阅读说明：本技术 一种乙丙胶浆组合物及其制备方法 (Ethylene-propylene rubber cement composition and preparation method thereof ) 是由 李斌 王德庆 丁一 李锴 刘松涛 于 2021-09-22 设计创作，主要内容包括：本发明提出一种乙丙胶浆组合物及其制备方法,属于橡胶软管生产技术领域,能够解决目前制动软管两层增强层之间耐热和粘合性差,不能连续、安全生产的问题。该乙丙胶浆组合物包括以下重量份的原料：液体三元乙丙橡胶90-100份,液体聚丁二烯270-300份,白炭黑5-15份,甲基丙烯酸锌40-50份,过氧化物5-15份。本发明所提供的的环保乙丙胶浆组合物耐热和粘合性能良好,能够应用于制动软管两层增强层之间的粘合,实现制动软管的安全、连续生产。(The invention provides an ethylene-propylene rubber cement composition and a preparation method thereof, belongs to the technical field of rubber hose production, and can solve the problems that the two reinforcing layers of the conventional brake hose are poor in heat resistance and adhesion, and cannot be continuously and safely produced. The ethylene-propylene rubber cement composition comprises the following raw materials in parts by weight: 90-100 parts of liquid ethylene propylene diene monomer, 300 parts of liquid polybutadiene 270-one, 5-15 parts of white carbon black, 40-50 parts of zinc methacrylate and 5-15 parts of peroxide. The environment-friendly ethylene propylene rubber cement composition provided by the invention has good heat resistance and bonding performance, can be applied to bonding between two reinforcing layers of a brake hose, and realizes safe and continuous production of the brake hose.)

1. The ethylene-propylene rubber cement composition is characterized by comprising the following raw materials in parts by weight: 90-100 parts of liquid ethylene propylene diene monomer, 300 parts of liquid polybutadiene 270-one, 5-15 parts of white carbon black, 40-50 parts of zinc methacrylate and 5-15 parts of peroxide.

2. The ethylene-propylene rubber cement composition as claimed in claim 1, wherein the weight portion ratio of the liquid ethylene-propylene-diene rubber to the liquid polybutadiene is 1: 3.

3. the ethylene-propylene rubber cement composition as claimed in claim 1, wherein the liquid ethylene-propylene-diene monomer rubber is T-65; the liquid polybutadiene is LITHENE ULTRA P4-25P.

4. The ethylene-propylene rubber cement composition as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight: 90 parts of liquid ethylene propylene diene monomer, 270 parts of liquid polybutadiene, 5 parts of white carbon black, 40 parts of zinc methacrylate and 5 parts of peroxide.

5. The ethylene-propylene rubber cement composition as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight: 95 parts of liquid ethylene propylene diene monomer, 285 parts of liquid polybutadiene, 10 parts of white carbon black, 45 parts of zinc methacrylate and 10 parts of peroxide.

6. The ethylene-propylene rubber cement composition as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight: 100 parts of liquid ethylene propylene diene monomer, 300 parts of liquid polybutadiene, 15 parts of white carbon black, 50 parts of zinc methacrylate and 15 parts of peroxide.

7. The ethylene-propylene rubber cement composition as claimed in claim 1, wherein liquid polybutadiene is used as solvent, and a composition of liquid ethylene-propylene-diene monomer, white carbon black, zinc methacrylate and peroxide is used as solute.

8. A method for preparing the ethylene-propylene rubber cement composition according to any one of claims 1 to 7, characterized by comprising the following steps:

1) respectively preparing the raw materials according to the weight parts of the raw materials;

2) adding liquid ethylene propylene diene monomer into liquid polybutadiene, and mechanically stirring under a heating condition until the liquid ethylene propylene diene monomer is completely dissolved in the liquid polybutadiene;

3) and sequentially adding white carbon black, zinc methacrylate and peroxide into the solution, continuously mechanically stirring until the white carbon black, the zinc methacrylate and the peroxide are uniformly mixed, and then cooling to room temperature to obtain the ethylene-propylene rubber cement composition.

9. The preparation method of the ethylene-propylene rubber cement composition according to claim 8, wherein the heating temperature in the step 2) is 80-90 ℃, and the stirring time is 15-30 minutes.

10. The preparation method of the ethylene propylene rubber cement composition according to claim 9, wherein the stirring time in the step 3) is 15-30 minutes.

Technical Field

The invention belongs to the technical field of rubber hose production, and particularly relates to an environment-friendly ethylene propylene rubber cement composition and a preparation method thereof.

Background

The automobile hydraulic brake hose is a key part of an automobile safety system, and the enhancement layer are required to have good heat resistance and adhesive property during the production of the brake hose, so that the hose is prevented from being buckled, pressed and dislocated, rubbed and even failed in the working process.

At present, methods for improving the bonding performance between the reinforcing layer and the reinforcing layer of the brake hose mainly comprise a rubber sheet and a water-based or solvent-based adhesive in use, but the rubber sheet is not beneficial to reducing the overall wall thickness of the hose in use and is not beneficial to improving the expansion performance of the hose; the use of aqueous adhesives requires lengthy impregnation and drying lines, which is not conducive to continuous production; the use of solvent-based adhesives requires stringent ventilation and protective equipment, which is not conducive to safe production. Therefore, how to provide a substance capable of improving heat resistance and adhesion between the reinforcing layer and the reinforcing layer of the brake hose and a method capable of realizing continuous safe production of the brake hose has become a problem to be appreciated by those skilled in the art.

Disclosure of Invention

Aiming at the technical problems that the two reinforcing layers of the brake hose are poor in heat resistance and adhesion and cannot be continuously and safely produced, the invention provides the environment-friendly ethylene propylene rubber cement composition with good heat resistance and adhesion performance and the preparation method thereof, and the environment-friendly ethylene propylene rubber cement composition can be applied to adhesion between the two reinforcing layers of the brake hose and can realize safe and continuous production of the brake hose.

In order to achieve the above purpose, the invention provides an ethylene-propylene rubber cement composition, which adopts the following technical scheme:

the ethylene-propylene rubber cement composition comprises the following raw materials in parts by weight: 90-100 parts of liquid ethylene propylene diene monomer, 300 parts of liquid polybutadiene 270-one, 5-15 parts of white carbon black, 40-50 parts of zinc methacrylate and 5-15 parts of peroxide.

Further, the weight part ratio of the liquid ethylene propylene diene monomer to the liquid polybutadiene is 1: 3.

further, the liquid ethylene propylene diene monomer is T-65; the liquid polybutadiene is LITHENE ULTRA P4-25P.

Further, the ethylene-propylene rubber cement composition comprises the following raw materials in parts by weight: 90 parts of liquid ethylene propylene diene monomer, 270 parts of liquid polybutadiene, 5 parts of white carbon black, 40 parts of zinc methacrylate and 5 parts of peroxide.

Further, the ethylene-propylene rubber cement composition comprises the following raw materials in parts by weight: 95 parts of liquid ethylene propylene diene monomer, 285 parts of liquid polybutadiene, 10 parts of white carbon black, 45 parts of zinc methacrylate and 10 parts of peroxide.

Further, the ethylene-propylene rubber cement composition comprises the following raw materials in parts by weight: 100 parts of liquid ethylene propylene diene monomer, 300 parts of liquid polybutadiene, 15 parts of white carbon black, 50 parts of zinc methacrylate and 15 parts of peroxide

Further, liquid polybutadiene is used as a solvent, and a composition of liquid ethylene propylene diene monomer, white carbon black, zinc methacrylate and peroxide is used as a solute.

In another aspect, the present invention provides a method for preparing an ethylene-propylene rubber cement composition according to any one of the above technical solutions, comprising the following steps:

1) respectively preparing the raw materials according to the weight parts of the raw materials;

2) adding liquid ethylene propylene diene monomer into liquid polybutadiene, and mechanically stirring under a heating condition until the liquid ethylene propylene diene monomer is completely dissolved in the liquid polybutadiene;

3) and sequentially adding white carbon black, zinc methacrylate and peroxide into the solution, continuously mechanically stirring until the white carbon black, the zinc methacrylate and the peroxide are uniformly mixed, and then cooling to room temperature to obtain the ethylene-propylene rubber cement composition.

Further, the heating temperature of the step 2) is 80-90 ℃, and the stirring time is 15-30 minutes.

Further, the stirring time in the step 3) is 15-30 minutes.

Compared with the prior art, the invention has the advantages and positive effects that:

1. the invention provides an environment-friendly ethylene propylene rubber cement composition and a preparation method thereof, the environment-friendly ethylene propylene rubber cement composition has good heat resistance and bonding performance, and can realize safe and continuous production of brake hoses.

2. The environment-friendly ethylene propylene rubber cement composition takes liquid polybutadiene as a solvent, other solvents are not required to be added, the problems of long impregnation and drying production line, inconvenience for continuous production of brake hoses and the like in the process of using a water-based adhesive can be solved, and the problems of strict ventilation and protection equipment, inconvenience for safe production of the brake hoses and the like in the process of using a solvent-based adhesive can be solved.

3. The liquid ethylene propylene diene monomer has excellent heat resistance and intermiscibility by taking the composition of the liquid ethylene propylene diene monomer, the white carbon black, the zinc methacrylate and the peroxide as a solute, and the adsorption property, the solidification property and the scratch resistance of the liquid ethylene propylene diene monomer can be improved by adding the white carbon black; the added zinc methacrylate is a heat-resistant additive and can be diffused and combined with liquid ethylene propylene diene monomer, liquid polybutadiene and dipping latex on the surface of a reinforcing layer under the initiation of peroxide to obtain salt crosslinking. The components of the invention have the combined action to realize good heat resistance and bonding performance between the reinforced layers.

4. The preparation method of the environment-friendly ethylene propylene rubber cement composition does not need to grind the raw materials, and the preparation process is simpler and quicker.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment of the invention provides an environment-friendly ethylene propylene rubber cement composition which comprises the following raw materials in parts by weight: 90-100 parts of liquid ethylene propylene diene monomer, 300 parts of liquid polybutadiene 270-containing silica, 5-15 parts of white carbon black, 40-50 parts of zinc methacrylate (ZDMA) and 5-15 parts of peroxide (BIPB).

The preparation method of the environment-friendly ethylene propylene rubber cement composition comprises the following steps:

1) respectively preparing the raw materials according to the weight parts of the raw materials;

2) adding liquid ethylene propylene diene monomer into liquid polybutadiene, and mechanically stirring under a heating condition until the liquid ethylene propylene diene monomer is completely dissolved in the liquid polybutadiene;

3) adding white carbon black, zinc methacrylate and peroxide into the solution in sequence, continuously mechanically stirring until the white carbon black, the zinc methacrylate and the peroxide are uniformly mixed, and then cooling to room temperature to obtain the environment-friendly ethylene propylene rubber cement composition.

The viscosity of the obtained environmentally friendly ethylene propylene rubber cement composition was measured by using an NDJ-5S digital viscometer (rotor: SP4, rotation speed: 30.0RPM, test time: 1min), and the viscosity test results were as follows: (10000. + -. 1000) mPas.

The environment-friendly ethylene propylene rubber cement composition provided by the embodiment takes liquid polybutadiene as a solvent, takes a composition of liquid ethylene propylene diene monomer, white carbon black, zinc methacrylate (ZDMA) and peroxide (BIPB) as a solute, and replaces mixing with mechanical dissolution, so that the process is simple and efficient, and the composition has good adhesive property, and can be used for adhesion between the reinforcing layer and the reinforcing layer of the brake hose, thereby improving the adhesive effect between the reinforcing layers, avoiding the use defect that a water-based adhesive needs a long impregnation and drying production line, and being beneficial to realizing continuous production of the brake hose. Good heat resistance and adhesion properties between the reinforcement layers are achieved by the combined action of the above components of the invention, in particular:

(1) the liquid polybutadiene has the advantages of extremely low odor and volatile components, no toxicity and the like, has a medium content of 1, 4-vinyl microstructure, and can be co-crosslinked with other high polymer rubbers to form a very stable bonding system. The environment-friendly ethylene propylene rubber cement composition provided by the embodiment of the invention takes liquid polybutadiene as a solvent, other solvents are not required to be added, under the initiation of peroxide, the liquid polybutadiene, the liquid ethylene propylene diene and the dipping latex on the surface of the enhancement layer are subjected to co-crosslinking to form a bonding system, so that the problems of long dipping and drying production line, inconvenience for continuous production of a brake hose and the like in the use of a water-based adhesive can be solved, and the problems of strict ventilation and protection equipment, inconvenience for safe production of the brake hose and the like in the use of a solvent-based adhesive can be solved.

(2) The liquid ethylene propylene diene monomer has excellent heat resistance, intermiscibility, wear resistance and film forming strength, and is low in cost, and the adsorption, solidification and scratch resistance of the liquid ethylene propylene diene monomer can be improved by adding the white carbon black; the added zinc methacrylate is a heat-resistant additive, can be diffused and combined with liquid ethylene propylene diene monomer, liquid polybutadiene and dipping latex on the surface of a reinforcing layer under the initiation of peroxide to obtain salt crosslinking (such as rubber-metal ion crosslinking bonds), and has strong adhesive force.

In the embodiment of the invention, the weight part ratio of the liquid ethylene propylene diene monomer to the liquid polybutadiene is 1:3, the maximum solubility of the liquid ethylene propylene diene rubber in the liquid polybutadiene at room temperature can be ensured, and the liquid ethylene propylene diene rubber is prevented from being separated out of the liquid polybutadiene. The environment-friendly ethylene propylene rubber cement composition cannot be obtained when the weight part ratio of the liquid ethylene propylene diene rubber to the liquid polybutadiene is too large or too small, and the liquid ethylene propylene diene rubber can be separated from the liquid polybutadiene and cannot be used when the weight part ratio of the liquid ethylene propylene diene rubber to the liquid polybutadiene is larger than the weight part ratio; less than the proportion, the problems of reduced rubber coating amount, poor film forming property and the like of the liquid ethylene propylene diene monomer rubber due to insufficient dosage cause that the effect of the liquid ethylene propylene diene monomer rubber cannot be maximized, thereby reducing the final use effect of the environment-friendly ethylene propylene rubber cement composition.

The liquid ethylene propylene diene monomer rubber adopted in the embodiment of the invention is T-65 produced by American lion chemistry; the liquid polybutadiene is LITHENEEULTRAP 4-25P from Xinte Ma.

The white carbon black, zinc methacrylate (ZDMA) and peroxide (BIPB) adopted in the embodiment of the invention are all commercial products.

The zinc methacrylate in the examples of the present invention may be replaced with magnesium methacrylate.

In the step 2) of the preparation method, mechanical stirring is carried out for 15-30 minutes under the heating condition of 80-90 ℃, and the heating temperature can be any value of 80-90 ℃, such as 80 ℃, 85 ℃ or 90 ℃; the stirring time can be any value of 15-30 minutes, such as 15 minutes, 20 minutes, 25 minutes or 30 minutes. As the viscosity of the liquid ethylene propylene diene monomer T-65 is low compared with that of the traditional solid ethylene propylene diene monomer, the liquid ethylene propylene diene monomer T-65 is in a semisolid or waxy state at room temperature, the viscosity is reduced along with the rise of the temperature, the Brookfield viscosity of 1900000cps at 60 ℃ is reduced to 177000cps at 100 ℃, the heating temperature of the embodiment of the invention is 80-90 ℃, and the liquid ethylene propylene diene monomer T-65 can be in a better fluid state, thereby being beneficial to the compatibility with liquid polybutadiene LITHENE ULTRA P4-25P. Heating temperatures lower than the heating temperature of the embodiment of the invention may have the problems of poor dispersion, time consumption and the like; the heating temperature higher than the heating temperature in the embodiment of the present invention may be theoretically not higher than the safe processing temperature of the peroxide used in the embodiment of the present invention, but increasing the temperature increases the energy consumption and lowers the safety of the production.

In the step 3) of the preparation method, the mechanical stirring is continued for 15 to 30 minutes until the mixture is uniformly mixed, and the stirring time can be any value of 15 to 30 minutes, such as 15 minutes, 20 minutes, 25 minutes or 30 minutes.

In order to more clearly and specifically describe the preparation method of the environment-friendly ethylene propylene rubber cement composition provided in the embodiments of the present invention, the following description will be made with reference to specific embodiments.

Example 1

The preparation method of the environment-friendly ethylene propylene rubber cement composition comprises the following steps: adding 90 parts of liquid ethylene propylene diene monomer T-65 into 270 parts of liquid polybutadiene LITHENE ULTRA P4-25P, mechanically stirring for 30 minutes under the heating condition of 80 ℃ until the liquid ethylene propylene diene monomer T-65 is completely dissolved in the liquid polybutadiene LITHENE ULTRA P4-25P, then sequentially adding 5 parts of white carbon black, 40 parts of zinc methacrylate and 5 parts of peroxide into the solution, continuously mechanically stirring for 30 minutes until the mixture is uniformly mixed, and finally cooling to room temperature to obtain the environment-friendly ethylene propylene rubber slurry composition in the embodiment 1 of the invention.

Example 2

The preparation method of the environment-friendly ethylene propylene rubber cement composition comprises the following steps: adding 95 parts of liquid ethylene propylene diene monomer T-65 into 285 parts of liquid polybutadiene LITHENE ULTRA P4-25P, mechanically stirring for 25 minutes under the heating condition of 85 ℃ until the liquid ethylene propylene diene monomer T-65 is completely dissolved in the liquid polybutadiene LITHENE ULTRA P4-25P, then sequentially adding 10 parts of white carbon black, 45 parts of zinc methacrylate and 10 parts of peroxide into the solution, continuously mechanically stirring for 25 minutes until the mixture is uniformly mixed, and finally cooling to room temperature to obtain the environment-friendly ethylene propylene rubber slurry composition in the embodiment 2 of the invention.

Example 3

The preparation method of the environment-friendly ethylene propylene rubber cement composition comprises the following steps: 100 parts of liquid ethylene propylene diene monomer T-65 is added into 300 parts of liquid polybutadiene LITHENE ULTRA P4-25P, mechanical stirring is carried out for 15 minutes under the heating condition of 90 ℃ until the liquid ethylene propylene diene monomer T-65 is completely dissolved into the liquid polybutadiene LITHENE ULTRA P4-25P, then 15 parts of white carbon black, 50 parts of zinc methacrylate and 15 parts of peroxide are sequentially added into the solution, mechanical stirring is continued for 15 minutes until the mixture is uniform, and finally the mixture is cooled to room temperature, so that the environment-friendly ethylene propylene rubber slurry composition of the embodiment 3 is obtained.

Comparative example 1

The preparation method of the ethylene-propylene rubber cement composition comprises the following steps: 100 parts of liquid ethylene propylene diene monomer T-65 is added into 270 parts of liquid polybutadiene LITHENE ULTRA P4-25P, mechanical stirring is carried out for 30 minutes under the heating condition of 80 ℃ until the liquid ethylene propylene diene monomer T-65 is completely dissolved in the liquid polybutadiene LITHENE ULTRA P4-25P, then 5 parts of white carbon black, 40 parts of zinc methacrylate and 5 parts of peroxide are sequentially added into the solution, mechanical stirring is continuously carried out for 30 minutes until the mixture is uniform, and finally, the mixture is cooled to room temperature, thus obtaining the ethylene propylene rubber slurry composition of the comparative example 1.

Comparative example 2

The preparation method of the ethylene-propylene rubber cement composition comprises the following steps: adding 90 parts of liquid ethylene propylene diene monomer T-65 into 300 parts of liquid polybutadiene LITHENE ULTRA P4-25P, mechanically stirring for 30 minutes under the heating condition of 80 ℃ until the liquid ethylene propylene diene monomer T-65 is completely dissolved in the liquid polybutadiene LITHENE ULTRA P4-25P, then sequentially adding 5 parts of white carbon black, 40 parts of zinc methacrylate and 5 parts of peroxide into the solution, continuously mechanically stirring for 30 minutes until the mixture is uniformly mixed, and finally cooling to the room temperature to obtain the ethylene propylene rubber cement composition of the comparative example 2.

Comparative example 3

A common middle rubber sheet is used between the two reinforcing layers, the material of the middle rubber sheet is ethylene propylene diene monomer rubber, and the thickness of the middle rubber sheet is 0.3 mm.

Performance test experiments:

the ethylene-propylene rubber cement compositions of examples 1-3 and comparative examples 1-2 are respectively uniformly coated between two 1000D polyester dipping line woven reinforcement layers, and the coating thickness is 0.1 mm-0.2 mm so as to bond the reinforcement layers; coating the middle rubber sheet of the comparative example 3 between two 1000D polyester dipping line woven enhancement layers to bond the enhancement layers; the co-vulcanization condition is 160 ℃ multiplied by 30min, and then the adhesion test is carried out, the adhesion test method is carried out according to GB/T14905-one 2009, and the test results are shown in the following table:

from the above experimental results it can be seen that:

comparative example 1 and comparative example 2 correspond to example 1, and the difference is that the weight part ratio of the raw material liquid ethylene propylene diene monomer to the liquid polybutadiene is different, and the weight part ratio of the liquid ethylene propylene diene monomer to the liquid polybutadiene in the comparative example 1 is more than 1:3, at the moment, the liquid ethylene propylene diene monomer is separated out from the liquid polybutadiene and cannot be used; in the comparative example 2, the weight part ratio of the liquid ethylene propylene diene monomer to the liquid polybutadiene is less than 1:3, and the problems of reduced rubber coating amount, poor film forming property and the like of the liquid ethylene propylene diene monomer due to insufficient use amount cause that the effect of the liquid ethylene propylene diene monomer cannot be maximized, so that the final use effect of the ethylene propylene rubber cement composition is reduced.

Examples 1 to 3, the weight parts of which are limited in the examples of the present invention, the initial adhesion and the adhesion after aging at 120 ℃ for 166 hours of the obtained environmentally friendly ethylene propylene rubber cement composition are significantly better than the corresponding performance indexes of the common middle rubber sheet used in the comparative example 3, and the environmentally friendly ethylene propylene rubber cement composition has better heat resistance and adhesion performance.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein. In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on the realization of those skilled in the art; where combinations of features are mutually inconsistent or impractical, such combinations should not be considered as being absent and not within the scope of the claimed invention.