阅读说明：本技术 一种耐磨耐腐蚀橡胶管的制备方法 (Preparation method of wear-resistant and corrosion-resistant rubber pipe ) 是由 陈莉莉 于 2020-05-29 设计创作，主要内容包括：本发明属于橡胶制品技术领域,具体涉及一种耐磨耐腐蚀橡胶管的制备方法。本发明将高岭土、铝矾土、钛白粉、磷酸铝与水,搅拌分散制成分散液,向分散液中加入磷酸溶液调节pH,得到高铝泥浆,将粘土、二氧化硅水溶胶混合制得二氧化硅水溶胶浆液,将高铝泥浆、二氧化硅水溶胶浆液混合加热熔融,得到熔融料液,通过离心甩丝得到改性硅酸铝纤维,随后将丁腈橡胶粉、改性纳米氮化铝、EPDM原胶氧化锌、硬脂酸铝、甲基丙烯酸锌密炼得到橡胶基体物,将橡胶基体物送入螺旋管复合缠绕成型机进行成型,在橡胶管硬化前将改性硅酸铝纤维作为内衬挤入橡胶管内部,得到耐磨耐腐蚀橡胶管,本发明制备的橡胶管,耐磨性良好,耐酸碱性优异,有广阔的应用前景。(The invention belongs to the technical field of rubber products, and particularly relates to a preparation method of a wear-resistant and corrosion-resistant rubber pipe. The invention mixes kaolin, bauxite, titanium dioxide, aluminum phosphate and water, disperses to prepare dispersion liquid, adds phosphoric acid solution to the dispersion liquid to adjust pH value to obtain high alumina slurry, mixes clay and silicon dioxide hydrosol to prepare silicon dioxide hydrosol slurry, mixes the high alumina slurry and the silicon dioxide hydrosol slurry, heats and melts to obtain molten feed liquid, obtaining modified aluminum silicate fiber by centrifugal spinning, banburying nitrile rubber powder, modified nano aluminum nitride, EPDM crude rubber zinc oxide, aluminum stearate and zinc methacrylate to obtain rubber matrix, feeding the rubber matrix into a spiral pipe composite winding forming machine for forming, the rubber pipe prepared by the invention has good wear resistance, excellent acid and alkali resistance and wide application prospect.)

1. A preparation method of a wear-resistant corrosion-resistant rubber pipe is characterized by comprising the following specific preparation steps:

(1) mixing 100-200 meshes of nitrile rubber powder, modified nano aluminum nitride and EPDM (ethylene-propylene-diene monomer) raw rubber, placing the mixture into an internal mixer, internally mixing for 8-10 min at 80-90 ℃, adding zinc oxide, aluminum stearate and zinc methacrylate, and continuously internally mixing for 5-8 min to obtain a rubber matrix;

(2) feeding the rubber matrix into a spiral pipe composite winding forming machine for forming, controlling the forming temperature to be 50-55 ℃, forming to obtain a rubber pipe, extruding modified aluminum silicate fiber serving as a lining into the rubber pipe before the rubber pipe is hardened, cooling to room temperature, and performing high-energy electron beam irradiation crosslinking to obtain a wear-resistant and corrosion-resistant rubber pipe;

the modified nano aluminum nitride is prepared by the following specific steps:

(1) adding ethyl acetate into a four-neck flask, heating in a water bath to 50-55 ℃ under the nitrogen atmosphere, stirring and reacting glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azobisisobutyronitrile and dodecyl mercaptan for 30-35 min, heating to 60-65 ℃, preserving heat, stirring and reacting for 3-4 h to obtain viscous liquid, washing with n-hexane to remove the upper layer liquid, washing for 2-3 times, and drying in vacuum to constant weight to obtain a macromolecular coupling agent;

(2) pouring 40-50 parts by weight of nano aluminum nitride powder into a stirring reaction kettle, adding 300-350 parts by weight of acetone as a reaction solvent, heating in a water bath, stirring at a rotating speed of 500-1000 r/min, adding the macromolecular coupling agent GBM, performing reflux reaction for 4-5 hours, discharging, ultrasonically cleaning at a frequency of 2000-2500 kHz, filtering, collecting precipitates, and performing vacuum drying for 10-12 hours to obtain modified nano aluminum nitride;

the modified aluminum silicate fiber is prepared by the following specific steps:

(1) adding 40-50 parts of kaolin, 20-30 parts of bauxite and 20-22 parts of aluminum phosphate into 300-350 parts of water by weight, stirring and dispersing to prepare a dispersion liquid, adding a phosphoric acid solution with the mass fraction of 20% into the dispersion liquid to adjust the pH value of the dispersion liquid, heating to 50-60 ℃, and preserving heat for 10-15 hours to obtain high-aluminum slurry;

(2) mixing 30-50 parts of silica hydrosol with the mass fraction of 50%, 30-40 parts of clay and 200-300 parts of water to obtain silica hydrosol slurry, then mixing the high-aluminum slurry and the silica hydrosol slurry, putting the mixture into a crucible in a muffle furnace, heating to 700-800 ℃, preheating for 40-50 min, heating to 1300-1350 ℃, preserving heat for 30-35 min to obtain molten feed liquid, centrifuging and throwing filaments, and collecting to obtain the modified aluminum silicate fibers.

2. The method for preparing the wear-resistant and corrosion-resistant rubber tube according to claim 1, wherein the method comprises the following steps: the wear-resistant corrosion-resistant rubber pipe is characterized in that the raw materials of the wear-resistant corrosion-resistant rubber pipe in the step (1) comprise, by weight, 50-60 parts of 100-200-mesh nitrile rubber powder, 10-15 parts of modified nano aluminum nitride, 10-12 parts of EPDM virgin rubber, 5-10 parts of zinc oxide, 7-8 parts of aluminum stearate and 10-15 parts of zinc methacrylate.

3. The method for preparing the wear-resistant and corrosion-resistant rubber tube according to claim 1, wherein the method comprises the following steps: the ethylene content in the EPDM virgin rubber in the specific preparation step (1) of the wear-resistant corrosion-resistant rubber pipe is 50-55%.

4. The method for preparing the wear-resistant and corrosion-resistant rubber tube according to claim 1, wherein the method comprises the following steps: the radiation dose is controlled to be 18-20 kGy in the specific preparation step (2) of the wear-resistant corrosion-resistant rubber tube.

5. The method for preparing the wear-resistant and corrosion-resistant rubber tube according to claim 1, wherein the method comprises the following steps: the modified nano aluminum nitride is prepared from the raw materials in the step (1) in parts by weight, 200-220 parts of ethyl acetate, 20-25 parts of glycidyl methacrylate, 55-60 parts of n-butyl methacrylate, 18-20 parts of maleic anhydride, 1-2 parts of azodiisobutyronitrile and 2-3 parts of dodecanethiol.

6. The method for preparing the wear-resistant and corrosion-resistant rubber tube according to claim 1, wherein the method comprises the following steps: the specific preparation step (2) of the modified nano aluminum nitride is to control the water bath temperature to be constant at 50 ℃.

7. The method for preparing the wear-resistant and corrosion-resistant rubber tube according to claim 1, wherein the method comprises the following steps: and (3) specifically preparing the modified nano aluminum nitride, wherein before the nano aluminum nitride powder is used, the nano aluminum nitride powder is dried to constant weight at the temperature of 90-100 ℃ through a vacuum drying oven.

8. The method for preparing the wear-resistant and corrosion-resistant rubber tube according to claim 1, wherein the method comprises the following steps: the modified aluminum silicate fiber is prepared by specifically adjusting the pH of the dispersion to be 5-6 by using phosphoric acid solution in the step (1).

9. The method for preparing the wear-resistant and corrosion-resistant rubber tube according to claim 1, wherein the method comprises the following steps: and (3) mixing the high-alumina slurry and the silica hydrosol slurry in the specific preparation step (2) of the modified alumina silicate fiber according to a volume ratio of 5: 1.

Technical Field

The invention belongs to the technical field of rubber products, and particularly relates to a preparation method of a wear-resistant and corrosion-resistant rubber pipe.

Background

Rubber has a reversibly deformable, highly elastic polymeric material. The elastic material is elastic at room temperature, can generate large deformation under the action of small external force, and can recover the original shape after the external force is removed. The rubber is a completely amorphous polymer, and has a low glass transition temperature and a molecular weight which is often very large and is more than hundreds of thousands.

The rubber industry is one of the important basic industries of national economy. It not only provides daily and medical light industrial rubber products which are indispensable to daily life for people, but also provides various rubber production equipment or rubber parts for heavy industries such as excavation, traffic, construction, machinery, electronics and the like and emerging industries. The rubber tube is classified into a nitrile rubber tube, a fluororubber tube, a chloroprene rubber tube, a natural rubber tube, an ethylene propylene diene monomer rubber tube, a silicone rubber tube, and the like according to the rubber component contained in the rubber tube. The performances of high temperature resistance, low temperature resistance, wear resistance, environmental protection and the like of the existing rubber pipe can not meet the requirements of various industries, so that how to improve the performance of the rubber pipe is a research hotspot of the rubber pipe industry.

At present, with the development of industrial technology in China, the variety of industrial products is increasingly diversified. The conveying pipelines for conveying fluid materials such as sand, ore particles and the like are various, but the most used wear-resistant pipelines are steel pipe products made of high-strength steel materials at present, the wear resistance of the pipelines is completely dependent on the wear resistance of the steel materials, the inner wall of the steel pipe can fall off layer by layer under the action of long-time fluid, iron filings are mixed into the conveyed fluid, and the grade of the fluid can be reduced due to the use of the steel pipe under the condition that the quality requirement of the conveyed fluid is very high; the steel wire framework is fixed on the inner wall of the rubber tube, and the process method improves the wear resistance of the rubber tube, but the steel wire framework and the inner wall of the rubber tube are peeled off due to the large fluid friction force after long-time use, so that the service life of the rubber tube is shortened; the present wear-resistant pipe is a ceramic wear-resistant composite pipe, also called ceramic lining composite steel pipe, and is formed from three layers of corundum ceramic, transition layer and steel respectively from interior to exterior, and its production process adopts high-technology production process-self-propagation high-temperature clutch synthesis method to make said pipe fully utilize the high hardness, corrosion resistance and heat resistance of corundum ceramic, and can overcome the defect of low hardness of steel pipe, but its production process is complex, cost is high, and the flexibility, plasticity and wear resistance of steel pipe are poor. Therefore, it is necessary to develop a rubber tube having high abrasion resistance.

Rubber has a reversibly deformable, highly elastic polymeric material. The elastic material is elastic at room temperature, can generate large deformation under the action of small external force, and can recover the original shape after the external force is removed. The rubber is a completely amorphous polymer, and has a low glass transition temperature and a molecular weight which is often very large and is more than hundreds of thousands.

The rubber industry is one of the important basic industries of national economy. It not only provides daily and medical light industrial rubber products which are indispensable to daily life for people, but also provides various rubber production equipment or rubber parts for heavy industries such as excavation, traffic, construction, machinery, electronics and the like and emerging industries. The rubber tube is classified into a nitrile rubber tube, a fluororubber tube, a chloroprene rubber tube, a natural rubber tube, an ethylene propylene diene monomer rubber tube, a silicone rubber tube, and the like according to the rubber component contained in the rubber tube. The performances of high temperature resistance, low temperature resistance, wear resistance, environmental protection and the like of the existing rubber pipe can not meet the requirements of various industries, so that how to improve the performance of the rubber pipe is a research hotspot of the rubber pipe industry.

With the wider application of rubber products in life, people put higher requirements on the elasticity, the insulating property and other properties of the rubber products. Because the traditional rubber tube product has lower elasticity, the requirements of people on shock resistance and shock absorption can not be met, and the application range of the rubber tube product is limited; the insulation performance has great influence on the safety of consumers, so that more and more attention is paid to the insulation performance, for example, if a rubber tube used on an electric appliance cannot play a role in preventing electric insulation, the rubber tube is a great potential safety hazard, so that the high-elasticity high-insulation rubber tube not only can provide living convenience for users, but also can provide sufficient safety guarantee.

At present, rubber tubes exist: general wear resistance, general acid and alkali resistance, poor corrosion resistance and the like.

Therefore, the invention of the excellent rubber tube has positive significance to the technical field of rubber products.

Disclosure of Invention

The invention mainly solves the technical problem, and provides a preparation method of a wear-resistant corrosion-resistant rubber pipe aiming at the defects that the variety of industrial products is increasingly diversified along with the development of industrial technology in China, and the wear resistance and the acid and alkali corrosion resistance of a transmission rubber pipeline for transmitting fluid materials such as sand, stone, mineral particles and the like are poor.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a preparation method of a wear-resistant corrosion-resistant rubber pipe is characterized by comprising the following specific preparation steps:

(1) mixing 100-200 meshes of nitrile rubber powder, modified nano aluminum nitride and EPDM (ethylene-propylene-diene monomer) raw rubber, placing the mixture into an internal mixer, internally mixing for 8-10 min at 80-90 ℃, adding zinc oxide, aluminum stearate and zinc methacrylate, and continuously internally mixing for 5-8 min to obtain a rubber matrix;

(2) feeding the rubber matrix into a spiral pipe composite winding forming machine for forming, controlling the forming temperature to be 50-55 ℃, forming to obtain a rubber pipe, extruding modified aluminum silicate fiber serving as a lining into the rubber pipe before the rubber pipe is hardened, cooling to room temperature, and performing high-energy electron beam irradiation crosslinking to obtain a wear-resistant and corrosion-resistant rubber pipe;

the modified nano aluminum nitride is prepared by the following specific steps:

(1) adding ethyl acetate into a four-neck flask, heating in a water bath to 50-55 ℃ under the nitrogen atmosphere, stirring and reacting glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azobisisobutyronitrile and dodecyl mercaptan for 30-35 min, heating to 60-65 ℃, preserving heat, stirring and reacting for 3-4 h to obtain viscous liquid, washing with n-hexane to remove the upper layer liquid, washing for 2-3 times, and drying in vacuum to constant weight to obtain a macromolecular coupling agent;

(2) pouring 40-50 parts by weight of nano aluminum nitride powder into a stirring reaction kettle, adding 300-350 parts by weight of acetone as a reaction solvent, heating in a water bath, stirring at a rotating speed of 500-1000 r/min, adding the macromolecular coupling agent GBM, performing reflux reaction for 4-5 hours, discharging, ultrasonically cleaning at a frequency of 2000-2500 kHz, filtering, collecting precipitates, and performing vacuum drying for 10-12 hours to obtain modified nano aluminum nitride;

the modified aluminum silicate fiber is prepared by the following specific steps:

(1) adding 40-50 parts of kaolin, 20-30 parts of bauxite and 20-22 parts of aluminum phosphate into 300-350 parts of water by weight, stirring and dispersing to prepare a dispersion liquid, adding a phosphoric acid solution with the mass fraction of 20% into the dispersion liquid to adjust the pH value of the dispersion liquid, heating to 50-60 ℃, and preserving heat for 10-15 hours to obtain high-aluminum slurry;

(2) mixing 30-50 parts of silica hydrosol with the mass fraction of 50%, 30-40 parts of clay and 200-300 parts of water to obtain silica hydrosol slurry, then mixing the high-aluminum slurry and the silica hydrosol slurry, putting the mixture into a crucible in a muffle furnace, heating to 700-800 ℃, preheating for 40-50 min, heating to 1300-1350 ℃, preserving heat for 30-35 min to obtain molten feed liquid, centrifuging and throwing filaments, and collecting to obtain the modified aluminum silicate fibers.

The wear-resistant corrosion-resistant rubber pipe is characterized in that the raw materials of the wear-resistant corrosion-resistant rubber pipe in the step (1) comprise, by weight, 50-60 parts of 100-200-mesh nitrile rubber powder, 10-15 parts of modified nano aluminum nitride, 10-12 parts of EPDM virgin rubber, 5-10 parts of zinc oxide, 7-8 parts of aluminum stearate and 10-15 parts of zinc methacrylate.

The ethylene content in the EPDM virgin rubber in the specific preparation step (1) of the wear-resistant corrosion-resistant rubber pipe is 50-55%.

The radiation dose is controlled to be 18-20 kGy in the specific preparation step (2) of the wear-resistant corrosion-resistant rubber tube.

The modified nano aluminum nitride is prepared from the raw materials in the step (1) in parts by weight, 200-220 parts of ethyl acetate, 20-25 parts of glycidyl methacrylate, 55-60 parts of n-butyl methacrylate, 18-20 parts of maleic anhydride, 1-2 parts of azodiisobutyronitrile and 2-3 parts of dodecanethiol.

The specific preparation step (2) of the modified nano aluminum nitride is to control the water bath temperature to be constant at 50 ℃.

And (3) specifically preparing the modified nano aluminum nitride, wherein before the nano aluminum nitride powder is used, the nano aluminum nitride powder is dried to constant weight at the temperature of 90-100 ℃ through a vacuum drying oven.

The modified aluminum silicate fiber is prepared by specifically adjusting the pH of the dispersion to be 5-6 by using phosphoric acid solution in the step (1).

And (3) mixing the high-alumina slurry and the silica hydrosol slurry in the specific preparation step (2) of the modified alumina silicate fiber according to a volume ratio of 5: 1.

The beneficial technical effects of the invention are as follows:

(1) kaolin, bauxite, titanium dioxide, aluminum phosphate and water are stirred and dispersed to prepare dispersion liquid, phosphoric acid solution is added into the dispersion liquid to adjust the pH value to obtain high-alumina slurry, clay and silica hydrosol are mixed to prepare silica hydrosol slurry, the high-alumina slurry and the silica hydrosol slurry are mixed and heated to be molten to obtain molten feed liquid, centrifugal spinning is carried out to obtain modified aluminum silicate fibers, then nitrile rubber powder, modified nano aluminum nitride, EPDM crude rubber zinc oxide, aluminum stearate and zinc methacrylate are banburied to obtain rubber matrix, the rubber matrix is sent into a spiral tube composite winding forming machine to be formed, the modified aluminum silicate fibers are extruded into the rubber tube as a lining before the rubber tube is hardened, and radiation crosslinking is carried out after cooling to obtain the wear-resistant and corrosion-resistant rubber tube Synthesizing a macromolecular coupling agent by using three monomers of n-butyl methacrylate and maleic anhydride, carrying out surface modification on nano aluminum nitride powder to prepare modified aluminum nitride, wherein a large number of epoxy groups are carried on the surface of the modified aluminum nitride particle to be coupled with the modified aluminum silicate fiber more easily, so that the adhesive force of the lining is improved, the wear resistance of the rubber tube is enhanced, and the coupling agent has a certain curing catalysis effect and accelerates the forming of the rubber tube;

(2) the invention takes nitrile rubber as main raw material to vulcanize and form and prepare the rubber tube, strengthens the rubber tube by using the modified aluminum silicate fiber layer as the inner liner, improves the wear resistance and reduces the damage of the rubber tube when being bent, uses EPDM raw rubber to dope and modify the nitrile rubber, can effectively improve the low-temperature flexibility and elasticity of the rubber tube, and the EPDM has oil resistance and better acid-base corrosion resistance, is equivalent to provide a layer of anticorrosion protective film for the rubber tube, simultaneously adds zinc methacrylate as heat resistance agent in the inner layer heat insulation filler, and can also be used as auxiliary vulcanizing agent to promote the crosslinking of the rubber in the rubber tube, because divalent zinc ions in the zinc methacrylate are firstly used as Lewis acid to catalyze the ring-opening reaction of EPDM or macromolecule coupling agent epoxy compound in the rubber tube, and generate hydroxyl along with the generation, the hydroxyl generated by the ring-opening further generates nucleophilic addition reaction with the double bond on the unsaturated carboxylic acid metal salt, namely, the oxa-Michael reaction, improves the compatibility of the doped components in the rubber pipe, and simultaneously, the inorganic aluminum silicate fiber lining can further improve the corrosion resistance, thereby having wide application prospect.

Detailed Description

Adding 200-220 parts by weight of ethyl acetate into a four-neck flask, heating in a water bath to 50-55 ℃ under a nitrogen atmosphere, stirring and reacting for 30-35 min at 20-25 parts of glycidyl methacrylate, 55-60 parts of n-butyl methacrylate, 18-20 parts of maleic anhydride, 1-2 parts of azodiisobutyronitrile and 2-3 parts of dodecanethiol for 30-35 min, heating to 60-65 ℃, preserving heat, stirring and reacting for 3-4 h to obtain viscous liquid, washing with n-hexane, removing upper-layer liquid, washing for 2-3 times, and drying in vacuum to constant weight to obtain a macromolecular coupling agent; pouring 40-50 parts by weight of nano aluminum nitride powder into a stirring reaction kettle, adding 300-350 parts by weight of acetone as a reaction solvent, heating in a water bath, stirring at a rotating speed of 500-1000 r/min, adding the macromolecular coupling agent GBM, controlling the constant water bath temperature to be 50 ℃, performing reflux reaction for 4-5 hours, discharging, ultrasonically cleaning at a frequency of 2000-2500 kHz, filtering, collecting precipitates, and performing vacuum drying for 10-12 hours to obtain modified nano aluminum nitride, wherein before use, the nano aluminum nitride powder is dried to constant weight at a temperature of 90-100 ℃ through a vacuum drying oven; adding 40-50 parts of kaolin, 20-30 parts of bauxite and 20-22 parts of aluminum phosphate into 300-350 parts of water by weight, stirring and dispersing to prepare a dispersion liquid, adding a phosphoric acid solution with the mass fraction of 20% into the dispersion liquid to adjust the pH value of the dispersion liquid to 5-6, heating to 50-60 ℃, and preserving heat for 10-15 hours to obtain high-alumina slurry; mixing 30-50 parts of silica hydrosol with the mass fraction of 50%, 30-40 parts of clay and 200-300 parts of water to obtain silica hydrosol slurry, then mixing the high-alumina slurry and the silica hydrosol slurry according to the volume ratio of 5: 1, putting the mixture into a crucible in a muffle furnace, heating to 700-800 ℃, preheating for 40-50 min, heating to 1300-1350 ℃, preserving the temperature for 30-35 min to obtain molten feed liquid, centrifugally throwing filaments, and collecting to obtain modified aluminum silicate fibers; mixing 50-60 parts by weight of 100-200-mesh nitrile rubber powder, 10-15 parts by weight of modified nano aluminum nitride and 10-12 parts by weight of EPDM (ethylene-propylene-diene monomer) virgin rubber, placing the mixture into an internal mixer, internally mixing for 8-10 min at the temperature of 80-90 ℃, then adding 5-10 parts by weight of zinc oxide, 7-8 parts by weight of aluminum stearate and 10-15 parts by weight of zinc methacrylate, and continuously internally mixing for 5-8 min to obtain a rubber matrix, wherein the ethylene content of the EPDM virgin rubber is 50-55%; feeding the rubber matrix into a spiral pipe composite winding forming machine for forming, controlling the forming temperature to be 50-55 ℃, forming to obtain a rubber pipe, extruding modified aluminum silicate fiber serving as a lining into the rubber pipe before the rubber pipe is hardened, cooling to room temperature, then carrying out high-energy electron beam irradiation crosslinking, and controlling the irradiation dose to be 18-20 kGy to obtain the wear-resistant and corrosion-resistant rubber pipe.