CN106117531B - A kind of synthetic method and performance of novel optical copolyesters - Google Patents
A kind of synthetic method and performance of novel optical copolyesters Download PDFInfo
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- CN106117531B CN106117531B CN201610439564.4A CN201610439564A CN106117531B CN 106117531 B CN106117531 B CN 106117531B CN 201610439564 A CN201610439564 A CN 201610439564A CN 106117531 B CN106117531 B CN 106117531B
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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Abstract
The invention belongs to polymer luminescent material field, and in particular to one kind possess blue emission characteristic and toughness it is good end hydroxy polyether modification optics polyester copolymer synthetic method and its luminescent properties research.Such novel optical polyester is obtained by the copolyreaction of end hydroxy polyether and ethylene glycol terephthalate, the introducing of end hydroxy polyether, on the one hand can be used as copolymer molecule chain soft segment, improves the toughness of polyester；On the other hand it in situ can be pyrolyzed and produce carbon quantum dot, assign copolyesters special fluorescence emitting characteristics, strong blue fluorescent emissions characteristic is showed under solution and solid fabric state.Synthetic method of the present invention is easy and effective, and the novel optical copolyesters of acquisition has potential application prospect in fields such as bio-imaging, fluorescence sense, photodiode, photocatalysis.
Description
Technical field
The invention belongs to polymer luminescent material field, it is related to the synthetic method and its performance of a kind of novel optical copolyesters
Research.
Background technology
Polyethylene terephthalate (PET) is a kind of typical thermoplastic resin, due to containing fragrance on its main chain
Ring, the fusing point for being allowed to have higher compared with aliphatic polyester and more rich physicochemical property.Nineteen forty-one, British J.R.Whenfield
Use terephthalic acid (TPA) and ethylene glycol to synthesize PET polyester first for raw material with J.D.Dickson, polyester fiber and Shen has been made
Please patent, with after 1949 completes pilot scale in Britain.Since the spinning effect of PET is good, obtained fibre property is excellent,
Found the factory first after patent is purchased and realize the industrialized production of PET polyester fibers in du pont company.PET is fine as a kind of synthesis
Tie up and be just widely applied once coming out, be made that tremendous contribution for human lives and production and be sure to occupy first of synthetic fibers.
And since PET has the characteristics that heat endurance is good, hygroscopicity is small, hardness is big, easy to process, resistant to chemical etching at the same time, 80
Since age, PET also has breakthrough development as engineering plastics, in industries such as organic electro-optic device, packaging, automobile, buildings
With extensive use, it has also become one of five large-engineering plastics.It is more crisp yet with PET quality, therefore limit to a certain extent
Some application fields more demanding to toughness of material, while PET polyester should in the major part of optical material and devices field
With being all based on its high transparency in visible light wave range, thus it is necessary to carry out appropriate modification to PET to improve its toughness simultaneously
The optical property of polyester is further enriched, so as to expand polyester in engineering plastics and optical material and the application model of devices field
Enclose.
Carbon quantum dot (CDs) is the fluorescence carbon nano-particle with torispherical structure that a kind of size is less than 10nm.2004
Year, Xu etc. is found that luminous carbon is received first during single-walled carbon nanotube is prepared by arc discharge using Purified in electrophoresis
Rice corpuscles, is known as carbon quantum dot.Then, the Sun Ya equalitys people of Clemson University was in first time laser etching method in 2006
It is prepared for carbon quantum dot.Thereafter, researcher is prepared using electrochemical oxidation, pyrolysis, microwave cracking, hydro-thermal method successively again.
Since carbon quantum dot compared with conventional semiconductors quantum dot and organic dyestuff has higher biocompatibility, hypotoxicity, stability of photoluminescence,
Thus since self-discovery, just have received widespread attention, at present in bio-imaging, fluorescence sense, organic photovoltaic, light emitting diode
Potential application value is shown with catalytic field.However, most methods for preparing CDs are related to multiple steps or passivation at present
Processing, therefore develop a kind of method for simplifying synthesis carbon quantum dot and be necessary.
The content of the invention
The present invention provides the synthetic method and its photoluminescence property of a kind of new high tenacity optics copolyesters.There is provided
There is fluorescent emission property and the good novel optical copolyesters of toughness, synthetic method is simple, by single step reaction by end hydroxyl
Base polyethers is introduced into polyester molecule chain, on the one hand enhances the toughness of copolyesters, on the other hand assigns copolyesters good photic
The characteristics of luminescence, shows as its solid fabric and solution and strong blue emission characteristic is provided with ultraviolet excitation.
The technical scheme is that：
(1) structure of novel copolymerized ester.
Novel copolymerized ester occurs polycondensation reaction by the oligomer and end hydroxy polyether of ethylene glycol terephthalate and obtains, its
Structural formula is as follows：
(2) synthetic method of blue emission copolyesters and water-solubility fluorescent carbon quantum dot.
It is a kind of that there is blue emission and the novel copolymerized ester of good toughness and the synthetic method of water-solubility fluorescent carbon quantum dot, bag
Include following steps：
(1) 20 parts of terephthalic acid (TPA)s, 0.5-2.5 parts of M-phthalic acids and 13 parts of ethylene glycol are sequentially added into reaction kettle.
(2) gained mixture in step (1) is forced into 2-3bars under nitrogen protection, is stirred back at 220-240 DEG C
When stream 2~4 is small.
(3) reactor pressure is down to normal pressure, and the water of step (2) reaction generation and unnecessary ethylene glycol are discharged.
(4) temperature of reaction kettle rises to 265~285 DEG C, and into the reaction solution obtained by step (3), 3-5 parts of addition is true through 120 DEG C
Empty dried end hydroxy polyether, adds 0.2-0.3 parts of Sb2O3Make catalyst, increase to melt viscosity, reaction about 2~4 is small
When.
(5) quick cooling in fusant injection flowing water obtained by step (4) is obtained into novel fluorescence copolyesters.
(6) 10~30mmol end hydroxy polyethers are added into the reaction vessel with stirring and heating unit, are passed through nitrogen,
Be stirred at reflux at 260~280 DEG C 3~4 it is small when, obtain being dispersed in the carbon quantum dot in alcohol.
Reaction mechanism of the present invention can be described as follows：
The novel copolymerized ester of tool blue emission provided by the present invention and good toughness is by a kind of PET oligomer and end hydroxyl
Base polyethers occurs polycondensation reaction and forms the method synthesis of block copolymer.Higher temperature in preparation process makes part end hydroxyl
Base polyethers, which has been decomposed thermally to form carbon quantum dot, to be disperseed in the copolymer, so as to obtain the fluorescence copolymerization with blue emission characteristic
Thing.Further, since insertion of the end hydroxy polyether soft segment in PET skeletons causes copolymer to have higher toughness.
In conclusion the present invention technical characterstic be it is following some：
1st, synthesized possess high tenacity and with blue emission characteristic novel copolymerized ester, its simple synthetic method, efficiently,
It is easily industrialized, blue emission characteristic is shown in aqueous solution and solid fabric.
2nd, the fluorescent characteristic of synthesized novel copolymerized ester comes from the carbon quantum dot in situ produced in building-up process.
3rd, the adjustable carbon quantum dot of fluorescence emission wavelengths is prepared for by one-step synthesis, its preparation method is easy, does not make
With strong acid and strong base and passivator, and there is good water solubility.
4th, by controlling the time of prepared carbon quantum dot, the particle size of carbon quantum dot can be adjusted.
Brief description of the drawings
Fig. 1 is that the aqueous solution of fluorescence quantum provided by the invention is inhaled in the ultraviolet-visible corresponding to the differential responses time
Receive spectrum and fluorescence emission spectrum.
Fig. 2 is the synthetic route of novel copolymerized ester provided by the invention and its differential scanning amount with traditional pet polymer
Hot instrument and thermogravimetric analysis data.
Fig. 3 is the resonance offset effect and X-ray diffraction spectrum of novel copolymerized ester provided by the invention and traditional pet polymer
Figure.
Fig. 4 is the fluorescence excitation of novel copolymerized ester provided by the invention in the solution and emission spectrum and its solid fabric
Emission spectrum.
Embodiment
Below by way of the description of embodiment, the present invention will be further described, but this is not to the limit of the present invention
System, those skilled in the art's basic thought according to the present invention, can make various modifications, without departing from the basic of the present invention
Thought, within the scope of the present invention.
Embodiment 1：The synthesis of the novel copolymerized ester of blue emission of the present invention
(1) 20 parts of terephthalic acid (TPA)s, 2 parts of M-phthalic acids and 13 parts of ethylene glycol are sequentially added into reaction kettle.
(2) gained mixture in step (1) is forced into 2.7bars under nitrogen protection, is stirred at reflux at 230 DEG C
2.5 it is small when.
(3) reactor pressure is down to normal pressure, and the water of step (2) reaction generation and unnecessary ethylene glycol are discharged.
(4) temperature of reaction kettle rises to 280 DEG C, and add 4.2 parts into the reaction solution obtained by step (3) does through 120 DEG C of vacuum
End hydroxy polyether after dry, adds 0.26 part of Sb2O3Make catalyst, increase to melt viscosity, when reaction 3.5 is small.
(5) quick cooling in fusant injection flowing water obtained by step (4) is obtained into fluorescence copolyesters.
Embodiment 2：The optical property of fluorescent carbon quantum dot of the present invention
(1) 30mmol end hydroxy polyethers are added into the reaction vessel with stirring and heating unit, are passed through nitrogen,
Be stirred at reflux at 280 DEG C 3.5 it is small when, must disperse with the carbon quantum dot of polyethers.
(2) using pure water as solvent, the reaction time for configuring low concentration is respectively 0.5h, 1.5h, 2.0h, 2.5h, 3.0h
The carbon quantum dot solution being dispersed in PEG obtained with 3.5h, carries out uv-visible absorption spectra scanning respectively.
(3) using pure water as solvent, the carbon quantum dot solution obtained under the 0.25g/mL differential responses times is configured.
(4) sepectrophotofluorometer is used, setting wavelength of transmitted light is 450nm, slit width 10nm, and PMT voltage is
400V, response time 0.1s, obtain the excitation spectrum of each solution in (2), so as to determine excitation wavelength range by length scanning.
(5) use sepectrophotofluorometer, set excitation wavelength be respectively 300nm, 330nm, 365nm, 420nm and
420nm, slit width 10nm, PMT voltage 400V, response time 0.1s, is obtained by being scanned under different excitation wavelengths
(2) fluorescence emission spectrum of each solution in.
Thus the uv-visible absorption spectra and fluorescence emission of carbon quantum dot obtained under the differential responses time is obtained
Spectrum is as shown in Figure 1, show the characteristic absorption peak of 245nm in ultra-violet absorption spectrum；In fluorescence emission spectrum it can be seen that with
There is red shift in the increase maximum emission peak in reaction time, and emission band broadens after the longer reaction time, maximum excitation ripple
Length is basically unchanged positioned at 365nm, and launch wavelength red shift with the increase of excitation wavelength, shows to have obtained the carbon amounts in the present invention
Sub- point.
Embodiment 3：The crystallinity and thermal stability of the novel copolymerized ester of the present invention
(1) the temperature control program for setting differential scanning calorimeter (DSC) is to rise to 280 DEG C from 25 DEG C with the speed of 50 DEG C/min
10min is kept then to be down to 40 DEG C with the speed of 15 DEG C/min to eliminate thermal history afterwards, then with the speed falling-rising of 15 DEG C/min extremely
320 DEG C, PET polyester and novel copolymerized ester are tested respectively, obtain its differential scanning (DSC) curve.
(2) the temperature control program for setting thermogravimetric analyzer is to rise to 600 DEG C with the speed of 20 DEG C/min, is divided under nitrogen atmosphere
It is other that thermogravimetric analysis is carried out to pet polymer and novel copolymerized ester, obtain its thermogravimetric analysis (TGA) curve.
(3) sight of nonisothermal crystallization behavior is carried out respectively to pet polymer and novel copolymerized ester with PLM with heating stage
Examine, obtain its polarized light microscopy picture.
(4) setting X-ray diffractometer working voltage 40kV, electric current 30mA and launch wavelength areTo pet polymer
X-ray diffraction (XRD) scanning is carried out with novel copolymerized ester, obtains its XRD spectra.
Thus the DSC, TGA, polarized light microscopy and XRD spectrum of PET and novel copolymerized ester are obtained as shown in Figure 2,3, Fig. 2 is presented
The route map for going out the novel copolymerized ester of synthesis shows that end hydroxy polyether segment is embedded in PET skeletons, so as to show higher
Toughness；And novel copolymerized ester is with respect to pet polymer fusing point reduces by 20 DEG C, degree of supercooling increases and cold crystallization peak in DSC curve
Appearance all prove novel copolymerized ester crystallization imperfection, i.e. the introducings of PEG flexible chains reduce the regularity of PET strands and then
Influence its crystallinity.At the same time from the figure 3, it may be seen that relative to PET, synthesizing new copolyesters owes regular spherocrystal pattern and its wider
XRD diffraction maximums have further proved this viewpoint；Fig. 2 also embodies crystallization imperfection and result in novel copolymerized ester heat endurance at the same time
Decline.
Embodiment 4：The photoluminescent property of the novel copolymerized ester of the present invention
(1) with tetrachloroethanes and phenol volume ratio 1:1 makees solvent, and configuration concentration is the copolymerization ester solution of 0.5g/mL.
(2) sepectrophotofluorometer is used, setting fluorescence emission wavelengths are 450nm, slit width 10nm, PMT voltage
For 400V, response time 0.1s, the excitation spectrum of solution in (1) is obtained by length scanning.
(3) sepectrophotofluorometer is used, setting fluorescence exciting wavelength is 385nm, slit width 10nm, PMT voltage
For 400V, response time 0.1s, the emission spectrum of solution in (1) is obtained by length scanning.
(4) sample microcell is excited using 405nm lasers, obtains the fluorescent emission of novel copolymerized ester solid fabric
Spectrum.
Obtained copolyesters fluorescence excitation and emission spectrum is as shown in figure 4, can be seen that the transmitting light of copolyesters from spectrum
Spectrum with it is of the invention in carbon quantum dot emission spectrum it is close, show the fluorescent light source of the copolyesters end hydroxy polyether in building-up process
The thermal decomposition of segment and the carbon quantum dot formed, while solid-state emission spectrum has obvious red shift compared with solution emission spectrum.
Claims (3)
1. a kind of preparation method of novel optical copolyesters, it is characterised in that include the following steps：
(1) 20 parts of terephthalic acid (TPA)s, 0.5-2.5 parts of M-phthalic acids and 13 parts of ethylene glycol are sequentially added into reaction kettle；
(2) gained mixture in step (1) is forced into 2-3bars under nitrogen protection, 2 is stirred at reflux at 220-240 DEG C
~4 it is small when；
(3) reactor pressure is down to normal pressure, and the water of step (2) reaction generation and unnecessary ethylene glycol are discharged；
(4) temperature of reaction kettle rises to 265~285 DEG C, and add 3-5 parts into the reaction solution obtained by step (3) does through 120 DEG C of vacuum
End hydroxy polyether after dry, adds 0.2-0.3 parts of Sb2O3Make catalyst, increase to melt viscosity, when reaction 2~4 is small；
(5) quick cooling in fusant injection flowing water obtained by step (4) is obtained into the novel optical copolyesters containing carbon quantum dot.
A kind of 2. preparation method of novel optical copolyesters according to claim 1, it is characterised in that：Added in step (4)
Flexible end hydroxy polyether is to improve the toughness of traditional PET polyester.
A kind of 3. preparation method of novel optical copolyesters according to claim 1, it is characterised in that：Its characteristics of luminescence comes from
The carbon quantum dot being formed in situ in building-up process.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087302A (en) * | 2013-01-22 | 2013-05-08 | 金发科技股份有限公司 | Copolyester, preparation method and application thereof |
| CN103387831A (en) * | 2013-07-24 | 2013-11-13 | 中国科学院长春光学精密机械与物理研究所 | Carbon nano point with high fluorescence quantum efficiency and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087302A (en) * | 2013-01-22 | 2013-05-08 | 金发科技股份有限公司 | Copolyester, preparation method and application thereof |
| CN103387831A (en) * | 2013-07-24 | 2013-11-13 | 中国科学院长春光学精密机械与物理研究所 | Carbon nano point with high fluorescence quantum efficiency and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Photoluminescent carbon dots directly derived from polyethylene glycol and their application for cellular imaging";Rui-Jun Fan等;《CARBON》;20140116;第71卷;第87-93页 * |
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