CN109181020B - High-hardness damping rubber and preparation method thereof - Google Patents
High-hardness damping rubber and preparation method thereof Download PDFInfo
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- CN109181020B CN109181020B CN201810874755.2A CN201810874755A CN109181020B CN 109181020 B CN109181020 B CN 109181020B CN 201810874755 A CN201810874755 A CN 201810874755A CN 109181020 B CN109181020 B CN 109181020B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention discloses a high-hardness damping rubber which comprises the following components in parts by weight: 100 parts of raw rubber, 7.8-12.2 parts of an active protection system, 90.8-121.2 parts of a reinforcing system and 3.7-5.7 parts of a vulcanization system, wherein the reinforcing system comprises glycerol methacrylate. According to the high-hardness damping rubber, the glyceryl methacrylate is added into the formula, so that the high-hardness damping rubber has dual effects of plasticization and hardness improvement, the limit value of the rubber product on high-hardness processing and performance is overcome, and the rubber has high hardness (the hardness is 92 degrees Shore A), excellent rigidity and mechanical property, a good damping effect and a long service life; the obtained rubber product can be well applied to the buffer rubber matched with the rail transit gear transmission device. Meanwhile, the invention also discloses a preparation method of the high-hardness damping rubber.
Description
Technical Field
The invention belongs to the field of rubber products, and particularly relates to high-hardness damping rubber and a preparation method thereof.
Background
The problems of poor elasticity and difficult forming and healing of high-hardness rubber products generally exist, and in addition, the products have larger size and high thickness, so higher requirements are provided for the manufacturing and processing of the high-hardness rubber products. By adopting the traditional rubber matching scheme, the problems of difficult flowing and easy layering of rubber materials during molding exist, and particularly, the problem of abnormal cracking easily occurs when a product is installed and used under a high-pressure condition.
The 'compression molding' is a commonly adopted rubber molding processing mode, rubber raw materials are manually placed in a mold cavity of a vulcanization molding machine, and a needed product is obtained after mold closing and hot pressing for a certain time. Compared with the compression molding, the injection molding is suitable for products with higher precision and relatively complex structure. The material is not required to be manually placed in a mold cavity, but is automatically fed into an injection tube of a machine table through an injection molding machine, and the material is injected into the mold cavity through a mold injection port and a flow passage after being plasticized by a screw. The injection molding process has the following distinct advantages: the degree of mechanization and automation is high, and the labor intensity of personnel is reduced; artificial errors are reduced, and the product has accurate size, stable performance and high quality, and is particularly suitable for thick products; thirdly, the rubber product is quickly and uniformly vulcanized, and the production period is shortened; fourthly, the product has less hair, less loss and rubber material saving, and the production efficiency and the qualification rate are improved.
However, the injection process requires high fluidity of the raw material, and the high hardness product has high flow resistance of the raw material, so that it is difficult to apply the injection process to the molding process.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a high-hardness damping rubber.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a high-hardness damping rubber comprises the following components in parts by weight: 100 parts of raw rubber, 7.8-12.2 parts of an active protection system, 90.8-121.2 parts of a reinforcing system and 3.7-5.7 parts of a vulcanization system, wherein the reinforcing system comprises glycerol methacrylate.
The novel rubber additive is added into the high-hardness damping rubber: the glycerol methacrylate has the following advantages:
the rubber has the plasticizing effect in rubber mixing, so that the filler is promoted to be fed into the elastomer more quickly, the filler is dispersed uniformly better, the mixing operation time is reduced, and the performance of rubber compound is improved;
secondly, the product is liquid, has obvious plasticizing effect on injection molding and is beneficial to the flowing of rubber materials on a screw. Under the hardness of 90 Shore A, the flow resistance of the mixed rubber is too high, and the injection molding process cannot be adopted. Through the application of the auxiliary agent, the processing characteristic of the 92 Shore A hardness rubber compound can be comparable to that of 70 Shore A hardness rubber compound, and the injection problem of a high-hardness product is solved.
And function as a cross-linking agent in the vulcanization process. The material can greatly improve the hardness by improving the crosslinking density of rubber. The traditional formula design of the rubber utilizes the addition of reinforcing filler to promote the rubber to obtain the desired hardness and strength. Excessive filler is added, so that mixing difficulty and poor forming are caused, particularly, after the hardness is increased to a certain level, the linear relation cannot be increased, and the continuous addition of the filler after 90 Shore A does not contribute to hardness improvement.
The hardness of the product can be greatly reduced after the traditional liquid plasticizer is added, the auxiliary agent just integrates the dual effects of plasticizing and hardness increasing, and the limit value of the rubber product on the processing and performance of high hardness is overcome.
Preferably, the weight part of the glycerol methacrylate is 8-12 parts.
Preferably, the reinforcing system further comprises the following components in parts by weight: 12-18 parts of medium super wear-resistant carbon black, 35-45 parts of high wear-resistant carbon black, 35-45 parts of fast extrusion carbon black and 0.8-1.2 parts of rhinestone powder. The invention adopts a plurality of carbon black fillers to be used together, reasonably utilizes the synergistic reinforcement effect of rubber, exerts the effect of 1+1>2, and prepares a product which has balanced elasticity, hardness, modulus, dynamic performance and the like and can be used for a long service life. Meanwhile, the defect that poor dispersion is easy to occur due to the addition of single high-dose carbon black is overcome; and effectively avoids the phenomenon that single high-filling carbon black is easy to generate five colors.
More preferably, the reinforcing system further comprises the following components in parts by weight: 15 parts of medium and super wear-resistant carbon black, 40 parts of high wear-resistant carbon black, 40 parts of fast extrusion carbon black, 10 parts of glycerol methacrylate and 1 part of rhinestone.
Preferably, the active protection system comprises the following components in parts by weight: 4-6 parts of zinc oxide, 1.5-2.5 parts of stearic acid, 0.8-1.2 parts of p-phenylenediamine anti-aging agent and 1.5-2.5 parts of ketoamine anti-aging agent. Particularly, the protection system better improves the aging characteristics of weather resistance, ozone resistance, fatigue resistance and the like of the product.
More preferably, the active protection system comprises the following ingredients in parts by weight: 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of p-phenylenediamine anti-aging agent and 2 parts of ketoamine anti-aging agent.
Preferably, the vulcanization system comprises the following ingredients in parts by weight: 1.5 to 2.5 parts of sulfur, 0.4 to 0.6 part of 2-thiol benzothiazole, 0.6 to 1.0 part of dibenzothiazyl disulfide and 1.2 to 1.6 parts of N-cyclohexyl-2-benzothiazole sulfonamide.
More preferably, the vulcanization system comprises the following ingredients in parts by weight: 2 parts of sulfur, 0.5 part of 2-thiol benzothiazole, 0.8 part of dibenzothiazyl disulfide and 1.4 parts of N-cyclohexyl-2-benzothiazole sulfonamide.
Meanwhile, the invention also discloses a preparation method of the high-hardness damping rubber, which comprises the following steps: uniformly mixing the components to obtain a mixture; and (3) automatically feeding the mixture into an injection tube of a machine table through an injection molding machine, plasticizing the mixture by a screw, and injecting the plasticized mixture into a mold cavity through a mold injection port and a runner for molding to obtain the high-hardness damping rubber.
The preparation method of the invention has the following advantages:
1. the method improves the abnormal occurrence of the common mould pressing process, insufficient healing pressure among sizing materials, poor bonding among flowing joint surfaces and easy rupture under high pressure;
2. the glue dropping amount of the product can be accurately controlled through the parameter setting of the equipment, the preforming process is simplified, the production efficiency of the product is improved,
3. the automation degree is improved, the production links of personnel contact are reduced, and the product quality is more stable.
Compared with the prior art, the invention has the beneficial effects that:
according to the high-hardness damping rubber, the glycerol methacrylate is added into the formula, so that the high-hardness damping rubber has dual effects of plasticization and hardness improvement, the limit value of the rubber product on high hardness processing and performance is overcome, the rubber has high hardness (the hardness is 92 degrees Shore A), excellent rigidity and mechanical performance, a good damping effect and a long service life, meanwhile, through a full-automatic injection process, the personnel error is reduced, and the consistency of product performance and quality is further improved; the obtained rubber product can be well applied to the buffer rubber matched with the rail transit gear transmission device.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
In one embodiment of the high hardness damping rubber of the present invention, the high hardness damping rubber of the present embodiment comprises the following components in parts by weight:
100 parts of raw rubber (No. 3 natural smoke rubber: NR), 15 parts of medium and super wear-resistant carbon black (N220), 40 parts of high wear-resistant carbon black (N330), 40 parts of fast extrusion carbon black (N550), 1 part of rhinestone, 10 parts of glycerol methacrylate, 5 parts of zinc oxide (ZnO with the purity of more than or equal to 99.7%), 2 parts of Stearic Acid (SA), 1 part of p-phenylenediamine anti-aging agent (4010), 2 parts of ketoamine anti-aging agent (RD), 2 parts of sulfur, 0.5 part of 2-thiol benzothiazole, 0.8 part of dibenzothiazyl disulfide and 1.4 parts of N-cyclohexyl-2-benzothiazole sulfonamide.
The preparation method of the high-hardness damping rubber comprises the following steps: uniformly mixing the components to obtain a mixture; and (3) automatically feeding the mixture into an injection tube of a machine table through an injection molding machine, plasticizing the mixture by a screw, and injecting the plasticized mixture into a mold cavity through a mold injection port and a runner for molding to obtain the high-hardness damping rubber.
Example 2
In one embodiment of the high hardness damping rubber of the present invention, the high hardness damping rubber of the present embodiment comprises the following components in parts by weight:
100 parts of raw rubber (No. 3 natural smoke rubber: NR), 12 parts of medium and super wear-resistant carbon black (N220), 35 parts of high wear-resistant carbon black (N330), 35 parts of fast extrusion carbon black (N550), 0.8 part of rhinestone, 8 parts of glycerol methacrylate, 4 parts of zinc oxide (ZnO with the purity of more than or equal to 99.7%), 1.5 parts of Stearic Acid (SA), 0.8 part of p-phenylenediamine anti-aging agent (4010), 1.5 parts of ketoamine anti-aging agent (RD), 1.5 parts of sulfur, 0.4 part of 2-thiol benzothiazole, 0.6 part of dibenzothiazyl disulfide and 1.2 parts of N-cyclohexyl-2-benzothiazole sulfonamide.
The preparation method of the high-hardness damping rubber comprises the following steps: uniformly mixing the components to obtain a mixture; and (3) automatically feeding the mixture into an injection tube of a machine table through an injection molding machine, plasticizing the mixture by a screw, and injecting the plasticized mixture into a mold cavity through a mold injection port and a runner for molding to obtain the high-hardness damping rubber.
Example 3
In one embodiment of the high hardness damping rubber of the present invention, the high hardness damping rubber of the present embodiment comprises the following components in parts by weight:
100 parts of raw rubber (No. 3 natural smoke rubber: NR), 18 parts of medium and super wear-resistant carbon black (N220), 45 parts of high wear-resistant carbon black (N330), 45 parts of fast extrusion carbon black (N550), 1.2 parts of rhinestone, 12 parts of glycerol methacrylate, 6 parts of zinc oxide (ZnO with the purity of more than or equal to 99.7%), 2.5 parts of Stearic Acid (SA), 1.2 parts of p-phenylenediamine anti-aging agent (4010), 2.5 parts of ketoamine anti-aging agent (RD), 2.5 parts of sulfur, 0.6 part of 2-thiol benzothiazole, 1.0 part of dibenzothiazyl disulfide and 1.6 parts of N-cyclohexyl-2-benzothiazole sulfonamide.
The preparation method of the high-hardness damping rubber comprises the following steps: uniformly mixing the components to obtain a mixture; and (3) automatically feeding the mixture into an injection tube of a machine table through an injection molding machine, plasticizing the mixture by a screw, and injecting the plasticized mixture into a mold cavity through a mold injection port and a runner for molding to obtain the high-hardness damping rubber.
Example 4
Because large-size and high-hardness products are molded, dense and stable-quality products can be manufactured by extremely high pressure; and different production processes have great influence on the material performance. This example uses the rubber formulated in example 1 as an example (examples 2 and 3 have the same effects as example 1 and are not described here), and it was produced by a general press vulcanizer having a molding pressure of 150kg/cm and a full-automatic injection molding machine, respectively2And the mould pressing of the full-automatic injection machine reaches 1900kg/cm2. In order to facilitate detection and recording, the test piece produced by a common plate vulcanizing machine is coded into No. 1, and automatic injection is carried outThe product slices produced by the injection molding machine are coded as # 2, and the test analysis is performed respectively for the performance of the test pieces produced by two different production processes, and the results are shown in tables 1, 2, 3 and 4:
TABLE 1 results of conventional Performance testing
TABLE 2 test results of hot air aging Performance (70 ℃ X168h) (test method: GB/T3512-2014)
TABLE 3 compression set test results
TABLE 4 test results for radial stiffness of the product
As can be seen from the data in Table 1, the conventional performances (Shore A hardness, tensile strength and 100% elongation strength) of the 1# and 2# samples both meet and exceed the standard value data by a certain range, and both the samples can better meet the use requirements of products. But the sample 2# molded by the full-automatic injection molding machine has more excellent mechanical properties and can be used in a more harsh environment.
The hot air aging characteristic is generally a demonstration of the service life of the product, and as can be seen from the data in table 2, the difference between the two samples # 1 and # 2 is not obvious in the hot air aging characteristic, wherein the performance of the sample # 2 is slightly better. The fact shows that different molding processes have no obvious influence on aging, the key point influencing the aging performance of hot air is the formula design, and the formula design of the rubber can further meet the designed service life through the data in the table 2.
The compression permanent deformation is used as a very key index of the rubber product, and the sealing and damping performance of the product is shown. As can be seen from the data in Table 3, the two samples 1# and 2# both well meet the design requirements of the product, wherein the performance of the sample 2# is slightly superior; the fact shows that different molding processes have no obvious influence on the compression set, the key influencing the compression set performance is the formula design, and the formula design of the rubber can further meet the designed product sealing and damping performance through the data in the table 3.
As can be seen from the data in Table 4, the comparison with the static stiffness of the international inlet piece shows that the stiffness of the product is higher than that of the imported product, and the deformation is small under the same stress condition; and sample 2# was slightly higher by molding using a full automatic injection molding machine.
In conclusion, through the innovative formula design of the application, the manufactured product reaches a higher industrial application level, and is combined with a more advanced forming process to prepare a more excellent product. The No. 1 sample is manufactured by adopting a traditional compression molding process, and each datum value is higher than a required standard value. However, the 2# sample manufactured by the advanced injection molding process has more advanced advantages in various modes including conventional mechanical properties, heat aging retention, pressure change, rigidity and the like.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. The high-hardness damping rubber is characterized by comprising the following components in parts by weight: 100 parts of No. 3 natural tobacco glue, 7.8-12.2 parts of an active protection system, 90.8-121.2 parts of a reinforcement system and 3.7-5.7 parts of a vulcanization system;
the reinforcing system comprises the following components in parts by weight: 8-12 parts of glycerol methacrylate, 12-18 parts of medium super wear-resistant carbon black, 35-45 parts of high wear-resistant carbon black, 35-45 parts of fast extrusion carbon black and 0.8-1.2 parts of rhinestone powder;
the active protection system comprises the following components in parts by weight: 4-6 parts of zinc oxide, 1.5-2.5 parts of stearic acid, 0.8-1.2 parts of p-phenylenediamine anti-aging agent and 1.5-2.5 parts of ketoamine anti-aging agent;
the vulcanization system comprises the following components in parts by weight: 1.5 to 2.5 parts of sulfur, 0.4 to 0.6 part of 2-thiol benzothiazole, 0.6 to 1.0 part of dibenzothiazyl disulfide and 1.2 to 1.6 parts of N-cyclohexyl-2-benzothiazole sulfonamide.
2. The high-hardness vibration damper rubber according to claim 1, wherein the reinforcing system comprises the following components in parts by weight: 15 parts of medium and super wear-resistant carbon black, 40 parts of high wear-resistant carbon black, 40 parts of fast extrusion carbon black, 10 parts of glycerol methacrylate and 1 part of rhinestone.
3. The high hardness cushion rubber according to claim 1, wherein the active protection system comprises the following components in parts by weight: 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of p-phenylenediamine anti-aging agent and 2 parts of ketoamine anti-aging agent.
4. The high-hardness vibration damper rubber according to claim 1, wherein said vulcanization system comprises the following components in parts by weight: 2 parts of sulfur, 0.5 part of 2-thiol benzothiazole, 0.8 part of dibenzothiazyl disulfide and 1.4 parts of N-cyclohexyl-2-benzothiazole sulfonamide.
5. A method for preparing a high-hardness vibration damping rubber according to any one of claims 1 to 4, wherein the method comprises:
uniformly mixing the components to obtain a mixture; and (3) automatically feeding the mixture into an injection tube of a machine table through an injection molding machine, plasticizing the mixture by a screw, and injecting the plasticized mixture into a mold cavity through a mold injection port and a runner for molding to obtain the high-hardness damping rubber.
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| CN1654526A (en) * | 2005-01-14 | 2005-08-17 | 四川大学 | Butyl rubber/poly(meth)acrylate blend composite damping material and process for preparing same |
| CN1777635A (en) * | 2003-11-17 | 2006-05-24 | Jsr株式会社 | Molded article of thermoplastic elastomer composition and process for producing the same |
| WO2012120638A1 (en) * | 2011-03-08 | 2012-09-13 | 東海ゴム工業株式会社 | Rubber vibration-damping composition, production method therefor, and vulcanized product thereof |
| CN102827476A (en) * | 2012-09-05 | 2012-12-19 | 中国科学院长春应用化学研究所 | Composite material and preparation method thereof |
| JP2013155292A (en) * | 2012-01-30 | 2013-08-15 | Bridgestone Corp | Vibration-proof rubber composition, crosslinked vibration-proof rubber composition and vibration-proof rubber |
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- 2018-08-02 CN CN201810874755.2A patent/CN109181020B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1777635A (en) * | 2003-11-17 | 2006-05-24 | Jsr株式会社 | Molded article of thermoplastic elastomer composition and process for producing the same |
| CN1654526A (en) * | 2005-01-14 | 2005-08-17 | 四川大学 | Butyl rubber/poly(meth)acrylate blend composite damping material and process for preparing same |
| WO2012120638A1 (en) * | 2011-03-08 | 2012-09-13 | 東海ゴム工業株式会社 | Rubber vibration-damping composition, production method therefor, and vulcanized product thereof |
| JP2013155292A (en) * | 2012-01-30 | 2013-08-15 | Bridgestone Corp | Vibration-proof rubber composition, crosslinked vibration-proof rubber composition and vibration-proof rubber |
| CN102827476A (en) * | 2012-09-05 | 2012-12-19 | 中国科学院长春应用化学研究所 | Composite material and preparation method thereof |
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