Radiation-resistant phenyl silicone rubber composite and its manufacturing method

Abstract

The radiation degradation-resistant phenylsilicone rubber composite provided by the present invention is composed of the following components by weight: 100 parts phenylsilicone rubber premix, 1-3 parts processing aid, 20-30 parts radiation-resistant additive, and 0.5-2 parts peroxide crosslinker. The manufacturing method specifically follows the following steps: First, the following components are weighed out by weight: 100 parts phenylsilicone rubber premix, 1-3 parts processing aid, 20-30 parts radiation-resistant additive, and 0.5-2 parts peroxide crosslinker. Next, the phenylsilicone rubber premix, processing aid, and radiation-resistant additive are first mixed in an open roll mill and then passed through a first thin pass to obtain a masterbatch rubber. The masterbatch rubber and peroxide crosslinker are then second mixed in an open roll mill and then passed through a second thin pass to obtain a final mixed rubber. Finally, the final mixed rubber is vulcanized to obtain a radiation degradation-resistant phenylsilicone rubber composite. The present invention solves the problem of the deterioration of mechanical properties of rubber after radiation exposure, which is a problem encountered in the prior art.

Description

[Technical Field]

[0001] The present invention relates to the technical field of methods for manufacturing rubber materials, and more particularly to a radiation-degradation-resistant phenylsilicone rubber compound, and further to a method for manufacturing a radiation-degradation-resistant phenylsilicone rubber compound. [Background technology]

[0002] With the rapid development of nuclear power plants and space technology, more and more rubber products are being used in fields such as nuclear reactor equipment, space equipment, medical radiation protection equipment, and protective clothing. The interaction of high-energy radiation particles with polymeric materials can cause ionization and activation of rubber materials, which can change the mechanical properties of rubber compounds and result in varying degrees of performance impairment of rubber products. Therefore, higher requirements are being placed on the radiation resistance of rubber products.

[0003] Conventional silicone rubber sealing composites have excellent resistance to high and low temperatures, but they have poor resistance to radiation degradation, and the mechanical properties (tensile strength and elongation at break) of the rubber composites are significantly reduced after radiation degradation, especially due to gamma rays. Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a phenylsilicone rubber composite that is resistant to radiation degradation and to solve the problem of the prior art in that the mechanical performance of rubber composites deteriorates after radiation degradation.

[0005] Another object of the present invention is to provide a method for producing a radiation degradation resistant phenylsilicone rubber composite. [Means for solving the problem]

[0006] The technical concept of this invention proposes a radiation-resistant phenylsilicone rubber composite, which is composed of the following components (parts by weight): 100 parts phenylsilicone rubber premix, 1-3 parts processing aid, 20-30 parts radiation-resistant additive, and 0.5-2 parts peroxide crosslinker. The phenylsilicone rubber premix is ​​RBB-2060-50 silicone rubber or SR3250UDP silicone rubber.

[0007] The processing aid is 201 methyl silicone oil or KF-96 silicone oil.

[0008] The radiation-resistant additives include lead oxide, dibismuth trioxide, and gadolinium oxide, with the weight ratio of lead oxide to dibismuth trioxide being (3-7):(1-4), and the weight ratio of dibismuth trioxide to gadolinium oxide being (1-4):(0.5-2).

[0009] The peroxide crosslinker is either 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, di-tert-butylperoxyisopropylbenzene, or diisopropylbenzene peroxide.

[0010] Another technical solution adopted by the present invention is a method for producing a radiation-resistant phenyl silicone rubber composite, which is carried out according to the following steps:

[0011] Step 1: Weigh out the following ingredients based on parts by weight of each: 100 parts phenyl silicone rubber premix, 1-3 parts processing aid, 20-30 parts radiation resistant additive, 0.5-2 parts peroxide crosslinker.

[0012] Step 2: The phenyl silicone rubber premix, processing aids, and radiation-resistant additives are first mixed in an open roll mill, and then subjected to a first thin pass to obtain the masterbatch rubber.

[0013] Step 3: The masterbatch rubber and peroxide crosslinking agent are mixed a second time in an open roll mill and then subjected to a second thin pass to obtain the final mixed rubber.

[0014] Step 4: The final mixed rubber is vulcanized to obtain a radiation degradation resistant phenyl silicone rubber composite.

[0015] Another technical solution of the present invention has the following features:

[0016] The temperature of the first kneading in step 2 is 60°C to 80°C, and the time is 30 to 40 minutes.

[0017] The temperature of the second kneading in step 3 is 40°C to 50°C, and the time is 15 to 20 minutes.

[0018] Step 4 is specifically implemented as follows:

[0019] Step 4.1: The final mixed rubber is first vulcanized in a mold using a press vulcanizer to obtain an intermediate product. The first vulcanization temperature is 175°C to 185°C, the first vulcanization time is 5 to 10 minutes, and the first vulcanization pressure is 8 MPa to 12 MPa.

[0020] Step 4.2: The intermediate is subjected to a second vulcanization in a high-temperature drying oven to obtain a radiation-resistant phenylsilicone rubber composite. The second vulcanization is carried out by holding the intermediate at 90-110°C for 1-2 hours, then heating to 140-160°C and holding for 1-2 hours, and then further heating to 170-190°C and holding for 3-6 hours. [Effects of the Invention]

[0021] The beneficial effects of the present invention are as follows:

[0022] This invention uses phenylsilicone rubber as the base material and lead oxide, bismuth trioxide, and gadolinium oxide as radiation-resistant additives in combination. The phenylsilicone rubber premix, processing aids, radiation-resistant additives, and peroxide crosslinking agent are uniformly mixed and then vulcanized at high temperatures. Performance indicators include a hardness of 60±5 Shore A, a tensile strength of ≥7 MPa, an elongation of ≥200%, and a brittle temperature of ≤-75°C. After 72 hours of aging in hot air at 200°C, the rubber composite retains ≥90% of its tensile strength and elongation properties. Furthermore, after radiation aging testing in a gamma-ray radiation field, the rubber composite retains ≥85% of its tensile strength and elongation properties.

[0023] The phenylsilicone rubber composite produced by the present invention has excellent low-temperature resistance and is able to maintain excellent mechanical properties even after radiation aging due to gamma rays, demonstrating excellent resistance to gamma-ray radiation degradation. DETAILED DESCRIPTION OF THE INVENTION

[0024] The present invention will be described in detail below with reference to specific examples.

[0025] The radiation degradation-resistant phenylsilicone rubber composite of the present invention is composed of the following components based on parts by weight: 100 parts by weight of phenylsilicone rubber premix, 1 to 3 parts of processing aid, 20 to 30 parts of radiation-resistant additive, and 0.5 to 2 parts of peroxide crosslinking agent.

[0026] The phenyl silicone rubber premix is ​​RBB-2060-50 silicone rubber or SR3250UDP silicone rubber. The processing aid is 201 methyl silicone oil or KF-96 silicone oil. The radiation-resistant additive contains lead oxide, dibismuth trioxide, and gadolinium oxide, with the weight ratio of lead oxide to dibismuth trioxide being (3-7):(1-4), and the weight ratio of dibismuth trioxide to gadolinium oxide being (1-4):(0.5-2). The peroxide crosslinking agent is selected from 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, di-tert-butylperoxyisopropylbenzene, and diisopropylbenzene peroxide.

[0027] The present invention also provides a method for producing a radiation degradation resistant phenylsilicone rubber composite, which is specifically carried out according to the following steps:

[0028] Step 1: Weigh out the following ingredients based on parts by weight: 100 parts phenyl silicone rubber premix, 1-3 parts processing aid, 20-30 parts radiation resistant additive, 0.5-2 parts peroxide crosslinker.

[0029] Step 2: The phenyl silicone rubber premix, processing aids, and radiation-resistant additives are first mixed using an open roll mill, followed by a first pass. This produces the masterbatch rubber. The first mix is ​​performed at a temperature of 60°C to 80°C for 30 to 40 minutes.

[0030] Step 3: The masterbatch rubber and peroxide crosslinker are mixed in an open roll mill for a second time, followed by a second thin pass to obtain the final mixed rubber. The second mixing temperature is 40°C to 50°C, and the time is 15 to 20 minutes.

[0031] Step 4: Vulcanize the final mixed rubber to obtain a radiation degradation resistant phenyl silicone rubber composite.

[0032] Step 4.1: The final mixed rubber is first vulcanized in a mold using a press vulcanizer to obtain an intermediate product. The first vulcanization temperature is 175°C to 185°C, the time is 5 to 10 minutes, and the pressure is 8 MPa to 12 MPa.

[0033] Step 4.2: The intermediate is subjected to a second vulcanization in a high-temperature drying oven to obtain a radiation-resistant phenylsilicone rubber composite. The second vulcanization is performed by holding the composite at 90-110°C for 1-2 hours, then heating to 140-160°C and holding for 1-2 hours, and then further heating to 170-190°C and holding for 3-6 hours. [Example]

[0034] The radiation degradation-resistant phenylsilicone rubber composite of this example was composed of the following raw materials: 200 grams of RBB-2060-50 silicone rubber, 4 grams of 201 methyl silicone oil, 30 grams of lead oxide, 12 grams of bismuth trioxide, 6 grams of gadolinium oxide, and 2 grams of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0035] The manufacturing method of the above embodiment includes the following steps:

[0036] Step 1: Weigh out the following ingredients: 200 grams of RBB-2060-50 silicone rubber, 4 grams of 201 methyl silicone oil, 30 grams of lead oxide, 12 grams of bismuth trioxide, 6 grams of gadolinium oxide, and 2 grams of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0037] Step 2: RBB-2060-50 silicone rubber, 201 methyl silicone oil, lead oxide, bismuth trioxide, and gadolinium oxide are first mixed in an open roll mill, and then the first pass is performed to obtain the masterbatch rubber. The first mixing temperature is 60°C and the time is 35 minutes.

[0038] Step 3: The masterbatch rubber and 2,5-dimethyl-2,5-di-tert-butylperoxyhexane are mixed in an open roll mill for a second time, followed by a second thin pass to obtain the final mixed rubber. The temperature of the second mix is ​​40°C, and the time is 18 minutes.

[0039] Step 4: Vulcanize the final mixed rubber to obtain a radiation degradation resistant phenyl silicone rubber composite.

[0040] Step 4.1: The final mixed rubber is first vulcanized in a mold using a press vulcanizer to obtain an intermediate product. The first vulcanization temperature is 180°C, the time is 6 minutes, and the pressure is 10 MPa.

[0041] Step 4.2: The intermediate is subjected to a second vulcanization in a high-temperature drying oven to obtain a radiation-degradation-resistant phenylsilicone rubber composite. The second vulcanization is performed by holding the composite at 100°C for 1.5 hours, then heating to 150°C and holding for 1.5 hours, and then heating to 180°C and holding for 4 hours. [Example]

[0042] The radiation degradation-resistant phenylsilicone rubber composite of this example was composed of the following raw materials: 200 grams of RBB-2060-50 silicone rubber, 2 grams of 201 methyl silicone oil, 30 grams of lead oxide, 12 grams of bismuth trioxide, 6 grams of gadolinium oxide, and 1.6 grams of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0043] The manufacturing method of the above embodiment includes the following steps:

[0044] Step 1: Weigh out the following ingredients: 200 grams of RBB-2060-50 silicone rubber, 2 grams of 201 methyl silicone oil, 30 grams of lead oxide, 12 grams of bismuth trioxide, 6 grams of gadolinium oxide, and 1.6 grams of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0045] Step 2: RBB-2060-50 silicone rubber, 201 methyl silicone oil, lead oxide, bismuth trioxide, and gadolinium oxide are first mixed in an open roll mill, and then the first pass is performed to obtain the masterbatch rubber. The first mixing temperature is 60°C and the time is 35 minutes.

[0046] Step 3: The masterbatch rubber and 2,5-dimethyl-2,5-di-tert-butylperoxyhexane are mixed in an open roll mill for a second time, followed by a second thin pass to obtain the final mixed rubber. The temperature of the second mix is ​​40°C, and the time is 18 minutes.

[0047] Step 4: Vulcanize the final mixed rubber to obtain a radiation degradation resistant phenyl silicone rubber composite.

[0048] Step 4.1: The final mixed rubber is first vulcanized in a mold using a press vulcanizer to obtain an intermediate product. The first vulcanization temperature is 182°C, the time is 8 minutes, and the pressure is 10 MPa.

[0049] Step 4.2: The intermediate is subjected to a second vulcanization in a high-temperature drying oven to obtain a radiation-resistant phenylsilicone rubber composite. The second vulcanization is performed by holding the mixture at 100°C for 1.5 hours, then heating to 150°C and holding for 1.5 hours, and then heating to 180°C and holding for 4 hours. [Example]

[0050] The radiation degradation-resistant phenylsilicone rubber composite of this example was composed of the following raw ingredients: 400 grams of RBB-2060-50 silicone rubber, 6 grams of 201 methyl silicone oil, 60 grams of lead oxide, 24 grams of bismuth trioxide, 12 grams of gadolinium oxide, and 3 grams of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0051] The manufacturing method of the above embodiment includes the following steps:

[0052] Step 1: Weigh out the following ingredients: 400 grams of RBB-2060-50 silicone rubber, 6 grams of 201 methyl silicone oil, 60 grams of lead oxide, 24 grams of bismuth trioxide, 12 grams of gadolinium oxide, and 3 grams of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0053] Step 2: RBB-2060-50 silicone rubber, 201 methyl silicone oil, lead oxide, bismuth trioxide, and gadolinium oxide are first mixed in an open roll mill, and then the first pass is performed to obtain the masterbatch rubber. The first mixing temperature is 60°C and the time is 35 minutes.

[0054] Step 3: The masterbatch rubber and 2,5-dimethyl-2,5-di-tert-butylperoxyhexane are mixed in an open roll mill for a second time, followed by a second thin pass to obtain the final mixed rubber. The temperature of the second mix is ​​40°C, and the time is 18 minutes.

[0055] Step 4: Vulcanize the final mixed rubber to obtain a radiation degradation resistant phenyl silicone rubber composite.

[0056] Step 4.1: The final mixed rubber is first vulcanized in a mold using a press vulcanizer to obtain an intermediate product. The first vulcanization temperature is 180°C, the time is 6 minutes, and the pressure is 10 MPa.

[0057] Step 4.2: The intermediate is subjected to a second vulcanization in a high-temperature drying oven to obtain a radiation-degradation-resistant phenylsilicone rubber composite. The second vulcanization is performed by holding the composite at 105°C for 1.2 hours, then heating to 155°C and holding for 1.4 hours, and then heating to 175°C and holding for 5 hours.

[0058] [Control Example 1] Based on Example 1, the ingredients included 200 grams of NE-151 silicone rubber, but no RBB-2060-50 silicone rubber or SR3250UDP silicone rubber.

[0059] [Control Example 2] Based on Example 1, no radiation-resistant additive was added to the raw material components, and the contents of lead oxide, bismuth trioxide, and gadolinium oxide were 0.

[0060] The radiation-resistant phenyl silicone rubber composites prepared in Examples 1 to 3 and Control Examples 1 and 2 were subjected to performance tests in accordance with the corresponding national standards. The performance results after the tests are shown in Table 1. [Table 1]

[0061] The phenylsilicone rubber composites produced in Examples 1 to 3 satisfied the following performance indicators: hardness 60±5 Shore A, tensile strength ≥ 7 MPa, elongation ≥ 200%, and brittle temperature ≤ -75°C. After aging in hot air at 200°C for 72 hours, the rubber composites retained tensile strength and elongation performance by ≥ 90%. Furthermore, when the rubber composites were subjected to a radiation aging test in a gamma-ray radiation field (unit time dose rate 0.5 Gy / s, cumulative dose 100 kGy), the rubber composites retained tensile strength and elongation performance by ≥ 85%.

[0062] Comparing Example 1 and Control Example 1 in Table 1, when 200 grams of NE-151 grade silicone rubber was used in the radiation degradation-resistant phenylsilicone rubber composite without RBB-2060-50 or SR3250UDP silicone rubber, the brittle temperature did not pass the -75°C test. This indicates that the low-temperature resistance of the resulting rubber composite was poor, and its radiation degradation resistance was also insufficient. Furthermore, after radiation aging using gamma rays, the mechanical properties of the rubber composite were significantly reduced.

[0063] Comparing Example 1 and Control Example 2 in Table 1, the radiation-resistant phenylsilicone rubber composites made using RBB-2060-50 silicone rubber or SR3250UDP silicone rubber without a radiation-resistant additive exhibited poor radiation-resistant performance. Furthermore, after radiation aging due to gamma rays, the mechanical properties (tensile strength and elongation) of the rubber composites were significantly reduced.

[0064] This is because the radiation-resistant additive has the effect of shielding and absorbing gamma rays. When radiation enters the rubber substrate, it collides with and acts on the radiation-resistant additive, attenuating the radiation to a certain extent, thereby reducing damage to the rubber molecular structure and ultimately improving the radiation degradation resistance of the rubber compound.

[0065] The phenylsilicone rubber composite with excellent radiation degradation resistance produced by the present invention uses phenylsilicone rubber as the base material and uses lead oxide, bismuth trioxide, and gadolinium oxide as radiation-resistant additives in a coordinated manner. It is produced by uniformly mixing a phenylsilicone rubber premix, processing aids, radiation-resistant additives, and peroxide crosslinking agent, followed by vulcanization at high temperature. This composite has excellent low-temperature resistance and maintains excellent mechanical properties even after radiation aging due to gamma rays, demonstrating excellent resistance to gamma-ray radiation degradation. Such a phenylsilicone rubber composite with excellent radiation degradation resistance has the potential for a wide range of applications in gamma-ray radiation environments.

Claims

1. A radiation degradation-resistant phenylsilicone rubber composite, characterized by being composed of the following components by weight: 100 parts of a phenylsilicone rubber premix, 1 to 3 parts of a processing aid, 20 to 30 parts of a radiation-resistant additive, and 0.5 to 2 parts of a peroxide crosslinker; the phenylsilicone rubber premix is ​​RBB-2060-50 silicone rubber or SR3250UDP silicone rubber.

2. The radiation degradation-resistant phenyl silicone rubber composite according to claim 1, wherein the processing aid is 201 methyl silicone oil or KF-96 silicone oil.

3. 2. The radiation-degradation-resistant phenylsilicone rubber composite according to claim 1, wherein the radiation-resistant additive comprises lead oxide, dibismuth trioxide, and gadolinium oxide, and the weight ratio of the lead oxide to dibismuth trioxide is (3-7):(1-4), and the weight ratio of the dibismuth trioxide to gadolinium oxide is (1-4):(0.5-2).

4. The radiation degradation-resistant phenylsilicone rubber composite according to claim 1, characterized in that the peroxide crosslinking agent is any one of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, di-tert-butylperoxyisopropylbenzene, and diisopropylbenzene peroxide.

5. A method for producing a radiation degradation-resistant phenyl silicone rubber composite, characterized in that the method is specifically carried out according to the following procedure: Step 1: Weigh out the following ingredients based on parts by weight of each: 100 parts phenyl silicone rubber premix, 1-3 parts processing aid, 20-30 parts radiation resistant additive, 0.5-2 parts peroxide crosslinker. Step 2: The phenyl silicone rubber premix, processing aids, and radiation-resistant additives are first mixed in an open roll mill, and then first passed through a thin pass to obtain a masterbatch rubber. Step 3: The masterbatch rubber and peroxide crosslinking agent are secondly kneaded in an open roll mill, and then secondly passed through a thin pass to obtain the final mixed rubber. Step 4: Vulcanizing the final mixed rubber to obtain a radiation degradation resistant phenyl silicone rubber composite.

6. The method for producing a radiation-degradation-resistant phenyl silicone rubber composite according to claim 5, characterized in that the temperature of the first kneading in step 2 is 60°C to 80°C and the time is 30 to 40 minutes.

7. The method for producing a radiation-degradation-resistant phenyl silicone rubber composite according to claim 5, characterized in that the temperature of the second kneading in step 3 is 40°C to 50°C and the time is 15 to 20 minutes.

8. The method for producing a radiation degradation-resistant phenyl silicone rubber composite according to claim 5, characterized in that step 4 is specifically carried out according to the following procedure: Step 4.1: The final mixed rubber is first vulcanized in a mold using a press vulcanizer to obtain an intermediate product, where the first vulcanization temperature is 175°C to 185°C, the first vulcanization time is 5 minutes to 10 minutes, and the first vulcanization pressure is 8MPa to 12MPa; Step 4.2: The intermediate product is subjected to a second vulcanization in a high-temperature drying oven to obtain a radiation degradation-resistant phenylsilicone rubber composite. The second vulcanization is carried out by holding the product at 90-110°C for 1-2 hours, then heating to 140-160°C and holding for 1-2 hours, and then further heating to 170-190°C and holding for 3-6 hours.

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