A hydrogenated nitrile rubber material, its preparation method and application in an automotive timing belt

Abstract

The present invention provides a hydrogenated nitrile rubber material, a preparation method thereof, and an application thereof in an automotive timing belt. The components for preparing the hydrogenated nitrile rubber material include: 30 to 60 parts of hydrogenated nitrile raw rubber, 80 to 130 parts of weight-increasing masterbatch, 2 to 4 parts of antioxidant, 5 to 50 parts of carbon black, 1 to 15 parts of plasticizer, 0.1 to 4 parts of flow dispersant, 3 to 10 parts of short fiber, 1 to 10 parts of vulcanizing agent, and 0.1 to 5 parts of co-crosslinking agent. The hydrogenated nitrile rubber material of the present invention improves the material density and has excellent comprehensive properties. The automotive timing belt prepared therefrom can reduce the natural frequency of the timing belt, control the resonance frequency within the low-speed range, and effectively alleviate the formation of high-speed rotation noise.

Description

Technical Field

[0001] The present invention belongs to the technical field of rubber materials for automobiles, and particularly relates to a hydrogenated nitrile rubber material, a preparation method thereof, and an application thereof in an automotive timing belt. Background Art

[0002] The main material of the timing belt is rubber, and it also contains a tensile cord as a skeleton material and a tooth cloth fabric for protecting the tooth body. Compared with a metal chain, the timing belt has an incomparable low-noise advantage, but the resonance noise during its transmission is still inevitable. Especially at high speeds, if the transmission system is not properly designed, the belt meshing noise can be clearly heard, reducing the driving comfort. Patent CN203248603U discloses a low-noise automotive timing belt, which is provided with an irregularly wavy and continuously distributed interlayer fabric between the belt back and the meshing part to reduce noise, but this solution has a complex forming process and a high cost.

[0003] Therefore, there is an urgent need to provide a high-density hydrogenated nitrile rubber material that can meet the requirements of automotive timing belts and its application in the preparation of automotive timing belts to reduce the belt noise. Summary of the Invention

[0004] Based on the defects existing in the prior art, the first object of the present invention is to provide a hydrogenated nitrile rubber material; the second object of the present invention is to provide a preparation method of the hydrogenated nitrile rubber material; the third object of the present invention is to provide an application of the hydrogenated nitrile rubber material in the preparation of an automotive timing belt.

[0005] The objects of the present invention are achieved by the following technical solutions:

[0006] On the one hand, the present invention provides a hydrogenated nitrile rubber material. Calculated by weight parts, the components for preparing the hydrogenated nitrile rubber material include:

[0007] 30 - 60 parts of hydrogenated nitrile raw rubber;

[0008] 80 - 130 parts of weight-increasing masterbatch;

[0009] 2 - 4 parts of antioxidant;

[0010] 5 - 50 parts of carbon black;

[0011] 1 - 15 parts of plasticizer;

[0012] 0.1 - 4 parts of flow dispersant;

[0013] 3 - 10 parts of short fiber;

[0014] 1 - 10 parts of vulcanizing agent;

[0015] 0.1 - 5 parts of co-crosslinking agent.

[0016] The rubber materials of the existing timing belts include neoprene and hydrogenated nitrile butadiene. The density of neoprene rubber is generally 1.4 - 1.5 g / cm 3 , through experimental comparison, the synchronous belt made of neoprene has better noise performance than that made of hydrogenated nitrile butadiene. However, the high-temperature resistance of neoprene is limited and it is difficult to meet the application requirements of modern automobile engines. At the same time, the density of hydrogenated nitrile butadiene is generally 1.2 - 1.3 g / cm 3 , so it is necessary to further increase the density of hydrogenated nitrile butadiene rubber and meet the performance requirements of the timing belt. The common method to increase the weight of rubber materials is to directly add heavy substances (high specific gravity fillers), such as carbon black / metal and its oxides. This will result in poor compatibility between the heavy substances and the rubber matrix, leading to poor dynamic and static properties of the material and unable to meet the application requirements of automobile synchronous belts. In the present invention, the heavy substances are added in the form of premixed masterbatch and the mixing process is optimized, obtaining a high-density hydrogenated nitrile material with excellent comprehensive performance. When applied to automobile synchronous belts, it can reduce noise and has the advantages of easy implementation and low cost, expanding the application of hydrogenated nitrile materials.

[0017] In the above hydrogenated nitrile rubber material, preferably, based on the mass of the heavy substance masterbatch being 100%, the raw material components for preparing the heavy substance masterbatch include:

[0018] Hydrogenated nitrile raw rubber 40% - 60%;

[0019] Zinc oxide 40% - 60%;

[0020] Stearic acid 1% - 5%;

[0021] Silane coupling agent 1% - 5%;

[0022] Trioctyl trimellitate 1% - 5%.

[0023] In the above hydrogenated nitrile rubber material, preferably, the preparation method of the heavy substance masterbatch includes:

[0024] Using a Banbury mixer, first charge the hydrogenated nitrile raw rubber for plasticization according to the proportion, and then successively charge zinc oxide, stearic acid, silane coupling agent and trioctyl trimellitate according to the proportion. After downward mixing, lift the ram for cleaning, and then carry out downward mixing again and discharge the rubber to obtain the heavy substance masterbatch.

[0025] In the above hydrogenated nitrile rubber material, preferably, the loading coefficient of the Banbury mixer is 0.6 - 0.8; the rotational speed is controlled at 10 - 100 r / min.

[0026] In the above hydrogenated nitrile rubber material, preferably, the time for charging the hydrogenated nitrile raw rubber for plasticization is 2 - 5 min.

[0027] In the above hydrogenated nitrile rubber material, preferably, after pressing and kneading for 2 to 3 minutes, lift the ram to clean up.

[0028] In the above hydrogenated nitrile rubber material, preferably, press and knead again until the temperature reaches 120°C to 160°C, and then discharge the rubber.

[0029] In the above hydrogenated nitrile rubber material, preferably, the total kneading time is controlled to be 6 to 15 minutes.

[0030] In the above hydrogenated nitrile rubber material, preferably, the silane coupling agent is selected from one or a combination of more than one of 3-aminopropyltrimethoxysilane, methyltris(methoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and 3-propenoxypropyltrimethoxysilane, but not limited thereto.

[0031] In the above hydrogenated nitrile rubber material, preferably, the anti-aging agent is selected from one or a combination of more than one of anti-aging agent CDPA, anti-aging agent ZMTI, anti-aging agent RD, anti-aging agent DBHQ, anti-aging agent WSP, and anti-aging agent BLE, but not limited thereto.

[0032] In the above hydrogenated nitrile rubber material, preferably, the plasticizer is selected from one or a combination of more than one of trioctyl trimellitate, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, dioctyl sebacate, and dioctyl adipate, but not limited thereto.

[0033] In the above hydrogenated nitrile rubber material, preferably, the flow dispersant is selected from one or a combination of more than one of fatty acid esters, polyethylene glycol, polyvinylpyrrolidone, and zinc stearate, but not limited thereto.

[0034] In the above hydrogenated nitrile rubber material, preferably, the short fibers are selected from one or a combination of more than one of aramid short fibers, polyester short fibers, and nylon short fibers, but not limited thereto.

[0035] In the above hydrogenated nitrile rubber material, preferably, the vulcanizing agent is selected from bis(tert-butylperoxy)cumene and / or dicumyl peroxide, but not limited thereto.

[0036] In the above hydrogenated nitrile rubber material, preferably, the co-crosslinking agent is selected from one or a combination of more than one of zinc acrylate, zinc methacrylate, trimethylolpropane trimethacrylate, and triallyl isocyanurate, but not limited thereto.

[0037] On the other hand, the present invention also provides a preparation method of the above hydrogenated nitrile rubber material, and the method includes:

[0038] Using a Banbury mixer, first charge hydrogenated nitrile raw rubber and weight-increasing masterbatch in proportion for mixing, then successively charge antioxidant, carbon black, plasticizer, flow dispersant and short fiber in proportion. After pressing down for mixing, lift the ram for cleaning, press down for mixing again and discharge the rubber to an open mill. Add vulcanizing agent and co-crosslinking agent on the open mill for cutting and mixing, adjust the roll gap for thin pass, and take off the sheet for cooling to prepare the hydrogenated nitrile rubber material.

[0039] In the above preparation method, preferably, the loading coefficient of the Banbury mixer is 0.55 - 0.75; the rotational speed is controlled at 10 - 50 r / min.

[0040] In the above preparation method, preferably, the mixing time of the hydrogenated nitrile raw rubber and the weight-increasing masterbatch is 2 - 5 min.

[0041] In the above preparation method, preferably, lift the ram for cleaning after pressing down for mixing for 4 - 8 min.

[0042] In the above preparation method, preferably, discharge the rubber when pressing down for mixing again until the temperature reaches 120°C - 160°C.

[0043] In the above preparation method, preferably, the cutting and mixing time is 5 - 10 min.

[0044] In the above preparation method, preferably, adjust the roll gap to a film thickness of 4 mm for thin pass 5 - 8 times.

[0045] On the other hand, the present invention also provides the application of the above hydrogenated nitrile rubber material or the hydrogenated nitrile rubber material prepared by the above preparation method in the preparation of automotive timing belts.

[0046] Advantages of the present invention:

[0047] The hydrogenated nitrile rubber material of the present invention is added with a weight-increasing agent in the form of a masterbatch to achieve the effect of improving the rubber density and excellent comprehensive performance, and has the advantages of easy implementation and low cost; using the hydrogenated nitrile rubber material of the present invention to prepare an automotive timing belt, by increasing the density of the belt rubber, the natural frequency of the timing belt is reduced, so the resonance frequency can be controlled within the low-speed range, effectively alleviating the formation of high-speed rotation noise.

[0048] The above description is only an overview of the technical solution of the present invention. In order to be able to understand the technical means of the present invention more clearly and implement it according to the content of the specification, the following provides a detailed description of the preferred embodiments of the present invention. Description of the Drawings

[0049] To more clearly illustrate the technical solutions in the embodiments of this specification or the prior art, the following will briefly introduce the attached drawings required for the description of the embodiments or the prior art. Obviously, the attached drawings in the following description are only some embodiments recorded in this specification. For those of ordinary skill in the art, without creative efforts, other attached drawings can also be obtained based on these attached drawings.

[0050] Figure 1 It is a result diagram of performance test experiments on the hydrogenated nitrile rubber materials prepared in Examples 1 - 3 and Comparative Examples 1 - 2 of the present invention. Detailed implementation manners

[0051] The following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope protected by the present invention. The processes, conditions, reagents, experimental methods, etc. for implementing the present invention, except for the specifically mentioned content below, are all common knowledge and well - known common sense in the art, and the present invention has no special restrictions.

[0052] Example 1:

[0053] This example provides a hydrogenated nitrile rubber material. Calculated by weight parts, the components for preparing this hydrogenated nitrile rubber material include:

[0054] 40 parts of hydrogenated nitrile raw rubber;

[0055] 120 parts of weight - increasing masterbatch;

[0056] 1 part of antioxidant RD;

[0057] 1 part of antioxidant ZMTI

[0058] 40 parts of carbon black N550;

[0059] 5 parts of plasticizer (trioctyl trimellitate);

[0060] 2 parts of flow dispersant (zinc stearate);

[0061] 5 parts of nylon short fibers;

[0062] 5 parts of vulcanizing agent (di - tert - butyl peroxide cumene);

[0063] 2 parts of co - crosslinking agent (zinc methacrylate).

[0064] Among them, the weight - increasing composite masterbatch is prepared by the following preparation method:

[0065] Use a Banbury mixer with a loading factor in the range of 0.6 and a rotational speed controlled at 50 r / min. Based on the mass of the weight-increasing composite masterbatch being 100%, first charge 50% of the hydrogenated nitrile raw rubber for plasticizing for 3 minutes. Then, sequentially charge 45% of zinc oxide, 2% of stearic acid, 2% of silane coupling agent (3-aminopropyltrimethoxysilane), and 1% of trioctyl trimellitate (TOTM). After pressing and mixing for 2 minutes, lift the ram for cleaning, and then press and mix again until reaching 130 °C for discharging to obtain the weight-increasing composite masterbatch, with the total mixing time controlled at 8 minutes.

[0066] This example also provides a preparation method for the above hydrogenated nitrile rubber material, and the preparation method includes:

[0067] Use a Banbury mixer with a loading factor in the range of 0.6 and a rotational speed controlled at 50 r / min. First charge 40 parts of hydrogenated nitrile raw rubber and 120 parts of the weight-increasing composite masterbatch for mixing for 3 minutes. Then, sequentially charge the above-measured antioxidant, carbon black, plasticizer, dispersant, and short fiber. After pressing and mixing for 5 minutes, lift the ram for cleaning, and then press and mix again until the temperature reaches 130 °C for discharging to an open mill. Add a vulcanizing agent and a co-crosslinking agent on the open mill for cutting and mixing for 8 minutes. Adjust the roll gap to a film thickness of 4 mm for thin passing 5 times, and then take off the film for cooling to prepare the hydrogenated nitrile rubber material.

[0068] This example also provides the application of the hydrogenated nitrile rubber material in the preparation of automotive synchronous belts.

[0069] Example 2:

[0070] This example provides a hydrogenated nitrile rubber material. Calculated by weight parts, the components for preparing the hydrogenated nitrile rubber material include:

[0071] 50 parts of hydrogenated nitrile raw rubber;

[0072] 100 parts of weight-increasing masterbatch;

[0073] 1 part of antioxidant RD;

[0074] 1 part of antioxidant ZMTI

[0075] 40 parts of carbon black N550;

[0076] 5 parts of plasticizer (trioctyl trimellitate);

[0077] 2 parts of flow dispersant (zinc stearate);

[0078] 5 parts of nylon short fiber;

[0079] 5 parts of vulcanizing agent (bis(tert-butylperoxy)diisopropylbenzene);

[0080] 2 parts of co-crosslinking agent (zinc methacrylate).

[0081] Among them, the preparation method of the weight-increasing masterbatch is the same as that in Example 1.

[0082] This example also provides a preparation method of the above hydrogenated nitrile rubber material, and the preparation method includes:

[0083] Using a Banbury mixer, with a loading coefficient ranging from 0.6 and a rotational speed controlled at 50 r / min, first put 50 parts of hydrogenated nitrile raw rubber and 100 parts of the weight-increasing composite masterbatch into the mixer for kneading for 3 min, then successively put the above-measured antioxidant, carbon black, plasticizer, dispersant and short fibers, lower the pressure and knead for 5 min, then lift the ram to clean, lower the pressure again and knead until the temperature reaches 130 °C for discharging to an open mill, add a vulcanizing agent and a co-crosslinking agent on the open mill for cutting and kneading for 8 min, adjust the roll gap to a film thickness of 4 mm and conduct thin pass for 5 times, take off the film and cool to prepare the hydrogenated nitrile rubber material.

[0084] This example also provides an application of the hydrogenated nitrile rubber material in the preparation of automotive synchronous belts.

[0085] Example 3:

[0086] This example provides a hydrogenated nitrile rubber material. Calculated by weight parts, the components for preparing the hydrogenated nitrile rubber material include:

[0087] 60 parts of hydrogenated nitrile raw rubber;

[0088] 80 parts of weight-increasing masterbatch;

[0089] 1 part of antioxidant RD;

[0090] 1 part of antioxidant ZMTI;

[0091] 40 parts of carbon black N550;

[0092] 5 parts of plasticizer (trioctyl trimellitate);

[0093] 2 parts of flow dispersant (zinc stearate);

[0094] 5 parts of nylon short fibers;

[0095] 5 parts of vulcanizing agent (bis(tert-butylperoxyisopropyl)benzene);

[0096] 2 parts of co-crosslinking agent (zinc methacrylate).

[0097] Among them, the preparation method of the weight-increasing masterbatch is the same as that in Example 1.

[0098] This example also provides a preparation method of the above hydrogenated nitrile rubber material, and the preparation method includes:

[0099] Use a Banbury mixer with a charging coefficient in the range of 0.6 and a rotational speed controlled at 50 r / min. First, charge 60 parts of hydrogenated nitrile raw rubber and 80 parts of weight-increasing composite masterbatch and knead for 3 minutes. Then, successively add the above-measured antioxidant, carbon black, plasticizer, dispersant, and short fibers. After kneading under pressure for 5 minutes, lift the ram to clean, and then knead under pressure again until the temperature reaches 130 °C for discharging to an open mill. Add a vulcanizing agent and a co-crosslinking agent to the open mill and perform cutting and kneading for 8 minutes. Adjust the roll gap to a film thickness of 4 mm and perform thin pass 5 times. Take off the film and cool to prepare a hydrogenated nitrile rubber material.

[0100] This example also provides the application of the hydrogenated nitrile rubber material in the preparation of automotive synchronous belts.

[0101] Comparative Example 1:

[0102] This comparative example provides a hydrogenated nitrile rubber material. In terms of parts by weight, the components for preparing the hydrogenated nitrile rubber material include:

[0103] 100 parts of hydrogenated nitrile raw rubber;

[0104] 54 parts of zinc oxide;

[0105] 1 part of antioxidant RD;

[0106] 1 part of antioxidant ZMTI;

[0107] 40 parts of carbon black N550;

[0108] 5 parts of plasticizer (trioctyl trimellitate);

[0109] 2 parts of flow dispersant (zinc stearate);

[0110] 5 parts of nylon short fiber;

[0111] 5 parts of vulcanizing agent (bis(tert-butylperoxy) diisopropylbenzene);

[0112] 2 parts of co-crosslinking agent (zinc methacrylate).

[0113] Compared with Example 1, the weight-increasing zinc oxide is added directly.

[0114] Comparative Example 2:

[0115] This comparative example provides a hydrogenated nitrile rubber material. In terms of parts by weight, the components for preparing the hydrogenated nitrile rubber material include:

[0116] 100 parts of hydrogenated nitrile raw rubber;

[0117] 5 parts of zinc oxide;

[0118] 1 part of antioxidant RD;

[0119] 1 part of antioxidant ZMTI;

[0120] 40 parts of carbon black N550;

[0121] 5 parts of plasticizer (trioctyl trimellitate);

[0122] 2 parts of flow dispersant (zinc stearate);

[0123] 5 parts of nylon staple fiber;

[0124] 5 parts of vulcanizing agent (bis(tert-butylperoxyisopropyl)benzene);

[0125] 2 parts of co-crosslinking agent (zinc methacrylate).

[0126] This comparative example is a conventional density hydrogenated nitrile rubber material.

[0127] Performance test experiments were carried out on the hydrogenated nitrile rubber materials prepared in Examples 1 to 3 and Comparative Examples 1 to 2 of the present invention, and the experimental results are as Figure 1 shown.

[0128] Specific embodiments are applied in the present invention to elaborate on the principle and implementation manner of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention; at the same time, for those of ordinary skill in the art, based on the idea of the present invention, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present invention.

Claims

1. An application of a hydrogenated nitrile rubber material in the preparation of an automobile timing belt, wherein the components for preparing the hydrogenated nitrile rubber material include, by weight: 30-60 parts of hydrogenated nitrile rubber; 80~130 parts of weight-added masterbatch; 2~4 parts of antioxidant; Carbon black 5-50 parts; Plasticizer 1~15 parts; 0.1~4 parts of mobile dispersant; 3~10 parts of short fibers; 1~10 parts of vulcanizing agent; 0.1~5 parts of auxiliary cross-linking agent; Wherein, taking the mass of the weight-increasing masterbatch as 100%, the raw material components for preparing the weight-increasing masterbatch include: Hydrogenated nitrile rubber 40%~60%; Zinc oxide 40%~60%; Stearic acid 1%~5%; Silane coupling agent 1%~5%; Trioctyl trimellitate 1%~5%; The preparation method of the weight-increasing masterbatch comprises: Using an internal mixer, hydrogenated nitrile raw rubber is first added in proportion for plasticization, and then zinc oxide, stearic acid, silane coupling agent and trioctyl trimellitate are added in proportion. After pressing down for mixing, the bolt is lifted for cleaning, and then pressing down for mixing again and separating the rubbers to obtain a weighted masterbatch.

2. The use of the hydrogenated nitrile rubber material according to claim 1 in preparing an automobile timing belt, characterized in that: The charging coefficient of the internal mixer is 0.6-0.8; the speed is controlled at 10-100 r / min; The time for putting hydrogenated nitrile rubber into plasticizing is 2~5min; Press down and mix for 2~3 minutes, then lift the bolt and clean; Press down and mix again until the temperature reaches 120℃~160℃ for debinding; The total mixing time is controlled to be 6~15min; The silane coupling agent is selected from one or more combinations of 3-aminopropyltrimethoxysilane, methyltri(methoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

3. The use of the hydrogenated nitrile rubber material according to claim 1 in the preparation of an automobile timing belt, characterized in that: The antioxidant is selected from one or more combinations of antioxidant CDPA, antioxidant ZMTI, antioxidant RD, antioxidant DBHQ, antioxidant WSP and antioxidant BLE.

4. The use of the hydrogenated nitrile rubber material according to claim 1 in the preparation of an automobile timing belt, characterized in that: The plasticizer is selected from the group consisting of one or more combinations of trioctyl trimellitate, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, dioctyl sebacate and dioctyl adipate.

5. The use of the hydrogenated nitrile rubber material according to claim 1 in the preparation of an automobile timing belt, characterized in that: The flow dispersant is selected from a combination of one or more of fatty acid esters, polyethylene glycol, polyvinyl pyrrolidone and zinc stearate; The short fibers are selected from a combination of one or more of polyester short fibers and nylon short fibers; The vulcanizing agent is selected from di-tert-butyl peroxide isopropylbenzene and / or diisopropylbenzene peroxide; The auxiliary cross-linking agent is selected from one or more combinations of zinc acrylate, zinc methacrylate, trimethylolpropane trimethacrylate and triallyl isocyanurate.

6. The use of the hydrogenated nitrile rubber material according to claim 1 in preparing an automobile timing belt, characterized in that: The preparation method of the hydrogenated nitrile rubber material comprises: An internal mixer is used to first add hydrogenated nitrile raw rubber and weighted masterbatch in proportion for mixing, then add antioxidant, carbon black, plasticizer, flow dispersant and short fiber in sequence in proportion, press down for mixing and lift the bolt for cleaning, press down for mixing again and discharge the rubber to an open mixer, add vulcanizing agent and cross-linking aid on the open mixer for cutting and mixing, adjust the roller distance for thinning, and cool the sheet down to prepare a hydrogenated nitrile rubber material.

7. The use of the hydrogenated nitrile rubber material according to claim 6 in the preparation of an automobile timing belt, characterized in that: In the preparation method of the hydrogenated nitrile rubber material, the charging coefficient of the internal mixer is 0.55-0.75; the rotation speed is controlled at 10-50 r / min; Add hydrogenated nitrile rubber and weight-added masterbatch for mixing, and the mixing time is 2-5 minutes; Press down and mix for 4 to 8 minutes, then lift the bolt and clean; Press down and mix again until the temperature reaches 120℃~160℃ for debinding; The cutting and mixing time is 5~10min; Adjust the roller distance to the film thickness of 4mm and perform thin pass 5 to 8 times.

Images