Acid-resistant composite rubber material with good elasticity as well as preparation method and application of acid-resistant composite rubber material

Abstract

The invention provides an acid-resistant composite rubber material with good elasticity. The acid-resistant composite rubber material is prepared from the following raw materials in parts by mass: 100 parts of a rubber matrix; 40 to 50 parts of inorganic filler; 8-12 parts of a plasticizer; 4-8 parts of zinc oxide; 1-2 parts of stearic acid; 2-3 parts of a compound anti-aging agent; 0.8 to 1.5 parts of sulfur; and 3-6 parts of a compound accelerant. Therefore, according to the technical scheme, on the premise that sufficient acid resistance is guaranteed, the hardness is accurately controlled to be 60 degrees A by adjusting the filler and the plasticizer, the elastic recovery is maximized, and the water squeezing property depends on the elastic recovery capacity of the rubber roller. And the water film can be quickly recovered after instant deformation under pressure, so that the water film can be bounced off and scraped. Therefore, the technical scheme of the invention has excellent acid resistance and water squeezing property, and can meet the water squeezing requirement of the electronic industry (copper foil).

Description

Technical Field

[0001] This invention relates to the field of electrochemical technology, and in particular to a composite rubber material with good acid resistance and elasticity, its preparation method, and its application. Background Technology

[0002] Rubber extrusion rollers are essential in the electronics industry (copper foil). After cleaning, the surface of the copper foil is covered with a water film. At this point, it needs to be squeezed out by one or more pairs of extrusion rollers using mechanical pressure to remove most of the water. Therefore, the core task of the extrusion rollers is to efficiently and evenly remove most of the water and residual acid from the surface of the copper foil by mechanical means before it enters the final drying stage.

[0003] However, existing rubber extrusion rollers suffer from poor dewatering properties (poor elasticity), directly reducing drying efficiency, energy consumption, and the surface quality of copper foil. They also have poor acid resistance, leading to swelling, softening, hardening, cracking, and surface powdering. Once these issues occur, the extrusion roller quickly loses elasticity and pressure, drastically reducing the dewatering effect and contaminating the copper foil product.

[0004] Therefore, developing a composite rubber material with good acid resistance and elasticity is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a composite rubber material with good acid resistance and elasticity, its preparation method, and its application.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: According to one aspect of this application, a composite rubber material with good acid resistance and elasticity is provided, which is made from raw materials of the following components in parts by weight: Rubber matrix: 100 parts; Inorganic filler: 40-50 parts; Plasticizer: 8-12 parts; Zinc oxide: 4-8 parts; Stearic acid: 1-2 parts; Compound anti-aging agent: 2-3 parts; Sulfur: 0.8-1.5 parts; Compound accelerator: 3-6 parts.

[0007] In some embodiments, the rubber matrix is ​​nitrile rubber, wherein the acrylonitrile content in the nitrile rubber is 31-35%.

[0008] In some embodiments, the inorganic filler is carbon black N550; And / or the particle size of the carbon black is 39-48 nm.

[0009] In some embodiments, the plasticizer is trioctyl trimellitate.

[0010] In some embodiments, the compound antioxidant is antioxidant RD and antioxidant MB, with a mass ratio of 3:2.

[0011] In some implementations, the compound accelerator is a mixture of accelerators CZ, TMTD, and DTDM, with a mass ratio of 1:1:1.

[0012] In some embodiments, the raw material components are: 100 parts of nitrile rubber; 40 parts of inorganic filler; 12 parts plasticizer; 6 parts zinc oxide; 1 part stearic acid; Anti-aging agent 2.5 parts; 1.2 parts sulfur; Accelerator 4.5 parts.

[0013] According to another aspect of this application, a method for preparing a high-temperature-resistant, high-pressure-resistant, and high-hardness rubber composite material as described above is provided, comprising the following steps: S1: Add the rubber matrix, zinc oxide, stearic acid, and compound antioxidants to a mixer according to the specified ratio. Mix at 100-120℃ for 3-6 minutes to obtain the first mixed rubber compound. S2: Add inorganic fillers and plasticizers to the first mixed rubber compound according to the proportion, and perform secondary mixing at 120-140℃ for 3-5 minutes; S3: Continue to mix the rubber compound obtained in S2 at 120-150℃ for 3-5 minutes, then discharge the rubber and cool it fully to room temperature; S4: Add sulfur and compound accelerator to the cooled rubber compound according to the formula. Mix in an internal mixer at 90-100℃ for 3-8 minutes. After uniform mixing, discharge the rubber to obtain the rubber material.

[0014] Therefore, the technical solution of this application can achieve better dispersion and is easy to mix evenly. It can also react better at the temperature specified in this application, effectively avoiding scorching and dead rubber formation. This results in a composite rubber material with good acid resistance and elasticity.

[0015] In some implementations, in step S1, the mixing temperature is 110°C and the time is 5 minutes. And / or in step S2, the secondary mixing temperature is 130℃; the time is 5 minutes; And / or in step S3, the additional mixing temperature is 140°C; the time is 4 minutes; and the cooling temperature is 65°C. And / or in step S4, the temperature is 95°C and the mixing time is 2 minutes.

[0016] According to another aspect of this application, there is an application of the aforementioned composite rubber material in the preparation of rubber extrusion rollers.

[0017] Compared with the prior art, this application has the following advantages: The technical solution of this application, while ensuring sufficient acid resistance, achieves... fillers and plasticizers The adjustment precisely controls the hardness at 60°A and maximizes elastic recovery. Water-recovery performance depends on the elastic recovery capability of the roller. Only by rapidly returning to its original shape after instantaneous deformation under pressure can the water film be "bounced away" and scraped off. Therefore, the technical solution of this application has excellent acid resistance and water-recovery performance, sufficient to meet the water-recovery requirements of the electronics industry (copper foil). Detailed Implementation

[0018] The present invention will be further described below with reference to embodiments.

[0019] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other.

[0020] I. Specific Implementation Examples and Comparative Examples Example 1 This embodiment provides a composite rubber material with good acid resistance and elasticity, the raw material composition (parts by weight) of which is as follows: The composition includes 100 parts nitrile rubber, 45 parts inorganic filler, 10 parts plasticizer, 6 parts zinc oxide, 1 part stearic acid, 1.5 parts antioxidant RD, 1 part antioxidant MB, 1.2 parts sulfur, 1.5 parts accelerator CZ, 1.5 parts accelerator TMTD, and 1.5 parts accelerator DTDM. The nitrile rubber used is JSR N230S (acrylonitrile content 33%), the inorganic filler is carbon black N550, and the plasticizer is trioctyl trimellitate (TOTM).

[0021] The specific grades of the components are as follows: Nitrile rubber JSR N230S, Nitrile rubber NBR 3555J (acrylonitrile content 36%), Nitrile rubber NBR 1051 (acrylonitrile content 41%), inorganic filler CABOT N550, plasticizer selected as trioctyl trimellitate (TOTM), zinc oxide ZNOA, stearic acid SA, antioxidant RD, antioxidant MB, sulfur S, accelerator CZ, accelerator TMTD, and accelerator DTDM.

[0022] The preparation method includes the following steps: S1: Nitrile rubber, carbon black N550, and plasticizer TOTM are added into an internal mixer according to the specified ratio and mixed at 110°C for 5 minutes to obtain the first mixed rubber compound. S2: Add zinc oxide, stearic acid, antioxidant RD, and antioxidant MB to the first mixed rubber compound according to the ratio, and perform a second mixing at 130°C for 5 minutes; S3: Continue to mix the rubber compound obtained in S2 at 140°C for 4 minutes, then discharge the rubber and cool it to room temperature at 60°C. S4: Add sulfur, accelerator CZ, accelerator, and accelerator DTDM to the cooled rubber compound according to the formula. Mix in a two-roll mill or internal mixer at 95°C for 2 minutes. After uniform mixing, discharge the rubber to obtain the rubber material.

[0023] Example 2 The difference from Example 1 is that the raw material composition (parts by weight) is as follows: The composition includes 100 parts nitrile rubber, 40 parts inorganic filler, 8 parts plasticizer, 4 parts zinc oxide, 1 part stearic acid, 1.2 parts antioxidant RD, 0.8 parts antioxidant MB, 0.8 parts sulfur, 1 part accelerator CZ, 1 part accelerator TMTD, and 1 part accelerator DTDM. The nitrile rubber used is JSR N230S (acrylonitrile content 33%), the inorganic filler is carbon black N550, and the plasticizer is trioctyl trimellitate (TOTM). All other components are identical to those in Example 1.

[0024] Example 3 The difference from Example 1 is that the raw material composition (parts by weight) is as follows: The composition includes 100 parts nitrile rubber, 50 parts inorganic filler, 12 parts plasticizer, 8 parts zinc oxide, 2 parts stearic acid, 1.8 parts antioxidant RD, 1.2 parts antioxidant MB, 1.5 parts sulfur, 2 parts accelerator CZ, 2 parts accelerator TMTD, and 2 parts accelerator DTDM. The nitrile rubber used is JSR N230S (acrylonitrile content 33%), the inorganic filler is carbon black N550, and the plasticizer is trioctyl trimellitate (TOTM). All other components are identical to those in Example 1.

[0025] Comparative Example 1 The difference from Example 1 is that the nitrile rubber used is nitrile rubber 3555J with an acrylonitrile content of 36%; the other components, dosages, and preparation methods are exactly the same as in Example 1.

[0026] Comparative Example 2 The nitrile rubber used is nitrile rubber 1051-acrylonitrile content 41%; the remaining components, dosages, and preparation methods are exactly the same as in Example 1.

[0027] Comparative Example 3 The difference from Example 1 is that the amount of carbon black N550 was adjusted to 0 parts; the other components, amounts, and preparation methods are exactly the same as in Example 1.

[0028] Comparative Example 4 The difference from Example 1 is that the amount of plasticizer TOTM was adjusted to 0 parts; the other components, amounts, and preparation methods are exactly the same as in Example 1.

[0029] Comparative Example 5 The difference from Example 1 is that the amount of zinc oxide was adjusted to 0 parts; the other components, amounts, and preparation methods are exactly the same as in Example 1.

[0030] Comparative Example 6 The difference from Example 1 is that the amount of stearic acid was adjusted to 0 parts; the remaining components, amounts, and preparation methods are exactly the same as in Example 1.

[0031] Comparative Example 7 The difference from Example 1 is that the amount of antioxidant was adjusted to 0 parts; the other components, amounts, and preparation methods are exactly the same as in Example 1.

[0032] Comparative Example 8 The difference from Example 1 is that the amount of antioxidant RD was adjusted to 2.5 parts; the remaining components, amounts, and preparation methods are exactly the same as in Example 1.

[0033] Comparative Example 9 The difference from Example 1 is that the amount of antioxidant MB was adjusted to 2.5 parts; the other components, amounts, and preparation methods are exactly the same as in Example 1.

[0034] Comparative Example 10 The difference from Example 1 is that the amount of sulfur used was adjusted to 0 parts; the other components, amounts, and preparation methods are exactly the same as in Example 1.

[0035] Comparative Example 11 The difference from Example 1 is that the amount of accelerator was adjusted to 0 parts; the other components, amounts, and preparation methods are exactly the same as in Example 1.

[0036] Comparative Example 12 The difference from Example 1 is that the amount of accelerator CZ was adjusted to 4.5 parts; the remaining components, amounts, and preparation methods are exactly the same as in Example 1.

[0037] Comparative Example 13 The difference from Example 1 is that the amount of accelerator TMTD was adjusted to 4.5 parts; the remaining components, amounts, and preparation methods are exactly the same as in Example 1.

[0038] Comparative Example 14 The difference from Example 1 is that the amount of DTDM accelerator was adjusted to 4.5 parts; the other components, amounts, and preparation methods are exactly the same as in Example 1.

[0039] The proportions of the above embodiments and comparative examples can be found in Table 1 below: Examples and comparative formulations (based on 100 parts by weight of rubber matrix) Table 1 - Examples and Comparative Examples

[0040] All of the above components are commercially available.

[0041] II. Experimental Results Data of Examples and Comparative Examples The materials in the above embodiments and comparative examples were subjected to performance tests. Specifically, the performance tests were conducted in accordance with GB / T 531.1 "Test Method for Indentation Hardness of Vulcanized Rubber or Thermoplastic Rubber - Part 1: Shore Hardness Tester Method (Shore Hardness)"; GB / T 528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber"; GB / T 529-2008 "Determination of Tear Strength of Vulcanized Rubber or Thermoplastic Rubber (Pants-Shaped, Right-Angle and Crescent-Shaped Specimens)"; GB / T 1681-2009 "Determination of Resilience of Vulcanized Rubber"; and GB / T 1690-2010 "Test Method for Liquid Resistance of Vulcanized Rubber or Thermoplastic Rubber". The performance test results are shown in Table 2 below. Table 2 - Performance Test Results

[0042] Based on the above embodiments and comparative data, the technical solution of this application can achieve the following performance: Shore hardness A is 60±2; tensile strength / MPa ≥15; elongation at break / % ≥300; tear strength kN / m ≥30; resilience (%) ≥50; volume change after immersion in pH=4-5H2SO4 at 70°C for 72h: ΔV (%) ±5.

[0043] As can be seen from the above embodiments and comparative data, this application is not a simple sum of the functions of each component, but rather the result of careful design and synergistic cooperation between the components and their proportions. Through the precise coordination of each component, the two properties of "high elasticity" and "acid resistance," which are often contradictory in traditional understanding, are unified under low hardness (60°A) conditions.

[0044] Good acid resistance: The acid resistance of NBR is usually enhanced by increasing the acrylonitrile (ACN) content. However, a high ACN content will lead to increased rubber hardness and decreased elasticity, which is detrimental to extrusion performance. Therefore, nitrile butadiene rubber with a high acrylonitrile (ACN) content should be selected as much as possible without affecting extrusion performance.

[0045] Good water-repellent properties (resilience): 1. While ensuring sufficient acid resistance, the hardness is precisely controlled at 60°A by adjusting the fillers and plasticizers, and elastic recovery is maximized. Squeezability depends on the elastic recovery ability of the rubber roller. Rubber with the lowest possible acrylonitrile content should be selected while ensuring acid resistance. 2. The technical solution of this application is a "low-sulfur, high-accelerator" system, which is a dense and stable three-dimensional network structure. This structure can provide rapid and sufficient elastic recovery after removal by external force (squeezing water film), thereby "bounced" the water film and scraped it off, effectively avoiding water residue. Compared with traditional single accelerator systems, this composite system ensures the efficiency and stability of the cross-linking network.

[0046] Therefore, this application presents an integrated technical solution based on high-nitrile NBR, with the plasticizer TOTM stabilizing the reaction system and composite vulcanization improving resilience. This solution effectively resists acid corrosion, thus solving the two major technical defects of existing copper foil dewatering rollers: poor dewatering effect and short service life. It has significant progressiveness and application value.

[0047] The above descriptions are merely some embodiments of the present invention. It should be noted that those skilled in the art can make other modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A composite rubber material with good acid resistance and elasticity, characterized in that, Made from the following components in parts by weight: Rubber matrix: 100 parts; Inorganic filler: 40-50 parts; Plasticizer: 8-12 parts; Zinc oxide: 4-8 parts; Stearic acid: 1-2 parts; Compound anti-aging agent: 2-3 parts; Sulfur: 0.8-1.5 parts; Compound accelerator: 3-6 parts.

2. The rubber material according to claim 1, characterized in that, The rubber matrix is ​​nitrile rubber, wherein the acrylonitrile content in the nitrile rubber is 31-35%.

3. The rubber material according to claim 1, characterized in that, The inorganic filler is carbon black N550; And / or the particle size of the carbon black is 39-48 nm.

4. The rubber material according to claim 1, characterized in that, The plasticizer is trioctyl trimellitate.

5. The rubber material according to claim 1, characterized in that, The compound antioxidant consists of antioxidant RD and antioxidant MB, with a mass ratio of 3:

2.

6. The rubber material according to claim 1, characterized in that, The compound accelerator is a mixture of accelerators CZ, TMTD, and DTDM, with a mass ratio of 1:1:

1.

7. The rubber material according to claim 1, characterized in that, The raw material components are: 100 parts of nitrile rubber; 40 parts of inorganic filler; 12 parts plasticizer; 6 parts zinc oxide; 1 part stearic acid; Anti-aging agent 2.5 parts; 1.2 parts sulfur; Accelerator 4.5 parts.

8. A method for preparing a high-temperature-resistant, high-pressure-resistant, and high-hardness rubber composite material as described in any one of claims 1-7, characterized in that, Includes the following steps: S1: Add the rubber matrix, zinc oxide, stearic acid, and compound antioxidants to a mixer according to the specified ratio. Mix at 100-120℃ for 3-6 minutes to obtain the first mixed rubber compound. S2: Add inorganic fillers and plasticizers to the first mixed rubber compound according to the proportion, and perform secondary mixing at 120-140℃ for 3-5 minutes; S3: Continue to mix the rubber compound obtained in S2 at 120-150℃ for 3-5 minutes, then discharge the rubber and cool it fully to room temperature; S4: Add sulfur and compound accelerator to the cooled rubber compound according to the formula. Mix in an internal mixer at 90-100℃ for 3-8 minutes. After uniform mixing, discharge the rubber to obtain the rubber material.

9. The method according to claim 8, characterized in that, In step S1, the mixing temperature is 110℃ and the time is 5 minutes. And / or in step S2, the secondary mixing temperature is 130℃; the time is 5 minutes; And / or in step S3, the additional mixing temperature is 140℃; the time is 4 minutes; And / or in step S4, the temperature is 95°C and the mixing time is 2 minutes.

10. The use of the composite rubber material according to any one of claims 1-7 in the preparation of rubber extrusion rollers.

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