CN104098816A - Polyolefin/graphene nanocomposite and preparation method thereof - Google Patents
Polyolefin/graphene nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyolefin/graphene nanocomposite. According to the invention, two-dimensional nano-material graphene is used as a reinforcing agent, and through graft modification of polyolefin, polyolefin grafted-modified graphene is formed and uniformly dispersed in a polyolefin material. A preparation method for the polyolefin/graphene nanocomposite comprises the following steps: functionalized modification of graphene; preparation of polyolefin grafted-modified graphene; and preparation of the polyolefin/graphene nanocomposite. The preparation method overcomes the problems of easy agglomeration and difficult dispersion of graphene in graphene-enhanced non-polar polymers; in the prepared polyolefin/graphene nanocomposite, graphene is uniformly distributed; and the polyolefin/graphene nanocomposite has excellent flame retardation performance and mechanical properties.
Description
Technical field
The invention belongs to technical field of polymer processing and field of nanometer technology, relate in particular to a kind of polyolefine/graphene nanocomposite material and preparation method thereof.
Background technology
Graphene is to adopt SP by monolayer carbon atom
2hydridization is piled up the honeycomb crystal lattice forming, and is typical two-dimensional nano material, and its thickness is only 0.35nm.This special construction makes Graphene show excellent mechanical property, peculiar electrical properties and good thermal property, for example Graphene Young's modulus can reach 11000GPa, breaking tenacity reaches 125GPa, and thermal conductivity reaches 5000W/mK, and theoretical specific surface area is up to 2630m
2/ g, and there is the character such as the specific conductivity of perfect quantum tunneling effect, half integral quantum hall effect and superelevation, have a good application prospect in fields such as aerospace, novel material, electric power, electronics.
In the real application research of Graphene, polymer/graphene nano composite material is considered to have one of direction of application prospect most, and research finds, when taking Graphene as nanometer additive, when addition is lower, the performance of polymkeric substance can significantly strengthen.And in daily life, polyolefin plastics, because the advantages such as easily processing, corrosion-resistant, cheap, light weight, over-all properties is superior are widely used, is therefore developed polyolefine/graphene nanocomposite material and is had great theory and realistic meaning.But, between the huge and lamella of Graphene specific surface area, have intrinsic Van der Waals force, thereby Graphene is very easily reunited.As everyone knows, polyolefine is non-polar polymer, and Graphene consistency is poor, causes Graphene to be difficult to effectively peel off in polyolefine, and therefore, dispersed in polyolefin substrate of Graphene is the key issue of preparing polyolefine/graphene nanocomposite material.
Prior art discloses the method for the good polyolefine/graphene nanocomposite material of multiple processability.Number of patent application 201110313859.4 discloses a kind of strongthener composition, strongthener high-abrasive material and method for making of graphene-containing, in coupling agent solution, by ultrasonic dispersion treatment, Graphene is carried out to surface modification, after dry, mix with polyolefine again, melt blending obtains polymer composites, this preparation method is simple, easily implement, but coupling agent and matrix only exists physical force, supersonic modifying inefficiency, modified effect is not obvious.Number of patent application 201010128271.7 provides a kind of graphene-based barrier composite material and preparation method thereof, first with coupling agent, functional modification is carried out in the surface of graphene oxide, again the graphene oxide after modifying is reduced into Graphene, finally modified graphene uniform is distributed in polyolefin solution, crosslinked bonding under the effect of initiator, obtain high comprehensive performance nano composite material, just in this patent, be only applicable to the coupling agent with unsaturated double-bond, general coupling agent and matrix are without obvious bonding action power, the scope of application is narrow, and to use a large amount of solvents in preparation process, contaminate environment.Above-mentioned two sections of patents are all by adding coupling agent to improve Graphene and polyolefinic consistency, Graphene and basal body interface reactive force relatively a little less than, the dispersiveness of Graphene is bad, affects its reinforced effects.
Summary of the invention
The present invention is conceived to solve Graphene and compatible polyolefin is poor, time prepared by scorification, Graphene is difficult to disperse, time prepared by solvent method, the problem such as organic solvent usage quantity large (environmental pollution is serious), provides a kind of polyolefine/graphene nanocomposite material and preparation method thereof.The present invention is by carrying out the chemical modification of polyolefine grafting to graphite oxide, improve the consistency of itself and polyolefin substrate, thereby realize dispersed in polyolefin substrate, obtain the nano material of the good polyolefine/Graphene of over-all properties, and can scale operation.
The preparation method of a kind of polyolefine/graphene nanocomposite material provided by the invention, comprises the steps:
(1) functionalized modification of Graphene: graphite oxide is obtained to finely dispersed suspension by ultrasonic being dispersed in solvent; Then under agitation, add the ethanolic soln that contains diamine compounds, at N
2under protection, carry out back flow reaction 2-24h, temperature of reaction is 60-120 DEG C; Then add the reductive agent aqueous solution to carry out reduction reaction 2-12h; Finally cooling, suction filtration, product is alternately with deionized water and ethanol repetitive scrubbing, and the solid product obtaining is dry in the vacuum drying oven of 50-80 DEG C, obtains the Graphene that functionalisation of surfaces is modified; The consumption of described diamine compounds is 2-20 times of graphite oxide weight; The consumption of described reductive agent is 2-11 times of graphite oxide weight;
(2) preparation of Graft Modification of Polyolefine Graphene: by ultrasonic being dispersed in solvent of Graphene of preparation in step (1), then under agitation, add the maleic anhydride stem grafting polyolefin of 2-10 times of Graphene weight, pass into N at the temperature of 120-160 DEG C
2reaction 2-8h; Last suction filtration, product washing with alcohol, the solid product obtaining is dry in the vacuum drying oven of 80-120 DEG C, obtains Graft Modification of Polyolefine Graphene;
(3) preparation of polyolefine/graphene nanocomposite material: be by weight (1-10): 100, polyolefine graft grapheme prepared by step (2) and polyolefine mix, in Banbury mixer, in 160-230 DEG C of melt blending 5-30min, obtain polyolefine/graphene nanocomposite material.
In described step (1), the mass volume ratio of graphite oxide and solvent is 1g/200ml, and the mass concentration of the reductive agent aqueous solution is 30-70%.
In described step (1), diamine compounds is selected from the one in quadrol, propylene diamine, hexanediamine, O-Phenylene Diamine, mphenylenediamine, Ursol D, diaminodiphenyl oxide, diaminodiphenylsulfone(DDS), diaminodiphenylmethane.
Solvent in described step (1) is methyl alcohol, ethanol or propyl alcohol.
In described step (1), reductive agent is the one of hydrazine hydrate, urea, sodium borohydride, sodium bisulfite, S-WAT, sodium sulphite, ammoniacal liquor, Hydrogen bromide, hydroiodic acid HI.
Solvent in described step (2) is at least one in dimethylbenzene, toluene, tetracol phenixin.
In described step (3), polyolefine is at least one in polyethylene, polypropylene.
In described step (2), in maleic anhydride stem grafting polyolefin, the percentage of grafting of maleic anhydride is 0.5-4%.
The frequency of the ultrasonic dispersion in described step (1) and step (2) is that 40-100Hz, time are 0.5-1.5h.
Another object of the present invention is the polyolefine/graphene nanocomposite material being made by above-mentioned preparation method.
Compared with prior art, the present invention has following beneficial effect:
1, preparation method provided by the invention has improved the dispersiveness of Graphene, easily curls and height fold thereby overcome Graphene when in prior art prepared by scorification under high shear action, is difficult to the shortcoming of disperseing; Overcome usual vehicle legal system for time the environmental pollution that with an organic solvent causes in a large number and the problem of the wasting of resources, long-time or high-power ultrasonic graphene sheet layer structure is damaged while also having avoided solvent method to prepare, declines aspect mechanics, electric property and cause;
2, the Graphene that the present invention adopts maleic anhydride stem grafting polyolefin and surface amino groups to modify carries out amidate action, can be on Graphene surface grafting polyolefine, thereby improve the consistency of itself and polyolefine material, make in the polyolefinic matrix of being dispersed in of graphene uniform, do not reunite, thereby can prepare the olefin polymerization nanometer material of high Graphene content.
3, because the dispersiveness of Graft Modification of Polyolefine Graphene is good, make polyolefine/graphene nanocomposite material of finally preparing not only there is the improvement of intensity and toughness, also there is thermally-stabilised and flame retardant properties preferably.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the polypropylene grafted modified graphene (b) prepared of graphite oxide (a) and the embodiment of the present invention 1.
Fig. 2 is the Raman spectrogram of the polypropylene grafted modified graphene (b) prepared of graphite oxide (a) and the embodiment of the present invention 1.
Fig. 3 is the profile scanning electron microscope picture of polypropylene/graphene nanocomposite material (b) of preparing of virgin pp (a) and the embodiment of the present invention 1.
Fig. 4 is comparative example 1(a) and the section transmission electron microscope figure of polypropylene/graphene nanocomposite material (b) of preparing of the embodiment of the present invention 1.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that, these embodiment are only for the present invention is described, and are not intended to limit the scope of the invention.Technician makes according to the present invention in actual applications improvement and adjustment, still belong to protection scope of the present invention.
comparative example 1
Get 5 parts of unmodified Graphenes and 100 parts of polypropylene mix, in Banbury mixer under 200 DEG C of temperature ranges melt blending 20min, obtain polypropylene/graphene nanocomposite material.
embodiment 1
(1) functionalized modification of Graphene: 1g graphite oxide and 200ml ethanol are mixed, ultrasonic dispersion 1h, ultrasonic frequency is 70Hz, obtains finely dispersed suspension; Under agitation condition, the ethanolic soln that adds 100ml to contain 10g hexanediamine, afterwards at N
2under protection, carry out back flow reaction 12h, temperature of reaction is 80 DEG C; Then adding 12g mass concentration is that 50% hydrazine hydrate solution carries out reduction reaction, and the reaction times is 6h; Finally cooling, suction filtration, product is alternately with deionized water and ethanol repetitive scrubbing, and the solid product obtaining is dry in the vacuum drying oven of 60 DEG C, obtains the Graphene that functionalisation of surfaces is modified.
(2) preparation of polypropylene grafted modified graphene: the Graphene of getting the above-mentioned functionalized modification of 0.5g is dispersed in the dimethylbenzene of 200ml, ultrasonic dispersion 1h, ultrasonic frequency is 70Hz; Then under agitation condition, add the polypropylene (percentage of grafting is 2%) of 2.5g maleic anhydride graft, reactant is in 140 DEG C of logical N
2reaction 5h; Last suction filtration, product washing with alcohol, the solid product obtaining is dry in the vacuum drying oven of 100 DEG C, obtains polypropylene grafted modified graphene.
(3) preparation of polypropylene/graphene nanocomposite material
The Graphene of 5 parts of polypropylene grafted modifications and 100 parts of polypropylene are mixed, in Banbury mixer under 200 DEG C of temperature ranges melt blending 20min, obtain graphene uniform disperse polypropylene/graphene nanocomposite material.
Graphite oxide of the present invention and polypropylene grafted modified graphene are carried out to Infrared spectroscopy, and result is referring to Fig. 1, after polypropylene grafted modification, and the characteristic feature carbonyl peak (1721cm of graphite oxide
-1) intensity weakens greatly, epoxy group(ing) (1225cm
-1) completely dissolve, ehter bond (1040cm
-1) peak widens, this is because C-N key newly-generated after amination causes.In addition, the Graphene of graft modification is at 2925cm
-1and 2845cm
-1the new peak that place occurs, corresponding to the c h bond on polypropylene, shows that polypropylene chains is successfully grafted to Graphene surface.
Described graphite oxide and polypropylene grafted modified graphene are carried out to Raman spectrum analysis, and result is referring to Fig. 2, and D is with at 1300-1360 wave number (cm
-1), G is with at 1570-1600 wave number (cm
-1), and the intensity rate (I of D band and G band
d/ I
g) show defect/greying intensity ratio of Graphene, wherein, the I of graphite oxide
d/ I
gbe 1.48, the grapheme modified I of polypropylene
d/ I
gbe 1.88, this is because the graft polypropylene that introduce on surface causes the surperficial order of Graphene to reduce, and shows graft modification success.
Fig. 3 is the scanning electron microscope diagram sheet that virgin pp and the present embodiment 1 are prepared polypropylene/graphene nanocomposite material section, can find out, virgin pp section smoother is even, the surface of polypropylene/grapheme material is relatively coarse, this is because the introducing of Graphene causes, wherein Graphene is dispersed in polypropylene, and does not obviously give prominence on surface, agglomeration.
The transmission electron microscope figure (Fig. 4) of polypropylene/graphene composite material section of preparing by comparative example 1 and comparative example 1, can draw: Graphene is before without any processing, in polypropylene, disperse very poor, can obviously observe lamella agglomeration, this be because between Graphene and polypropylene matrix without any reactive force; And adopt after this patent method, modified graphene can effectively be peeled off, be dispersed in matrix, therefore can find out that the application's patent can solve the key issue existing in polypropylene/graphene composite material process preparing, and has clear superiority.
embodiment 2
(1) functionalized modification of Graphene: 1g graphite oxide and 200ml ethanol are mixed, ultrasonic dispersion 1h, ultrasonic frequency is 70Hz, obtains finely dispersed suspension; Under agitation condition, the ethanolic soln that adds 150ml to contain 15g Ursol D, afterwards at N
2under protection, carry out back flow reaction 8h, temperature of reaction is 100 DEG C; Then adding 7g mass concentration is that 60% hydrobromic acid solution carries out reduction reaction, and the reaction times is 10h; Finally cooling, suction filtration, product is alternately with deionized water and ethanol repetitive scrubbing, and the solid product obtaining is dry in the vacuum drying oven of 80 DEG C, obtains the Graphene that functionalisation of surfaces is modified.
(2) preparation of polypropylene grafted modified graphene: the Graphene of getting the above-mentioned functionalized modification of 0.5g is dispersed in the dimethylbenzene of 200ml, ultrasonic dispersion 1h, ultrasonic frequency is 70Hz, obtains finely dispersed suspension; Then under agitation condition, add the polypropylene (containing 1% maleic anhydride) of 4g maleic anhydride graft, reactant is in 140 DEG C of logical N
2reaction 5h; Last suction filtration, product washing with alcohol, the solid product obtaining is dry in the vacuum drying oven of 100 DEG C, obtains the Graphene of polypropylene grafted modification.
(3) preparation of polyethylene/graphene nano composite material
The Graphene of 1 part of polypropylene grafted modification and 100 parts of polyethylene are mixed, in Banbury mixer under 180 DEG C of temperature ranges melt blending 25min, obtain graphene uniform disperse polyethylene/graphene nano composite material.
Polyethylene/graphene nano composite material prepared by the present embodiment obtains analog result as shown in Figure 1,2,3, 4 equally.
embodiment 3
(1) functionalized modification of Graphene: 1g graphite oxide and 200ml ethanol are mixed, ultrasonic dispersion 1h, ultrasonic frequency is 70Hz, obtains finely dispersed suspension; Under agitation condition, the ethanolic soln that adds 50ml to contain 5g diaminodiphenylmethane, afterwards at N
2under protection, carry out back flow reaction 2h, temperature of reaction is 120 DEG C; Then adding 20g mass concentration is that 40% sodium borohydride solution carries out reduction reaction, and the reaction times is 2h; Finally cooling, suction filtration, product is alternately with deionized water and ethanol repetitive scrubbing, and the solid product obtaining is dry in the vacuum drying oven of 50 DEG C, obtains the Graphene that functionalisation of surfaces is modified.
(2) preparation of polycthylene grafted modified graphene: the Graphene of getting the above-mentioned functionalized modification of 0.5g is dispersed in the dimethylbenzene of 200ml, ultrasonic dispersion 1h, ultrasonic frequency is 70Hz, obtains finely dispersed suspension; Then under agitation condition, add the polyethylene (containing 1.5% maleic anhydride) of 4g maleic anhydride graft, reactant is in 160 DEG C of logical N
2reaction 2h; Last suction filtration, product washing with alcohol, the solid product obtaining is dry in the vacuum drying oven of 120 DEG C, obtains the Graphene of polycthylene grafted modification.
(3) preparation of polypropylene/graphene nanocomposite material
The Graphene of 5 parts of polycthylene grafted modifications and 100 parts of polypropylene are mixed, in Banbury mixer under 160 DEG C of temperature ranges melt blending 30min, obtain graphene uniform disperse polypropylene/graphene nanocomposite material.
Polypropylene/graphene nanocomposite material prepared by the present embodiment obtains analog result as shown in Figure 1,2,3, 4 equally.
embodiment 4
(1) functionalized modification of Graphene: by 1g graphite oxide and 200ml methanol mixed, ultrasonic dispersion 1.5h, ultrasonic frequency is 40Hz, obtains finely dispersed suspension; Under agitation condition, the ethanolic soln that adds 200ml to contain 20g diaminodiphenylsulfone(DDS), afterwards at N
2under protection, carry out back flow reaction 24h, temperature of reaction is 60 DEG C; Then adding 7g mass concentration is that 30% sodium hydroxide solution carries out reduction reaction, and the reaction times is 12h; Finally cooling, suction filtration, product is alternately with deionized water and ethanol repetitive scrubbing, and the solid product obtaining is dry in the vacuum drying oven of 60 DEG C, obtains the Graphene that functionalisation of surfaces is modified.
(2) preparation of polycthylene grafted modified graphene: the Graphene of getting the above-mentioned functionalized modification of 0.5g is dispersed in the toluene of 200ml, ultrasonic dispersion 1.5h, ultrasonic frequency is 40Hz, obtains finely dispersed suspension; Then under agitation condition, add the polyethylene (containing 0.5% maleic anhydride) of 5g maleic anhydride graft, reactant is in 120 DEG C of logical N
2reaction 8h; Last suction filtration, product is with boiling toluene extraction, and the solid product obtaining is dry in the vacuum drying oven of 80 DEG C, obtains the Graphene of polycthylene grafted modification.Product washing with alcohol, obtains polycthylene grafted Graphene.
(3) preparation of polyethylene/graphene nano composite material
The Graphene of 10 parts of polycthylene grafted modifications and 100 parts of polyethylene are mixed, in Banbury mixer under 210 DEG C of temperature ranges melt blending 15min, obtain graphene uniform disperse polyethylene/graphene nano composite material.
Polyethylene/graphene nano composite material prepared by the present embodiment obtains analog result as shown in Figure 1,2,3, 4 equally.
embodiment 5
(1) functionalized modification of Graphene: 1g graphite oxide and 200ml propyl alcohol are mixed, ultrasonic dispersion 0.5h, ultrasonic frequency is 100Hz, obtains finely dispersed suspension; Under agitation condition, the ethanolic soln that adds 20ml to contain 2g diaminodiphenyl oxide, afterwards at N
2under protection, carry out back flow reaction 8h, temperature of reaction is 100 DEG C; Then adding 15g mass concentration is that 70% sodium sulfite solution carries out reduction reaction, and the reaction times is 5h; Finally cooling, suction filtration, product is alternately with deionized water and ethanol repetitive scrubbing, and the solid product obtaining is dry in the vacuum drying oven of 70 DEG C, obtains the Graphene that functionalisation of surfaces is modified.
(2) preparation of polypropylene grafted modified graphene: the Graphene of getting the above-mentioned functionalized modification of 0.5g is dispersed in the tetracol phenixin of 200ml, ultrasonic dispersion 0.5h, ultrasonic frequency is 100Hz, obtains finely dispersed suspension; Then under agitation condition, add the polypropylene (containing 4% maleic anhydride) of 1g maleic anhydride graft, reactant is in 130 DEG C of logical N
2reaction 6h; Last suction filtration, product washing with alcohol, the solid product obtaining is dry in the vacuum drying oven of 80 DEG C, obtains polypropylene grafted Graphene.
(3) preparation of polyolefine/graphene nanocomposite material
The Graphene of 5 parts of polypropylene grafted modifications, 50 parts of polypropylene and 50 parts of polyethylene are mixed, in Banbury mixer under 230 DEG C of temperature ranges melt blending 5min, obtain graphene uniform disperse polyolefine/graphene nanocomposite material.
Polyolefine/graphene nanocomposite material prepared by the present embodiment obtains analog result as shown in Figure 1,2,3, 4 equally.
Claims (10)
1. a preparation method for polyolefine/graphene nanocomposite material, is characterized in that: comprise the steps:
(1) functionalized modification of Graphene: graphite oxide is obtained to finely dispersed suspension by ultrasonic being dispersed in solvent; Then under agitation, add the ethanolic soln that contains diamine compounds, at N
2under protection, carry out back flow reaction 2-24h, temperature of reaction is 60-120 DEG C; Then add the reductive agent aqueous solution to carry out reduction reaction 2-12h; Finally cooling, suction filtration, product is alternately with deionized water and ethanol repetitive scrubbing, and the solid product obtaining is dry in the vacuum drying oven of 50-80 DEG C, obtains the Graphene that functionalisation of surfaces is modified; The consumption of described diamine compounds is 2-20 times of graphite oxide weight; The consumption of described reductive agent is 2-11 times of graphite oxide weight;
(2) preparation of Graft Modification of Polyolefine Graphene: by ultrasonic being dispersed in solvent of Graphene of preparation in step (1), then under agitation, add the maleic anhydride stem grafting polyolefin of 2-10 times of Graphene weight, pass into N at the temperature of 120-160 DEG C
2reaction 2-8h; Last suction filtration, product washing with alcohol, the solid product obtaining is dry in the vacuum drying oven of 80-120 DEG C, obtains Graft Modification of Polyolefine Graphene;
(3) preparation of polyolefine/graphene nanocomposite material: be by weight (1-10): 100, polyolefine graft grapheme prepared by step (2) and polyolefine mix, in Banbury mixer, in 160-230 DEG C of melt blending 5-30min, obtain polyolefine/graphene nanocomposite material.
2. the preparation method of a kind of polyolefine/graphene nanocomposite material according to claim 1, is characterized in that: in described step (1), the mass volume ratio of graphite oxide and solvent is 1g/200ml, and the mass concentration of the reductive agent aqueous solution is 30-70%.
3. the preparation method of a kind of polyolefine/graphene nanocomposite material according to claim 1, is characterized in that: in described step (1), diamine compounds is selected from the one in quadrol, propylene diamine, hexanediamine, O-Phenylene Diamine, mphenylenediamine, Ursol D, diaminodiphenyl oxide, diaminodiphenylsulfone(DDS), diaminodiphenylmethane.
4. the preparation method of a kind of polyolefine/graphene nanocomposite material according to claim 1, is characterized in that: the solvent in described step (1) is methyl alcohol, ethanol or propyl alcohol.
5. the preparation method of a kind of polyolefine/graphene nanocomposite material according to claim 1, is characterized in that: in described step (1), reductive agent is the one of hydrazine hydrate, urea, sodium borohydride, sodium bisulfite, S-WAT, sodium sulphite, ammoniacal liquor, Hydrogen bromide, hydroiodic acid HI.
6. the preparation method of a kind of polyolefine/graphene nanocomposite material according to claim 1, is characterized in that: the solvent in described step (2) is at least one in dimethylbenzene, toluene, tetracol phenixin.
7. the preparation method of a kind of polyolefine/graphene nanocomposite material according to claim 1, is characterized in that: in described step (3), polyolefine is at least one in polyethylene, polypropylene.
8. the preparation method of a kind of polyolefine/graphene nanocomposite material according to claim 1, is characterized in that: in described step (2), in maleic anhydride stem grafting polyolefin, the percentage of grafting of maleic anhydride is 0.5-4%.
9. the preparation method of a kind of polyolefine/graphene nanocomposite material according to claim 1, is characterized in that: the frequency of the ultrasonic dispersion in described step (1) and step (2) is that 40-100Hz, time are 0.5-1.5h.
10. polyolefine/the graphene nanocomposite material being made by preparation method described in claim 1.
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