CN114350142A - Reinforced nylon 12 composite material for MJR3D printed coconut shell fiber surface grafted graphene oxide and preparation method thereof - Google Patents
Reinforced nylon 12 composite material for MJR3D printed coconut shell fiber surface grafted graphene oxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a reinforced nylon 12 composite material for grafting graphene oxide on the surface of MJR3D printed coconut shell fiber and a preparation method thereof, and aims to solve the technical problems of low surface energy, large surface inertia and poor mechanical property of the existing coconut shell fiber. The method comprises the following steps: 1. preparing graphene oxide; 2. alkalizing the coconut shell fibers; 3. modifying and aminating the surface of the coconut shell fiber; 4. grafting graphene oxide on the surface of the coconut shell fiber; 5. and grafting graphene oxide on the surface of the coconut shell fiber to reinforce the nylon 12 composite material. The roughness of the coconut shell fiber surface grafted graphene oxide is obviously increased, the transfer effect between a matrix and a reinforcement in the nylon 12 composite material is favorably enhanced, the interface performance is improved, and the mechanical property and the biodegradability of the composite material are further improved. The prepared CSSP @ GO-g-PA12 composite material can be used in a MJR3D printing process.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a MJR3D coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite material and a preparation method thereof.
Background
Nylon (PA) 12 is a semi-crystalline polymer, has good mechanical properties and wear resistance, good thermal stability and low melt viscosity, and in nylon products, PA12 has the lowest melt temperature and smaller water absorption and molding shrinkage, is the best material for preparing plastic functional parts by current 3D printing, and occupies more than 95% of the current 3D printing material market. In order to meet the requirements of different plastic functional parts on performance, different nylon (PA 12) composite powder materials need to be prepared, so that the performance of formed parts of the materials is more outstanding than that of pure PA powder.
Coconut shell (CSSP) fiber has proven to be a potential option for reinforcing new composite materials due to its high strength and modulus properties. Coconut shell consists of cellulose (26.6%), hemicellulose (21%), lignin (29.4%), pentosan (27.7%), solvent extract (4.2%), furfural anhydride (3.5%) and ash (0.6%). In essence, the coconut shell has a high carbon content (49.86%), is eco-friendly and biodegradable, and has been widely used in current polymer technology as a substitute filler for synthetic materials. However, because the surface of the coconut shell fiber lacks active functional groups, the reactivity is low, the adhesion with a matrix is poor, and a plurality of defects exist in the interface, the mechanical property of the composite material is directly influenced, and the function of MJR3D printing samples is limited.
Based on the above, the invention provides a reinforced nylon 12 composite material for grafting graphene oxide on the surface of MJR3D printed coconut shell fiber and a preparation method thereof, the graphene oxide is adopted to modify the surface of the coconut shell so as to improve the wettability and the cohesiveness of the coconut shell fiber to a substrate, improve the interface performance and further improve the mechanical property and the thermal stability of the composite material, and the surface of the graphene oxide has a large number of functional groups, such as carboxyl, hydroxyl and epoxy, so that the graphene oxide is easy to react with organic matters in a combination manner, and the composite material has very important significance in the field of 3D printing technical materials.
Disclosure of Invention
The invention aims to solve the problems of material shortage in the existing 3D printing technology, insufficient mechanical property of pure nylon 3D printing and the like, and provides a reinforced nylon 12 composite material for MJR3D printing coconut shell fiber surface grafted graphene oxide and a preparation method thereof, wherein the composite material has higher strength and biodegradability through a graphene oxide thin layer constructed on the surface of a coconut shell, and is used in a MJR3D printing process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the graphene oxide grafted coconut shell fiber reinforced nylon 12 composite material for MJR3D printing and the preparation method thereof are characterized in that the coconut shell fiber reinforced nylon 12 composite material is prepared by firstly alkalizing and aminating coconut shell fibers and then grafting graphene oxide on the surfaces of the coconut shell fibers to reinforce the nylon 12 composite material, and the preparation method comprises the following steps:
(1) preparing graphene oxide;
(2) carrying out alkalization treatment on the coconut shell fibers;
(3) modifying and aminating the surface of the coconut shell fiber;
(4) grafting graphene oxide on the surface of the coconut shell fiber;
(5) and grafting graphene oxide on the surface of the coconut shell fiber to reinforce the nylon 12 composite material.
The method specifically comprises the following steps:
(1) preparing graphene oxide GO;
(2) carrying out alkalization treatment on the coconut shell fiber CSSP:
soaking the coconut shell fiber in a 5wt% NaOH solution for 6h to remove surface impurities, then washing with distilled water until the pH value is 7, and drying in an oven at 60 ℃ for 48h to obtain the alkalized coconut shell fiber;
(3) surface modification amination treatment of coconut shell fibers:
a. adding deionized water into the alkalized coconut shell fiber obtained in the step (2), stirring, titrating with acid to adjust the pH value to 5-6, adding N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, and activating for 15min to obtain an activated coconut shell fiber suspension; wherein the volume ratio of the mass of the alkalized coconut shell fibers to the deionized water is 1mg: 0.25-0.55 mL; the mass ratio of the alkalized coconut shell fibers to the sum of N- (3-dimethylaminopropyl) -N '-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is 1-3: 1, wherein the mass ratio of the N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide is 1:1;
b. adding gamma-mercaptopropyltrimethoxysilane (KH 590) and deionized water into a round-bottom flask, heating to 60 ℃, hydrolyzing for 10min, adding the activated coconut shell fiber suspension obtained in the step (3) a into the round-bottom flask, stirring and reacting for 10h, washing with deionized water, and drying in vacuum to obtain aminated coconut shell fibers; wherein the mass ratio of the gamma-mercaptopropyltrimethoxysilane (KH 590) to the activated coconut shell suspension is 1: 1-4;
(4) preparing the coconut shell fiber surface grafted graphene oxide CSSP @ GO:
dispersing the graphene oxide obtained in the step (1) in water, performing ultrasonic treatment for 2-3 hours to obtain a graphene oxide dispersion liquid with the concentration of 0.1-0.5 mg/mL, then sequentially adding 4-dimethylaminopyridine and the aminated coconut shell fiber obtained in the step (3), reacting for 2 hours under stirring at normal temperature, and performing vacuum drying to obtain the graphene oxide grafted on the surface of the coconut shell fiber; wherein the mass ratio of the graphene oxide to the aminated coconut shell fiber is 0.01-0.1: 1, and the mass ratio of the aminated coconut shell fiber to the 4-dimethylaminopyridine is 1-10: 1;
(5) preparing a coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite material CSSP @ GO-g-PA 12:
preparing a mixed solvent which is prepared by grafting graphene oxide on the surface of coconut shell fiber, nylon 12 material particles, hindered phenol and phosphite composite antioxidant, calcium stearate and ethanol, butanone, diethylene glycol and deionized water according to a certain proportion; placing the reaction system in a stainless steel high-temperature reaction kettle, and reacting in an oil bath kettle at the reaction temperature of 170 ℃ for 2 hours; after nylon 12 material particles in a reaction system are completely dissolved, violently stirring, cooling at a certain speed, taking CSSP @ GO as a core heterogeneous nucleation of the nylon 12 material particles in the process, coating the core heterogeneous nucleation on the surface of the CSSP @ GO, and rapidly cooling to room temperature to obtain CSSP @ GO-g-PA12 composite powder suspension; and carrying out vacuum filtration to recover the solvent, drying and ball milling to obtain CSSP @ GO-g-PA12 composite powder.
Further, the hindered phenol and phosphite ester compound antioxidant comprises hindered phenol CHEMNOX1010 with the content of 60-80 wt%; the phosphite ester antioxidant is triphenyl phosphite TPP, the content is 20wt% -40 wt%, and the sum of the mass percentages of the triphenyl phosphite TPP and the TPP is 100%. The mass of the added composite antioxidant is 0.5 percent of the mass of the nylon 12, and the mass of the added calcium stearate is 0.5 percent of the mass of the nylon 12.
Further, the mass ratio of the sum of the nylon 12 particles and CSSP @ GO to the mixed solvent is 1: 10-1: 20.
furthermore, the content of deionized water in the mixed solvent is controlled below 1wt%, and the content of butanone and diethylene glycol does not exceed 10 wt%.
The coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite material prepared by the preparation method is used in MJR3D printing process.
The invention has the beneficial effects that:
the invention relates to a reinforced nylon 12 composite material grafted with graphene oxide on the surface of MJR3D printed coconut shell fiber and a preparation method thereof, and aims to solve the technical problems of low surface energy, large surface inertia and poor thermodynamic performance of the conventional coconut shell fiber. The method comprises the following steps: 1. preparing graphene oxide; 2. alkalizing the coconut shell fibers; 3. modifying and aminating the surface of the coconut shell fiber; 4. grafting graphene oxide on the surface of the coconut shell fiber; 5. and grafting graphene oxide on the surface of the coconut shell fiber to reinforce the nylon 12 composite material. The surface of the coconut shell fiber lacks active functional groups, the reactivity is low, the cohesiveness with a matrix is poor, and more defects exist in an interface, so that the mechanical property of the composite material is directly influenced, the function of MJR3D printing sample pieces is limited, and the surface of graphene oxide has a large number of functional groups such as carboxyl, hydroxyl and epoxy, so that the graphene oxide is easy to combine and react with organic matters. The prepared CSSP @ GO-g-PA12 can be used in MJR3D printing process.
The alkalization of the coconut shell fibers is to remove impurities on the surfaces of the fibers; the purpose of the coconut shell surface modification amination treatment is as follows: the surface of the coconut shell fiber lacks active functional groups and has poor reactivity. In the preparation of CSSP @ GO, the added 4-dimethylaminopyridine is a novel efficient catalyst and can promote the better and faster combination of aminated coconut shell fiber and graphene oxide.
Drawings
FIG. 1 is an SEM image of pure CSSP powder used in the present invention;
FIG. 2 is an SEM image of an alkalized CSSP powder made in accordance with the present invention;
FIG. 3 is an SEM image of CSSP @ GO prepared in accordance with the present invention;
FIG. 4 is an SEM image of CSSP @ GO-g-PA12 prepared in example 3 of the present invention;
FIG. 5 is an infrared spectrum of CSSP @ GO prepared in accordance with the present invention versus neat CSSP;
FIG. 6 is a DSC of pure PA12 used in the present invention and CSSP @ GO-g-PA12 prepared in example 3;
FIG. 7 is a sample pattern diagram printed in experimental examples 1 to 5 and comparative examples 1 to 2 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
A composite material used for MJR3D printing coconut shell fiber surface grafting graphene oxide reinforced nylon 12 and a preparation method thereof are disclosed, and the specific process is as follows:
(1) preparing graphene oxide;
weighing 1.5g of flake graphite, placing the flake graphite in a 250ml beaker, adding 60ml of 98wt% concentrated sulfuric acid, slowly stirring at room temperature, and weighing 7.5g of KMnO4Solid, spooned to remove small amounts of KMnO4And (3) adding the solid once within 10min, finishing the addition within 2.5h, raising the temperature to 40 ℃, reacting for 6h, slowly adding 120mL of deionized water by using a dropper, raising the temperature of the water bath kettle to 90 ℃ after the addition is finished, reacting for 15min, continuously dropwise adding 10mL of 30wt% hydrogen peroxide solution and 5mL of 5wt% hydrochloric acid aqueous solution after the reaction is finished, adding deionized water to 1L after the beaker is free from yellow bubbles, standing for one night, pouring supernate, centrifuging, collecting the bottom thick liquid in the centrifuge tube, placing the thick liquid in an iron plate, and freeze-drying to obtain the graphene oxide.
(2) Carrying out alkalization treatment on the coconut shell fibers:
the coconut shell fiber is soaked in 5wt% NaOH solution for 6h to remove surface impurities. Subsequently, the fibres were washed with distilled water until the pH was 7 and the filler was dried in an oven at 60 ℃ for 48 h. To obtain the alkalized coconut shell fiber.
(3) Surface modification amination treatment of coconut shell fibers:
a. putting 200mg of the alkalized coconut shell fiber obtained in the step (2) into a round-bottom flask, adding 100ml of deionized water, stirring, adjusting the pH value to 5 by acid titration, adding 200mg of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and 200mg of N-hydroxysuccinimide, and activating for 15min to obtain an activated coconut shell fiber suspension;
b. adding 10mg of gamma-mercaptopropyltrimethoxysilane (KH 590) and 200ml of deionized water into a round-bottom flask, heating to 60 ℃, hydrolyzing for 10min, putting 40mg of the coconut shell fiber suspension obtained in the step (3) a after activation into the round-bottom flask, stirring and reacting for 10h, washing with deionized water, and drying in vacuum to obtain aminated coconut shell fibers;
(4) CSSP @ GO preparation:
adding 50mg of graphene oxide obtained in the step (1) into a beaker filled with 100mL of deionized water, placing the beaker at 60 ℃ for ultrasonic uniform dispersion until the concentration of the graphene oxide is 0.5mg/mL, then sequentially adding 50mg of 4-dimethylaminopyridine and 500mg of aminated coconut shell fiber obtained in the step (3), reacting for 2 hours under stirring at normal temperature, and performing vacuum drying to obtain the graphene oxide grafted on the surface of the coconut shell fiber;
(5) CSSP @ GO-g-PA12 composite preparation:
preparing 600ml of mixed solution according to the mass ratio of the material to the mixed solution of 1:6 under the protection of nitrogen, placing 5g of CSSP @ GO, 95g of PA12 (the mass ratio of CSSP @ GO: PA12 is 5: 95), 0.6g of hindered phenol CHEMNOX1010, 0.4g of phosphite TPP composite antioxidant and 0.5g of calcium stearate in a mixed solution of 575ml of absolute ethyl alcohol, 10ml of butanone, 10ml of diethylene glycol and 5ml of deionized water, placing the mixed solution into a high-temperature high-pressure reaction kettle, gradually heating the material from room temperature to 170 ℃, reacting for 2 hours at a constant temperature, uniformly cooling to 120 ℃ until the nylon 12 is completely dissolved, allowing the nylon 12 to take CSSP GO @ powder as a core heterogeneous core in the process, crystallizing and wrapping the core on the surface of the CSSP @ GO powder, rapidly cooling to room temperature, and discharging the obtained coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite powder suspension, and recovering the solvent through vacuum filtration, drying and ball milling to obtain the CSSP @ GO-g-PA12 composite material.
Example 2
A composite material used for MJR3D printing coconut shell fiber surface grafting graphene oxide reinforced nylon 12 and a preparation method thereof are disclosed, and the specific process is as follows:
(1) preparing graphene oxide;
weighing 1.5g of flake graphite, placing the flake graphite in a 250ml beaker, adding 60ml of 98wt% concentrated sulfuric acid, slowly stirring at room temperature, and weighing 7.5g of KMnO4Solid, spooned to remove small amounts of KMnO4And (3) adding the solid once within 10min, finishing the addition within 2.5h, raising the temperature to 40 ℃, reacting for 6h, slowly adding 120mL of deionized water by using a dropper, raising the temperature of the water bath kettle to 90 ℃ after the addition is finished, reacting for 15min, continuously dropwise adding 10mL of 30wt% hydrogen peroxide solution and 5mL of 5wt% hydrochloric acid aqueous solution after the reaction is finished, adding deionized water to 1L after no yellow bubbles exist in a beaker, standing for one night, pouring supernate, centrifuging, collecting the bottom thick liquid in a centrifuge tube, placing the thick liquid in an iron disc, and freeze-drying to obtain the graphene oxide.
(2) Carrying out alkalization treatment on the coconut shell fibers:
the coconut shell fiber is soaked in 5wt% NaOH solution for 6h to remove surface impurities. Subsequently, the fibres were washed with distilled water until the pH was 7 and the filler was dried in an oven at 60 ℃ for 48 h. To obtain the alkalized coconut shell fiber.
(3) Surface modification amination treatment of coconut shell fibers:
a. putting 200mg of the alkalized coconut shell fiber obtained in the step (2) into a round-bottom flask, adding 100ml of deionized water, stirring, adjusting the pH value to 5 by acid titration, adding 200mg of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and 200mg of N-hydroxysuccinimide, and activating for 15min to obtain an activated coconut shell fiber suspension;
b. adding 10mg of gamma-mercaptopropyltrimethoxysilane (KH 590) and 200ml of deionized water into a round-bottom flask, heating to 60 ℃, hydrolyzing for 10min, putting 40mg of the activated coconut shell fiber suspension obtained in the step (3) a into the round-bottom flask, stirring and reacting for 10h, washing with deionized water, and drying in vacuum to obtain aminated coconut shell fibers;
(4) CSSP @ GO preparation:
adding 50mg of graphene oxide obtained in the step (1) into a beaker filled with 100mL of deionized water, placing the beaker at 60 ℃ for ultrasonic uniform dispersion until the concentration of the graphene oxide is 0.5mg/mL, then sequentially adding 50mg of 4-dimethylaminopyridine and 500mg of aminated coconut shell fiber obtained in the step (3), reacting for 2 hours under stirring at normal temperature, and performing vacuum drying to obtain the graphene oxide grafted on the surface of the coconut shell fiber;
(5) preparation of CSSP @ GO-g-PA12 composite material
Preparing 600ml of mixed solution according to the mass ratio of the material to the mixed solution of 1:6 under the protection of nitrogen, placing 10g of CSSP @ GO, 90g of PA12 (the mass ratio of CSSP @ GO: PA12 is 10: 90), 0.6g of hindered phenol CHEMNOX1010, 0.4g of phosphite TPP composite antioxidant and 0.5g of calcium stearate in a mixed solution of 575ml of absolute ethyl alcohol, 10ml of butanone, 10ml of diethylene glycol and 5ml of deionized water, placing the mixed solution into a high-temperature high-pressure reaction kettle, gradually heating the material from room temperature to 170 ℃, reacting for 2 hours at a constant temperature, uniformly cooling to 120 ℃ until the nylon 12 is completely dissolved, allowing the nylon 12 to take CSSP GO @ powder as a core heterogeneous core in the process, crystallizing and wrapping the core on the surface of the CSSP @ GO powder, rapidly cooling to room temperature, and discharging the obtained coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite powder suspension, and recovering the solvent through vacuum filtration, drying and ball milling to obtain the CSSP @ GO-g-PA12 composite material.
Example 3
A composite material used for MJR3D printing coconut shell fiber surface grafting graphene oxide reinforced nylon 12 and a preparation method thereof are disclosed, and the specific process is as follows:
(1) preparing graphene oxide;
weighing 1.5g of flake graphite, placing the flake graphite in a 250ml beaker, adding 60ml of 98wt% concentrated sulfuric acid, slowly stirring at room temperature, and weighing 7.5g of KMnO4Solid, spooned to remove small amounts of KMnO4And (3) adding the solid once within 10min, finishing the addition within 2.5h, raising the temperature to 40 ℃, reacting for 6h, slowly adding 120mL of deionized water by using a dropper, raising the temperature of the water bath kettle to 90 ℃ after the addition is finished, reacting for 15min, continuously dropwise adding 10mL of 30wt% hydrogen peroxide solution and 5mL of 5wt% hydrochloric acid aqueous solution after the reaction is finished, adding deionized water to 1L after no yellow bubbles exist in a beaker, standing for one night, pouring supernate, centrifuging, collecting the bottom thick liquid in a centrifuge tube, placing the thick liquid in an iron disc, and freeze-drying to obtain the graphene oxide.
(2) Carrying out alkalization treatment on the coconut shell fibers:
the coconut shell fiber is soaked in 5wt% NaOH solution for 6h to remove surface impurities. Subsequently, the fibres were washed with distilled water until the pH was 7 and the filler was dried in an oven at 60 ℃ for 48 h. To obtain the alkalized coconut shell fiber.
(3) Surface modification amination treatment of coconut shell fibers:
a. putting 200mg of the alkalized coconut shell fiber obtained in the step (2) into a round-bottom flask, adding 100ml of deionized water, stirring, adjusting the pH value to 5 by acid titration, adding 200mg of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and 200mg of N-hydroxysuccinimide, and activating for 15min to obtain an activated coconut shell fiber suspension;
b. adding 10mg of gamma-mercaptopropyltrimethoxysilane (KH 590) and 200ml of deionized water into a round-bottom flask, heating to 60 ℃, hydrolyzing for 10min, putting 40mg of the activated coconut shell fiber suspension obtained in the step (3) a into the round-bottom flask, stirring and reacting for 10h, washing with deionized water, and drying in vacuum to obtain aminated coconut shell fibers;
(4) CSSP @ GO preparation:
adding 50mg of graphene oxide obtained in the step (1) into a beaker filled with 100mL of deionized water, placing the beaker at 60 ℃ for ultrasonic uniform dispersion until the concentration of the graphene oxide is 0.5mg/mL, then sequentially adding 50mg of 4-dimethylaminopyridine and 500mg of aminated coconut shell fiber obtained in the step (3), reacting for 2 hours under stirring at normal temperature, and performing vacuum drying to obtain the graphene oxide grafted on the surface of the coconut shell fiber;
(5) preparation of CSSP @ GO-g-PA12 composite material
Preparing 600ml of mixed solution according to the mass ratio of the material to the mixed solution of 1:6 under the protection of nitrogen, placing 15g of CSSP @ GO, 85g of PA12 (the mass ratio of CSSP @ GO: PA12 is 15: 85), 0.6g of hindered phenol CHEMNOX1010, 0.4g of phosphite TPP composite antioxidant and 0.5g of calcium stearate in a mixed solution of 575ml of absolute ethyl alcohol, 10ml of butanone, 10ml of diethylene glycol and 5ml of deionized water, placing the mixed solution into a high-temperature high-pressure reaction kettle, gradually heating the material from room temperature to 170 ℃, reacting for 2 hours at a constant temperature, uniformly cooling to 120 ℃ until the nylon 12 is completely dissolved, allowing the nylon 12 to take CSSP GO @ powder as a core heterogeneous core in the process, crystallizing and wrapping the core on the surface of the CSSP @ GO powder, rapidly cooling to room temperature, and discharging the obtained coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite powder suspension, and recovering the solvent through vacuum filtration, drying and ball milling to obtain the CSSP @ GO-g-PA12 composite material.
Example 4
A composite material used for MJR3D printing coconut shell fiber surface grafting graphene oxide reinforced nylon 12 and a preparation method thereof are disclosed, and the specific process is as follows:
(1) preparing graphene oxide;
weighing 1.5g of flake graphite, placing the flake graphite in a 250ml beaker, adding 60ml of 98wt% concentrated sulfuric acid, slowly stirring at room temperature, and weighing 7.5g of KMnO4Solid, spooned to remove small amounts of KMnO4And (3) adding the solid once within 10min, finishing the addition within 2.5h, raising the temperature to 40 ℃, reacting for 6h, slowly adding 120mL of deionized water by using a dropper, raising the temperature of the water bath kettle to 90 ℃ after the addition is finished, reacting for 15min, continuously dropwise adding 10mL of 30wt% hydrogen peroxide solution and 5mL of 5wt% hydrochloric acid aqueous solution after the reaction is finished, adding deionized water to 1L after no yellow bubbles exist in a beaker, standing for one night, pouring supernate, centrifuging, collecting the bottom thick liquid in a centrifuge tube, placing the thick liquid in an iron disc, and freeze-drying to obtain the graphene oxide.
(2) Carrying out alkalization treatment on the coconut shell fibers:
the coconut shell fiber is soaked in 5wt% NaOH solution for 6h to remove surface impurities. Subsequently, the fibres were washed with distilled water until the pH was 7 and the filler was dried in an oven at 60 ℃ for 48 h. To obtain the alkalized coconut shell fiber.
(3) Surface modification amination treatment of coconut shell fibers:
a. putting 200mg of the alkalized coconut shell fiber obtained in the step (2) into a round-bottom flask, adding 100ml of deionized water, stirring, adjusting the pH value to 5 by acid titration, adding 200mg of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and 200mg of N-hydroxysuccinimide, and activating for 15min to obtain an activated coconut shell fiber suspension;
b. adding 10mg of gamma-mercaptopropyltrimethoxysilane (KH 590) and 200ml of deionized water into a round-bottom flask, heating to 60 ℃, hydrolyzing for 10min, putting 40mg of the activated coconut shell fiber suspension obtained in the step (3) a into the round-bottom flask, stirring and reacting for 10h, washing with deionized water, and drying in vacuum to obtain aminated coconut shell fibers;
(4) CSSP @ GO preparation:
adding 50mg of graphene oxide obtained in the step (1) into a beaker filled with 100mL of deionized water, placing the beaker at 60 ℃ for ultrasonic uniform dispersion until the concentration of the graphene oxide is 0.5mg/mL, then sequentially adding 50mg of 4-dimethylaminopyridine and 500mg of aminated coconut shell fiber obtained in the step (3), reacting for 2 hours under stirring at normal temperature, and performing vacuum drying to obtain the graphene oxide grafted on the surface of the coconut shell fiber;
(5) preparation of CSSP @ GO-g-PA12 composite material
Preparing 600ml of mixed solution according to the mass ratio of the material to the mixed solution of 1:6 under the protection of nitrogen, placing 20g of CSSP @ GO, 80g of PA12 (the mass ratio of CSSP @ GO: PA12 is 20: 80), 0.6g of hindered phenol CHEMNOX1010, 0.4g of phosphite TPP composite antioxidant and 0.5g of calcium stearate in a mixed solution of 575ml of absolute ethyl alcohol, 10ml of butanone, 10ml of diethylene glycol and 5ml of deionized water, placing the mixed solution into a high-temperature high-pressure reaction kettle, gradually heating the material from room temperature to 170 ℃, reacting for 2 hours at a constant temperature, uniformly cooling to 120 ℃ until the nylon 12 is completely dissolved, allowing the nylon 12 to take CSSP GO @ powder as a core heterogeneous core in the process, crystallizing and wrapping the core on the surface of the CSSP @ GO powder, rapidly cooling to room temperature, and discharging the obtained coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite powder suspension, and recovering the solvent through vacuum filtration, drying and ball milling to obtain the CSSP @ GO-g-PA12 composite material.
Example 5
A composite material used for MJR3D printing coconut shell fiber surface grafting graphene oxide reinforced nylon 12 and a preparation method thereof are disclosed, and the specific process is as follows:
(1) preparing graphene oxide;
weighing 1.5g of flake graphite, placing the flake graphite in a 250ml beaker, adding 60ml of 98wt% concentrated sulfuric acid, slowly stirring at room temperature, and weighing 7.5g of KMnO4Solid, spooned to remove small amounts of KMnO4Adding the solid once in 10min, finishing the addition for 2.5h, raising the temperature to 40 ℃ for reaction for 6h, then slowly adding 120mL of deionized water by using a dropper, raising the temperature of a water bath kettle to 90 ℃ after the addition is finished, reacting for 15min, continuously dropwise adding 10mL of 30wt% hydrogen peroxide solution and 5mL of 5wt% hydrochloric acid aqueous solution after the reaction is finished, adding deionized water to 1L after no yellow bubbles exist in a beaker, standing for one night, pouring supernate, centrifuging, collecting the thick liquid at the bottom in a centrifuge tube, adding the thick liquid into ironAnd (5) freeze-drying in a plate to obtain the graphene oxide.
(2) Carrying out alkalization treatment on the coconut shell fibers:
the coconut shell fiber is soaked in 5wt% NaOH solution for 6h to remove surface impurities. Subsequently, the fibres were washed with distilled water until the pH was 7 and the filler was dried in an oven at 60 ℃ for 48 h. To obtain the alkalized coconut shell fiber.
(3) Surface modification amination treatment of coconut shell fibers:
a. putting 200mg of the alkalized coconut shell fiber obtained in the step (2) into a round-bottom flask, adding 100ml of deionized water, stirring, adjusting the pH value to 5 by acid titration, adding 200mg of N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and 200mg of N-hydroxysuccinimide, and activating for 15min to obtain an activated coconut shell fiber suspension;
b. adding 10mg of gamma-mercaptopropyltrimethoxysilane (KH 590) and 200ml of deionized water into a round-bottom flask, heating to 60 ℃, hydrolyzing for 10min, putting 40mg of the activated coconut shell fiber suspension obtained in the step (3) a into the round-bottom flask, stirring and reacting for 10h, washing with deionized water, and drying in vacuum to obtain aminated coconut shell fibers;
(4) CSSP @ GO preparation:
adding 50mg of graphene oxide obtained in the step (1) into a beaker filled with 100mL of deionized water, placing the beaker at 60 ℃ for ultrasonic uniform dispersion until the concentration of the graphene oxide is 0.5mg/mL, then sequentially adding 50mg of 4-dimethylaminopyridine and 500mg of aminated coconut shell fiber obtained in the step (3), reacting for 2 hours under stirring at normal temperature, and performing vacuum drying to obtain the graphene oxide grafted on the surface of the coconut shell fiber;
(5) preparation of CSSP @ GO-g-PA12 composite material
Preparing 600ml of mixed solution according to the mass ratio of the material to the mixed solution of 1:6 under the protection of nitrogen, placing 25g of CSSP @ GO, 75g of PA12 (the mass ratio of CSSP @ GO: PA12 is 25: 75), 0.6g of hindered phenol CHEMNOX1010, 0.4g of phosphite TPP composite antioxidant and 0.5g of calcium stearate into a mixed solution of 575ml of absolute ethyl alcohol, 10ml of butanone, 10ml of diethylene glycol and 5ml of deionized water, placing the mixed solution into a high-temperature high-pressure reaction kettle, gradually heating the material from room temperature to 170 ℃, reacting for 2 hours at a constant temperature, uniformly cooling to 120 ℃ until the nylon 12 is completely dissolved, allowing the nylon 12 to take CSSP GO @ powder as a core heterogeneous core in the process, crystallizing and wrapping the core on the surface of the CSSP @ GO powder, rapidly cooling to room temperature, and discharging the obtained coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite powder suspension, and recovering the solvent through vacuum filtration, drying and ball milling to obtain the CSSP @ GO-g-PA12 composite material.
Comparative example 1
A CSSP/PA12 composite was prepared using 15g of pure coconut shell fiber reinforced 75g of nylon 12 powder.
Comparative example 2
An f-CSSP/PA12 composite powder was prepared using 15g of the alkalized and aminated coconut shell fiber obtained in step (3) of example 1 to reinforce 75g of nylon 12 powder.
Performance testing
MJR3D printing forming main parameters are as follows: a printing mode: a fine printing mode; preheating temperature: 175 ℃; height of the powder layer: 110 microns; printing the spraying times of a spraying head of a powder layer: 4 pass; ink scraping distance of the nozzle: 15.8 inches, squeegee height: 6.0 inches, inking time: 4 s; negative pressure: 3.0Kpa, head voltage: 28V, spray head temperature: at 55 ℃.
3D printing process: powder paving is carried out on the modified nylon 12 powder prepared in the examples 1-5 and the comparative examples 1-2 by a MJR printer powder bed, then the temperature of the powder bed is raised to 175 ℃ (which is close to the melting point of the nylon 12 powder) to preheat the modified nylon 12 powder, a fluxing agent is selectively sprayed on the powder layer according to the layer printing data, and the fluxing agent absorbs infrared light to convert the infrared light into heat after infrared illumination, so that the modified nylon 12 powder is melted and shaped; after the first layer is printed, the powder bed is lowered by one layer height (lowered height: powder layer thickness), and then the steps of powder laying, preheating, flux spraying and the like are repeated to print the second layer. And the required 3D printing spline is finally printed by analogy.
Table two shows the mechanical property data of the samples printed by the MJR3D printer from the powder materials prepared in each example and comparative example. From the above physical property test results, it is obvious that with the increase of the amount of CSSP @ GO, the tensile strength, the bending strength and the fracture impact toughness of the CSSP @ GO-g-PA12 composite materials of examples 1 to 5 show a tendency of increasing first and then decreasing, and from the DSC diagram of fig. 6, it can be seen that the crystallization peak temperature of the composite powder is higher than that of the pure nylon 12 powder, which indicates that the addition of CSSP @ GO can contribute to the crystallization of the nylon 12 powder, and as the nylon 12 powder is a semi-crystalline polymer, the larger the crystallinity of the semi-crystalline polymer is, the better the mechanical properties are; however, as the CSSP @ GO is continuously increased, the mechanical properties tend to increase and decrease because the nylon 12 cannot be well wrapped on the coconut shell fibers due to the fact that the coconut shell fibers are too large in mass part, the interface bonding strength is low, and the strength of the composite material is reduced. The interaction between the CSSP @ GO and a PA12 matrix is beneficial to the transmission of stress load, and the optimal addition amount of the CSSP @ GO is 15% in view of comprehensive performance. The two comparative examples are respectively a 75g nylon 12 composite material reinforced by 15g pure coconut shell fiber and 15g alkalized aminated coconut shell fiber, and the mechanical properties of the composite material are lower than those of the alkalized and aminated grafted graphene oxide reinforced nylon 12 composite material, which shows that the roughness of the grafted graphene oxide on the surface of the coconut shell fiber is obviously increased, and the composite material is beneficial to enhancing the transfer effect between a matrix and a reinforcement in the nylon 12 composite material, improving the interface performance and further improving the mechanical properties of the composite material.
FIG. 1 shows untreated coconut shell powder with many impurities on the surface, while FIG. 2 shows alkalized coconut shell powder with smoother and cleaner surface. Due to the fact that the surface of the alkalized coconut shell fiber is lack of active groups and is subjected to amination treatment, the aminated coconut shell fiber is better combined with graphene oxide, and a CSSP @ GO scanning diagram in figure 3 shows that the roughness of the grafted graphene oxide on the surface of the coconut shell fiber is obviously increased, and the grafted graphene oxide is favorably combined with nylon 12; FIG. 4 is a scan of CSSP @ GO-g-PA12 showing that nylon 12 powder is coated with a core of CSSP @ GO in combination with CSSP @ GO to form a CSSP @ GO-g-PA12 composite.
As can be seen from FIG. 5, the CSSP @ GO of aminated CSSP and graphene oxide is compared with pure CSSP at 3500cm-1Has amino infrared peak at1500cm-1There is a strong hydroxyl peak nearby. As can be seen in FIG. 6, the CSSP @ GO-g-PA12 composite material has a higher crystallization temperature than pure nylon 12, indicating that CSSP @ GO has heterogeneous nucleation; and compared with pure nylon 12, the melting temperature of the CSSP @ GO-g-PA12 composite material is also higher, and as the nylon 12 coated with the CSSP @ GO is preferentially melted and absorbs heat in the heating process, the melting peak is also increased, so that the sintering window (namely the range between the initial crystallization temperature and the initial melting temperature) is increased, which also means that the CSSP @ GO-g-PA12 composite material is less prone to warping and has higher mechanical properties in the printing process.
Table one: index and test standard
Table two: performance testing
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. A preparation method of a composite material of enhanced nylon 12 grafted with graphene oxide and used for MJR3D printed coconut shell fiber surface is characterized by comprising the following steps:
(1) preparing graphene oxide GO;
(2) carrying out alkalization treatment on the coconut shell fiber CSSP:
soaking the coconut shell fiber in a 5wt% NaOH solution for 6h to remove surface impurities, then washing with distilled water until the pH value is 7, and drying in an oven at 60 ℃ for 48h to obtain the alkalized coconut shell fiber;
(3) surface modification amination treatment of coconut shell fibers:
a. adding deionized water into the alkalized coconut shell fiber obtained in the step (2), stirring, titrating with acid to adjust the pH value to 5-6, adding N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, and activating for 15min to obtain an activated coconut shell fiber suspension; wherein the volume ratio of the mass of the alkalized coconut shell fibers to the deionized water is 1mg: 0.25-0.55 mL; the mass ratio of the alkalized coconut shell fibers to the sum of N- (3-dimethylaminopropyl) -N '-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is 1-3: 1, wherein the mass ratio of the N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide is 1:1;
b. adding gamma-mercaptopropyl trimethoxy silane into deionized water, heating to 60 ℃, hydrolyzing for 10min, then adding activated coconut shell fiber suspension, stirring for reaction for 10h, then washing with deionized water, and drying in vacuum to obtain aminated coconut shell fiber; wherein the mass ratio of the gamma-mercaptopropyltrimethoxysilane to the activated coconut shell fiber suspension is 1: 1-4;
(4) preparing the coconut shell fiber surface grafted graphene oxide CSSP @ GO:
dispersing the graphene oxide obtained in the step (1) in water, performing ultrasonic treatment for 2-3 hours to obtain a graphene oxide dispersion liquid with the concentration of 0.1-0.5 mg/mL, then sequentially adding 4-dimethylaminopyridine and the aminated coconut shell fiber obtained in the step (3), reacting for 2 hours under stirring at normal temperature, and performing vacuum drying to obtain the graphene oxide grafted on the surface of the coconut shell fiber; wherein the mass ratio of the graphene oxide to the aminated coconut shell fiber is 0.01-0.1: 1; the mass ratio of the aminated coconut shell fiber to the 4-dimethylaminopyridine is 1-10: 1;
(5) preparing a coconut shell fiber surface grafted graphene oxide reinforced nylon 12 composite material CSSP @ GO-g-PA 12:
preparing a mixed solvent which is prepared by grafting graphene oxide on the surface of coconut shell fiber, nylon 12 material particles, hindered phenol and phosphite composite antioxidant, calcium stearate and ethanol, butanone, diethylene glycol and deionized water according to a certain proportion; placing the reaction system in a stainless steel high-temperature reaction kettle, and reacting in an oil bath kettle at the reaction temperature of 170 ℃ for 2 hours; after nylon 12 material particles in a reaction system are completely dissolved, violently stirring, cooling at a certain speed, taking CSSP @ GO as a core heterogeneous nucleation of the nylon 12 material particles in the process, coating the core heterogeneous nucleation on the surface of the CSSP @ GO, and rapidly cooling to room temperature to obtain CSSP @ GO-g-PA12 composite powder suspension; and carrying out vacuum filtration to recover the solvent, drying and ball milling to obtain CSSP @ GO-g-PA12 composite powder.
2. The method of claim 1, wherein: the hindered phenol and phosphite compound antioxidant comprises a hindered phenol antioxidant CHEMNOX1010 with the content of 60-80 wt%; the phosphite antioxidant triphenyl phosphite TPP accounts for 20-40 wt%; the mass of the added composite antioxidant is 0.5 percent of the mass of the nylon 12, and the mass of the added calcium stearate is 0.5 percent of the mass of the nylon 12.
3. The method of claim 1, wherein: the mass ratio of the sum of the nylon 12 granules and CSSP @ GO to the mixed solvent is 1: 10-1: 20.
4. the method of claim 1, wherein: the content of deionized water in the mixed solvent is controlled below 1wt%, and the content of butanone and diethylene glycol is not more than 10 wt%.
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