CN114685785A - Cyanate ester resin luminescent material doped with anchored europium carbon nano tube and preparation method thereof - Google Patents

Cyanate ester resin luminescent material doped with anchored europium carbon nano tube and preparation method thereof Download PDF

Info

Publication number
CN114685785A
CN114685785A CN202210219298.XA CN202210219298A CN114685785A CN 114685785 A CN114685785 A CN 114685785A CN 202210219298 A CN202210219298 A CN 202210219298A CN 114685785 A CN114685785 A CN 114685785A
Authority
CN
China
Prior art keywords
europium
unzipped
mixed solution
carbon nanotube
doped
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210219298.XA
Other languages
Chinese (zh)
Inventor
唐建国
胡子瑶
王瑶
巩学忠
毛遂
黄林军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao University
Original Assignee
Qingdao University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao University filed Critical Qingdao University
Priority to CN202210219298.XA priority Critical patent/CN114685785A/en
Publication of CN114685785A publication Critical patent/CN114685785A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065—Preparatory processes
    • C08G73/0655—Preparatory processes from polycyanurates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide

Abstract

The invention discloses an europium-anchored carbon nanotube doped cyanate ester resin luminescent material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing an oligomer; (2) preparing luminescent doped particles: and (3) oxidizing and stretching the multi-wall carbon nano-tube, and adhering and anchoring the multi-wall carbon nano-tube and the high-concentration europium complex to prepare europium complex zipper-releasing carbon nano-tube doped particles. (3) Preparing a double-effect composite material: and mixing the prepolymer with high-concentration europium complex unzipping carbon nanotube doped particles, casting and molding, and performing gradient heating and curing to generate the stable triazine ring structure. The composite material utilizes the catalytic action of the carbon nano tube, retains the high heat resistance of the cyanate resin matrix, and is widely applied to the fields of coatings, temperature sensing detection and the like.

Description

Cyanate ester resin luminescent material doped with anchored europium carbon nano tube and preparation method thereof
Technical Field
The invention relates to the technical field of functional luminescent composite materials, in particular to an anchoring europium carbon nanotube doped cyanate ester resin luminescent material and a preparation method thereof.
Background
The bisphenol E type monomer can realize free radical initiation under the action of high temperature to generate self-polymerization curing reaction, and the generated active intermediate has self-polymerization catalysis effect, but the binary intermediate has high activity and less content, so that the needed curing temperature is higher, the time is longer, and the higher conversion rate can not be achieved under the condition of not adding any catalyst. The conventional catalytic system can reduce the excellent performance of a cured product, and the high-temperature decomposition can cause a part of small molecules to cause bubbles to be generated in the composite material, so that the mechanical property is influenced. Meanwhile, the nanoparticles are doped into the resin matrix, and the aggregation phenomenon is generated at the same time, so that the mechanical property cannot be highlighted, and the stability of the luminescent particles under the high-temperature condition is poor. Therefore, the single-phase particle system cannot exhibit excellent performance, and has drawbacks, and further improvement is required.
The carbon nano tube is used as a polymer nano composite filling material with excellent mechanical, electrical and thermal properties, and the problem of poor dispersibility caused by agglomeration can occur in blending and forming.
Europium complexes composed of lanthanide luminescent elements exhibit strong ultraviolet absorption in the ultraviolet visible region, and in recent years, the europium complexes are often used as ultraviolet protective materials and are novel linear materials emitting red light under ultraviolet radiation.
Disclosure of Invention
The invention aims to solve the technical problem of providing an europium-anchored carbon nanotube doped cyanate resin luminescent material and a preparation method thereof aiming at the defects of the prior art.
The technical scheme of the invention is as follows:
a method for anchoring a europium carbon nanotube doped cyanate ester resin luminescent material comprises the following steps:
(1) selecting low-melting-point monomer bisphenol E (DCBE), bisphenol F (DCBF) or bisphenol M (DCBM) cyanate ester resin to carry out prepolymerization, and heating the prepolymerization for 8-9h at the temperature of 90-110 ℃ to obtain prepolymer (pre-CE);
(2) unzipping multi-walled carbon nanotubes (MWCNTs) to obtain unzipped multi-walled carbon nanotubes (uMWCNTs), and preparing a rare earth europium complex mixed solution (Eu complex); weighing a certain amount of unzipped multi-walled carbon nanotubes (uMWCNTs), adding the unzipped multi-walled carbon nanotubes into an acetone solvent for dispersion, adding a rare earth europium complex mixed solution, and stirring and performing ultrasonic treatment; finally, centrifugally washing the mixed solution, and drying in vacuum to obtain europium-complexed unzipped carbon nanotube doped particle (REuCNT) powder;
rare earth europium complex mixed solution (Eu complex): mu.L of 0.1mol/L Phen solution was prepared in advance, stirred for 3h, and then 400. mu.L of 0.1mol/L EuCl was added3Regulating the pH value of the solution and 400 mu L of 0.3mol/L TTA solution and 1mol/L of dilute ammonia water to 7, stirring for 4 hours, and mixing and stirring to obtain a rare earth europium complex mixed solution (Eu complex);
(3) adding europium complex unzipped carbon nanotube doped particles (REuCNTs) into a prepolymer (pre-CE) according to a certain proportion, ultrasonically dispersing, mixing and stirring, and drying in a vacuum drying oven to remove a solvent to obtain a mixed solution;
(4) and casting the prepared mixed solution into a mold, moving the mold to a vacuum drying oven for degassing treatment, and carrying out gradient temperature rise curing.
According to the method, the viscosity of the prepolymer (pre-CE) obtained in the step (1) is 0.09-1Pa.s, and the casting forming is facilitated.
The different specifications in step (2) are 0.01-0.1mol/L europium complex solution (Eu (TTA)3phen, Eu (TTA)3(TPPO)2, Eu (Dbm)3 Tpy).
The method comprises the steps of washing the europium-complexed unzipped carbon nanotube doped particles (REuCNTs) in the step (2) by using an alcohol solution, drying in vacuum to remove a solvent, drying, and preparing a powder solid for later use.
In the method, the ratio of the unzipped multi-walled carbon nanotubes to acetone in the step (2) is 10mg:10mL, ultrasonic dispersion.
In the method, in the step (2), 30mL of rare earth europium complex solution is correspondingly added into each 10mg of unzipped multi-wall carbon nano tube.
According to the method, in the step (2), the drying temperature of the vacuum drying oven is 90 ℃/60-90min to prevent bubbles from being generated.
In the step (3), the amount of doped europium-complexed unzipped carbon nanotube particles (REuCNTs) is 0.2-1.0 wt% of the prepolymer (pre-CE).
According to the method, the casting mould in the step (4) needs to be preheated in an electric heating air blowing oven for 40-90min, and a layer of vacuum silicone grease release agent is coated.
According to the method, the gradient heating curing process in the step (4) is 100 ℃/3h +150 ℃/2h +180 ℃/2h +230 ℃/1 h.
The europium-anchored carbon nanotube-doped cyanate resin luminescent material prepared by any one of the methods
Compared with multi-walled carbon nanotubes (MWCNTs), the oxygen-containing groups on the surface of the unzipped carbon nanotubes are combined with rare earth ions, so that the europium complex is more effectively anchored in the unzipped multi-walled carbon nanotubes (uMWCNTs), and precursor conditions are provided for preparing the luminescent nano material. Mixing prepolymer (pre-CE) and high-concentration europium complex unzipping carbon nano tube doped particles (REuCNTs), casting and molding, and performing gradient heating curing to generate a stable triazine ring structure, thereby preparing the double-efficient heat-resistant high-molecular fluorescent composite material.
Experiments show that compared with pure cyanate ester resin, the europium-complexed unzipped carbon nanotube doped particles (REuCNTs) solve agglomeration, enhance Eu3+ adsorption, improve interface bonding capability, reduce activation energy in a polymerization process and keep high heat resistance of a matrix. The tensile strength, the bending strength and the impact strength are correspondingly improved; the thermal stability is greatly higher than that of a single modification system, partial absorption of ultraviolet light is realized between 200 nm and 400nm, and the visible fluorescence intensity is higher.
In the invention, Eu complex with low electronegativity and high activity is taken as a second phase and introduced into the nano-scale particles uMWCNTs, and a large number of coordination bonds are formed by utilizing the self characteristics of the phase strengthening and aggregation MWCNTs, so that the nano-doped linear luminescent material REuCNTs is prepared. The invention combines resin prepolymer (pre-CE) with REuCNTs luminescent particles. Two-phase organic compounds having luminescent particles at the same time: the first phase MWCNTs have catalytic action on resin monomers and excellent mechanical properties; under the condition of excellent luminescent property of the europium complex, the empty electron orbit can form corresponding coordination bonding with N, O groups of the matrix, and the interface bonding force of the resin matrix is enhanced. The europium complexes are "grafted" to the composite material by means of uMWCNTs, so that the performance shows dual characteristics.
The invention provides a preparation method of an anchoring europium carbon nanotube doped cyanate ester resin luminescent material, which utilizes the catalytic action of carbon nanotubes, retains the high heat resistance of a cyanate ester resin matrix, and utilizes europium to complex and unzip carbon nanotube doped particles to obtain excellent mechanical properties and fluorescence properties.
Drawings
FIG. 1 is a preparation method of a dual-efficient-function luminescent composite material with both mechanical properties and fluorescent properties.
FIG. 2 is a TEM image of MWCNT (a) and uCNTs (b) REuCNTs (c); the figure shows that the specific surface area of the unzipped carbon nanotube is obviously increased, the adhesion area of the europium complex is increased, the interface bonding capability is improved, and the excellent performance of two-phase particles in a resin matrix is highlighted.
FIG. 3 is an FTIR plot of an oligomeric resin (pre-CE); it is obvious from the figure that as the curing gradient is increased, a triazine ring semi-continuous interpenetrating structure with high thermal stability is generated.
FIG. 4 is a non-isothermal DSC curve of bisphenol M cyanate ester resin. Compared with the polymerization peak value of Pure CE composite material system, the polymerization peak value of REuCNTs/CE is reduced by about 30 ℃, which proves that the rare earth complex unzipping multi-wall carbon nanotube REuCNTs has catalytic effect on the curing of monomer resin.
FIG. 5 is a TG curve of bisphenol E type cyanate ester resin and composites incorporating 0.8 wt% MWCNTs, uMWCNTs, REuCNTs. Researches show that under a high-temperature environment (800 ℃), the residual carbon amount and the decomposition initial temperature of a CE/REuCNTs composite material system are maximum, and the results prove that the rare earth complex unzipped multi-walled carbon nanotube REuCNT shows stronger heat-resistant and high-temperature-resistant performances, the REuCNTs catalyze the CE composite material system to generate a triazine ring structure with high thermal stability while the heat resistance of a resin structure is kept, the heat resistance of the CE/REuCNTs composite material system is further enhanced, and the DSC catalytic performance analysis is met.
FIG. 6 is a graph of the mechanical properties of the CE/MWCNTs and CE/REuCNTs composite materials at different concentrations. It can be seen that the mechanical properties of the CE/REuCNTs composite material are improved by utilizing the strong dispersion property of the novel derivative nano luminescent fillers (REuCNTs) under the relatively high concentration (0.8 wt%);
FIG. 7 is fluorescence excitation (a) emission (b) spectra of pure CE, CE/MWCNTs, CE/REMMWCNTs and CE/REuCNTs composites.
FIG. 8 shows fluorescence emission spectra of CE/REMMWCNTs and CE/REuCNTs light-emitting composite materials composed of bisphenol cyanate ester resin (DCBA, DCBM, DCBE) as matrix. It can be seen that the fluorescence peak (612nm) of the CE/REuCNTs composite material synthesized by mixing the low-viscosity bisphenol E cyanate ester resin (DCBE) with the hybrid fluorescent particle catalytic system is stronger, the fluorescence peak (430nm) of the resin is suppressed, and the fluorescence property of the composite material is improved.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The invention provides a preparation method of an anchoring europium carbon nanotube doped cyanate ester resin luminescent material, which comprises the following steps:
different cyanate ester resin monomers are selected in comparison: bisphenol E (DCBE), bisphenol F (DCBF), and bisphenol M (DCBM), and pre-polymer (pre-CE) is prepared by pre-polymerizing for 8-12h under heating at 80-110 deg.C.
And (3) taking multi-walled carbon nanotubes (MWCNTs) for unzipping, and obtaining unzipped multi-walled carbon nanotubes (uMWCNTs) for later use.
Mixing 1, 10-phenanthroline (Phen) solution with EuCl3The solution and 2-Thenoyl Trifluoroacetone (TTA) solution are mixed and stirred to prepare the rare earth europium complex mixed solution.
Weighing a certain amount of unzipped carbon nanotubes (uMWCNTs) and 10mL of acetone, dispersing, adding the dispersed solution, adding 30mL of rare earth europium complex mixed solution (Eu complex), and stirring and performing ultrasonic treatment; and finally, centrifugally washing the mixed solution, and drying in vacuum to obtain europium-complexed unzipped carbon nanotube doped particle (REuCNT) powder solid. Adding self-made europium complex unzipped carbon nanotube doped particles (REuCNTs) with different specifications into a prepolymer (pre-CE) according to a certain proportion (0.2-1.0 wt%), ultrasonically dispersing, mixing and stirring for 4-5h, and drying in a vacuum drying oven to remove the solvent to obtain a mixed solution. Casting the prepared mixed solution into a mould, carrying out vacuum drying and degassing treatment at 90-100 ℃ for 60-90min, then carrying out gradient heating and curing at 100 ℃/3h +150 ℃/2h +180 ℃/2h +230 ℃/1h, and finally carrying out demoulding treatment to obtain the solid sample composite material (CE/REuCNTs).
Example 1
Step (1), weighing 10mL of resin monomer DCBE, and prepolymerizing at 90 ℃ for 7h to obtain prepolymerized resin (pre-DCBE) at room temperature.
Step (2), taking 200mg MWCNTs and adding 35mL of concentrated H2SO4Uniformly stirring the solution, mixing for 10min, and performing ultrasonic treatment for 10h to prepare a solution; under the condition of strictly controlling the temperature to be about 20 ℃, taking 5 parts of 200mg KMnO on average4Slowly adding the mixture (10 min/time), uniformly stirring to obtain a black mixed solution, and then reacting for 2 hours at the temperature of 50 ℃ to obtain a tan mixed solution; the mixture was poured into a flask containing 0.3% H under ice-bath conditions2O2Eliminating residual KMnO in ice cubes4Until no gas is present; and finally, centrifugally washing the mixed solution (HCl/water solution) until the pH value is about 4-5, and freeze-drying to obtain unzipped carbon nanotube powder (uMWCNTs) for later use.
Step (3), preparing 400 mu L of 0.1mol/L Phen solution in advance, stirring for 3h, and then adding 400 mu L of 0.1mol/L LEuCl3The solution and 400 mu L of 0.3mol/L TTA solution and 1mol/L of dilute ammonia water are mixed and stirred for 4 hours to obtain a rare earth europium complex mixed solution (Eu complex).
Step (4), respectively weighing 10mg of MWCNTs and uMWCNTs, uniformly dispersing in 10mL of acetone solution, adding 30mL of rare earth europium complex mixed solution (Eu complex), and stirring and performing ultrasonic treatment; and finally, centrifugally washing the mixed solution, and drying in vacuum to obtain solid remCNTs and remCNTs powder.
FIG. 2 is a TEM image of MWCNT (a) and uMWCNTs (b) REuCNTs (c), which clearly shows that the specific surface area of the unzipped carbon nanotube is obviously increased, the adhesion area of the europium complex is increased, the interface bonding capability is improved, and the excellent performance of the two-phase particles in the resin matrix is highlighted.
And (5) weighing solid REMMWCNTs and REuCNT powder with the mass of 0.2 wt% of the resin matrix, respectively dispersing the solid REMMWCNTs and REuCNT powder in pre-polymerization resin pre-DCBE, and intensively stirring for 4 hours to form a mixed solution. And casting the prepared mixed solution into a preheated tetrafluoroethylene mold coated with vacuum silicone grease, and moving the tetrafluoroethylene mold to a vacuum drying oven for 90 ℃/1h degassing treatment to eliminate bubbles generated by the solvent. Then carrying out gradient temperature rise curing: 100 ℃/3h +150 ℃/2h +180 ℃/2h +230 ℃/1h, and finally obtaining solid samples of CE/REMMWCNTs and CE/REuCNTs through demoulding treatment.
FIG. 3 is an FTIR chart of the CE/REuCNTs composite material, and it is obvious that a triazine ring semi-continuous interpenetrating structure with high heat-resistant stability is generated along with the temperature rise of the curing gradient.
Example 2
Step (1), weighing 10mL resin monomer DCBM, and pre-polymerizing for 10h at 120 ℃ to proper viscosity (pre-DCBM) at room temperature.
Step (2), taking 200mg MWCNTs and adding 35mL of concentrated H2SO4Uniformly stirring the solution, mixing for 10min, and performing ultrasonic treatment for 10h to prepare a solution; under the condition of strictly controlling the temperature to be about 20 ℃, taking 5 parts of 200mg KMnO on average4Slowly adding the mixture (10 min/time), uniformly stirring to obtain a black mixed solution, and then reacting for 2 hours at the temperature of 50 ℃ to obtain a tan mixed solution; the mixture was poured into a flask containing 0.3% H under ice-bath conditions2O2Eliminating residual KMnO in ice cubes4Until no gas is present; and finally, centrifugally washing the mixed solution (HCl/water solution) until the pH value is about 4-5, and freeze-drying to obtain unzipped carbon nanotube powder (uMWCNTs) for later use.
Step (3), preparing 400 mu L of 0.1mol/L Phen solution in advance, stirring for 3h, and then adding 400 mu L of 0.1mol/L LEuCl3The solution and 400 mu L of 0.3mol/L TTA solution and 1mol/L of dilute ammonia water are mixed and stirred for 4 hours to obtain a rare earth europium complex mixed solution (Eu complex).
Step (4), respectively weighing 10mg of MWCNTs and uMWCNTs, uniformly dispersing in 10mL of acetone solution, adding 30mL of rare earth europium complex mixed solution (Eu complex), and stirring and performing ultrasonic treatment; and finally, centrifugally washing the mixed solution, and drying in vacuum to obtain solid remCNTs and remCNTs powder.
And (5) weighing solid REMMWCNTs and REuCNT powder accounting for 0.4 wt%, 0.6 wt%, 0.8 wt% and 1.0 wt% of the mass of the resin matrix, respectively dispersing in pre-polymerized resin pre-DCBE, and intensively stirring for 4h to form a mixed solution. And casting the prepared mixed solution into a preheated tetrafluoroethylene mold coated with vacuum silicone grease, and moving the tetrafluoroethylene mold to a vacuum drying oven for 90 ℃/1h degassing treatment to eliminate bubbles generated by the solvent. Then carrying out gradient temperature rise curing: 100 ℃/3h +150 ℃/2h +180 ℃/2h +230 ℃/1h, and finally obtaining solid samples of CE/REMMWCNTs and CE/REuCNTs through demoulding treatment.
FIG. 4 is a non-isothermal DSC curve of bisphenol M cyanate ester resin. The Pure CE, CE/MWCNTs, CE/uMWCNTs and CE/REuCNTs systems all have downward endothermic peaks at about 84 ℃, namely monomer melting peaks; the exothermic polymerization of the monomers was confirmed by the sequential appearance of different volume curing peaks in the range of about 320 c to 350 c. The polymerization peak value of Pure CE is 358.03 ℃, the polymerization peak value of the REuCNTs/CE composite material system is 326.26 ℃, the reduction is about 30 ℃, and the rare earth complex unzipping multi-wall carbon nano-tube REuCNTs have a catalytic effect on the curing of monomer resin.
Example 3
Step (1), weighing 10mL of resin monomer DCBF to pre-polymerize for 8h at 100 ℃ to reach proper viscosity (pre-DCBF) at room temperature.
Step (2), taking 200mg MWCNTs and adding 35mL of concentrated H2SO4Uniformly stirring the solution, mixing for 10min, and performing ultrasonic treatment for 10h to prepare a solution; under the condition of strictly controlling the temperature to be about 20 ℃, taking 5 parts of 200mg KMnO on average4Slowly adding the mixture (10 min/time), uniformly stirring to obtain a black mixed solution, and then reacting for 2 hours at the temperature of 50 ℃ to obtain a tan mixed solution; the mixture was poured into a flask containing 0.3% H in ice bath2O2Eliminating residual KMnO in ice cubes4Until no gas is present; and finally, centrifugally washing the mixed solution (HCl/water solution) until the pH value is about 4-5, and freeze-drying to obtain unzipped carbon nanotube powder (uMWCNTs) for later use.
Step (3), preparing 400 mu L of 0.1mol/L Phen solution in advance, stirring for 3h, and then adding 400 mu L of 0.1mol/L Phen solutionmol/LEuCl3The solution and 400 mu L of 0.3mol/L TTA solution and 1mol/L of dilute ammonia water are mixed and stirred for 4 hours to obtain a rare earth europium complex mixed solution (Eu complex).
Step (4), respectively weighing 10mg of MWCNTs and uMWCNTs, uniformly dispersing in 10mL of acetone solution, adding 30mL of rare earth europium complex mixed solution (Eu complex), and stirring and performing ultrasonic treatment; and finally, centrifugally washing the mixed solution, and drying in vacuum to obtain solid remCNTs and remCNTs powder.
And (5) weighing and respectively dispersing 0.4 wt%, 0.6 wt%, 0.8 wt% and 1.0 wt% of REMWCNTs and REuCNT powder solid in the mass of the resin matrix in the pre-polymerized resin pre-DCBE, and intensively stirring for 4 hours to form a mixed solution. And casting the prepared mixed solution into a preheated tetrafluoroethylene mold coated with vacuum silicone grease, and moving the tetrafluoroethylene mold to a vacuum drying oven for 90 ℃/1h degassing treatment to eliminate bubbles generated by the solvent. Then carrying out gradient temperature rise curing: 100 ℃/3h +150 ℃/2h +180 ℃/2h +230 ℃/1h, and finally obtaining solid samples of CE/REMMWCNTs and CE/REuCNTs through demoulding treatment.
FIG. 5 is a TG curve for characterizing monomers and incorporating 0.8 wt% MWCNTs, uMWCNTs, REuCNTs composites under nitrogen atmosphere. Research shows that under high-temperature environment (800 ℃), the CE/MWCNTs composite material system is increased by about 2 percent compared with Pure CE, and the CE/REuCNTs composite material system is increased by about 5 percent; meanwhile, the initial mass loss temperature of the Pure CE composite material system is 286 ℃, the initial temperature of the CE/REuCNTs system is 290 ℃, and the results prove that the rare earth complex unzipping multi-walled carbon nanotube REuCNT shows stronger heat resistance and high temperature resistance, the CE/REuCNTs composite material system catalyzes the generation of a triazine ring structure while the heat resistance of a resin structure is kept, the heat resistance is further enhanced, and the DSC catalytic performance analysis is met.
Example 4
Step (1), weighing 10mL of resin monomer DCBE, and prepolymerizing at 90 ℃ for 7h to obtain the appropriate viscosity (pre-DCBE) at room temperature.
Step (2), taking 200mg MWCNTs and adding 35mL of concentrated H2SO4Uniformly stirring the solution, mixing for 10min, and performing ultrasonic treatment for 10h to prepare a solution; under the condition of strictly controlling the temperature to be about 20 ℃, taking 5 parts of 200mg KMn on averageO4Slowly adding the mixture (10 min/time), uniformly stirring to obtain a black mixed solution, and then reacting for 2 hours at the temperature of 50 ℃ to obtain a tan mixed solution; the mixture was poured into a flask containing 0.3% H under ice-bath conditions2O2Eliminating residual KMnO in ice cubes4Until no gas is present; and finally, centrifugally washing the mixed solution (HCl/water solution) until the pH value is about 4-5, and freeze-drying to obtain unzipped carbon nanotube powder (uMWCNTs) for later use.
Step (3), preparing 400 mu L of 0.1mol/L Phen solution in advance, stirring for 3h, and then adding 400 mu L of 0.1mol/L LEuCl3The solution and 400 mu L of 0.3mol/L TTA solution and 1mol/L of dilute ammonia water are mixed and stirred for 4h to obtain a rare earth europium complex mixed solution (Eu complex).
Step (4), respectively weighing 10mg of MWCNTs and uMWCNTs, uniformly dispersing in 10mL of acetone solution, adding 30mL of rare earth europium complex mixed solution (Eu complex), and stirring and performing ultrasonic treatment; and finally, centrifugally washing the mixed solution, and drying in vacuum to obtain solid remCNTs and remCNTs powder.
And (5) weighing and respectively dispersing 0.4 wt%, 0.6 wt%, 0.8 wt% and 1.0 wt% of REMWCNTs and REuCNT powder solid in the mass of the resin matrix in the pre-polymerized resin pre-DCBE, and intensively stirring for 4 hours to form a mixed solution. And casting the prepared mixed solution into a preheated tetrafluoroethylene mold coated with vacuum silicone grease, and moving the tetrafluoroethylene mold to a vacuum drying oven for 90 ℃/1h degassing treatment to eliminate bubbles generated by the solvent. Then carrying out gradient temperature rise curing: 100 ℃/3h +150 ℃/2h +180 ℃/2h +230 ℃/1h, and finally obtaining solid samples of CE/REMMWCNTs and CE/REuCNTs through demoulding treatment.
FIG. 6 shows the mechanical properties of the composite material with MWCNTs and REuCNTs added at different concentrations, which characterize the changes of tensile strength, flexural strength and impact strength of cyanate ester resin. The Eu3+ complex is introduced to unzip the multi-walled carbon nanotube REuCNT, so that the problems of poor dispersibility and incapability of breaking through high-concentration doping amount under the condition of high concentration of MWCNTs are solved, and the mechanical property of the composite material is improved.
FIG. 8 shows fluorescence emission spectra of CE/REMMWCNTs and CE/REuCNTs light-emitting composite materials composed of bisphenol cyanate ester resin (DCBA, DCBM, DCBE) as matrix. It can be seen that the fluorescence peak (612nm) of the CE/REuCNTs composite material synthesized by mixing the low-viscosity bisphenol E cyanate ester resin (DCBE) with the hybrid fluorescent particle catalytic system is stronger, the fluorescence peak (430nm) of the resin is suppressed, and the fluorescence property of the composite material is improved.
It will be appreciated that modifications and variations are possible to those skilled in the art in light of the above teachings, and it is intended to cover all such modifications and variations as fall within the scope of the appended claims.

Claims (10)

1. A method for anchoring a europium carbon nanotube doped cyanate ester resin luminescent material is characterized by comprising the following steps:
(1) selecting low-melting-point monomer bisphenol E (DCBE), bisphenol F (DCBF) or bisphenol M (DCBM) cyanate ester resin to carry out prepolymerization, and heating the prepolymerization for 8-9h at the temperature of 90-110 ℃ to obtain prepolymer (pre-CE);
(2) unzipping multi-walled carbon nanotubes (MWCNTs) to obtain unzipped multi-walled carbon nanotubes (uMWCNTs), and preparing a rare earth europium complex mixed solution (Eu complex); weighing a certain amount of unzipped multi-walled carbon nanotubes (uMWCNTs), adding the unzipped multi-walled carbon nanotubes into an acetone solvent for dispersion, adding a rare earth europium complex mixed solution, and stirring and performing ultrasonic treatment; finally, centrifugally washing the mixed solution, and drying in vacuum to obtain europium-complexed unzipped carbon nanotube doped particle (REuCNT) powder;
(3) adding europium complex unzipped carbon nanotube doped particles (REuCNTs) into a prepolymer (pre-CE) according to a certain proportion, ultrasonically dispersing, mixing and stirring, and drying in a vacuum drying oven to remove a solvent to obtain a mixed solution;
(4) and casting the prepared mixed solution into a mold, moving the mold to a vacuum drying oven for degassing treatment, and carrying out gradient temperature rise curing.
2. The method of claim 1, wherein the prepolymer (pre-CE) obtained in step (1) has a viscosity of 0.09 to 1Pa.s, which facilitates casting.
3. The method according to claim 1, wherein the different specifications in step (2) are 0.01-0.1mol/L europium complex solution (Eu (TTA)3phen, Eu (TTA)3(TPPO)2, Eu (Dbm)3 Tpy).
4. The method of claim 1, wherein the europium-complexed unzipped carbon nanotube doped particles (REuCNTs) in step (2) are washed with an alcohol solution, dried under vacuum to remove the solvent, and dried to form a powder solid for later use.
5. The method of claim 1, wherein the unzipped multi-walled carbon nanotubes to acetone ratio in step (2) is 10mg:10mL, ultrasonic dispersion.
6. The method of claim 1, wherein 30mL of the rare earth europium complex solution is added per 10mg of unzipped multi-walled carbon nanotubes in step (2).
7. The method as claimed in claim 1, wherein the vacuum drying in step (2) is performed at a drying temperature of 90 ℃/60-90min to prevent the generation of bubbles.
8. The method of claim 1, wherein in the step (3), the pre-polymer (pre-CE) is doped with europium-complexed unzipped carbon nanotube-doped particles (REuCNTs) in an amount of 0.2 to 1.0 wt%.
9. The method as claimed in claim 1, wherein the gradient temperature-rising curing process in step (4) is 100 ℃/3h +150 ℃/2h +180 ℃/2h +230 ℃/1 h.
10. The europium-anchored carbon nanotube-doped cyanate ester resin phosphor prepared according to any one of claims 1 to 9.
CN202210219298.XA 2022-03-08 2022-03-08 Cyanate ester resin luminescent material doped with anchored europium carbon nano tube and preparation method thereof Pending CN114685785A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210219298.XA CN114685785A (en) 2022-03-08 2022-03-08 Cyanate ester resin luminescent material doped with anchored europium carbon nano tube and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210219298.XA CN114685785A (en) 2022-03-08 2022-03-08 Cyanate ester resin luminescent material doped with anchored europium carbon nano tube and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114685785A true CN114685785A (en) 2022-07-01

Family

ID=82136772

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210219298.XA Pending CN114685785A (en) 2022-03-08 2022-03-08 Cyanate ester resin luminescent material doped with anchored europium carbon nano tube and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114685785A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155593A (en) * 2007-12-28 2009-07-16 Mitsubishi Rayon Co Ltd Composition containing carbon nanotube and cured product
US20090220408A1 (en) * 2008-02-29 2009-09-03 Korea University Industrial & Academic Foundation Method of cutting carbon nanotubes and carbon nanotubes prepared by the same
US20100051471A1 (en) * 2008-08-29 2010-03-04 Tsinghua University Method for manufacturing carbon nanotube-conducting polymer composite
US20130035419A1 (en) * 2010-02-09 2013-02-07 Nanyang Technological University Methods for dispersing carbon nanotubes and compositions used for the methods
CN105754276A (en) * 2016-03-25 2016-07-13 惠州学院 Polymer film material with temperature fluorescence response and preparation method of polymer film material
CN112852152A (en) * 2021-03-02 2021-05-28 青岛大学 Flexible heat-resistant ultraviolet aging-resistant high-efficiency luminous high polymer material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009155593A (en) * 2007-12-28 2009-07-16 Mitsubishi Rayon Co Ltd Composition containing carbon nanotube and cured product
US20090220408A1 (en) * 2008-02-29 2009-09-03 Korea University Industrial & Academic Foundation Method of cutting carbon nanotubes and carbon nanotubes prepared by the same
US20100051471A1 (en) * 2008-08-29 2010-03-04 Tsinghua University Method for manufacturing carbon nanotube-conducting polymer composite
US20130035419A1 (en) * 2010-02-09 2013-02-07 Nanyang Technological University Methods for dispersing carbon nanotubes and compositions used for the methods
CN105754276A (en) * 2016-03-25 2016-07-13 惠州学院 Polymer film material with temperature fluorescence response and preparation method of polymer film material
CN112852152A (en) * 2021-03-02 2021-05-28 青岛大学 Flexible heat-resistant ultraviolet aging-resistant high-efficiency luminous high polymer material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NA YANG ET AL.: "Improved Mechanical, Anti-UV Irradiation, and Imparted Luminescence Properties of Cyanate Ester Resin/Unzipped Multiwalled Carbon Nanotubes/Europium Nanocomposites", MATERIALS, pages 1 - 14 *
杨莉蓉等: "多壁碳纳米管改性氰酸酯树脂体系的研究", 中国胶粘剂, pages 1 - 4 *
陈帅金等: "羟基化多壁碳纳米管对氰酸酯树脂的复合改性研究", 化工新型材料, pages 95 - 99 *

Similar Documents

Publication Publication Date Title
US7244374B2 (en) Composite and method of manufacturing the same
Konyushenko et al. Multi-wall carbon nanotubes coated with polyaniline
JP5764732B2 (en) Heat resistant high thermal conductive adhesive
KR20060133099A (en) Methods for the synthesis of modular poly(phenyleneethynylenes) and fine tuning the electronic properties thereof for the functionalization of nanomaterials
WO2017186127A1 (en) Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity
Karim et al. Conducting polyaniline‐titanium dioxide nanocomposites prepared by inverted emulsion polymerization
CN113368077B (en) Polydopamine-modified nano covalent organic framework and preparation method and application thereof
CN110885419B (en) Ultrahigh-frequency low-dielectric-property carboxylated graphene reinforced poly (benzoxazine-urethane) nano composite resin and preparation method thereof
CN114685785A (en) Cyanate ester resin luminescent material doped with anchored europium carbon nano tube and preparation method thereof
KR101395843B1 (en) Graphene-polyamide based composite and manufacturing method thereof
CN106995948B (en) A kind of nitrogen-doped carbon nano dot/magnetic metal oxide composite nano-fiber material, preparation method and applications
CN115286895B (en) Rare earth complex modified epoxy resin composite material and preparation method thereof
Nosheen et al. Synthesis and characterization of polypyrrole and graphene/polypyrrole/epoxy composites
KR100542660B1 (en) Expanded graphite/epoxy nano composite composition
CN114621382B (en) High-entropy insulating polymer for electrocaloric refrigeration and preparation method thereof
CN115926379A (en) Non-covalent modified boron nitride/epoxy resin heat-conducting and insulating composite material and preparation method thereof
CN101906249A (en) Method for preparing quantum dot/polyurethane nano crystal composite
CN113416383B (en) Flexible linear polymer and inorganic nanoparticle composite modified graphene oxide-epoxy resin composite material and preparation method thereof
CN114507417A (en) Modified epoxy resin and use method thereof
CN108727782B (en) Phosphorus-nitrogen nanometer flame-retardant epoxy resin composite material and preparation method thereof
Dutremez et al. Metal Alkoxide/Hexa‐2, 4‐diyne‐1, 6‐diol Hybrid Polymers: Synthesis and Use as Precursors to Metal Carbides and Nitrides
Fang et al. Curing behavior and kinetic analysis of epoxy resin/multi-walled carbon nanotubes composites
Kim et al. Thermal properties of poly (ε-caprolactone)/multiwalled carbon nanotubes composites
CN114958037B (en) Preparation method of carbon quantum dot coated carbonaceous material, composite material and application
CN112745478B (en) High-thermal-conductivity thermoplastic polyurethane composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination