阅读说明：本技术 一种氧化石墨烯和丁基橡胶复合材料的制备方法 (Preparation method of graphene oxide and butyl rubber composite material ) 是由 夏和生 郝帅 程振刚 王占华 费国霞 于 2019-11-14 设计创作，主要内容包括：本发明公开了氧化石墨烯和丁基橡胶复合材料的制备方法,步骤为S1、得到氧化石墨烯分散液；S2、得到丁基橡胶溶液；S3、制备表面活性剂水溶液；S4、将丁基橡胶溶液滴加到表面活性剂水溶液中并高速搅拌混合分散；S5、将氧化石墨烯分散液加入到制备好的丁基橡胶乳液中去,搅拌混合分散得到混合分散液；S6、将硫化助剂硫磺、四甲基二硫代秋兰姆、2-巯基苯并噻唑、氧化锌、硬脂酸加入到混合分散液中继续分散；得到未硫化的原始材料溶液；S7、将得到的混合物中的溶液除去；S8、干燥后即得到氧化石墨烯和丁基橡胶的原材；S9、将原材热压即可得到复合的石墨烯/丁基橡胶材料。本发明所制备的复合材料。(The invention discloses a preparation method of a graphene oxide and butyl rubber composite material, which comprises the steps of S1, obtaining a graphene oxide dispersion liquid; s2, obtaining a butyl rubber solution; s3, preparing a surfactant aqueous solution; s4, dropwise adding the butyl rubber solution into the surfactant aqueous solution, and stirring at high speed, mixing and dispersing; s5, adding the graphene oxide dispersion liquid into the prepared butyl rubber emulsion, and stirring, mixing and dispersing to obtain a mixed dispersion liquid; s6, adding a vulcanization aid, namely sulfur, tetramethylthiuram dithionate, 2-mercaptobenzothiazole, zinc oxide and stearic acid into the mixed dispersion liquid for continuous dispersion; obtaining an unvulcanized raw material solution; s7, removing the solution in the obtained mixture; s8, drying to obtain raw materials of graphene oxide and butyl rubber; and S9, hot-pressing the raw material to obtain the composite graphene/butyl rubber material. The composite material prepared by the invention.)

1. A preparation method of a graphene oxide and butyl rubber composite material is characterized by comprising the following steps: the method comprises the following steps:

s1, dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the water in the graphene oxide dispersion liquid is 0.001-0.1: 1;

s2, dissolving butyl rubber in a solvent to obtain a butyl rubber solution, wherein the mass ratio of the butyl rubber in the butyl rubber solution to the solvent is (0.1-1): 20;

s3, mixing sodium dodecyl benzene sulfonate and sodium dihydrogen phosphate according to the weight ratio of 17: 2, preparing a surfactant aqueous solution; the mass ratio of the sum of the mass of the sodium dodecyl benzene sulfonate and the mass of the sodium dihydrogen phosphate to the mass of the water is 0.01: 0.1;

s4, and mixing the components in a volume ratio of 0.01: 1, slowly dripping a butyl rubber solution into a surfactant aqueous solution, stirring at a high speed, mixing, dispersing, and obtaining a butyl rubber emulsion after the dispersion is finished; the rotating speed of the dispersion machine is 4000-9000 rpm, and the dispersion time is 20-60 min;

s5, mixing the graphene oxide dispersion liquid according to a mass ratio of 0.01: 150, adding the obtained product into the prepared butyl rubber emulsion, stirring, mixing and dispersing to obtain a mixed dispersion liquid; continuously dispersing by using a dispersing machine, wherein the dispersing time is 1-10 min, and the rotating speed of the dispersing machine is 4000-9000 rpm;

s6, adding a vulcanization aid, namely sulfur, tetramethyldithiothiuram, 2-mercaptobenzothiazole, zinc oxide and stearic acid into the mixed dispersion liquid according to the proportion of 1.25phr, 1.5phr, 1phr, 5phr and 2phr, and continuing to disperse; obtaining an unvulcanized raw material solution; continuously dispersing by using a dispersing machine, wherein the dispersing time is 1-10 min, and the rotating speed of the dispersing machine is 4000-9000 rpm;

s7, removing the solution in the obtained mixture; adding CaCl₂Adding into the mixed dispersion as demulsifier, adding CaCl₂The mass ratio of the butyl rubber to the butyl rubber is 0.01: 0.1; then, performing oil-water separation on the flocculated and layered mixed dispersion liquid by using a paging funnel to obtain an unvulcanized raw material;

s8, pouring unvulcanized raw materials into a watch glass, drying for 2 hours by using a blast oven, transferring into a vacuum oven to dry for 36-64 hours with the vacuum degree of 0.1MPa, and drying to obtain raw materials of graphene oxide and butyl rubber;

s9, carrying out hot pressing on the raw material to obtain the composite graphene/butyl rubber material, wherein the hot pressing temperature is 145-160 ℃, the pressure is 13-20 MPa, and the time is 10-20 min.

2. The method of preparing a graphene oxide and butyl rubber composite according to claim 1, wherein: the solvent includes, but is not limited to, petroleum ether, hexane, nonane, cyclopentane, decane, chloroform, toluene, methylene chloride, carbon tetrachloride, 1-chlorobutane, 2-chlorobutane, heptane.

3. The method of preparing a graphene oxide and butyl rubber composite according to claim 1, wherein: the surfactant is an anionic surfactant, and includes but is not limited to sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate, sodium methyl palmitate sulfonate, sodium a-alkenyl sulfonate, secondary alkyl sulfonate, lauryl alcohol ether phosphate, isooctyl alcohol ether phosphate and the like.

4. The method of preparing a graphene oxide and butyl rubber composite according to claim 1, wherein: the dispersing cutter head used is a high-shear high-speed dispersing head.

5. The method of preparing a graphene oxide and butyl rubber composite according to claim 1, wherein: the vulcanization assistant can be directly dispersed in the solution mixture, the dispersion is carried out at room temperature, the stirring speed is 4000-9000 rpm, and the dispersion time is 10-60 min.

6. The method of preparing a graphene oxide and butyl rubber composite according to claim 1, wherein: and removing the solvent by using a blast oven or a vacuum oven, wherein the temperature of the blast oven is 40-90 ℃, stirring at a low speed in the drying process, drying into sheets, cutting into pieces, placing the pieces in the vacuum oven for continuous drying, and the temperature of the vacuum oven is 40-70 ℃ and the drying time is 36-72 hours.

7. The method of preparing a graphene oxide and butyl rubber composite according to claim 1, wherein: the hot pressing temperature is 130-180 ℃, the pressure is 8-25 MPa, and the time is 5-40 min.

Technical Field

The invention relates to the technical field of composite polymers, in particular to a preparation method of a graphene oxide and butyl rubber composite material.

Background

The influence of the dispersed structure of the nano filler in the high polymer material matrix on the performance of the high polymer material is very large. Graphene has remarkable mechanical properties, electrical conductivity and thermal conductivity. Due to the regular structure of the graphene nanosheets and the strong pi-pi interaction between the sheets, the direct use of graphene as a polymer composite material can cause a great amount of agglomeration of graphene, which leads to the reduction of material performance. Graphite can be exfoliated into graphite oxide by a strong oxidation reaction and a large number of oxygen-containing functional groups, such as carboxyl, epoxy, hydroxyl, carbonyl and the like, are introduced to the carbon plane. Due to the existence of the oxygen-containing functional groups, the graphene oxide has good dispersion performance in water or other organic solvents, and can be dispersed into single graphene. The addition of the graphene oxide lamella can effectively improve the comprehensive performance of the polymer matrix.

Chinese patent CN201010191018 discloses an in-situ reduction preparation method of polymer/graphene composite rubber, belonging to the field of rubber composite materials. Graphene/rubber composite materials are prepared by combining graphene oxide and rubber latex emulsion compounding, composite emulsion co-flocculation and mechanical blending under the assistance of ultrasound. The emulsion compounding can enable the graphene to be uniformly dispersed in the rubber, and an isolation net structure can be formed, so that the overall performance of the material is improved. However, in the patent, graphene oxide is reduced in situ by using a chemical reducing agent, the degree of reduction is not easy to control, the reaction time is long, expensive and energy-consuming ultrasonic equipment is required for assisting dispersion, and even then, the aggregation of graphene sheets in the reduction process cannot be avoided. Meanwhile, the performance of the material is improved limitedly under the condition of low addition amount of graphene, the flexibility of the material is obviously reduced under the condition of high content, and the fracture elongation is reduced.

Disclosure of Invention

The invention aims to overcome the defects in the prior art, and provides a method for improving the performance of a matrix material by directly using graphene oxide, wherein the graphene oxide is uniformly dispersed in a polymer matrix by using an emulsion co-flocculation method to form an isolated network structure. According to the method, graphene oxide is not required to be reduced, the performance of the polymer material is improved by directly using the graphene oxide, the use of a dangerous chemical reduction reagent is avoided, the damage of the reduction reagent to the performance of the base material and the stacking of reduced graphene oxide sheets in the reduction process are eliminated, and the mechanical property of the material can be greatly improved under the condition of very low addition amount. Under the condition that the content of graphene oxide is 0.5 wt%, the mechanical property of the material is greatly improved, the strength is improved by more than 250%, the elongation at break is improved by more than 130%, and the elongation at break is more than 2200%.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a preparation method of a graphene oxide and butyl rubber composite material comprises the following steps:

s1, dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the water in the graphene oxide dispersion liquid is 0.001-0.1: 1;

s2, dissolving butyl rubber in a solvent to obtain a butyl rubber solution, wherein the mass ratio of the butyl rubber in the butyl rubber solution to the solvent is (0.1-1): 20;

s3, mixing sodium dodecyl benzene sulfonate and sodium dihydrogen phosphate according to the weight ratio of 17: 2, preparing a surfactant aqueous solution; the mass ratio of the sum of the mass of the sodium dodecyl benzene sulfonate and the mass of the sodium dihydrogen phosphate to the mass of the water is 0.01: 0.1;

s4, and mixing the components in a volume ratio of 0.01: 1, slowly dripping the butyl rubber solution into the surfactant aqueous solution, stirring at a high speed, mixing, dispersing, and obtaining the butyl rubber emulsion after the dispersion is finished; the rotating speed of the dispersion machine is 4000-9000 rpm, and the dispersion time is 20-60 min;

s5, mixing the graphene oxide dispersion liquid according to a mass ratio of 0.01: 150, adding the obtained product into the prepared butyl rubber emulsion, stirring, mixing and dispersing to obtain a mixed dispersion liquid; continuously dispersing by using a dispersing machine, wherein the dispersing time is 1-10 min, and the rotating speed of the dispersing machine is 4000-9000 rpm;

s6, adding the vulcanization aids of sulfur, tetramethyldithiothiuram, 2-mercaptobenzothiazole, zinc oxide and stearic acid into the mixed dispersion according to the proportion of 1.25phr, 1.5phr, 1phr, 5phr and 2phr, and continuing to disperse; obtaining an unvulcanized raw material solution; continuously dispersing by using a dispersing machine, wherein the dispersing time is 1-10 min, and the rotating speed of the dispersing machine is 4000-9000 rpm;

s7, removing the solution in the obtained mixture; adding CaCl₂Adding into the mixed dispersion as demulsifier, adding CaCl₂The mass ratio of the butyl rubber to the butyl rubber is 0.01: 0.1; then, performing oil-water separation on the flocculated and layered mixed dispersion liquid by using a paging funnel to obtain an unvulcanized raw material;

s8, pouring unvulcanized raw materials into a watch glass, drying for 2 hours by using a blast oven, transferring into a vacuum oven to dry for 36-64 hours with the vacuum degree of 0.1MPa, and drying to obtain raw materials of graphene oxide and butyl rubber;

s9, carrying out hot pressing on the raw material to obtain the composite graphene/butyl rubber material, wherein the hot pressing temperature is 145-160 ℃, the pressure is 13-20 MPa, and the time is 10-20 min.

As a modification of the above technical solution, the solvent includes, but is not limited to, petroleum ether, hexane, nonane, cyclopentane, decane, chloroform, toluene, dichloromethane, carbon tetrachloride, 1-chlorobutane, 2-chlorobutane, heptadecane.

As an improvement to the technical scheme, the surfactant is an anionic surfactant, and includes but is not limited to sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate, sodium methyl palmitate sulfonate, sodium a-alkenyl sulfonate, sodium secondary alkyl sulfonate, lauryl alcohol ether phosphate, isooctanol ether phosphate and the like.

As an improvement to the above technical scheme, the used dispersing cutter head is a high-shear high-speed dispersing cutter head.

As an improvement of the technical scheme, the vulcanization auxiliary agent can be directly dispersed in the solution mixture at room temperature, the stirring speed is 4000-9000 rpm, and the dispersion time is 10-60 min.

The technical scheme is improved by removing the solvent by using a blast oven or a vacuum oven, wherein the temperature of the blast oven is 40-90 ℃, the solvent is slowly stirred in the drying process, the sheet is cut after being dried into sheets and is placed in the vacuum oven for continuous drying, the temperature of the vacuum oven is 40-70 ℃, and the drying time is 36-72 hours.

As an improvement on the technical scheme, the hot pressing temperature is 130-180 ℃, the pressure is 8-25 MPa, and the time is 5-40 min.

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

in the preparation process, the butyl rubber emulsion is prepared at room temperature, the graphene oxide dispersion liquid is mixed with the butyl rubber emulsion, and the graphene oxide is uniformly dispersed by utilizing shearing force and vortex generated by high-speed stirring, so that high-energy ultrasonic equipment is not needed. The adoption of a higher rotating speed can provide enough shearing force near the dispersing head to disperse the graphene oxide, and on the other hand, a laminar flow area far away from the dispersing head can realize large-range flow of a dispersing system, further improve the uniformity of dispersion and obviously shorten the time of a dispersing step. And adding a demulsifier calcium chloride after the dispersion is finished, removing water after the flocculation, and drying to obtain the graphene oxide and butyl rubber composite material.

According to the invention, the functionalized composite high polymer material is prepared by directly using graphene, so that the performance damage of a reduction reaction on the polymer material is avoided. The high-speed stirring dispersion in a short time can replace high-power ultrasonic equipment, the equipment cost and the factory energy consumption are effectively reduced, various auxiliaries are directly added into the emulsion for co-flocculation, and the dried raw materials can be directly hot-pressed without other processing to obtain the composite graphene oxide and butyl rubber composite material. According to the graphene oxide and butyl rubber composite material prepared by the method, under the condition that the content of graphene oxide is 0.5 wt%, the mechanical property of the material is greatly improved, the strength is improved by more than 250%, and the elongation at break is improved by more than 130%.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art without any creative effort, should be included in the protection scope of the present invention.