CN109705843A

CN109705843A - Silica modified terbium complex PET luminescent material and preparation method thereof

Info

Publication number: CN109705843A
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: 2019-05-03
Anticipated expiration: 2039-01-22
Also published as: CN109705843B

Abstract

The invention discloses a kind of silica modified terbium complex PET luminescent materials and preparation method thereof, comprising the following steps: the first step prepares nanometer chlorine silicon ball；Second step, nanometer chlorine silicon ball surface are grafted tetraethylene glycol (4G) or 1,5 pentanediols (5CG)；Third step, LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation；4th step, nano silica/LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation；5th step, by two kinds of good Nano-meter SiO_2s of obtained modification₂Terbium complex hybrid material is evenly spread in PET resin matrix as nanometer nucleating additive, obtains two kinds of PET base terbium complexing hybrid luminescent materials.The material not only has the luminescent properties of terbium complex, and the machinery and crystal property of PET matrix itself also maintain to stablize and obtain a degree of improvement.

Description

Silica modified terbium complex PET luminescent material and preparation method thereof

Technical field

The present invention relates to PET luminescent material preparation field, especially a kind of silica modified terbium complex PET shines Material and preparation method thereof.

Background technique

Rare earth ion has many advantages, such as that luminous intensity height, pure color, the high spectral line of fluorescence efficiency are abundant.And rare earth ion is sent out The color of light and the environment where rare earth ion are substantially unrelated, depend primarily on rare earth ion itself.Rare earth compounding tool itself There are excellent luminescent properties, but because its thermal stability is poor, limits their application.In recent years, people started with various Method, at a lower temperature that organic photoactive substance and inorganic matrix progress is evenly dispersed compound, preparation may have organic With the recombination luminescence functional material of inorganic material characteristic.Rare earth element itself have luminescent color purity is high, launch wavelength it is stable, The advantages that luminous intensity is big.

Summary of the invention

The purpose of the present invention is to provide a kind of silica modified terbium complex PET luminescent materials and its preparation side Low molecular weight PET hydridization luminophore is coated on nano-silica surface by method, and then melting mixing is added to industrialization Improve it in PET polyester matrix to light and heat stability.

To realize above-mentioned technical purpose and the technique effect, the invention adopts the following technical scheme:

A kind of preparation method of silica modified terbium complex PET luminescent material, comprising the following steps:

The first step prepares nanometer chlorine silicon ball:

Second step, nanometer chlorine silicon ball surface are grafted tetraethylene glycol (4G) or 1,5 pentanediols (5CG)

The preparation of nano-silica surface grafting tetraethylene glycol: chlorine silicon ball is added in toluene, is added under magnetic agitation Tetraethylene glycol, 65 DEG C of nitrogen protections are reacted 5 hours；It is finally centrifugated reaction mixture, 8000r/min, 15min, and uses toluene It washes twice, when centrifuge separation twice with acetone washing；Vacuum drying products obtained therefrom；The mass volume ratio of chlorine silicon ball and tetraethylene glycol Example is 1:10-25g/ml；Chlorine silicon ball and the mass volume ratio example of toluene are 1:9-16g/ml；

Nano-silica surface is grafted the preparation of 1,5 pentanediols: chlorine silicon ball being added in toluene, is added under magnetic agitation Enter tetraethylene glycol, 65 DEG C of nitrogen protections are reacted 5 hours；It is finally centrifugated reaction mixture, 8000r/min, 15min, and uses first Benzene washes twice, when centrifuge separation twice with acetone washing；Vacuum drying products obtained therefrom；

Chlorine silicon ball and the mass volume ratio example of 1,5 pentanediols are 1:10-25g/ml；The mass volume ratio of chlorine silicon ball and toluene Example is 1:9-16ml/g；

Third step, LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation

The preparation of LMPET-4G: LMPET is taken to be dissolved in phenol and carbon tetrachloride solution that mass ratio is 1: 1, under magneton stirring 2h is reacted in 60 DEG C of oil baths, and a small amount of crosslinking agent tetraethylene glycol is added in reaction process for several times；Then polycondensation catalyst Sb is added₂O₃ And tetraethylene glycol, 100 DEG C are warming up to, continues to be stirred to react 2-3 hours；After reaction, after mixture solution being centrifuged, quality is used After the LMPET for removing dereaction remnants with carbon tetrachloride solution washing than the phenol for 1: 1, acetone and ethanol washing two are used respectively It is secondary, mixed liquor is centrifugated to remove the impurity of dereaction remnants, and LMPET-4G obtained is dried in vacuo；LMPET and tetraethylene glycol Mass volume ratio example be 1:2-5g/ml；Polycondensation catalyst Sb₂O₃Mass volume ratio example with tetraethylene glycol is 1:30-100g/ml, The mass mixings such as phenol and tetrachloroethanes；

The preparation of LMPET-5CG: LMPET is taken to be dissolved in phenol and carbon tetrachloride solution that mass ratio is 1: 1, under magneton stirring 2h is reacted in 60 DEG C of oil baths, and a small amount of 1,5 pentanediol of crosslinking agent is added in reaction process for several times；Then polycondensation catalyst is added Sb₂O₃With 1,5 pentanediols are warming up to 100 DEG C, continue to be stirred to react 2-3 hours；After reaction, mixture solution is centrifuged Afterwards, after the phenol and carbon tetrachloride solution for being 1: 1 with mass ratio wash the LMPET except dereaction remnants, acetone and second are used respectively Alcohol washes twice, and is centrifugated mixed liquor to remove the impurity of dereaction remnants, by LMPET-1 obtained, 5 pentanediol vacuum are dry It is dry；The mass volume ratio example of LMPET and 1,5 pentanediols is 1:2-5g/ml；Polycondensation catalyst Sb₂O₃With the quality volume of tetraethylene glycol Ratio is 1:30-100g/ml, the mass mixings such as phenol and tetrachloroethanes；

LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation: take TbCl₃Solution, LMPET-4G or LMPET-5CG polymer solution is in container, inflated with nitrogen, 70 DEG C, is stirred at reflux 1 hour, adds Phen solution, keeps 70 DEG C, the reaction was continued 6 hours；TbCl₃, polymer and Phen three's the mass ratio of the material example meet 1:3:1；

4th step, nano silica/LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation

Nano silica/LMPET-4G/Phen/Tb³⁺Preparation: LMPET-4G/Phen/Tb³⁺, phenol/tetra- chloroethenes Alkane, tetraethylene glycol, 60 DEG C of reactions are warming up to 100 DEG C to fully reacting, Sb are added₂O₃,SiO₂- 4G (nanometer chlorine silicon ball surface grafting Tetraethylene glycol), it reacts 2 hours, is centrifuged 8000r/min, 8min, 100 DEG C of dryings；

LMPET-4G/Phen/Tb³⁺Mass volume ratio example with tetraethylene glycol is 1:2-5g/ml；Polycondensation catalyst Sb₂O₃With SiO₂The mass volume ratio example of -4G is 1:30-100g/ml, the mass mixings such as phenol and tetrachloroethanes；

Nano silica/LMPET-5CG/Phen/Tb³⁺Preparation: LMPET-5CG/Phen/Tb³⁺, phenol/tetra- chloroethenes Alkane, 1,5 pentanediol, 60 DEG C of reactions are warming up to 100 DEG C to fully reacting, Sb are added₂O₃,SiO₂- 5CG (nanometer chlorine silicon ball surface It is grafted 41,5 pentanediols), it reacts 2 hours, is centrifuged 8000r/min, 8min, 100 DEG C of dryings；

LMPET-5CG/Phen/Tb³⁺With 1, the mass volume ratio example of 5 pentanediols is 1:2-5g/ml；Polycondensation catalyst Sb₂O₃With SiO₂The mass volume ratio example of -5CG is 1:30-100g/ml, the mass mixings such as phenol and tetrachloroethanes；

5th step, by two kinds of good Nano-meter SiO_2s of obtained modification₂Terbium complex hybrid material is as nanometer nucleating additive It evenly spreads in PET resin matrix, obtains two kinds of PET base terbium complexing hybrid luminescent materials.

The preparation method, the preparation of chlorine silicon ball: being added benzene in nano silica and make it dissolve, nitrogen protection, And thionyl chloride is added dropwise, 65 DEG C are reacted 4 hours；Then reaction mixture is centrifugated, and is washed three times with benzene, by what is obtained Chlorine silicon ball vacuum drying, and be stored in closed container；Nano silica and the mass volume ratio example of benzene are 1:8-15g/ml； Nano silica and the mass volume ratio example of thionyl chloride are 1:6-8g/ml.

The preparation method, in third step, LMPET is the preparation method is as follows: by dimethyl terephthalate (DMT), ethylene glycol, Zinc acetate is added in container on a small quantity, and 2h, mechanical stirring are reacted at 190 DEG C；Then polycondensation catalyst Sb is added₂O₃With 2~3 drops Heat stabilizer triphenyl phosphite reacts half an hour, is evaporated under reduced pressure 1h when temperature rises at 220 DEG C, mixed liquor is poured into In distilled water, room temperature is down to temperature and is filtered, products obtained therefrom is dried in vacuo to obtain low molecular weight polyethylene terephthalate Ester；The mass volume ratio example of dimethyl terephthalate (DMT) and ethylene glycol is 1:1.59g/ml；The mass body of zinc acetate and ethylene glycol Product ratio is 1:480g/ml；Polycondensation catalyst Sb₂O₃Mass volume ratio example with ethylene glycol is 1:30-100g/ml.

The preparation method, the rare earth ion uses commercially available terbium oxide, ionized to obtain.

The preparation method, LMPET surface grafting object are polymerize to obtain by tetraethylene glycol or 1,5 pentanediols, and the degree of polymerization is greater than 1 It and is positive integer.

The preparation method, the nano silica particle size range are 20-200nm.

The preparation method, the linear polyester are sliced using commercially available PET, inherent viscosity 0.676dL/g.

The PET luminescent material prepared according to the preparation method.

The invention has the following advantages:

By introducing tetraethylene glycol or 1 in LMPET, 5 pentanediol sections obtain two different hybridized polymers (LMPET-4G and LMPET-5CG), is then complexed with rare earth terbium ion, and two different LMPET bases are then respectively obtained Hydridization luminophore is complexed in terbium, obtained hydridization luminophore is coated on the homemade nano-silica surface in laboratory, so Silica modified terbium complex PET luminescent material is evenly spread in PET resin matrix again afterwards, obtains a kind of titanium dioxide Hybrid luminescent materials are complexed in the PET base terbium of Si modification, which not only has the luminescent properties of terbium complex, PET matrix itself Machinery and crystal property also maintains stabilization and obtain a degree of improvement.

Detailed description of the invention

Fig. 1 is reaction process schematic diagram of the invention.

Fig. 2 is the emission spectrum that hydridization luminophore is complexed in low molecular weight PET base europium；

Fig. 3 is respectively LMPET-4G and LMPET-4G/Phen/Tb³⁺Infrared spectrum；

Specific embodiment

Below in conjunction with specific embodiment, the present invention is described in detail.

Embodiment 1

As shown in Figure 1, the invention discloses a kind of preparation sides of silica modified terbium complex PET luminescent material Method comprises the steps that

Firstly, in nano silica (SiO₂) on the basis of prepare nanometer chlorine silicon ball:

The preparation of chlorine silicon ball: nano silica (size about 20-200nm, in vacuum drying oven is added in three-necked flask At 80 DEG C, prebake 24 hours), benzene is added and makes it dissolve, nitrogen protection, and thionyl chloride is added dropwise by separatory funnel, it connects Just have HCl and SO₂It generates, 65 DEG C are reacted 4 hours.Then reaction mixture is centrifugated, 8000r/min, 15min. And it is washed three times with benzene, the chlorine silicon ball vacuum drying that will be obtained, and be stored in closed container, the matter of nano silica and benzene Amount volume ratio is 1:8-15g/ml；Nano silica and the mass volume ratio example of thionyl chloride are 1:6-8g/ml.

The preparation of nano-silica surface grafting tetraethylene glycol: chlorine silicon ball is added in toluene, is added under magnetic agitation Tetraethylene glycol, 65 DEG C of nitrogen protections are reacted 5 hours.It is finally centrifugated reaction mixture, 8000r/min, 15min, and uses toluene It washes twice, to remove unreacted tetraethylene glycol, when centrifuge separation twice with acetone washing.Vacuum drying products obtained therefrom.Chlorine silicon The mass volume ratio example of ball and tetraethylene glycol is 1:10-25g/ml.Chlorine silicon ball and the mass volume ratio example of toluene are 1:9-16ml/g.

Nano-silica surface be grafted 1,5 pentanediols preparation: chlorine silicon ball is added in toluene, under magnetic agitation Tetraethylene glycol is added, 65 DEG C of nitrogen protections are reacted 5 hours.It is finally centrifugated reaction mixture, 8000r/min, 15min are used in combination Toluene washes twice, to remove unreacted 1,5 pentanediol, when centrifuge separation twice with acetone washing.It is produced obtained by vacuum drying Product.Chlorine silicon ball and the mass volume ratio example of 1,5 pentanediols are 1:10-25g/ml.Chlorine silicon ball and the mass volume ratio example of toluene are 1:9-16ml/g.

Third step, LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation

For LMPET the preparation method is as follows: by dimethyl terephthalate (DMT), ethylene glycol, zinc acetate is added to 250mL volumetric flask on a small quantity It is interior, 2h, mechanical stirring are reacted at 190 DEG C.Then a small amount of polycondensation catalyst Sb is added₂O₃With 2~3 drop heat stabilizer phosphorous acid Triphenylmethyl methacrylate reacts half an hour, is evaporated under reduced pressure 1h when temperature rises at 220 DEG C, mixed liquor is poured into distilled water, to temperature It is down to room temperature suction filtration, products obtained therefrom is dried in vacuo to obtain low molecular weight polyethylene terephthalate.Terephthalic acid (TPA) two The mass volume ratio example of methyl esters and ethylene glycol is 1:1.59g/ml；The mass volume ratio example of zinc acetate and ethylene glycol is 1:480g/ ml；Polycondensation catalyst Sb₂O₃Mass volume ratio example with ethylene glycol is 1:30-100g/ml.

The preparation of LMPET-4G: LMPET is taken to be dissolved in phenol and carbon tetrachloride solution that mass ratio is 1: 1, under magneton stirring 2h is reacted in 60 DEG C of oil baths, and a small amount of crosslinking agent tetraethylene glycol is added in reaction process for several times.Then 0.03g polycondensation catalyst is added Sb₂O₃And tetraethylene glycol, 100 DEG C are warming up to, continues to be stirred to react 2-3 hours.After reaction, it after mixture solution being centrifuged, uses After phenol and the carbon tetrachloride solution washing that mass ratio is 1: 1 are except the LMPET of dereaction remnants, acetone and ethanol washing are used respectively Twice, LMPET- tetraethylene glycol obtained is dried in vacuo by centrifuge separation mixed liquor with the impurity except dereaction remnants.LMPET with The mass volume ratio example of tetraethylene glycol is 1:2-5g/ml.Polycondensation catalyst Sb₂O₃Mass volume ratio example with tetraethylene glycol is 1:30- 100g/ml, the mass mixings such as phenol and tetrachloroethanes.

The preparation of LMPET-5CG: LMPET is taken to be dissolved in phenol and carbon tetrachloride solution that mass ratio is 1: 1, under magneton stirring 2h is reacted in 60 DEG C of oil baths, and a small amount of 1,5 pentanediol of crosslinking agent is added in reaction process for several times.Then 0.03g polycondensation is added to urge Agent Sb₂O₃With 1,5 pentanediols are warming up to 100 DEG C, continue to be stirred to react 2-3 hours.After reaction, by mixture solution from After the heart, after the phenol and carbon tetrachloride solution for being 1: 1 with mass ratio washs the LMPET except dereaction remnants, use respectively acetone with Ethanol washing twice, is centrifugated mixed liquor to remove the impurity of dereaction remnants, by LMPET-1 obtained, 5 pentanediol vacuum are dry It is dry.The mass volume ratio example of LMPET and 1,5 pentanediols is 1:2-5g/ml.Polycondensation catalyst Sb₂O₃With the quality volume of tetraethylene glycol Ratio is 1:30-100g/ml, the mass mixings such as phenol and tetrachloroethanes.

LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation: take TbCl₃Solution, polymer solution (LMPET-4G or LMPET-5CG) in a round bottom flask, inflated with nitrogen, is stirred at reflux 1 hour, adds Phen by 70 DEG C Solution is kept for 70 DEG C, and the reaction was continued 6 hours.TbCl₃, polymer and Phen three's the mass ratio of the material example meet 1:3: 1。

4th step, nano silica/LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation

Nano silica/LMPET-4G/Phen/Tb³⁺Preparation: LMPET-4G/Phen/Tb³⁺(third step self-control), Phenol (freezing point very it is low will whole bottle pkt. flap heating in advance, quickly weigh, be otherwise sticked to wall of cup)/tetrachloroethanes (all toxic will be Draught cupboard weighs, ratio 1:1, as solvent), tetraethylene glycol, 60 DEG C of reactions are warming up to 100 to fully reacting dissolution (1 hour) DEG C, Sb is added₂O₃,SiO₂- 4G (second step self-control) reacts 2 hours, and 8000r/min, 8min, 100 DEG C of dryings of centrifugation (are placed on A The drying box of room heats timing).LMPET-4G/Phen/Tb³⁺Mass volume ratio example with tetraethylene glycol is 1:2-5g/ml.Polycondensation Catalyst Sb₂O₃With SiO₂The mass volume ratio example of -4G is 1:30-100g/ml, the mass mixings such as phenol and tetrachloroethanes.

Nano silica/LMPET-5CG/Phen/Tb³⁺Preparation: LMPET-5CG/Phen/Tb³⁺, phenol/tetra- chloroethenes Alkane, 1,5 pentanediol, 60 DEG C of reactions are warming up to 100 DEG C to fully reacting dissolution (1 hour), Sb are added₂O₃,SiO₂- 5CG (second Step self-control), it reacts 2 hours, is centrifuged 8000r/min, 8min, 100 DEG C of dryings (being placed on the drying box of the room A, heat timing). LMPET-5CG/Phen/Tb³⁺With 1, the mass volume ratio example of 5 pentanediols is 1:2-5g/ml.Polycondensation catalyst Sb₂O₃With SiO₂- The mass volume ratio example of 5CG is 1:30-100g/ml, the mass mixings such as phenol and tetrachloroethanes.

Wherein the terbium ion uses commercially available terbium oxide, ionized to obtain.

Wherein the LMPET surface grafting object is polymerize by the dihydric alcohol (tetraethylene glycol or 1,5 pentanediols) that general formula is HOROH It obtains, the degree of polymerization is greater than 1 and is positive integer.

Wherein the low molecular weight polyethylene terephthalate (LMPET) the preparation method is as follows:

By dimethyl terephthalate (DMT), ethylene glycol, zinc acetate is added on a small quantity in 250mL volumetric flask, is reacted at 190 DEG C 2h, mechanical stirring.Then a small amount of polycondensation catalyst Sb is added₂O₃With 2~3 drop heat stabilizer triphenyl phosphites, first react half Hour, it is evaporated under reduced pressure 1h when temperature rises at 220 DEG C, mixed liquor is poured into distilled water, room temperature is down to temperature and filters, it will Products obtained therefrom is dried in vacuo to get low molecular weight polyethylene terephthalate.

Embodiment 2

Experiment purpose and method: in order to study low molecular weight PET base terbium complexing hydridization luminophore to rare earth luminous performance Influence, the low molecular weight PET base terbium complexing hydridization luminophore solution that the present embodiment synthesize using embodiment 1 as research object, Research method are as follows: RF-5301P sepectrophotofluorometer is used, it is molten to a kind of low molecular weight PET base terbium complexing hydridization luminophore Liquid carries out fluorometric investigation.

As shown in Fig. 2, the emission spectrum of low molecular weight PET base europium complexing hydridization luminophore, excitation wavelength exist 331.07nm, for launch wavelength at 544.02nm, the method successfully prepares two kinds of luminous bases of low molecular weight PET base terbium complexing hydridization Group, and the introducing of the block polymer does not influence the luminescent properties of rare earth ion itself, will finally contain low molecular weight PET base Complexing hydridization luminophore be coated on nano-silica surface.

As shown in figure 3, in order to study the feature of the low molecular weight PET base terbium that will successfully prepare complexing hydridization luminophore The variation of group carries out structural analysis to low molecular weight PET base terbium complexing hydridization luminophore, and the present embodiment is with the conjunction of embodiment 1 At low molecular weight PET based polyalcohol powder and low molecular weight PET base terbium complexing hydridization luminophore powder (LMPET-4G and LMPET-4G/Phen/Tb³⁺) be used as research object, research method are as follows: using infrared spectrometer (U.S. Nicolet produce, 5700 Type, 4000~400cm of wave-number range^-1), to LMPET-4G and LMPET-4G/Phen/Tb³⁺Carry out structural analysis test.

As shown in figure 3, respectively LMPET-4G and LMPET-4G/Phen/Tb³⁺Infrared spectrum.In this spectrogram, LMPET-4G (Fig. 3 .a) and LMPET-4G/Phen/Tb³⁺The most characteristic absorption peak position intensity of (Fig. 3 .b) is all similar. Wherein on curve b, there is new 1663.97cm in correlation curve a^-1Characteristic absorption peak, in characteristic absorption peak 1663.97cm^-1Near, 1715.66cm^-1Out it is the characteristic absorption peak of C=O, illustrates that low molecular weight base pet polymer is occurring Complexing generates low molecular weight PET base terbium and hydridization luminophore is complexed, and is complexed on the position of C=O, so that 1663.97cm^-1Characteristic absorption peak appearance.

Embodiment 3

Experiment purpose and method: in order to study nano silica/LMPET-4G or LMPET-5CG/Phen/Tb³⁺This two Influence of the kind hybrid luminescent materials to the mechanical performance of industrialization PET crystallizing polyester, the nanometer that the present embodiment is synthesized with embodiment 1 Silica/LMPET-4G or LMPET-5CG/Phen/Tb³⁺It is right to study its as experimental subjects for both hybrid luminescent materials Linear polyester is sliced the influence of mechanical performance, method particularly includes: use the miniature blender melt blending of DSM Xplore 5&15 type Method is sufficiently mixed, and standard sample is made in DSM Xplore 10cc type micro-injection moulding instrument.290 DEG C of melting temperature in blender, It is 50 DEG C when the purely linear polyester of mold temperature in injection molding machine, the low molecular weight PET base europium complexing hydridization hair that addition embodiment 1 synthesizes 40 DEG C are changed to after light group.Nano silica/the LMPET-4G or LMPET-5CG/Phen/Tb of preparation synthesis altogether³⁺Both Hybrid luminescent materials carry out 0%, 2.0%, 4.0%, 6.0% 4 group of sample respectively, to carry out the test of mechanical performance etc..

Experimental result:

Nano silica/LMPET-4G/Phen/Tb of 1 different proportion of table³⁺The mechanical performance for being added to linear polyester is surveyed Test result

Additive amount %	Elongation at break/%	Tensile strength/MPa	Yield strength/MPa	Stretch 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, nano silica/LMPET-4G/Phen/Tb of different proportion³⁺Additive amount is to linear polyester Measuring mechanical property result shows the raising with additive amount, first increases the trend subtracted afterwards to the mechanical performance presentation of linear polyester, Illustrate that, when additive amount is lower than 4%, addition hydridization luminophore has improvement to the intensity of linear polyester.

Nano silica/LMPET-5CG/Phen/Tb of 2 different proportion of table³⁺It is added to the mechanical performance of linear polyester Test result

Also there is table 2 in nano silica/LMPET-5CG/Phen/Tb of different proportion in same situation³⁺Additive amount Occur into the measuring mechanical property of linear polyester, possible reason is processing method of the invention: first is that low molecular weight PET Ontology increases its compatibility and interface binding power with matrix, is conducive to keep the fine dispersion state of filler in the base； Second is that, by the shear action of the blending of twin-screw in the miniature blending instrument of macromolecule, hydridization luminophore obtains under lower content More uniform dispersion is arrived.Both the above reason enhances the adsorption capacity of hybrid luminescent materials and macromolecular chain, and occurs one Crosslinking, the winding for determining degree, form a kind of reticular structure, so that intensity be made to be higher than conventional polyester.(it is more than when additive amount is excessive 4%) uniformity that, hydridization luminophore disperses in polyester matrix is deteriorated, and easily formation aggregate, these aggregates are known as material Defect, cause stress raisers in stress, decline the intensity of polyester material.

It should be understood that for those of ordinary skills, it can be modified or changed according to the above description, And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.

Claims

1. a kind of preparation method of silica modified terbium complex PET luminescent material, which is characterized in that including following step It is rapid:

The first step prepares nanometer chlorine silicon ball；

The preparation of nano-silica surface grafting tetraethylene glycol: chlorine silicon ball is added in toluene, and it is sweet that four are added under magnetic agitation Alcohol, 65 DEG C of nitrogen protections are reacted 5 hours；It is finally centrifugated reaction mixture, 8000r/min, 15min, and is washed with toluene Twice, when centrifuge separation with acetone washing twice；Vacuum drying products obtained therefrom；Chlorine silicon ball and the mass volume ratio example of tetraethylene glycol are 1:10-25g/ml；Chlorine silicon ball and the mass volume ratio example of toluene are 1:9-16g/ml；

Nano-silica surface is grafted the preparation of 1,5 pentanediols: chlorine silicon ball being added in toluene, is added four under magnetic agitation Glycol, 65 DEG C of nitrogen protections are reacted 5 hours；It is finally centrifugated reaction mixture, 8000r/min, 15min, and is washed with toluene It washs twice, when centrifuge separation twice with acetone washing；Vacuum drying products obtained therefrom；

Chlorine silicon ball and the mass volume ratio example of 1,5 pentanediols are 1:10-25g/ml；Chlorine silicon ball and the mass volume ratio example of toluene are 1:9-16ml/g；

Third step, LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation

The preparation of LMPET-4G: LMPET is taken to be dissolved in phenol and carbon tetrachloride solution that mass ratio is 1: 1,60 under magneton stirring 2h is reacted in DEG C oil bath, a small amount of crosslinking agent tetraethylene glycol is added in reaction process for several times；Then polycondensation catalyst Sb is added₂O₃With four Glycol is warming up to 100 DEG C, continues to be stirred to react 2-3 hours；After reaction, after mixture solution being centrifuged, it is with mass ratio After 1: 1 phenol and carbon tetrachloride solution washing is except the LMPET of dereaction remnants, respectively twice with acetone and ethanol washing, from The heart separates mixed liquor to remove the impurity of dereaction remnants, and LMPET-4G obtained is dried in vacuo；The quality of LMPET and tetraethylene glycol Volume ratio is 1:2-5g/ml；Polycondensation catalyst Sb₂O₃Be 1:30-100g/ml with the mass volume ratio example of tetraethylene glycol, phenol with The mass mixings such as tetrachloroethanes；

The preparation of LMPET-5CG: LMPET is taken to be dissolved in phenol and carbon tetrachloride solution that mass ratio is 1: 1,60 under magneton stirring 2h is reacted in DEG C oil bath, a small amount of 1,5 pentanediol of crosslinking agent is added in reaction process for several times；Then polycondensation catalyst Sb is added₂O₃With 1,5 pentanediol is warming up to 100 DEG C, continues to be stirred to react 2-3 hours；After reaction, after mixture solution being centrifuged, matter is used After amount washs the LMPET except dereaction remnants with carbon tetrachloride solution than the phenol for 1: 1, acetone and ethanol washing two are used respectively It is secondary, mixed liquor is centrifugated to remove the impurity of dereaction remnants, by LMPET-1 obtained, the vacuum drying of 5 pentanediols；LMPET with The mass volume ratio example of 1,5 pentanediols is 1:2-5g/ml；Polycondensation catalyst Sb₂O₃Mass volume ratio example with tetraethylene glycol is 1: 30-100g/ml, the mass mixings such as phenol and tetrachloroethanes；

4th step, nano silica/LMPET-4G/Phen/Tb³⁺Or LMPET-5CG/Phen/Tb³⁺Preparation

Nano silica/LMPET-4G/Phen/Tb³⁺Preparation: LMPET-4G/Phen/Tb³⁺, phenol/tetrachloroethanes, four is sweet Alcohol, 60 DEG C of reactions are warming up to 100 DEG C to fully reacting, Sb are added₂O₃,SiO₂(grafting four of nanometer chlorine silicon ball surface is sweet by -4G Alcohol), it reacts 2 hours, is centrifuged 8000r/min, 8min, 100 DEG C of dryings；

LMPET-4G/Phen/Tb³⁺Mass volume ratio example with tetraethylene glycol is 1:2-5g/ml；Polycondensation catalyst Sb₂O₃With SiO₂- The mass volume ratio example of 4G is 1:30-100g/ml, the mass mixings such as phenol and tetrachloroethanes；

Nano silica/LMPET-5CG/Phen/Tb³⁺Preparation: LMPET-5CG/Phen/Tb³⁺, phenol/tetrachloroethanes, 1, 5 pentanediols, 60 DEG C of reactions are warming up to 100 DEG C to fully reacting, Sb are added₂O₃,SiO₂- 5CG (nanometer chlorine silicon ball surface grafting 41,5 pentanediols), it reacts 2 hours, is centrifuged 8000r/min, 8min, 100 DEG C of dryings；

5th step, by two kinds of good Nano-meter SiO_2s of obtained modification₂Terbium complex hybrid material is uniform as nanometer nucleating additive It is distributed in PET resin matrix, obtains two kinds of PET base terbium complexing hybrid luminescent materials.

2. preparation method according to claim 1, it is characterised in that: the preparation of chlorine silicon ball: adding in nano silica Enter benzene to make it dissolve, nitrogen protection, and thionyl chloride is added dropwise, 65 DEG C are reacted 4 hours；Then reaction mixture is centrifugated, And it is washed three times with benzene, the chlorine silicon ball vacuum drying that will be obtained, and be stored in closed container；The matter of nano silica and benzene Amount volume ratio is 1:8-15g/ml；Nano silica and the mass volume ratio example of thionyl chloride are 1:6-8g/ml.

3. preparation method according to claim 1, it is characterised in that: in third step, LMPET is the preparation method is as follows: by right Rutgers, ethylene glycol, zinc acetate are added in container on a small quantity, and 2h, mechanical stirring are reacted at 190 DEG C；Then it is added Polycondensation catalyst Sb₂O₃With 2~3 drop heat stabilizer triphenyl phosphites, half an hour is reacted, is subtracted when temperature rises at 220 DEG C Pressure distillation 1h, mixed liquor is poured into distilled water, is down to room temperature to temperature and is filtered, products obtained therefrom is dried in vacuo to obtain low molecule Measure polyethylene terephthalate；The mass volume ratio example of dimethyl terephthalate (DMT) and ethylene glycol is 1:1.59g/ml；Vinegar The mass volume ratio example of sour zinc and ethylene glycol is 1:480g/ml；Polycondensation catalyst Sb₂O₃Mass volume ratio example with ethylene glycol is 1:30-100g/ml.

4. preparation method according to claim 1, it is characterised in that: the rare earth ion use commercially available terbium oxide, through from Sonization obtains.

5. preparation method according to claim 1, it is characterised in that: LMPET surface grafting object is by tetraethylene glycol or 1, and 5 penta 2 Alcohol polymerize to obtain, and the degree of polymerization is greater than 1 and is positive integer.

6. preparation method according to claim 1, it is characterised in that: the nano silica particle size range is 20- 200nm。

7. preparation method according to claim 1, it is characterised in that: the linear polyester is sliced using commercially available PET, special Property viscosity 0.676dL/g.

8. the PET luminescent material of -7 any preparation method preparations according to claim 1.