CN107325498B - A kind of PET base europium complexing hybrid luminescent materials and preparation method thereof - Google Patents
A kind of PET base europium complexing hybrid luminescent materials and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
Abstract
The invention discloses a kind of PET base europium complexing hybrid luminescent materials and preparation method thereof, by introducing polyethylene glycol segment in low molecular weight polyethylene terephthalate, obtain a kind of hybridized polymer of low molecular weight polyethylene terephthalate-polyethylene glycol, then it is complexed with rare-earth europium ion, obtain a kind of low molecular weight PET base europium complexing hydridization luminophore, obtained hydridization luminophore is evenly spread in PET resin matrix, obtain a kind of PET base europium complexing hybrid luminescent materials, the material not only has the luminescent properties of europium complex, the machinery and crystal property of PET matrix itself also maintain to stablize and obtain a degree of improvement.
Description
Technical field
The present invention relates to PET luminescent material preparation field, especially a kind of PET base europium complexing hybrid luminescent materials and its system
Preparation Method.
Background technique
Rare earth ion makes rare earth organic fluorescent materials have luminous intensity height, color pure with distinct electrical sublayer structure
Just, the advantages that high spectral line of fluorescence efficiency is abundant, and luminescent color and the environment where rare earth ion are substantially unrelated, mainly depend on
In rare earth ion itself.However, the application of all rare earth ion complex compounds is all limited to their light and heat stability, pass through handle
Function rare-earth complex, which is added in organic Polymeric ligands, can improve this problem, since rare earth element has strong light
Greatly, the advantages that excitation purity is high, launch wavelength is stablized, Luminescent Material of Rare Earth Polymer is compared to the luminous material of rare earth small molecule in recent years
Material has many advantages, such as that good abundant raw material, stability, light weight, processing and forming at low cost are easy, therefore rare earth small molecule shone
Material producing high-molecular is research hotspot in recent years.Rare earth europium complex is a kind of high luminescent quantum effect for having both organic compound
The red fluorescence material of rate and inorganic compound good stability, has a good application prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of PET base europium complexing hybrid luminescent materials, and hydridization is shone
Group, which is added in organic polymeric matrix, improves its light and heat stability.
A kind of preparation method of PET base europium complexing hybrid luminescent materials, comprising the following steps:
Firstly, preparation low molecular weight polyethylene terephthalate:
The preparation of low molecular weight polyethylene terephthalate: by dimethyl terephthalate (DMT), ethylene glycol, zinc acetate is a small amount of
It is added in 250mL volumetric flask, 2h, mechanical stirring is reacted at 190 DEG C；Then a small amount of polycondensation catalyst Sb2O3 is added and heat is steady
Determine agent triphenyl phosphite, first react half an hour, is evaporated under reduced pressure 1h when temperature rises at 220 DEG C, mixed liquor is poured into steaming
In distilled water, room temperature is down to temperature and is filtered, products obtained therefrom is dried in vacuo to get low molecular weight polyethylene terephthalate
Ester；
Then, low molecular weight polyethylene terephthalate-polyethyleneglycol block copolymer preparation: poly- pair of low molecular weight
Ethylene terephthalate and polyethylene glycol, using antimony oxide as catalyst reaction, keep low molecular weight poly- to benzene at 100 DEG C
Transesterification occurs for naphthalate and polyethylene glycol, and poly- second two is introduced on low molecular weight polyethylene terephthalate
Alcohol groups generate low molecular weight polyethylene terephthalate-polyethylene glycol hybridized polymer, then prepare certain density low
Molecular weight polyisoprene ethylene glycol terephthalate-polyethylene glycol hybridized polymer solution；
Take a certain amount of EuCl3In conical flask the complex phenanthroline and TTA solution of certain mass is added, instead in solution
The hybridized polymer that certain density low molecular weight polyethylene terephthalate-polyethylene glycol should be added after a certain period of time is molten
Liquid is stirred to react obtains a kind of low molecular weight PET base europium complexing hydridization luminophore after a certain period of time at room temperature；
Low molecular weight PET base europium obtained above complexing hydridization luminophore is evenly spread to linearly by melt blending
In polyester, a kind of PET base europium complexing hybrid luminescent materials are obtained.
A kind of preparation method of the PET base europium complexing hybrid luminescent materials, comprising the following steps:
Firstly, preparation low molecular weight polyethylene terephthalate:
The preparation of low molecular weight polyethylene terephthalate: by 44.5g dimethyl terephthalate (DMT), 28mlg ethylene glycol,
Zinc acetate 0.03g is added in 250mL volumetric flask, and 2h, mechanical stirring are reacted at 190 DEG C；Then 0.03g polycondensation catalyst is added
Sb2O3It with 2-3 drop heat stabilizer triphenyl phosphite, first reacts half an hour, temperature rises to 220 DEG C of vacuum distillation 1h, will mix
It closes liquid to pour into distilled water, is down to room temperature to temperature and filters, products obtained therefrom is dried in vacuo to get the poly- terephthaldehyde of low molecular weight
Sour glycol ester；
Then, low molecular weight polyethylene terephthalate-polyethyleneglycol block copolymer preparation: low point of 12.2g is taken
Son measures polyethylene terephthalate and 3g polyethylene glycol at 100 DEG C using antimony oxide as catalyst reaction, makes low point
Transesterification occurs for son amount polyethylene terephthalate and polyethylene glycol, on low molecular weight polyethylene terephthalate
Polyethylene group is introduced, generates low molecular weight polyethylene terephthalate-polyethylene glycol hybridized polymer, then prepare one
Determine low molecular weight polyethylene terephthalate-polyethylene glycol hybridized polymer solution of concentration；
Take 300 μ l 0.01mol/L EuCl3Solution in conical flask, be added 300 μ l 0.01mol/L phenanthroline and
300 μ l0.01mol/L TTA solution react the low molecular weight polyethylene terephthalate of addition 3ml0.01mol/L after 0.5h
Ester-polyethylene glycol hybridized polymer solution obtains a kind of low molecular weight PET base europium complexing hydridization after being stirred to react 2h at room temperature
Luminophore；
Low molecular weight PET base europium obtained above complexing hydridization luminophore is evenly spread to linearly by melt blending
In polyester, a kind of PET base europium complexing hybrid luminescent materials are obtained.
A kind of preparation method of PET base europium complexing hybrid luminescent materials, the EuCl3It is passed through using commercially available europium oxide
Ionization obtains.
Hybrid luminescent materials preparation method is complexed in a kind of PET base europium, and the linear polyester is cut using commercially available PET
Piece, inherent viscosity 0.676dL/g.
Hybrid luminescent materials are complexed according to the PET base europium of any the method preparation.
The invention has the following advantages:
Whole design is carried out according to the application demand of PET and europium complex, by poly- to benzene two in homemade low molecular weight
Polyethylene glycol segment is introduced in formic acid glycol ester, obtains a kind of low molecular weight polyethylene terephthalate-polyethylene glycol
Hybridized polymer, be then complexed with rare-earth europium ion, obtain a kind of low molecular weight PET base europium complexing hydridization and shine base
Group, obtained hydridization luminophore is evenly spread in PET resin matrix, obtains a kind of luminous material of PET base europium complexing hydridization
Material, the material not only have the luminescent properties of europium complex, and the machinery and crystal property of PET matrix itself are also maintained to stablize and be obtained
Improvement to a certain extent.
Detailed description of the invention
Fig. 1 is reaction process schematic diagram of the invention.
Fig. 2 is the fluorescence property transmitting figure that hydridization luminophore is complexed in low molecular weight PET base europium.
Fig. 3 is the fluorescence property excitation figure that hydridization luminophore is complexed in low molecular weight PET base europium.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
As shown in Figure 1, including the invention discloses a kind of PET base europium complexing hybrid luminescent materials and preparation method thereof
Following steps:
Firstly, preparation low molecular weight polyethylene terephthalate:
The preparation of low molecular weight polyethylene terephthalate: by 44.5g dimethyl terephthalate (DMT), 28mlg ethylene glycol,
Zinc acetate 0.03g is added in 250mL volumetric flask, and 2h, mechanical stirring are reacted at 190 DEG C.Then 0.03g polycondensation catalyst is added
Sb2O3It with 2-3 drop heat stabilizer triphenyl phosphite, first reacts half an hour, temperature rises to 220 DEG C of vacuum distillation 1h, will mix
It closes liquid to pour into distilled water, is down to room temperature to temperature and filters, products obtained therefrom is dried in vacuo to get the poly- terephthaldehyde of low molecular weight
Sour glycol ester.
Then, low molecular weight polyethylene terephthalate-polyethylene glycol hybridized polymer preparation: take 12.2g low
Molecular weight polyisoprene ethylene glycol terephthalate and 3g polyethylene glycol, using antimony oxide as catalyst reaction, make low at 100 DEG C
Transesterification occurs for molecular weight polyisoprene ethylene glycol terephthalate and polyethylene glycol, in low molecular weight polyethylene terephthalate
Upper introducing polyethylene group generates low molecular weight polyethylene terephthalate-polyethylene glycol hybridized polymer, then prepares
The hybridized polymer solution of certain density low molecular weight polyethylene terephthalate-polyethylene glycol.
Take 300 μ l 0.01mol/L EuCl3Solution in conical flask, be added 300 μ l 0.01mol/L phenanthroline and
300 μ l 0.01mol/L TTA solution react the low molecular weight poly terephthalic acid second two of addition 3ml0.01mol/L after 0.5h
Alcohol ester-polyethylene glycol hybridized polymer solution, is stirred to react after 2h that obtain a kind of low molecular weight PET base europium complexing miscellaneous at room temperature
Change luminophore.
Wherein the europium ion uses commercially available europium oxide, ionized to obtain.
Embodiment 2
Experiment purpose and method: in order to study low molecular weight PET base europium complexing hydridization luminophore to rare earth luminous performance
Influence, the low molecular weight PET base europium 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 europium complexing hydridization luminophore
Liquid carries out fluorometric investigation.
As shown in Figure 2,3, hydridization luminophore is complexed at excitation wavelength 614.05nm in low molecular weight PET base europium, transmitting
Intensity is 363a.u., and the method successfully prepares a kind of low molecular weight PET base europium complexing hydridization luminophore, and the block is poly-
The introducing for closing object does not influence the luminescent properties of rare earth ion itself.
Embodiment 3
Experiment purpose and method: linear polyester is crystallized in order to study low molecular weight PET base europium complexing hydridization luminophore
Mechanical performance influence, the low molecular weight PET base europium complexing hydridization luminophore that the present embodiment is synthesized using embodiment 1 is as reality
Object is tested, its influence to linear polyester slice mechanical performance is studied, method particularly includes: it is micro- using DSM Xplore 5&15 type
Type blender melt-blending process is sufficiently mixed, and standard sample is made in DSM Xplore 10cc type micro-injection moulding instrument.Blender
290 DEG C of interior melting temperature is 50 DEG C when the purely linear polyester of mold temperature in injection molding machine, the low molecular weight that addition embodiment 1 synthesizes
40 DEG C are changed to after PET base europium complexing hydridization luminophore.The block polymer engrafted nanometer silica 0% of total preparation synthesis,
2.0%, 4.0%, 6.0% 4 group of sample, to carry out the test of mechanical performance etc..
Experimental result:
The hydridization luminophore of 1 different proportion of table is added to the measuring mechanical property result of linear polyester
| Additive amount % | Elongation at break/% | Tensile strength/MPa | Yield strength/MPa | Stretch modulus/MPa |
| 0 | 140 | 59.382 | 62.23 | 1232.76 |
| 2 | 160 | 64.72 | 65.04 | 1398.02 |
| 4 | 128 | 59.474 | 58.02 | 1456.05 |
| 6 | 110 | 56.857 | 54.40 | 1765.30 |
As shown in table 1, the measuring mechanical property result that the hydridization luminophore of different proportion is added to linear polyester shows
With the raising of additive amount, the trend subtracted afterwards is first increased to the mechanical performance presentation of linear polyester, is illustrated when additive amount is lower than 4%
When, addition hydridization luminophore has improvement to the intensity of linear polyester.Reason is: first is that low molecular weight PET ontology increases
Its compatibility and interface binding power with matrix are added, have been conducive to keep the fine dispersion state of filler in the base；Second is that
Under lower content, by the shear action of the blending of twin-screw in the miniature blending instrument of macromolecule, hydridization luminophore obtained compared with
Uniform dispersion.Both the above reason enhances the adsorption capacity of hydridization luminophore and macromolecular chain, and occurs to a certain degree
Crosslinking, winding, form a kind of reticular structure, thus make intensity be higher than conventional polyester.When additive amount is excessive (more than 4%),
The uniformity that hydridization luminophore disperses in polyester matrix is deteriorated, easily formation aggregate, these aggregates are known as lacking for material
It falls into, causes 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 (5)
1. a kind of preparation method of PET base europium complexing hybrid luminescent materials, which comprises the following steps:
Firstly, preparation low molecular weight polyethylene terephthalate:
The preparation of low molecular weight polyethylene terephthalate: by dimethyl terephthalate (DMT), ethylene glycol, zinc acetate is added on a small quantity
In 250mL volumetric flask, 2h, mechanical stirring are reacted at 190 DEG C；Then a small amount of polycondensation catalyst Sb2O3 and heat stabilizer is added
Triphenyl phosphite first reacts half an hour, is evaporated under reduced pressure 1h when temperature rises at 220 DEG C, mixed liquor is poured into distilled water
In, room temperature is down to temperature and is filtered, and products obtained therefrom is dried in vacuo to get low molecular weight polyethylene terephthalate；
Then, low molecular weight polyethylene terephthalate-polyethyleneglycol block copolymer preparation: low molecular weight is poly- to benzene two
Formic acid glycol ester and polyethylene glycol, using antimony oxide as catalyst reaction, make the poly- terephthaldehyde of low molecular weight at 100 DEG C
Transesterification occurs for sour glycol ester and polyethylene glycol, introduces polyethylene glycol groups on low molecular weight polyethylene terephthalate
Group generates low molecular weight polyethylene terephthalate-polyethylene glycol hybridized polymer, then prepares certain density low molecule
Measure polyethylene terephthalate-polyethylene glycol hybridized polymer solution；
Take a certain amount of EuCl3The complex phenanthroline and TTA solution of certain mass is added in conical flask in solution, and reaction is certain
The hybridized polymer solution of certain density low molecular weight polyethylene terephthalate-polyethylene glycol, room are added after time
It is stirred to react under temperature and obtains a kind of low molecular weight PET base europium complexing hydridization luminophore after a certain period of time；
Low molecular weight PET base europium obtained above complexing hydridization luminophore is evenly spread into linear polyester by melt blending
In, a kind of PET base europium complexing hybrid luminescent materials are obtained, the additive amount of hydridization luminophore is complexed not in low molecular weight PET base europium
Greater than 4%.
2. a kind of preparation method of PET base europium complexing hybrid luminescent materials according to claim 1, which is characterized in that packet
Include following steps:
Firstly, preparation low molecular weight polyethylene terephthalate:
Low molecular weight polyethylene terephthalate preparation: by 44.5g dimethyl terephthalate (DMT), 28mlg ethylene glycol, acetic acid
Zinc 0.03g is added in 250mL volumetric flask, and 2h, mechanical stirring are reacted at 190 DEG C；Then 0.03g polycondensation catalyst Sb is added2O3
It with 2-3 drop heat stabilizer triphenyl phosphite, first reacts half an hour, temperature rises to 220 DEG C of vacuum distillation 1h, by mixed liquor
It pours into distilled water, is down to room temperature to temperature and filters, products obtained therefrom is dried in vacuo to get low molecular weight poly terephthalic acid second
Diol ester；
Then, low molecular weight polyethylene terephthalate-polyethyleneglycol block copolymer preparation: 12.2g low molecular weight is taken
Polyethylene terephthalate and 3g polyethylene glycol, using antimony oxide as catalyst reaction, make low molecular weight at 100 DEG C
Transesterification occurs for polyethylene terephthalate and polyethylene glycol, introduces on low molecular weight polyethylene terephthalate
Polyethylene group generates low molecular weight polyethylene terephthalate-polyethylene glycol hybridized polymer, then prepares certain dense
Low molecular weight polyethylene terephthalate-polyethylene glycol hybridized polymer solution of degree；
Take 300 μ l 0.01mol/L EuCl3The phenanthroline and 300 μ l of 300 μ l 0.01mol/L is added in conical flask in solution
0.01mol/L TTA solution, react be added after 0.5h 3ml0.01mol/L low molecular weight polyethylene terephthalate-it is poly-
The hybridized polymer solution of ethylene glycol is stirred to react after 2h at room temperature and obtains a kind of low molecular weight PET base europium complexing hydridization and shine
Group；
Low molecular weight PET base europium obtained above complexing hydridization luminophore is evenly spread into linear polyester by melt blending
In, obtain a kind of PET base europium complexing hybrid luminescent materials.
3. a kind of preparation method of PET base europium complexing hybrid luminescent materials according to claim 1, it is characterised in that: institute
State EuCl3It is obtained using commercially available europium oxide is ionized.
4. a kind of preparation method of PET base europium complexing hybrid luminescent materials according to claim 1, it is characterised in that: institute
It states linear polyester to be sliced using commercially available PET, inherent viscosity 0.676dL/g.
5. hybrid luminescent materials are complexed in the PET base europium of -4 any the method preparations according to claim 1.
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| CN109777015B (en) * | 2019-01-22 | 2021-04-13 | 青岛大学 | Preparation method of PEG (polyethylene glycol) grafted polymer luminescent hydrogel material |
| CN109705843B (en) * | 2019-01-22 | 2022-03-08 | 青岛大学 | Silicon dioxide modified terbium complex PET luminescent material and preparation method thereof |
| CN109972232A (en) * | 2019-03-26 | 2019-07-05 | 南通楠桥纹织有限公司 | A kind of production technology of light storage towel |
| CN115094534A (en) * | 2022-08-08 | 2022-09-23 | 浙江理工大学 | Preparation method of luminous polyester fiber |
| CN117209889A (en) * | 2023-09-14 | 2023-12-12 | 常州威材新材料科技有限公司 | High-strength engineering plastic capable of utilizing fluorescence detection and preparation process thereof |
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| CN1397587A (en) * | 2002-08-21 | 2003-02-19 | 北京大学 | Multi-allochroic composite fluorescent film and its preparing process and application |
| CN103374120A (en) * | 2012-04-13 | 2013-10-30 | 中国石油天然气股份有限公司 | Preparation method of luminous polyethylene terephthalate |
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| CN1397587A (en) * | 2002-08-21 | 2003-02-19 | 北京大学 | Multi-allochroic composite fluorescent film and its preparing process and application |
| CN103374120A (en) * | 2012-04-13 | 2013-10-30 | 中国石油天然气股份有限公司 | Preparation method of luminous polyethylene terephthalate |
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