CN109679161B - Carboxyl nitrile rubber/graphene oxide nanocomposite capable of blocking hazardous chemical solvents and preparation method thereof - Google Patents
Carboxyl nitrile rubber/graphene oxide nanocomposite capable of blocking hazardous chemical solvents and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carboxyl nitrile rubber/graphene oxide nano composite material for blocking hazardous chemical solvents and a preparation method thereof, wherein graphene oxide nano sheets are oriented in a carboxyl nitrile rubber matrix along a plane direction, and the permeation blocking of the chemical solvents is effectively realized in a thickness direction, wherein the mass fraction of polyethyleneimine in the composite material is 0.001-0.10wt%, the mass fraction of graphene oxide is 0.01-1wt%, and the mass fraction of carboxyl nitrile rubber is 98.90-99.99 wt%. The thickness of the carboxyl nitrile rubber/graphene oxide nano composite film is 1mm, the protection time of the carboxyl nitrile rubber/graphene oxide nano composite film to various chemical solvents is longer than 2h, and the mechanical property is good. The preparation method is simple and ingenious, is convenient to operate, is easy to realize large-scale industrial production and preparation, has good processability, and can be used for preparing the fire protection boots, the fire protection gloves and the like by a melt extrusion method.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and relates to a carboxylated nitrile rubber/graphene oxide nano composite material for blocking hazardous chemical solvents and a preparation method thereof.
Background
The graphene oxide is sp2A two-dimensional monoatomic layer composed of hybridized carbon atoms. As a novel nano material, the nano material has wide application in various fields, such as new energy, catalysis, sensing devices, electromagnetic shielding and reinforcement of gas by compounding with traditional rubber and plastic materialsBulk barrier properties. However, the graphene is difficult to disperse in the polymer and is easy to agglomerate due to the small amount of functional groups on the surface of the graphene. Compared with graphene, graphene oxide has a chemical interaction with a polymer due to the fact that the surface of graphene oxide contains more oxygen-containing functional groups such as carboxyl, hydroxyl, epoxy, sulfonic acid groups and the like, and can overcome the problem of agglomeration and increase the interaction force (electrostatic force and hydrogen bond) between graphene oxide and the polymer. Therefore, at present, people often adopt graphene oxide to fill a polymer matrix so as to prepare various graphene functional composite materials.
The carboxyl nitrile rubber is the rubber with the best non-polar medium resistance in general rubber, and has high wear resistance, good heat resistance and strong binding power. The carboxyl nitrile rubber is excellent in comprehensive performances such as oil resistance, physical and mechanical properties, chemical resistance and the like, and is one of the most representative rubbers. When hazardous substances such as hazardous organic solvents, inorganic acid, alkali salts and the like contact working gloves of firemen, the surface of the rubber material can firstly play a role of a first layer of protective barrier.
However, after the hazardous organic solvent or the hazardous acid base salt contacts the protective material, the organic solvent swells and damages the surface layer of the rubber material, and the inorganic acid base salt can chemically passivate the surface of the rubber material to generate cracks and continuously permeate inwards along the cracks. For example, in 2015, a large explosion of an Tianjin hazardous chemical warehouse occurs, and since the protection effect of a common firefighter uniform is not good after an early emergency firefighter enters a dangerous operation field, unnecessary casualties are caused in the early period.
Similar materials exist in the prior art, for example, chinese patent application No. 201510095850.9 discloses a carboxyl nitrile rubber/graphene nanocomposite with good dispersibility, which comprises the following main raw materials: 0.1-8 parts of graphite oxide, 10 parts of carboxyl nitrile latex, 0.1-8 parts of hydrazine hydrate and a coagulant, the used amount of the organic solvent in the preparation method is small, graphene is dispersed in a carboxyl nitrile rubber matrix in a nano-scale graphite sheet form to obtain co-coagulated particles with uniform particle size, no auxiliary equipment is required to be added, the process is simple and environment-friendly, and the cost is low. In addition, chinese patent application 201611203880.8 discloses a functionalized rubber/modified graphene oxide composite material and a preparation method thereof, wherein the functionalized rubber/modified graphene oxide composite material is composed of a rubber matrix and modified graphene oxide dispersed in the rubber matrix, wherein the amount of the modified graphene oxide is 0.1-30 wt%. The functional groups such as hydroxyl, carboxyl and the like on the surface of the graphene oxide are utilized to graft amino modified nano ZnO onto the surface of the graphene oxide, so that the graphene oxide can play a role of nano reinforcement even an active agent in a composite material. CTBN grafting modification is continuously adopted, so that the modified graphene oxide and rubber can be entangled with a polymer matrix and subjected to co-vulcanization during blending modification, and the interface interaction is improved. However, the required barrier property can not be achieved, and the problems of poor dispersibility, easy agglomeration and poor binding force of the graphene oxide in the emulsion blending process still need to be solved urgently.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a carboxylated nitrile rubber/graphene oxide nanocomposite material for blocking hazardous chemical solvents and a preparation method thereof, so that the problems of poor dispersibility, easy agglomeration and poor bonding force of graphene oxide in the emulsion blending process are solved, and the carboxylated nitrile rubber/graphene oxide nanocomposite material with high barrier permeability to chemical solvents is obtained.
The scheme adopted by the invention is as follows: a carboxyl nitrile rubber/graphene oxide nano composite material for blocking hazardous chemical solvents is characterized in that graphene oxide nano sheets are oriented in a plane direction in a carboxyl nitrile rubber matrix, and the chemical solvents are effectively blocked in a thickness direction, wherein the mass fraction of polyethyleneimine in the composite material is 0.001-0.10wt%, the mass fraction of graphene oxide is 0.01-1wt%, and the mass fraction of carboxyl nitrile rubber is 98.90-99.99 wt%.
In a preferred embodiment of the present invention, the acrylonitrile content of said carboxylated nitrile rubber is very high acrylonitrile content, high acrylonitrile content or medium high acrylonitrile content; wherein, the extremely high acrylonitrile content is more than 43 percent by mass, the high acrylonitrile content is 36 to 42 percent by mass, and the medium and high acrylonitrile content is 31 to 35 percent by mass.
In a preferred embodiment of the present invention, the graphene oxide has a sheet size of 0.5 to 50 μm and a number of layers of 1 to 10.
In a preferred embodiment of the present invention, the graphene oxide is prepared by a modified Hummers method.
The invention also provides a preparation method of the carboxyl nitrile rubber/graphene oxide nano composite material, which comprises the following steps:
(1) diluting and dispersing the graphene oxide concentrated solution prepared by a Hummers method by adding water, performing ultrasonic oscillation to obtain a graphene oxide dispersion solution, uniformly mixing the graphene oxide dispersion solution and a polyethyleneimine water dispersion solution, and performing ultrasonic treatment;
(2) mixing and stirring the graphene oxide/polyethyleneimine dispersion liquid and the diluted carboxylated nitrile-butadiene latex uniformly;
(3) controlling the system temperature of the step (2) at 30-60 ℃ and stirring, then transferring the mixed emulsion into an ultrasonic oscillator, and carrying out ultrasonic treatment at 30-60 ℃;
(4) in the ultrasonic process, adding a calcium chloride saturated solution, carrying out dynamic flocculation, namely stirring while carrying out ultrasonic treatment, and finally washing and drying the obtained block rubber by using deionized water to serve as a master batch;
(5) and (4) mixing the masterbatch obtained in the step (4) with the block carboxyl nitrile rubber according to a ratio, rolling, and vulcanizing to obtain the carboxyl nitrile rubber/graphene oxide nano composite material.
In a preferred embodiment of the present invention, the stirring speed in step (4) is 600-2000rpm, and the ultrasonic power is 60-100W.
The structure of the carboxyl nitrile rubber/graphene oxide nano composite material prepared by the invention is that graphene oxide sheets are oriented in a plane direction in a carboxyl nitrile rubber substrate, and based on the structure, the composite material can effectively protect various gases, dust, common hazardous chemicals and other pollutants. According to the preparation method, the graphene oxide is compounded with the rubber in a water system, so that nanoscale dispersion can be realized, the dispersion degree is high, and the dispersion method is green and efficient.
In one aspect, the graphene oxide of the present invention is obtained by a modified Hummers method, with a lamella size between 0.5-50 μm and a number of layers between 1-10. And the polyethyleneimine is added into the graphene oxide, and the graphene oxide/carboxyl nitrile rubber nanocomposite which is uniformly dispersed and not easy to agglomerate is obtained by adopting a dynamic flocculation method of ultrasonic flocculation, and the graphene oxide and the carboxyl nitrile rubber form a bridge-shaped covalent bond effect through the polyethyleneimine, so that the combination between the graphene oxide and the molecular chain of the carboxyl nitrile rubber is firmer, the flocculation time is shortened while the graphene oxide is uniformly dispersed in the carboxyl nitrile rubber latex, and the preparation efficiency is improved.
On the other hand, as the carboxyl nitrile rubber has strong polar-CN and-COOH, on one hand, a hydrogen bond interaction is formed between a rubber molecular chain and the graphene oxide, so that the graphene oxide is uniformly dispersed in a carboxyl nitrile rubber matrix; on the other hand, an amido bond is formed between-COOH carried on the graphene oxide sheet layer and the polyethyleneimine, and an amido bond is formed between the polyethyleneimine and a carboxyl nitrile rubber molecular chain, so that the graphene oxide and the carboxyl nitrile rubber molecular chain have covalent bond connection, and the graphene oxide stably exists in the carboxyl nitrile rubber matrix. The two aspects enable the carboxylated nitrile rubber/graphene oxide nanocomposite to play a good role in the first-step protective barrier. The hazardous chemical organic solvent and the inorganic acid-base salt break through the situation that the surface layer is protected and then enters the graphene oxide/rubber material, and in the process, the two-dimensional graphene oxide nanosheet and the rubber material play a synergistic effect.
Compared with the prior art, the carboxyl nitrile rubber/graphene oxide barrier protection material has the following advantages: the graphene nanosheets are uniformly oriented and dispersed in the rubber matrix, have excellent mechanical properties, and are strong in barrier property to chemical reagents and good in flexibility. The thickness of the carboxyl nitrile rubber/graphene oxide nano composite film is 1mm, the protection time of the carboxyl nitrile rubber/graphene oxide nano composite film to various chemical solvents is longer than 2h, and the mechanical property is good. The preparation method is simple and ingenious, is convenient to operate, is easy to realize large-scale industrial production and preparation, has good processability, and can be used for preparing the fire protection boots, the fire protection gloves and the like by a melt extrusion method.
Drawings
The following is further described with reference to the accompanying drawings:
FIGS. 1-2 are microscopic scanning electron micrographs of carboxylated nitrile rubber/graphene oxide prepared in example 1;
FIGS. 3 to 4 are microscopic scanning electron micrographs of the carboxylated nitrile rubber/graphene oxide prepared in example 2;
FIGS. 5 to 6 are microscopic scanning electron micrographs of carboxylated nitrile rubber/graphene oxide prepared in example 3;
FIGS. 7 to 8 are microscopic scanning electron micrographs of the carboxylated nitrile rubber/graphene oxide prepared in example 4.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
Synthesizing graphene oxide:
(1) weighing 10g of 300-mesh high-quality natural crystalline flake graphite and 10g of NaNO3Putting the mixture into a 1000ml three-neck flask for later use;
(2) in a 1000ml three-neck flask, 300ml of concentrated H was added under ice-bath (below 5 ℃ C.)2SO4Then stirring for 30min under a moxa-card stirrer to reduce the temperature of the whole system;
(3) 30g of KMnO4Adding the mixture every 12min for 5 times, and finishing the addition after 1h, wherein T is less than 5 ℃ in the process, and the last KMnO addition is finished4Then reacting for 10min, removing the ice bath, and reacting for 30min at normal temperature;
(4) heating the three-neck flask to 35 ℃ and reacting for 6 hours;
(5) adding 400ml of deionized water into a three-neck flask, ensuring that T is less than 100 ℃, and keeping the temperature at 95-100 ℃ for 15 min;
(6) the reacted product was poured into a large beaker, 400ml of deionized water was added, and100ml of H2O2To remove excess KMnO4Standing and layering;
(7) washing twice with 1000ml dilute hydrochloric acid, centrifuging, stopping centrifuging after the supernatant becomes neutral, and collecting precipitate.
Preparing a carboxyl nitrile rubber/graphene oxide nano composite material:
(1) weighing 0.1 part of graphene oxide concentrated solution, diluting and dispersing with a certain amount of water, and performing ultrasonic oscillation for 2 hours to obtain diluted graphene oxide dispersion liquid;
(2) mixing the graphene oxide dispersion liquid with 0.001-0.1 part of polyethyleneimine, and performing ultrasonic dispersion for 2 hours;
(3) mixing the dispersion liquid (1) and the dispersion liquid (2) with the carboxylated butyronitrile latex, stirring for 6 hours, and then carrying out ultrasonic treatment for 2 hours, wherein the stirring temperature and the ultrasonic temperature are both 35 ℃;
(4) when the ultrasonic dispersion is about to finish, CaCl is added while stirring and changing into ultrasonic2After the dynamic flocculation is finished, washing the carboxylic nitrile rubber/graphene oxide rubber block body with deionized water for 1h, and repeating for 5 times.
(5) And (4) preparing the barrier protective film by taking the block rubber obtained in the step (4) as a master batch, and carrying out open milling, calendering and vulcanization to obtain the barrier protective film with the thickness of 1 mm.
The morphology of the prepared carboxyl nitrile rubber/graphene oxide is shown in figure 1-2. The barrier protective film prepared in example 1 has a significantly improved protective property against chemical solvents compared to the protective property of a pure carboxylated nitrile rubber film, and the results are shown in table 1.
Example 2
Graphene oxide was synthesized according to the procedure in example 1.
Preparing a carboxyl nitrile rubber/graphene oxide nano composite material:
(1) weighing 0.3 part of graphene oxide concentrated solution, adding a certain amount of water for dilution, and performing ultrasonic oscillation for 2 hours to obtain a graphene oxide dispersion solution;
(2) mixing the graphene oxide dispersion liquid with 0.001-0.1 part of polyethyleneimine, and performing ultrasonic dispersion for 2 hours;
(3) mixing the dispersion liquid (1) and the dispersion liquid (2) with the carboxylated butyronitrile latex, stirring for 6 hours, and then carrying out ultrasonic treatment for 2 hours, wherein the stirring temperature and the ultrasonic temperature are both 35 ℃;
(4) when the ultrasonic dispersion is about to finish, CaCl is added while stirring and changing into ultrasonic2After the dynamic flocculation is finished, washing the carboxylic nitrile rubber/graphene oxide rubber block body with deionized water for 1h, and repeating for 5 times.
(5) And (4) preparing the barrier protective film by taking the block rubber obtained in the step (4) as a master batch, and carrying out open milling, calendering and vulcanization to obtain the barrier protective film with the thickness of 1 mm.
The morphology of the prepared carboxylated nitrile rubber/graphene oxide is shown in figures 3-4. The barrier protective film prepared in example 2 has a very significant improvement in the protection against chemical solvents compared to the protection against pure carboxylated nitrile rubber film, and the protection against chemical solvents is also prolonged compared to example 1, and the results are shown in table 1.
Example 3
Graphene oxide was synthesized according to the procedure in example 1.
Preparing a carboxyl nitrile rubber/graphene oxide nano composite material:
(1) weighing 0.6 part of graphene oxide concentrated solution, adding a certain amount of water for dilution, and performing ultrasonic oscillation for 2 hours to obtain a graphene oxide dispersion solution;
(2) mixing the graphene oxide dispersion liquid with 0.001-0.1 part of polyethyleneimine, and performing ultrasonic dispersion for 2 hours;
(3) mixing the dispersion liquid (1) and the dispersion liquid (2) with the carboxylated butyronitrile latex, stirring for 6 hours, and then carrying out ultrasonic treatment for 2 hours, wherein the stirring temperature and the ultrasonic temperature are both 35 ℃;
(4) when the ultrasonic dispersion is about to finish, CaCl is added while stirring and changing into ultrasonic2After the dynamic flocculation is finished, washing the carboxylic nitrile rubber/graphene oxide rubber block body with deionized water for 1h, and repeating for 5 times.
(5) And (4) preparing the barrier protective film by taking the block rubber obtained in the step (4) as a master batch, and carrying out open milling, calendering and vulcanization to obtain the barrier protective film with the thickness of 1 mm.
The morphology of the prepared carboxylated nitrile rubber/graphene oxide is shown in figures 5-6. The barrier protective film prepared in example 3 has a very obvious improvement in the protection against chemical solvents compared with the protection against pure carboxylated nitrile rubber film, and the protection time against chemical solvents is also prolonged compared with examples 1 and 2, and the results are shown in table 1.
Example 4
Graphene oxide was synthesized according to the procedure in example 1.
Preparing a carboxyl nitrile rubber/graphene oxide nano composite material:
(1) weighing 0.9 part of graphene oxide concentrated solution, adding a certain amount of water for dilution, and performing ultrasonic oscillation for 2 hours to obtain a graphene oxide dispersion solution;
(2) mixing the graphene oxide dispersion liquid with 0.001-0.1 part of polyethyleneimine, and performing ultrasonic dispersion for 2 hours;
(3) mixing the dispersion liquid (1) and the dispersion liquid (2) with the carboxylated butyronitrile latex, stirring for 6 hours, and then carrying out ultrasonic treatment for 2 hours, wherein the stirring temperature and the ultrasonic temperature are both 35 ℃;
(4) when the ultrasonic dispersion is about to finish, CaCl is added while stirring and changing into ultrasonic2After the dynamic flocculation is finished, washing the carboxylic nitrile rubber/graphene oxide rubber block body with deionized water for 1h, and repeating for 5 times.
(5) And (4) preparing the barrier protective film by taking the block rubber obtained in the step (4) as a master batch, and carrying out open milling, calendering and vulcanization to obtain the barrier protective film with the thickness of 1 mm.
The morphology of the prepared carboxylated nitrile rubber/graphene oxide is shown in FIGS. 7-8. The barrier protective film prepared in example 4 has a very obvious improvement in the protection against chemical solvents compared with the protection against pure carboxylated nitrile rubber film, and the protection time against chemical solvents is also prolonged compared with examples 1, 2 and 3, and the results are shown in table 1:
the results of the experiments performed in examples 1 to 4 are shown in Table 1 below.
TABLE 1 protective Effect of carboxylated nitrile rubber/graphene oxide nanocomposites prepared in examples 1-4
In conclusion, compared with the prior art, the carboxyl nitrile rubber/graphene oxide nanocomposite obtained by the preparation method provided by the invention has good chemical solvent barrier property. And the barrier property of the carboxylated nitrile rubber/graphene oxide nanocomposite material obtained under the conditions of the example 4 to a chemical solvent is particularly outstanding, and is not only remarkably higher than the common level in the prior art, but also far higher than the levels of the examples 1-3.
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Claims (5)
1. The carboxylic acrylonitrile butadiene rubber/graphene oxide nano composite material for blocking hazardous chemical solvents is characterized in that graphene oxide nano sheets are oriented in a planar direction in a carboxylic acrylonitrile butadiene rubber matrix, and the permeation and blocking of the chemical solvents are effectively realized in the thickness direction, wherein the mass fraction of polyethyleneimine in the composite material is 0.001-0.10wt%, the mass fraction of graphene oxide is 0.01-1wt%, the mass fraction of the carboxylic acrylonitrile butadiene rubber is 98.90-99.99wt%, and the sum of the mass fractions of the two materials is 100%; the acrylonitrile content of the carboxyl acrylonitrile-butadiene rubber is extremely high acrylonitrile content, high acrylonitrile content or medium and high acrylonitrile content; wherein, the extremely high acrylonitrile content is more than 43 percent by mass, the high acrylonitrile content is 36 to 42 percent by mass, and the medium and high acrylonitrile content is 31 to 35 percent by mass.
2. The composite material according to claim 1, wherein the graphene oxide has a sheet size of 0.5-50 μm and a number of layers of 1-10.
3. The composite material according to claim 1, wherein the graphene oxide is prepared by a modified Hummers method.
4. A process for the preparation of a carboxylated nitrile rubber/graphene oxide nanocomposite according to any of the claims from 1 to 3, characterised in that it comprises the following steps:
(1) diluting and dispersing the graphene oxide concentrated solution prepared by a Hummers method by adding water, performing ultrasonic oscillation to obtain a graphene oxide dispersion solution, uniformly mixing the graphene oxide dispersion solution and a polyethyleneimine water dispersion solution, and performing ultrasonic treatment;
(2) mixing and stirring the graphene oxide/polyethyleneimine dispersion liquid and the diluted carboxylated nitrile-butadiene latex uniformly;
(3) controlling the system temperature of the step (2) at 30-60 ℃ and stirring, then transferring the mixed emulsion into an ultrasonic oscillator, and carrying out ultrasonic treatment at 30-60 ℃;
(4) in the ultrasonic process, adding a calcium chloride saturated solution, carrying out dynamic flocculation, namely stirring while carrying out ultrasonic treatment, and finally washing and drying the obtained block rubber by using deionized water to serve as a master batch;
(5) and (4) mixing the masterbatch obtained in the step (4) with the block carboxyl nitrile rubber according to a ratio, rolling, and vulcanizing to obtain the carboxyl nitrile rubber/graphene oxide nano composite material.
5. The preparation method according to claim 4, wherein the stirring speed in step (4) is 600-2000rpm and the ultrasonic power is 60-100W.
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| CN102532629A (en) * | 2011-12-30 | 2012-07-04 | 北京化工大学 | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material |
| CN103408855A (en) * | 2013-08-29 | 2013-11-27 | 滁州旭中化工有限公司 | Rubber composite containing graphene oxide |
| CN105038222A (en) * | 2015-08-11 | 2015-11-11 | 河南科技大学 | Graphene/PEI (polyethyleneimine) gas barrier composite membrane and preparing method of graphene/PEI gas barrier composite membrane |
| WO2018190645A1 (en) * | 2017-04-14 | 2018-10-18 | 세종대학교 산학협력단 | Nanocellulose composite, and method for manufacturing same |
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| CN102532629A (en) * | 2011-12-30 | 2012-07-04 | 北京化工大学 | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material |
| CN103408855A (en) * | 2013-08-29 | 2013-11-27 | 滁州旭中化工有限公司 | Rubber composite containing graphene oxide |
| CN105038222A (en) * | 2015-08-11 | 2015-11-11 | 河南科技大学 | Graphene/PEI (polyethyleneimine) gas barrier composite membrane and preparing method of graphene/PEI gas barrier composite membrane |
| WO2018190645A1 (en) * | 2017-04-14 | 2018-10-18 | 세종대학교 산학협력단 | Nanocellulose composite, and method for manufacturing same |
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