阅读说明：本技术 一种用于发动机悬置的金属无机盐耐高温橡胶及其制备方法 (Metal inorganic salt high-temperature-resistant rubber for engine suspension and preparation method thereof ) 是由 慕文伟 李晓武 于 2020-12-22 设计创作，主要内容包括：本发明公开了一种用于发动机悬置的金属无机盐耐高温橡胶,具有氧化镁、磷酸锆、氢氧化铝、二氧化钛、硼酸锌五种金属无机盐,都是隔热阻燃的优秀材料,这5种耐热金属无机盐混合添加,既可以屏蔽热辐射导热,也可以阻隔热传导和热对流传热,5种耐热金属无机盐组合后,高效互补使得混炼胶有着优异的的耐热性；硫黄、促进剂CBS,促进剂TBzTD按照特定比例配合,可以在提高耐热性的同时,兼顾流动性、强度、硬度、回弹等各个方面的物理性能；炭黑N550,其在能够补强天然橡胶的同时,兼顾橡胶流动加工性,不仅有利于混炼胶的流动,也有利于延长橡胶产品使用寿命。本发明还公开了一种用于发动机悬置的金属无机盐耐高温橡胶的制备方法。(The invention discloses a metal inorganic salt high-temperature resistant rubber for engine suspension, which comprises five metal inorganic salts of magnesium oxide, zirconium phosphate, aluminum hydroxide, titanium dioxide and zinc borate, wherein the five metal inorganic salts are excellent heat-insulating and flame-retardant materials, the 5 heat-resistant metal inorganic salts are mixed and added, so that heat radiation and heat conduction can be shielded, heat conduction and heat convection can be blocked, and after the 5 heat-resistant metal inorganic salts are combined, high-efficiency complementation is realized, so that the rubber compound has excellent heat resistance; the sulfur, the accelerator CBS and the accelerator TBzTD are mixed according to a specific proportion, so that the heat resistance is improved, and the physical properties of various aspects such as fluidity, strength, hardness, resilience and the like are considered; the carbon black N550 can reinforce natural rubber and simultaneously give consideration to rubber flow processability, thereby being beneficial to the flow of rubber compound and prolonging the service life of rubber products. The invention also discloses a preparation method of the metal inorganic salt high-temperature-resistant rubber for the engine mount.)

1. The metal inorganic salt high-temperature-resistant rubber for the engine mount is characterized by comprising the following components in percentage by weight:

the sum of the weight percentages of all the components is 100 percent.

2. The metal inorganic salt high temperature resistant rubber for engine mount according to claim 1, wherein the metal inorganic salt high temperature resistant rubber has 5 metal inorganic salt heat resistant components of magnesium oxide, zirconium phosphate, aluminum hydroxide, titanium dioxide and zinc borate, respectively.

3. The metal inorganic salt high-temperature resistant rubber for the engine mount as claimed in claim 1 or 2, wherein the mass ratio of the magnesium oxide, the zirconium phosphate, the aluminum hydroxide, the titanium dioxide and the zinc borate is in the range of 22% to 23% in sequence: 20% -24%: 25% -30%: 14% -15%: 14 to 15 percent.

4. The metal inorganic salt high temperature resistant rubber for engine mount of claim 1, wherein the sulfur, accelerator CBS and accelerator TBzTD constitute a vulcanization system having heat resistance.

5. The metal inorganic salt high temperature resistant rubber for engine mount as claimed in claim 1, wherein the natural rubber is TSR CV60, TSR CV40 or SVR 3L;

the carbon black adopts N550.

6. The preparation method of the metal inorganic salt high-temperature resistant rubber for the engine mount as claimed in claim 1, characterized by comprising the following steps:

s1, mixing step:

adding natural rubber into a meshing type rotor internal mixer, mixing the natural rubber for 20s, and heating the rotor in the meshing type rotor internal mixer to 110 ℃;

then, sequentially adding magnesium oxide, zirconium phosphate, aluminum hydroxide, titanium dioxide, zinc borate, carbon black and an environment-friendly plasticizer into a meshing type rotor internal mixer for banburying, keeping the rotor temperature in the meshing type rotor internal mixer at 120-140 ℃, and continuously banburying for 60-80 s;

then, sequentially adding stearic acid SA, an anti-aging agent IPPD, an anti-aging agent RD and microcrystalline wax into a meshing type rotor internal mixer, and reducing the rotating speed of the meshing type rotor internal mixer to reduce the rotor temperature in the meshing type rotor internal mixer and keep the rotor temperature at 120 ℃;

finally, controlling the rotor temperature of the meshing type rotor internal mixer, continuously reducing the internal mixing temperature, keeping the internal mixing temperature at 90-100 ℃, sequentially adding sulfur, an accelerator CBS and an accelerator TBzTD in the temperature range, mixing for 15-30 s, and then discharging rubber; discharging the rubber sheets through an extruder or a double-roller open mill, cooling and drying the rubber sheets through a separating agent, and performing performance test to prepare final rubber compound;

s2, vulcanization step: and (3) heating the temperature of a charging barrel of an injection molding machine to 70 ℃, injecting the rubber compound prepared in the step S1 into the injection molding machine, vulcanizing at the temperature of 150-155 ℃, vulcanizing for 10-12 min under the pressure of 155 +/-10 Bar, removing the waste edges of the vulcanized product, and carrying out size and appearance inspection to obtain the engine suspension.

7. The method for preparing a metal inorganic salt high-temperature resistant rubber for engine suspension according to claim 6, wherein the mixing step is completed only by one process of internal mixing in the meshing type rotor internal mixer.

8. The method for preparing the metal inorganic salt high-temperature resistant rubber for the engine mount as claimed in claim 6, wherein the intermeshing rotor internal mixer is an HF/M190E intermeshing rotor internal mixer;

the injection molding machine was a 250 ton Desma injection molding machine.

Technical Field

The invention relates to a metal inorganic salt high-temperature-resistant rubber for engine suspension and a preparation method thereof.

Background

The engine mount made of the rubber material can reduce the vibration of the engine, reduce the noise of the engine and a power assembly, and has excellent NVH vibration reduction and noise reduction performances. However, since the working temperature of the engines of passenger vehicles and commercial vehicles is about 90 ℃, rubber (organic) products which are not optimized and improved are difficult to resist the high temperature for a long time, and the rubber products are aged and invalid after long-term use.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, and provides the metal inorganic salt high-temperature resistant rubber for the engine mount, which has 5 metal inorganic salt heat-resistant components and is assisted by an optimized high-temperature resistant vulcanization system, so that the rubber heat insulation and heat resistance can be enhanced, the heat resistance and heat insulation performance of the rubber for the engine mount of the high-grade car are improved, and the service life of the engine mount product in a high-temperature environment is prolonged.

Another object of the invention is to provide a preparation method of the metal inorganic salt high-temperature resistant rubber for engine suspension.

One technical scheme for achieving the purpose is as follows: a metal inorganic salt high-temperature resistant rubber for engine suspension comprises the following components in percentage by weight:

the sum of the weight percentages of all the components is 100 percent.

The metal inorganic salt high-temperature resistant rubber for the engine mount comprises 5 metal inorganic salt heat-resistant components, namely magnesium oxide, zirconium phosphate, aluminum hydroxide, titanium dioxide and zinc borate.

The metal inorganic salt high-temperature-resistant rubber for the engine mount is characterized in that the magnesium oxide, the zirconium phosphate, the aluminum hydroxide, the titanium dioxide and the zinc borate are sequentially 22-23% by mass: 20% -24%: 25% -30%: 14% -15%: 14 to 15 percent.

The metal inorganic salt high-temperature-resistant rubber for the engine mount comprises sulfur, an accelerator CBS and an accelerator TBzTD, wherein the sulfur, the accelerator CBS and the accelerator TBzTD form a vulcanization system with heat resistance.

The metal inorganic salt high-temperature resistant rubber for the engine mount is characterized in that the natural rubber adopts TSR CV60, TSR CV40 or SVR 3L;

the carbon black adopts N550.

The invention also provides a preparation method of the metal inorganic salt high-temperature-resistant rubber for the engine mount, which comprises the following steps:

s1, mixing step:

adding natural rubber into a meshing type rotor internal mixer, mixing the natural rubber for 20s, and heating the rotor in the meshing type rotor internal mixer to 110 ℃;

then, sequentially adding magnesium oxide, zirconium phosphate, aluminum hydroxide, titanium dioxide, zinc borate, carbon black and an environment-friendly plasticizer into a meshing type rotor internal mixer for banburying, keeping the rotor temperature in the meshing type rotor internal mixer at 120-140 ℃, and continuously banburying for 60-80 s;

then, sequentially adding stearic acid SA, an anti-aging agent IPPD, an anti-aging agent RD and microcrystalline wax into a meshing type rotor internal mixer, and reducing the rotating speed of the meshing type rotor internal mixer to reduce the rotor temperature in the meshing type rotor internal mixer and keep the rotor temperature at 120 ℃;

finally, controlling the rotor temperature of the meshing type rotor internal mixer, continuously reducing the internal mixing temperature, keeping the internal mixing temperature at 90-100 ℃, sequentially adding sulfur, an accelerator CBS and an accelerator TBzTD in the temperature range, mixing for 15-30 s, and then discharging rubber; discharging the rubber sheets through an extruder or a double-roller open mill, cooling and drying the rubber sheets through a separating agent, and performing performance test to prepare final rubber compound;

s2, vulcanization step: and (3) heating the temperature of a charging barrel of an injection molding machine to 70 ℃, injecting the rubber compound prepared in the step S1 into the injection molding machine, vulcanizing at the temperature of 150-155 ℃, vulcanizing for 10-12 min under the pressure of 155 +/-10 Bar, removing the waste edges of the vulcanized product, and carrying out size and appearance inspection to obtain the engine suspension.

In the preparation method of the metal inorganic salt high-temperature resistant rubber for the engine suspension, the mixing step is completed only by one process of internal mixing in the meshing type rotor internal mixer.

The preparation method of the metal inorganic salt high-temperature resistant rubber for engine suspension is characterized in that an HF/M190E meshing type rotor internal mixer is adopted as the meshing type rotor internal mixer;

the injection molding machine was a 250 ton Desma injection molding machine.

According to the technical scheme of the metal inorganic salt high-temperature resistant rubber for the engine mount and the preparation method thereof, the metal inorganic salt high-temperature resistant rubber has 5 metal inorganic salt heat-resistant components, is assisted by an optimized high-temperature resistant vulcanization system, can play a role in enhancing heat insulation and heat resistance of rubber, improves the heat insulation and heat-proof performance of rubber for the engine mount of a high-grade car, and prolongs the service life of the engine mount product in a high-temperature environment.

Detailed Description

In order that those skilled in the art will better understand the technical solution of the present invention, the following detailed description will be given of specific embodiments thereof:

example (b):

TABLE 1

The metal inorganic salt high temperature resistant rubber for engine mount according to the present invention was prepared according to the formulation of table 1, and the preparation method comprises the steps of:

s1, mixing step:

adding natural rubber into a meshing type rotor internal mixer, mixing the natural rubber for 20s, and heating the rotor in the meshing type rotor internal mixer to 110 ℃;

then, sequentially adding magnesium oxide, zirconium phosphate, aluminum hydroxide, titanium dioxide, zinc borate, carbon black and an environment-friendly plasticizer into a meshing type rotor internal mixer for banburying, keeping the rotor temperature in the meshing type rotor internal mixer at 120-140 ℃, and continuously banburying for 60-80 s;

then, sequentially adding stearic acid SA, an anti-aging agent IPPD, an anti-aging agent RD and microcrystalline wax into a meshing type rotor internal mixer, and reducing the rotating speed of the meshing type rotor internal mixer to reduce the rotor temperature in the meshing type rotor internal mixer and keep the rotor temperature at 120 ℃;

finally, controlling the rotor temperature of the meshing type rotor internal mixer, continuously reducing the internal mixing temperature, keeping the internal mixing temperature at 90-100 ℃, sequentially adding sulfur, an accelerator CBS and an accelerator TBzTD in the temperature range, mixing for 15-30 s, and then discharging rubber; discharging the rubber sheets through an extruder or a double-roller open mill, cooling and drying the rubber sheets through a separating agent, and performing performance test to prepare final rubber compound;

s2, vulcanization step: and (3) heating the temperature of a charging barrel of an injection molding machine to 70 ℃, injecting the rubber compound prepared in the step S1 into the injection molding machine, vulcanizing at the temperature of 150-155 ℃, vulcanizing for 10-12 min under the pressure of 155 +/-10 Bar, removing the waste edges of the vulcanized product, and carrying out size and appearance inspection to obtain the engine suspension.

According to the preparation method of the metal inorganic salt high-temperature-resistant rubber for the engine suspension, the mixing step is completed only by one procedure of internal mixing in the meshing type rotor internal mixer, and the mixing method of each component is simple. The meshed rotor internal mixer adopts an HF/M190E meshed rotor internal mixer. The injection molding machine used in the vulcanization step was a 250 ton Desma injection molding machine.

The natural rubber TSR CV60 can be replaced by TSR CV40 or SVR 3L.

Comparative example:

the formula of the traditional rubber for engine suspension is shown in table 2:

serial number	Material	Suppliers of goods	Amount/% of
				1	Natural rubber TSR CV60	Zhonghuan International group Co., Ltd	60.4％
2	Naphthenic oil	Tin-free tin smelting	2.4％
				3	N550	Jiangxi black cat	27.2％
4	wax	Tin-free tin smelting	1.8％
				5	ZnO	Changzhou magnesium zinc	3.0
6	SA	Fengyi grease	1.2％
				7	6PPD	Yanggugu Huatai tea	1.5％
8	TMQ	Yanggugu Huatai tea	0.7％
				9	S	Yanggugu Huatai tea	0.5％
10	CBS	Yanggugu Huatai tea	0.9％
				11	TBzTD	Yanggugu Huatai tea	0.3％
Total up to			100.0％

TABLE 2

The metal inorganic salt high-temperature resistant rubber for engine suspension comprises 5 metal inorganic salts, namely magnesium oxide MgO and zirconium phosphate Zr (HPO)₄)₂·H₂O, aluminum hydroxide Al (OH) c, titanium dioxide TiO₂And zinc borate B₂O₆Zn₃They can cooperate with each other to improve the high temperature resistance of the rubber. A large amount of experimental data prove that the heat-resistant effect required by the design is achieved by magnesium oxide MgO and zirconium phosphate Zr (HPO)₄)₂·H₂O, aluminum hydroxide Al (OH) c, titanium dioxide TiO₂And zinc borate B₂O₆Zn₃The optimal mass ratio among the components is 22 to 23 percent in sequence: 20% -24%: 25% -30%: 14% -15%: 14 to 15 percent.

Through multiple tests, the heat resistance of the rubber can be negatively affected by the absence of any one of the 5 metal inorganic salts; meanwhile, the mass ratio of the 5 metal inorganic salts is also the optimal ratio range obtained after a plurality of tests, and the 5 heat-resistant metal inorganic salts are used in the ratio range, so that the performances of the heat-resistant rubber, such as strength, rebound resilience, elongation and the like, can be well balanced, and the performances of the heat-resistant rubber in all aspects are balanced and good, therefore, the rubber is negatively influenced when the ratio is more than or less than the ratio.

Magnesium oxide (chemical formula: MgO) is an oxide of magnesium, and has high refractory and insulating properties. The magnesium oxide can be converted into crystal after high-temperature ignition, and compared with some traditional organic flame retardants containing phosphorus or halogen, the magnesium oxide is nontoxic, tasteless and small in addition amount, and is an ideal additive for developing flame retardants and heat insulating agents.

Zirconium phosphate (chemical formula: Zr (HPO)₄)₂·H₂O) is a novel multifunctional mesoporous material, is one of layered solid acid materials, is used in a polymer composite material, can increase the toughness and the tensile degree of the composite material, improves the stability, the oxidation resistance and the aging resistance of the material, and simultaneously increases the friction resistance, the acid and alkali resistance and the high temperature resistance of the composite material.

Aluminum hydroxide (chemical formula: Al (OH))₃Is a hydroxide of aluminum. Aluminum hydroxide is the largest and most widely used inorganic flame retardant additive. The aluminum hydroxide serving as a flame retardant not only can resist flame, but also can form an oxide isolation layer on the surface of the rubber at high temperature, thereby achieving the purposes of flame retardance and heat insulation.

Titanium dioxide (chemical formula: TiO)₂) White solid or powdery amphoteric oxide, excellent in chemical stability, thermal stability and non-migration. The titanium dioxide has strong ultraviolet resistance, and has a barrier effect on ultraviolet rays in a medium wave region and a long wave region and other forms of electromagnetic wave heat radiation.

Zinc borate (chemical formula: B)₂O₆Zn₃) Is an inorganic compound, can be used as a flame retardant, can form a glassy inorganic expansion coating, can be dehydrated at high temperature, and has heat absorption and heat insulation properties.

Heat transfer is generally divided into three basic ways, namely heat conduction, heat convection, heat radiation. In the invention, the 5 heat-resistant components have different functions but are cooperated with each other, so that the 3 heat conduction modes can be effectively avoided, and the performance of the rubber is ensured without loss due to heat insulation.

The heat radiation is carried out in the form of electromagnetic waves, all objects with the temperature higher than absolute zero can generate heat radiation, and after the titanium dioxide is added into the rubber, the titanium dioxide is properly frosted and separated out on the surface of a rubber product, so that the infrared wave heat radiation brought by an internal combustion engine can be effectively isolated.

For heat conduction of heat conduction and heat convection, zinc borate and aluminum hydroxide have enough thermal stability, and stable oxide and glassy state inorganic layers can be formed on the surface of rubber under special conditions, so that the effects of isolating heat conduction and heat convection heat transfer can be achieved.

Zirconium phosphate and magnesium oxide can both play a certain role in heat insulation and heat resistance, but the two functions are not only the same. Zirconium hydrogen phosphate is used as a filler, so that the heat stability of rubber is improved, and simultaneously, the toughness and the tensile degree of rubber compound can be increased, and the stability of the material is improved; the magnesium oxide can improve the heat resistance and play a role in improving the rubber strength, activating the rubber and promoting vulcanization.

Meanwhile, in order to match the heat-resistant effect of 5 kinds of metal inorganic salts in the formula, the invention adopts the following vulcanization system with heat resistance: 0.5 to 1.0 percent of sulfur, 0.9 to 1.5 percent of accelerant CBS and 0.9 to 1.5 percent of accelerant TBzTD. The vulcanizing agent combination with the special proportion can generate molecular bonds with high bond energy among rubber molecular chain segments during vulcanization of rubber, so that the molecular bonds can ensure the cross-linking integrity of the molecular chains after vulcanization of the rubber for a long time at the use temperature of 85-100 ℃ to play a role in heat resistance, and meanwhile, the vulcanizing system with the special proportion can also ensure the rubber containing 5 metal inorganic salts, and the performance can also reach the best when the technical requirement on heat resistance is met.

Compared with the existing single-component heat-resistant rubber, the heat-resistant components of the 5 metal inorganic salts in the invention exert effects synergistically, and the optimized heat-resistant vulcanization system is used, so that the defects of single heat-resistant component in the existing heat-resistant rubber formula and instability of the vulcanization system during heat resistance are avoided, the condition that the heat-resistant component fails under complex thermal conditions is also avoided, and the high-efficiency complementary heat-resistant effect is achieved, which is the innovation of the invention different from other heat-resistant rubbers.

The carbon black N550 is selected, so that the natural rubber can be reinforced, the rubber flow processability is considered, the flowing of the rubber compound is facilitated, and the service life of a rubber product is prolonged.

And (3) performance testing:

the measured performance results of the examples and the comparative examples are shown in table 3:

TABLE 3

As can be seen from the comparison of the tests in Table 3, the metal inorganic salt high temperature resistant rubber for engine mount in the example formulation can completely pass the material test specified by the Daimler DBL5557.61 (Daimler group powertrain rubber part test specification), and compared with the comparative examples of the conventional formulation, the metal inorganic salt high temperature resistant rubber has obvious advantages in the tests of items 4 to 9 and 17 on the heat aging resistance of the rubber; and other properties are at the same level as compared to conventional formulations.

After the metal inorganic salt high-temperature resistant rubber for the engine mount in the embodiment is prepared into an automobile engine mount product, in a thermal condition endurance test, compared with a product of the same type prepared by using a traditional formula of a comparison example, the metal inorganic salt high-temperature resistant rubber for the engine mount also has a more excellent endurance test result, and the service time and mileage are longer.

The metal inorganic salt high-temperature resistant rubber for the engine suspension and the preparation method thereof have five metal inorganic salts of magnesium oxide, zirconium phosphate, aluminum hydroxide, titanium dioxide and zinc borate, which are excellent heat-insulating and flame-retardant materials, the 5 heat-resistant metal inorganic salts are mixed and added, so that heat radiation and heat conduction can be shielded, heat conduction and heat convection can be blocked, and after the 5 heat-resistant metal inorganic salts are combined, high-efficiency complementation is realized, so that the rubber compound has excellent heat resistance; the sulfur, the accelerator CBS and the accelerator TBzTD are mixed according to a specific proportion, so that the heat resistance is improved, and the physical properties of various aspects such as fluidity, strength, hardness, resilience and the like are considered; the carbon black N550 can reinforce natural rubber and simultaneously give consideration to rubber flow processability, thereby being beneficial to the flow of rubber compound and prolonging the service life of rubber products.

In conclusion, the metal inorganic salt high-temperature resistant rubber for the engine mount has 5 metal inorganic salt heat-resistant components, is assisted by an optimized high-temperature resistant vulcanization system, can play a role in enhancing heat insulation and heat resistance of rubber, improves the heat insulation and heat-proof performance of the rubber for the engine mount of the high-grade car, and prolongs the service life of the engine mount product in a high-temperature environment. According to the preparation method of the metal inorganic salt high-temperature-resistant rubber for the engine suspension, the mixing step is completed only by one procedure of internal mixing in the meshing type rotor internal mixer, and the mixing method of each component is simple.

It should be understood by those skilled in the art that the above embodiments are only for illustrating the present invention and are not to be used as a limitation of the present invention, and that changes and modifications to the above described embodiments are within the scope of the claims of the present invention as long as they are within the spirit and scope of the present invention.