CN106854387A - A kind of rubber antioxidant reduction and modified graphene oxide and preparation method and application - Google Patents
A kind of rubber antioxidant reduction and modified graphene oxide and preparation method and application Download PDFInfo
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- CN106854387A CN106854387A CN201710005595.3A CN201710005595A CN106854387A CN 106854387 A CN106854387 A CN 106854387A CN 201710005595 A CN201710005595 A CN 201710005595A CN 106854387 A CN106854387 A CN 106854387A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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Abstract
The invention discloses a kind of reduction of rubber antioxidant and modified graphene oxide and preparation method and application, the method can only be reduced and modified graphene oxide simultaneously with single step reaction, specially graphite oxide is mixed with water, ultrasound is peeled off, and obtains graphene oxide aqueous dispersions；Rubber chemicals solution is mixed with graphene oxide aqueous dispersions, heating stirring, obtain rubber antioxidant modified graphene.Reducing agent asepsis environment-protecting, method be simple and easy to apply in the present invention, reaction condition is gentle, and gained Graphene oxygen-containing functional group is low, conjugated degree is high；Part age resistor chemical graft is in graphenic surface, both the interface cohesion of Graphene dispersed in rubber, enhancing and rubber matrix can have been promoted to act on, the migration and volatilization of age resistor can be avoided again, its functioning efficiency is improved, so as to improve the performance of rubber/graphene composite material.The present invention is that green macroscopic preparation of graphene and acquisition high-performance rubber/graphene nanocomposite material provide new chance and approach.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of rubber chemicals reduction and modified graphene oxide and its system
Preparation Method and application.
Background technology
Graphene is a kind of two-dimentional conjugated structure nano material being made up of single layer of carbon atom, mechanics and pole with superelevation
The performances such as good heat conduction, conduction.Due to its unique chemical constitution and excellent combination property, Graphene becomes present material
The focus of area research, extensive concern is all caused in fields such as new energy, biotechnology, new materials.Graphene is usually
Obtained by reduction by graphene oxide, its main preparation method has chemical reduction method, solvothermal method, photo catalytic reduction
Method etc..Wherein, chemical reduction method due to process is simple, cost it is relatively low, be most to be expected to realize the extensive method for preparing Graphene
One of.Currently, the reducing agent that chemical reduction method is used is mainly hydrazine hydrate.However, hydrazine hydrate toxicity is big, and it is susceptible to quick-fried
It is fried.So, ensureing process is simple, on the premise of reaction condition is gentle, develops nontoxic, environmentally friendly reducing agent and just seem particularly heavy
Will.
Rubber as the indispensable strategic goods and materials of country, be national economy, new and high technology and defence and military field not
Alternative critical material.However, the intensity of rubber raw rubber and elasticity are undesirable, it is necessary to add reinforced filling and various rubber
Auxiliary agent can improve the combination property of rubber, obtain use value.Developing rapidly for current China's national defense military project is passed through with industry
Ji transition and upgrade the performance of rubber is proposed the fillers such as requirement higher, conventional carbon black, white carbon be difficult to meet using will
Ask.Graphene is applied in rubber composite as Nano filling, is expected to significantly improve the mechanics of material, thermal conductivity, is moved
The performances such as state viscoelastic, with vast potential for future development.However, be difficult in rubber be uniformly dispersed due to Graphene, and and rubber
Interface cohesion is weak, and its unique advantage is difficult to play.To solve above problem, Graphene is entered by additional organic matter mainly so far
Row is modified to improve its dispersion and interface cohesion in rubber, but modified technique is complicated, and high cost, pollution is big, and effect is failed to understand
It is aobvious.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of process is simple, reaction condition are gentle, cost
Low, free of contamination rubber antioxidant reduction and the preparation method of modified graphene oxide, additionally provide a kind of oxygen-containing functional group it is low,
Conjugated degree rubber antioxidant reduction high, dispersed in organic solvent and modified graphene oxide and its rubber combined
Application technology in material.
In order to solve the above technical problems, the present invention provides following technical scheme.
A kind of rubber antioxidant reduction and the preparation method of modified graphene oxide, comprise the following steps：
（1）Graphite oxide is mixed with water, ultrasound is peeled off, and obtains graphene oxide aqueous dispersions；
（2）Rubber antioxidant is dissolved in organic solvent, rubber antioxidant solution is formed；
（3）Rubber antioxidant solution is mixed with graphene oxide aqueous dispersions, the stirring reaction at 60 ~ 100 DEG C；
（4）By step（3）The washing of gained product, vacuum drying, obtain final product rubber antioxidant reduction and modified graphene oxide.
Preferably, step（1）The concentration of the graphene oxide aqueous dispersions is 0.5 ~ 1.5mg/ml.
Preferably, step（2）The rubber antioxidant is N- phenyl-N'- cyclohexyl p-phenylenediamine（Antioxidant 4010）、N,
N'- diphenyl-para-phenylene diamines（Antioxidant H）, N- isopropyls-N '-diphenyl-para-phenylene diamine（Antioxidant 4010NA）, N- (1,3- diformazans
Base) butyl-N'- diphenyl-para-phenylene diamines（Antioxidant 4020）, N, N'- diphenyl trimethylene diamines（Antioxidant D PD）, N- cyclohexyl-
P-nethoxyaniline（Age resistor CMA）In one kind.
Preferably, step（2）The organic solvent is methyl alcohol, ethanol, toluene, benzene, dimethylbenzene, acetone, ether and chloroform
In one or more mixed solvents.
Preferably, step（2）The quality of the rubber antioxidant is 0.5 ~ 3 times of graphite oxide quality, further preferably
It is 0.8 ~ 2 times, most preferably 1.75-2 times.
Preferably, step（2）The concentration of the rubber antioxidant solution is 5 ~ 15 mg/ml, more preferably 6 ~ 9
mg/ml。
Preferably, step（3）The time of the reaction is 1 ~ 8 hour, more preferably 3 ~ 6 hours.
Preferably, step（3）The temperature of the reaction is 65 ~ 90 DEG C, more preferably 70-85 DEG C.
Preferably, step（4）The vacuum drying temperature is 50 ~ 60 DEG C.
A kind of rubber antioxidant reduction and modified graphene oxide as obtained in above-described preparation method, the rubber are prevented
Old agent reduction and modified graphene oxide are applied to prepare in rubber composite.
Preferably, rubber antioxidant reduction and modified graphene oxide are in the list glue such as natural rubber and butadiene-styrene rubber and simultaneously
With the application in glue.
The present invention prepare rubber antioxidant reduction and modified graphene oxide can be applied to natural rubber, synthetic rubber with
And in blend compounds, there is significant reinforcement to rubber, promote vulcanization, improve the effects such as ageing-resistant, improvement heat conduction, conduction, can increase
Strong interfacial interaction between rubber and Graphene, improves the anti-aging property of rubber composite, reduces rubber product（As taken turns
Tire）Rolling resistance, while improve anti-slippery, had broad application prospects in the Rubber Industries such as green tire.
Compared with prior art, the invention has the advantages that：
（1）The invention provides a kind of preparation method using nontoxic rubber antioxidant as the Graphene of reducing agent, with anti-
Answer mild condition, the features such as the reaction time is short.The rubber antioxidant modified graphene surface oxygen functional group that is obtained is low, conjugation
Degree is high, structurally consummate.
（2）Partial rubber age resistor in the present invention as reducing agent can be supported on graphite by covalent bond or non-covalent bond
Alkene surface, realizes the surface organic modification to Graphene, so as to significantly improve modified graphene dispersion in organic solvent
Performance；Additionally, after rubber antioxidant is supported on graphenic surface, it can be avoided to migrate and volatilize, so as to reduce rubber chemicals
Physical Loss or Damage, improve its functioning efficiency, and mitigate the pollution to environment.
（3）The rubber antioxidant that the present invention is obtained is reduced and modified graphene oxide is due to have passed through surface organic modification,
Its dispersity in rubber is uniform, the interface cohesion enhancing between rubber, such that it is able to significantly improve rubber combined material
The performances such as the ageing-resistant, conductive of material, mechanics, Dynamic Viscoelastic, embody high-performance, multi-functional feature.
（4）Rubber antioxidant reduction and the preparation process is simple of modified graphene oxide that the present invention is provided, are conducive to protecting
Retaining ring border, reduces cost and realizes industrial applications.
Brief description of the drawings
Fig. 1 is the FTIR spectrograms of GO and 4020-G.
Fig. 2 a and Fig. 2 b are respectively the C1s high-resolution XPS spectrum figures of GO and 4020-G.
Fig. 3 is the thermogravimetric curve figure of GO and 4020-G.
Fig. 4 a and Fig. 4 b are respectively the TEM photos of HH-G and 4020-G.
Specific embodiment
Specific implementation of the invention is further described below in conjunction with example and accompanying drawing, but embodiments of the present invention
Not limited to this.
Embodiment 1
300mg graphite oxides are distributed in 300ml deionized waters, ultrasound is peeled off, form graphene oxide（GO）Moisture dissipates
Liquid；By 600mg rubber antioxidants N- (1,3- dimethyl) butyl-N'- diphenyl-para-phenylene diamines（Antioxidant 4020）It is dissolved in 120ml third
In ketone, and it is added in above-mentioned GO aqueous dispersions, stirring reaction 4.5 hours at 80 DEG C, after product is washed through ethanol, puts
Enter in vacuum drying oven, dried to constant weight at 60 DEG C, obtain antioxidant 4020 modified graphene（4020-G）.In order to preferably say
Bright characteristic of the invention, the Graphene of hydrazine hydrate reduction is prepared for by existing conventional method, is named as HH-G, to compare.
The infrared spectrogram of 4020-G manufactured in the present embodiment and GO（FTIR）As shown in Figure 1.As seen from the figure, contrast GO's
FTIR spectrograms, the spectrogram of 4020-G is in 1729 cm-1、1396 cm-1、1219 cm-1、1051 cm-1The oxygen-containing functional group at place absorbs
Peak substantially weakens even disappearance, and this explanation 4020 can effectively reduce GO.Additionally, occurred in that in the spectrogram of 4020-G C-N and
C-S（1100~1400 cm-1Near）Characteristic peak, the surfaces that this explanation 4020 has been supported on Graphene by chemical action.It is anti-
Old agent 4020 to the reduction effect of GO can also from Fig. 2 a, Fig. 2 b C1s high-resolution x-ray photoelectron spectroscopy figure（XPS）'s
Result is confirmed.As can be observed from Figure, C=O bond in GO, carbon oxygen singly-bound peak intensity it is very high, and by 4020 also
After original, the peak intensity of carbon and oxygen functional group substantially weakens, and again demonstrating 4020 can effectively reduce GO.Fig. 3 is GO, 4020-G
Thermogravimetric curve figure, in figure show, the mass fraction of contained MB is about 35 % in 4020-G.Fig. 4 a, Fig. 4 b be HH-G and
The transmission electron microscope of 4020-G（TEM）Photo.It can be seen that the surface of HH-G is had no with other materials, and 4020-G
Surface has nano-scale particle thing, and these particulate matters are the age resistor that reduced graphene surface is grafted on by chemical action
4020。
With 4020-G manufactured in the present embodiment and HH-G and butadiene-styrene rubber（SBR）It is compound, prepare SBR composites（SBR/
4020-G and SBR/HH-G）, its formula is as follows（Unit：phr）：SBR 100;Antioxidant 4020 2；Accelerant CZ 1.2;Oxygen
Change zinc 5；Stearic acid 2；Filler（4020-G or HH-G）4.It is pointed out that the 4020 of 4020-G surface graftings need to calculate
In total accelerator number, to ensure that accelerator number is identical contained by all formulas.
Static mechanical property result shows that 4020-G is more preferable to the reinforcing effect of the reinforcing effect than HH-G of SBR, and stretching is strong
Degree brings up to 12.6 MPa from 9.8, and tearing strength brings up to 23.9 kN/m from 20.5, and conductivity percolation threshold is down to 1.9 from 5.3
vol%.Dynamic Viscoelastic performance result shows that SBR/4020-G rubber composites are than SBR/HH-G rubber composite in 0 DEG C of tool
There is fissipation factor higher（tanδ）（Improve 5%）, and possess relatively low tan δ values at 60 DEG C（Reduce by 13%）.Result above is said
Bright, the wet-sliding resistant performance of SBR/4020-G rubber composites is improved, and rolling resistance declines, and illustrates that 4020-G is multiple in rubber for tire
Had a good application prospect in condensation material, can effectively reduce automobile fuel consumption and exhaust emissions, met national " energy-saving and emission-reduction "
The strategy of sustainable development.Additionally, oxidation of the oxidation induction period of SBR/4020-G composites than SBR/HH-G composite
Induction period increased 16 minutes.
Embodiment 2
200mg graphite oxides are distributed in 400ml deionized waters, ultrasound is peeled off, form graphene oxide（GO）Moisture dissipates
Liquid；By 600mg rubber antioxidant N- phenyl-N'- cyclohexyl p-phenylenediamine（Antioxidant 4010）It is dissolved in 60ml toluene, and adds
To in above-mentioned GO aqueous dispersions, stirring reaction 8 hours under the conditions of 60 DEG C after product is washed through ethanol, are put into vacuum baking
In case, dried to constant weight at 50 DEG C, obtain antioxidant 4010 modified graphene（4010-G）.
FTIR and13C nuclear-magnetism results are shown, compared with GO, the oxygen-containing functional group peak intensity in 4010-G is substantially reduced, while
Organic peak is occurred in that on spectrogram, illustrates that antioxidant 4010 can effectively reduce GO, and there is part age resistor to be supported on to be gone back
Surface of graphene oxide after original.
It is combined with 4010-G manufactured in the present embodiment and HH-G and SBR, prepares rubber composite, its formula is removed will be anti-old
Agent 4020 is changed into beyond 4010, and remaining is same as Example 1, while ensureing the antioxidant 4010 number phase contained by all formulas
Together.Result shows that 4010-G is dispersed with monolithic layer in SBR matrixes.The tensile strength of SBR/4010-G composites and
Tearing strength is higher by 2.3 MPa and 2.1 kN/m than SBR/HH-G composite respectively.
Embodiment 3
150mg graphite oxides are distributed in 100ml deionized waters, ultrasound is peeled off, form graphene oxide（GO）Moisture dissipates
Liquid；By 300mg rubber antioxidant N- isopropyls-N '-diphenyl-para-phenylene diamine（Antioxidant 4010NA）It is dissolved in 20ml absolute ethyl alcohols,
And be added in above-mentioned GO aqueous dispersions, stirring reaction 1 hour under the conditions of 100 DEG C, after product is washed through ethanol, it is put into
In vacuum drying oven, dried to constant weight at 55 DEG C, obtain antioxidant 4010NA modified graphene（4010NA-G）.
FTIR and XPS show that the oxygen-containing functional group in 4010NA-G is substantially reduced compared to GO, illustrates antioxidant 4010NA
GO can effectively be reduced.
It is combined with 4010NA-G manufactured in the present embodiment and HH-G and SBR, prepares rubber composite, its formula is removed will be anti-
Old agent 4020 is changed into beyond 4010NA, and remaining is same as Example 1, while ensureing the 4010NA number phases contained by all formulas
Together.Result shows that 4010NA-G is disperseed in SBR matrixes with monolithic layer.The tensile strength of SBR/4010NA-G composites and
Tearing strength is higher by 3.2 MPa and 4.0 kN/m than SBR/HH-G composite respectively.Meanwhile, SBR/4010NA-G composites
Oxidation induction period be increased 11 minutes than the oxidation induction period of SBR/HH-G composite.
Embodiment 4
60mg graphite oxides are distributed in 60ml deionized waters, ultrasound is peeled off, form graphene oxide（GO）Aqueous dispersions；
By 105mg rubber antioxidants N, N'- diphenyl trimethylene diamines（Antioxidant D PD）It is dissolved in 50ml toluene, and is added to above-mentioned GO
In aqueous dispersions, stirring reaction 6 hours under the conditions of 70 DEG C after product is washed through ethanol, are put into vacuum drying oven, 60
Dried to constant weight at DEG C, obtain antioxidant D PD modified graphenes（DPD-G）.
XPS and nuclear magnetic resonance13C is as a result, it was confirmed that DPD can effectively reduce GO.
It is combined with DPD-G manufactured in the present embodiment and HH-G and natural rubber (NR), prepares rubber composite, it is matched somebody with somebody
In addition to antioxidant 4020 is changed into DPD, its formula is same as Example 1, while ensureing DPD parts contained by all formulas for side
Number is identical.Result shows that DPD-G can significantly improve the heatproof air aging performance of composite, NR/DPD-G composites
Oxidation induction period improves 9 minutes than NR/HH-G composite, and tensile strength improves 2.6 MPa.
Embodiment 5
60mg graphite oxides are distributed in 60ml deionized waters, ultrasound is peeled off, form graphene oxide（GO）Aqueous dispersions；
By 105mg rubber antioxidants N- cyclohexyl-P-nethoxyaniline（Age resistor CMA）It is dissolved in 50ml toluene, and is added to above-mentioned
In GO aqueous dispersions, stirring reaction 6 hours under the conditions of 70 DEG C after product is washed through ethanol, are put into vacuum drying oven,
Dried to constant weight at 60 DEG C, obtain age resistor CMA modified graphenes（CMA-G）.
XPS and nuclear magnetic resonance13C is as a result, it was confirmed that CMA can effectively reduce GO.
It is combined with CMA-G manufactured in the present embodiment and HH-G and NR, prepares rubber composite, its formula is removed will be anti-old
Agent 4020 is changed into beyond CMA, and its formula is same as Example 1, while ensureing that the CMA numbers contained by all formulas are identical.Knot
Fruit shows that NR/CMA-G rubber composites have fissipation factor higher than NR/HH-G rubber composite at 0 DEG C（tanδ）
（Improve 8%）, and possess relatively low tan δ values at 60 DEG C（Reduce by 9%）；CMA-G can also significantly improve the heat-resisting of composite
Oxidative aging energy, the oxidation induction period of NR/CMA-G composites improves 9 minutes than NR/HH-G composite.
Claims (9)
1. a kind of rubber antioxidant reduces the preparation method with modified graphene oxide, it is characterised in that comprise the following steps：
（1）Graphite oxide is mixed with water, ultrasound is peeled off, and obtains graphene oxide aqueous dispersions；
（2）Rubber antioxidant is dissolved in organic solvent, rubber antioxidant solution is formed；
（3）Rubber antioxidant solution is mixed with graphene oxide aqueous dispersions, the stirring reaction at 60 ~ 100 DEG C；
（4）By step（3）The washing of gained product, vacuum drying, obtain final product rubber antioxidant reduction and modified graphene oxide.
2. preparation method according to claim 1, it is characterised in that step（1）The graphene oxide aqueous dispersions
Concentration is 0.5 ~ 1.5mg/ml.
3. preparation method according to claim 1, it is characterised in that step（2）The rubber antioxidant be N- phenyl-
N'- cyclohexyl p-phenylenediamine, N, N'- diphenyl-para-phenylene diamines, N- isopropyls-N '-diphenyl-para-phenylene diamine, N- (1,3- dimethyl)
Butyl-N'- diphenyl-para-phenylene diamines, N, the one kind in N'- diphenyl trimethylene diamines and N- cyclohexyl-P-nethoxyaniline.
4. preparation method according to claim 1, it is characterised in that step（2）The organic solvent be methyl alcohol, ethanol,
One or more mixed solvents in toluene, benzene, dimethylbenzene, acetone, ether and chloroform.
5. preparation method according to claim 1, it is characterised in that step（2）The quality of the rubber antioxidant is oxygen
0.5 ~ 3 times of graphite quality.
6. preparation method according to claim 1, it is characterised in that step（2）The concentration of the rubber antioxidant solution
It is 5 ~ 15mg/ml.
7. preparation method according to claim 1, it is characterised in that step（3）The time of the reaction is 1~8 hour.
8. a kind of rubber antioxidant is reduced and modified graphite oxide obtained in the preparation method as described in claim any one of 1-7
Alkene.
9. a kind of reduction of rubber antioxidant and modified graphene oxide described in claim 8 is applied in rubber composite.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314014A (en) * | 2018-03-14 | 2018-07-24 | 华南理工大学 | A kind of reduction of thiofide and modified graphene oxide and the preparation method and application thereof |
| CN109021293A (en) * | 2018-06-12 | 2018-12-18 | 华南理工大学 | A kind of functional graphene oxide support type rubber antioxidant and the preparation method and application thereof |
| CN109679155A (en) * | 2018-12-10 | 2019-04-26 | 内蒙古第一机械集团股份有限公司 | A kind of veneer list pin vehicle track pin bush(ing) rubber |
| CN109679156A (en) * | 2018-12-10 | 2019-04-26 | 内蒙古第一机械集团股份有限公司 | A kind of preparation method of veneer list pin vehicle track pin rubber bushing |
| CN112980217A (en) * | 2021-02-21 | 2021-06-18 | 安徽理工大学 | Modified GO-SiO2Preparation method of composite filler and application of composite filler in rubber |
| CN112980217B (en) * | 2021-02-21 | 2023-10-24 | 安徽理工大学 | Modified GO-SiO 2 Preparation method of composite filler and application of composite filler in rubber |
| CN113980357A (en) * | 2021-12-27 | 2022-01-28 | 河北铁科翼辰新材科技有限公司 | Functionalized graphene, preparation method thereof and application of functionalized graphene in rubber base plate |
| CN113980357B (en) * | 2021-12-27 | 2022-03-18 | 河北铁科翼辰新材科技有限公司 | Functionalized graphene, preparation method thereof and application of functionalized graphene in rubber base plate |
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Application publication date: 20170616 |