CN103483516A - Preparation method of graphene oxide-boron-modified phenolic resin - Google Patents
Preparation method of graphene oxide-boron-modified phenolic resin Download PDFInfo
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Abstract
The invention discloses a preparation method of graphene oxide-boron-modified phenolic resin, and relates to the phenolic resin. The preparation method comprises the following steps: firstly, preparing graphene oxide by an improved Hummers method; secondly, ultrasonically dispersing the obtained graphene oxide in a mixture of phenol and formaldehyde; thirdly, adding sodium hydroxide as a catalyst, and smoothly inserting small molecules of the phenolic resin into the middle of the graphene oxide through reaction between reactive groups of the graphene oxide itself and the phenol and the formaldehyde; finally, introducing boric acid, initiating the polymerization reaction between the small molecules in the phenolic resin in the graphene oxide and the boric acid by varying reaction conditions, and thus preparing the high-performance graphite oxide-boron-modified phenolic resin. With the preparation method, not only are the structure and the properties of grapheme maintained, but also certain retained oxygen-containing functional groups can well solve the problems of poor dispersion, solubility and processability of graphene and the like.
Description
Technical field
The present invention relates to resol, especially relate to a kind of preparation method of graphene oxide-boron modified phenolic resin.
Background technology
Resol, as one of three large synthetic thermosetting resins, has experienced and has exceeded century-old history, has been widely used in so far sizing agent, moulding compound, coating, porous plastics etc.Although amount ratio unsaturated polyester resin and epoxy resin are less, also in military industry field, building trade, automobile industry etc., bringing into play huge effect, not only with resin form, and obtain application with the form of matrix material.In order to make resol just need in resol, add various materials to carry out modification in the more application of wide spectrum, improve its over-all properties.Add inorganic nano material (nanometer SiO in the oriented resol of modification technology extensively adopted
2, nano-TiO
2, nano imvite (MMT) etc.), organic compound (organosilicon, organic boron, cashew nut shell oil etc.), mineral compound (boride, molybdenum etc.) etc.But a lot of modifications can only solely improve thermal characteristics or the mechanical property of resol, and can not improve its thermal characteristics and mechanical property simultaneously.In addition, inorganic particulate can't fully disperse in organic polymer, affects the performance of material.At present, the method that the raising inorganic particulate disperses in organic polymer has ultrasonic method, mechanical process and surface-modification method etc., but still is difficult to realize the compound of polymkeric substance and inorganic particulate.
Research about the boride modified phenolic resins shows, improving aspect resol resistance toheat and ablation resistance, and the effect of boron is remarkable.No matter introduce inorganic boride or organic boride in molecular structure, can both significantly improve resol thermotolerance and carbon residue rate ([1] Xu Peijun, Liu Yuhong, well is profit newly. boride Progress On Modified Pf Resin [J]. and aerospace material technique, 2009 (6): 1-5), but inorganic boride modified phenolic resins defect aspect manufacturability and mechanical property is still comparatively obvious.Therefore, need to add other compound to carry out modification, thereby improve the mechanical property of modified phenolic resins.
Graphene is the thinnest a kind of at present known material, and its thickness only has an atom, but because the singularity of this body structure makes it have very large hardness, hard 300 times than iron and steel.In addition, Graphene also has a lot of peculiar character aspect electricity and magnetic property, as room temperature quantum hall effect, bipolarity electrical effect, ferromegnetism, supraconductivity and high electronic mobility, especially its thermal conductivity can reach 5300W/ (mK), is more than 10 times of copper thermal conductivity.Therefore, Graphene has quite wide application prospect.And Graphene is applied in the middle of macromolecular material, be one of its application.Although Graphene has the huge market space, because the singularity of itself structure makes its suitability for industrialized production and the market requirement all be in the junior stage, much study also in development.In the end of the year 2012, European Union is following has given Nokia 13.5 hundred million dollars of reasearch funds with emerging technology tissue (Future Emerging Technologies), for the research of grapheme material (Graphene).It is many peculiar and be better than the physicochemical property of most of material now that this special hexagonal structure of Graphene contains it, as high specific surface area and good heat conductivility, mechanical property and electronics transmission capacity.At present, the main method for preparing Graphene has: mechanically peel method, chemical Vapor deposition process, epitaxial growth method, oxidation reduction process ([2] Chen Ruican, Wang Haiyan, Han Yonggang, Deng. oxidation reduction process prepares Graphene and sign [J] thereof. material Leader B: a research piece of writing, 26 (6): 114-117).
One of approach of using mineral carbon alkene excellent properties is graphene film and the compound matrix material for preparing of superpolymer.Producing such matrix material requires Graphene to be evenly distributed on matrix.But the structural stability of Graphene own and stronger Van der Waals force between layers, make its can not be well with other body materials carry out compound, thereby further research and development and the utilization of restriction Graphene.Therefore, generally by Graphene is carried out to chemical modification, usually the method adopted is the Hummers method, principle is similar to above-mentioned oxidation reduction process, graphite is obtained containing through row intercalation oxidation under cold condition with strong acid and enrich the oxy radical graphite oxide, obtain graphene oxide by the ultrasonic graphene oxide that obtains the nitrogen-atoms layer thickness again, improve consistency ([3] Deng Yao between itself and polymer monomer or polymkeric substance by introducing active group, Huang Xiaorong, Wu Xiaoling. the progress of graphene oxide composite material [J]. material Leader A: a summary piece of writing, 2012, 26 (8): 84-87).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of graphene oxide-boron modified phenolic resin.
The present invention includes following steps:
1) add the vitriol oil in three mouthfuls of round-bottomed flasks, then be placed in ice-water bath, add graphite and SODIUMNITRATE, then add solid potassium permanganate, keep the temperature of ice-water bath to be no more than 5 ℃, then add deionized water, holding temperature is reacted between 32～38 ℃, when reaction approaches terminal, at room temperature places, with the warm water dilution, then add H again
2o
2reduce remaining value Mn ion, till becoming glassy yellow to solution, then centrifuge washing to solution is neutral and detects in supernatant liquor without SO with barium salt
4 2-till, then use absolute ethanol washing, obtain graphene oxide after drying;
2) phenol and formaldehyde are added in the there-necked flask that agitator, thermometer, prolong are housed, then add graphene oxide, after ultrasonic dispersion, add flaky sodium hydrate, after the temperature rising reflux reaction, decompression dehydration, obtain graphene oxide resol emulsion;
3) to step 2) add boric acid in the graphene oxide resol emulsion of gained, after the temperature rising reflux reaction, pour out blackish green dope, be cooled to room temperature, obtain graphene oxide-boron modified phenolic resin after vacuum-drying.
In step 1), described graphite, the vitriol oil, SODIUMNITRATE, solid potassium permanganate, deionized water, H
2o
2mass ratio can be 1: (35～45): (0.3～0.6): (2.5～3.5): (40～60): (15～20); The time of described reaction can be 30～60min; The described time of at room temperature placing can be 72～96h; The temperature of described warm water can be 50～60 ℃; The condition of described centrifuge washing can be speed 10000～12000rpm, time 10～20min.
In step 2) in, the mass ratio of described phenol, formaldehyde, graphene oxide, flaky sodium hydrate can be 1: (0.97～1.14): (0.005～0.01): (0.01～0.03); The condition of described ultrasonic dispersion can be 50～60 ℃ of temperature, time 20～30min; The condition of described temperature rising reflux reaction can be 60～65 ℃ of temperature, time 1～2h.
In step 3), the add-on of described boric acid and the mass ratio of the phenol in step 1) can be 1: (0.13～0.27); The condition of described temperature rising reflux reaction can be 90～100 ℃ of temperature, time 1～2h; Described vacuum drying condition can be 50～60 ℃ of temperature, time 24～36h.
Principle of the present invention is: at first utilize improved Hummers method, prepare graphene oxide; Again by the ultrasonic dispersion in the mixed solution of phenol and formaldehyde of the graphene oxide of gained; Add subsequently sodium hydroxide as catalyzer, reacting between the active group that utilizes graphene oxide itself and phenol, formaldehyde, be inserted in the middle of the graphene oxide layer resol small molecules smoothly; Finally introduce boric acid, by changing reaction conditions, make resol small molecular and boric acid initiated polymerization in graphene oxide, thereby prepare high-performance graphene oxide-boron modified phenolic resin.
Principal feature of the present invention is: the controlled reduction of graphene oxide has not only kept structure and the performance (as good thermostability and mechanical property) of Graphene, but also gives its some new performance: the part oxygen-containing functional group of reservation can solve the difficult problems such as Graphene dispersiveness, solvability and poor in processability well.The carbon yield of this method is 70.41%, and more common boron modified phenolic resin thermal characteristics improves 2.1%.And its flexural strength is that 96.5MPa, tensile strength are that 48.3MPa, shock strength are 9.7kJ/m
2, more common boron modified phenolic resin flexural strength has increased by 46%, tensile strength has increased by 38%, shock strength is high by 53%.
The accompanying drawing explanation
The carbon yield that Fig. 1 is Graphene and graphene oxide in embodiment 2.In Fig. 1, mark ■ is graphene oxide; ● be Graphene.
The thermal destruction curve of carbon yield graphene oxide-boron modified phenolic resin that Fig. 2 is graphene oxide-boron modified phenolic resin, Graphene-boron modified phenolic resin and common boron modified phenolic resin in embodiment 2.In Fig. 2, mark ■ is Graphene-boron modified phenolic resin; ● be graphene oxide-boron modified phenolic resin;
for boron modified phenolic resin.
The shock strength that Fig. 3 is graphene oxide-boron modified phenolic resin and common boron modified phenolic resin in embodiment 2 relatively.In Fig. 3, a is graphene oxide-boron modified phenolic resin, and b is common boron modified phenolic resin.
The tensile strength that Fig. 4 is graphene oxide-boron modified phenolic resin and common boron modified phenolic resin in embodiment 2 relatively.In Fig. 4, a is graphene oxide-boron modified phenolic resin, and b is common boron modified phenolic resin.
The flexural strength that Fig. 5 is graphene oxide-boron modified phenolic resin and common boron modified phenolic resin in embodiment 2 relatively.In Fig. 5, a is graphene oxide-boron modified phenolic resin, and b is common boron modified phenolic resin.
Embodiment
Embodiment 1
The first step, graphene oxide preparation;
The vitriol oil to adding 75ml98% in three mouthfuls of round-bottomed flasks, then be placed in ice-water bath, then add the SODIUMNITRATE of graphite and the 1.6g of 3.5g, after stirring, slowly adds solid potassium permanganate, keeps stirring 2h, keeps the temperature of ice-water bath to be no more than 5 ℃; Then, slowly add deionized water, heat release with a small amount of Bubble formation strongly around here, holding temperature is reacted 45min between 32～38 ℃, and when reaction approaches terminal, the suspension liquid of black becomes dun dope, then at room temperature places 72h.By the 500ml temperature, be finally 60 ℃ of warm water dilutions, then drip 60mlH
2o
2reduce remaining value Mn ion (because excessive high manganese ion can to environment), till becoming glassy yellow to solution.Centrifuge washing (11000rpm, 20min), be washed till solution and be neutral and detect in supernatant liquor without SO with barium salt
4 2-till, then use absolute ethanol washing twice, the product after washing is dry in vacuum drying oven.Obtain graphene oxide after drying.
Second step, the preparation of graphene oxide liquid phenolic resin;
First 47g phenol and 56.8g formaldehyde are added in the there-necked flask that agitator, thermometer, prolong are housed, the graphene oxide 0.47g that adds again 1% phenol quality, add 1.4g flaky sodium hydrate (catalyzer) after 60 ℃ of ultrasonic dispersion 30min, continue to be warmed up to lentamente 65 ℃, after continuing back flow reaction 1.5h, decompression dehydration 15min.
The 3rd step, the preparation of graphene oxide-boron modified phenolic resin;
Add 9.3g boric acid in reaction vessel on last stage, be warmed up to 95 ℃, back flow reaction 2h, pour out blackish green dope while hot, is cooled to room temperature and obtains graphene oxide-boron modified phenolic resin, vacuum-drying 24h under 60 ℃ of conditions.
The first step, graphene oxide preparation;
The vitriol oil to adding about 75ml98% in three mouthfuls of round-bottomed flasks, then be placed in ice-water bath, then add 3.5g graphite and 1.6g SODIUMNITRATE, after stirring, slowly adds solid potassium permanganate, keeps stirring 2h, keeps the temperature of ice-water bath to be no more than 5 ℃; Then, slowly add deionized water, heat release with a small amount of Bubble formation strongly around here, holding temperature is reacted 45min between 32～38 ℃, and when reaction approaches terminal, the suspension liquid of black becomes dun dope, then at room temperature places 72h.By the 500ml temperature, be finally 60 ℃ of warm water dilutions, then drip 60mlH
2o
2reduce remaining value Mn ion (because excessive high manganese ion can to environment), till becoming glassy yellow to solution.Centrifuge washing (10000rpm, 15min), be washed till solution and be neutral and detect in supernatant liquor without SO with barium salt
4 2-till, then use absolute ethanol washing twice, the product after washing is dry in vacuum drying oven.Obtain graphene oxide after drying.
Second step, the preparation of graphene oxide liquid phenolic resin;
First 47g phenol and 56.8g formaldehyde are added in the there-necked flask that agitator, thermometer, prolong are housed, the graphene oxide 0.235g that adds again 0.5% phenol quality, add 1.4g flaky sodium hydrate (catalyzer) after 60 ℃ of ultrasonic dispersion 30min, continue to be warmed up to lentamente 65 ℃, after continuing back flow reaction 1.5h, decompression dehydration 15min.
The 3rd step, the preparation of graphene oxide-boron modified phenolic resin;
Add 9.3g boric acid in reaction vessel on last stage, be warmed up to 95 ℃, back flow reaction 2h, pour out blackish green dope while hot, is cooled to room temperature and obtains graphene oxide-boron modified phenolic resin, vacuum-drying 24h under 60 ℃ of conditions.
The residual rate of Graphene is 85.44% as can be seen from Figure 1, and weightless reason may be the moisture that Graphene also has the unreduced oxy radical of small part and interlayer, makes Graphene produce weightlessness 0～200 ℃ of stage.And the carbon yield of graphene oxide is 44.49%, its thermolysis is divided into two stages: in the mass loss in 0～100 ℃ of stage, be mainly to contain losing of moisture in due to graphene oxide to cause; Be that mass loss may be oxy radical generation thermolysis in graphene oxide at 150～240 ℃, produced CO, CO
2and H
2o causes.
As can be seen from Figure 2, graphene oxide-boron modified phenolic resin is mild than other two groups, and its carbon yield is 70.41%.Obviously be better than Graphene modified phenolic resins 53.08% and common boron modified phenolic resin 68.31%.
From Fig. 3～5, can find out, when being doped into a small amount of graphene oxide, the flexural strength of graphene oxide-boron modified phenolic resin is 96.5MP
a, tensile strength is 48.3MP
a, shock strength is 9.7kJ/m
2, more common boron modified phenolic resin flexural strength has increased by 46%, and tensile strength has increased by 38%, and shock strength is high by 53%.
Claims (10)
1. the preparation method of a graphene oxide-boron modified phenolic resin is characterized in that comprising the following steps:
1) add the vitriol oil in three mouthfuls of round-bottomed flasks, then be placed in ice-water bath, add graphite and SODIUMNITRATE, then add solid potassium permanganate, keep the temperature of ice-water bath to be no more than 5 ℃, then add deionized water, holding temperature is reacted between 32～38 ℃, when reaction approaches terminal, at room temperature places, with the warm water dilution, then add H again
2o
2reduce remaining value Mn ion, till becoming glassy yellow to solution, then centrifuge washing to solution is neutral and detects in supernatant liquor without SO with barium salt
4 2-till, then use absolute ethanol washing, obtain graphene oxide after drying;
2) phenol and formaldehyde are added in the there-necked flask that agitator, thermometer, prolong are housed, then add graphene oxide, after ultrasonic dispersion, add flaky sodium hydrate, after the temperature rising reflux reaction, decompression dehydration, obtain graphene oxide resol emulsion;
3) to step 2) add boric acid in the graphene oxide resol emulsion of gained, after the temperature rising reflux reaction, pour out blackish green dope, be cooled to room temperature, obtain graphene oxide-boron modified phenolic resin after vacuum-drying.
2. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, is characterized in that in step 1) described graphite, the vitriol oil, SODIUMNITRATE, solid potassium permanganate, deionized water, H
2o
2mass ratio be 1: (35～45): (0.3～0.6): (2.5～3.5): (40～60): (15～20).
3. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, is characterized in that in step 1), and the time of described reaction is 30～60min.
4. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, is characterized in that in step 1), and the described time of at room temperature placing is 72～96h.
5. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, is characterized in that in step 1), and the temperature of described warm water is 50～60 ℃.
6. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, is characterized in that in step 1), and the condition of described centrifuge washing is speed 10000～12000rpm, time 10～20min.
7. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, it is characterized in that in step 2) in, the mass ratio of described phenol, formaldehyde, graphene oxide, flaky sodium hydrate is 1: (0.97～1.14): (0.005～0.01): (0.01～0.03).
8. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, is characterized in that in step 2) in, the condition of described ultrasonic dispersion is 50～60 ℃ of temperature, time 20～30min.
9. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, is characterized in that in step 2) in, the condition of described temperature rising reflux reaction is 60～65 ℃ of temperature, time 1～2h.
10. a kind of preparation method of graphene oxide-boron modified phenolic resin as claimed in claim 1, is characterized in that in step 3), and the add-on of described boric acid and the mass ratio of the phenol in step 1) are 1: (0.13～0.27); The condition of described temperature rising reflux reaction can be 90～100 ℃ of temperature, time 1～2h; Described vacuum drying condition can be 50～60 ℃ of temperature, time 24～36h.
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