CN110437407A - A kind of preparation method of the modified ether-ether of graphene oxide - Google Patents
A kind of preparation method of the modified ether-ether of graphene oxide Download PDFInfo
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- CN110437407A CN110437407A CN201910885690.6A CN201910885690A CN110437407A CN 110437407 A CN110437407 A CN 110437407A CN 201910885690 A CN201910885690 A CN 201910885690A CN 110437407 A CN110437407 A CN 110437407A
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- ether
- graphene oxide
- preparation
- reaction
- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention discloses a kind of preparation methods of the modified ether-ether of graphene oxide, obtain pre-oxidation object using graphite, phosphorus pentoxide, potassium peroxydisulfate and strong sulfuric acid response, graphene oxide is made with potassium permanganate and strong sulfuric acid response again in pre-oxidation object.The graphene oxide is the presoma of graphene, and a kind of nano material, surface contains a large amount of oxide groups, it is not only made to obtain good dispersion in a polymer matrix, and provides a large amount of active sites, to form stable chemical bond with polymeric matrix.
Description
Technical field
The present invention relates to graphene technical field of modification, and in particular to a kind of preparation side of the modified ether-ether of graphene oxide
Method.
Background technique
Polymer polyatomic alcohol is widely used in sponge family property, footwear material and high-speed rail aircraft due to good performance
Deng interior trim.But its structure is simpler, hardness, tear strength and in terms of can't use up people's will, therefore limit
Its extensive use.
Therefore a kind of modified ether-ether of graphene oxide is researched and developed, product mechanical property not only can be improved, can also improve product
Thermal property is suitable for entire polyurethane industries among others.
Summary of the invention
The present invention is directed to missing of the existing technology, and its object is to propose a kind of system of modified ether-ether of graphene oxide
The hardness and tear strength of ether-ether not only can be improved, moreover it is possible to improve the thermal stability of product in Preparation Method.
It is a further object of the present invention to provide the purposes of the above method.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of the modified ether-ether of graphene oxide, the ether-ether use crystalline flake graphite, specifically include following step
It is rapid:
1) graphite, phosphorus pentoxide, potassium peroxydisulfate are injected into the concentrated sulfuric acid, are uniformly mixed, reaction solution A is made.
2) first reaction solution A heating is reacted, then reaction solution A is cooled to room temperature, be finally washed with deionized to
Neutrality obtains pre-oxidation object.
3) obtained pre-oxidation object is added in the concentrated sulfuric acid, cold bath stirring is then slowly added into potassium permanganate, maintains
At a certain temperature, mixed liquor is made in temperature.
4) mixed liquor is added distilled water heating, reaction, reaction solution B is made in water-bath.
5) by reaction solution B down to dropwise addition hydrogen peroxide in distilled water until becoming glassy yellow, then by centrifugation, dialysis to anti-
Liquid B is answered to be post-processed, last ultrasonic disperse obtains the aqueous dispersions of graphene oxide.
6) polymer polyatomic alcohol, azodiisobutyronitrile are uniformly mixed under the conditions of nitrogen, condensed water and are slowly added into oxygen
In the aqueous dispersions of graphite alkene, graphene oxide/polymer polyatomic alcohol ether-ether is made in this way.
Preferably, the relative mass of graphite described in the step 1), phosphorus pentoxide, potassium peroxydisulfate and the concentrated sulfuric acid it
Than being 1-5: 1-5: 2-6: 30-40.
Preferably, the step 1), concentrated sulfuric acid concentration described in step 3) are 98%.
Preferably, the technological parameter in the step 2) are as follows: 70-90 DEG C of reaction temperature, reaction time 3-5h.
Preferably, the ratio between pre-oxidation object described in the step 3), the relative mass of potassium permanganate and the concentrated sulfuric acid are 1-5
∶5-10∶50-60。
Preferably, the technological parameter in the step 4) are as follows: water-bath 35-45 DEG C of reaction 1-1.5h, 95-105 DEG C of reaction 15-
25min。
Preferably, polymer polyatomic alcohol described in the step 6), azodiisobutyronitrile and graphene oxide water dispersion
The ratio between relative mass of liquid is 1-5: 40-50: 95-105.
Preferably, the technological parameter in the step 6) are as follows: 80-90 DEG C of reaction temperature, it is more that polymer is slowly added dropwise in early period
The mixed liquor of the pure and mild azodiisobutyronitrile of member is into the aqueous dispersions of graphene oxide, time for adding 1-2h.
To realize above-mentioned second purpose, the technical solution adopted by the present invention is that:
The method is preparing the application on polymer polyatomic alcohol.
As can be seen from the above description, the present invention compared with prior art, present invention has the advantage that:
1, the present invention selects the crystalline flake graphite of layer structure to prepare graphene oxide, convenient for dispersion, and provides a large amount of
Active site, to form stable chemical bond with polymeric matrix；
2, preparation method of the invention effectively improves product hardness, tear strength and thermal stability, meets continuous improvement
Downstream customer requirement；
3, the modified ether-ether of the graphene that the present invention develops will can sufficiently meet the market demand, improve the competitiveness of product,
Superfluous production capacity is reduced, market product quality is greatly improved.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
A kind of preparation method of the modified ether-ether of graphene oxide, the ether-ether use crystalline flake graphite, specifically include following step
It is rapid:
1) graphite, phosphorus pentoxide, potassium peroxydisulfate are injected into the concentrated sulfuric acid, are uniformly mixed, reaction solution A is made.
2) first reaction solution A heating is reacted, then reaction solution A is cooled to room temperature, be finally washed with deionized to
Neutrality obtains pre-oxidation object.
3) obtained pre-oxidation object is added in the concentrated sulfuric acid, cold bath stirring is then slowly added into potassium permanganate, maintains
At a certain temperature, mixed liquor is made in temperature.
4) mixed liquor is added distilled water heating, reaction, reaction solution B is made in water-bath.
5) by reaction solution B down to dropwise addition hydrogen peroxide in distilled water until becoming glassy yellow, then by centrifugation, dialysis to anti-
Liquid B is answered to be post-processed, last ultrasonic disperse obtains the aqueous dispersions of graphene oxide.
6) polymer polyatomic alcohol, azodiisobutyronitrile are uniformly mixed under the conditions of nitrogen, condensed water and are slowly added into oxygen
In the aqueous dispersions of graphite alkene, graphene oxide/polymer polyatomic alcohol ether-ether is made in this way.
Preferably, the relative mass of graphite described in the step 1), phosphorus pentoxide, potassium peroxydisulfate and the concentrated sulfuric acid it
Than being 1-5: 1-5: 2-6: 30-40.
Preferably, the step 1), concentrated sulfuric acid concentration described in step 3) are 98%.
Preferably, the technological parameter in the step 2) are as follows: 70-90 DEG C of reaction temperature, reaction time 3-5h.
Preferably, the ratio between pre-oxidation object described in the step 3), the relative mass of potassium permanganate and the concentrated sulfuric acid are 1-5
∶5-10∶50-60。
Preferably, the technological parameter in the step 4) are as follows: water-bath 35-45 DEG C of reaction 1-1.5h, 95-105 DEG C of reaction 15-
25min。
Preferably, polymer polyatomic alcohol described in the step 6), azodiisobutyronitrile and graphene oxide water dispersion
The ratio between relative mass of liquid is 1-5: 40-50: 95-105.
Preferably, the technological parameter in the step 6) are as follows: 80-90 DEG C of reaction temperature, it is more that polymer is slowly added dropwise in early period
The mixed liquor of the pure and mild azodiisobutyronitrile of member is into the aqueous dispersions of graphene oxide, time for adding 1-2h.
Embodiments of the present invention are able to further illustrative illustrate and not restrictive by following embodiment.
Prepare the general process of pre-oxidation object graphene oxide of the present invention:
Firstly, by 3g graphite, 3g P2O5,3g K2S2O8；Add people into the 40mL concentrated sulfuric acid, 80 DEG C of mixed liquor, reacts 5h
Afterwards, reaction solution is cooled to room temperature, is washed with deionized to neutrality and obtains pre-oxidation object；
Secondly, slowly adding people into the 50mL concentrated sulfuric acid 1.5g pre-oxidation object, ice-water bath stirs about 30min, then will
6g KMnO4 slowly adds people and temperature is maintained at 10 DEG C, hereinafter, after 2h, reaction to be transferred in 35 DEG C of water-baths and reacts 1h, then plus people
100mL distilled water makes temperature rise to 98 DEG C, and reaction solution is fallen in the certain distilled water of people and H2O2 is added dropwise until becoming by reaction 15min
Then glassy yellow post-processes reaction solution by centrifugation, dialysis；
Last ultrasonic disperse obtains graphene oxide aqueous dispersions.
General technology is produced using the modified ether-ether of graphene as described below, using graphene oxide of the present invention and
Polymer polyatomic alcohol product is obtained in the case where without using graphene oxide of the present invention.
Using the general technology of graphene oxide of the present invention, firstly, preparing the oxygen that graphene oxide mass fraction is 0.1%
Graphite alkene/polymer polyatomic alcohol, by 10g graphene oxide aqueous dispersions (2mg/g) plus people into container, in N2, condensed water
Under the conditions of, the pure and mild 0.3g azodiisobutyronitrile of 5g polymer polyol is uniformly mixed, is warming up to 85 DEG C, takes one third mixing single
Body is slowly added dropwise in people's container, and after reacting 30min, residual monomer is added in 1h.Prepare oxidation respectively in the same way
Graphene oxide/polymer polyatomic alcohol that graphene mass fraction is 0.2%, 0.3%, 0.4% and 0.5%.
By preparing graphene oxide of the present invention/polymer polyatomic alcohol preparation general process.It will then not use
The polymer polyatomic alcohol of graphene oxide, as a comparison polymer polyatomic alcohol.
The raw material substantially the same with above procedure, identical 5 batches of solid content, respectively as embodiment are used respectively
1-5 and comparative example 1-5.
Measure the hardness, tear strength and oxidation resistance temperature of these polymer polyatomic alcohols.The embodiment 1-5 and comparative example
Hardness, tear strength and the oxidation resistance temperature measurement result of 1-5 is summarised in table 1.As can be seen from the table using of the invention
After preparation method, hardness, tear strength and the oxidation resistance temperature of product are substantially improved.
Table 1 is hardness, tear strength and the oxidation resistance temperature measurement result of polymer polyatomic alcohol
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should be included within the protection scope of invention.
Claims (9)
1. a kind of preparation method of the modified ether-ether of graphene oxide, which is characterized in that the ether-ether is specifically wrapped using crystalline flake graphite
Include following steps:
1) graphite, phosphorus pentoxide, potassium peroxydisulfate are injected into the concentrated sulfuric acid, are uniformly mixed, reaction solution A is made.
2) first reaction solution A heating is reacted, then reaction solution A is cooled to room temperature, be finally washed with deionized to neutrality,
Obtain pre-oxidation object.
3) obtained pre-oxidation object is added in the concentrated sulfuric acid, cold bath stirring is then slowly added into potassium permanganate, maintains temperature
At a certain temperature, mixed liquor is made.
4) mixed liquor is added distilled water heating, reaction, reaction solution B is made in water-bath.
5) by reaction solution B down to dropwise addition hydrogen peroxide in distilled water until becoming glassy yellow, then by centrifugation, dialysis to reaction solution
B is post-processed, and last ultrasonic disperse obtains the aqueous dispersions of graphene oxide.
6) polymer polyatomic alcohol, azodiisobutyronitrile are uniformly mixed under the conditions of nitrogen, condensed water and are slowly added into oxidation stone
In the aqueous dispersions of black alkene, graphene oxide/polymer polyatomic alcohol ether-ether is made in this way.
2. a kind of preparation method of the modified ether-ether of graphene oxide according to claim 1, it is characterised in that: the step
1) the ratio between relative mass of graphite, phosphorus pentoxide, potassium peroxydisulfate and the concentrated sulfuric acid described in is 1-5: 1-5: 2-6: 30-40.
3. a kind of preparation method of the modified ether-ether of graphene oxide according to claim 1, it is characterised in that: the step
1), concentrated sulfuric acid concentration described in step 3) is 98%.
4. a kind of preparation method of the modified ether-ether of graphene oxide according to claim 1, it is characterised in that: the step
2) technological parameter in are as follows: 70-90 DEG C of reaction temperature, reaction time 3-5h.
5. a kind of preparation method of the modified ether-ether of graphene oxide according to claim 1, it is characterised in that: the step
3) the ratio between pre-oxidation object, the relative mass of potassium permanganate and the concentrated sulfuric acid described in are 1-5: 5-10: 50-60.
6. a kind of preparation method of the modified ether-ether of graphene oxide according to claim 1, it is characterised in that: the step
4) technological parameter in are as follows: water-bath 35-45 DEG C of reaction 1-1.5h, 95-105 DEG C of reaction 15-25min.
7. a kind of preparation method of the modified ether-ether of graphene oxide according to claim 1, it is characterised in that: the step
6) the ratio between relative mass of polymer polyatomic alcohol, azodiisobutyronitrile and graphene oxide aqueous dispersions described in is 1-5:
40-50∶95-105。
8. a kind of preparation method of the modified ether-ether of graphene oxide according to claim 1, it is characterised in that: the step
6) technological parameter in are as follows: 80-90 DEG C of reaction temperature, the mixing of the pure and mild azodiisobutyronitrile of polymer polyol is slowly added dropwise early period
Liquid is into the aqueous dispersions of graphene oxide, time for adding 1-2h.
9. method as claimed in claim 1 to 7 is preparing the application on polymer polyatomic alcohol.
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Application publication date: 20191112 |