阅读说明：本技术 一种氧化石墨烯增强型吸水膨胀橡胶的制备方法及吸水膨胀橡胶 (Preparation method of graphene oxide enhanced water-swelling rubber and water-swelling rubber ) 是由 温世鹏 苏玉仙 郑龙 刘力 于 2019-01-07 设计创作，主要内容包括：本发明涉及一种氧化石墨烯增强型吸水膨胀橡胶的制备方法,属于橡胶技术领域领域。本发明采用绿色的乳液复合法,首先制备了均匀分散的氧化石墨烯/橡胶母胶,再将其与吸水材料和其他橡胶助剂混合,最后硫化得到了高性能的氧化石墨烯增强型吸水膨胀橡胶。该方法实现了氧化石墨烯在橡胶中的均匀分散,充分发挥了GO二维大片层材料的优势,得到了力学性能和吸水性能优异的高性能吸水膨胀橡胶。此外,本发明还具有设备简单、操作简单、可控性好、无有机溶剂污染并且利于工业化生产等优点。(The invention relates to a preparation method of graphene oxide enhanced water-swelling rubber, and belongs to the technical field of rubber. The invention adopts a green emulsion compounding method, firstly prepares uniformly dispersed graphene oxide/rubber master batch, then mixes the graphene oxide/rubber master batch with a water absorbing material and other rubber auxiliaries, and finally vulcanizes the mixture to obtain the high-performance graphene oxide enhanced water-absorbing expansion rubber. The method realizes the uniform dispersion of graphene oxide in rubber, fully exerts the advantages of a GO two-dimensional large sheet material, and obtains the high-performance water-absorbing expansion rubber with excellent mechanical property and water absorption property. In addition, the method has the advantages of simple equipment, simple operation, good controllability, no organic solvent pollution, contribution to industrial production and the like.)

1. A preparation method of graphene oxide reinforced water-swelling rubber is characterized by comprising the following steps:

(1) preparing graphene oxide aqueous dispersion, namely ultrasonically dispersing graphene oxide in deionized water to obtain the graphene oxide aqueous dispersion;

(2) preparing graphene oxide/rubber master batch, namely mixing rubber latex with the graphene oxide aqueous dispersion, stirring to obtain a graphene oxide/rubber latex mixed solution, pouring the graphene oxide/rubber latex mixed solution into a flocculant solution, fully stirring until the graphene oxide/rubber latex mixed solution is completely flocculated to obtain graphene oxide/rubber floc, washing the floc clean and fully drying to obtain the graphene oxide/rubber master batch;

(3) preparing graphene oxide reinforced water-absorbing expanded rubber, mixing graphene oxide/rubber master batch, a water-absorbing material and an auxiliary agent to prepare a mixed rubber, and finally vulcanizing to obtain the graphene oxide reinforced water-absorbing expanded rubber;

wherein the rubber accounts for 100 parts by weight, and the graphene oxide accounts for 0.1-50 parts by weight.

2. The preparation method of the graphene oxide reinforced water swellable rubber as claimed in claim 1, wherein the method comprises the following steps:

the flocculating agent is at least one selected from sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, acetic acid, calcium chloride, sodium chloride, potassium chloride, sodium sulfate, ethanol and formic acid.

3. The preparation method of the graphene oxide reinforced water swellable rubber as claimed in claim 1, wherein the method comprises the following steps:

the rubber latex is selected from at least one of natural latex, styrene-butadiene latex, carboxylated styrene-butadiene-pyridine latex, acrylonitrile-butadiene latex, carboxylated acrylonitrile-butadiene latex, butyl latex, brominated butyl latex, chlorinated butyl latex, epoxy natural latex, acrylate latex, neoprene latex, carboxylated chloroprene latex, butadiene latex, ethylene-propylene latex, epoxidized ethylene-propylene latex, polyisoprene latex, fluorine rubber latex, silicone rubber latex, epoxidized silicone rubber latex, butadiene-pyridine rubber latex, polyurethane rubber latex, chlorosulfonated polyethylene rubber latex, chlorohydrin rubber latex and polysulfide rubber latex.

4. The preparation method of the graphene oxide reinforced water swellable rubber as claimed in claim 1, wherein the method comprises the following steps:

the water absorbing material is selected from acrylic acid, acrylate, acrylamide, di (methyl) acrylate, polyacrylic acid, polyacrylate, polyacrylamide, poly (methyl) acrylate of polyalcohol, acrylic acid-acrylamide copolymer, cross-linked polyacrylate, starch grafted acrylonitrile, starch grafted acrylate, starch grafted acrylamide, starch grafted acrylate, cellulose grafted acrylonitrile, cellulose grafted acrylate, cellulose grafted acrylamide, hydroxymethylated cellulose, polyethylene glycol acrylate, polyvinyl alcohol-anhydride cross-linked copolymer, polyvinyl alcohol-acrylic acid cross-linked copolymer, vinyl acetate-acrylate copolymer hydrolysate, polyurethane prepolymer, polyvinyl alcohol-acrylate copolymer, polyvinyl alcohol-acrylate, At least one of hydrotalcite, bentonite, clay and white carbon black.

5. The preparation method of the graphene oxide reinforced water swellable rubber as claimed in claim 1, wherein the method comprises the following steps:

the thickness of the graphene oxide is 0.335-5 nm, and the transverse dimension is 50 nm-500 mu m.

6. The preparation method of the graphene oxide reinforced water swellable rubber as claimed in claim 1, wherein the method comprises the following steps:

in the step (1), the mass fraction of graphene oxide in the graphene oxide aqueous dispersion is 0.01-50%.

7. The preparation method of the graphene oxide reinforced water swellable rubber as claimed in claim 1, wherein the method comprises the following steps:

in the step (1), the ultrasonic time is 10-300 min, the ultrasonic power is 100-2000 w, and the ultrasonic frequency is 1-30 kHz.

8. The preparation method of the graphene oxide reinforced water swellable rubber as claimed in claim 1, wherein the method comprises the following steps:

in the step (2), the mixing speed of the rubber latex and the graphene oxide aqueous dispersion is 50-5000 rpm/min, and the mixing time is 1-300 min.

9. The preparation method of the graphene oxide reinforced water swellable rubber as claimed in claim 1, wherein the method comprises the following steps:

1-15 parts by weight of graphene oxide.

10. The graphene oxide reinforced water swellable rubber obtained by the preparation method according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of rubber, in particular to a preparation method of graphene oxide enhanced water-swelling rubber and the water-swelling rubber.

Background

The water-swelling rubber is a novel functional material with excellent elasticity and water-swelling performance, and the main components of the water-swelling rubber are composed of a rubber matrix and a water-absorbing material. When it contacts with water, it can absorb water and expand its volume by several times or even hundreds times its own weight or volume, and at the same time it can retain the inherent elasticity and strength of rubber, and also has good water-retaining rate. This characteristic makes it play a dual role of elastic sealing water and water swelling water stopping in the effective volume expansion range. At present, the waterproof sealing material is widely applied to waterproof sealing of building projects such as tunnels, subways, dams, reservoirs, instruments, engineering deformation joints, construction joints and the like.

Graphene Oxide (GO) is a two-dimensional lamellar material, the surface of the graphene oxide is rich in oxygen-containing functional groups, and the GO lamellar is very easy to aggregate. At present, a large number of researches show that on the premise of solving the dispersion problem of GO in rubber, a small amount of GO is added into the rubber, so that the mechanical property, the gas barrier property and the like of the rubber can be greatly improved, and the possibility is provided for the application of GO in water-swelling rubber. At present, the literature also reports that GO is filled into nitrile rubber (NBR) in an acetone solvent, and then a novel water-swellable rubber containing GO is prepared (the preparation and performance of GO/NBR water-swellable rubber [ J ]. colloid and polymer, 2018 (2)). Water absorption performance tests show that the water absorption performance of the rubber is improved by adding GO, and the water absorption multiplying power is obviously increased. However, the addition of GO also reduces the mechanical properties of the water-swellable rubber. In addition, a large amount of organic solvents are used in the process of preparing the GO/rubber composite material through solvent compounding, the problems of solvent pollution, solvent recovery and the like exist, and large-scale industrial preparation is difficult to carry out. Therefore, how to adopt a green composite process to prepare the high-performance GO/water-swellable rubber which is easy to industrially produce becomes a difficult point and a key for research.

Disclosure of Invention

In order to solve the problems existing in the prior art, the method adopts a green, environment-friendly and efficient emulsion flocculation method, firstly, GO is pre-dispersed in a rubber matrix to obtain GO/rubber master batch, and in the next step, a water absorption material and other rubber auxiliaries are filled into rubber by a mechanical blending method.

One of the purposes of the invention is to provide a preparation method of graphene oxide reinforced water-swelling rubber, which comprises the following steps:

(1) preparing graphene oxide aqueous dispersion, namely ultrasonically dispersing graphene oxide in deionized water to obtain the graphene oxide aqueous dispersion;

(2) preparing graphene oxide/rubber master batch, namely mixing rubber latex with the graphene oxide aqueous dispersion, stirring to obtain a graphene oxide/rubber latex mixed solution, pouring the graphene oxide/rubber latex mixed solution into a flocculant solution, fully stirring until the graphene oxide/rubber latex mixed solution is completely flocculated to obtain graphene oxide/rubber floc, washing the floc clean and fully drying to obtain the graphene oxide/rubber master batch;

(3) preparing graphene oxide reinforced water-absorbing expanded rubber, mixing graphene oxide/rubber master batch, a water-absorbing material and an auxiliary agent to prepare a mixed rubber, and finally vulcanizing to obtain the graphene oxide reinforced water-absorbing expanded rubber;

wherein the rubber latex comprises 100 parts by weight of rubber and 0.1-50 parts by weight of graphene oxide, preferably 1-15 parts by weight of graphene oxide, based on the dry rubber content.

The flocculating agent used in the present invention is preferably at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, acetic acid, calcium chloride, sodium chloride, potassium chloride, sodium sulfate, ethanol, and formic acid, and more preferably sulfuric acid, hydrochloric acid, calcium chloride, sodium chloride, and formic acid.

The rubber latex used in the present invention is preferably at least one of natural latex, styrene-butadiene latex, carboxylated styrene-butadiene-pyridine latex, acrylonitrile-butadiene latex, carboxylated acrylonitrile-butadiene latex, butyl latex, bromobutyl latex, chlorobutyl latex, epoxidized natural latex, acrylate latex, polychloroprene latex, carboxylated polychloroprene latex, butadiene latex, ethylene-propylene latex, epoxidized ethylene-propylene latex, polyisoprene latex, fluorine rubber latex, silicone rubber latex, epoxidized silicone rubber latex, butadiene-pyridine rubber latex, polyurethane rubber latex, chlorosulfonated polyethylene rubber latex, chlorohydrin rubber latex, and polysulfide rubber latex, and more preferably natural latex, styrene-butadiene latex, carboxylated acrylonitrile-butadiene latex, acrylonitrile-butadiene latex.

The water-absorbing material adopted by the invention is acrylic acid, acrylate, acrylamide, di (methyl) acrylate, polyacrylic acid, polyacrylate, polyacrylamide, poly (methyl) acrylate of polyalcohol, acrylic acid-acrylamide copolymer, cross-linked polyacrylate, starch grafted acrylonitrile, starch grafted acrylate, starch grafted acrylamide, starch grafted acrylate, cellulose grafted acrylonitrile, cellulose grafted acrylate, cellulose grafted acrylamide, hydroxymethylated cellulose, polyethylene glycol acrylate, polyvinyl alcohol-anhydride cross-linked copolymer, polyvinyl alcohol-acrylic acid cross-linked copolymer, vinyl acetate-acrylate copolymer hydrolysate, acrylic acid ester copolymer, acrylic acid, At least one of polyurethane prepolymer, hydrotalcite, bentonite, clay and white carbon black, and more preferably polyacrylate, polyacrylamide, starch grafted acrylate, cellulose grafted acrylate and polyurethane prepolymer.

The thickness of the graphene oxide adopted by the invention is preferably 0.335-5 nm, and the transverse dimension is preferably 50 nm-500 μm.

In the step (1), the mass fraction of the graphene oxide in the graphene oxide aqueous dispersion is preferably 0.01-50%, and more preferably 1-15%.

In the step (1), preferably, the ultrasonic time is 10-300 min, the ultrasonic power is 100-2000 w, and the ultrasonic frequency is 1-30 kHz; more preferably, the ultrasonic time is 30-120 min, the ultrasonic power is 400-1500 w, and the ultrasonic frequency is 5-15 Hz.

In the step (2), preferably, the mixing speed of the rubber latex and the graphene oxide aqueous dispersion is 50-5000 rpm/min, and the mixing time is 1-300 min; more preferably, the stirring speed is 100-800 rpm/min, and the stirring time is 5-120 min.

In the step (3), the graphene oxide/rubber master batch is mixed with an activator, an anti-aging agent, a plasticizer, a reinforcing agent and a water absorbing material, then an accelerator and a vulcanizing agent are added to prepare a rubber compound, and finally the graphene oxide reinforced water absorbing expanded rubber is obtained through vulcanization.

The auxiliary agents are commonly used auxiliary agents in the field, such as an active agent, an anti-aging agent, a plasticizer, a reinforcing agent, an accelerator, a vulcanizing agent and the like, and the dosage of the auxiliary agents is conventional dosage or is adjusted according to the requirement of actual conditions.

The preparation method of the invention can specifically adopt the following steps:

(1) preparation of graphene oxide aqueous dispersion

And ultrasonically dispersing a certain amount of graphene oxide in deionized water, wherein the ultrasonic time is 10-300 min, the ultrasonic power is 100-2000 w, and the ultrasonic frequency is 1-30 kHz, so as to obtain the graphene oxide aqueous dispersion.

(2) Preparation of graphene oxide/rubber master batch

And mixing a certain amount of rubber latex with the graphene oxide aqueous dispersion, and stirring at the speed of 50-5000 rpm/min for 1-300 min to obtain a graphene oxide/rubber latex mixed solution. And pouring the graphene oxide/rubber latex mixed solution into the flocculation liquid, and fully stirring until complete flocculation to obtain the graphene oxide/rubber flocculent gel. And washing and fully drying the flocculent gel to obtain the graphene oxide/rubber master batch.

(3) Preparation of graphene oxide enhanced water-swelling rubber

The preparation process comprises the following steps:

placing the graphene oxide/rubber master batch into a rubber open mill or an internal mixer, adding an active agent, an anti-aging agent, a plasticizer, a reinforcing agent and a water-absorbing material, adding an accelerator and a vulcanizing agent to prepare a rubber compound, and finally vulcanizing to obtain the graphene oxide reinforced water-absorbing expanded rubber.

The invention also aims to provide the graphene oxide enhanced water-swelling rubber prepared by the preparation method.

The invention adopts a green emulsion compounding method, firstly prepares uniformly dispersed graphene oxide/rubber master batch, then mixes the graphene oxide/rubber master batch with a water absorbing material and other rubber auxiliaries, and finally vulcanizes the mixture to obtain the high-performance graphene oxide enhanced water-absorbing expanded rubber.

The technology realizes the uniform dispersion of GO in rubber, fully exerts the advantages of a two-dimensional large sheet material of GO, and obtains high-performance water-absorbing expansion rubber with excellent mechanical property and water absorption property.

Drawings

Fig. 1 is an Atomic Force (AFM) diagram of graphene oxide prepared according to the present invention.

Fig. 2 is a corresponding height view of fig. 1.

FIG. 3 is a Transmission Electron Microscope (TEM) image of graphene oxide/nitrile rubber (containing 5 parts of graphene oxide) prepared in example 3 of the present invention.

Detailed Description

The present invention will be further described with reference to the following specific embodiments.

The mass of the latex added in the following examples is calculated by dry mass, and the graphene oxide used in each example is prepared according to the document Preparation of graphic oxide.Jamchemmoc.1958; 80(6) 1339 with a thickness of 0.8-1 nm and a lateral dimension of 1-3 μm.