CN106423274B - A kind of composite material and preparation method and application of the macromolecule grafting carbon nanotube of sulfonic acid functional - Google Patents
A kind of composite material and preparation method and application of the macromolecule grafting carbon nanotube of sulfonic acid functional Download PDFInfo
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Abstract
The present invention relates to the composite material and preparation methods and application of a kind of macromolecule of sulfonic acid functional grafting carbon nanotube.By covalence graft, the carbon nanotube (CNT-PSSA) of the multi-walled carbon nanotube (CNT-PVSAIC) of poly- (the chlorfulfonated imidazoles of 3- vinyl -1-) grafting, the multi-walled carbon nanotube (CNT-PVSAPC) of poly- (4- vinyl -1- chlorosulfonic acid pyridiniujm) grafting and polystyrolsulfon acid grafting is obtained.Esterification of the solid acid catalyst prepared by the present invention for the ester exchange reaction and oleic acid and methanol of triglyceride and methanol, shows fabulous catalytic activity, can reduce the cost of industrial production biodiesel, and improve the yield of biodiesel.
Description
Technical field
Macromolecule (the P-SO of carbon nanotube and sulfonic acid functional3H) composite material (the CNT-P- that covalence graft obtains
SO3H), it is used for ester exchange reaction and esterification as the solid acid of carbon-based material, shows significant catalytic performance.CNT-
P-SO3The outstanding property of H catalyst is attributed to the fact that meso-hole structure and the P-SO that the outer surface CNT is coated3Long-chain.Such structure
So that the intensive active site in carbon nanotube outer surface is uniformly distributed.Thus, it is possible to promote the contact between reactant and be conducive to examination
Agent is detached from catalyst.These properties make CNT-P-SO3H composite material becomes a kind of ideal carbon material solid acid and hands over for ester
Change reaction and esterification.
Sulfonated macromolecule is covalently grafted onto carbon nanotube and obtains a series of polymer-carbon nanotube composites
Material.Many walls nanotube (CNT-PVSAIC) is grafted including poly- (the chlorfulfonated imidazoles of 3- vinyl -1-), poly- (4- vinyl -1- chlorine
Sulfonated pyridine) graft multi-walled carbon nanotube (CNT-PVSAPC) and polystyrolsulfon acid grafting multi-walled carbon nanotube (CNT-
PSSA).In order to improve the dispersibility of carbon nanotube and adjust acidity, this Functionalization is easy to get various carbon nano tube surfaces
Polyelectrolyte brush.For potential catalytic applications, selectively introduces functional group on the carbon nanotubes and densely create activity
Position.CNT-PVSAIC and CNT-PVSAPC includes by the functionalized cationic polyelectrolyte chain of sulfonic group.But CNT-PSSA
It is made of the anionic polymer brush that sulfonic group is grafted.In the ester exchange reaction and oleic acid and first of triglyceride and methanol
In the esterification of alcohol, resulting CNT-P-SO3H material shows significant catalytic as carbon-based solid acid in the liquid phase
Energy.CNT-P-SO3The excellent in performance of H material is attributed to meso-hole structure and one layer of P-SO is wrapped up in carbon nanotube outer surface3H high score
Son provides intensive but unified active sites surface distribution.In addition, the active sites of surface exposure are conducive to the contact of reactant,
And reagent can be promoted to be detached from catalyst.These feature performance benefits make CNT-P-SO3H synthetic material is conducive to as carbon-based solid acid
Ester exchange reaction and esterification.
Background technique
Biodiesel refines from vegetable and animals oils, is commonly used to tractor, truck, ship etc..It refers to oil crops such as
The water plants such as soybean, rape, cotton, palm etc., Wild oil plant and engineering microalgae grease and animal fat, food and drink rubbish
Rubbish oil etc. can be replaced the reproducibility diesel fuel of petrifaction diesel by feedstock oil made of ester exchange process.Biodiesel is raw
One kind of substance energy, it is a kind of monoalkyl ester for long chain fatty acids that the technologies such as biomass economy thermal cracking obtain.Biological bavin
Oil is the mixture of the high complicated organic principle of oxygen content, these mixtures are mainly the big organic matter of number molecular weight, several
It include the oxygen-bearing organic matter of all kinds, such as: ether, aldehyde, ketone, phenol, organic acid, alcohol.Composite biodiesel is with discarded
Vegetable and animals oils, used oil and oil plant byproduct be raw material, add catalyst, closed through special equipment and special process
At.
A kind of substitute as non-renewable petroleum diesel increasingly causes to pay close attention to.Currently, the life of industrial bio diesel oil
Production is mainly based upon ester exchange reaction and esterification to obtain fatty acid methyl ester.By can be with base catalyst or acid catalyst
Improve yield.It is easy to the recycling of simple product separation and catalyst using solid acid catalyst.Except this time, solid acid is used
Catalyst is because in petroleum, the ester exchange reaction of triglyceride while promotes free fatty acid as preferred
Esterification and no saponification.Therefore, during production of biodiesel, solid acid can be reduced production stage.Thus
Meet the requirement of catalyzed production biodiesel Green and sustainable chemistry.Pass through the ester exchange reaction and trip of triglyceride
Esterification from fatty acid, various solid acid catalysts have been used to the synthesis of fatty acid methyl ester.Sulfonic group is agraphitic carbon,
Referred to as " sugared catalyst " promotes the diffusion of organic reagent because of the surface nature of their hydrophobic oleophilic oils, in catalyst surface acid
Property-SO3The presence of H functional group, report are referred to as a kind of very promising acid material.But most of sulfonation agraphitic carbons
Specific surface area is extremely low, thus limits reactant molecule close to acidic site.In addition, sugared catalyst generally uses oleum sulfonation
Partially carbonized organic molecule is made, and random, unformed acid position is obtained in catalyst surface.The above problem, which can overcome, is gathering around
There is the carbon edge-SO of the nano structural material of a big surface area3The selective deposition problem of H functional group, to promote big
Molecule reactant oxytropism site it is close.
By improving synthesis control, a series of by carbon nanotube, carbon nano-fiber, the solid acid that graphene derives possesses
Fine structure, adjustable surface composition, texture and acidity.Coming in, they are developed to answer for carbon-based acidic catalyst
For various reactions.For example, poly- (4- p styrene sulfonic acid) grafting carbon nanotube (CNT-PSSA) is dehydrated to obtain 5- for fructose
The esterification of hydroxymethylfurfural and lauric acid and methanol.Report points out, the hydridization of heteropoly acid and the functionalized carbon nanotube of nitrogen
Material can be used for the hydrolysis of ethyl acetate, the Beckmann rearrangement and toluene of cyclohexanone oxime and the Friedel-Crafts of positive octene
Reaction.The polyaniline sulfate of deposition on the carbon nanotubes is exploited for the methanol decomposition reaction of triglyceride.Benzene sulfonic acid
Functionalized carbon nano-fiber generates 5- methylol for the dehydration of the ester exchange reaction and fructose of triglyceride and methanol
The reaction of furfural.The graphene of sulfonation and the graphene oxide of sulfonation may act on the hydrolysis of ethyl acetate, ethyl acetate
With the ester exchange reaction of alcohols, xylose is dehydrated into furfural, and carbohydrate is converted into levulic acid, and hydroxymethylfurfural is converted into giving birth to
Object fuel.
Summary of the invention
In view of the foregoing, it is an object to provide the composite wood of the macromolecule grafting carbon nanotube of sulfonic acid functional
Material and its preparation method and application.Specific technical solution is as follows:
A kind of composite material of the macromolecule grafting carbon nanotube of sulfonic acid functional, has the following structure formula:
Wherein, Y indicates the degree of polymerization of recyclable poly- (the chlorfulfonated imidazoles of 3- vinyl -1-), is 5000~6000
Integer, X indicate the degree of polymerization of irretrievable poly- (the chlorfulfonated imidazoles of 3- vinyl -1-), are 2000~3000；
It is on the left of structural formula multi-walled carbon nanotube (CNT).
The preparation method of above-mentioned composite material, includes the following steps:
(1) it weighs 40~60mg carbon nanotube and is put into preparatory Si Laike bottles of drying for being equipped with magnetic stirrer, vacuumize, rush
Nitrogen, in triplicate；
(2) open the flow rate of big nitrogen, measure respectively 200~300mL DMF (n,N-Dimethylformamide) and 0.5~
Described Si Laike bottles of the injection of 1.0mL 1- vinyl imidazole, the Si Laike bottles of logical nitrogen are put into Ultrasound Instrument, ultrasound 0.5
~1.5h；
(3) ultrasound finishes, and 5~10mg initiator is added, places a device into 65~75 DEG C of constant temperature oil baths under a nitrogen atmosphere
40~50h is stirred to react in pot；
(4) after having reacted, nitrogen valve is closed, reaction unit is taken out from oil bath pan, is cooled to room temperature；It is dilute with DMF reagent
It releases to 400~600mL；Centrifuge separation is removed the black solid on centrifugation tube wall, is filtered with nylon membrane, and with DMF and anhydrous
Ethyl alcohol rinses, and drains；
(5) black product is removed from nylon membrane, is dried in 75~85 DEG C of vacuum ovens, is obtained PVI/CNT；
(6) 40~60mg PVI/CNT, 200~300mL 1,2- dichloroethanes and 0.1~0.15mL chlorosulfonic acid are weighed
In Si Laike bottles；At room temperature, be stirred to react 1.5~2.5h, then in 60~70 DEG C of thermostatical oil bath reaction 20~
30h；After having reacted, it is centrifugated resulting solid product CNT-PVSAIC, is rinsed with methylene chloride and anhydrous ether, water pump is taken out
It is dry, dry 20~30h in 75~85 DEG C of vacuum ovens.
The initiator is AIBN.
The application of above-mentioned composite material is used for ester exchange reaction and esterification, shows fabulous catalytic activity, can drop
The cost of low industrial production biodiesel, and improve the yield of biodiesel.
The ester exchange reaction is the ester exchange reaction of triglyceride and methanol, and the esterification is oleic acid and methanol
Esterification.
The ester exchange reaction of triglyceride and methanol, process are as follows:
The esterification of oleic acid and methanol, process are as follows:
Advantages of the present invention is embodied in: the solid acid catalyst of preparation is used for the ester exchange reaction of triglyceride and methanol
With the esterification of oleic acid and methanol, fabulous catalytic activity is shown, the cost of industrial production biodiesel can be reduced, and
Improve the yield of biodiesel.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of 1 composite material of embodiment；
Fig. 2 is the molecular structure of CNT-PVSAIC；
Fig. 3 is pure nano-carbon tube and CNT-P-SO3The Fourier transform infrared spectroscopy of H composite material；
Fig. 4 is the nitrogen adsorption-desorption isothermal curve and corresponding pore size distribution curve of three kinds of catalyst；
Fig. 5 is the TG curve of CNT-PVSAIC, CNT-PVSAPC and CNT-PSSA；
Fig. 6 is the XRD curve of CNT-PVSAIC, CNT-PVSAPC, CNT-PSSA and CNT；
Fig. 7 is the Raman curve of CNT-PVSAIC, CNT-PVSAPC, CNT-PSSA and CNT；
Fig. 8 is high resolution transmission electron microscope figure, in which: (a), (b), (c) are CNT-PVSAIC, CNT- respectively
PVSAPC and CNT-PSSA；
Fig. 9 is the schematic diagram that reaction condition influences product；Wherein: being (a) CNT-PVSAIC catalysis tributyrin
It is distributed with the product of the ester exchange reaction of methanol；It (b) is influence of the temperature to the ester exchange reaction of tributyrin and methanol；
It (c) is influence of the molar ratio of tributyrin and methanol to tributyrin methanol decomposition reaction；
Figure 10 is catalyst circulation recycling schematic diagram.
Specific embodiment
In the following, further illustrating the content of present invention with embodiment, but protection scope of the present invention is not limited in implementing
Example.The others that those skilled in the art makes without departing substantially from spirit of that invention and protection scope are changed and repaired
Change, is included within the scope of the present invention.
Embodiment 1
Fourier Transform Infrared Spectroscopy is analyzed using Bruker Tensor 27spectrotometer type infrared spectrometer,
Using KBr support chip, in 400~4000cm-1The skeletal vibration and infrared absorption peak of record sample in range.Take sample (about
2mg) and dry potassium bromide powder (about 100mg) is in agate mortar, and mixture is firmly ground into uniform superfine powder
End, then (107Pa) is pressed into self-supporting circle sheet (the area 2cm being almost transparent on tablet press machine2).Fu of sample sheet
In the infrared transform analysis of leaf connection computer Bruker Tensor 27spectrotometer infrared spectrometer on,
1cm-1Spectral resolution and 128 accumulative conditions of scanning under analyzed.The FT-IR figure of catalyst is as shown in Figure 3.
For CNT-PVSAIC, Fourier transform infrared spectroscopy is in 1066cm-1Characteristic peak is shown, corresponding is symmetrical N-
SO3The stretching vibration of key shows to be successfully incorporated into sulfonic acid group on imidazole ring, 1290 centimetres and 1178 centimetres of strong absworption peak
Corresponding is the stretching vibration of asymmetric and symmetrical S-O key in sulfonic acid group.In addition, the broad peak pair of 3430 centimeters
Answer the stretching vibration of O-H key in sulfonic acid group.The absorption peak of 1638 centimetres and 1463 centimeters respectively corresponds the C=in imidazole ring
The stretching vibration of N key and C=C key.The peak of 3110 centimetres and 850 centimeters respectively corresponds the stretching vibration of C-H key in imidazole ring
And bending vibration.
In the Fourier transform infrared spectroscopy of CNT-PVSAPC, the three of 1054 centimetres, 1162 centimetres and 1235 centimeters
A characteristic peak respectively corresponds N-SO2The vibration mode of key, O-SO2The symmetrical and asymmetric extension vibration mode of key.Thus, it was demonstrated that
SO3N-SO between N in H group and pyridine ring3The formation of H key.The corresponding wide absorption peak of 3417 centimeters is SO3H base
The stretching vibration of O-H in group.C=C key, the vibration peak of C=N key is respectively in 1506 centimetres and 1652 centimeters.On the other hand,
The peak position of c h bond stretching vibration and bending vibration in PVSAPC sections of pyridine ring is respectively 3123 centimetres and 850 centimetres.With
On each group peak mentioned confirm [C5H5N–SO3H] Cl structure presence.Finally, the Fourier transform infrared spectroscopy of CNT-PSSA
It coincide with documents and materials result.The strong characteristic peak of 1593 centimetres and 1392 centimeters respectively indicates stretching vibration and the sulfonic acid of phenyl
Group.Likewise, the broadband peak centered on 3445 centimetres corresponds to SO3The stretching vibration of-OH functional group in H group.2918 lis
Rice and the characteristic peak of 2816 centimeters respectively correspond the absorption of vibrations of the asymmetric and symmetric of C-H key in alkane.It is above-mentioned as a result,
Fourier transform infrared spectroscopy result is confirmed in obtained CNT-P-SO3Polymer P-SO in H composite material3The presence of H.
Embodiment 2
The measurement of the specific surface area of catalyst, pore-size distribution and Kong Rong in SI-MP-10/PoreMaster 33,
It is completed on Quantachrome adsorption instrument.BET specific surface area is measured using the nitrogen adsorption desorption under liquid nitrogen temperature 77K (- 196 DEG C)
And pore-size distribution, sample pre-process for 24 hours under 120 DEG C of high vacuum.In 0.05 < P/P0Brunauer- is used in < 0.3 range
Emmett-Teller (BET) calculates specific surface area；Sample is calculated using Barrett-Joyner-Halenda (BJH) method
Pore size distribution curve, Kong Rong is determined by Density Functional Theory (DFT) method.As shown in Figure 4.
Using relative pressure as X-axis, nitrogen adsorption capacity is Y-axis, then X-axis relative pressure is roughly classified into low pressure (0.0-
0.1), middle pressure (0.3-0.8), three sections of high pressure (0.90-1.0).It is known that adsorption curve is in low-pressure end X so from Fig. 4
Axis then illustrates three kinds of catalyst materials CNT-PVSIAC, CNT-PVSAPC, CNT-PSSA and CNT and nitrogen interaction force
It is weaker；Intermediate voltage terminal is mostly nitrogen in the intracorporal accumulation of catalyst backbone support, be may determine that by it as mesoporous analysis.The side BJH
Method is namely based on the pore size data that this section obtains；High pressure section deduces the accumulation degree of molecule in institute's sample.
The feature of hysteresis loop corresponds to specific pore structure information.The producing cause of hysteresis loop, this is because capillary is solidifying
Poly- effect makes N2Molecule is being filled with mesopore orbit lower than condensation under normal pressure, and taking place is the ring on hole wall when capillary condensation
It is carried out on shape adsorbed film liquid level, and being desorbed is since the spherical meniscus liquid level in aperture, therefore Adsorption and desorption isotherms do not coincide,
Often form a hysteresis loop.And catalyst and the hysteresis loop of carbon nanotube belong to H in Fig. 43Type, the adsorbance ratio of high-voltage end
It is larger, so that hysteresis loop thermoisopleth is not obviously saturated absorption platform in higher relative pressure region.Show carbon pipe supporter
Cellular structure is not very regular, it is believed that is constantly to be accumulated to obtain long and narrow slot apertures by the ground of platy particle in layer.
Embodiment 3
The thermogravimetric analysis of carbon-based solid acid catalyst sample is on TA Instrument Q600 SDT type thermogravimetric analyzer
Carry out, temperature elevating range be room temperature~600 DEG C, heating rate 10K/min, carrier gas flux 50mL/min, sample mass be 5~
10mg.As shown in Figure 5.
CNT-P-SO is had studied by TG-DTA analysis (TG-DTA, Fig. 5)3The thermal stability of H composite material.Fig. 5 is aobvious
The weight loss variation with temperature curve of CNT, CNT-PVSAIC, CNT-PVSAPC and CNT-PSSA are shown.As expected,
For pure nano-carbon tube until 600 DEG C, mass loss is negligible.But CNT-P-SO3The macromolecule of H composite material is degraded
Keep it weightless obvious.CNT-PVSAIC probably starts at 227 DEG C obvious weightless, and similarly, probably at 214 DEG C, it is poly- by CNT-PVSAPC
It closes object to start to crack, the glass transition temperature of CNT-PSSA is 309 DEG C.Obviously, CNT-PSSA ratio CNT-PVSAIC and CNT-
The thermal stability of PVSAPC is higher.In addition, according to their own thermogravimetric as a result, by comparing CNT-P-SO3H composite material with
Weight loss between pure nano-carbon tube estimates CNT-P-SO3P-SO in H composite material3The loading level of H.It can from TG result
To find out, CNT-PVSAIC, CNT-PVSAPC, P-SO in CNT-PSSA3The content of H is 26.6wt% respectively, 24.5wt% and
8.2wt%.
Embodiment 4
The physical property of catalyst is characterized on Bruker Advance D8diffractometer and carries out, tube voltage 40KV, pipe
Electric current 40mA, characteristic ray Cu-K α radiating light source, small 2 θ=5~50 of angular scan range, 0.02 ° of scanning step, the sampling time
0.3s.Sample (about 3mg) after taking 100 DEG C of high vacuum dries, using quartz plate, sample makes powder sample in quartz through levigate
The area Ban Tianyang being uniformly distributed and being flattened with glass plate real, it is desirable that test face is flushed with glass surface, presses re-test after piece.
XRD diagram is as shown in Figure 6.
In the powder x ray diffraction pattern of CNT-PVSAIC, CNT-PVSAPC and CNT-PSSA, two spies are illustrated only
Peak is levied, respectively in the 2 θ values of 43 ゜ of 2 θ values and low-intensity of 26 ゜ of high intensity.Respectively with the characteristic peak of carbon nanotube (002) and
(100) (Fig. 6) is matched.These are the result shows that during functionalization of polymers carbon nanotube, the crystallinity of pure nano-carbon tube
There is no by very big destruction for structure.Compared with CNT, CNT-P-SO3The intensity of the characteristic diffraction peak of H composite material is significant
It reduces, this can be attributed to CNT-P-SO3The variation of the microstructure of carbon table in carbon nanotube in H composite material.
Embodiment 5
The instrument that Raman characterization uses is LabRAM HR800-LS55 LR laser raman instrument.It is characterized in room temperature in air atmosphere
Lower progress, generallys use Ar ion laser source, wavelength 532nm, and the light intensity of laser is 30KeV.As shown in Figure 7.
Raman spectrum is used to determine CNT-P-SO3Before and after H composite material polymerization process, part carbon nanotube defect density
Situation of change (such as Fig. 7).By taking pure nano-carbon tube as an example, carbon atom in the peak of 1342 centimeters and unordered graphite-structure (D mould)
Vibration it is related.Corresponding is the defect of curved graphite flake layer, sp3 carbon hydridization and other impurities.And 1572 centimeters
Peak it is corresponding be carbon nanotube graphite-structure (G mould).The intensity at the peak D and the peak G ratio (ID/IG), reflect single wall carbon in sample
The relative extent of the relative amount and purity of nanotube, fault of construction.Compared to pure nano-carbon tube, CNT-P-SO3H composite material
In, by P-SO3The variation of the D mould and G mould of carbon nanotube is negligible after H covalence graft.
Embodiment 6
The morphological analysis of three kinds of catalyst is carried out on TEM, JEM-2100HR.Sample is polished, takes a small amount of
Sample ultrasonic disperse is and online in ultra-thin carbon by the ultrasonic drop of high dispersive with capillary in dehydrated alcohol, after its drying
Directly observed.As shown in Figure 8.
The typical high-resolution transmitted electron that CNT-PVSAIC, CNT-PVSAPC and CNT-PSSA is shown in Fig. 8 is aobvious
Micro mirror figure.The form of these CNT-P-SO3H composite materials is approximate, their HRTEM image is clearly demonstrated in carbon nanotube
On have the thin polymeric coating layer of one layer of 3-5nm, successfully confirm macromolecule functionalized carbon nanotubes (Fig. 8).In addition, all these
CNT-P-SO3Primary structure subject to H composite material.Compared to pure nano-carbon tube, CNT-P-SO can be clearly observed3H composite wood
The rough surface of material.In particular, in resulting CNT-P-SO3In H composite material, P-SO3H is specially wrapped in the appearance of carbon nanotube
Face obtains the material of polymeric layer package carbon nanotube support, forms the structure that one kind is named as " fiber in jacket ".Cause
This, in preparation CNT-P-SO3During H presoma (CNT-PVI, CNT-PVP and CNT-PSSNa), carbon nanotube and corresponding
The covalent grafting of monomer may be carried out only in the outer surface of carbon nanotube.It is being previously reported statistics indicate that, polyaniline package carbon receive
Mitron only occurs in carbon nanotube outer surface, since limited reactions object enters inside carbon nanotube, exists so hindering aniline
Polymerization in carbon nanotube.Therefore, outside the carbon nanotube of functionalization of polymers, P-SO3H sections are wrapped in carbon nanotube appearance
Face, so that the intensive active site of carbon nanotube outer surface is uniformly distributed.Such surface texture, connects conducive to reactant
Touching is detached from catalyst convenient for reagent.In addition, the covalence graft of polymer can explain well why carbon nano tube surface ratio and
Porosity declines so many.
Embodiment 7
As can be seen that CNT-P-SO3H composite material is easily catalyzed glyceryl triacetate and the transesterification of methanol is anti-in table 1
It answers, obtains significant conversion ratio.Under the conditions of 60 DEG C of temperature, the conversion ratio of glyceryl triacetate is from > 99.9% to 90.4% (table
1, arrange 3-5).These conversion ratios are much higher than urging without the functionalized catalyst precursor of persulfonic acid group corresponding with them
Change reaction result, such as the catalytic result (table 1,1-2 column) of CNT-PVI and CNT-PVP.In addition to this, three kinds of CNT-P-SO3H
Composite material solid acid catalyst also shows fabulous catalytic performance to the ester exchange reaction of tributyrin and methanol, makes
The conversion ratio of tributyrin is obtained from 98.5% to 85.4% (table 1,9-11 column).Expected as expected, in given catalysis
Under agent load capacity and specific reaction condition, by comparing the methanol decomposition reaction of glyceryl triacetate and tributyrin,
The reaction rate of the triglyceride molecule of short chain, glyceryl triacetate is higher than long chain triglycerides molecule, three butyric acid glycerol
The reaction rate of ester, this result are coincide with the data in literature reported.In the methanol of glyceryl triacetate and tributyrin
In decomposition reaction, the catalytic activity of CNT-P-SO3H composite material presses CNT-PVSAIC > CNTPVSAPC > CNT-PSSA sequence
Weaken (table 1,6-8 column, 12-14 column).Ester exchange reaction in addition to studying triglyceride and methanol, CNT-P-SO3H composite wood
The esterification of material catalyst unsaturated oleic acid mono- to C18 and methanol still has good catalytic effect (table 1,15-20 column).First
The preceding methanol decomposition reaction for also having been reported that various solid acid catalysis glyceryl triacetates is reacted 3 hours at a temperature of 55 DEG C,
The conversion ratio of Amberlyst-15 and CNT-PANI-S catalysis glyceryl triacetate is 50.2% and 31.4% respectively.At 120 DEG C
Under the conditions of react 4 hours, the CNF and Amberlyst-15 of benzene sulfonic acid functionalization catalysis triglyceride are reacted with methanol,
The yield for obtaining methyl oleate is respectively 72% and 22%.Result above all confirms the fabulous catalysis of CNT-P-SO3H composite material
Activity.Finally, from table 1 it follows that the ester exchange reaction of either glyceryl triacetate and methanol or three butyric acid glycerol
The ester exchange reaction of ester and methanol, or it is the esterification of unsaturated oleic acid and methanol, under the same reaction conditions, compared to
Catalyst CNT-PVSAPC and CNT-PSSA, catalyst CNT-PVSAIC show better catalytic activity.CNT-PVSAIC
It is the major catalyst of this research.
The ester exchange reaction of triglyceride and methanol:
The esterification of oleic acid and methanol:
The various CNT-P-SO of table 13H acts on ester exchange reaction and esterification
| Serial number | Catalyst | R | Time, [h] | Conversion ratio, [%] |
| 1 | CNT-PVI | Me | 10 | 12.3 |
| 2 | CNT-PVP | Me | 10 | 15.1 |
| 3 | CNT-PVSAIC | Me | 10 | >99.9 |
| 4 | CNT-PVSAPC | Me | 10 | >99.9 |
| 5 | CNT-PSSA | Me | 10 | 90.4 |
| 6 | CNT-PVSAIC | Me | 5 | 85.8 |
| 7 | CNT-PVSAPC | Me | 5 | 81.3 |
| 8 | CNT-PSSA | Me | 5 | 75.2 |
| 9 | CNT-PVSAIC | nPr | 10 | 98.5 |
| 10 | CNT-PVSAPC | nPr | 10 | 97.6 |
| 11 | CNT-PSSA | nPr | 10 | 85.4 |
| 12 | CNT-PVSAIC | nPr | 5 | 81.6 |
| 13 | CNT-PVSAPC | nPr | 5 | 78.1 |
| 14 | CNT-PSSA | nPr | 5 | 70.3 |
| 15 | CNT-PVSAIC | C17H33 | 10 | 93.0 |
| 16 | CNT-PVSAPC | C17H33 | 10 | 86.3 |
| 17 | CNT-PSSA | C17H33 | 10 | 80.9 |
| 18 | CNT-PVSAIC | C17H33 | 5 | 77.2 |
| 19 | CNT-PVSAPC | C17H33 | 5 | 69.1 |
| 20 | CNT-PSSA | C17H33 | 5 | 63.6 |
Reaction conditions:Catal.(20mg),triglyceride or oleic acid(1.0mmol),
methanol(1.2mL),60℃,(Entries 1–14for Scheme 1a and Entries 15–20for Scheme
1b).
Reaction condition: catalyst (20mg), tributyrin or oleic acid (1.0mmol), methanol (1.2mL), 60 DEG C,
(the 1st group to the 14th group is reaction 1a, that is, ester exchange reaction, and the 15th group to the 20th group is reaction 1b, that is, esterification).
The product that (a) CNT-PVSAIC is catalyzed the ester exchange reaction of tributyrin and methanol in Fig. 9 is distributed；(b) warm
Spend the influence to the ester exchange reaction of tributyrin and methanol；(c) molar ratio of tributyrin and methanol is to three fourths
The influence of acid glyceride methanol decomposition reaction.Figure 10 is catalyst circulation recycling.
Embodiment 8
Fig. 9 (a) reaction condition: tributyrin (302mg, 1.0mmol), CNT-PVSAIC (20mg), methanol
(1.2mL), temperature 60 C.Fig. 9 (a) is one of the Methanol Decomposition that CNT-PVSAIC is used for tributyrin as catalyst
Typical ester exchange reaction.Tributyrin can soon be converted to methyl butyrate and diglyceride.It is sweet after 128 minutes
Oily two acid esters can be converted further into monoglyceride immediately, so the yield of diglyceride reaches maximum at this time.Then, it
Yield can decline with the generation of monoglyceride.
Fig. 9 (b) reaction condition: tributyrin (302mg, 1.0mmol), CNT-PVSAIC (20mg), methanol
(1.2mL), 30 DEG C and 60 DEG C of temperature.Even if from Fig. 9 (b) as can be seen that reacting at a lower temperature, as long as the reaction time is sufficient
Enough long ester exchange reactions equally can achieve higher conversion ratio, and influence of the temperature to ester exchange reaction is not especially greatly, instead
Time of ester exchange reaction can be effectively shortened by answering the raising of temperature, but after reaction temperature is more than the boiling point of methanol, body
Methanol boiling causes part methanol loss in being, whole system reaches energy balance, even if continuing to improve reaction temperature, reaction flask
Interior temperature almost no longer rises, and causes the loss and waste of a large amount of thermal energy, increases the cost of reaction in industrial application.Institute
With, reaction temperature selection is convenient in methanol boiling point or so ratio, i.e., and 65 DEG C.The transesterification that reaction temperature is catalyzed CNT-PVSAIC
The influence of reaction shows that within the temperature range of lower than methanol boiling point, improving reaction temperature can promote reaction to carry out.Temperature is higher,
Reaction rate is faster.
Fig. 9 (c) reaction condition: tributyrin (302mg, 1.0mmol), CNT-PVSAIC (20mg), methanol is (respectively
It is 0.2,1.2 and 2.5mL), temperature 50 C.Another key factor for influencing ester exchange reaction is methanol and triglyceride
Thus molar ratio further studies the molar ratio of methanol and tributyrin.Although methanol is reacted with tributyrin
Stoichiometric ratio be 3:1, but ester exchange reaction is reversible reaction, and excessive methanol can make reversible balanced reaction to generating rouge
The direction of fatty acid methyl esters is mobile, and thus molar ratio of methanol to oil is greater than stoichiometric ratio in actual production process.Fig. 9 (c) is listed not
Influence with molar ratio of methanol to oil to triglyceride conversion ratio.It can be seen from the figure that in specific reaction temperature and quantitative
Under conditions of CNT-PVSAIC, tests tributyrin and methanol molar ratio is three kinds of situations of (1:60,1:29,1:5).
Obviously, the molar ratio of methanol is higher, and ester conversion rate is higher, and excessive alcohol can promote ester exchange reaction to carry out.
Embodiment 9
Figure 10 reaction condition: CNT-PVSAIC (15mg), tributyrin (302mg, 1.0mmol), methanol
(1.2mL), 60 DEG C, 4h.As a kind of solid catalyst for ester exchange reaction, it is catalyzed with conventional homogeneous ester exchange reaction
Agent is compared to be recycled the biggest advantage is to recyclable, but the loss of active component is to cause to urge in supported solid catalyst
One main cause of agent inactivation.Pass through the repetition of tributyrin and the ester exchange reaction research CNT-PVSAIC of methanol
Usability.By the catalyst for recycling and handling well under identical reaction condition, in the lower conversion ratio feelings of tributyrin
6 recycling experiments have been carried out under condition, and the stability of catalyst is deeply probed into this.As shown in Figure 10, it is followed by 6 times
Loopback is received, and the conversion ratio for measuring tributyrin drops to 40.9% from 52.4%, shows that catalyst CNT-PVSAIC is being recycled
It is lost in removal process amount of activated.This phenomenon may be due to being covalently attached in macromolecule layer swelling and then carbon nanotube
The portion fractures of PVSAIC chain cause during circulation and stress, a part of catalytic active center (- SO of CNT-PVSAIC3H)
Missing.
Claims (2)
1. a kind of preparation method of the composite material of the macromolecule grafting carbon nanotube of sulfonic acid functional, has the following structure formula:
Wherein, Y indicates the degree of polymerization of recyclable poly- (the chlorfulfonated imidazoles of 3- vinyl -1-), is 5000~6000 integer；
X indicates the degree of polymerization of irretrievable poly- (the chlorfulfonated imidazoles of 3- vinyl -1-), is 2000~3000；Table on the left of structural formula
Show multi-walled carbon nanotube CNT；
It is put into it is characterized by comprising the following steps: (1) weighs 40~60mg carbon nanotube and is equipped with magnetic stirrer in advance
It is Si Laike bottles dry, it vacuumizes, rushes nitrogen, in triplicate；(2) flow rate of big nitrogen is opened, measures 200~300mL N respectively,
Dinethylformamide and 0.5~1.0mL 1- vinyl imidazole inject described Si Laike bottles, by the Si Laike of logical nitrogen
Bottle is put into Ultrasound Instrument, 1~1.5h of ultrasound；(3) ultrasound finishes, and 5~10mg initiator is added, under a nitrogen atmosphere by device
It is put into 75~85 °C of thermostatical oil baths and is stirred to react 40~50h；(4) after having reacted, nitrogen valve is closed, is taken from oil bath pan
Reaction unit out is cooled to room temperature；With DMF reagent dilutions to 500~600mL；The black on centrifugation tube wall is removed in centrifuge separation
Solid is filtered with nylon membrane, and is rinsed with DMF and dehydrated alcohol, is drained；(5) black product is removed from nylon membrane, in 75
It is dried in~85 °C of vacuum ovens, obtains PVI/CNT；(6) 40~60mg PVI/CNT, 200~300mL 1,2- bis- are weighed
Chloroethanes and 0.1~0.15mL chlorosulfonic acid are in Si Laike bottles；At room temperature, be stirred to react 1.5~2.5h, then 60~
20~30h is reacted in 70 °C of thermostatical oil bath；After having reacted, it is centrifugated resulting solid product CNT-PVSAIC, with two
Chloromethanes and anhydrous ether rinse, and water pump is drained, dry 20~30h in 75~85 °C of vacuum ovens.
2. the preparation method of the composite material of the macromolecule grafting carbon nanotube of sulfonic acid functional according to claim 1,
It is characterized in that, the initiator is AIBN.
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