CN114716743B

CN114716743B - Hydrogenated nitrile rubber reinforcing agent and preparation method and application thereof

Info

Publication number: CN114716743B
Application number: CN202210317803.4A
Authority: CN
Inventors: 王亚男; 索军营; 魏莉; 侯平安; 唐帅
Original assignee: Chengdu Aircraft Industrial Group Co Ltd
Current assignee: Chengdu Aircraft Industrial Group Co Ltd
Priority date: 2022-03-25
Filing date: 2022-03-25
Publication date: 2023-05-09
Anticipated expiration: 2042-03-25
Also published as: CN114716743A

Abstract

The hydrogenated nitrile rubber reinforcing agent is a compound of platy hydrotalcite and nano silicon dioxide particles, nano silicon dioxide particles are used as carriers, and platy hydrotalcite grows on the surfaces of the nano silicon dioxide particles; in the composite, the weight ratio of the flaky hydrotalcite to the nano silicon dioxide particles is 0.2-1: 1. the hydrogenated nitrile rubber reinforcing agent disclosed by the invention is a compound of platy hydrotalcite and nano silicon dioxide particles, the nano silicon dioxide particles are used as a carrier, the platy hydrotalcite grows on the surfaces of the nano silicon dioxide particles, the modified nano silicon dioxide particles are used as the hydrogenated nitrile rubber reinforcing agent and have good reinforcing property and excellent dispersibility in the hydrogenated nitrile rubber, and the platy hydrotalcite can generate orientation behavior when the rubber is subjected to tensile force, so that the stress transfer rate is improved, and the reinforcing agent is more efficient.

Description

Hydrogenated nitrile rubber reinforcing agent and preparation method and application thereof

Technical Field

The invention relates to the technical field of hydrogenated nitrile rubber reinforcing agents, in particular to a hydrogenated nitrile rubber reinforcing agent, a preparation method and application thereof.

Background

Hydrogenated nitrile rubber is widely used as a synthetic rubber with high saturation in the fields of aviation, oil fields, sealing and the like. Reinforcing agents are added in the preparation process of the hydrogenated nitrile rubber to improve the mechanical properties of the rubber product.

The conventional reinforcing agent for the conventional hydrogenated nitrile rubber is mainly carbon black, but the carbon black has the defects of low reinforcing efficiency, low reinforcing effect and poor environmental protection in the use process of the carbon black as the reinforcing agent. The silicon dioxide has the characteristics of no environmental pollution, low price and excellent reinforcing performance, and is considered to be a new generation green filler capable of replacing carbon black. However, the nano-particles are easy to agglomerate in rubber, and the formation of agglomerates limits the exertion of the reinforcing effect on the rubber, so that the high-performance hydrogenated nitrile rubber composite material is not beneficial to the large-scale application of the hydrogenated nitrile rubber.

Disclosure of Invention

The invention aims at: aiming at the problems of poor dispersibility and poor reinforcing effect when the silicon dioxide material is used as a hydrogenated nitrile rubber reinforcing agent in the prior art, the hydrogenated nitrile rubber reinforcing agent, the preparation method and the application thereof are provided, and the hydrogenated nitrile rubber reinforcing agent is modified nano silicon dioxide particles and has excellent dispersibility and good reinforcing effect.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:

the hydrogenated nitrile rubber reinforcing agent is a compound of platy hydrotalcite and nano silicon dioxide particles, nano silicon dioxide particles are used as carriers, and platy hydrotalcite grows on the surfaces of the nano silicon dioxide particles; in the composite, the weight ratio of the flaky hydrotalcite to the nano silicon dioxide particles is 0.2-1: 1.

the hydrogenated nitrile rubber reinforcing agent disclosed by the invention is a compound of platy hydrotalcite and nano silicon dioxide particles, the nano silicon dioxide particles are used as a carrier, the platy hydrotalcite grows on the surfaces of the nano silicon dioxide particles, and the modified nano silicon dioxide particles have good reinforcing property and excellent dispersibility in the hydrogenated nitrile rubber as the reinforcing agent of the hydrogenated nitrile rubber by limiting the weight ratio of the platy hydrotalcite to the nano silicon dioxide particles.

The hydrotalcite nanosheets and the silicon dioxide nanoparticles in the reinforcing agent have the effect of promoting dispersion mutually, so that the problem that the nano reinforcing agent is easy to agglomerate in rubber is effectively solved, and the excellent dispersion effect of the reinforcing agent is ensured; meanwhile, the flaky hydrotalcite can generate orientation behavior when the rubber is subjected to tensile force, so that the stress transfer rate is improved, the reinforcing agent is more efficient, the diffusion of hot air and ageing products can be weakened by the flaky hydrotalcite, and the heat-resistant air ageing performance of the rubber is improved.

Further, in the composite, the particle size of the nano silicon dioxide particles is 10 nm-100 nm; the side length of the flaky hydrotalcite is 100 nm-1000 nm.

Further, the hydrogenated nitrile rubber reinforcing agent is a hydrotalcite-nano silicon dioxide particle compound, and a stress dissipation center is formed.

Further, the flaky hydrotalcite-nano silicon dioxide particle compound is prepared by adopting an in-situ growth method.

Further, the weight ratio of the platy hydrotalcite to the nano silicon dioxide particles is 0.5-0.8:1. For example, 0.2:1;0.3:1;0.4:1;0.5:1;0.6:1;0.7:1;0.8:1;0.9:1;1:1. Through a great deal of experimental researches by the inventor, the weight ratio of the flaky hydrotalcite to the nano silicon dioxide particles has close relation with the reinforcing property of the reinforcing agent, and the excessive weight ratio can influence the reinforcing effect, and the too small weight ratio can hardly improve the dispersibility of the nano carbon dioxide particles and also influence the reinforcing effect.

It is another object of the present invention to provide a process for the preparation of the hydrogenated nitrile rubber reinforcing agent described above.

The preparation method of the hydrogenated nitrile rubber reinforcing agent comprises the following steps:

step 1, sequentially adding nano silicon dioxide particles and sodium carbonate solution into a reaction device, and performing ultrasonic treatment to obtain a first solution;

step 2, dropwise adding a zinc nitrate hexahydrate solution and an aluminum nitrate nonahydrate solution into the first solution obtained in the step 1, and stirring to obtain a second solution;

and 3, regulating the pH value of the second solution obtained in the step 2 to 8.5-9.5, standing, washing to neutrality, filtering and drying to obtain the hydrogenated nitrile rubber reinforcing agent.

The hydrotalcite-silicon dioxide composite reinforcing agent is prepared by taking zinc nitrate hexahydrate and aluminum nitrate nonahydrate as precursors through an in-situ assembly method, and the preparation method is simple to operate and convenient to control.

Further, the concentration of the sodium carbonate solution is 0.3mol/L to 0.5mol/L. The addition amount of the sodium carbonate solution is 2-8 times of the volume of the nano silicon dioxide particles.

Further, in the step 1, the time of the ultrasonic treatment is 2-3 hours.

Further, in the step 2, the dropping speed is 1-3 drops/second. Researches show that the adding speed of dripping is too high or the adding is directly carried out by adopting a pouring mixing mode, the reinforcing effect of the reinforcing agent can be seriously influenced, the dripping speed is too high or the adding is directly carried out by adopting the pouring mixing mode, the prepared hydrotalcite sheet-like effect is poor, and the product is easy to agglomerate.

Further, in the step 3, the pH of the second solution obtained in the step 2 is adjusted to 9 to 9.5. For example, a pH of 8.5; the pH was 8.6; the pH was 8.7; the pH was 8.8; the pH was 8.9; the pH was 9.0; the pH was 9.1; the pH was 9.2; the pH was 9.3; the pH was 9.4; the pH was 9.5. Through a great deal of experimental study by the inventor, the final pH value of the second solution is regulated to have close relation with the reinforcing effect of the prepared reinforcing agent. Too large and too small pH value can affect the flaky morphology and agglomeration of hydrotalcite, so that the reinforcing effect is obviously reduced.

Further, the step 3 adopts at least one of deionized water and absolute ethyl alcohol as a detergent.

Further, in the step 1, the added nano silica particles are liquid phase nano silica particles. According to the preparation method, the water phase nano silicon dioxide particles prepared by a precipitation method are added as the carrier, so that hydrotalcite nano sheets can directly form crystal nuclei on the surface of silicon dioxide, and further, the hydrotalcite nano sheets grow on the surface of silicon dioxide in situ, so that the dispersibility of nano fillers in rubber is improved.

Further, in the step 2, the concentration of the zinc nitrate hexahydrate solution is 0.3mol/L to 0.5mol/L; the concentration of the aluminum nitrate nonahydrate solution is 0.2 mol/L-0.6 mol/L. Preferably, in the step 2, the concentration of the zinc nitrate hexahydrate solution is 0.4mol/L to 0.5mol/L; the concentration of the aluminum nitrate nonahydrate solution is 0.3 mol/L-0.5 mol/L. It is found that the concentration of zinc nitrate and aluminum nitrate is also a key factor affecting the effect of the reinforcing agent, and that too large or too small concentration affects the deposition state and the deposition dispersity of hydrotalcite, resulting in a decrease in the reinforcing effect.

Further, in the step 2, the adding mass ratio of the nitrate compound to the nano silicon dioxide particles is 0.2-1:1. Preferably, in the step 2, the adding mass ratio of the nitrate compound to the nano silicon dioxide particles is 0.5-0.8: 1. for example, 0.2:1;0.3:1;0.4:1;0.5:1;0.6:1;0.7:1;0.8:1;0.9:1;1:1. The mass ratio of nitrate compound to nano-silica particles was found to be a key factor affecting the effectiveness of the strengthening agent. Wherein the mass of the nitrate compound refers to the sum of the mass of zinc nitrate hexahydrate and the mass of aluminum nitrate nonahydrate.

In step 3, stirring is performed for 2 to 2.5 hours before standing.

Further, in the step 3, the standing time is 10 to 15 hours.

It is a further object of the present invention to provide the use of the hydrogenated nitrile rubber reinforcing agent described above.

The hydrogenated nitrile rubber reinforcing agent is applied to raw materials in the preparation process of hydrogenated nitrile rubber.

The modified nano silicon dioxide particles are used as a reinforcing agent of hydrogenated butyronitrile, and have good reinforcing property and excellent dispersing effect.

In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:

1. the hydrogenated nitrile rubber reinforcing agent disclosed by the invention is a compound of platy hydrotalcite and nano silicon dioxide particles, the nano silicon dioxide particles are used as carriers, the platy hydrotalcite grows on the surfaces of the nano silicon dioxide particles, and the modified nano silicon dioxide particles have good reinforcing property and excellent dispersing effect as the reinforcing agent of the hydrogenated nitrile by limiting the weight ratio of the platy hydrotalcite to the nano silicon dioxide particles.

2. According to the reinforcing agent disclosed by the invention, the hydrotalcite nano-sheets and the silicon dioxide nano-particles mutually promote the dispersion effect, so that the problem that the nano-reinforcing agent is easy to agglomerate in rubber is effectively solved, and the excellent dispersion effect of the reinforcing agent is ensured; meanwhile, the flaky hydrotalcite can generate orientation behavior when the rubber is subjected to tensile force, so that the stress transfer rate is improved, the reinforcing agent is more efficient, a higher reinforcing effect can be achieved by adding fewer reinforcing agents, and the flaky hydrotalcite can weaken the diffusion of hot air and ageing products and improve the heat-resistant air ageing performance of the rubber.

3. The hydrotalcite-silicon dioxide composite reinforcing agent is prepared by taking zinc nitrate hexahydrate and aluminum nitrate nonahydrate as precursors through an in-situ assembly method, and the preparation method is simple to operate and convenient to control.

Drawings

FIG. 1 is a scanning electron micrograph of a hydrogenated nitrile rubber reinforcing agent of example 1 of the present invention.

FIG. 2 is a graph showing the mechanical property reinforcing property of the hydrogenated nitrile rubber prepared in example 1 of the present invention.

Detailed Description

The present invention will be described in detail with reference to the accompanying drawings.

The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.

Example 1

Preparation of hydrogenated nitrile rubber Reinforcement

(1) Weighing 25g of liquid phase nano silicon dioxide particle powder in a three-mouth bottle, adding 82.48ml of commercial 0.5mol/L sodium carbonate aqueous solution, and performing ultrasonic treatment at room temperature for 2.5 hours to fully disperse the nano silicon dioxide particles in the sodium carbonate aqueous solution;

(2) Under the action of mechanical stirring, dropwise adding 82.48ml of 0.5mol/L zinc nitrate hexahydrate solution and 82.48ml of 0.25mol/L aluminum nitrate nonahydrate solution into the three-port bottle in the step (1), and fully stirring to obtain a mixed solution, wherein the dropwise adding speed of the solution is 1-3 drops/second;

(3) Dropwise adding a commercial 2mol/L sodium hydroxide aqueous solution under the action of mechanical stirring to regulate the pH=9.0 of the mixed solution in the step (2), and maintaining for 2 hours to obtain hydrotalcite-silicon dioxide slurry;

(4) And (3) standing the hydrotalcite-silicon dioxide slurry in the step (3) for 10 hours after the reaction, sequentially using deionized water and ethanol as detergents after the standing, centrifugally separating and washing until the mixture is neutral, detecting whether the mixture is neutral by using pH test paper, putting the obtained solid into an oven after the washing, and drying at 60 ℃ for 18 hours to obtain the hydrogenated nitrile rubber reinforcing agent.

The hydrogenated nitrile rubber reinforcing agent prepared in example 1 was subjected to scanning electron microscopy using JSM-7800 scanning electron microscope from JEOL corporation, as shown in FIG. 1, and it was found that the reinforcing agent was supported on silica surfaces by nano silica particles, hydrotalcite nano sheets, wherein the mechanical dissipation center (stress dissipation center) was a composite nano material composed of nano silica particles and hydrotalcite nano sheets, the particle size of the nano silica was 10 to 100nm, and the side lengths of the hydrotalcite nano sheets were 100 to 1000nm.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of example 1 is prepared by a mechanical blending method, and the concrete process is as follows:

the roller temperature of a double-roller open mill is kept below 55 ℃, 5g of zinc oxide and 2g of stearic acid are added into 100g of nitrile rubber, then 30g of reinforcing agent is added, and then 5g of vulcanizing agent, 2g of auxiliary cross-linking agent and 1.5g of anti-aging agent are added, and the mixture is fully mixed and then the mixture is discharged. Then vulcanizing at 170 ℃ by a plate vulcanizing instrument to obtain the hydrotalcite-silicon dioxide reinforced hydrogenated nitrile-butadiene rubber.

The static mechanical properties of the vulcanized rubber are tested by using a SANS CMT4203 electronic tensile machine, the test method conforms to the standard sample preparation and measurement of GB/T528-2009 rubber stretching, the mechanical properties of the vulcanized rubber and the stress-strain curve are obtained, and the detection result is shown in figure 2.

Example 2

Preparation of hydrogenated nitrile rubber Reinforcement

(1) Weighing 25g of liquid phase nano silicon dioxide particle powder into a three-mouth bottle, adding 61.86ml of commercial 0.5mol/L sodium carbonate aqueous solution, and performing ultrasonic treatment at room temperature for 2 hours to fully disperse nano silicon dioxide particles in the sodium carbonate aqueous solution;

(2) Under the action of mechanical stirring, dropwise adding 103.1ml of 0.3mol/L zinc nitrate hexahydrate solution and 30.93ml of 0.5mol/L aluminum nitrate nonahydrate solution into the three-port bottle in the step (1), and fully stirring to obtain a mixed solution, wherein the dropwise adding speed of the solution is 1-3 drops/second;

(3) Dropwise adding a commercial 2mol/L sodium hydroxide aqueous solution under the action of mechanical stirring to regulate the pH=9.5 of the mixed solution in the step (2), and maintaining for 2.5 hours to obtain hydrotalcite-silicon dioxide slurry;

(4) And (3) standing the hydrotalcite-silicon dioxide slurry obtained in the step (3) for 12 hours after the reaction, sequentially using deionized water and ethanol as detergents after the standing, centrifugally separating and washing until the mixture is neutral, detecting whether the mixture is neutral by using pH test paper, putting the obtained solid into an oven after the washing, and drying at 60 ℃ for 18 hours to obtain the hydrogenated nitrile rubber reinforcing agent.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of example 2 is prepared by a mechanical blending method, and the concrete process is as follows:

the roller temperature of a double-roller open mill is kept below 55 ℃, 5g of zinc oxide and 2g of stearic acid are added into 100g of nitrile rubber, then 30g of reinforcing agent is added, and then 5g of vulcanizing agent, 2g of auxiliary cross-linking agent and 1.5g of anti-aging agent are added, and the mixture is fully mixed and then the mixture is discharged. And then vulcanizing at 170 ℃ by a plate vulcanizing instrument to obtain the hydrogenated nitrile-butadiene vulcanized rubber.

Example 3

Preparation of hydrogenated nitrile rubber Reinforcement

(1) Weighing 25g of liquid phase nano silicon dioxide particle powder in a three-mouth bottle, adding 41.24ml of commercial 0.5mol/L sodium carbonate aqueous solution, and carrying out ultrasonic treatment at room temperature for 3 hours to fully disperse the nano silicon dioxide particles in the sodium carbonate aqueous solution;

(2) Under the action of mechanical stirring, dropwise adding 41.24ml of 0.5mol/L zinc nitrate hexahydrate solution and 17.18ml of 0.6mol/L aluminum nitrate nonahydrate solution into the three-port bottle in the step (1), and fully stirring to obtain a mixed solution, wherein the dropwise adding speed of the solution is 1-3 drops/second;

(3) Dropwise adding and adjusting the pH=8.5 of the mixed solution in the step (2) by using 2mol/L sodium hydroxide solution which is commercially available under the action of mechanical stirring, and maintaining for 2 hours to obtain hydrotalcite-silicon dioxide slurry;

(4) And (3) standing the hydrotalcite-silicon dioxide slurry in the step (3) for 15 hours after the reaction, sequentially using deionized water and ethanol as detergents after the standing, centrifugally separating and washing until the mixture is neutral, detecting whether the mixture is neutral by using pH test paper, putting the obtained solid into an oven after the washing, and drying at 60 ℃ for 18 hours to obtain the hydrogenated nitrile rubber reinforcing agent.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of example 3 is prepared by a mechanical blending method, and the concrete process is as follows:

Example 4

Preparation of hydrogenated nitrile rubber Reinforcement

(1) Weighing 25g of liquid phase nano silicon dioxide particle powder in a three-mouth bottle, adding 20.62ml of commercial 0.5mol/L sodium carbonate aqueous solution, and performing ultrasonic treatment at room temperature for 2 hours to fully disperse nano silicon dioxide particles in the sodium carbonate aqueous solution;

(2) Under the action of mechanical stirring, 29.46ml of 0.35mol/L zinc nitrate hexahydrate solution and 25.78ml of 0.2mol/L aluminum nitrate nonahydrate solution are dropwise added into the three-port bottle in the step (1), the dropping speed of the solution is 1-3 drops/second, and the solution is fully stirred to obtain a mixed solution;

(3) Dropwise adding and adjusting the pH=9.0 of the mixed solution in the step (2) by using 2mol/L sodium hydroxide solution which is commercially available under the action of mechanical stirring, and maintaining for 2.5 hours to obtain hydrotalcite-silicon dioxide slurry;

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of example 4 is prepared by a mechanical blending method, and the concrete process is as follows:

the roller temperature of a double-roller open mill is kept below 55 ℃, 5g of zinc oxide and 2g of stearic acid are added into 100g of nitrile rubber, then 30g of reinforcing agent is added, and then 5g of vulcanizing agent, 2g of auxiliary cross-linking agent and 1.5g of anti-aging agent are added, and the mixture is fully mixed and then the mixture is discharged. And then vulcanizing at 170 ℃ by a plate vulcanizing instrument to obtain the hydrogenated nitrile-butadiene vulcanized rubber. The static mechanical properties of the vulcanizates prepared in examples 2-4 were tested in the same manner as in example 1, with the test results set forth in Table 1.

TABLE 1

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The hydrogenated nitrile rubber reinforcing agent disclosed by the invention is a compound of platy hydrotalcite and nano silicon dioxide particles, the nano silicon dioxide particles are used as carriers, the platy hydrotalcite grows on the surfaces of the nano silicon dioxide particles, and the modified nano silicon dioxide particles have good reinforcing property and excellent dispersing effect as the reinforcing agent of the hydrogenated nitrile by limiting the weight ratio of the platy hydrotalcite to the nano silicon dioxide particles.

Comparative example 1

Preparation of hydrogenated nitrile rubber Reinforcement

The reinforcing agent prepared in comparative example 1 was a mixture of the same amount of liquid phase nano silica particles as in example 1 with the same hydrotalcite.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of comparative example 1 is prepared by a mechanical blending method, and the concrete process is as follows:

Comparative example 2

Preparation of hydrogenated nitrile rubber Reinforcement

Comparative example 2 differs from the preparation of example 1 in that comparative example 2 uses fumed silica particle powder as the starting material, and that comparative example 2 prepares a reinforcing agent in exactly the same manner as in example 1 as well as other process parameters.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of comparative example 2 is prepared by a mechanical blending method, and the concrete process is as follows:

Comparative example 3

Preparation of hydrogenated nitrile rubber Reinforcement

Comparative example 3 the procedure was different from example 1 in that comparative example 3 was carried out by weighing 25g of liquid phase nano silica particle powder in a three-necked flask and then adding 82.48ml of water for ultrasonic treatment, and other preparation procedures and process parameters were identical to example 1.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of comparative example 3 is prepared by a mechanical blending method, and the concrete process is as follows:

Comparative example 4

Comparative example 4 carbon black was used as a reinforcing agent.

Preparation of hydrogenated nitrile rubber

Comparative example 4-1 group

The roller temperature of a double-roller open mill is kept below 55 ℃, 5g of zinc oxide and 2g of stearic acid are added into 100g of nitrile rubber, then 30g of carbon black is added, then 5g of vulcanizing agent, 2g of auxiliary cross-linking agent and 1.5g of anti-aging agent are added, and the mixture is fully mixed and then discharged. And then vulcanizing at 170 ℃ by a plate vulcanizing instrument to obtain the hydrogenated nitrile-butadiene vulcanized rubber.

Comparative examples 4-2 groups

The roller temperature of a double-roller open mill is kept below 55 ℃, 5g of zinc oxide and 2g of stearic acid are added into 100g of nitrile rubber, then 50g of carbon black is added, then 5g of vulcanizing agent, 2g of auxiliary cross-linking agent and 1.5g of anti-aging agent are added, and the mixture is fully mixed and then discharged. And then vulcanizing at 170 ℃ by a plate vulcanizing instrument to obtain the hydrogenated nitrile-butadiene vulcanized rubber.

Comparative example 5

Preparation of hydrogenated nitrile rubber

Comparative example 5 was prepared without any reinforcing agent added.

The roller temperature of a double-roller open mill is kept below 55 ℃, 5g of zinc oxide and 2g of stearic acid are added into 100g of nitrile rubber, then 5g of vulcanizing agent, 2g of auxiliary cross-linking agent and 1.5g of anti-aging agent are added, and the mixture is fully mixed and then the mixture is discharged. And then vulcanizing at 170 ℃ by a plate vulcanizing instrument to obtain the hydrogenated nitrile-butadiene vulcanized rubber.

The static mechanical properties of the vulcanizates prepared in comparative examples 1-5 were tested in the same manner as in example 1, with the test results set forth in Table 2.

TABLE 2

Examples/comparative examples	Elongation at break%	Tensile strength MPa
			Comparative example 1	300％	3.52
Comparative example 2	300％	3.92
			Comparative example 3	300％	3.24
Comparative example 4-1	300％	4.05
			Comparative example 4-2	300％	6.08
Comparative example 8	300％	2.04

Through a great deal of experimental researches, the hydrogenated nitrile rubber reinforcing agent with high reinforcing effect and high reinforcing efficiency is prepared, and has close relation with the selection of the type of the nano silicon dioxide particles and the dissolution method. Meanwhile, carbon black is often selected as a hydrogenated nitrile rubber reinforcing agent in the prior art, but when the carbon black is used as the reinforcing agent, the adding amount is large, the reinforcing efficiency is low, and the cost is high. The reinforcing agent prepared by the method can achieve higher reinforcing effect by adding a small amount of reinforcing agent, and is high in reinforcing efficiency and low in cost.

Comparative example 6

Preparation of hydrogenated nitrile rubber Reinforcement

Comparative example 6A reinforcing agent was prepared in the same manner as in example 1, with the difference that in comparative example 6, the pH was adjusted to 8.0 with sodium hydroxide solution in the group 6-I and 10.0 with sodium hydroxide solution in the group 6-II. Other preparation processes, raw material ratios and process parameters of comparative example 6 were the same as in example 1.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of comparative example 6 is prepared by a mechanical blending method, and the concrete process is as follows:

Comparative example 7

Preparation of hydrogenated nitrile rubber Reinforcement

Comparative example 7 the same preparation method as in example 1 was adopted, and zinc nitrate hexahydrate solution and aluminum nitrate nonahydrate solution of the same concentration were adopted in the preparation process of comparative example 7, and the mass ratio of the nitrate compound to the nano silica particles in comparative example 7-1 group was 0.1:1, and the mass ratio of the nitrate compound to the nano silica particles in comparative example 7-2 group was 1.5:1 by adjusting the addition amount. Comparative example 7 the preparation procedure was otherwise identical to example 1.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of comparative example 7 is prepared by a mechanical blending method, and the concrete process is as follows:

Comparative example 8

Preparation of hydrogenated nitrile rubber Reinforcement

Comparative example 8 the same preparation as in example 1 was adopted, and comparative example 8 was different from example 1 in that the concentration of zinc nitrate hexahydrate solution and the concentration of aluminum nitrate nonahydrate solution were changed, and the total molar amount added was made the same as in example 1 by adjusting the addition amount. Comparative example 8 the remaining preparation process and process parameters were the same as in example 1. Wherein, in the group 8-1 of the comparative example, the concentration of the zinc nitrate hexahydrate solution is 0.8mol/L; the concentration of the aluminum nitrate nonahydrate solution is 0.8mol/L.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of the group 8-1 of the comparative example is prepared by a mechanical blending method, and the concrete process is as follows:

In the comparative example 8-2, the concentration of the zinc nitrate hexahydrate solution was 0.15mol/L; the concentration of the aluminum nitrate nonahydrate solution is 0.1mol/L.

Preparation of hydrogenated nitrile rubber

The hydrogenated nitrile rubber compound reinforced by the reinforcing agent of the group 8-2 of the comparative example is prepared by a mechanical blending method, and the concrete process is as follows:

The static mechanical properties of the vulcanizates prepared in comparative examples 6-8 were tested in the same manner as in example 1, with the test results set forth in Table 3.

TABLE 3 Table 3

Examples/comparative examples	Elongation at break%	Tensile strength MPa
			Comparative example 6-I	300％	3.33
Comparative example 6-II	300％	3.56
			Comparative example 7-1	300％	2.94
Comparative example 7-2	300％	3.35
			Comparative example 8-1	300％	2.56
Comparative example 8-2	300％	3.26

The research shows that the reinforcing effect of the hydrogenated nitrile rubber reinforcing agent prepared by the method has close relation with the pH value, the mass ratio of hydrotalcite to silicon dioxide particles and the concentration of nitrate solution in the preparation process, the nano silicon dioxide particles can be used as carriers by purposefully adjusting various influencing factors, the flaky hydrotalcite grows on the surfaces of the nano silicon dioxide particles, and the hydrogenated nitrile rubber reinforcing agent has good reinforcing property and excellent dispersion effect.

The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims

1. The hydrogenated nitrile rubber reinforcing agent is characterized in that the hydrogenated nitrile rubber reinforcing agent is a compound of platy hydrotalcite and nano silicon dioxide particles, the nano silicon dioxide particles are taken as a carrier, and the platy hydrotalcite grows on the surfaces of the nano silicon dioxide particles; in the composite, the weight ratio of the flaky hydrotalcite to the nano silicon dioxide particles is 0.2-1: 1, a step of;

the hydrogenated nitrile rubber reinforcing agent is mainly prepared by the following method: step 1, sequentially adding nano silicon dioxide particles and sodium carbonate solution into a reaction device, and performing ultrasonic treatment to obtain a first solution;

step 2, dropwise adding a zinc nitrate hexahydrate solution and an aluminum nitrate nonahydrate solution into the first solution obtained in the step 1, and stirring to obtain a second solution; the concentration of the hexahydrate zinc nitrate solution is 0.3mol/L to 0.5mol/L; the concentration of the aluminum nitrate nonahydrate solution is 0.2 mol/L-0.6 mol/L; the adding mass ratio of the nitrate compound to the nano silicon dioxide particles is 0.2-1:1;

2. The hydrogenated nitrile rubber reinforcing agent according to claim 1, characterized in that in the composite, the particle diameter of the nano silica particles is 10nm to 100nm; the side length of the flaky hydrotalcite is 100 nm-1000 nm.

3. The hydrogenated nitrile rubber reinforcing agent according to claim 1, wherein in said step 1, the added nano silica particles are liquid phase nano silica particles.

4. The hydrogenated nitrile rubber reinforcing agent according to claim 1, characterized in that in said step 2, the concentration of the zinc nitrate hexahydrate solution is 0.4mol/L to 0.5mol/L; the concentration of the aluminum nitrate nonahydrate solution is 0.3 mol/L-0.5 mol/L.

5. The hydrogenated nitrile rubber reinforcing agent according to claim 1, wherein in the step 2, the addition mass ratio of the nitrate compound to the nano silica particles is 0.5 to 0.8:1.

6. The hydrogenated nitrile rubber reinforcing agent according to claim 1, wherein in step 3, stirring treatment is performed for a period of 2 to 2.5 hours before standing.

7. The hydrogenated nitrile rubber reinforcing agent according to claim 1, wherein in the step 3, the standing time is 10 to 15 hours.

8. Use of a hydrogenated nitrile rubber reinforcing agent according to claim 1 or 2 as a starting material in the preparation of a hydrogenated nitrile rubber.