CN109467656A - A kind of New type atom transferred free radical technology synthesis graphene oxide/poly styrene composite material and preparation method thereof - Google Patents
A kind of New type atom transferred free radical technology synthesis graphene oxide/poly styrene composite material and preparation method thereof Download PDFInfo
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- CN109467656A CN109467656A CN201811141407.0A CN201811141407A CN109467656A CN 109467656 A CN109467656 A CN 109467656A CN 201811141407 A CN201811141407 A CN 201811141407A CN 109467656 A CN109467656 A CN 109467656A
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Abstract
The invention discloses a kind of New type atom transferring free-radical polymerization technologies to synthesize graphene oxide poly styrene composite material, it is based on graphene oxide, polystyrene is the graphene oxide based composites of macromolecular chain, wherein, nano graphene oxide is obtained after oxidation processes, polystyrene is covalently bonded to the surface of nano graphene oxide, also discloses preparation method.The problems such as a kind of preparation method of graphene oxide composite material provided by the invention, product is difficult to clean during capable of improving conventional preparation techniques, seriously polluted；It is high molecular to solve the problems, such as that the more difficult valence bond of graphene oxide closes simultaneously；While not influencing composite property have environmental protection, it is easy to operate, it is inexpensive the features such as；Preparation method of the invention, step is simple, easy to operate, and preparation condition is mildly easy to control, high-efficient.
Description
Technical field
The present invention relates to organic polymer fields more particularly to a kind of New type atom transferring free-radical polymerization technology to synthesize oxygen
Graphite alkene poly styrene composite material and preparation method thereof.
Background technique
Graphene oxide is a kind of new carbon haveing excellent performance, specific surface area with higher and surface official abundant
It can group.Graphene oxide composite material, which includes polymerization species composite material, and inorganic species composite material is even more has widely
Application field, therefore the surface of graphene oxide is modified as a research emphasis.
However, modern crafts are when using atom transferred free radical technology (ATRP) surface modified graphene oxide, usually
Use alkyl halide as active matter, the hydroxyl with surface of graphene oxide, carboxyl, epoxy group and unsaturated conjugated double bond it
Between valence bond close, but efficiency is general lower and relatively difficult.And the residual of metal salt is always to restrict its application in polymer
One of problem.Heavy metallic salt not only accelerates the aging of polymer, but also limits application of the resulting polymers in medical material.
The catalysis controllable polymerization reaction of no metal includes the controllable polymerization for making catalyst with organic compound, this kind of reaction
Advantage is do not have remaining metal impurities in gained polymerizate, greatly expands the application range of polymer.Green ring
It protects, reduces experimental cost, the surface modification of graphene oxide is had a very important significance and is worth, there is good hair
Exhibition prospect.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides a kind of synthesis of New type atom transferring free-radical polymerization technology
Graphene oxide poly styrene composite material and preparation method thereof；Experimental procedure is simple, and pure organic catalyst avoids metal
Introducing, greatly improve the residue problem of metal impurities in polymerizate, it is environmentally protective and easy to operate, reduce experiment at
This, expands the application field of polymer.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, is with nano oxidized graphite
Based on alkene, polystyrene is macromolecular chain covalent bonding in surface of graphene oxide, forms the composite wood of graphite oxide alkenyl
Material, the nano graphene oxide pass through oxidation processes, the styrene by atom transferred free radical technology covalent bond with
The surface of the graphene oxide.
A kind of New type atom transferred free radical technology synthesis graphene oxide/poly styrene composite material preparation method,
The following steps are included:
The surface treatment of S1, graphene oxide: graphene oxide, preparation are handled using the organic reaction liquid with acyl function
Provide active graphene oxide；
S2, styrene and graphene oxide it is compound: the active graphene oxide that will be prepared in S1 passes through atom
Transferred free radical technology and styrene are compound, so that the polystyrene generated covalently bind in surface of graphene oxide；Form oxygen
Fossil mertenyl composite material.
Further, in the S1 early period of graphene oxide oxidation processes, specifically includes the following steps:
S1.1, graphene oxide is taken, be dissolved in n,N-Dimethylformamide, 5~15min of ultrasonic disperse is placed on flask
It is interior；
S1.2, it is put into triethanolamine, 5-10min is placed in ice-water bath and is reduced to 0 DEG C, is stirred evenly；Flask is vacuumized and is filled
Nitrogen repeatedly 3-5 times until the air in flask is drained, 2- bromo isobutyl acylbromide is added, is sufficiently stirred after 5-10min slowly
It is warming up to 70-80 DEG C, is reacted 16-20 hours；
S1.3, reaction product is washed 3-5 times with chloroform, unreacted reactant is cleaned, 60 DEG C of -80 DEG C of dryings of vacuum
20-24 hours, obtain active graphene oxide composite material.
Innovation of the invention is:
(1) present invention can be realized the uniform compound of polystyrene and graphene oxide, promote the comprehensive performance of composite material；
(2) present invention is evenly dispersed in polystyrene by nano graphene oxide, is greatly improved polystyrene material
Properties；
(3) oxidation processes for carrying out early period in the present invention to graphene oxide first, increase its surface by the position of active function groups
Point makes styrene in-situ polymerization on graphene oxide followed by using novel atom transferred free radical technology (ATRP),
And then prepare novel oxidized graphene poly styrene composite material；Wherein, graphene oxide makes by the oxidation processes of early period
Surface-active functional group become it is more, make it possible in-situ polymerization styrene and efficiency raising；New type atom transfer is freely
Base polymerization technique (ATRP) makes active graphene oxide become substrate, and pure organic catalyst is recycled to keep styrene poly- in situ
It closes on graphene oxide, the combination of covalent bond makes graphene oxide is more uniform to be dispersed in polystyrene material, oxygen
The evenly dispersed properties for making polystyrene material of graphite alkene obtain very big promotion；Compared with current techniques, not only
Solve the problems, such as in polymerizate that metal residual difficulty removes, also add the application of polymerizate, improve polystyrene with
The load capacity of graphene oxide, covalent bond between the two are dispersed in graphene oxide in polystyrene material,
The performance advantage of graphene oxide is greatly played.
(4) under the premise of not influencing graphene oxide and polystyrene composite effect, preparation method of the invention is simple
It is easy, it is environmentally protective, and experimental cost is reduced, it is high-efficient.
Detailed description of the invention
Fig. 1 is the TEM figure of graphene oxide of the present invention；
Fig. 2 is the TEM figure of composite material of the present invention.
Specific embodiment
The present invention is described further in the following with reference to the drawings and specific embodiments.It should be noted that below
Technical characteristic involved in the described each embodiment of the present invention can be tied mutually as long as they do not conflict with each other
It closes.
Composite material of the invention first makes it have certain activity by graphene oxide by oxidation processes early period, then makes
Make surface of graphene oxide in-situ polymerization polyphenyl second using atom transfer radical polymerisation technique (ATRP) with pure organic catalyst
Alkene macromolecular chain, to obtain the graphene oxide poly styrene composite material using graphene oxide as substrate, polystyrene is total
Valence link closes the surface with graphene oxide.
Fig. 2 is New type atom transferred free radical technology (ATRP) synthesis graphene oxide polystyrene composite wood of the invention
The TEM of material schemes, and as can be seen from the figure the design feature of this product is that polystyrene is attached to surface of graphene oxide, in figure
Dash area indicates that polystyrene has uniformly been attached to above.
Embodiment 1
A kind of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, is with nano oxidized graphite
Based on alkene, polystyrene is macromolecular chain covalent bonding in surface of graphene oxide, forms the composite wood of graphite oxide alkenyl
Material.Wherein, nano graphene oxide passes through oxidation processes, and styrene passes through atom transferred free radical technology covalent bond and oxidation
The surface of graphene.
A kind of preparation method of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, packet
Include following steps:
Oxidation processes early period of S1, graphene oxide: handling graphene oxide using the organic reaction liquid with acyl function,
Prepare active graphene oxide；
S2, styrene and graphene oxide it is compound: at 80 DEG C, the active graphene oxide that will be prepared in S1
It is compound by atom transferred free radical technology and styrene, so that the polystyrene generated covalently bind in graphene oxide table
Face；Form graphene oxide based composites.
Embodiment 2
A kind of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, is with nano oxidized graphite
Based on alkene, polystyrene is macromolecular chain covalent bonding in surface of graphene oxide, forms the composite wood of graphite oxide alkenyl
Material.Wherein, nano graphene oxide passes through oxidation processes, and styrene passes through atom transferred free radical technology covalent bond and oxidation
The surface of graphene.
A kind of preparation method of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, packet
Include following steps:
Oxidation processes early period of S1 graphene oxide:
S1.1,0.2g graphene oxide is taken, be dissolved in 30ml n,N-Dimethylformamide, ultrasonic disperse 10min is placed on
In flask；
S1.2, it is put into 1ml triethanolamine, 10min is placed in ice-water bath and is down to 0 DEG C, is stirred evenly.By flask vacuum nitrogen filling
Gas repeatedly 3 times until the air in flask is drained, 1ml 2- bromo isobutyl acylbromide is added, slowly heats up after 5min is sufficiently stirred
To 80 DEG C, react 18 hours；
S1.3, reaction product is cleaned 5 times with chloroform, unreacted reactant is cleaned, the drying 24 hours of 70 DEG C of vacuum,
Obtain active graphene oxide composite material；
S2 styrene and graphene oxide it is compound:
S2.1, active graphene oxide 0.5g is taken to be dissolved in 30ml n,N-Dimethylformamide, ultrasonic disperse 5 ~
15min；
S2.2, the styrene 40ml being added after purification, reaction flask vacuumize, and inflated with nitrogen 3 times repeatedly；
S2.3,2ml triethanolamine is added, 1ml 2- bromo isobutyl acylbromide is added while stirring, 5 are sufficiently stirred in a nitrogen atmosphere
~10min；
S2.4, temperature slowly risen to 80 DEG C, reacted 16 ~ 20 hours, reaction product washes of absolute alcohol is not repeatedly until will
The monomer and organic solvent of reaction remove, and product is in canescence, the drying 20 ~ 24 hours of 60 DEG C ~ 80 DEG C of vacuum；Up to graphite oxide
Alkene poly styrene composite material.
Embodiment 3
A kind of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, is with nano oxidized graphite
Based on alkene, polystyrene is macromolecular chain covalent bonding in surface of graphene oxide, forms the composite wood of graphite oxide alkenyl
Material.Wherein, nano graphene oxide passes through oxidation processes, and styrene passes through atom transferred free radical technology covalent bond and oxidation
The surface of graphene.
A kind of preparation method of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, packet
Include following steps:
Oxidation processes early period of S1 graphene oxide:
S1.1,0.2g graphene oxide is taken, be dissolved in 30ml n,N-Dimethylformamide, ultrasonic disperse 10min is placed on
In flask；
S1.2, it is put into 2ml triethanolamine, 10min is placed in ice-water bath and is down to 0 DEG C, is stirred evenly.By flask vacuum nitrogen filling
Gas repeatedly 3 times until the air in flask is drained, 1ml 2- bromo isobutyl acylbromide is added, slowly heats up after 5min is sufficiently stirred
To 80 DEG C, react 18 hours；
S1.3, reaction product is cleaned 5 times with chloroform, unreacted reactant is cleaned, the drying 24 hours of 70 DEG C of vacuum,
Obtain active graphene oxide composite material；
S2 styrene and graphene oxide it is compound:
S2.1, active graphene oxide 0.5g is taken to be dissolved in 30ml n,N-Dimethylformamide, ultrasonic disperse 5 ~
15min；
S2.2, the styrene 40ml being added after purification, reaction flask vacuumize, and inflated with nitrogen 3 times repeatedly；
S2.3,2ml triethanolamine is added, 1ml 2- bromo isobutyl acylbromide is added while stirring, 5 are sufficiently stirred in a nitrogen atmosphere
~10min；
S2.4, temperature slowly risen to 80 DEG C, reacted 16 ~ 20 hours, reaction product washes of absolute alcohol is not repeatedly until will
The monomer and organic solvent of reaction remove, and product is in canescence, the drying 20 ~ 24 hours of 60 DEG C ~ 80 DEG C of vacuum；Up to graphite oxide
Alkene poly styrene composite material.
Embodiment 4
A kind of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, is with nano oxidized graphite
Based on alkene, polystyrene is macromolecular chain covalent bonding in surface of graphene oxide, forms the composite wood of graphite oxide alkenyl
Material.Wherein, nano graphene oxide passes through oxidation processes, and styrene passes through atom transferred free radical technology covalent bond and oxidation
The surface of graphene.
A kind of preparation method of New type atom transferred free radical technology synthesis graphene oxide poly styrene composite material, packet
Include following steps:
Oxidation processes early period of S1 graphene oxide:
S1.1,0.2g graphene oxide is taken, be dissolved in 30ml n,N-Dimethylformamide, ultrasonic disperse 10min is placed on
In flask；
S1.2, it is put into 3ml triethanolamine, 10min is placed in ice-water bath and is down to 0 DEG C, is stirred evenly.By flask vacuum nitrogen filling
Gas repeatedly 3 times until the air in flask is drained, 1ml 2- bromo isobutyl acylbromide is added, slowly heats up after 5min is sufficiently stirred
To 80 DEG C, react 18 hours；
S1.3, reaction product is cleaned 5 times with chloroform, unreacted reactant is cleaned, the drying 24 hours of 70 DEG C of vacuum,
Obtain active graphene oxide composite material；
S2 styrene and graphene oxide it is compound:
S2.1, active graphene oxide 0.5g is taken to be dissolved in 30ml n,N-Dimethylformamide, ultrasonic disperse 5 ~
15min；
S2.2, the styrene 40ml being added after purification, reaction flask vacuumize, and inflated with nitrogen 3 times repeatedly；
S2.3,2ml triethanolamine is added, 1ml 2- bromo isobutyl acylbromide is added while stirring, 5 are sufficiently stirred in a nitrogen atmosphere
~10min；
S2.4, temperature slowly risen to 80 DEG C, reacted 16 ~ 20 hours, reaction product washes of absolute alcohol is not repeatedly until will
The monomer and organic solvent of reaction remove, and product is in canescence, the drying 20 ~ 24 hours of 60 DEG C ~ 80 DEG C of vacuum；Up to graphite oxide
Alkene poly styrene composite material.
Degree of oxidation is different when aoxidizing graphene oxide by comparing different proportion of the invention, when 2- bromo isobutyl
Acylbromide: when triethanolamine is 1:1, degree of oxidation is little, when 2- bromo isobutyl acylbromide: when triethanolamine is 1:2 and 1:3, oxidation
Degree is essentially identical, and graphene oxide has had activity at this time, lays the groundwork for the in-situ polymerization of following styrene.Graphite oxide
When the different amounts of styrene of alkene in-situ polymerization, weightless temperature is changed, it is higher to measure more weightless temperatures, illustrates to aoxidize stone
The black more styrene of alkene in-situ polymerization.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore the changes or modifications that claim under this invention and specification are done in every case, it all should belong to the range that the invention patent covers
Within.
Claims (3)
1. a kind of New type atom transferred free radical technology synthesizes graphene oxide/poly styrene composite material, which is characterized in that with
Based on nano graphene oxide, polystyrene is macromolecular chain covalent bonding in surface of graphene oxide, forms graphite oxide
The composite material of alkenyl, the nano graphene oxide pass through oxidation processes, and the styrene passes through atom transferred free radical skill
Art is covalently bonded in the surface of the graphene oxide.
2. a kind of New type atom transferred free radical technology synthesis graphene oxide/polystyrene according to claim 1 is multiple
The preparation method of condensation material, which comprises the following steps:
The surface treatment of S1, graphene oxide: graphene oxide, preparation are handled using the organic reaction liquid with acyl function
Provide active graphene oxide；
S2, styrene and graphene oxide it is compound: the active graphene oxide that will be prepared in S1 passes through atom
Transferred free radical technology and styrene are compound, and the polystyrene of generation covalently bind in surface of graphene oxide, form oxidation stone
Mertenyl composite material.
3. a kind of New type atom transferred free radical technology synthesis graphene oxide polystyrene according to claim 2 is compound
The preparation method of material, which is characterized in that the oxidation processes of the early period of graphene oxide in the S1 specifically include following step
It is rapid:
S1.1, graphene oxide is taken, be dissolved in n,N-Dimethylformamide, 5~15min of ultrasonic disperse is placed on flask
It is interior；
S1.2, it is put into triethanolamine, 5-10min is placed in ice-water bath and is reduced to 0 DEG C, is stirred evenly；Flask is vacuumized and is filled
Nitrogen repeatedly 3-5 times until the air in flask is drained, 2- bromo isobutyl acylbromide is added, is sufficiently stirred after 5-10min slowly
It is warming up to 70-80 DEG C, is reacted 16-20 hours；
S1.3, reaction product is washed 3-5 times with chloroform, unreacted reactant is cleaned, 60 DEG C of -80 DEG C of dryings of vacuum
20-24 hours, obtain active graphene oxide composite material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627977A (en) * | 2019-09-27 | 2019-12-31 | 黔南民族师范学院 | Preparation method of graphene oxide grafted styrene |
| CN114085484A (en) * | 2021-11-26 | 2022-02-25 | 江南大学 | High-strength high-toughness composite material, preparation method and application |
-
2018
- 2018-09-28 CN CN201811141407.0A patent/CN109467656A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627977A (en) * | 2019-09-27 | 2019-12-31 | 黔南民族师范学院 | Preparation method of graphene oxide grafted styrene |
| CN114085484A (en) * | 2021-11-26 | 2022-02-25 | 江南大学 | High-strength high-toughness composite material, preparation method and application |
| CN114085484B (en) * | 2021-11-26 | 2022-09-27 | 江南大学 | High-strength high-toughness composite material, preparation method and application |
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