A high-adhesion hot-melt adhesive material for yaw and pitch sealing rings and its preparation method

Abstract

The present invention discloses a high-adhesion hot-bonding rubber material for yaw and pitch seals, which is made from the following raw materials in parts by weight: 60-150 parts of nitrile rubber, 1-50 parts of telechelic liquid nitrile rubber, 1-15 parts of activator, 1-15 parts of anti-ager, 0.5-30 parts of adhesive resin, 10-60 parts of carbon black, 5-40 parts of plasticizer, 0.5-10 parts of vulcanizing agent, and 1-10 parts of accelerator. The vulcanizing agent is selected from one or more of sulfur, sulfur carriers or peroxides. The telechelic liquid nitrile rubber and the adhesive resin have abundant end groups. During vulcanization, they can fully infiltrate the cross-section of the seal strip, contact, entangle with the rubber molecular chains in the cross-section of the seal strip and form hydrogen bond interactions between polar groups. The peroxide releases free radicals at high temperature, initiating chemical cross-linking of the liquid nitrile rubber, epoxy resin and the sealing ring body material, and finally endowing the sealing ring with high adhesion.

Description

Technical Field

[0001] The present invention belongs to the technical field of rubber oil seal bonding, and particularly relates to a high-adhesion hot-bonding rubber material for yaw and pitch seals and a preparation method thereof, and particularly relates to a hot-bonding rubber for yaw and pitch seals of wind turbines and a preparation method thereof. Background Art

[0002] The yaw and pitch bearings in wind turbines are all extra-large bearings, which are the core key components for efficiently converting wind energy into electrical energy. Sealing devices need to be provided for yaw and pitch bearings to solve the problems of internal grease leakage of the bearings and preventing external dust, sand and water mist from entering the bearing raceways and causing metal wear or corrosion. The sealing structures used for yaw and pitch bearings are the following three structures: single-lip rubber oil seal, double-lip rubber oil seal and triple-lip rubber oil seal. At present, the above rubber oil seal products are mainly produced by continuous microwave vulcanization processing. The continuously produced sealing rubber strips are cut to a fixed length and thermally vulcanized and bonded to form an integral seal ring. The bonding strength of the rubber strips directly determines the sealing effect and service life of the entire seal ring.

[0003] Previously, resin glue was mainly used to bond the sealing rubber strips, and the products had problems such as poor heat-resistant grease and hot water performance of the glue, which easily caused failure modes such as breakage of the sealing strips. By using a rubber material as the hot-bonding transition area, the problem of poor medium resistance of the glue can be solved. At the same time, during the continuous microwave vulcanization process, the main body sealing strip rubber compound has been vulcanized, and the molecular chain migration activity has completely disappeared. Using traditional rubber compounds for thermal vulcanization ring bonding only achieves physical contact and cannot produce chemical interaction, making it difficult to ensure the bonding strength between the hot-bonding rubber and the main body rubber. Summary of the Invention

[0004] The purpose of the present invention is to solve the above problems and provide a high-adhesion hot-bonding rubber material for yaw and pitch seals of wind turbines by using a compounding method of telechelic liquid nitrile rubber and reactive adhesive resin.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] A high-adhesion hot-bonding rubber material for yaw and pitch seals is made from the following raw materials in parts by weight: 60 - 150 parts of nitrile rubber, 1 - 50 parts of telechelic liquid nitrile rubber, 1 - 15 parts of activator, 1 - 15 parts of anti-aging agent, 0.5 - 30 parts of adhesive resin, 10 - 60 parts of carbon black, 5 - 40 parts of plasticizer, 0.5 - 10 parts of vulcanizing agent, and 1 - 10 parts of accelerator.

[0007] Preferably, the high adhesion hot bonding adhesive material for the yaw and pitch sealing rings is made of the following raw materials in parts by weight: 100 parts of nitrile rubber, 5 - 35 parts of telechelic liquid nitrile rubber, 3 - 12 parts of activator, 3 - 12 parts of anti-aging agent, 1 - 12 parts of adhesive resin, 50 - 60 parts of carbon black, 5 - 30 parts of plasticizer, 0.5 - 7 parts of vulcanizing agent, and 2 - 7 parts of accelerator.

[0008] More preferably, the high adhesion hot bonding adhesive material for the yaw and pitch sealing rings is made of the following raw materials in parts by weight: 100 parts of nitrile rubber, 10 - 20 parts of telechelic liquid nitrile rubber, 5 - 8 parts of activator, 5 - 10 parts of anti-aging agent, 5 - 10 parts of adhesive resin, 50 - 60 parts of carbon black, 5 - 15 parts of plasticizer, 0.5 - 5 parts of vulcanizing agent, and 3 - 5 parts of accelerator.

[0009] The nitrile rubber has an acrylonitrile content of 25 - 30% and a Mooney viscosity of 45 - 55 MU. Specifically, the nitrile rubber is selected from NBR2850.

[0010] The telechelic liquid nitrile rubber is selected from one or more of carboxyl-terminated liquid nitrile rubber, amino-terminated liquid nitrile rubber, epoxy-terminated liquid nitrile rubber, or hydroxyl-terminated liquid nitrile rubber.

[0011] Preferably, the telechelic liquid nitrile rubber is carboxyl-terminated liquid nitrile rubber, and further selected from Nipol DN601 of Zeon Japan. Based on 100 parts by weight of the nitrile rubber component, 10 - 20 parts by weight of Nipol DN601 are selected.

[0012] The activator is one or more of stearic acid, zinc oxide, or zinc stearate.

[0013] Preferably, the activator is a combination of stearic acid and zinc oxide with a weight ratio of 1:5 - 1:8.

[0014] The anti-aging agent is one or more of amine anti-aging agents, phenolic anti-aging agents, or physical anti-aging agents.

[0015] Preferably, the anti-aging agent is a combination of microcrystalline wax, anti-aging agent RD, and anti-aging agent 4010NA with a weight ratio of 1:(1 - 3):(1 - 3).

[0016] The adhesive resin is selected from one or more of resorcinol formaldehyde condensation resin, resorcinol & hexamethylenetetramine complex, melamine resin, coumarone resin, or epoxy resin. Preferably, the adhesive resin is epoxy resin. Specifically, the adhesive resin is selected from NPES-901 epoxy resin of Nan Ya.

[0017] The carbon black is selected from one or more of commercial carbon blacks. Specifically, the carbon black is selected from carbon black N550.

[0018] The plasticizer selected is one or a mixture of more than one selected from polyester plasticizers, phosphate plasticizers, and polyether plasticizers. Preferably, the plasticizer is selected from ester plasticizers. Specifically, the plasticizer is bis(2-butoxyethoxyethyl) adipate (trade name: TP95).

[0019] The vulcanizing agent selected is one or more of sulfur (S), sulfur carriers, or peroxides.

[0020] Preferably, the vulcanizing agent is a combination of sulfur and dicumyl peroxide (DCP) with a weight ratio of 1:1 to 1:2.

[0021] The accelerator selected is one or more used in combination selected from thiazoles, guanidines, sulfenamides, thiurams, or thiocarbamates.

[0022] Preferably, the accelerator is dibenzothiazole disulfide (accelerator DM), N-cyclohexyl-2-benzothiazole sulfenamide (accelerator CZ), and tetramethylthiuram disulfide (accelerator TMTD) with a weight ratio of 1:(1 - 3):(1 - 3).

[0023] Another object of the present invention is to provide a method for preparing the high-adhesion hot-bonding rubber material for yaw and pitch seals, including: adding nitrile rubber to a two-roll mill with a roll temperature of 40 - 50 °C for plasticizing for 1 - 2 min, then adding an activator and an antioxidant for mixing. After mixing evenly, add a mixture of carbon black, telechelic liquid nitrile rubber, adhesive resin, and plasticizer. After completely mixing evenly, add a vulcanizing agent and an accelerator, make five triangle packs, and finally take off the sheet on the two-roll mill to obtain a mixed rubber, namely the high-adhesion hot-bonding rubber material for yaw and pitch seals.

[0024] Another object of the present invention is to provide a yaw and pitch seal. It uses a special injection mold for bonding seals to inject the high-adhesion hot-bonding rubber material for yaw and pitch seals into the cross-section of the seal and vulcanize it at a temperature of 150 - 170 °C to obtain the seal.

[0025] The beneficial effects of the present invention:

[0026] In the present invention, telechelic liquid nitrile rubber and adhesive resin are used as adhesives. Telechelic liquid nitrile rubber and adhesive resin have abundant end-group functional groups, which can fully infiltrate the cross-section of the sealing strip during high-temperature hot vulcanization, contact, entangle with the rubber molecular chains of the cross-section of the sealing strip, and form hydrogen bond interactions between polar groups. Among them, peroxide DCP releases free radicals at high temperature, initiating chemical cross-linking of liquid nitrile rubber, epoxy resin, and the sealing ring body material, endowing the bonding rubber and the sealing ring material with strong chemical bond interactions, and finally endowing the sealing ring with high adhesion. Detailed implementation mode

[0027] Table 1. Rubber compound formulations (parts by weight) of Example 1 and Comparative Examples 1 - 4

[0028]

[0029] Example 1

[0030] Add 100 parts by weight of NBR2850 to an open mill with a roll temperature of 40 - 50 °C and first carry out plasticizing for 1 min. Then add 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 2 parts by weight of microcrystalline wax, 2 parts by weight of antioxidant RD and 2 parts by weight of antioxidant 4010NA for mixing. After mixing evenly, add a mixture of 60 parts by weight of carbon black N550, 10 parts by weight of liquid nitrile rubber Nipol DN601, 5 parts by weight of epoxy resin NPWS - 901 and 5 parts by weight of plasticizer TP95. After completely mixing evenly, add 1 part by weight of sulfur (S), 2 parts by weight of DCP, 0.5 part by weight of accelerator DM, 1.5 parts by weight of accelerator CZ and 1.5 parts by weight of accelerator TMTD. Make 5 triangular bales, and finally take off the sheet from the open mill. The thickness of the rubber sheet is about 2 mm, thus obtaining the hot - bonding rubber material.

[0031] Using a special injection - molding die for bonding gaskets, inject the hot - bonding rubber material of this example into the cross - section of the gasket. Use a flat vulcanizer to vulcanize at a temperature of 160 °C to obtain a wind power yaw and pitch sealing strip. Test the breaking force of the completely - bonded sealing strip under various experimental conditions, that is, the bonding force.

[0032] Comparative Example 1

[0033] Add 100 parts by weight of NBR2850 to an open mill with a roll temperature of 40 - 50 °C and first carry out plasticizing for 1 min. Then add 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 2 parts by weight of microcrystalline wax, 2 parts by weight of antioxidant RD and 2 parts by weight of antioxidant 4010NA for mixing. After mixing evenly, add a mixture of 60 parts by weight of carbon black N550, 10 parts by weight of liquid nitrile rubber Nipol DN601 and 5 parts by weight of TP95. After completely mixing evenly, add 1 part by weight of S, 2 parts by weight of DCP, 0.5 part by weight of accelerator DM, 1.5 parts by weight of accelerator CZ and 1.5 parts by weight of accelerator TMTD. Make 5 triangular bales, and finally take off the sheet from the open mill. The thickness of the rubber sheet is about 2 mm, thus obtaining the rubber compound.

[0034] Using a special injection - molding die for bonding gaskets, inject the prepared rubber compound into the cross - section of the gasket. Use a flat vulcanizer to vulcanize at a temperature of 160 °C to obtain a wind power yaw and pitch sealing strip. Test the breaking force of the completely - bonded sealing strip under various experimental conditions, that is, the bonding force.

[0035] Comparative Example 2

[0036] On an open mill with a roll temperature of 40 - 50 °C, add 100 parts by weight of NBR2850 and first carry out plasticizing for 1 min. Then add 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 2 parts by weight of microcrystalline wax, 2 parts by weight of antioxidant RD and 2 parts by weight of antioxidant 4010NA for mixing. After mixing evenly, add a mixture of 60 parts by weight of carbon black N550, 5 parts by weight of epoxy resin NPWS - 901 and 5 parts by weight of TP95. After complete mixing, add 1.0 part by weight of S, 2.0 parts by weight of DCP, 0.5 part by weight of accelerator DM, 1.5 parts by weight of accelerator CZ and 1.5 parts by weight of accelerator TMTD. Make triangular bales 5 times, and finally take off the sheet on the open mill. The thickness of the sheet is about 2 mm, thus obtaining the rubber compound.

[0037] Using a special injection mold for bonding the sealing ring, inject the prepared rubber compound into the cross - section of the sealing ring. Use a flat vulcanizing machine to carry out vulcanization at a temperature of 160 °C to obtain the wind power yaw and pitch sealing strip. Test the breaking force of the completely bonded sealing strip under various experimental conditions, that is, the bonding force.

[0038] Comparative Example 3

[0039] On an open mill with a roll temperature of 40 - 50 °C, add 100 parts by weight of NBR2850 and first carry out plasticizing for 1 min. Then add 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 2 parts by weight of microcrystalline wax, 2 parts by weight of antioxidant RD and 2 parts by weight of antioxidant 4010NA for mixing. After mixing evenly, add a mixture of 60 parts by weight of carbon black N550 and 5 parts by weight of TP95. After complete mixing, add 1 part by weight of S, 2 parts by weight of DCP, 0.5 part by weight of accelerator DM, 1.5 parts by weight of accelerator CZ and 1.5 parts by weight of accelerator TMTD. Make triangular bales 5 times, and finally take off the sheet on the open mill. The thickness of the sheet is about 2 mm, thus obtaining the rubber compound.

[0040] Using a special injection mold for bonding the sealing ring, inject the prepared rubber compound into the cross - section of the sealing ring. Use a flat vulcanizing machine to carry out vulcanization at a temperature of 160 °C to obtain the wind power yaw and pitch sealing strip. Test the breaking force of the completely bonded sealing strip under various experimental conditions, that is, the bonding force.

[0041] Comparative Example 4

[0042] Apply commercial Passco P4401 instant glue on the two cross - sections of the sealing strip respectively. Place the sealing strip in a docking mold, dock and bond the cross - sections of the sealing strip, and keep it for 10 min. After the glue cures, take off the bonded sealing strip and test the breaking force of the completely bonded sealing strip under various experimental conditions.

[0043] Table 2. Bonding forces of the sealing strips in Example 1 and Comparative Examples 1 - 4 under different experimental conditions

[0044]

[0045] As can be seen from Table 1, compared with the rubber compounds prepared in Comparative Examples 1 - 3, the rubber compound prepared in Example 1 uses both a telechelic liquid nitrile rubber and an adhesion resin. Under different experimental conditions, the adhesion force of the wind power yaw and pitch sealing strips is greater than 800 N. For the rubber compounds prepared by using only the telechelic liquid nitrile rubber (Comparative Example 2) or only the adhesion resin (Comparative Example 1) or neither the telechelic liquid nitrile rubber nor the adhesion resin (Comparative Example 3), the adhesion force of the sealing strips is below 700 N. By comparing Example 1 with Comparative Example 4, it can be seen that when using glue to bond the wind power yaw and pitch sealing strips, although the conventional adhesion force is nearly 1000 N, the glue has poor performance under the inspection conditions of oil resistance and hot water resistance, and is prone to breakage and failure during the use of the sealing strip.

Claims

1. A high adhesion hot bonding adhesive material for yaw and pitch sealing rings, characterized in that: The hot-bonding adhesive material described above is a film, which is made from the following raw materials in parts by weight: 60-150 parts of nitrile rubber, 1-50 parts of telechelic liquid nitrile rubber, 1-15 parts of activator, 1-15 parts of antioxidant, 0.5-30 parts of adhesive resin, 10-60 parts of carbon black, 5-40 parts of plasticizer, 0.5-10 parts of vulcanizing agent, and 1-10 parts of accelerator; among them, the nitrile rubber is selected from NBR2850; the telechelic liquid nitrile rubber is selected from Nipol DN601; the adhesive resin is selected from South Asia NPES-901 epoxy resin; the vulcanizing agent is a combination of sulfur and dicumyl peroxide with a weight ratio of 1:1 to 1:

2.

2. The high-viscosity heat-sealing adhesive material for yaw and pitch sealing rings according to claim 1, wherein: It is made from the following raw materials in parts by weight: 100 parts of nitrile rubber, 5-35 parts of telechelic liquid nitrile rubber, 3-12 parts of activator, 3-12 parts of antioxidant, 1-12 parts of adhesive resin, 50-60 parts of carbon black, 5-30 parts of plasticizer, 0.5-7 parts of vulcanizing agent, and 2-7 parts of accelerator.

3. The high-viscosity thermal bonding adhesive material for yaw and pitch sealing rings according to claim 2, characterized in that: It is made from the following raw materials in parts by weight: 100 parts of nitrile rubber, 10-20 parts of telechelic liquid nitrile rubber, 5-8 parts of activator, 5-10 parts of antioxidant, 5-10 parts of adhesive resin, 50-60 parts of carbon black, 5-15 parts of plasticizer, 0.5-5 parts of vulcanizing agent, and 3-5 parts of accelerator.

4. The high-viscosity heat-sealing adhesive material for yaw and pitch sealing rings according to claim 1, wherein: The activator described above is one or more of stearic acid, zinc oxide, or zinc stearate; The antioxidant described above is one or more of amine antioxidants, phenolic antioxidants, or physical antioxidants; The plasticizer is selected from one or more mixtures of polyester plasticizers, phosphate plasticizers, and polyether plasticizers; The accelerator is selected from one or more combinations of thiazoles, guanidines, sulfenamides, thiurams, or thiocarbamates.

5. The high-viscosity adhesive material for heat-sealing of yaw and pitch sealing rings according to claim 4, characterized in that: The activator is a combination of stearic acid and zinc oxide with a weight ratio of 1:5 to 1:8; The antioxidant is a combination of microcrystalline wax, antioxidant RD, and antioxidant 4010NA with a weight ratio of 1:(1-3):(1-3); The plasticizer is selected from bis(2-butoxyethyl) adipate; The accelerator is a combination of accelerator DM, accelerator CZ, and accelerator TMTD with a weight ratio of 1:(1-3):(1-3).

6. The high-viscosity heat-sealing adhesive material for yaw and pitch sealing rings according to claim 1, wherein: The carbon black is selected from carbon black N550.

7. A method for preparing a high-adhesion hot-melt adhesive material for a yaw and pitch sealing ring according to claim 1, characterized in that: Including: Add nitrile rubber to a two-roll mill with a roll temperature of 40-50°C for plasticizing for 1-2 minutes, then add the activator and antioxidant for mixing. After mixing evenly, add a mixture of carbon black, telechelic liquid nitrile rubber, adhesive resin, and plasticizer. After complete mixing, add the vulcanizing agent and accelerator, make five triangle packages, and finally take off the sheet from the two-roll mill to obtain the mixed rubber, that is, the high-adhesion hot-bonding adhesive material for the yaw and pitch seals.

8. A yaw and pitch seal ring, characterized in that: It uses a special injection mold for bonding the seals, injects the high-adhesion hot-bonding adhesive material for the yaw and pitch seals described in claim 1 into the cross-section of the seal, and vulcanizes at a temperature of 150-170°C to obtain the seal.

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