阅读说明：本技术 一种硫化胶囊用粘合促进剂及其制备方法 (Adhesion promoter for curing bladder and preparation method thereof ) 是由 赵会岩 范屏 赵海林 张凯 于 2021-12-09 设计创作，主要内容包括：本发明涉及硫化胶囊用助剂技术领域,尤其涉及一种硫化胶囊用粘合促进剂及其制备方法,一种硫化胶囊用粘合促进剂,所述硫化胶囊用粘合促进剂为核-壳结构,核体为改性氧化锌/凹凸棒土复合物,壳体为液体顺丁橡胶接枝马来酸酐；氧化锌占所述核体总量的(35～40)wt%；马来酸酐占所述壳体总量的(17～25)wt%；所述壳体占所述硫化胶囊用粘合促进剂总量的(60～65)wt%。本发明提供的硫化胶囊用粘合剂在丁基橡胶中具有良好的分散性和补强效果,降低了生产成本,能够改善丁基橡胶与纤维填料以及各种加工助剂的粘合性,大幅度降低胶料的密炼时间和硫化时间,提高了硫化胶囊的生产效率和整体力学性能。(The invention relates to the technical field of auxiliary agents for curing capsules, in particular to an adhesion promoter for curing capsules and a preparation method thereof, wherein the adhesion promoter for curing capsules is of a core-shell structure, the core body is a modified zinc oxide/attapulgite compound, and the shell body is liquid butadiene rubber grafted maleic anhydride; zinc oxide accounts for (35-40) wt% of the total amount of the nuclei; maleic anhydride accounts for (17-25) wt% of the total amount of the shell; the shell accounts for (60-65) wt% of the total amount of the adhesion promoter for the curing bladder. The adhesive for the curing bladder provided by the invention has good dispersibility and reinforcing effect in butyl rubber, reduces the production cost, can improve the adhesion of the butyl rubber, fiber fillers and various processing aids, greatly reduces the banburying time and the curing time of rubber materials, and improves the production efficiency and the overall mechanical property of the curing bladder.)

1. The adhesion promoter for the curing bladder is characterized in that the adhesion promoter for the curing bladder is of a core-shell structure, a core body is a modified zinc oxide/attapulgite compound, and a shell body is liquid butadiene rubber grafted maleic anhydride; zinc oxide accounts for (35-40) wt% of the total amount of the nuclei; maleic anhydride accounts for (17-25) wt% of the total amount of the shell; the shell accounts for (60-65) wt% of the total amount of the adhesion promoter for the curing bladder.

2. The method of producing an adhesion promoter for a curing bladder as claimed in claim 1, comprising the steps of:

step S100, preparing zinc oxide: acetic acid =1:2, mixing zinc oxide and an acetic acid solution for reaction to obtain a zinc acetate solution;

step S200, according to the attapulgite dispersion: deionized water = (30-40): 100, and adding the attapulgite dispersion into deionized water for ultrasonic dispersion to obtain a first suspension;

step S300, according to the attapulgite dispersion: hydrolyzing polymaleic anhydride: zinc =100:0.5:50, adding hydrolyzed polymaleic anhydride and the zinc acetate solution obtained by step S100 to the first suspension in step S200, and stirring to react to obtain a second suspension;

step S400, according to zinc: sodium hydroxide =1 (2-2.4), and a saturated sodium hydroxide solution is added to the second suspension in the step S300, and a third suspension is obtained through stirring reaction;

step S500, centrifugally separating the third suspension obtained in the step S400 to obtain a precipitate, grinding the precipitate in a ball mill to obtain a ground product, and calcining, washing and drying the ground product to obtain a zinc oxide/attapulgite composite;

step S600, according to the zinc oxide/attapulgite composite: silane coupling agent: maleic anhydride =100 (0.75-2.75) by mass, mixing the zinc oxide/attapulgite composite obtained in step S500 with a silane coupling agent and maleic anhydride, and stirring for reaction to obtain a modified zinc oxide/attapulgite composite;

step S700, according to the modified zinc oxide/attapulgite composite: liquid butadiene rubber: maleic anhydride: and (4) adding the modified zinc oxide/attapulgite composite obtained in the step S600, liquid butadiene rubber, maleic anhydride and dicumyl peroxide into a reaction kettle, and reacting to obtain the adhesion promoter for the vulcanized capsule, wherein the mass ratio of dicumyl peroxide = (30-40) to 45 (10-15) to (1-2).

3. The method of claim 2, wherein the silane coupling agent in step S600 is at least one of gamma-mercaptopropyltrimethoxysilane or bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide.

4. The process for producing an adhesion promoter for a curing bladder according to claim 2, wherein,

in step S100, the reaction conditions are: stirring and reacting for 1-1.5 hours at the temperature of 2-15 ℃;

in step S200, the ultrasonic dispersion conditions are: the ultrasonic power is 200-500W, the ultrasonic frequency is 20-25 kHz, and the ultrasonic dispersion time is 15-30 minutes;

in step S300, the reaction conditions are: stirring and reacting for 50-60 minutes;

in step S400, the reaction conditions are: stirring and reacting for 30-60 minutes at the temperature of 60-100 ℃, and then aging for 20-30 minutes;

in step S500, the calcination conditions are: calcining for 2-5 hours at 300-800 ℃;

in step S600, the reaction conditions are: stirring and reacting for 2-3 hours at 85 ℃;

in step S700, the reaction conditions are: stirring and reacting for 3-4 hours at 180-200 ℃.

5. The method of producing an adhesion promoter for a curing bladder according to claim 2, wherein the attapulgite dispersion in step S200 is a double-modified attapulgite, and the production thereof comprises the steps of:

s210, grinding attapulgite in a ball mill, and sieving to obtain nano attapulgite with the particle size of 0.5-1 mu;

step S220, dispersing the nano-attapulgite obtained in the step S210 in deionized water, performing ultrasonic dispersion by using an ultrasonic emulsion disperser, standing for precipitation, filtering out precipitates, and drying to obtain pure nano-attapulgite;

step S230, according to pure nano attapulgite: deionized water =1: (10-12) dispersing the pure nano-attapulgite obtained in the step S220 in deionized water to prepare a fourth suspension, uniformly stirring the fourth suspension, and coating the fourth suspension on a vessel for drying to obtain a nano-attapulgite coating;

step S240, putting the nano attapulgite coating obtained in the step S230 into an ion beam irradiation device, and performing ion beam bombardment to obtain primary modified attapulgite;

step S250, modifying the attapulgite according to the proportion: hydrochloric acid =1: (2-3) adding the primary modified attapulgite obtained in the step S240 into a dilute hydrochloric acid solution, ultrasonically dispersing the primary modified attapulgite by using an ultrasonic emulsion disperser, and washing, filtering and drying the mixture to obtain the double modified attapulgite.

6. The method of producing an adhesion promoter for a curing bladder according to claim 5,

when the ultrasonic emulsification disperser performs ultrasonic dispersion in the steps S220 and S250, the ultrasonic power is 200-500W, the ultrasonic frequency is 20-25 kHz, and the ultrasonic dispersion time is 1-2 hours.

7. The method of producing an adhesion promoter for a curing bladder according to claim 5,

in the step S230, the thickness of the nanometer attapulgite coating is less than or equal to 1 millimeter;

in step S240, the ion beam irradiation device has an ion beam energy range of 5-1000 keV and a dose range of 20-100000 keV.

8. The method of producing an adhesion promoter for a curing bladder as claimed in claim 5, wherein the mass fraction of the dilute hydrochloric acid solution in step S250 is (0.5-1) wt%.

9. A method for producing a curing bladder, wherein the adhesion promoter for a curing bladder according to any one of claims 1 to 8 is used, comprising the steps of:

s1, preheating butyl rubber, and granulating by using a granulator to obtain rubber particles with the particle size of 15-25 mm;

step S2, according to rubber particles: carbon black: fiber filler: castor oil: zinc stearate: stearic acid: zinc oxide: adhesion promoter for curing bladder: =100: 40: 5: 3: 1: 1: 2: (5-10) banburying the rubber particles obtained in the step S1 with carbon black, a fiber filler, castor oil, zinc stearate, stearic acid, zinc oxide and an adhesion promoter for a curing capsule at 130-150 ℃ to obtain a rubber compound;

step S3, according to rubber particles: vulcanization accelerator (b): sulfur =100: 4: 1, adding a vulcanization accelerator and sulfur into the banbury mixer in the step S2, and mixing in an open mill at the temperature of 80-90 ℃ to obtain a mixed rubber;

and S4, cooling and curing the mixed rubber in the step S3, and injecting and vulcanizing at 160-180 ℃ to obtain the vulcanized capsule.

Technical Field

The invention relates to the technical field of auxiliary agents for curing capsules, in particular to an adhesion promoter for curing capsules and a preparation method thereof.

Background

The vulcanization capsule plays roles of inflation expansion shaping, transmission of superheated water pressure, guarantee of the fact that the rubber material is filled in the mold cavity to achieve the required contour, transmission of heat required by tire vulcanization and the like in the tire vulcanization process. Therefore, the curing bladder needs to have strong stress-strain bearing capacity and good heat conduction capacity so as to meet the process requirements of repeated inflation and deflation cycles under high temperature and high pressure conditions.

In order to meet the above requirements, the vulcanized rubber capsule usually uses butyl rubber with high heat resistance and chemical degradation resistance as a main raw material, and is matched with various compounding agents and reinforcing fillers. However, butyl rubber has low cohesion and poor self-adhesiveness, the rubber material is easy to break up, and the process of re-agglomeration is very slow, so that a high banburying temperature and a long banburying time are required to ensure the uniform dispersion of various compounding agents when a banbury mixer is used for banburying. The fiber filler serving as a reinforcing filler can greatly improve the tear resistance of the vulcanized capsule, but the fiber filler is not easy to uniformly disperse in a rubber system, the adhesion with rubber is poor, the finally obtained vulcanized capsule is not uniform in mass distribution, and the comprehensive performance is not ideal.

For the above reasons, an adhesion promoter is added to the formulation of the curing bladder to improve the banburying effect of the butyl rubber and simultaneously improve the dispersibility and adhesion of the fibrous filler in the rubber compound. In the prior art, a m-methyl-white bonding system is often adopted to improve the mixing process, wherein m in the m-methyl-white bonding system refers to resorcinol which is used as a methylene acceptor; "A" refers to formaldehyde, typically a substance that releases formaldehyde at vulcanization temperatures, as a donor of methylene groups; "white" refers to white carbon black. The adhesive function of the adhesive system is shown in that resorcinol reacts with methylene compounds at vulcanization temperature to form resorcinol resins with strong adhesive activity, and the resins almost simultaneously undergo vulcanization reaction with fibers with dual characteristics of chemical bonds and intermolecular interaction. The white carbon black has an acidic silanol structure on the particle surface, and plays a role in catalyzing the generation of the meta-methyl adhesive resin.

However, the meta-methyl-white adhesive system has the following disadvantages during use: the white carbon black can delay the vulcanization reaction speed of the sulfur and influence the production efficiency; the butyl rubber needs to adopt higher banburying temperature to improve banburying effect during banburying, but the formaldehyde carrier has poor thermal stability, is easy to be heated to release formaldehyde in advance and loses adhesive property; in order to increase the vulcanization rate, it is necessary to increase the amount of the vulcanization system in the rubber compound or use an accelerator having higher efficiency, which leads to an increase in cost.

In addition, in the sulfur vulcanization process of butyl rubber, hydrogen sulfide is generated to destroy disulfide bonds in the rubber, so that redox reaction is caused, and the vulcanization is not facilitated. However, zinc oxide in butyl rubber also has the problem of poor dispersibility, and the excessive addition amount not only greatly increases the banburying time of rubber materials and reduces the production efficiency, but also causes inconsistent oxidation degree of disulfide bonds in vulcanization capsules due to uneven distribution of zinc oxide, thereby affecting the quality of final products.

Disclosure of Invention

The present invention is directed to solving at least one of the above problems.

Accordingly, a first object of the present invention is to provide an adhesion promoter for a curing bladder.

The second object of the present invention is to provide a method for producing an adhesion promoter for a curing bladder.

A third object of the present invention is to provide a method for preparing a curing bladder.

It is a fourth object of the present invention to provide a curing bladder.

In order to achieve the first object of the present invention, the embodiment of the present invention provides an adhesion promoter for a curing bladder, wherein the adhesion promoter for a curing bladder is of a core-shell structure, the core is a modified zinc oxide/attapulgite compound, and the shell is liquid butadiene rubber grafted maleic anhydride; the zinc oxide accounts for (35-40) wt% of the total mass of the core body; maleic anhydride accounts for (17-25) wt% of the total amount of the shell; the shell accounts for (60-65) wt% of the total amount of the adhesion promoter for the curing bladder.

Among the above-mentioned technical scheme, provide the adhesion promoter for the vulcanize capsule that has core-shell structure, the core body is modified zinc oxide/attapulgite complex, and the attapulgite is as the dispersion carrier, can play the effect of reinforcement filler in the vulcanize capsule after adding, and zinc oxide can react with butyl rubber at the hydrogen sulfide that the sulphur vulcanization process produced, consumes hydrogen sulfide, has avoided hydrogen sulfide and the disulfide bond in the rubber to take place redox reaction, thereby has guaranteed going on smoothly of vulcanizing.

The shell is liquid butadiene rubber grafted maleic anhydride, when the vulcanization capsule is vulcanized, the butadiene rubber can be combined with the butyl rubber during polymerization, and the maleic anhydride can be combined with the fiber filler, so that the adhesion of the fiber filler in the butyl rubber is improved.

In order to achieve the second object of the present invention, an embodiment of the present invention provides a method for preparing an adhesion promoter for a curing bladder, comprising the steps of:

step S100, preparing zinc oxide: acetic acid =1:2, mixing zinc oxide and an acetic acid solution for reaction to obtain a zinc acetate solution;

step S200, according to the attapulgite dispersion: deionized water = (30-40): 100, and adding the attapulgite dispersion into deionized water for ultrasonic dispersion to obtain a first suspension;

step S300, according to the attapulgite dispersion: hydrolyzing polymaleic anhydride: zinc =100:0.5:50, adding hydrolyzed polymaleic anhydride and the zinc acetate solution obtained by step S100 to the first suspension in step S200, and stirring to react to obtain a second suspension;

step S400, according to zinc: sodium hydroxide =1 (2-2.4), and a saturated sodium hydroxide solution is added to the second suspension in the step S300, and a third suspension is obtained through stirring reaction;

step S500, centrifugally separating the third suspension obtained in the step S400 to obtain a precipitate, grinding the precipitate in a ball mill to obtain a ground product, and calcining, washing and drying the ground product to obtain a zinc oxide/attapulgite composite;

step S600, according to the zinc oxide/attapulgite composite: silane coupling agent: maleic anhydride =100 (0.75-2.75) by mass, mixing the zinc oxide/attapulgite composite obtained in step S500 with a silane coupling agent and maleic anhydride, and stirring for reaction to obtain a modified zinc oxide/attapulgite composite;

step S700, according to the modified zinc oxide/attapulgite composite: liquid butadiene rubber: maleic anhydride: and (4) adding the modified zinc oxide/attapulgite composite obtained in the step S600, liquid butadiene rubber, maleic anhydride and dicumyl peroxide into a reaction kettle, and reacting to obtain the adhesion promoter for the vulcanized capsule, wherein the mass ratio of dicumyl peroxide = (30-40) to 45 (10-15) to (1-2).

In the technical scheme, zinc is precipitated through acetic acid to form turbid liquid, hydrolyzed polymaleic anhydride is adopted as an activating agent to be chelated with zinc ions and then coated on the surface of the attapulgite dispersion body and the surfaces of pores of micropores, and the hydrolyzed polymaleic anhydride can be combined with fiber fillers to improve the adhesion of the fiber fillers in butyl rubber. The saturated sodium hydroxide solution and the zinc acetate are subjected to double decomposition synthesis reaction to obtain basic zinc acetate, the basic zinc acetate uniformly grows on the surface of the attapulgite dispersion body and the surfaces of pores of the attapulgite dispersion body, and sodium oxalate obtained by the double decomposition synthesis reaction is uniformly separated on the surface of the attapulgite dispersion body and the surfaces of the pores of the attapulgite dispersion body due to supersaturated crystals to uniformly isolate the basic zinc acetate crystals. By grinding through a ball mill, the basic zinc acetate and sodium acetate crystals can be distributed and isolated more uniformly on the surface of the attapulgite dispersion body and the surfaces of pores of the attapulgite dispersion body. The basic zinc acetate can be oxidized into zinc oxide by calcination, sodium acetate is removed by washing, and the surface of part of the attapulgite dispersoid and the surfaces of pores thereof are released to obtain the zinc oxide/attapulgite composite.

The surface activity of the zinc oxide/attapulgite composite is improved by surface modification of the silane coupling agent and maleic anhydride, and the maleic anhydride can participate in the grafting reaction with the liquid butadiene rubber in the subsequent process.

Stirring and reacting the modified zinc oxide/attapulgite composite, the liquid butadiene rubber and the maleic anhydride under the initiation of dicumyl peroxide, and carrying out grafting reaction on the liquid butadiene rubber and the maleic anhydride and coating the liquid butadiene rubber and the maleic anhydride on the surface and the pore surfaces of the modified zinc oxide/attapulgite composite to form a shell.

Preferably, the silane coupling agent in step S600 is at least one of γ -mercaptopropyltrimethoxysilane or bis- [ γ - (triethoxysilyl) propyl ] tetrasulfide.

Preferably, the first and second liquid crystal materials are,

in step S100, the reaction conditions are: stirring and reacting for 1-1.5 hours at the temperature of 2-15 ℃;

in step S200, the ultrasonic dispersion conditions are: the ultrasonic power is 200-500W, the ultrasonic frequency is 20-25 kHz, and the ultrasonic dispersion time is 15-30 minutes;

in step S300, the reaction conditions are: stirring and reacting for 50-60 minutes;

in step S400, the reaction conditions are: stirring and reacting for 30-60 minutes at the temperature of 60-100 ℃, and then aging for 20-30 minutes;

in step S500, the calcination conditions are: calcining for 2-5 hours at 300-800 ℃;

in step S600, the reaction conditions are: stirring and reacting for 2-3 hours at 85 ℃;

in step S700, the reaction conditions are: stirring and reacting for 3-4 hours at 180-200 ℃.

In some embodiments of the present invention, the attapulgite dispersion in step S200 is a dual modified attapulgite, the preparation of which comprises the steps of:

s210, grinding attapulgite in a ball mill, and sieving to obtain nano attapulgite with the particle size of 0.5-1 mu;

step S220, dispersing the nano-attapulgite obtained in the step S210 in deionized water, performing ultrasonic dispersion by using an ultrasonic emulsion disperser, standing for precipitation, filtering out precipitates, and drying to obtain pure nano-attapulgite;

step S230, according to pure nano attapulgite: deionized water =1: (10-12) dispersing the pure nano-attapulgite obtained in the step S220 in deionized water to prepare a fourth suspension, uniformly stirring the fourth suspension, and coating the fourth suspension on a vessel for drying to obtain a nano-attapulgite coating;

step S240, putting the nano attapulgite coating obtained in the step S230 into an ion beam irradiation device, and performing ion beam bombardment to obtain primary modified attapulgite;

step S250, modifying the attapulgite according to the proportion: hydrochloric acid =1: (2-3) adding the primary modified attapulgite obtained in the step S240 into a dilute hydrochloric acid solution, ultrasonically dispersing the primary modified attapulgite by using an ultrasonic emulsion disperser, and washing, filtering and drying the mixture to obtain the double modified attapulgite.

In the technical scheme, the attapulgite is subjected to double modification through ion beam bombardment and dilute hydrochloric acid impregnation, so that the pore structure and the dispersity of the attapulgite are improved. The high-energy density ion beam bombardment can disperse the original attapulgite aggregation state structure in beam-shaped distribution into single rod crystals, and the rod crystals are mutually linked to form a three-dimensional porous nano network under the local heat effect of the ion beam, so that the dispersity of the attapulgite is greatly improved. The attapulgite is impregnated by dilute hydrochloric acid, internal tetrahedrons and octahedron structures of the attapulgite are partially dissolved after the attapulgite is impregnated by the dilute hydrochloric acid, and the number of pore channels and the specific surface area are increased due to the supporting effect of undissolved octahedron structures. Meanwhile, impurities distributed in the attapulgite pore channels can be removed through dilute hydrochloric acid soaking treatment, so that the pore channels are dredged, the cation exchangeability is increased, and potassium ions, sodium ions, calcium ions, magnesium ions and the like in the interlayer part of the attapulgite can be replaced by hydrogen ions with smaller radius, so that the volume of the pore channels is increased. The attapulgite subjected to double modification has a larger specific surface area, the number of the pore channels is increased, the volume of the pore channels is increased, and the zinc oxide and the shell can be coated in the subsequent process.

Preferably, the first and second liquid crystal materials are,

when the ultrasonic emulsification disperser performs ultrasonic dispersion in the steps S220 and S250, the ultrasonic power is 200-500W, the ultrasonic frequency is 20-25 kHz, and the ultrasonic dispersion time is 1-2 hours.

Preferably, the first and second liquid crystal materials are,

in the step S230, the thickness of the nanometer attapulgite coating is less than or equal to 1 millimeter;

in step S240, the ion beam irradiation device has an ion beam energy range of 5-1000 keV and a dose range of 20-100000 keV.

Preferably, the mass fraction of the dilute hydrochloric acid solution in the step S250 is (0.5-1) wt%.

In order to achieve the third object of the present invention, an embodiment of the present invention provides a method for preparing a curing bladder, which uses the adhesion promoter for a curing bladder, and specifically comprises the following steps:

s1, preheating butyl rubber, and granulating by using a granulator to obtain rubber particles with the particle size of 15-25 mm;

step S2, according to rubber particles: carbon black: fiber filler: castor oil: zinc stearate: stearic acid: zinc oxide: adhesion promoter for curing bladder: =100: 40: 5: 3: 1: 1: 2: (5-10) banburying the rubber particles obtained in the step S1 with carbon black, a fiber filler, castor oil, zinc stearate, stearic acid, zinc oxide and an adhesion promoter for a curing capsule at 130-150 ℃ to obtain a rubber compound;

step S3, according to rubber particles: vulcanization accelerator (b): sulfur =100: 4: 1, adding a vulcanization accelerator and sulfur into the banbury mixer in the step S2, and mixing in an open mill at the temperature of 80-90 ℃ to obtain a mixed rubber;

and S4, cooling and curing the mixed rubber in the step S3, and injecting and vulcanizing at 160-180 ℃ to obtain the vulcanized capsule.

To achieve the fourth object of the present invention, embodiments of the present invention provide a curing bladder, which is prepared by the above-mentioned curing bladder preparation method.

Compared with the prior art, the invention has the following beneficial technical effects:

1. the core body is a modified zinc oxide/attapulgite composite, the attapulgite is used as a dispersing carrier, and the attapulgite can play a role of a reinforcing filler in the curing capsule after being added, the zinc oxide can react with hydrogen sulfide generated in the sulfur vulcanization process of the butyl rubber, the hydrogen sulfide is consumed, the hydrogen sulfide is prevented from carrying out redox reaction with disulfide bonds in the rubber, and the smooth proceeding of the vulcanization is ensured; the shell is liquid butadiene rubber grafted maleic anhydride, when the vulcanization capsule is vulcanized, the butadiene rubber can be combined with the butyl rubber during polymerization, and the maleic anhydride can be combined with the fiber filler, so that the adhesion of the fiber filler in the butyl rubber is improved;

2. the adhesion promoter for the curing capsule does not contain formaldehyde, is environment-friendly, eliminates the limitation on banburying temperature, further improves banburying efficiency, avoids the loss of effective components of the adhesion promoter and reduces production cost;

3. carrying out double modification on attapulgite by using ion beam bombardment and dilute hydrochloric acid impregnation to obtain an attapulgite dispersion with high activity and dispersibility, wherein the attapulgite dispersion has more pore channel number, larger pore channel volume and specific surface area, and after zinc oxide is uniformly coated on the attapulgite dispersion, carrying out surface modification on the attapulgite dispersion by using a silane coupling agent and hydrolyzed maleic anhydride to improve the surface activity of the attapulgite dispersion, so as to obtain a modified zinc oxide/attapulgite composite with high dispersibility, wherein the maleic anhydride can further participate in a grafting reaction with liquid butadiene rubber in a subsequent process;

4. the modified zinc oxide/attapulgite composite, the liquid butadiene rubber and the maleic anhydride are stirred and react under the initiation of dicumyl peroxide, and the liquid butadiene rubber and the maleic anhydride are grafted and uniformly coated on the surface and the pore surfaces of the modified zinc oxide/attapulgite composite to form a shell, so that the particle size of the adhesive for the vulcanized capsule is increased, and the dispersibility of the adhesive in a rubber material is further improved;

5. the adhesion promoter for the curing bladder is used for preparing the curing bladder containing the fiber filler, so that the dispersion and adhesion effects of the fiber filler in rubber are improved, the banburying and curing time is greatly reduced, the production efficiency is improved, and the obtained curing bladder has excellent physical and mechanical properties;

in conclusion, the adhesive for the curing bladder provided by the invention has good dispersibility and reinforcing effect in butyl rubber, reduces the production cost, can improve the adhesion of the butyl rubber, fiber filler and various processing aids, greatly reduces the banburying time and the vulcanizing time of rubber materials, and improves the production efficiency and the overall mechanical property of the curing bladder.

Detailed Description

In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

Examples 1 to 1

This example prepared a dual modified attapulgite, and its preparation included the following steps:

s210, grinding attapulgite in a ball mill, and sieving to obtain nano attapulgite with the particle size of 0.5-1 mu;

s220, dispersing the nano-attapulgite obtained in the step S210 in deionized water, putting the deionized water into an ultrasonic emulsification disperser, ultrasonically dispersing for 1 hour under the conditions that the ultrasonic power is 200-500W and the ultrasonic frequency is 20-25 kHz, standing for precipitation, filtering out the precipitate, and drying to obtain pure nano-attapulgite;

step S230, according to pure nano attapulgite: deionized water =1: 10, dispersing the pure nano attapulgite obtained in the step S220 in deionized water to prepare a fourth suspension, uniformly stirring the fourth suspension, coating the fourth suspension on a vessel, and drying to obtain a nano attapulgite coating with the thickness of less than or equal to 1 mm;

step S240, placing the nano attapulgite coating obtained in the step S230 into an ion beam irradiation device, and performing ion beam bombardment under the conditions of 20keV energy and 2500keV dose to obtain primary modified attapulgite;

step S250, modifying the attapulgite according to the proportion: hydrochloric acid =1:2, adding the primary modified attapulgite obtained in the step S240 into a dilute hydrochloric acid solution with the mass fraction of 1%, ultrasonically dispersing for 1 hour by using an ultrasonic emulsification disperser under the conditions that the ultrasonic power is 200-500W and the ultrasonic frequency is 20-25 kHz, and washing, filtering and drying to obtain the dual modified attapulgite.

Example 2-1

An adhesion promoter for a curing bladder was prepared using the double modified attapulgite of example 1-1 as the attapulgite dispersion, by the following specific steps:

step S100, preparing zinc oxide: acetic acid =1:2, mixing zinc oxide and an acetic acid solution for reaction to obtain a zinc acetate solution;

step S200, according to the attapulgite dispersion: deionized water =30:100, adding the attapulgite dispersion into deionized water, and ultrasonically dispersing for 15 minutes under the conditions that the ultrasonic power is 200W and the ultrasonic frequency is 20kHz to obtain a first suspension;

step S300, according to the attapulgite dispersion: hydrolyzing polymaleic anhydride: zinc =100:0.5:50, adding hydrolyzed polymaleic anhydride and the zinc acetate solution obtained by step S100 to the first suspension in step S200, and stirring to react for 50 minutes to obtain a second suspension;

step S400, according to zinc: sodium hydroxide =1:2, and a saturated sodium hydroxide solution is added to the second suspension in step S300, stirred and reacted at 60 ℃ for 60 minutes, and then aged for 20 minutes to obtain a third suspension;

step S500, centrifugally separating the third suspension obtained in the step S400 to obtain a precipitate, grinding the precipitate in a ball mill to obtain a ground product, calcining the ground product at 300 ℃ for 5 hours, and then washing and drying to obtain a zinc oxide/attapulgite composite;

step S600, according to the zinc oxide/attapulgite composite: gamma-mercaptopropyl trimethoxysilane: maleic anhydride =100:0.75:2.75 mass ratio, and the zinc oxide/attapulgite composite obtained by step S500 is mixed with a silane coupling agent and maleic anhydride, and stirred and reacted at 85 ℃ for 2 hours to obtain a modified zinc oxide/attapulgite composite;

step S700, according to the modified zinc oxide/attapulgite composite: liquid butadiene rubber: maleic anhydride: dicumyl peroxide =40:45:13:2 mass ratio, the modified zinc oxide/attapulgite composite obtained by step S600 and liquid butadiene rubber, maleic anhydride, and dicumyl peroxide were added to a reaction kettle, and stirred and reacted at 180 ℃ for 4 hours to obtain an adhesion promoter for a vulcanized capsule.

Examples 2 to 2

An adhesion promoter for a curing bladder was prepared using the double modified attapulgite of example 1-1 as the attapulgite dispersion, by the following specific steps:

step S100, preparing zinc oxide: acetic acid =1:2, mixing zinc oxide and an acetic acid solution for reaction to obtain a zinc acetate solution;

step S200, according to the attapulgite dispersion: deionized water =40:100, adding the attapulgite dispersion into deionized water, and performing ultrasonic dispersion for 30 minutes under the conditions that the ultrasonic power is 200W and the ultrasonic frequency is 20kHz to obtain a first suspension;

step S300, according to the attapulgite dispersion: hydrolyzing polymaleic anhydride: zinc =100:0.5:50, adding hydrolyzed polymaleic anhydride and the zinc acetate solution obtained by step S100 to the first suspension in step S200, and stirring to react for 50 minutes to obtain a second suspension;

step S400, according to zinc: sodium hydroxide =1:2.4, and a saturated sodium hydroxide solution is added to the second suspension in step S300, and after stirring and reacting for 30 minutes at 100 ℃, aging is performed for 30 minutes to obtain a third suspension;

step S500, centrifugally separating the third suspension obtained in the step S400 to obtain a precipitate, grinding the precipitate in a ball mill to obtain a ground product, calcining the ground product at 800 ℃ for 2 hours, and then washing and drying to obtain a zinc oxide/attapulgite composite;

step S600, according to the zinc oxide/attapulgite composite: bis- [ γ - (triethoxysilyl) propyl ] tetrasulfide: maleic anhydride =100:2.75:0.75 mass ratio, and the zinc oxide/attapulgite composite obtained by step S500 is mixed with a silane coupling agent and maleic anhydride, and stirred and reacted at 85 ℃ for 3 hours to obtain a modified zinc oxide/attapulgite composite;

step S700, according to the modified zinc oxide/attapulgite composite: liquid butadiene rubber: maleic anhydride: dicumyl peroxide =30:45:10:1 mass ratio, the modified zinc oxide/attapulgite composite obtained by step S600 and liquid butadiene rubber, maleic anhydride, and dicumyl peroxide were added to a reaction kettle, and stirred and reacted at 200 ℃ for 3 hours to obtain an adhesion promoter for a vulcanized capsule.

Examples 2 to 3

The preparation method of the adhesion promoter for the curing capsule by using the unmodified attapulgite as the attapulgite dispersion comprises the following steps:

step S100, preparing zinc oxide: acetic acid =1:2, mixing zinc oxide and an acetic acid solution for reaction to obtain a zinc acetate solution;

step S200, according to the attapulgite dispersion: deionized water =30:100, adding the attapulgite dispersion into deionized water, and ultrasonically dispersing for 15 minutes under the conditions that the ultrasonic power is 200W and the ultrasonic frequency is 20kHz to obtain a first suspension;

step S300, according to the attapulgite dispersion: hydrolyzing polymaleic anhydride: zinc =100:0.5:50, adding hydrolyzed polymaleic anhydride and the zinc acetate solution obtained by step S100 to the first suspension in step S200, and stirring to react for 50 minutes to obtain a second suspension;

step S400, according to zinc: sodium hydroxide =1:2, and a saturated sodium hydroxide solution is added to the second suspension in step S300, stirred and reacted at 60 ℃ for 60 minutes, and then aged for 20 minutes to obtain a third suspension;

step S500, centrifugally separating the third suspension obtained in the step S400 to obtain a precipitate, grinding the precipitate in a ball mill to obtain a ground product, calcining the ground product at 300 ℃ for 5 hours, and then washing and drying to obtain a zinc oxide/attapulgite composite;

step S600, according to the zinc oxide/attapulgite composite: gamma-mercaptopropyl trimethoxysilane: maleic anhydride =100:0.75:2.75 mass ratio, and the zinc oxide/attapulgite composite obtained by step S500 is mixed with a silane coupling agent and maleic anhydride, and stirred and reacted at 85 ℃ for 2 hours to obtain a modified zinc oxide/attapulgite composite;

step S700, according to the modified zinc oxide/attapulgite composite: liquid butadiene rubber: maleic anhydride: dicumyl peroxide =40:45:13:2 mass ratio, the modified zinc oxide/attapulgite composite obtained by step S600 and liquid butadiene rubber, maleic anhydride, and dicumyl peroxide were added to a reaction kettle, and stirred and reacted at 180 ℃ for 4 hours to obtain an adhesion promoter for a vulcanized capsule.

Example 3-1

The vulcanization bladder was prepared using the adhesion promoter for vulcanization bladder in example 2-1, specifically including the following steps:

s1, preheating butyl rubber, and granulating by using a granulator to obtain rubber particles with the particle size of 15-25 mm;

step S2, according to rubber particles: carbon black: fiber filler: castor oil: zinc stearate: stearic acid: zinc oxide: adhesion promoter for curing bladder: =100: 40: 5: 3: 1: 1: 2: 5, banburying the rubber particles obtained in the step S1 with carbon black, a fibrous filler, castor oil, zinc stearate, stearic acid, zinc oxide and an adhesion promoter for a curing bladder at 130 ℃ to obtain a rubber compound;

step S3, according to rubber particles: vulcanization accelerator (b): sulfur =100: 4: 1, adding a vulcanization accelerator and sulfur into the internal mixing rubber in the step S2, and mixing in an open mill at 80 ℃ to obtain mixed rubber;

and S4, cooling and curing the mixed rubber in the step S3, and injecting and vulcanizing at 160 ℃ to obtain a vulcanized capsule.

Examples 3 to 2

The vulcanization bladder was prepared using the adhesion promoter for vulcanization bladder in example 2-1, specifically including the following steps:

s1, preheating butyl rubber, and granulating by using a granulator to obtain rubber particles with the particle size of 15-25 mm;

step S2, according to rubber particles: carbon black: fiber filler: castor oil: zinc stearate: stearic acid: zinc oxide: adhesion promoter for curing bladder: =100: 40: 5: 3: 1: 1: 2: 10 by mass, banburying the rubber particles obtained by the step S1 with carbon black, a fibrous filler, castor oil, zinc stearate, stearic acid, zinc oxide and an adhesion promoter for a curing bladder at 130 ℃ to obtain a rubber compound;

step S3, according to rubber particles: vulcanization accelerator (b): sulfur =100: 4: 1, adding a vulcanization accelerator and sulfur into the internal mixing rubber in the step S2, and mixing in an open mill at 80 ℃ to obtain mixed rubber;

and S4, cooling and curing the mixed rubber in the step S3, and injecting and vulcanizing at 160 ℃ to obtain a vulcanized capsule.

Examples 3 to 3

The vulcanization bladder was prepared using the adhesion promoter for vulcanization bladder in example 2-2, specifically including the following steps:

s1, preheating butyl rubber, and granulating by using a granulator to obtain rubber particles with the particle size of 15-25 mm;

step S2, according to rubber particles: carbon black: fiber filler: castor oil: zinc stearate: stearic acid: zinc oxide: adhesion promoter for curing bladder: =100: 40: 5: 3: 1: 1: 2: 10 by mass, banburying the rubber particles obtained by the step S1 with carbon black, a fibrous filler, castor oil, zinc stearate, stearic acid, zinc oxide and an adhesion promoter for a curing bladder at 130 ℃ to obtain a rubber compound;

step S3, according to rubber particles: vulcanization accelerator (b): sulfur =100: 4: 1, adding a vulcanization accelerator and sulfur into the internal mixing rubber in the step S2, and mixing in an open mill at 80 ℃ to obtain mixed rubber;

and S4, cooling and curing the mixed rubber in the step S3, and injecting and vulcanizing at 160 ℃ to obtain a vulcanized capsule.

Examples 3 to 4

The use of the adhesion promoter for a curing bladder in examples 2-3 to prepare a curing bladder specifically comprises the steps of:

s1, preheating butyl rubber, and granulating by using a granulator to obtain rubber particles with the particle size of 15-25 mm;

step S2, according to rubber particles: carbon black: fiber filler: castor oil: zinc stearate: stearic acid: zinc oxide: adhesion promoter for curing bladder: =100: 40: 5: 3: 1: 1: 2: 10 by mass, banburying the rubber particles obtained by the step S1 with carbon black, a fibrous filler, castor oil, zinc stearate, stearic acid, zinc oxide and an adhesion promoter for a curing bladder at 130 ℃ to obtain a rubber compound;

step S3, according to rubber particles: vulcanization accelerator (b): sulfur =100: 4: 1, adding a vulcanization accelerator and sulfur into the internal mixing rubber in the step S2, and mixing in an open mill at 80 ℃ to obtain mixed rubber;

and S4, cooling and curing the mixed rubber in the step S3, and injecting and vulcanizing at 160 ℃ to obtain a vulcanized capsule.

Comparative examples 1 to 1

On the basis of the formulation of example 3-1, an adhesion promoter for a curing bladder was removed, and the same procedure was followed to prepare a curing bladder.

Comparing process parameters and performances:

TABLE 1 Effect of adhesion promoters for curing bladders on curing bladder mixing time and curing time

As can be seen from Table 1, the mixing time and the vulcanization time of examples 3-2, 3-3 and 3-4, in which the amount of the adhesion promoter for the curing bladder was large, were the shortest, and the mixing and vulcanization efficiencies of the curing bladder were improved. Among them, examples 3-4 used an attapulgite dispersion which was not doubly modified, and the improvement effect on banburying and vulcanization was slightly lower than that of example 3-2 which was the same formulation as that of the dispersion.

TABLE 2 Effect of adhesion promoters for curing bladders on the mechanical Properties of the curing bladders

As can be seen from Table 2, the physical and mechanical properties of examples 3-2, 3-3 and 3-4 in which the adhesion promoter for a curing bladder was used in a large amount were significantly higher than those of comparative example 1-1 in which the adhesion promoter for a curing bladder was not used. Of these, examples 3-4 used an attapulgite dispersion which had not been doubly modified and had overall slightly lower physical and mechanical properties than example 3-2, which had the same formulation.

The present invention is not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention are intended to be equivalent substitutions and should be included in the scope of the present invention.