CN109705843B

CN109705843B - Silicon dioxide modified terbium complex PET luminescent material and preparation method thereof

Info

Publication number: CN109705843B
Application number: CN201910055896.6A
Authority: CN
Inventors: 王瑶; 李�浩; 唐建国; 刘继宪; 黄林军; 王彦欣; 王薇; 邢丽
Original assignee: Qingdao University
Current assignee: Qingdao University
Priority date: 2019-01-22
Filing date: 2019-01-22
Publication date: 2022-03-08
Anticipated expiration: 2039-01-22
Also published as: CN109705843A

Abstract

The invention discloses a silicon dioxide modified terbium complex PET luminescent material and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, preparing nano chlorine silicon spheres; secondly, grafting tetraethylene glycol (4G) or 1,5 pentanediol (5CG) on the surface of the nano silicon chloride spheres; the third step, LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparing; fourthly, nano silicon dioxide/LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparing; fifthly, the two modified nano SiO obtained₂The terbium complex hybrid material is uniformly dispersed into a PET resin matrix as a nano nucleating additive to obtain two PET-based terbium complex hybrid luminescent materials. The material not only has the luminescent property of terbium complex, but also maintains the mechanical and crystallization properties of the PET matrix and is improved to a certain extent.

Description

Silicon dioxide modified terbium complex PET luminescent material and preparation method thereof

Technical Field

The invention relates to the field of preparation of PET luminescent materials, in particular to a silicon dioxide modified terbium complex PET luminescent material and a preparation method thereof.

Background

The rare earth ions have the advantages of high luminous intensity, pure color, high fluorescence efficiency, rich spectral lines and the like. The color of the rare earth ion luminescence is basically independent of the environment of the rare earth ion, and mainly depends on the rare earth ion. The rare earth complex has excellent luminescence property, but the application of the rare earth complex is limited due to poor thermal stability. In recent years, various methods have been used to uniformly disperse and compound organic photoactive materials with inorganic substrates at relatively low temperatures to prepare composite luminescent materials that may have the characteristics of organic and inorganic materials. The rare earth element has the advantages of high luminescent color purity, stable emission wavelength, high light intensity and the like.

Disclosure of Invention

The invention aims to provide a silicon dioxide modified terbium complex PET luminescent material and a preparation method thereof.

In order to achieve the technical purpose and achieve the technical effect, the invention adopts the following technical scheme:

a preparation method of a silicon dioxide modified terbium complex PET luminescent material comprises the following steps:

step one, preparing nano chlorine silicon spheres:

secondly, grafting tetraethylene glycol (4G) or 1,5 pentanediol (5CG) on the surface of the nano silicon chloride spheres

Preparing nano silicon dioxide surface grafted tetraethylene glycol: adding the silicon chloride balls into toluene, adding tetraethylene glycol under magnetic stirring, and reacting for 5 hours at 65 ℃ under the protection of nitrogen; finally, centrifugally separating the reaction mixed solution at 8000r/min for 15min, washing twice with toluene, and washing twice with acetone during centrifugal separation; vacuum drying the obtained product; the mass volume ratio of the silicon chloride spheres to the tetraethyleneglycol is 1: 10-25 g/ml; the mass volume ratio of the silicon chloride spheres to the toluene is 1: 9-16 g/ml;

preparing 1,5 pentanediol grafted on the surface of the nano silicon dioxide: adding the silicon chloride balls into toluene, adding tetraethylene glycol under magnetic stirring, and reacting for 5 hours at 65 ℃ under the protection of nitrogen; finally, centrifugally separating the reaction mixed solution at 8000r/min for 15min, washing twice with toluene, and washing twice with acetone during centrifugal separation; vacuum drying the obtained product;

the mass volume ratio of the silicon chloride spheres to the 1,5 pentanediol is 1: 10-25 g/ml; the mass volume ratio of the silicon chloride spheres to the toluene is 1: 9-16 ml/g;

the third step, LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation of

Preparation of LMPET-4G: dissolving LMPET in a solution of phenol and carbon tetrachloride in a mass ratio of 1:1, reacting for 2h in an oil bath at 60 ℃ under stirring of magnetons, and adding a small amount of cross-linking agent tetraethyleneglycol for several times in the reaction process; then adding a polycondensation catalyst Sb₂O₃Heating tetraethyleneglycol to 100 ℃, and continuously stirring for reaction for 2-3 hours; after the reaction is finished, centrifuging the mixture solution, washing the mixture solution by using a phenol and carbon tetrachloride solution with the mass ratio of 1:1 to remove the residual LMPET in the reaction, washing the mixture solution by using acetone and ethanol twice respectively, centrifuging the mixed solution to remove the residual impurities in the reaction, and drying the prepared LMPET-4G in vacuum; the mass volume ratio of LMPET to tetraethyleneglycol is 1: 2-5 g/ml; polycondensation catalyst Sb₂O₃The mass-volume ratio of the compound to the tetraethyleneglycol is 1: 30-100g/ml, and mixing phenol and tetrachloroethane in equal mass;

preparation of LMPET-5 CG: dissolving LMPET in a solution of phenol and carbon tetrachloride in a mass ratio of 1:1, reacting for 2h in an oil bath at 60 ℃ under stirring of magnetons, and adding a small amount of cross-linking agent 1,5 pentanediol for several times in the reaction process; then adding a polycondensation catalyst Sb₂O₃And 1,5 pentanediol, heating to 100 ℃, and continuously stirring for reaction for 2-3 hours; after the reaction is finished, centrifuging the mixture solution, washing the mixture solution by using phenol and carbon tetrachloride solution with the mass ratio of 1:1 to remove the residual LMPET in the reaction, washing the mixture solution by using acetone and ethanol twice respectively, centrifuging the mixed solution to remove the residual impurities in the reaction, and drying the prepared LMPET-1,5 pentanediol in vacuum; the mass volume ratio of LMPET to 1,5 pentanediol is 1: 2-5 g/ml; polycondensation catalyst Sb₂O₃The mass-volume ratio of the compound to the tetraethyleneglycol is 1: 30-100g/ml, and mixing phenol and tetrachloroethane in equal mass;

LMPET-4G/Phen/Tb³⁺or LMPET-5CG/Phen/Tb³⁺The preparation of (1): taking TbCl₃Putting the solution, namely LMPET-4G or LMPET-5CG polymer solution into a container, charging nitrogen, stirring and refluxing for 1 hour at 70 ℃, then adding phenanthroline solution, keeping the temperature at 70 ℃, and continuing to react for 6 hours; TbCl₃The amounts of the three substances of polymer and phenanthrolineThe ratio satisfies 1:3: 1;

fourthly, nano silicon dioxide/LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation of

Nano silicon dioxide/LMPET-4G/Phen/Tb³⁺The preparation of (1): LMPET-4G/Phen/Tb³⁺Reacting phenol/tetrachloroethane and tetraethylene glycol at 60 ℃, heating to 100 ℃ after the reaction is completed, and adding Sb₂O₃,SiO ₂4G (grafting tetraethyleneglycol on the surface of the nano silicon chloride spheres), reacting for 2 hours, centrifuging at 8000r/min for 8min, and drying at 100 ℃;

LMPET-4G/Phen/Tb³⁺the mass-volume ratio of the compound to the tetraethyleneglycol is 1: 2-5 g/ml; polycondensation catalyst Sb₂O₃With SiO₂-4G in a mass to volume ratio of 1: 30-100g/ml, and mixing phenol and tetrachloroethane in equal mass;

nano silicon dioxide/LMPET-5 CG/Phen/Tb³⁺The preparation of (1): LMPET-5CG/Phen/Tb³⁺Reacting phenol/tetrachloroethane and 1,5 pentanediol at 60 ℃, heating to 100 ℃ after the reaction is completed, and adding Sb₂O₃,SiO₂5CG (grafting tetra-1, 5 pentanediol on the surface of the nano silicon chloride spheres), reacting for 2 hours, centrifuging at 8000r/min for 8min, and drying at 100 ℃;

LMPET-5CG/Phen/Tb³⁺the mass volume ratio of the 1, 5-pentanediol to the 1: 2-5 g/ml; polycondensation catalyst Sb₂O₃With SiO₂-5CG mass to volume ratio of 1: 30-100g/ml, and mixing phenol and tetrachloroethane in equal mass;

fifthly, the two modified nano SiO obtained₂The terbium complex hybrid material is uniformly dispersed into a PET resin matrix as a nano nucleating additive to obtain two PET-based terbium complex hybrid luminescent materials.

The preparation method comprises the following steps: adding benzene into the nano silicon dioxide to dissolve the nano silicon dioxide, dropwise adding thionyl chloride under the protection of nitrogen, and reacting for 4 hours at 65 ℃; then centrifugally separating the reaction mixed liquid, washing the reaction mixed liquid for three times by using benzene, drying the obtained silicon chloride balls in vacuum, and storing the silicon chloride balls in a closed container; the mass volume ratio of the nano silicon dioxide to the benzene is 1: 8-15 g/ml; the mass volume ratio of the nano silicon dioxide to the thionyl chloride is 1: 6-8 g/ml.

In the third step, the preparation method of LMPET is as follows: adding a small amount of dimethyl terephthalate, ethylene glycol and zinc acetate into a container, reacting for 2 hours at 190 ℃, and mechanically stirring; then adding a polycondensation catalyst Sb₂O₃Reacting with 2-3 drops of heat stabilizer triphenyl phosphite for half an hour, distilling under reduced pressure for 1 hour when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, filtering, and drying the obtained product in vacuum to obtain low molecular weight polyethylene glycol terephthalate; the mass volume ratio of dimethyl terephthalate to ethylene glycol is 1: 1.59 g/ml; the mass volume ratio of the zinc acetate to the ethylene glycol is 1:480 g/ml; polycondensation catalyst Sb₂O₃The mass volume ratio of the ethylene glycol to the ethylene glycol is 1: 30-100 g/ml.

According to the preparation method, the rare earth ions are obtained by ionizing commercially available terbium oxide.

According to the preparation method, the LMPET surface graft is obtained by polymerizing tetraethylene glycol or 1,5 pentanediol, and the polymerization degree is greater than 1 and is a positive integer.

According to the preparation method, the particle size range of the nano silicon dioxide is 20-200 nm.

According to the preparation method, the linear polyester adopts the commercial PET slices, and the intrinsic viscosity of the linear polyester is 0.676 dL/g.

The PET luminescent material prepared by the preparation method.

The invention has the following beneficial effects:

the preparation method comprises the steps of introducing tetraethylene glycol or 1,5 pentanediol segments into LMPET to obtain two different hybrid polymers (LMPET-4G and LMPET-5CG), complexing with rare earth terbium ions, respectively obtaining two different LMPET-based terbium complex hybrid luminescent groups, coating the obtained hybrid luminescent groups on the surface of nano-silica self-made in a laboratory, and uniformly dispersing a silica-modified terbium complex PET luminescent material into a PET resin matrix to obtain the silica-modified PET-based terbium complex hybrid luminescent material.

Drawings

FIG. 1 is a schematic diagram of the reaction scheme of the present invention.

FIG. 2 is an emission spectrum of a low molecular weight PET-based europium-complex hybrid luminescent group;

FIG. 3 shows LMPET-4G and LMPET-4G/Phen/Tb, respectively³⁺(ii) an infrared spectrum;

Detailed Description

The present invention will be described in detail with reference to specific examples.

Example 1

As shown in figure 1, the invention discloses a preparation method of a silicon dioxide modified terbium complex PET luminescent material, which comprises the following steps:

first, in nano Silica (SiO)₂) Preparing nano chlorine silicon balls on the basis:

preparing the silicon chloride balls: adding nano-silica (about 20-200nm in size, pre-dried in a vacuum oven at 80 deg.C for 24 hr), adding benzene to dissolve, adding thionyl chloride dropwise through a separating funnel under nitrogen protection, and then adding HCl and SO₂The reaction was carried out at 65 ℃ for 4 hours. Then the reaction mixture is centrifuged at 8000r/min for 15 min. And washing with benzene for three times, drying the obtained silicon chloride spheres in vacuum, and storing the dried silicon chloride spheres in a closed container, wherein the mass volume ratio of the nano silicon dioxide to the benzene is 1: 8-15 g/ml; the mass volume ratio of the nano silicon dioxide to the thionyl chloride is 1: 6-8 g/ml.

Preparing nano silicon dioxide surface grafted tetraethylene glycol: adding the silicon chloride balls into toluene, adding tetraethylene glycol under magnetic stirring, and reacting for 5 hours at 65 ℃ under the protection of nitrogen. Finally, the reaction mixture is centrifugally separated, 8000r/min and 15min, and is washed twice by toluene, and in order to remove unreacted tetraethylene glycol, the reaction mixture is centrifugally separated, and is washed twice by acetone. And (5) drying the obtained product in vacuum. The mass volume ratio of the silicon chloride spheres to the tetraethyleneglycol is 1: 10-25 g/ml. The mass volume ratio of the silicon chloride spheres to the toluene is 1: 9-16 ml/g.

Preparing 1,5 pentanediol grafted on the surface of the nano silicon dioxide: adding the silicon chloride balls into toluene, adding tetraethylene glycol under magnetic stirring, and reacting for 5 hours at 65 ℃ under the protection of nitrogen. Finally, the reaction mixture was centrifuged at 8000r/min for 15min and washed twice with toluene, and twice with acetone for centrifugation to remove unreacted 1, 5-pentanediol. And (5) drying the obtained product in vacuum. The mass volume ratio of the silicon chloride spheres to the 1,5 pentanediol is 1: 10-25 g/ml. The mass volume ratio of the silicon chloride spheres to the toluene is 1: 9-16 ml/g.

The third step, LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation of

The preparation method of LMPET comprises the following steps: dimethyl terephthalate, ethylene glycol and zinc acetate are added into a 250mL volumetric flask in small amount, and the mixture reacts for 2 hours at 190 ℃ with mechanical stirring. Then adding a small amount of polycondensation catalyst Sb₂O₃And reacting with 2-3 drops of heat stabilizer triphenyl phosphite for half an hour, distilling under reduced pressure for 1 hour when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, carrying out suction filtration, and carrying out vacuum drying on the obtained product to obtain the low molecular weight polyethylene terephthalate. The mass volume ratio of dimethyl terephthalate to ethylene glycol is 1: 1.59 g/ml; the mass volume ratio of the zinc acetate to the ethylene glycol is 1:480 g/ml; polycondensation catalyst Sb₂O₃The mass volume ratio of the ethylene glycol to the ethylene glycol is 1: 30-100 g/ml.

Preparation of LMPET-4G: dissolving LMPET in a solution of phenol and carbon tetrachloride in a mass ratio of 1:1, reacting for 2h in an oil bath at 60 ℃ under stirring of magnetons, and adding a small amount of cross-linking agent tetraethyleneglycol for several times in the reaction process. 0.03g of polycondensation catalyst Sb was then added₂O₃And tetraethyleneglycol, heating to 100 ℃, and continuously stirring for reaction for 2-3 hours. After the reaction is finished, centrifuging the mixture solution, washing the mixture solution by using a phenol and carbon tetrachloride solution with the mass ratio of 1:1 to remove the residual LMPET in the reaction, washing the mixture solution by using acetone and ethanol twice respectively, centrifuging the mixed solution to remove the residual impurities in the reaction, and drying the prepared LMPET-tetraethyleneglycol in vacuum. The mass volume ratio of LMPET to tetraethyleneglycol is 1: 2-5 g/ml. Polycondensation catalysisAgent Sb₂O₃The mass-volume ratio of the compound to the tetraethyleneglycol is 1: 30-100g/ml, and mixing phenol and tetrachloroethane.

Preparation of LMPET-5 CG: dissolving LMPET in a solution of phenol and carbon tetrachloride in a mass ratio of 1:1, reacting for 2h in an oil bath at 60 ℃ under stirring of magnetons, and adding a small amount of cross-linking agent 1,5 pentanediol for several times in the reaction process. 0.03g of polycondensation catalyst Sb was then added₂O₃And 1,5 pentanediol, heating to 100 ℃, and continuously stirring for reaction for 2-3 hours. After the reaction is finished, centrifuging the mixture solution, washing the mixture solution by using a phenol and carbon tetrachloride solution with the mass ratio of 1:1 to remove the residual LMPET in the reaction, washing the mixture solution by using acetone and ethanol twice respectively, centrifuging the mixed solution to remove the residual impurities in the reaction, and drying the prepared LMPET-1,5 pentanediol in vacuum. The mass volume ratio of LMPET to 1,5 pentanediol is 1: 2-5 g/ml. Polycondensation catalyst Sb₂O₃The mass-volume ratio of the compound to the tetraethyleneglycol is 1: 30-100g/ml, and mixing phenol and tetrachloroethane.

LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺The preparation of (1): taking TbCl₃Putting the solution, namely polymer solution (LMPET-4G or LMPET-5CG) in a round-bottom flask, filling nitrogen, stirring and refluxing for 1 hour at 70 ℃, adding phenanthroline solution, keeping the temperature at 70 ℃, and continuing to react for 6 hours. TbCl₃The ratio of the polymer to the phenanthroline is 1:3: 1.

Nano silicon dioxide/LMPET-4G/Phen/Tb³⁺The preparation of (1): LMPET-4G/Phen/Tb³⁺(third step self-made), phenol (the whole bottle of bag cover needs to be heated in advance when the freezing point is very low, and is weighed quickly, otherwise, the phenol is stuck on the wall of the cup)/tetrachloroethane (which is toxic and is weighed in a fume hood, the ratio is 1:1, and is used as a solvent), tetraethyleneglycol, reacting at 60 ℃, heating to 100 ℃ after the reaction is completely dissolved (1 hour), and adding Sb₂O₃,SiO ₂4G (second step self-made), reacting for 2 hours, centrifuging at 8000r/min for 8min, and drying at 100 ℃ (placing in a drying box of A chamber, heating and timing). LMPET-4G/Phen/Tb³⁺Substances with tetraethylene glycolThe volume ratio is 1: 2-5 g/ml. Polycondensation catalyst Sb₂O₃With SiO₂-4G in a mass to volume ratio of 1: 30-100g/ml, and mixing phenol and tetrachloroethane.

Nano silicon dioxide/LMPET-5 CG/Phen/Tb³⁺The preparation of (1): LMPET-5CG/Phen/Tb³⁺Reacting phenol/tetrachloroethane and 1,5 pentanediol at 60 ℃, heating to 100 ℃ after the reaction is completely dissolved (1 hour), and adding Sb₂O₃,SiO₂5CG (second step self-made), reacting for 2 hours, centrifuging at 8000r/min,8min, and drying at 100 deg.C (placing in a drying box of A chamber, heating and timing). LMPET-5CG/Phen/Tb³⁺The mass volume ratio of the 1, 5-pentanediol to the 1: 2-5 g/ml. Polycondensation catalyst Sb₂O₃With SiO₂-5CG mass to volume ratio of 1: 30-100g/ml, and mixing phenol and tetrachloroethane.

Wherein the terbium ion is obtained by ionizing commercially available terbium oxide.

Wherein the LMPET surface graft is obtained by polymerizing dihydric alcohol (tetraethylene glycol or 1,5 pentanediol) with the general formula of HOROH, and the polymerization degree is more than 1 and is a positive integer.

The preparation method of the low molecular weight polyethylene terephthalate (LMPET) comprises the following steps:

dimethyl terephthalate, ethylene glycol and zinc acetate are added into a 250mL volumetric flask in small amount, and the mixture reacts for 2 hours at 190 ℃ with mechanical stirring. Then adding a small amount of polycondensation catalyst Sb₂O₃And 2-3 drops of heat stabilizer triphenyl phosphite, reacting for half an hour, distilling under reduced pressure for 1 hour when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, filtering, and drying the obtained product in vacuum to obtain the low molecular weight polyethylene glycol terephthalate.

Example 2

In order to research the influence of the low-molecular-weight PET-based terbium-complexed hybrid luminescent group on the luminescent performance of the rare earth, the embodiment takes the low-molecular-weight PET-based terbium-complexed hybrid luminescent group solution synthesized in the embodiment 1 as a research object, and the research method comprises the following steps: and performing fluorescence test on the low-molecular-weight PET-based terbium complex hybrid luminescent group solution by using an RF-5301P fluorescence spectrophotometer.

As shown in figure 2, the emission spectrum of the low molecular weight PET-based europium complex hybrid luminescent group has an excitation wavelength of 331.07nm and an emission wavelength of 544.02nm, the method successfully prepares two low molecular weight PET-based terbium complex hybrid luminescent groups, the introduction of the block polymer does not affect the luminescent performance of rare earth ions, and finally the low molecular weight PET-based complex hybrid luminescent group is coated on the surface of the nano silicon dioxide.

As shown in FIG. 3, in order to investigate the change of characteristic group of the successfully prepared low molecular weight PET-based terbium-complex hybrid luminescent group, the structural analysis of the low molecular weight PET-based terbium-complex hybrid luminescent group was performed, and this example used the low molecular weight PET-based polymer powder synthesized in example 1 and the low molecular weight PET-based terbium-complex hybrid luminescent group powders (LMPET-4G and LMPET-4G/Phen/Tb)³⁺) The study method is as follows: an infrared spectrometer (model 5700, manufactured by Nicolet of America, the wave number range of 4000-400 cm)^-1) For LMPET-4G and LMPET-4G/Phen/Tb³⁺And carrying out structural analysis testing.

As shown in FIG. 3, LMPET-4G and LMPET-4G/Phen/Tb, respectively³⁺An infrared spectrum of (1). In this spectrum, LMPET-4G (FIG. 3.a) and LMPET-4G/Phen/Tb³⁺(FIG. 3.b) most of the characteristic absorption peak positions are similar in intensity. Wherein on curve b, a new 1663.97cm appeared in comparison to curve a^-1Characteristic absorption peak of (2), 1663.97cm^-1Nearby, 1715.66cm^-1The characteristic absorption peak of C ═ O is shown, which indicates that the low molecular weight PET polymer generates low molecular weight PET based terbium complex hybridization luminescent group after complexing, and the complexing is generated at the position of C ═ O, so that 1663.97cm is obtained^-1The appearance of characteristic absorption peaks.

Example 3

The experimental purposes and methods: in order to study the nano-silica/LMPET-4G or LMPET-5CG/Phen/Tb³⁺The effect of the two hybrid luminescent materials on the mechanical properties of the industrial PET polyester crystals, the nano-silica/LMPET-4G or LMPET-5CG/Phen/Tb synthesized in example 1 is used in the example³⁺The two hybrid luminescent materials are used as experimental objects to research the influence of the experimental objects on the mechanical properties of linear polyester chips, and the specific method comprises the following steps: using DSM Xploore 5&Type 15 miniblender melt blending was mixed thoroughly and made into standard specimens on a DSM Xplore type 10cc minimolder. The melting temperature in the blender is 290 ℃, the temperature of a mould in the injection molding machine is 50 ℃ when pure linear polyester is adopted, and the temperature is changed to 40 ℃ after the low molecular weight PET-based europium complex hybrid luminescent group synthesized in the embodiment 1 is added. Co-preparation of synthetic nano-silica/LMPET-4G or LMPET-5CG/Phen/Tb³⁺The two hybrid luminescent materials are respectively subjected to four groups of samples of 0%, 2.0%, 4.0% and 6.0% so as to test the mechanical properties and the like.

The experimental results are as follows:

TABLE 1 different proportions of nanosilicon dioxide/LMPET-4G/Phen/Tb³⁺Mechanical property test results of addition to Linear polyester

The addition amount of	Elongation at break/%)	Tensile strength/MPa	Yield strength/MPa	Tensile modulus/MPa
					0	138	59.072	63.01	1231.98
2	163	65.031	64.07	1399.25
					4	125	59.686	57.97	1453.06
6	107	57.556	56.03	1767.01

As shown in Table 1, the nano-silica/LMPET-4G/Phen/Tb ratio is different³⁺The mechanical property test result of the addition amount of the hybrid luminescent group to the linear polyester shows that the mechanical property of the linear polyester is increased and then decreased along with the increase of the addition amount, which shows that the strength of the linear polyester is improved by adding the hybrid luminescent group when the addition amount is less than 4%.

TABLE 2 nanosilicon dioxide/LMPET-5 CG/Phen/Tb in different ratios³⁺Mechanical property test results of addition to Linear polyester

The same applies to the nanosilica/LMPET-5 CG/Phen/Tb ratios in Table 2³⁺Mechanical Property testing of addition amounts to Linear polyestersThe possible reasons are that the processing method of the invention: firstly, the compatibility and the interface bonding force of the low molecular weight PET body with a matrix are increased, and the good dispersion state of the filler in the matrix is favorably maintained; and secondly, under the condition of low content, the hybridized luminescent groups are dispersed more uniformly through the shearing action of the blending of double screws in the macromolecular micro blender. The two reasons enhance the adsorption capacity of the hybrid luminescent material and a polymer chain, and the hybrid luminescent material is crosslinked and wound to a certain degree to form a network structure, so that the strength is higher than that of common polyester. When the amount is too large (more than 4%), uniformity of dispersion of the hybrid luminescent group in the polyester matrix becomes poor, aggregates are easily formed, which are referred to as defects of the material, cause local stress concentration when a force is applied, and decrease the strength of the polyester material.

It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.

Claims

1. A preparation method of a silicon dioxide modified terbium complex PET luminescent material is characterized by comprising the following steps:

firstly, preparing nano chlorine silicon spheres;

secondly, grafting tetraethylene glycol or 1,5 pentanediol on the surface of the nano silicon chloride spheres

Preparing the nano silicon chloride spheres with the surface grafted with tetraethylene glycol: adding the silicon chloride balls into toluene, adding tetraethylene glycol under magnetic stirring, and reacting for 5 hours at 65 ℃ under the protection of nitrogen; finally, centrifugally separating the reaction mixed solution at 8000r/min for 15min, washing twice with toluene, and washing twice with acetone during centrifugal separation; vacuum drying the obtained product; the mass volume ratio of the silicon chloride spheres to the tetraethyleneglycol is 1: 10-25 g/ml; the mass volume ratio of the silicon chloride spheres to the toluene is 1: 9-16 g/ml;

preparing 1,5 pentanediol grafted on the surface of the nanometer silicon chloride spheres: adding silicon chloride spheres into toluene, adding 1, 5-pentanediol under magnetic stirring, and reacting for 5 hours at 65 ℃ under the protection of nitrogen; finally, centrifugally separating the reaction mixed solution at 8000r/min for 15min, washing twice with toluene, and washing twice with acetone during centrifugal separation; vacuum drying the obtained product;

the third step, LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation of

preparation of LMPET-5 CG: dissolving LMPET in a solution of phenol and carbon tetrachloride in a mass ratio of 1:1, reacting for 2h in an oil bath at 60 ℃ under stirring of magnetons, and adding a small amount of cross-linking agent 1,5 pentanediol for several times in the reaction process; then adding a polycondensation catalyst Sb₂O₃And 1,5 pentanediol, heating to 100 ℃, and continuously stirring for reaction for 2-3 hours; after the reaction is finished, centrifuging the mixture solution, washing the mixture solution by using a phenol and carbon tetrachloride solution with the mass ratio of 1:1 to remove the residual LMPET in the reaction, washing the mixture solution by using acetone and ethanol twice respectively, centrifuging the mixed solution to remove the residual impurities in the reaction, and drying the prepared LMPET-5CG in vacuum; the mass volume ratio of LMPET to 1,5 pentanediol is 1: 2-5 g/ml; polycondensation catalyst Sb₂O₃The mass-volume ratio of the compound to the tetraethyleneglycol is 1: 30-100g/ml, and mixing phenol and tetrachloroethane in equal mass;

LMPET-4G/Phen/Tb³⁺or LMPET-5CG/Phen/Tb³⁺System of (1)Preparing: taking TbCl₃Putting the solution, namely LMPET-4G or LMPET-5CG polymer solution into a container, charging nitrogen, stirring and refluxing for 1 hour at 70 ℃, then adding phenanthroline solution, keeping the temperature at 70 ℃, and continuing to react for 6 hours; TbCl₃The amount ratio of the polymer to the phenanthroline is 1:3: 1;

Nano silicon dioxide/LMPET-4G/Phen/Tb³⁺The preparation of (1): LMPET-4G/Phen/Tb³⁺Reacting phenol/tetrachloroethane and tetraethylene glycol at 60 ℃, heating to 100 ℃ after the reaction is completed, and adding Sb₂O₃Grafting tetraethylene glycol SiO on the surface of the nano silicon chloride ball₂4G, reacting for 2 hours, centrifuging at 8000r/min for 8min, and drying at 100 ℃;

LMPET-4G/Phen/Tb³⁺the mass-volume ratio of the compound to the tetraethyleneglycol is 1: 2-5 g/ml; polycondensation catalyst Sb₂O₃Grafting tetraethylene glycol SiO on the surface of the nano silicon chloride ball₂-4G in a mass to volume ratio of 1: 30-100g/ml, and mixing phenol and tetrachloroethane in equal mass;

nano silicon dioxide/LMPET-5 CG/Phen/Tb³⁺The preparation of (1): LMPET-5CG/Phen/Tb³⁺Reacting phenol/tetrachloroethane and 1,5 pentanediol at 60 ℃, heating to 100 ℃ after the reaction is completed, and adding Sb₂O₃Grafting 1,5 pentanediol SiO on the surface of the nanometer silicon chloride ball₂Reacting for 2 hours at-5 CG, centrifuging at 8000r/min for 8min, and drying at 100 ℃;

LMPET-5CG/Phen/Tb³⁺the mass volume ratio of the 1, 5-pentanediol to the 1: 2-5 g/ml; polycondensation catalyst Sb₂O₃Grafting 1,5 pentanediol SiO on the surface of the nano silicon chloride spheres₂-5CG mass to volume ratio of 1: 30-100g/ml, and mixing phenol and tetrachloroethane in equal mass;

2. The method of claim 1, wherein: preparing the silicon chloride balls: adding benzene into the nano silicon dioxide to dissolve the nano silicon dioxide, dropwise adding thionyl chloride under the protection of nitrogen, and reacting for 4 hours at 65 ℃; then centrifugally separating the reaction mixed liquid, washing the reaction mixed liquid for three times by using benzene, drying the obtained silicon chloride balls in vacuum, and storing the silicon chloride balls in a closed container; the mass volume ratio of the nano silicon dioxide to the benzene is 1: 8-15 g/ml; the mass volume ratio of the nano silicon dioxide to the thionyl chloride is 1: 6-8 g/ml.

3. The method of claim 1, wherein: in the third step, the preparation method of LMPET is as follows: adding a small amount of dimethyl terephthalate, ethylene glycol and zinc acetate into a container, reacting for 2 hours at 190 ℃, and mechanically stirring; then adding a polycondensation catalyst Sb₂O₃Reacting with 2-3 drops of heat stabilizer triphenyl phosphite for half an hour, distilling under reduced pressure for 1 hour when the temperature rises to 220 ℃, pouring the mixed solution into distilled water, reducing the temperature to room temperature, filtering, and drying the obtained product in vacuum to obtain low molecular weight polyethylene glycol terephthalate; the mass volume ratio of dimethyl terephthalate to ethylene glycol is 1: 1.59 g/ml; the mass volume ratio of the zinc acetate to the ethylene glycol is 1:480 g/ml; polycondensation catalyst Sb₂O₃The mass volume ratio of the ethylene glycol to the ethylene glycol is 1: 30-100 g/ml.

4. The method of claim 1, wherein: the particle size range of the nano silicon dioxide is 20-200 nm.

5. The PET luminescent material produced by the production method according to any one of claims 1 to 4.