and modified mixed powder are added, ram is used for mixing 30 s, a ram is used for mixing 10 s, the operation is repeated for 3 times, a vulcanizing agent is added, the ram is used for mixing 30 s, the ram is used for mixing 10 s, rubber discharging is repeated for 3 times, and the rubber discharging temperature is 110 ℃; after rubber is discharged, the rubber material is added into an open mill, the roll gap of the open mill is 3mm, the roll temperature is 60 ℃, the roll wrapping is 30 s, the left and right cutting knives are 3/4 once, and the rubber material is taken out, cooled and placed.
Taking a high-stiffness sizing material to perform sulfur transformation at 165 ℃ for 10 min, cooling the sizing material by 16 h, testing the hardness (Shore A type) to be 43 according to GB/T531.1-2008, testing the tensile strength to be 7.98 MPA according to GB/T528-2009, testing the elongation at break to be 650%, and testing the resilience to be 36% according to GB/T1681-2009.
Example 3
A high-stiffness rubber material comprises the following components in parts by mass: 85 parts of nitrile rubber, 15 parts of natural rubber, 2 parts of zinc oxide, 2 parts of sulfur, 4 parts of a dispersing agent, 3 parts of stearic acid, 4 parts of a silane coupling agent, 0.5 part of an initiator, 11 parts of a plasticizer, 1 part of paraffin and 45 parts of white carbon black.
Wherein the initiator is a photoinitiator 2959tos; the nitrile rubber is Krynac3311OF produced by Lanxess (Lanxess) OF Germany; the polyisoprene content in the natural rubber is 91-94%. The zinc oxide particle size range is 40-60 nm. The silane coupling agent is one of vinyl trimethoxy silane. The dispersant comprises a dispersant with a volume ratio of 1:4:2 calcium carbonate, oyster shell powder and shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing. The particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm. The decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 10 d.
A production process of the high-stiffness rubber compound comprises the following steps:
dissolving a silane coupling agent in an ethanol water solution according to the proportion of 3-8 g/L, adjusting the pH (citric acid and the like), adding white carbon black and zinc oxide, mixing 3 h under the condition of 1000-1500 r/min, cooling, carrying out solid-liquid separation, and drying to obtain modified mixed powder;
mixing and ball-milling the sulfur and the dispersing agent for 15 min to obtain a vulcanizing agent;
the rotation speed is 30 r/min, the initial temperature is 75 ℃, nitrile rubber and natural rubber are added into an internal mixer in 30 s, a ram is used for preheating and mixing 60 s, stearic acid, an initiator, a plasticizer, paraffin wax and modified mixed powder are added, ram is used for mixing 30 s, a ram is used for mixing 10 s, the operation is repeated for 3 times, a vulcanizing agent is added, the ram is used for mixing 30 s, the ram is used for mixing 10 s, rubber discharging is repeated for 3 times, and the rubber discharging temperature is 110 ℃; after rubber is discharged, the rubber material is added into an open mill, the roll gap of the open mill is 3mm, the roll temperature is 60 ℃, the roll wrapping is 30 s, the left and right cutting knives are 3/4 once, and the rubber material is taken out, cooled and placed.
The high-stiffness rubber material is irradiated for 20 min by ultraviolet light, then sulfur change is carried out at 165 ℃ for 10 min, cooling is carried out for 16 h, the hardness (Shore A type) is 42 according to GB/T531.1-2008 test, the tensile strength is 7.76 MPA according to GB/T528-2009 test, the elongation at break is 640%, and the resilience is 35% according to GB/T1681-2009 test.
Example 4
A high-stiffness rubber material comprises the following components in parts by mass: 85 parts of nitrile rubber, 15 parts of natural rubber, 3 parts of zinc oxide, 1 part of sulfur, 2 parts of a dispersing agent, 2 parts of stearic acid, 10 parts of a plasticizer, 1 part of paraffin and 40 parts of white carbon black.
Wherein the nitrile rubber is Krynac3311OF produced by Lanxess (Lanxess) in Germany; the polyisoprene content in the natural rubber is 91-94%. The plasticizer is alkyl polyether; the zinc oxide particle size range is 40-60 nm. The dispersant comprises a dispersant with a volume ratio of 1:2: 4 calcium carbonate, oyster shell powder and shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing. The particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm. The decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 10 d.
A production process of the high-stiffness rubber compound comprises the following steps:
mixing and ball-milling the sulfur and the dispersing agent for 10 min to obtain a vulcanizing agent;
the rotation speed is 30 r/min, the initial temperature is 75 ℃, nitrile rubber and natural rubber are added into an internal mixer in 30 s, a ram is preheated and mixed for 60 s, stearic acid, an initiator, a plasticizer, paraffin, white carbon black and zinc oxide are added, ram is mixed for 30 s, a ram is lifted for 10 s, the process is repeated for 3 times, a vulcanizing agent is added, the ram is mixed for 30 s, the ram is lifted for 10 s, the process is repeated for 3 times, and the rubber discharging temperature is 110 ℃; after rubber is discharged, the rubber material is added into an open mill, the roll gap of the open mill is 3mm, the roll temperature is 60 ℃, the roll wrapping is 30 s, the left and right cutting knives are 3/4 once, and the rubber material is taken out, cooled and placed.
Taking a high-stiffness sizing material to perform sulfur transformation at 165 ℃ for 10 min, cooling the sizing material by 16 h, testing the hardness (Shore A type) to be 31 according to GB/T531.1-2008, testing the tensile strength to be 5.62 MPA according to GB/T528-2009, testing the elongation at break to be 670%, and testing the resilience to be 36% according to GB/T1681-2009.
Example 5
A high-stiffness rubber material comprises the following components in parts by mass: 90 parts of nitrile rubber, 10 parts of natural rubber, 1 part of zinc oxide, 2 parts of sulfur, 3 parts of a dispersing agent, 3 parts of stearic acid, 83 parts of a plasticizer, 1 part of paraffin and 50 parts of white carbon black.
Wherein the nitrile rubber is Krynac3311OF produced by Lanxess (Lanxess) OF Germany; the natural rubber contains 91-94% of polyisoprene. The plasticizer is alkyl polyether; the zinc oxide particle size range is 40-60 nm. The dispersant comprises a dispersant with a volume ratio of 1:4:2 calcium carbonate, oyster shell powder and shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing. The particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm. The decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 10 d.
A production process of the high-stiffness rubber material comprises the following steps:
mixing and ball-milling the sulfur and the dispersing agent for 10 min to obtain a vulcanizing agent;
the rotation speed is 40 r/min, the initial temperature is 75 ℃, nitrile rubber and natural rubber are added into an internal mixer in 30 s, a ram is preheated and mixed for 60 s, stearic acid, an initiator, a plasticizer, paraffin, white carbon black and zinc oxide are added, ram is mixed for 30 s, a ram is lifted for 10 s, the process is repeated for 3 times, a vulcanizing agent is added, the ram is mixed for 30 s, the ram is lifted for 10 s, the process is repeated for 3 times, and the rubber discharging temperature is 110 ℃; after rubber is discharged, the rubber material is added into an open mill, the roll gap of the open mill is 3mm, the roll temperature is 60 ℃, the roll wrapping is 30 s, the left and right cutting knives are 3/4 once, and the rubber material is taken out, cooled and placed.
Taking a high-stiffness sizing material to perform sulfur transformation at 165 ℃ for 10 min, cooling the sizing material by 16 h, testing the hardness (Shore A type) to be 30 according to GB/T531.1-2008, testing the tensile strength to be 5.78 MPA according to GB/T528-2009, testing the elongation at break to be 680%, and testing the resilience to be 38% according to GB/T1681-2009.
Comparative example 1
A high-stiffness rubber material comprises the following components in parts by mass: 90 parts of nitrile rubber, 10 parts of natural rubber, 1 part of zinc oxide, 2 parts of sulfur, 3 parts of a dispersing agent, 3 parts of stearic acid, 83 parts of a plasticizer, 1 part of paraffin and 50 parts of white carbon black.
Wherein the nitrile rubber is Krynac3311OF produced by Lanxess (Lanxess) OF Germany; the natural rubber contains 91-94% of polyisoprene. The plasticizer is alkyl polyether; the zinc oxide particle size range is 40-60 nm. The dispersant is calcium carbonate.
A production process of the high-stiffness rubber material comprises the following steps:
mixing and ball-milling the sulfur and the dispersant for 10 min to obtain a vulcanizing agent;
the rotating speed is 40 r/min, the initial temperature is 75 ℃, nitrile rubber and natural rubber are added into an internal mixer in 30 s, a ram is preheated and mixed for 60 s, stearic acid, an initiator, a plasticizer, paraffin, white carbon black and zinc oxide are added, ram is mixed for 30 s, a ram is lifted for 10 s, the operation is repeated for 3 times, a vulcanizing agent is added, the ram is mixed for 30 s, the ram is lifted for 10 s, rubber discharging is repeated for 3 times, and the rubber discharging temperature is 110 ℃; after rubber is discharged, the rubber material is added into an open mill, the roll gap of the open mill is 3mm, the roll temperature is 60 ℃, the roll wrapping is 30 s, the left and right cutting knives are 3/4 once, and the rubber material is taken out, cooled and placed.
Taking a high-stiffness sizing material to perform sulfur transformation at 165 ℃ for 10 min, cooling the sizing material to 16 h, testing the hardness (Shore A type) to be 30 according to GB/T531.1-2008, testing the tensile strength to be 5.37 MPA according to GB/T528-2009, testing the elongation at break to be 600%, and testing the resilience to be 35% according to GB/T1681-2009.
Comparative example 2
A high-stiffness rubber material comprises the following components in parts by mass: 90 parts of nitrile rubber, 10 parts of natural rubber, 1 part of zinc oxide, 2 parts of sulfur, 3 parts of a dispersing agent, 3 parts of stearic acid, 83 parts of a plasticizer, 1 part of paraffin and 50 parts of white carbon black.
Wherein the nitrile rubber is Krynac3311OF produced by Lanxess (Lanxess) in Germany; the polyisoprene content in the natural rubber is 91-94%. The plasticizer is alkyl polyether; the zinc oxide particle size range is 40-60 nm. The dispersant comprises a dispersant with a volume ratio of 1:4:2 calcium carbonate, oyster shell powder and shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing. The particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm. The decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 10 d.
A production process of the high-stiffness rubber compound comprises the following steps:
the rotation speed is 40 r/min, the initial temperature is 75 ℃, nitrile rubber and natural rubber are added into an internal mixer in 30 s, a ram preheats and mixes 60 s, stearic acid, an initiator, a plasticizer, paraffin, white carbon black, zinc oxide and a dispersant are added, ram mixing is carried out for 30 s, ram lifting is carried out for 10 s, the operation is repeated for 3 times, a vulcanizing agent is added, ram mixing is carried out for 30 s, ram lifting is carried out for 10 s, rubber discharging is carried out for 3 times repeatedly, and the rubber discharging temperature is 110 ℃; after rubber is discharged, the rubber material is added into an open mill, the roll gap of the open mill is 3mm, the roll temperature is 60 ℃, the roll wrapping is 30 s, the left and right cutting knives are 3/4 once, and the rubber material is taken out, cooled and placed.
Taking a high-stiffness sizing material to perform sulfur transformation at 165 ℃ for 10 min, cooling to 16 h, testing the hardness (Shore A type) to be 30 according to GB/T531.1-2008, testing the tensile strength to be 5.42 MPA according to GB/T528-2009, testing the elongation at break to be 620%, and testing the resilience to be 36% according to GB/T1681-2009.
Dispersibility of Sulfur
After the film is parked at 2 h and is completely cooled, 200g of rubber material is randomly sheared, the roller distance of an open mill is 0.5 mm, the film is rolled and discharged, the number of sulfur beans is observed, the number of the sulfur beans is 0, and the number is marked as AA; the number of the sulfur beans is 1-5, and the number is marked as A; the number of the sulfur beans is 6-10, and the number is marked as B; the number of sulfur beans is 11-20, and is marked as C; the number of sulfur beans is more than 20 and is marked as D. The sulfur dispersibility measured in examples 1 to 5 and comparative examples 1 to 2 is shown in the following table.
Table 1 sulfur dispersibility data
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Dispersibility of sulfur | B | B | A | A | AA | C | C |
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (10)
1. A high-stiffness rubber material comprises the following components in parts by mass: 75-95 parts of nitrile rubber, 5-25 parts of natural rubber, 1-5 parts of zinc oxide, 1-5 parts of sulfur, 2-7 parts of dispersant, 1-5 parts of stearic acid, 8-15 parts of plasticizer, 1-2 parts of paraffin and 30-60 parts of white carbon black.
2. The high stiffness compound according to claim 1, wherein: the Mooney viscosity ML (1+4) of the nitrile rubber is 100-130 at 100 ℃, and the content of acrylonitrile in the nitrile rubber is 31-35%; the polyisoprene content in the natural rubber is 91-94%.
3. High stiffness compound according to claim 1 or 2, characterized in that: the zinc oxide particle size range is 40-60 nm.
4. High stiffness compound according to claim 1 or 2, characterized in that: also comprises 0.5-1 part of initiator and 3-8 parts of silane coupling agent.
5. The high stiffness compound according to claim 4, wherein: the silane coupling agent is selected from one of vinyl tri (2-methoxyethoxy) silane, vinyl triethoxysilane and vinyl trimethoxysilane.
6. High stiffness compound according to claim 1 or 2, characterized in that: the dispersant comprises a dispersant with a volume ratio of 1: (2-4): (2-4) calcium carbonate, oyster shell powder, shell powder; the oyster shell powder and the shell powder are prepared by the processes of putrefaction, cleaning, drying and crushing.
7. The high stiffness compound according to claim 6, characterized in that: the particle diameters of the calcium carbonate, the oyster shell powder and the shell powder are 100-300nm.
8. The high stiffness compound according to claim 6, wherein: the decomposition temperature is 35-40 ℃, the air humidity is 70-80%, and the decomposition time is 6-10 d.
9. A process for the production of a high stiffness compound according to any one of claims 1 to 8, comprising the steps of:
mixing and ball-milling the sulfur and the dispersing agent for 5-20 min to obtain a vulcanizing agent;
firstly, plasticizing nitrile rubber and natural rubber for 1-2min, and then adding stearic acid, a plasticizer, paraffin, zinc oxide and white carbon black for continuous mixing to obtain master batch; and adding a vulcanizing agent into the master batch, and continuously mixing to obtain the high-stiffness rubber material.
10. A process for the production of a high stiffness compound according to claim 9, comprising the steps of: dissolving a silane coupling agent in an ethanol water solution according to the proportion of 3-8 g/L, adjusting the pH, adding white carbon black and zinc oxide, mixing 1-3 h under the condition of 1000-1500 r/min, cooling, carrying out solid-liquid separation, and drying to obtain modified mixed powder;
mixing and ball-milling the sulfur and the dispersing agent for 5-20 min to obtain a vulcanizing agent;
firstly, plasticizing nitrile rubber and natural rubber for 1-2min, and then adding stearic acid, a plasticizer, paraffin and modified mixed powder for continuous mixing to obtain master batch; and adding a vulcanizing agent into the master batch, and continuously mixing to obtain the high-stiffness rubber material.
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