CN102786726B - High performance XNBR vulcanized rubber containing graphene oxide and its preparation method - Google Patents
High performance XNBR vulcanized rubber containing graphene oxide and its preparation method Download PDFInfo
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Abstract
The invention discloses a high performance XNBR rubber containing graphene oxide and its preparation method. The preparation method comprises the following steps: adding graphite oxide into a surface modifier for ultrasonic stripping; carrying out centrifugal separation so as to obtain surface modified single-layer graphene oxide; mixing the single-layer graphene oxide with XNBR rubber latex; then successively adding an anti-aging agent and a flocculant and preparing a rubber mixture by using a co-coagulation method; and adding a vulcanizing agent for vulcanization so as to obtain graphene oxide-containing XNBR vulcanized rubber with high mechanical properties and high thermal conductivity. According to the invention, since the surface modifier is added in the process of stripping, stability and surface tension of graphene oxide suspension are changed, graphene oxide and the latex are allowed be uniformly mixed, and the degree of homodisperse of graphene oxide in a polymer is improved, and therefore, the purpose of improving mechanical strength of XNBR is achieved.
Description
Technical field
The invention belongs to rubber polymer matrix material preparing technical field, particularly a kind of vulcanization of rubber glue containing the strong mechanical performance of monolithic layer structure graphene oxide and the carboxy nitrile rubber (XNBR) of high thermal conductivity and preparation method thereof.
Background technology
Graphene is by sp
2the cellular lattice structure of two dimension (2D) cycle of the monoatomic layer of the carbon atom composition of hydridization, has unique mechanical property (Young's modulus and ultimate strength are respectively up to 1TPa and 130GPa), (specific conductivity is up to 10 for conductivity
6s/m), heat conductivility (thermal conductivity is up to 5000W/mK), but the preparation difficulty of Graphene.
The preparation of graphene oxide (Graphene Oxide) is simple, to be oxidized by strong oxidizer by crystalline flake graphite, introduce polar group on graphite flake layer surface, the two-dimentional sheet layer material that struts graphite flake layer and obtain, the oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy group(ing) are contained on its surface, compared with Graphene, be only sp
2hybrid structure is destroyed, and therefore it still has higher mechanical property (ultimate strength 65GPa) and heat conductivility.Graphene oxide is easy to prepare, cheap, and raw material is easy to get, and is expected to become the high quality filler of polymer nanocomposites.
The method of preparing at present graphene oxide/rubber nano composite material mainly contains: solution blended process and emulsion dispersion.As the employing solution blended processes such as Bai have been prepared graphene oxide-hydrogenated nitrile-butadiene rubber composites (Carbon, 2011,49 (5): 1608-1613.), study the impact of graphene oxide on hydrogenated nitrile-butadiene rubber reinforcing property, when the consumption of graphene oxide reaches 0.44%(volume ratio) when (weight percent 1%), the tensile strength of hydrogenated butyronitrile/GO cross-linked rubber reaches maximum value, has increased by 51% than not filled.This solution blended process needs a large amount of solvents, and cost is high, and environmental pollution is large.Emulsion dispersion is a kind of green simple method, adopt emulsion dispersion to prepare graphene oxide/rubber nano composite material by some reports, the such as summer and raw etc. is dispersed in polymer latex Ruzhong graphene oxide, in latex, introduce reductive agent and carry out in-situ reducing graphene oxide, again through breakdown of emulsion, cohesion, dry Graphene/polymer composites (Xia Hesheng, the gorgeous tiger of fighting, the Fei Guoxia of obtaining, Wu Jinkui, Yan Ning.Chinese patent, application number 201010191018.6), Wu Jinrong improves on the basis of the methods such as Xia Hesheng, the aqueous solution of graphene oxide and latex blend, mix rear breakdown of emulsion, form graphene oxide/polymer slurry, add reductive agent to carry out in-situ reducing graphene oxide, obtain Graphene/polymer composites (Wu Jinrong through filtration drying again, gold-tinted speed, Li Hui, Weng Gengsheng, Wu Si is many, Liu Yufeng, Chinese patent, application number 201110057404.0). in above-mentioned technology, all need graphene oxide to be reduced into Graphene, it is many that reactions steps becomes, cost increases.Also there is people directly graphene oxide to be added in rubber latex, cross breakdown of emulsion, cohesion, the dry graphene oxide/native rubber composite material that obtains, as Wu Jinrong directly adds natural rubber latex Ruzhong to prepare graphene oxide/native rubber composite material (Wu Jinrong graphene oxide, Li Hui, Wu Si is many, Liu Yufeng, gold-tinted speed.The academic free paper session of national polymer in 2011, P1-3), study the impact of graphene oxide on natural rubber reinforcing property, find to add after graphene oxide, the mechanical property of natural rubber is higher than not adding can increase by 40%, in this digest, just mention the impact on performance, but how to prepare, its performance perameter index etc. do not describe.Above-mentioned several method is not all mentioned the effect in carboxy nitrile rubber, in experimentation, above-mentioned several method is used in to carboxy nitrile rubber, the implementation result of all not obtaining.
Summary of the invention
The object of the present invention is to provide a kind of XNBR vulcanization of rubber glue containing graphene oxide with high thermal conductivity and high reinforcing property and preparation method thereof.
The technical solution that realizes the object of the invention is: a kind of high-performance XNBR vulcanization of rubber glue containing graphene oxide and preparation method thereof, prepare and obtain by following steps: adding surface-modifying agent to carry out ultrasonic peeling off graphite oxide, by centrifugation, obtain the single-layer oxidized graphite alkene of surface modification, after this single-layer oxidized graphite alkene is mixed with XNBR rubber latex, successively add anti-aging agent, flocculation agent has been prepared rubber stock by co-agglomeration, by adding vulcanizing agent sulfuration processing, can obtain containing the strong mechanical performance of graphene oxide and the XNBR vulcanization of rubber glue of high thermal conductivity.
The present invention compared with prior art, its remarkable advantage is: (1) by adding surface-modifying agent in stripping process, change stability and the surface tension of graphene oxide suspension, graphene oxide and latex can evenly be mixed, improve the dispersed degree of graphene oxide in polymkeric substance, reach the object of the mechanical strength that improves XNBR.(2) by the ultrasonic rear suspension liquid of peeling off is carried out to centrifugation, obtain the graphene oxide of the monolithic layer structure of surface modification, improve the utilization ratio of graphene oxide, reach the object of the mechanical strength that improves XNBR, (3) use after a small amount of modified graphene oxide, than not using, graphene oxide is the highest can increase by 438% to the tensile strength of XNBR cross-linked rubber, the reinforcing effect of 3 parts of graphene oxides is better than 20 parts of N330 reinforcing effects, and the tensile strength of the cross-linked rubber of its reinforcement is 3.5 times of cross-linked rubber tensile strength of 4 parts of N330 reinforcement.That 1.7 times (4) of cross-linked rubber tensile strength of 20 parts of N330 reinforcement are due to the good heat conductivility of graphene oxide and two-dirnentional structure, in rubber, form good heat transfer path, amount of localized heat in rubber can be derived rapidly, avoid localized hyperthermia, improve the heat conductivility of cross-linked rubber.After using graphene oxide in the present invention, thermal conductivity ratio does not use graphene oxide to improve 36-68%.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Brief description of the drawings
Fig. 1 is the schematic flow sheet that the present invention contains the high heat conduction of graphene oxide and the XNBR vulcanization of rubber glue preparation method of strong mechanical performance.
Fig. 2 is the AFM figure of graphene oxide.
Fig. 3 is the SEM figure of graphene oxide/XNBR cross-linked rubber section.
Fig. 4 is the XRD figure of graphene oxide/XNBR cross-linked rubber section.
Embodiment
By reference to the accompanying drawings, the present invention is containing the high-performance XNBR vulcanization of rubber glue of graphene oxide, comprise following component: XNBR100 part, vulcanizing agent 1-3 part, anti-aging agent 0.5-1 part, single-layer oxidized graphite alkene 1-4 part of modification, adopt Hummers legal system for graphite oxide, add surface-modifying agent, carry out ultrasonic peeling off, obtain the single-layer oxidized graphite alkene of surface modification by centrifugation, after mixing with XNBR rubber latex, add flocculation agent to prepare rubber stock by co-agglomeration, by adding vulcanizing agent sulfuration processing, can obtain of the present invention containing the strong mechanical performance of graphene oxide and the XNBR vulcanization of rubber glue of high thermal conductivity.The present invention can be widely used in all kinds of specialty elastomer goods, is specially adapted to heat-resisting, oil resistant, mechanical property requires high specialty elastomer goods.
The present invention's preparation, containing the method for the high-performance XNBR vulcanization of rubber glue of graphene oxide, comprises the following steps:
Step 1: the preparation of surface modification single-layer oxidized graphite alkene: take graphite oxide and surface-modifying agent, add in deionized water, carry out ultrasonic peeling off, centrifugation, obtains the aqueous dispersions of the single-layer oxidized graphite alkene of surface modification.Wherein, ultrasonic time is 2-8 hour, ultrasonic power is 125-250W, 20-60 DEG C of temperature, surface-modifying agent consumption is 2-4 times of graphite oxide consumption, obtains the graphene oxide of modification, centrifuge speeds 5000-10000 rev/min, get supernatant liquid, obtain the aqueous dispersions of the single-layer oxidized graphite alkene of surface modification.The present invention is that graphite oxide obtains through centrifugation after supersound process again under surface-modifying agent exists containing the single-layer oxidized graphite alkene of the modification of the high-performance XNBR vulcanization of rubber glue of graphene oxide.Wherein the lamellar spacing of single-layer oxidized graphite alkene is 1-1.3nm left and right, and long is 0.8-1.2 μ m, and wide is 0.1-0.6 μ m.Adopt surface-modifying agent to process described single-layer oxidized graphite alkene.Surface-modifying agent is sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or cetyl trimethylammonium bromide.The present invention utilizes the modification of the graphene oxide of surface-modifying agent to monolithic layer structure, increases the degree of scatter of graphene oxide in XNBR latex, improves the mechanical strength of XNBR; Utilize the two-dirnentional structure of graphene oxide and good heat conductivility, the XNBR cross-linked rubber that preparation mechanical property and heat conductivility have concurrently.Compared with separately carbon black filled, the tensile strength of this matrix material and heat conductivility thereof can effectively be improved.Graphene oxide, can be dispersed in XNBR latex through surface modification.
Step 2: the aqueous dispersions of the graphene oxide of the surface modification that step 1 is obtained mixes with XNBR latex, ultrasonic, add anti-aging agent, stir, adjust pH, drip flocculation agent and carry out gel, adopt a large amount of deionized water wash gels, remove flocculation agent, use Büchner funnel suction filtration, the solids obtaining is put into constant temperature oven dries, and obtains the mixture of XNBR and graphene oxide, i.e. master batch.Wherein, the aqueous dispersions of graphene oxide mixes with XNBR latex, ultrasonic 1-2 hour, anti-aging agent is Wingstay@L, N-sec.-propyl-N diphenyl-para-phenylene diamine (4010NA) or 2,2,4-trimethylammonium-1, the water-dispersion liquid of 2-dihyaroquinoline polymer (RD), stirs, and adjust pH is 2-3, drip flocculation agent and carry out gel, flocculation agent is inorganic salt KCl, NaCl or CaCl2, and concentration is 5.5-6.5%, the drying conditions of gel is 100 DEG C, 2 ~ 2.5 hours time.
Step 3: the master batch after oven dry adds after vulcanizing agent mixing in mill, stops glue 24 hours, obtains the XNBR that graphene oxide strengthens rubber mixed.Vulcanizing agent is dicumyl peroxide (DCP), DTBP(ditertiary butyl peroxide) or BIPB(dual-tert-butyl peroxidation diisopropyl benzene).
Step 4: after the rubber unvulcanizate that step 3 obtains is parked, measure its sulfurizing time with vulkameter, sulfuration makes the XNBR vulcanization of rubber glue strengthening containing graphene oxide.
Below by embodiment and comparative example, the invention will be further described.
Embodiment 1
Take 10g graphene oxide, 50g sodium lauryl sulphate, is dissolved in 1L deionized water, ultrasonic power is 125W, 20 DEG C of temperature, ultrasonic 6h, adopt the speed of 6000 revs/min that the centrifugate on upper strata is carried out to centrifugation, get supernatant liquid, obtain the suspension of the graphene oxide of monolithic layer structure.The thickness of graphene oxide is shown in Fig. 2.
Take the suspension of the mono-layer graphite oxide alkene of respective quality, ultrasonic 20min, takes 30gXNBR latex, under magnetic agitation, graphene oxide solution (net content of graphene oxide is 0.3 gram) is added in latex, and ultrasonic 1h, adds anti-aging agent WL0.15 gram.Regulating the pH value of latex is 2 left and right, and latex is added in KCl solution and flocculated, and then adopts the deionized water of 100 DEG C repeatedly to clean the latex after flocculation, dry 2h at 110 DEG C.Take 10g Graphene/XNBR(master batch), add 0.3 gram of vulcanizing agent DCP, mixing in mill.After rubber unvulcanizate is parked 24 hours, then measure its sulfurizing time at 160 DEG C through vulkameter, finally on 50t evacuated flat panel vulcanizer, sulfuration makes cross-linked rubber.Seeing Fig. 3 from the SEM(of cross-linked rubber surface fracture) visible graphene oxide can be dispersed in XNBR rubber matrix figure, XRD (seeing Fig. 4) shows that graphene oxide exists with single layer structure in XNBR rubber matrix, does not occur the diffraction peak of graphite.The tensile strength 10.25MPa of this sizing material, elongation at break 470%, 100% tensile modulus 1.25MPa, shore hardness 71,464. ° of C of maximum heat decomposition temperature, thermal conductivity 0.219W × mK
-1, thermal diffusivity 0.098mm
2s
-1.Oil suction (ASTM1
#oil) tensile strength 8.25MPa after treatment, elongation at break 202%, shore hardness 69.
Embodiment 2
Repeat the method for embodiment 1 by each component concentration of specifying, but in formula, adopt 0.9 gram of graphene oxide, anti-aging agent WL0.3 gram, 0.3 gram of DTBP, the tensile strength 15.61MPa of the cross-linked rubber obtaining, elongation at break 177%, 100% tensile modulus 7.74MPa, shore hardness 77,473. ° of C of maximum heat decomposition temperature, thermal conductivity 0.233W × mK-1, thermal diffusivity 0.096mm
2s
-1.Oil suction (ASTM1
#oil) tensile strength 10.4MPa after treatment, elongation at break 176%, shore hardness 73.
Embodiment 3
Repeat the method for embodiment 1 by each component concentration of specifying, but in formula, adopt 1.2 grams of graphene oxides, 0.15 gram of antioxidant 4010NA, 0.2 gram of DCP, the tensile strength 12.9MPa of the cross-linked rubber obtaining, elongation at break 191%, 100% tensile modulus 5.0MPa, shore hardness 77,473. ° of C of maximum heat decomposition temperature, thermal conductivity 0.270W × mK-1, thermal diffusivity 0.096mm
2s
-1.Oil suction (ASTM1
#) tensile strength 12.1MPa after treatment, elongation at break 191%, shore hardness 75.
Comparative example 1
Repeat to implement 1 method by each component concentration of specifying, but do not use any graphene oxide.The tensile strength 2.9MPa of the cross-linked rubber obtaining, elongation at break 228%, 458. ° of C of maximum heat decomposition temperature, shore hardness 62, thermal conductivity 0.16W × mK-1, thermal diffusivity 0.084mm
2s
-1.Oil suction (ASTM1
#) tensile strength 1.4MPa after treatment, elongation at break 228%, shore hardness 58.
Comparative example 2
Repeat the method for embodiment 1 by each component concentration of specifying, but in formula, adopt 0.3 gram of graphene oxide of not using surface-modifying agent modification, the tensile strength 4.21MPa of the cross-linked rubber obtaining, elongation at break 202%, 100% tensile modulus 2.81MPa, 463. ° of C of maximum heat decomposition temperature, shore hardness 71, thermal conductivity 0.193W × mK-1, thermal diffusivity 0.092mm2s-1.Oil suction (ASTM1
#) tensile strength 3.3MPa after treatment, elongation at break 202%, shore hardness 69.
Comparative example 3
Repeat the method for embodiment 1 by each component concentration of specifying, but in formula, adopt 1.5 grams of graphene oxides, the tensile strength 8.06MPa of the cross-linked rubber obtaining, elongation at break 183%, 100% tensile modulus 3.46MPa, 473 ° of C of maximum heat decomposition temperature, shore hardness 76, thermal conductivity 0.203W × mK-1, thermal diffusivity 0.096mm
2s
-1.Oil suction (ASTM1
#) tensile strength 8.0MPa after treatment, elongation at break 152%, shore hardness 76.
Comparative example 4
Repeat the method for embodiment 1 by each component concentration of specifying, but in formula, adopt 1.2 grams of N330 carbon blacks, the tensile strength 4.39MPa of the cross-linked rubber obtaining, elongation at break 240%, 100% tensile modulus 1.45MPa,, thermal conductivity 0.19W × mK-1,475 ° of C of maximum heat decomposition temperature, thermal diffusivity 0.093mm
2s
-1.
Comparative example 5
Repeat the method for embodiment 1 by each component concentration of specifying, but in formula, adopt 6.0 grams of N330 carbon blacks, the tensile strength 9.11MPa of the cross-linked rubber obtaining, elongation at break 231%, 100% tensile modulus 2.25MPa, 476 ° of C of maximum heat decomposition temperature, thermal conductivity 0.20W × mK-1, thermal diffusivity 0.096mm
2s
-1.
In the present invention, adopt ultrasonic oxidation stripping method to prepare mono-layer graphite oxide alkene, by surface-modifying agent, mono-layer graphite oxide alkene is carried out to modification, adopt centrifugation to obtain the mono-layer graphite oxide alkene of surface-modifying agent modification, mix with XNBR latex again, greatly improve the dispersion of graphene oxide in XNBR matrix, reach and improve the mechanical property of XNBR cross-linked rubber and the object of heat conductivility simultaneously.While using 1-4 gram of modified graphene oxide in the every 100 grams of rubber of cross-linked rubber, than not using, graphene oxide is the highest increases by 438% to tensile strength, and thermal conductivity ratio does not use graphene oxide can improve 36-68%.The tensile strength of cross-linked rubber that uses 3 grams of modified graphene oxide reinforcement is 3.5 times of cross-linked rubber tensile strength of 4 parts of N330 reinforcement.Be 1.7 times of cross-linked rubber tensile strength of 20 parts of N330 reinforcement, therefore the invention provides a kind of XNBR cross-linked rubber that has strong mechanical performance and heat conductivility concurrently and preparation method thereof.
Claims (4)
1. the high-performance XNBR vulcanization of rubber glue containing graphene oxide, it is characterized in that preparing and obtaining by following steps: after graphite oxide is added to surface-modifying agent, carry out ultrasonic peeling off, again by centrifugation, the single-layer oxidized graphite alkene of preparation surface modification, after this single-layer oxidized graphite alkene is mixed with XNBR rubber latex, successively add anti-aging agent, flocculation agent to prepare rubber stock by co-agglomeration, by adding vulcanizing agent sulfuration processing, can obtain containing the strong mechanical performance of graphene oxide and the XNBR vulcanization of rubber glue of high thermal conductivity;
Component and proportioning thereof in described XNBR vulcanization of rubber glue are: XNBR100 part, vulcanizing agent 1-3 part, anti-aging agent 0.5-1 part, single-layer oxidized graphite alkene 1-4 part of modification;
The lamellar spacing of described single-layer oxidized graphite alkene is 1-1.3nm, and long is 0.8-1.2 μ m, and wide is 0.1-0.6 μ m.
2. the high-performance XNBR vulcanization of rubber glue containing graphene oxide according to claim 1, it is characterized in that: adopt surface-modifying agent to process described single-layer oxidized graphite alkene, surface-modifying agent is sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or cetyl trimethylammonium bromide.
3. the high-performance XNBR vulcanization of rubber glue containing graphene oxide according to claim 1, is characterized in that: vulcanizing agent is dicumyl peroxide, ditertiary butyl peroxide or dual-tert-butyl peroxidation diisopropyl benzene.
4. a method of preparing the high-performance XNBR vulcanization of rubber glue containing graphene oxide described in claim 1-3 any one, is characterized in that comprising the following steps:
Step 1: the preparation of surface modification graphene oxide: take graphite oxide and surface-modifying agent, add in deionized water, carry out ultrasonic peeling off, centrifugation, obtains the aqueous dispersions of the graphene oxide of surface modification; In step 1, ultrasonic time is 2-8 hour, and ultrasonic power is 125-250W, 20-60 DEG C of temperature, the consumption of surface-modifying agent is 2-4 times of graphite oxide consumption, centrifuge speeds 5000-10000 rev/min, get supernatant liquid, obtain the aqueous dispersions of the graphene oxide of individual layer surface modification;
Step 2: the aqueous dispersions of the graphene oxide of the surface modification that step 1 is obtained mixes with XNBR latex, ultrasonic, add anti-aging agent, stir, adjust pH, drip flocculation agent and carry out gel, adopt deionized water wash gel, remove flocculation agent, use Büchner funnel suction filtration, the solids obtaining is put into constant temperature oven dries, and obtains the mixture of XNBR and graphene oxide, i.e. master batch; In step 2, the graphene oxide aqueous dispersions of surface modification mixes with XNBR latex, ultrasonic 1-2 hour, stir, adjust pH is 2-3, drips flocculation agent and carries out gel, the concentration of flocculation agent is 5.5-6.5%, and the drying conditions of gel is 100-105 DEG C, 2 ~ 2.5 hours time;
Step 3: the master batch after oven dry adds after vulcanizing agent mixing in mill, stops glue, what obtain that graphene oxide strengthens is rubber mixed;
Step 4: after rubber mixed the parking that step 3 obtains, measure its sulfurizing time with vulkameter, sulfuration makes the XNBR vulcanization of rubber glue strengthening containing graphene oxide;
Component in each step and proportioning thereof are: XNBR100 part, vulcanizing agent 1-3 part, anti-aging agent 0.5-1 part, single-layer oxidized graphite alkene 1-4 part of modification.
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