CN108102289B - Phenolic resin grafted carbon nanotube composite material and preparation method thereof - Google Patents
Phenolic resin grafted carbon nanotube composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a phenolic resin grafted carbon nanotube composite material and a preparation method thereof, wherein the composite material comprises 100 parts by weight of phenolic resin and 0.1-5 parts by weight of carbon nanotubes. The preparation method of the composite material comprises the steps of mixing the azide phenolic resin and the carbon nano tube in a solvent I, and separating to obtain a product after the reaction is finished. The invention grafts the phenolic resin on the carbon nano tube by a chemical grafting method, solves the problems of easy agglomeration of the carbon nano tube and the interface between the carbon nano tube and the phenolic resin, and obtains the composite material with excellent mechanical property and thermal stability.
Description
Technical Field
The invention belongs to the field of phenolic resin composite materials, and particularly relates to a phenolic resin grafted carbon nanotube composite material and a preparation method thereof.
Background
The phenolic resin has the advantages of easily obtained raw materials, simple production process and equipment, low price and good mechanical property, and can be widely applied to the aspects of electronics, electrics, automobile manufacturing, mechanical industry and the like, so that the phenolic resin becomes one of the most common thermosetting resins. However, with the continuous development of modern industries, especially in automobiles, electronics, and aviation and other high and new technologies, higher requirements are placed on the performance of phenolic resins. Due to the requirements for the improvement of the performance of the phenolic resin and the expansion of the application range thereof, a large amount of reinforced modified phenolic resin is produced.
At present, the material widely used for modifying phenolic resin at present is nano material (such as nano SiO)2) Organic materials (silicones), inorganic materials (borides). Carbon materials such as carbon nanofibers, carbon nanotubes, graphite, and the like, are important candidates for phenolic resin modifiers due to their excellent mechanical and thermal conductivity properties. The vast majority of the composite materials are obtained by physical blending, which has a problem of compatibility and interface between the phenolic resin and the carbon nanotube, and the performance of the composite materials is influenced to a great extent. In order to overcome the problems of compatibility and interface, some add surfactant, such as a method for preparing wear-resistant nano material modified phenolic resin disclosed in chinese patent CN 104987657 a, to prepare nano particles such as nano graphite, nano graphene, nano fullerene and nano MoS2And carbon nano tubes and the like are modified by a surfactant and then mixed with phenolic resin to prepare the modified phenolic resin, but the added surfactant has high content and may limit the improvement of the material performance to a certain extent.
Disclosure of Invention
Based on the problems, the technical problem to be solved by the invention is to provide a preparation method of a carbon nano tube/phenolic resin composite material which overcomes the compatibility, and the prepared composite material has high mechanical property and thermal stability.
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: the carbon nano tube/phenolic resin composite material obtained by adopting the chemical grafting method not only can effectively avoid the problems, but also greatly improves the performance of the composite material, thereby completing the invention.
The object of the present invention is to provide the following:
(1) a phenolic resin grafted carbon nanotube composite material comprises the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight of carbon nanotubes,
the X-ray diffraction pattern of the composite material has diffraction peaks at the 2 theta angles of 18 degrees and 26 degrees;
in a thermogravimetric analysis curve, the temperature of 5% of mass loss of the composite material is 165 ℃, the mass loss rate is maximum at 500-580 ℃, and the residual amount at 800 ℃ is 57.3%.
(2) A process for preparing the phenolic resin grafted carbon nanotube composite material includes such steps as mixing the nitrified phenolic resin with carbon nanotubes in solvent I, reaction, and separating,
the carbon nano-tube is selected from single-wall carbon nano-tube or multi-wall carbon nano-tube which is not modified; and/or
The solvent I is selected from any one or more of N-methyl pyrrolidone, N-dimethylacetamide, nitrobenzene, ethylene glycol, dimethyl sulfoxide or diphenyl ether; and/or
The mass ratio of the azide phenolic resin to the carbon nano tube is 1 (0.001-0.10), preferably 1 (0.005-0.05); and/or
The reaction is carried out for 10-24 h at 120-210 ℃, preferably for 15-20 h at 150-180 ℃;
preferably, the reaction is carried out under an inert atmosphere which is nitrogen or argon, more preferably nitrogen.
According to the phenolic resin grafted carbon nanotube composite material and the preparation method thereof provided by the invention, the following beneficial effects are achieved:
(1) compared with the existing physical mixing, the phenolic resin is grafted to the carbon nano tube by a chemical grafting method, so that the carbon nano tube is uniformly dispersed in the phenolic resin, and the problems of easy agglomeration of the carbon nano tube and an interface between the carbon nano tube and the phenolic resin are solved;
(2) the grafted carbon nano tube is not modified, so that the damage to the molecular structure of the carbon nano tube in the re-modification process is reduced, and the mechanical property of the phenolic resin can be better improved by the carbon nano tube;
(3) the thermal stability of the phenolic resin added with the unmodified multi-wall carbon nano tube is obviously improved, and the final carbon residue of the phenolic resin grafted carbon nano tube composite material at 800 ℃ is 57.3 percent, which is obviously improved compared with 47.5 percent of the phenolic resin;
(4) compared with the traditional virulent and carcinogenic chloromethylation reagent (chloromethyl ether or dichloromethyl ether), the novel green chloromethylation reagent is more environment-friendly, so that the harm to a user is greatly reduced, the pollution to the environment is reduced, and the preparation method has good environment friendliness.
Drawings
FIG. 1 is an XRD pattern of a phenolic resin (A), unmodified multi-walled carbon nanotubes (B) and a composite material (C) synthesized in example 3 in comparative example 1 of the present invention;
FIG. 2 is a thermogravimetric analysis graph of the phenolic resin (A) of comparative example 1 and the composite material (B) synthesized in example 3 according to the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The invention aims to provide a phenolic resin grafted carbon nanotube composite material, which comprises the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.1 to 5 parts by weight of carbon nanotubes.
In a preferred embodiment, the composite material comprises the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.5 to 2 parts by weight of carbon nanotubes.
In a preferred embodiment, the composite material has an X-ray diffraction pattern having diffraction peaks at 18 ° and 26 ° 2 Θ angles;
in a thermogravimetric analysis curve, the decomposition temperature of 5% of the mass loss of the composite material is 165 ℃, the mass loss rate is maximum at 500-580 ℃, and the residual amount at 800 ℃ is 57.3%. The phenol resin in the present invention is a generic term for a resinous polymer obtained by polycondensation of phenol and aldehyde in the presence of an acidic or basic catalyst, and may be, for example, a resin synthesized from phenol and formaldehyde.
The carbon nano tube has strong mechanical property, and can effectively transfer the stress borne by the polymer material when being added into the polymer material, thereby improving the mechanical property of the polymer material. Meanwhile, the better the dispersibility of the carbon nanotubes in the polymer material is, the better the mechanical property is, the better the interfacial bonding property between the carbon nanotubes and the polymer material is, the better the load transfer is.
The carbon nano tube has excellent heat conduction performance, the heat transfer efficiency can be improved by adding the carbon nano tube into the polymer material, the thermal stability of the polymer material is enhanced, and the dispersibility of the carbon nano tube in the polymer material is closely related to the improvement of the thermal stability. Compared with physical mixing, the chemical synthesis method can better achieve the problem of high compatibility, and the compounding of the two materials is completed.
The invention also aims to provide a preparation method of the phenolic resin grafted carbon nanotube composite material, which comprises the steps of mixing the azide phenolic resin and the carbon nanotube in a solvent I, carrying out reaction, and separating after the reaction is finished to obtain the composite material.
The azide group contains three nitrogen atoms and has different resonance structures, and the structures of the azide groups enable the azide groups to have extremely high reactivity. The azide compound is thermally decomposed or photolyzed under the action of high temperature or ultraviolet light to generate a nitrene structure, and the nitrene can be inserted into a C-H or C ═ C bond in any molecule, so that the azide compound can be used for surface modification of the carbon nano tube.
In a preferred embodiment, the mass ratio of the azide phenolic resin to the carbon nanotubes is 1 (0.001 to 0.10), preferably 1 (0.005 to 0.05). Within this range, the phenolic resin grafted carbon nanotube composite has excellent mechanical properties and thermal stability.
In a preferred embodiment, the carbon nanotubes are selected from single-walled carbon nanotubes or multi-walled carbon nanotubes without a modification treatment. At present, the surface of the carbon nanotube is generally modified by strong acid treatment to generate carboxyl or hydroxyl on the surface, and then further modified, and the structure of the carbon nanotube is seriously damaged in the strong acid treatment process, possibly affecting the mechanical properties and the like of the carbon nanotube.
In a preferred embodiment, the azide phenolic resin and the carbon nanotubes are reacted at a relatively high temperature, so that a solvent with a high boiling point is selected. The solvent I is selected from any one or more of N-methyl pyrrolidone, N-dimethylacetamide, nitrobenzene, ethylene glycol, dimethyl sulfoxide or diphenyl ether.
In a preferred embodiment, in order to make the azide phenolic resin and the carbon nanotubes fully contact, ultrasonic dispersion is performed on a system formed after mixing, and ultrasonic waves of 40-120 KHz are preferably adopted for 15-60 min.
In a preferred embodiment, the reaction is carried out at 120-210 ℃ for 10-24 h; in a further preferred embodiment, the reaction is carried out at 150 to 180 ℃ for 15 to 20 hours.
In a preferred embodiment, since the phenol-formaldehyde azide resin requires a water and oxygen barrier during the reaction, the reaction is carried out under an inert atmosphere, which is nitrogen or argon, preferably nitrogen.
In a preferred embodiment, after the reaction is completed, the reaction solution is cooled and separated to obtain a solid material, and the solid material is washed and dried to obtain a final product. The separation mode comprises filtration or centrifugation, preferably at 5000-7500 rpm for 10-25 min. The cleaning solvent is selected from methanol, ethanol or acetone.
In the present invention, the azide phenolic resin may be commercially available or prepared according to a method comprising the steps of:
step 1, mixing phenolic resin, a catalyst and a chloromethylation reagent in a solvent II for reaction to obtain chloromethylated phenolic resin;
and 2, mixing the product obtained in the step 1 with an azide in a solvent III, and reacting to obtain the azido phenolic resin.
In step 1, in a preferred embodiment, the catalyst is selected from lewis acids selected from one or more of zinc chloride, tin tetrachloride, ferric chloride, aluminum chloride or copper chloride.
In a preferred embodiment, the chloromethylating agent is selected from the group consisting of chloromethylated alkyl ethers, such as ClCH2O(CH2)nCH3Or (ClCH)2O)2(CH2)nWherein n is 1 to 5, preferably 1, 4-dichloromethoxybutane. The classical chloromethylation reagent is prepared by compounding formaldehyde, trioxymethylene, paraformaldehyde and hydrochloric acid, and has the advantages of low price, low toxicity, low reaction activity and long reaction time. The other chloromethylation reagent is chloromethyl ether or bischloromethyl ether, which has strong activity, but poor stability, easy volatilization, corrosiveness and strong toxicity, and is a compound with carcinogenic toxicity. The invention selects the long carbon chain chloromethylation reagent which has high boiling point, low toxicity and high activity as the chloromethylation reagent, greatly lightens the harm to users, reduces the pollution to the environment and has good environmental friendliness.
In a preferred embodiment, the solvent II is selected from any one or more of acetone, methanol, ethanol, isopropanol or n-butanol, preferably acetone. The solvent II has better solubility to phenolic resin and chloromethylation reagent, homogeneous reaction is more favorable for reaction, and the solvent II is dissolved in water, so that the separation of products is convenient.
From the above, in step 1, the reaction mechanism of the phenolic resin and the chloromethylation reagent may be: first of all, electrophilic substitution on the benzene ring takes place under the catalysis of Lewis acids (attack by alkylcarbonium ions, e.g. by Lewis acids+CH2OCH2CH2CH2CH2O CH2Cl), followed by nucleophilic substitution (chloride ion Cl)-Attack), ether bond cleavage, and chloromethylated phenol resin.
In a preferred embodiment, the weight ratio of the phenolic resin, the catalyst and the chloromethylation reagent is (5-8): (3-5): 32.
in a further preferred embodiment, the chloromethylation reagent is added in a dropwise manner, stirring is carried out during the dropwise addition and the reaction process, the reaction is accelerated, and the degree of crosslinking among macromolecules of the phenolic resin is controlled.
In a preferred embodiment, the ratio of the total weight of the phenolic resin, the catalyst and the chloromethylation reagent to the volume of the solvent II is 1 (2-4.5). When the dosage of the solvent II is low (the weight-volume ratio is less than 1:2), the chloromethylated phenolic resin macromolecules in the reaction system are easy to be crosslinked, and the chloromethylation degree is reduced; the amount of solvent II used is high (weight to volume ratio > 1:4.5) and the reaction rate is relatively low.
In a preferred embodiment, in step 1, the phenolic resin and the chloromethylation reagent react at 40-80 ℃ for 4-10 h, preferably at 50-70 ℃ for 5-8 h, and within this temperature range, the cross-linking between the phenolic resin macromolecules can be effectively reduced, and the reaction rate is relatively fast.
In a preferred embodiment, after the reaction is completed, adding a large amount of deionized water into the reaction solution, stirring, standing for 12-24 h, separating solids, washing with deionized water for multiple times, and drying in vacuum to obtain the chloromethylated phenolic resin.
In step 2, in a preferred embodiment, the azide compound is selected from the group consisting of sodium azide, potassium azide and acyl azide, preferably sodium azide.
In a preferred embodiment, the solvent iii is selected from any one or more of N, N-dimethylformamide, N-dimethylacetamide, toluene, p-xylene, and ethylbenzene, preferably N, N-dimethylformamide.
In a preferred embodiment, the molar ratio of the chloromethylated phenolic resin to the azide compound is 1 (1.5-3). The molar equivalent of the reaction of the chloromethylated phenolic resin and the azide is 1:1, and the azide is selected to be excessive, so that the azide reaction is carried out more completely, and the yield is improved.
In a preferred embodiment, the chloromethylated phenolic resin is added dropwise, and stirring is carried out during the dropwise addition and the reaction process, so that the reaction is accelerated.
In a preferred embodiment, the chloromethylated phenolic resin and the azide react for 24-48 hours at 40-60 ℃.
In a preferred embodiment, the product is isolated after the reaction is complete. If the solvent III is water-soluble, a large amount of deionized water can be added into the reaction solution, stirred, stood, separated into solid matters, washed by the deionized water and dried in vacuum, and the azide phenolic resin is obtained.
In the present invention, the chloromethyl alkyl ether described in step 1 can be obtained commercially or prepared according to the following method: mixing alcohol, formaldehyde and a chlorinating agent, reacting, and carrying out aftertreatment to obtain a product, namely chloromethyl alkyl ether.
In a preferred embodiment, the alcohol is the alcohol corresponding to the chloromethylation reagent, such as 1, 4-dichloromethoxybutane corresponding to 1, 4-butanediol, 1, 5-dichloromethoxypentane corresponding to 1, 5-pentanediol;
the concentration (mass/volume) of the formaldehyde is 35-40%;
the chlorinating agent is selected from thionyl chloride (SOCl)2) Phosgene (COCl)2) And phosphorus chloride (PCl)3) Preferably, phosphorus trichloride.
In a preferred embodiment, the volume ratio of the alcohol, formaldehyde and chlorinating agent is 5: (11-20): (6-10), wherein the molar ratio is 1: (2.5-5): (1-2.5); the reaction is carried out for 3-5 h at the temperature of 10-30 ℃.
In a preferred embodiment, the chlorinating agent is added dropwise with stirring during the dropwise addition and during the reaction, so as to accelerate the reaction. Because the reaction is exothermic, the temperature of the ice-water bath is controlled in the dropping process so as to improve the yield.
In a preferred embodiment, the post-treatment comprises allowing the aqueous oil phase to separate by standing, separating the upper oil phase, drying the upper oil phase with a drying agent, and removing the drying agent to obtain the chloromethylation reagent. Wherein the drying agent is selected from anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate or anhydrous copper sulfate.
The reaction for preparing the chloromethylation reagent is a homogeneous reaction, while the reaction product is not water-soluble, and the product is continuously separated out from a water phase reaction system along with the reaction, so that the reaction for generating the product is facilitated, and the product purity is high.
Examples
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
The main raw materials and sources thereof in the invention are as follows: phenol resin (model: PF6808, Shandong Shengquan chemical Co., Ltd.); an unmodified multi-walled carbon nanotube (model: L-MWNT-1020, manufacturer: Shenzhen Nangang Limited).
Example 1
Adding a mixed solution of 50mL of 1, 4-butanediol and 140mL of formaldehyde solution into a reactor, placing the mixed solution into an ice water bath, dropwise adding 100mL of phosphorus trichloride while stirring, reacting for 5 hours at 20 ℃, standing the reaction mixed solution for 5 days to separate oil and water, separating supernatant, drying the supernatant by using anhydrous magnesium sulfate, and separating to obtain 1, 4-dichloromethoxybutane;
dissolving 6g of phenolic resin in 120mL of acetone, adding 4g of anhydrous zinc chloride, dropwise adding 32g of 1, 4-dichloromethoxybutane under stirring, reacting at the constant temperature of 50 ℃ for 8 hours, adding a large amount of deionized water into the reaction solution, stirring by using a glass rod, standing for 24 hours, performing suction filtration, washing with deionized water for multiple times, and performing vacuum drying to obtain chloromethylated phenolic resin;
dissolving 0.049g of sodium azide in 25mL of N, N-dimethylformamide, dropwise adding 1.95g of chloromethylated phenolic resin while stirring, reacting for 36 hours at 45 ℃, then adding a large amount of deionized water, stirring, standing, filtering, washing, and drying in vacuum to obtain azido phenolic resin;
ultrasonically dispersing 0.0025g of multi-walled carbon nano-tube and 0.5g of azido phenolic resin in N-methyl pyrrolidone, introducing protective gas, heating to 200 ℃, reacting for 15h, separating at 7500rpm by using a centrifuge when the temperature is reduced to room temperature, centrifuging for 10min, cleaning by using acetone, and drying to obtain the final product.
Example 2
Adding a mixed solution of 30mL of 1, 4-butanediol and 80mL of formaldehyde solution into a reactor, placing the mixed solution into an ice water bath, dropwise adding 50mL of phosphorus trichloride while stirring, reacting for 5 hours at 10 ℃, standing the reaction mixed solution for 2 days to separate oil and water, separating supernatant, drying the supernatant with anhydrous magnesium sulfate, and separating to obtain 1, 4-dichloromethoxybutane;
dissolving 5g of phenolic resin in 110mL of acetone, adding 3g of anhydrous zinc chloride, dropwise adding 25g of 1, 4-dichloromethoxybutane under stirring, reacting at the constant temperature of 70 ℃ for 5 hours, adding a large amount of deionized water into the reaction solution, stirring by using a glass rod, standing for 24 hours, performing suction filtration, washing with deionized water for multiple times, and performing vacuum drying to obtain chloromethylated phenolic resin;
dissolving 0.065g of sodium azide in 35mL of N, N-dimethylformamide, dropwise adding 1.56g of chloromethylated phenolic resin while stirring, reacting for 24 hours at 50 ℃, then adding a large amount of deionized water, stirring, standing, filtering, washing, and drying in vacuum to obtain azido phenolic resin;
ultrasonically dispersing 0.004g of multi-walled carbon nano-tube and 0.4g of azido phenolic resin in N-methyl pyrrolidone, introducing protective gas, heating to 120 ℃, reacting for 15h, separating at 6000rpm by using a centrifugal machine when the temperature is reduced to room temperature, centrifuging for 25min, cleaning by using acetone, and drying to obtain the final product.
Example 3
Adding a mixed solution of 60mL of 1, 4-butanediol and 150mL of formaldehyde solution into a reactor, placing the mixed solution into an ice water bath, dropwise adding 100mL of phosphorus trichloride while stirring, reacting for 4 hours at 25 ℃, standing the reaction mixed solution for 3 days to separate oil and water, separating supernatant, drying the supernatant with anhydrous magnesium sulfate, and separating to obtain 1, 4-dichloromethoxybutane;
dissolving 7g of phenolic resin in 120mL of acetone, adding 4g of anhydrous zinc chloride, dropwise adding 30g of 1, 4-dichloromethoxybutane under stirring, reacting at the constant temperature of 55 ℃ for 8 hours, adding a large amount of deionized water into the reaction solution, stirring with a glass rod, standing for 24 hours, performing suction filtration, washing with deionized water for multiple times, and performing vacuum drying to obtain chloromethylated phenolic resin;
dissolving 2.73g of sodium azide in 50mL of N, N-dimethylformamide, dropwise adding 0.091g of chloromethylated phenolic resin while stirring, reacting for 24 hours at 60 ℃, then adding a large amount of deionized water, stirring, standing, filtering, washing, and drying in vacuum to obtain azido phenolic resin;
ultrasonically dispersing 0.01g of multi-walled carbon nano-tube and 0.5g of azido phenolic resin in N-methyl pyrrolidone, introducing protective gas, heating to 180 ℃, reacting for 18h, separating by using a centrifuge at the rotating speed of 5500rpm when the temperature is reduced to room temperature, centrifuging for 15min, cleaning by using acetone, and drying to obtain the final product.
Comparative example 1
Phenolic resin without grafted multi-wall carbon nanotube.
Examples of the experiments
X-ray diffraction with a scanning interval of 5-80 degrees with a D8advance X-ray diffractometer manufactured by Japan chemical and electric appliances, using a Cu target K α ray, a graphite monochromator, a tube current of 100mA, a tube voltage of 50KV, and a scanning speed of 5 °/min.
TG test: TG209F3 model thermogravimetric analyzer manufactured by Shanghai electronic technology Limited company with a temperature rise rate of 5 ℃/min.
And (3) testing mechanical properties: the microcomputer controlled electronic universal tester produced by Shenzhen Kaiqiang mechanical Limited has a drafting rate of 5 mm/min.
Experimental example 1 XRD analysis
The phenolic resin (a), the unmodified multi-walled carbon nanotubes (B) in comparative example 1 and the composite material (C) synthesized in example 3 were subjected to XRD tests, and the XRD spectrum is shown in fig. 1.
As can be seen from fig. 1, the XRD patterns of the phenolic resin have diffraction peaks at the 2 θ positions of 18 °, 25 °, 31 ° and 44 °, and the XRD patterns of the unmodified multi-walled carbon nanotubes have diffraction peaks at the 2 θ position of 26 °, whereas the XRD patterns of the composite material synthesized in example 3 have diffraction peaks at the 18 ° and 26 °, which indicates that the phenolic resin grafted carbon nanotube composite material is synthesized in example 3.
Experimental example 2 thermal stability
The thermal stability of phenolic resins has a large impact on their processing and use properties. The phenolic resin (A) in comparative example 1 and the composite material (B) synthesized in example 3 were subjected to TG curve measurement.
As shown in FIG. 2, the thermal decomposition temperature of the phenolic resin is 92 ℃ when the weight loss rate is 5%, while the thermal weight loss rate of the composite material is only 1.8%, and the thermal decomposition temperature of the composite material is 165 ℃ when the thermal weight loss rate of the composite material reaches 5%, and the difference between the thermal decomposition temperature and the thermal decomposition temperature is 73 ℃. The weight loss rate of the phenolic resin is slow between 92 ℃ and 380 ℃, but is faster than that of the composite material between 165 ℃ and 470 ℃. The phenolic resin has obvious thermal weight loss phenomenon between 380 ℃ and 800 ℃, and the corresponding composite material has obvious thermal weight loss phenomenon between 470 ℃ and 735 ℃. The residual carbon content of the phenolic resin at 800 ℃ is 47.5 percent, while the final residual carbon content of the composite material synthesized in example 3 at 800 ℃ is 57.3 percent, and the thermal stability of the phenolic resin added with the unmodified multi-wall carbon nano tube is obviously improved.
Experimental example 3 mechanical Properties
The mechanical properties of the composite materials prepared in examples 1 to 3 and the phenolic resin of comparative example 1 were measured, and the results are shown in table 1.
As can be seen from table 1, the breaking strength of the phenolic resin grafted carbon nanotube composite material gradually increases with the increase of the content of the carbon nanotubes (within the range of the mass ratio of the carbon nanotubes to the phenol azide resin being 0.5-2: 100), and compared with the phenolic resin not grafted with the carbon nanotubes, the breaking strength of the phenolic resin grafted carbon nanotube composite material is significantly improved,
TABLE 1 mechanical Properties data
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (12)
1. The method for preparing the phenolic resin grafted carbon nanotube composite material is characterized by comprising the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.5 to 2 parts by weight of carbon nanotubes,
the X-ray diffraction pattern of the composite material has diffraction peaks at 18 degrees and 26 degrees of 2 theta angles,
the method comprises mixing azide phenolic resin and carbon nano tubes in a solvent I, reacting, separating after the reaction is finished to obtain a composite material,
the azide phenolic resin is prepared by a method comprising the following steps:
step 1, mixing phenolic resin, a catalyst and a chloromethylation reagent in a solvent II for reaction to obtain chloromethylated phenolic resin, wherein the catalyst is zinc chloride;
the volume ratio of the total weight of the phenolic resin, the catalyst and the chloromethylation reagent to the solvent II is 1 (2-4.5);
step 2, mixing the product obtained in the step 1 and an azide in a solvent III for reaction to obtain an azide phenolic resin;
the molar ratio of the chloromethylation phenolic resin to the azide is 1 (1.5-3).
2. The method of claim 1,
the temperature of 5% of the mass loss of the composite material is 165 ℃, the mass loss rate is the largest at 500-580 ℃, and the residual amount is 57.3% at 800 ℃.
3. The method of claim 1, wherein the carbon nanotubes are selected from unmodified single-walled carbon nanotubes or unmodified multi-walled carbon nanotubes; and/or
The solvent I is selected from any one or more of N-methyl pyrrolidone, N-dimethylacetamide, nitrobenzene, ethylene glycol, dimethyl sulfoxide or diphenyl ether; and/or
The mass ratio of the azide phenolic resin to the carbon nano tube is 1 (0.001-0.10), and/or
The reaction is carried out for 10-24 h at 120-210 ℃;
the reaction is carried out under an inert atmosphere, which is nitrogen or argon.
4. The production method according to claim 3,
the mass ratio of the azide phenolic resin to the carbon nano tube is 1 (0.005-0.05);
the reaction is carried out for 15-20 h at 150-180 ℃;
the inert atmosphere is nitrogen.
5. The production method according to claim 1, wherein, in step 1,
the chloromethylation reagent is selected from chloromethyl alkyl ether; and/or
The solvent II is selected from any one or more of acetone, methanol, ethanol, isopropanol or n-butanol.
6. The production method according to claim 5,
the chloromethylation reagent is ClCH2O(CH2)nCH3Or (ClCH)2O)2(CH2)nWherein n is 1-5; and/or
The solvent II is acetone.
7. The production method according to claim 5,
the chloromethylation reagent is 1, 4-dichloromethoxybutane.
8. The preparation method according to claim 1, wherein in the step 1, the weight ratio of the phenolic resin to the catalyst to the chloromethylation reagent is (5-8): (3-5): 32, a first step of removing the first layer; and/or
The reaction is carried out for 4-10 h at 40-80 ℃.
9. The method according to claim 8,
the reaction is carried out for 5-8 h at 50-70 ℃.
10. The method according to claim 1, wherein in step 2, the azide compound is selected from the group consisting of sodium azide, potassium azide and acyl azide; and/or
The solvent III is selected from any one or more of N, N-dimethylformamide, N-dimethylacetamide, toluene, p-xylene and ethylbenzene; and/or
The reaction is carried out at the temperature of 40-60 ℃ for 24-48 h.
11. The production method according to claim 10, wherein in step 2, the azide compound is sodium azide; and/or
The solvent III is N, N-dimethylformamide.
12. The process according to claim 5, wherein chloromethyl alkyl ether is prepared by: mixing alcohol, formaldehyde and chlorinating agent, reacting, and post-treating to obtain the product chloromethyl alkyl ether, wherein,
the molar ratio of the alcohol to the formaldehyde to the chlorinating agent is 1: (2.5-5): (1-2.5); and/or
The post-treatment comprises standing, layering, separating an upper organic phase, and drying the upper organic phase by using a drying agent, wherein the drying agent is selected from anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate or anhydrous copper sulfate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611056155.2A CN108102289B (en) | 2016-11-25 | 2016-11-25 | Phenolic resin grafted carbon nanotube composite material and preparation method thereof |
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| CN112608489A (en) * | 2020-12-16 | 2021-04-06 | 王京慧 | High-strength carbon nanotube modified phenolic resin flame-retardant material and preparation method thereof |
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