WO2024045392A1 - 一种柔性接头弹性体用橡胶及其制备方法 - Google Patents
一种柔性接头弹性体用橡胶及其制备方法 Download PDFInfo
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- WO2024045392A1 WO2024045392A1 PCT/CN2022/136075 CN2022136075W WO2024045392A1 WO 2024045392 A1 WO2024045392 A1 WO 2024045392A1 CN 2022136075 W CN2022136075 W CN 2022136075W WO 2024045392 A1 WO2024045392 A1 WO 2024045392A1
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- rubber
- parts
- flexible joint
- internal mixer
- mixing
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 117
- 239000005060 rubber Substances 0.000 title claims abstract description 74
- 239000000806 elastomer Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 19
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 16
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008117 stearic acid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 150000002978 peroxides Chemical class 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000010077 mastication Methods 0.000 claims description 16
- 230000018984 mastication Effects 0.000 claims description 16
- 150000002825 nitriles Chemical class 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- JJZFJUJKZUIFKN-UHFFFAOYSA-N 1,2-ditert-butyl-3-propan-2-ylbenzene Chemical group CC(C)C1=CC=CC(C(C)(C)C)=C1C(C)(C)C JJZFJUJKZUIFKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910021485 fumed silica Inorganic materials 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 abstract description 6
- 239000010959 steel Substances 0.000 abstract description 6
- 230000003712 anti-aging effect Effects 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 14
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 229920006170 Therban® Polymers 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2315/00—Characterised by the use of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
Definitions
- the present invention relates to rubber, specifically a rubber for flexible joint elastomers and a preparation method thereof.
- Flexible joints are the core mechanism in the riser system of offshore oil platforms and have certain load-bearing and rotation capabilities.
- the flexible joint can achieve a certain angle deflection through the torsional deformation of the elastomer, thereby reducing the bending stress on the platform and riser.
- Elastomer is a key component in flexible joints. It is composed of several rubber layers and spherical reinforced steel plates that are alternately bonded and vulcanized. Due to the difficulty of designing, analyzing, and manufacturing elastomers, they have been monopolized by foreign companies, the most representative of which are the American LORD Company and Oil States Company. As flexible joints develop towards high temperature, high pressure and high corrosion, foreign countries have accelerated the research pace of hydrogenated butadiene rubber materials for elastomers, and some products have been put into use. However, due to commercial interests and national security considerations, the elastomer material formula and manufacturing process of the flexible joint have been kept highly confidential, and there are no public reports. At present, my country's flexible joints are completely dependent on foreign imports, making domestic research on hydrogenated butadiene rubber materials for flexible joint elastomers currently in a blank, which seriously restricts the development of the offshore oil and gas industry.
- the component of a flexible joint that is most prone to fatigue failure during work is the elastomer.
- the elastomer of the flexible joint is used in harsh working conditions, so it is easily damaged.
- its reliability requirements are extremely high, and it is usually designed with a service life of 30 years and a safety factor of 10 times.
- technicians have found that the most critical factor leading to fatigue failure of elastomers is the tear resistance of rubber compounds, which plays a dominant role in fatigue failure.
- the purpose of the present invention is to provide a rubber for flexible joint elastomers and a preparation method thereof.
- the rubber obtained not only has excellent tear strength, but also has good bonding properties with reinforced steel plates. .
- the present invention adopts the following technical solutions to achieve it:
- a method for using rubber for flexible joint elastomers including the following steps:
- Step 1 Weigh 100 parts of hydrogenated nitrile raw rubber, 15-35 parts of silica reinforcing agent, 10-25 parts of aramid fiber pulp, 30-50 parts of carbon black, and 5-5 parts of liquid nitrile rubber according to the mass parts. 15 parts, zinc oxide 3-7 parts, stearic acid 0.5-3 parts, antioxidant 0.5-5 parts, peroxide cross-linking agent 2-8 parts;
- Step 2 Put the hydrogenated nitrile raw rubber into an internal mixer and perform mastication at 125-135°C. After the mastication is completed, the discharge is cooled to obtain the masticated rubber;
- Step 3 Preheat the weighed liquid nitrile rubber at 80 to 85°C;
- Step 4 First add the plasticized rubber to the internal mixer, then add aramid fiber pulp, zinc oxide, stearic acid and antioxidant to the internal mixer, then perform the first mixing; then add carbon black to the internal mixer.
- the mixer is used for the second mixing; then the silica reinforcing agent and the liquid nitrile rubber preheated in step 3 are added to the internal mixer for the third mixing.
- the internal mixer temperature reaches 140°C, start discharge;
- Step 5 After the discharge material in step 4 is cooled, put it into the open mill and add the peroxide cross-linking agent weighed in step 1. Thinly pass it through 5 to 7 times at a roller temperature of 45 to 55°C to obtain flexibility.
- the joint elastomer is made of rubber.
- silica reinforcing agent is fumed silica.
- the peroxide cross-linking agent is di-tert-butyl cumene peroxide.
- the mastication time of step 2 is 3 to 4 minutes.
- step 2 is 15 to 20 hours.
- the preheating time in step 3 is 3 to 4 hours.
- first mixing time and the second mixing time in step 4 are both 2 to 3 minutes, and the third mixing time is both 3 to 5 minutes.
- the invention also protects a rubber for flexible joint elastomers.
- the present invention has the following technical effects:
- the invention uses hydrogenated nitrile raw rubber, silica reinforcing agent, aramid fiber pulp and carbon black from a wide range of sources as main raw materials to prepare rubber for flexible joint elastomers, which has excellent tear strength and high temperature aging resistance. performance, and has good bonding properties with reinforced steel plates, and is suitable for joint elastomers.
- the present invention uses aramid fiber pulp as reinforcing fiber, which can give the elastomer rubber excellent high temperature aging resistance and high tear strength, because the length and diameter of aramid fiber are highly fibrillated varieties with a certain regular distribution.
- the surface contains a large number of fluffy ultrafine fibers, which makes it have a large specific surface area and high toughness. It will not break during the mixing process and will not reduce the aspect ratio of the fiber.
- the surface of aramid pulp fiber contains extremely Functional groups, such as amide groups, sulfonic acid groups, terminal amine groups, carboxylic acid groups, etc. These functional groups can be associated with some functional groups on the rubber matrix.
- the liquid nitrile rubber selected in the present invention is a reactive plasticizer and has a relatively large molecular weight.
- the molecular chain structure is close to that of hydrogenated nitrile rubber. Therefore, a cross-linking reaction will occur during the vulcanization process, which can improve the performance of hydrogenated nitrile rubber.
- the cross-linking density gives it higher mechanical strength and high temperature resistance.
- Preheating liquid nitrile rubber before mixing can increase the molecular activity of liquid nitrile rubber, facilitate the mutual solubility between liquid nitrile rubber and hydrogenated nitrile raw rubber molecules, and further increase the mechanical strength of elastomer rubber.
- Step 1 Weigh 100 parts of Therban 4307 hydrogenated nitrile raw rubber, 25 parts of fumed silica, 20 parts of aramid fiber pulp, 40 parts of Cabot N330 carbon black, 10 parts of liquid nitrile rubber, and oxidized nitrile rubber according to the mass parts. 5 parts of zinc, 1 part of stearic acid, 1 part of antioxidant 4010NA, 1.5 parts of antioxidant RD, 4.5 parts of di-tert-butyl cumene peroxide;
- Step 2 Put the hydrogenated nitrile raw rubber into the internal mixer and perform mastication at 130°C for 4 minutes. After the mastication is completed, cool the discharge material for 20 hours to obtain the masticated rubber;
- Step 3 Place the weighed liquid nitrile rubber in an induction cooker to preheat at 80°C for 3 hours;
- Step 4 First add the plasticizing rubber into the internal mixer, then add aramid fiber pulp, zinc oxide, stearic acid, antioxidant 4010NA and antioxidant RD into the internal mixer, and then perform the first mixing for 2 minutes; Then add Cabot N330 carbon black to the internal mixer and mix for the second time for 3 minutes; then add the fumed silica and the liquid nitrile rubber preheated in step 3 into the internal mixer and mix for the third time for 5 minutes.
- the internal mixer temperature reaches 140°C, discharge begins;
- Step 5 Put the discharged material in Step 4 into an open mill and add di-tert-butyl cumene peroxide, and thin it 7 times at a roller temperature of 45°C to obtain rubber for flexible joint elastomers.
- Step 1 Weigh 100 parts of Therban 4307 hydrogenated nitrile raw rubber, 30 parts of fumed silica, 15 parts of aramid fiber pulp, 35 parts of Cabot N330 carbon black, 12 parts of liquid nitrile rubber, and oxidized nitrile rubber according to the mass parts. 6 parts of zinc, 1.5 parts of stearic acid, 2 parts of antioxidant 4010NA, 3 parts of antioxidant RD, 8 parts of di-tert-butyl cumene peroxide;
- Step 2 Put the hydrogenated nitrile raw rubber into the internal mixer and perform mastication at 125°C for 3 minutes. After the mastication is completed, cool the discharge material for 15 hours to obtain the masticated rubber;
- Step 3 Place the weighed liquid nitrile rubber in an induction cooker to preheat at 85°C for 4 hours;
- Step 4 First add the plasticizing rubber into the internal mixer, then add aramid fiber pulp, zinc oxide, stearic acid, antioxidant 4010NA and antioxidant RD into the internal mixer, and then perform the first mixing for 3 minutes; Then add Cabot N330 carbon black to the internal mixer and mix for the second time for 3 minutes; then add the fumed silica and the liquid nitrile rubber preheated in step 3 into the internal mixer and mix for the third time for 4 minutes.
- the internal mixer temperature reaches 140°C, discharge begins;
- Step 5 Put the discharged material in Step 4 into an open mill and add di-tert-butyl cumene peroxide, and pass the mixture 6 times at a roller temperature of 55°C to obtain rubber for flexible joint elastomers.
- Step 1 Weigh 100 parts of Therban 4307 hydrogenated nitrile raw rubber, 20 parts of fumed silica, 20 parts of aramid fiber pulp, 45 parts of Cabot N330 carbon black, 8 parts of liquid nitrile rubber, and oxidized nitrile rubber according to the mass parts. 4 parts of zinc, 2 parts of stearic acid, 0.2 parts of antioxidant 4010NA, 0.3 parts of antioxidant RD, 2 parts of di-tert-butyl cumene peroxide;
- Step 2 Put the hydrogenated nitrile raw rubber into the internal mixer and perform mastication at 125°C for 3 minutes. After the mastication is completed, cool the discharge material for 18 hours to obtain the masticated rubber;
- Step 3 Place the weighed liquid nitrile rubber in an induction cooker and preheat it at 80°C for 3.5 hours;
- Step 4 First add the plasticizing rubber into the internal mixer, then add aramid fiber pulp, zinc oxide, stearic acid, antioxidant 4010NA and antioxidant RD into the internal mixer, and then perform the first mixing for 2 minutes; Then add Cabot N330 carbon black to the internal mixer and mix for the second time for 2 minutes; then add the fumed silica and the liquid nitrile rubber preheated in step 3 into the internal mixer and mix for the third time for 5 minutes.
- the internal mixer temperature reaches 140°C, discharge begins;
- Step 5 Put the discharged material in Step 4 into an open mill and add di-tert-butyl cumene peroxide, and pass the mixture 5 times at a roller temperature of 50°C to obtain rubber for flexible joint elastomers.
- Step 1 Weigh 100 parts of Therban 4307 hydrogenated nitrile raw rubber, 15 parts of fumed silica, 25 parts of aramid fiber pulp, 50 parts of Cabot N330 carbon black, 5 parts of liquid nitrile rubber, and oxidized nitrile rubber according to the mass parts. 3 parts of zinc, 0.5 parts of stearic acid, 0.6 parts of antioxidant 4010NA, 0.9 parts of antioxidant RD, 6 parts of di-tert-butyl cumene peroxide;
- Step 2 Put the hydrogenated nitrile raw rubber into the internal mixer and perform mastication at 135°C for 3 minutes. After the mastication is completed, cool the discharge material for 19 hours to obtain the masticated rubber;
- Step 3 Place the weighed liquid nitrile rubber in an induction cooker and preheat it at 85°C for 3.5 hours;
- Step 4 First add the plasticizing rubber into the internal mixer, then add aramid fiber pulp, zinc oxide, stearic acid, antioxidant 4010NA and antioxidant RD into the internal mixer, and then perform the first mixing for 2 minutes; Then add Cabot N330 carbon black to the internal mixer and mix for the second time for 2 minutes; then add the fumed silica and the liquid nitrile rubber preheated in step 3 into the internal mixer and mix for the third time for 3 minutes.
- the internal mixer temperature reaches 140°C, discharge begins;
- Step 5 Put the material discharged in Step 4 into an open mill and add di-tert-butyl cumene peroxide, and pass the mixture 6 times at a roller temperature of 50°C to obtain rubber for flexible joint elastomers.
- Step 1 Weigh 100 parts of Therban 4307 hydrogenated nitrile raw rubber, 35 parts of fumed silica, 10 parts of aramid fiber pulp, 30 parts of Cabot N330 carbon black, 15 parts of liquid nitrile rubber, and oxidized nitrile rubber according to the mass parts. 7 parts of zinc, 3 parts of stearic acid, 1.6 parts of antioxidant 4010NA, 2.4 parts of antioxidant RD, 7 parts of di-tert-butyl cumene peroxide;
- Step 2 Put the hydrogenated nitrile raw rubber into the internal mixer and perform mastication at 130°C for 4 minutes. After the mastication is completed, cool the discharge material for 16 hours to obtain the masticated rubber;
- Step 3 Place the weighed liquid nitrile rubber in an induction cooker to preheat at 80°C for 4 hours;
- Step 4 First add the plasticizing rubber into the internal mixer, then add aramid fiber pulp, zinc oxide, stearic acid, antioxidant 4010NA and antioxidant RD into the internal mixer, and then perform the first mixing for 3 minutes; Then add Cabot N330 carbon black to the internal mixer and mix for the second time for 2 minutes; then add the fumed silica and the liquid nitrile rubber preheated in step 3 into the internal mixer and mix for the third time for 4 minutes.
- the internal mixer temperature reaches 140°C, discharge begins;
- Step 5 Put the material discharged in Step 4 into an open mill and add di-tert-butyl cumene peroxide, and pass the mixture 6 times at a roller temperature of 50°C to obtain rubber for flexible joint elastomers.
- the present invention extracts the rubber for flexible joint elastomers prepared in Examples 1 to 3. After sampling according to conventional methods, it is tested for tear strength and high temperature aging resistance according to national standard methods that can be used in this technical field. The performance The test results are shown in Table 1:
- the rubber for flexible joint elastomers prepared in Examples 1 to 3 has excellent tear strength and good adhesion to the reinforced steel plate.
- the various properties of the rubber decreased slightly compared with the values before aging, and some performance data increased slightly.
- the rubber for flexible joint elastomers prepared by the present invention has excellent tear strength and high temperature aging resistance, and thus will greatly extend the fatigue life of the flexible joint elastomer.
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
本发明公开了一种柔性接头弹性体用橡胶及其制备方法，方法包括：1、取氢化丁腈生胶100份、二氧化硅15-35份、芳纶纤维浆粕10-25份、炭黑30-50份、液态丁腈橡胶5-15份、氧化锌3-7份、硬脂酸0.5-3份、防老剂0.5-5份、过氧化物交联剂2-8份；2、氢化丁腈生胶投入密炼机在125～135℃下塑炼后排料冷却得到塑炼胶；3、将液态丁腈橡胶在80～85℃下预热；4、塑炼胶、芳纶纤维浆粕、氧化锌、硬脂酸和防老剂加入密炼机进行第一次混炼，炭黑加入密炼机进行第二次混炼，二氧化硅补强剂和预热后的液态丁腈橡胶加入密炼机进行第三次混炼至140℃时开始排料；5、待排料冷却后投入开炼机中并加入过氧化物交联剂在辊温45～55℃下薄通5～7遍得柔性接头弹性体用橡胶，具有优异的撕裂强度且与钢板粘接良好。
Description
本发明涉及橡胶，具体是一种柔性接头弹性体用橡胶及其制备方法。
柔性接头是海洋石油平台立管系统中的核心机构，具有一定的承载和转动能力。当海洋石油平台与钢悬链立管受到海风、洋流的作用发生相对运动时，柔性接头通过弹性体的扭转变形可实现一定角度偏转，从而减小平台和立管受到的弯曲应力。
弹性体是柔性接头中的关键部件，其由若干橡胶层和球形增强钢板交替粘接硫化而成。由于弹性体的设计、分析、制造难度大，一直被国外公司所垄断，其中具有代表性的是美国的LORD公司和Oil States公司。随着柔性接头向高温高压高腐蚀方向发展，国外加快了弹性体用氢化丁晴橡胶材料的研究步伐，并有部分产品投入使用。但是，出于商业利益和国家安全的考虑，柔性接头的弹性体材料配方和制造工艺一直处于高度保密状态，没有公开的报道。目前，我国的柔性接头完全依赖国外进口，使得国内柔性接头弹性体用氢化丁晴橡胶材料方面的研究目前还处于空白，这严重制约了海洋油气行业的发展。
柔性接头在工作中最容易疲劳失效的部件为弹性体，加之柔性接头弹性体的使用工况恶劣，因此很容易损坏。但是，弹性体一旦损坏，不但现场无法修复，而且会导致柔性接头泄漏事故。因此，对其可靠性要求极高，通常为30年使用寿命及10倍的安全系数设计。目前，技术人员发现导致弹性体疲劳失效的最关键因素为橡胶胶料的抗撕裂性能，其对疲劳失效起着支配性地位。
亟待通过橡胶材料配方中各组分的配比调整，以及适宜的生产工艺来进行胶料制备，使弹性体用橡胶胶料具有优异的撕裂强度和耐高温老化性能，从而大幅延长柔性接头弹性体的疲劳寿命。
发明内容
针对现有技术存在的不足，本发明的目是提供一种柔性接头弹性体用橡胶及其制备方法，制得的胶料不仅具有优异的撕裂强度，而且与增强钢板具有良好的粘接性能。
为了实现上述目的，本发明采用以下技术方案予以实现：
一种柔性接头弹性体用橡胶的方法，包括如下步骤：
步骤1、按照质量份数分别称取氢化丁腈生胶100份、二氧化硅补强剂15-35份、芳纶纤维浆粕10-25份、炭黑30-50份、液态丁腈橡胶5-15份、氧化锌3-7份、硬脂酸0.5-3份、防老剂0.5-5份、过氧化物交联剂2-8份；
步骤2、将氢化丁腈生胶投入密炼机在125～135℃下进行塑炼，塑炼结束后将排料冷却，得到塑炼胶；
步骤3、将称量好的液态丁腈橡胶在80～85℃下预热；
步骤4、先将塑炼胶加入密炼机，再将芳纶纤维浆粕、氧化锌、硬脂酸和防老剂加入密炼机，接着进行第一次混炼；再接着将炭黑加入密炼机进行第二次混炼；然后将二氧化硅补强剂和步骤3预热后的液态丁腈橡胶加入密炼机进行第三次混炼，当密炼机温度达到140℃时，开始排料；
步骤5、待步骤4的排料冷却后将其投入开炼机中并加入步骤1称取的过氧化物交联剂，在辊温45～55℃条件下薄通5～7遍，得到柔性接头弹性体用橡胶。
进一步地，所述二氧化硅补强剂为气相二氧化硅。
进一步地，所述过氧化物交联剂为二叔丁基过氧化异丙基苯。
进一步地，所述步骤2的塑炼时间为3～4min。
进一步地，所述步骤2的冷却时间为15～20h。
进一步地，所述步骤3预热时间为3～4h。
进一步地，所述步骤4的第一次混炼和第二次混炼的时间均为2～3min，第三次混炼的时间均为3～5min。
本发明还保护一种柔性接头弹性体用橡胶。
本发明与现有技术相比，具有如下技术效果：
本发明以来源很广泛的氢化丁腈生胶、二氧化硅补强剂、芳纶纤维浆粕和炭黑为主要原料，制备出柔性接头弹性体用橡胶，其具有优异的撕裂强度和耐高温老化性能，且与增强钢板具有良好的粘接性能，适用于接头弹性体。
本发明选用芳纶纤维浆粕作为增强纤维，可以赋予弹性体用橡胶优异的耐高温老化性能和高撕裂强度，因为芳纶纤维高度原纤化的品种，长度和直径呈一定的规律 分布，表面含有大量呈绒毛状的超细纤维，使得其比表面积大、韧性高，在混合加工过程中不会发生断裂，也不会降低纤维的长径比，而且芳纶浆粕纤维的表面含有极性基团，如酰胺基、磺酸基以及末端胺基、羧酸基等，这些官能团能够与橡胶基体上的一些官能团缔合，其作用原理类似于炭黑增强橡胶的结合橡胶理论，即弹性体与填充粒子的活性点相互作用，使其与橡胶基质有较高的机械嵌合力，分散混合性能良好，具有尺寸稳定性好、密度低、强度高、耐高温、耐腐蚀、耐疲劳性能好的优点，所以其可以赋予弹性体用橡胶优异的耐高温老化性能和高撕裂强度。
本发明选用的液态丁腈橡胶是反应型增塑剂，且相对分子质量较大，分子链结构与氢化丁腈橡胶接近，因此在硫化过程中会发生交联反应，能提高氢化丁腈胶料的交联密度，赋予其更高的机械强度和耐高温性能。将液态丁腈橡胶在混炼前进行预热，可以增加液态丁腈橡胶的分子活性，有利于液态丁腈橡胶与氢化丁腈生胶分子间的互溶，进一步增加了弹性体用橡胶的机械强度。
以下结合实施例对本发明的具体内容做进一步详细解释说明。
实施例1
步骤1、按照质量份数分别称取Therban 4307氢化丁腈生胶100份、气相二氧化硅25份、芳纶纤维浆粕20份、卡博特N330炭黑40份、液态丁腈橡胶10份、氧化锌5份、硬脂酸1份、防老剂4010NA 1份、防老剂RD 1.5份、二叔丁基过氧化异丙基苯4.5份；
步骤2、将氢化丁腈生胶投入密炼机在130℃下进行塑炼4min，塑炼结束后将排料冷却20h，得到塑炼胶；
步骤3、将称量好的液态丁腈橡胶置于电磁炉内80℃下预热3h；
步骤4、先将塑炼胶加入密炼机，再将芳纶纤维浆粕、氧化锌、硬脂酸、防老剂4010NA和防老剂RD加入密炼机，接着进行第一次混炼2min；再接着将卡博特N330炭黑加入密炼机进行第二次混炼3min；然后将气相二氧化硅和步骤3预热后的液态丁腈橡胶加入密炼机进行第三次混炼5min，当密炼机温度达到140℃时，开始排料；
步骤5、将步骤4的排料投入开炼机中并加入二叔丁基过氧化异丙基苯，在辊温45℃条件下薄通7遍，得到柔性接头弹性体用橡胶。
实施例2
步骤1、按照质量份数分别称取Therban 4307氢化丁腈生胶100份、气相二氧化硅30份、芳纶纤维浆粕15份、卡博特N330炭黑35份、液态丁腈橡胶12份、氧化锌6份、硬脂酸1.5份、防老剂4010NA 2份、防老剂RD 3份、二叔丁基过氧化异丙基苯8份；
步骤2、将氢化丁腈生胶投入密炼机在125℃下进行塑炼3min，塑炼结束后将排料冷却15h，得到塑炼胶；
步骤3、将称量好的液态丁腈橡胶置于电磁炉内85℃下预热4h；
步骤4、先将塑炼胶加入密炼机，再将芳纶纤维浆粕、氧化锌、硬脂酸、防老剂4010NA和防老剂RD加入密炼机，接着进行第一次混炼3min；再接着将卡博特N330炭黑加入密炼机进行第二次混炼3min；然后将气相二氧化硅和步骤3预热后的液态丁腈橡胶加入密炼机进行第三次混炼4min，当密炼机温度达到140℃时，开始排料；
步骤5、将步骤4的排料投入开炼机中并加入二叔丁基过氧化异丙基苯，在辊温55℃条件下薄通6遍，得到柔性接头弹性体用橡胶。
实施例3
步骤1、按照质量份数分别称取Therban 4307氢化丁腈生胶100份、气相二氧化硅20份、芳纶纤维浆粕20份、卡博特N330炭黑45份、液态丁腈橡胶8份、氧化锌4份、硬脂酸2份、防老剂4010NA 0.2份、防老剂RD 0.3份、二叔丁基过氧化异丙基苯2份；
步骤2、将氢化丁腈生胶投入密炼机在125℃下进行塑炼3min，塑炼结束后将排料冷却18h，得到塑炼胶；
步骤3、将称量好的液态丁腈橡胶置于电磁炉内80℃下预热3.5h；
步骤4、先将塑炼胶加入密炼机，再将芳纶纤维浆粕、氧化锌、硬脂酸、防老剂4010NA和防老剂RD加入密炼机，接着进行第一次混炼2min；再接着将卡博特N330炭黑加入密炼机进行第二次混炼2min；然后将气相二氧化硅和步骤3预热后的液态丁腈橡胶加入密炼机进行第三次混炼5min，当密炼机温度达到140℃时，开始排料；
步骤5、将步骤4的排料投入开炼机中并加入二叔丁基过氧化异丙基苯，在辊温50℃条件下薄通5遍，得到柔性接头弹性体用橡胶。
实施例4
步骤1、按照质量份数分别称取Therban 4307氢化丁腈生胶100份、气相二氧化硅15份、芳纶纤维浆粕25份、卡博特N330炭黑50份、液态丁腈橡胶5份、氧化锌3份、硬脂酸0.5份、防老剂4010NA 0.6份、防老剂RD 0.9份、二叔丁基过氧化异丙基苯6份；
步骤2、将氢化丁腈生胶投入密炼机在135℃下进行塑炼3min，塑炼结束后将排料冷却19h，得到塑炼胶；
步骤3、将称量好的液态丁腈橡胶置于电磁炉内85℃下预热3.5h；
步骤4、先将塑炼胶加入密炼机，再将芳纶纤维浆粕、氧化锌、硬脂酸、防老剂4010NA和防老剂RD加入密炼机，接着进行第一次混炼2min；再接着将卡博特N330炭黑加入密炼机进行第二次混炼2min；然后将气相二氧化硅和步骤3预热后的液态丁腈橡胶加入密炼机进行第三次混炼3min，当密炼机温度达到140℃时，开始排料；
步骤5、将步骤4的排料投入开炼机中并加入二叔丁基过氧化异丙基苯，在辊温50℃条件下薄通6遍，得到柔性接头弹性体用橡胶。
实施例5
步骤1、按照质量份数分别称取Therban 4307氢化丁腈生胶100份、气相二氧化硅35份、芳纶纤维浆粕10份、卡博特N330炭黑30份、液态丁腈橡胶15份、氧化锌7份、硬脂酸3份、防老剂4010NA 1.6份、防老剂RD 2.4份、二叔丁基过氧化异丙基苯7份；
步骤2、将氢化丁腈生胶投入密炼机在130℃下进行塑炼4min，塑炼结束后将排料冷却16h，得到塑炼胶；
步骤3、将称量好的液态丁腈橡胶置于电磁炉内80℃下预热4h；
步骤4、先将塑炼胶加入密炼机，再将芳纶纤维浆粕、氧化锌、硬脂酸、防老剂4010NA和防老剂RD加入密炼机，接着进行第一次混炼3min；再接着将卡博特N330炭黑加入密炼机进行第二次混炼2min；然后将气相二氧化硅和步骤3预热后的液态丁腈橡胶加入密炼机进行第三次混炼4min，当密炼机温度达到140℃时，开始排料；
步骤5、将步骤4的排料投入开炼机中并加入二叔丁基过氧化异丙基苯，在辊温50℃条件下薄通6遍，得到柔性接头弹性体用橡胶。
本发明抽取实施例1～实施例3制备的柔性接头弹性体用橡胶，按照常规方法取样后，按照本技术领域能使用的国家标准的方法对其进行撕裂强度和耐高温老化性能测试，性能检测结果见表1：
表1柔性接头弹性体用橡胶胶料性能数据
由表1可以看出，实施例1～实施例3制备的柔性接头弹性体用橡胶具有优异的撕裂强度，与增强钢板具有良好的粘接性。在150℃的温度下，经过168h的热空气老化后，橡胶的各项性能与老化前数值相比下降量很小，部分性能数据还略有增加。可见本发明制备的柔性接头弹性体用橡胶具有优异的撕裂强度和耐高温老化性能，因而将会大幅延长柔性接头弹性体的疲劳寿命。
Claims (8)
- 一种柔性接头弹性体用橡胶的方法，其特征在于，包括如下步骤：步骤1、按照质量份数分别称取氢化丁腈生胶100份、二氧化硅补强剂15-35份、芳纶纤维浆粕10-25份、炭黑30-50份、液态丁腈橡胶5-15份、氧化锌3-7份、硬脂酸0.5-3份、防老剂0.5-5份、过氧化物交联剂2-8份；步骤2、将氢化丁腈生胶投入密炼机在125～135℃下进行塑炼，塑炼结束后将排料冷却，得到塑炼胶；步骤3、将称量好的液态丁腈橡胶在80～85℃下预热；步骤4、先将塑炼胶加入密炼机，再将芳纶纤维浆粕、氧化锌、硬脂酸和防老剂加入密炼机，接着进行第一次混炼；再接着将炭黑加入密炼机进行第二次混炼；然后将二氧化硅补强剂和步骤3预热后的液态丁腈橡胶加入密炼机进行第三次混炼，当密炼机温度达到140℃时，开始排料；步骤5、待步骤4的排料冷却后将其投入开炼机中并加入过氧化物交联剂，在辊温45～55℃条件下薄通5～7遍，得到柔性接头弹性体用橡胶。
- 根据权利要求1所述的柔性接头弹性体用橡胶的方法，其特征在于，所述二氧化硅补强剂为气相二氧化硅。
- 根据权利要求1所述的柔性接头弹性体用橡胶的方法，其特征在于，所述过氧化物交联剂为二叔丁基过氧化异丙基苯。
- 根据权利要求1所述的柔性接头弹性体用橡胶的方法，其特征在于，所述步骤2的塑炼时间为3～4min。
- 根据权利要求1所述的柔性接头弹性体用橡胶的方法，其特征在于，所述步骤2的冷却时间为15～20h。
- 根据权利要求1所述的柔性接头弹性体用橡胶的方法，其特征在于，所述步骤3预热时间为3～4h。
- 根据权利要求1所述的柔性接头弹性体用橡胶的方法，其特征在于，所述步骤4的第一次混炼、第二次混炼和第三次混炼的时间均为2～3min。
- 一种如权利要求1～7任一项所述方法制备的柔性接头弹性体用橡胶。
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| CN105086038A (zh) * | 2015-08-25 | 2015-11-25 | 安徽中鼎密封件股份有限公司 | 一种用于油田封隔器橡胶组件的复合材料及其制备方法 |
| CN109021342A (zh) * | 2017-06-08 | 2018-12-18 | 浙江赞昇新材料有限公司 | 一种高性能的氢化丁腈基橡胶复合物及其制备方法 |
| CN113667197A (zh) * | 2021-07-29 | 2021-11-19 | 中国海洋石油集团有限公司 | 一种胶料及其制备与在海洋柔性接头内部弹性体中的应用 |
| CN115322412A (zh) * | 2022-08-30 | 2022-11-11 | 西安向阳航天材料股份有限公司 | 一种柔性接头弹性体用橡胶及其制备方法 |
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| CN115322412B (zh) | 2023-09-26 |
| US20240084114A1 (en) | 2024-03-14 |
| CN115322412A (zh) | 2022-11-11 |
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