Hydrogenated butadiene-acrylonitrile rubber material, preparation method thereof and application of hydrogenated butadiene-acrylonitrile rubber material in automobile synchronous belt

Abstract

The invention provides a hydrogenated butadiene-acrylonitrile rubber material, a preparation method thereof and application of the hydrogenated butadiene-acrylonitrile rubber material in an automobile synchronous belt. The hydrogenated nitrile rubber material is prepared from the following components in parts by weight: 30-60 parts of hydrogenated nitrile rubber, 80-130 parts of weight-increasing masterbatch, 2-4 parts of an anti-aging agent, 5-50 parts of carbon black, 1-15 parts of a plasticizer, 0.1-4 parts of a flow dispersing agent, 3-10 parts of short fibers, 1-10 parts of a vulcanizing agent and 0.1-5 parts of an assistant crosslinking agent. The hydrogenated butadiene-acrylonitrile rubber material provided by the invention has improved material density and excellent comprehensive performance, and the automobile synchronous belt prepared from the hydrogenated butadiene-acrylonitrile rubber material can reduce the inherent frequency of the timing belt, control the resonant frequency within a low-speed range, and effectively relieve the formation of high-rotation-speed noise.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber materials for automobiles, and in particular relates to a hydrogenated nitrile rubber material and a preparation method thereof, and application thereof in automobile synchronous belts. Background Art

[0002] The main material of the timing belt is rubber, and it also contains tensile cords as the skeleton material and tooth cloth fabric to protect the tooth body. Compared with metal chains, the synchronous belt has an incomparable low noise advantage, but the resonance noise in the transmission process is still inevitable, especially at high speeds. If the transmission system is not designed properly, 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 a layer of irregular wavy and continuously distributed interlayer fabric between the belt back and the meshing part to reduce noise, but the molding process of this solution is complicated and the cost is high.

[0003] Therefore, it is urgent to provide a high-density hydrogenated nitrile rubber material that can meet the needs of automobile timing belts and its application in the preparation of automobile timing belts, so as to reduce belt noise. Summary of the invention

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

[0005] The purpose of the present invention is achieved through the following technical solutions: In one aspect, the present invention provides a hydrogenated nitrile rubber material. 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.

[0006] The rubber materials currently used for timing belts are chloroprene and hydrogenated nitrile. The density of chloroprene rubber is generally 1.4~1.5g / cm 3Through experimental comparison, chloroprene synchronous belts have better noise performance than hydrogenated nitrile synchronous belts. However, chloroprene's high temperature resistance is limited and it is difficult to meet the application of modern automobile engines. At the same time, the density of hydrogenated nitrile is generally 1.2~1.3 g / cm 3 , so it is necessary to further improve the density of hydrogenated nitrile rubber and meet the performance requirements of the timing belt. The common means of increasing the weight of rubber materials is to directly add weighting materials (high specific gravity fillers), such as carbon black / metals and their oxides, etc., which will have poor compatibility with the rubber matrix, resulting in poor dynamic and static performance of the material, and cannot meet the application of automotive timing belts; the present invention adds weighting materials in the form of premixed masterbatch and optimizes the mixing process to obtain a high-density hydrogenated nitrile material with excellent comprehensive performance. It can reduce noise when used in automotive timing belts, and has the advantages of being easy to implement and low cost, which expands the application of hydrogenated nitrile materials.

[0007] In the above hydrogenated nitrile rubber material, preferably, based on the mass of the weighting masterbatch as 100%, the raw material components for preparing the weighting masterbatch include: Hydrogenated nitrile rubber 40%~60%; Zinc oxide 40%~60%; Stearic acid 1%~5%; Silane coupling agent 1%~5%; Trioctyl trimellitate 1%~5%.

[0008] In the above hydrogenated nitrile rubber material, preferably, the method for preparing the weighting 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.

[0009] In the above hydrogenated nitrile rubber material, preferably, the charging factor of the internal mixer is 0.6-0.8; and the rotation speed is controlled to be 10-100 r / min.

[0010] In the above hydrogenated nitrile rubber material, preferably, the time for putting the hydrogenated nitrile rubber into the plasticizing process is 2 to 5 minutes.

[0011] In the above hydrogenated nitrile rubber material, preferably, the plug is lifted for cleaning after mixing under pressure for 2 to 3 minutes.

[0012] In the above hydrogenated nitrile rubber material, preferably, the rubber is discharged when the temperature is pressed down and mixed again to 120° C. to 160° C.

[0013] In the above hydrogenated nitrile rubber material, preferably, the total mixing time is controlled to be 6 to 15 minutes.

[0014] In the above hydrogenated nitrile rubber material, preferably, the silane coupling agent is selected from a combination of one or more of 3-aminopropyltrimethoxysilane, methyltri(methoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane and 3-propyleneoxypropyltrimethoxysilane, but is not limited thereto.

[0015] In the above-mentioned hydrogenated nitrile rubber material, preferably, the antioxidant is selected from one or more combinations of antioxidant CDPA, antioxidant ZMTI, antioxidant RD, antioxidant DBHQ, antioxidant WSP and antioxidant BLE, but is not limited thereto.

[0016] In the above hydrogenated nitrile rubber material, preferably, the plasticizer is selected from a combination of one or more of trioctyl trimellitate, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, dioctyl sebacate and dioctyl adipate, but is not limited thereto.

[0017] In the above hydrogenated nitrile rubber material, preferably, the flow dispersant is selected from a combination of one or more of fatty acid esters, polyethylene glycol, polyvinyl pyrrolidone and zinc stearate, but is not limited thereto.

[0018] In the above hydrogenated nitrile rubber material, preferably, the short fibers are selected from one or more combinations of aramid short fibers, polyester short fibers and nylon short fibers, but are not limited thereto.

[0019] In the above hydrogenated nitrile rubber material, preferably, the vulcanizing agent is selected from di-tert-butyl peroxide isopropylbenzene and / or diisopropylbenzene peroxide, but is not limited thereto.

[0020] In the above hydrogenated nitrile rubber material, preferably, the auxiliary cross-linking agent is selected from one or more combinations of zinc acrylate, zinc methacrylate, trimethylolpropane trimethacrylate and triallyl isocyanurate, but is not limited thereto.

[0021] On the other hand, the present invention also provides a method for preparing the above-mentioned hydrogenated nitrile rubber material, the method comprising: 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.

[0022] In the above preparation method, preferably, the charging factor of the internal mixer is 0.55-0.75; and the rotation speed is controlled to be 10-50 r / min.

[0023] In the above-mentioned preparation method, preferably, the time for mixing the hydrogenated nitrile rubber and the weighted masterbatch is 2 to 5 minutes.

[0024] In the above preparation method, preferably, the bolt is lifted for cleaning after the mixing is performed under pressure for 4 to 8 minutes.

[0025] In the above preparation method, preferably, the debinding is performed when the temperature is pressed down again and kneaded to 120° C. to 160° C.

[0026] In the above preparation method, preferably, the cutting and mixing time is 5 to 10 minutes.

[0027] In the above preparation method, preferably, the roller distance is adjusted to a film thickness of 4 mm and thin passes are performed 5 to 8 times.

[0028] In another aspect, the present invention also provides the use of the hydrogenated nitrile rubber material or the hydrogenated nitrile rubber material prepared by the above preparation method in the preparation of automotive timing belts.

[0029] Beneficial effects of the present invention: The hydrogenated nitrile rubber material of the present invention achieves the effect of increasing the rubber density and excellent comprehensive performance by adding weighting materials in the form of masterbatch, and has the advantages of being easy to implement and low in cost. The hydrogenated nitrile rubber material of the present invention is used to prepare an automobile synchronous belt, and the density of the belt body rubber is increased to reduce the natural frequency of the timing belt, so that the resonance frequency can be controlled within a low speed range, effectively alleviating the formation of high-speed noise.

[0030] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the preferred embodiments of the present invention are described in detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of this specification or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this specification. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0032] Figure 1 The figure is a result diagram of a performance test experiment on the hydrogenated nitrile rubber materials prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 2. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. The process, conditions, reagents, experimental methods, etc. for implementing the present invention, except for the contents specifically mentioned below, are all common knowledge and common common sense in the art, and the present invention does not particularly limit the contents.

[0034] Embodiment 1: This embodiment provides a hydrogenated nitrile rubber material. The components for preparing the hydrogenated nitrile rubber material include, by weight: 40 parts of hydrogenated nitrile rubber; 120 parts of weight-adding masterbatch; Anti-aging agent RD 1 part; Anti-aging agent ZMTI 1 part Carbon black N550 40 parts; Plasticizer (trioctyl trimellitate) 5 parts; Flowing dispersant (zinc stearate) 2 parts; 5 parts of nylon staple fiber; Curing agent (di-tert-butyl peroxide isopropylbenzene) 5 parts; Auxiliary cross-linking agent (zinc methacrylate) 2 parts.

[0035] The weight-enhanced composite masterbatch is prepared by the following preparation method: An internal mixer is used with a charging coefficient in the range of 0.6 and a rotation speed controlled at 50 r / min. Taking the weight of the increased composite masterbatch as 100%, 50% of hydrogenated nitrile rubber is first added for plasticization for 3 minutes, and then 45% of zinc oxide, 2% of stearic acid, 2% of silane coupling agent (3-aminopropyltrimethoxysilane) and 1% of trioctyl trimellitate (TOTM) are added in sequence. After pressing down and mixing for 2 minutes, the bolt is lifted for cleaning, and the mixture is pressed down again to 130° C. for degumming to obtain the increased composite masterbatch. The total mixing time is controlled to be 8 minutes.

[0036] This embodiment also provides a method for preparing the above hydrogenated nitrile rubber material, the preparation method comprising: An internal mixer was used with a charging coefficient of 0.6 and a rotation speed of 50 r / min. First, 40 parts of hydrogenated nitrile rubber and 120 parts of weight-added composite masterbatch were added for mixing for 3 minutes. Then, the antioxidant, carbon black, plasticizer, dispersant and short fiber in the above-mentioned amounts were added in turn. After mixing for 5 minutes, the bolt was lifted for cleaning. The mixture was mixed again at a temperature of 130°C and discharged to an open mixer. Vulcanizing agent and cross-linking agent were added on the mixer and the mixture was cut and mixed for 8 minutes. The roller spacing was adjusted to a film thickness of 4 mm and thinned through 5 times. The film was cooled to prepare a hydrogenated nitrile rubber material.

[0037] This embodiment also provides the use of the hydrogenated nitrile rubber material in preparing an automobile synchronous belt.

[0038] Embodiment 2: This embodiment provides a hydrogenated nitrile rubber material. The components for preparing the hydrogenated nitrile rubber material include, by weight: 50 parts of hydrogenated nitrile rubber; 100 parts of weight-adding masterbatch; Anti-aging agent RD 1 part; Anti-aging agent ZMTI 1 part Carbon black N550 40 parts; Plasticizer (trioctyl trimellitate) 5 parts; Flowing dispersant (zinc stearate) 2 parts; 5 parts of nylon staple fiber; Curing agent (di-tert-butyl peroxide isopropylbenzene) 5 parts; Auxiliary cross-linking agent (zinc methacrylate) 2 parts.

[0039] Wherein, the preparation method of the weight-increasing composite masterbatch is the same as that in Example 1.

[0040] This embodiment also provides a method for preparing the above hydrogenated nitrile rubber material, the preparation method comprising: An internal mixer was used with a charging coefficient in the range of 0.6 and a rotation speed controlled at 50 r / min. First, 50 parts of hydrogenated nitrile raw rubber and 100 parts of weight-added composite masterbatch were added for mixing for 3 minutes. Then, the antioxidant, carbon black, plasticizer, dispersant and short fiber in the above-mentioned amounts were added in sequence. After pressing down for mixing for 5 minutes, the bolt was lifted for cleaning. The mixer was pressed down again to a temperature of 130°C for discharging the rubber to an open mixer. Vulcanizing agent and cross-linking aid were added on the mixer and the mixture was cut and mixed for 8 minutes. The roller spacing was adjusted to a film thickness of 4 mm for thinning 5 times. The film was cooled to prepare a hydrogenated nitrile rubber material.

[0041] This embodiment also provides the use of the hydrogenated nitrile rubber material in preparing an automobile synchronous belt.

[0042] Embodiment 3: This embodiment provides a hydrogenated nitrile rubber material. The components for preparing the hydrogenated nitrile rubber material include, by weight: 60 parts of hydrogenated nitrile rubber; 80 parts of weight-added masterbatch; Anti-aging agent RD 1 part; 1 part of antioxidant ZMTI; Carbon black N550 40 parts; Plasticizer (trioctyl trimellitate) 5 parts; Flowing dispersant (zinc stearate) 2 parts; 5 parts of nylon staple fiber; Curing agent (di-tert-butyl peroxide isopropylbenzene) 5 parts; Auxiliary cross-linking agent (zinc methacrylate) 2 parts.

[0043] Wherein, the method for preparing the weight-increasing masterbatch is the same as that in Example 1.

[0044] This embodiment also provides a method for preparing the above hydrogenated nitrile rubber material, the preparation method comprising: An internal mixer was used with a charging coefficient of 0.6 and a rotation speed of 50 r / min. First, 60 parts of hydrogenated nitrile raw rubber and 80 parts of weight-added composite masterbatch were added and mixed for 3 minutes. Then, the antioxidant, carbon black, plasticizer, dispersant and short fiber in the above-mentioned amounts were added in sequence. After pressing down and mixing for 5 minutes, the bolt was lifted for cleaning. The mixture was pressed down again to a temperature of 130°C and discharged to an open mixer. Vulcanizing agent and cross-linking agent were added on the open mixer and the mixture was cut and mixed for 8 minutes. The roller spacing was adjusted to a film thickness of 4 mm and thinned through 5 times. The film was cooled to prepare a hydrogenated nitrile rubber material.

[0045] This embodiment also provides the use of the hydrogenated nitrile rubber material in the preparation of an automobile synchronous belt.

[0046] Comparative Example 1: This comparative example provides a hydrogenated nitrile rubber material. The components for preparing the hydrogenated nitrile rubber material include, by weight: 100 parts of hydrogenated nitrile rubber; Zinc oxide 54 parts; Anti-aging agent RD 1 part; 1 part of antioxidant ZMTI; Carbon black N550 40 parts; Plasticizer (trioctyl trimellitate) 5 parts; Flowing dispersant (zinc stearate) 2 parts; 5 parts of nylon staple fiber; Curing agent (di-tert-butyl peroxide isopropylbenzene) 5 parts; Auxiliary cross-linking agent (zinc methacrylate) 2 parts.

[0047] Compared with Example 1, the weighting agent zinc oxide is added directly.

[0048] Comparative Example 2: This comparative example provides a hydrogenated nitrile rubber material. The components for preparing the hydrogenated nitrile rubber material include, by weight: 100 parts of hydrogenated nitrile rubber; Zinc oxide 5 parts; Anti-aging agent RD 1 part; 1 part of antioxidant ZMTI; Carbon black N550 40 parts; Plasticizer (trioctyl trimellitate) 5 parts; Flowing dispersant (zinc stearate) 2 parts; 5 parts of nylon staple fiber; Curing agent (di-tert-butyl peroxide isopropylbenzene) 5 parts; Auxiliary cross-linking agent (zinc methacrylate) 2 parts.

[0049] This comparative example is a hydrogenated nitrile rubber material of normal density.

[0050] The performance test experiments were carried out on the hydrogenated nitrile rubber materials prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 2. The experimental results are as follows: Figure 1 shown.

[0051] The present invention uses specific embodiments to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. At the same time, for those skilled in the art, according to the idea of ​​the present invention, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present invention.

Claims

1. A hydrogenated nitrile rubber material, 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 hydrogenated nitrile rubber material according to claim 1, 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-propyleneoxypropyltrimethoxysilane.

3. The hydrogenated nitrile rubber material according to claim 1, 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 hydrogenated nitrile rubber material according to claim 1, 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 hydrogenated nitrile rubber material according to claim 1, 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 aramid short fibers, 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 method for preparing the hydrogenated nitrile rubber material according to any one of claims 1 to 5, characterized in that: The method 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 preparation method according to claim 6, characterized in that: The filling coefficient of the internal mixer is 0.55-0.75; the speed is controlled at 10-50r / 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.

8. Use of the hydrogenated nitrile rubber material according to any one of claims 1 to 5 or the hydrogenated nitrile rubber material prepared by the preparation method according to claim 6 or 7 in preparing an automobile synchronous belt.

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