CN1175021C - Prepn of energy-accumulating luminous polyester - Google Patents
Prepn of energy-accumulating luminous polyester Download PDFInfo
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- CN1175021C CN1175021C CNB021351112A CN02135111A CN1175021C CN 1175021 C CN1175021 C CN 1175021C CN B021351112 A CNB021351112 A CN B021351112A CN 02135111 A CN02135111 A CN 02135111A CN 1175021 C CN1175021 C CN 1175021C
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Abstract
The present invention relates to a method for preparing luminous energy-saving polyester, which belongs to the field of polymer materials. The method comprises: a reaction monomer carries out an esterification reaction or an ester interchange reaction and a polycondensation reaction in the presence of a catalyst and a stabilizing agent, the reaction monomer is fiber level refined terephthalic acid or dimethyl terephthalate and glycol, and the glycol and a luminous material are prepared into uniform suspension to be added in a reaction system. The obtained luminous energy-saving polyester comprises 0.1 to 9 wt% of luminous inorganic long-persistence material whose average grain size is less than 10 micrometers. The present invention has the advantages of simple method and process and easy commercial process, the obtained luminous energy-saving polyester has no toxicity and no harm and can send out visible light in dark places after irradiated by natural light, lamp light, etc., and the luminous persistence time is long. Pellets of the luminous energy-saving polyester can be used for manufacturing luminous polyester fibers through melt spinning and can be used in fabrics, and the pellets have good identification, indication and decoration effects in dark places and can increase fabric value.
Description
(1) technical field
The present invention relates to a kind ofly can absorb visible lights such as natural light, light, the preparation method of can be in the dark long-time luminous macromolecular material, be specifically related to a kind of preparation method who contains the energy-accumulating luminous polyester of inorganic long after glow luminous material, belong to polymeric material field.
(2) background technology
Energy-accumulating luminous polyester is meant that polyester is behind radiation of visible light such as natural light, light, excited, still can send visible light for a long time even stop the irradiation back in the dark place at visible light, the polymkeric substance and the goods that similarly have long-persistence luminous effect have related to many Application Areass, as plastic products luminous, noctilucence textiles etc., good sign, indication, decorative effect are in the dark arranged, rather well received, can satisfy the needs of people's nocturnalism.So far, be that the preparation method of raw material production luminous polyester (PET) does not still have bibliographical information with ethylene glycol (EG), terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT).
Current, preparation contains the polymkeric substance of phosphor and the method for fiber employing is direct and mixed with polymers phosphor, a kind of is the master batch method, mix after luminescent material and polymkeric substance such as the polyester thorough drying, after mixing extruding, make the luminescence polymer master batch, produce luminescent fibre with general polymer by blend melt spinning again, the defective of this technology is to make in the luminous master batch process, easily produce thermal destruction during the polymkeric substance heating and melting, oxicracking etc., cause viscosity degradation, the inner quality variation, luminescent material disperses inhomogeneous, the spinning property of polymkeric substance is poor, the manufacturing process complexity.
What the patent of invention of ZL94107601.6 adopted is to add luminescent material before spinning, granular or the sheet polymer that the surface scribbles lubricant is that long after glow luminous material mixes in mixing machine earlier with phosphorescent pigment, heating and melting in extrusion machine then, luminescent material is scattered in the polymer melt, extrude from the spinning mouth through extrusion machine and to be processed into luminescent fibre with luminous effect, as polymkeric substance is polyester (PET), and what then produce is the luminous polyester fiber.But there is following defective in this kind technology, conventional device for spinning need increase the equipment of corresponding luminescent powder and mixed with polymers, luminescent material need carry out thorough drying, complex process, this kind preparation technology is difficult to also guarantee that luminescent material is uniformly dispersed fully in polymkeric substance, bigger by the method difficulty in spinning of general melt-spinning.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, providing a kind of is raw material with ethylene glycol and terephthalic acid or dimethyl terephthalate (DMT), the preparation method of the energy-accumulating luminous polyester slice that preparation technology is simple, spinning properties is good.
Technical scheme of the present invention is as follows.
Method of the present invention comprises that reaction monomers carries out esterification or transesterification reaction, polycondensation in the presence of catalyzer, stablizer, it is characterized in that, reaction monomers is fibre-grade pure terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol, and the unit for uniform suspension that ethylene glycol and luminescent material are mixed with adds in the reaction system.
Above-mentioned luminescent material/glycolic suspension can be to join reaction system in esterification or transesterification reaction stage, also can be to join reaction system in the polycondensation stage.
Preferably interpolation scheme of the present invention is to finish the back interpolation in esterification or transesterification reaction, and the reactant viscosity in the system is lower at this moment, and therefore, luminescent material can be mixed in the reactant preferably.
The luminescent material that is suitable for the inventive method is rare-earth activated long after glow luminous material, can be any long after glow luminous material or its mixture in alkali earth metal aluminate, silicate, the aluminosilicate, this series luminescent material has advantages such as original intensity height, time of persistence length, "dead" harm.
1～10 micron of the median size of above-mentioned luminescent material, preferably 1～3 micron, consumption is 0.1～9% by the weight percent calculating of polyester, is preferably 2～8%, is preferably 3～6%.
Above-mentioned polycondensation catalyst adopts antimonous oxide, also can be antimony acetate, antimony glycol or germanium dioxide.
Phosphoric acid, phosphorous acid or its ester class are adopted in the aforementioned stable agent.
Method of the present invention specifically comprises the steps:
1, in material-compound tank, adds ethylene glycol, under condition of stirring, add inorganic long after glow luminous material and be made into slurries, pour grinding in ball grinder then into, be dispersed into uniform suspension.
2, pure terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT), ethylene glycol (EG), catalyzer, stablizer are joined in the reactor, heat up and carry out esterification or transesterification reaction.
3, after esterification or transesterification reaction finish, inorganic long after glow luminous material/the glycolic suspension of step 1 is joined in the reactant under non-pressurized situation, free ethylene glycol volatilization back is collected and is separated with reaction system, contain the atomic reactant of luminescent material and carry out polycondensation through heating up, reducing pressure, determine to reach discharging after the required viscosity according to the reactor motor power, promptly make energy-accumulating luminous polyester slice of the present invention through cooling, granulation.
Esterification, transesterification reaction are two kinds of synthesis techniques of carboxylate.Two kinds of synthesis techniques such as the carboxylate bishydroxyethyl terephthalate:
(1) terephthalic acid (PAT) direct esterification method: terephthalic acid, ethylene glycol join in the reactor, nitrogen pressure 0.35MPa, be warming up to 230 ℃ and begin to carry out esterification, water outlet, reach theoretical aquifer yield and finish esterification, pressure is reduced to normal pressure, and this moment, temperature rose to 255 ℃, obtained carboxylate.
(2) dimethyl terephthalate (DMT) (DMT) method: with dimethyl terephthalate (DMT), ethylene glycol and catalyst acetic acid magnesium, manganese acetate, be warming up to 175 ℃, pressure is to carry out transesterification reaction under the normal pressure, be warming up to 215 ℃ gradually, methyl alcohol among the DMT is cemented out by ethylene glycol, the methyl alcohol quantity of distillate reaches 95% o'clock of theoretical value, continues to be warming up to 255 ℃, steams excessive ethylene glycol and remaining methyl alcohol.Transesterification reaction finishes to obtain carboxylate.
Characteristics of the present invention are to add inorganic long after glow luminous material in the polyester synthetic reaction process.At first modulated luminescence material/glycolic suspension adds luminescent material in ethylene glycol under condition of stirring, is made into slurries, again through ball mill grinding, luminescent material is evenly spread in the ethylene glycol, obtains luminescent material/glycolic suspension.Can be to join reaction system in esterification or transesterification reaction stage, also can be to join reaction system in the polycondensation stage, preferably interpolation scheme of the present invention is to finish the back interpolation in esterification or transesterification reaction, reactant viscosity in the system is lower at this moment, therefore, luminescent material can be mixed in the reactant preferably.Two variations can take place in this process: the one, and system is a normal pressure, and temperature is higher, and ethylene glycol can at high temperature constantly evaporate, and collects after condensation, thereby is discharged from outside the reaction system; The 2nd, the luminescent material micropartical has a dispersive process again in reaction system, under the stirring action of reactor agitator, be distributed in the reactant.The present invention investigates the concentration of luminescent material in inorganic long after glow luminous material/glycolic suspension, concentration raises, be unfavorable for the homodisperse of luminescent material in polyester, and concentration reduces, need to consume more substantial ethylene glycol, the suitable concentration scope that final the present invention determines is 5～50%, is preferably 10～30%, is preferably 15～20%.
The energy-accumulating luminous polyester slice of the present invention after 10～30 minutes, can send tangible visible light in irradiations such as natural light, light in the dark place, be longer than time of persistence 10 hours.Section can be used for producing the luminous polyester fiber through melt-spinning, is applied to textile field, has effect preferably, can improve the value of fabric.
(4) specific embodiment
Below in conjunction with embodiment method of the present invention is described further.
The preparation method of embodiment 1. energy-accumulating luminous polyester
1, the modulation of inorganic long after glow luminous material/glycolic suspension
Take by weighing 1036.8g ethylene glycol, join in the material-compound tank, under condition of stirring, add the inorganic long after glow luminous material of 115.2g, poured grinding in ball grinder then into 30 minutes, promptly obtain the suspension of inorganic long after glow luminous material/ethylene glycol.Luminescent material is pressed the GB/T14633-93 standard testing, excite 15 seconds after luminosity be 700mcd/m
2, time of persistence is more than 10 hours.
2, energy-accumulating luminous polyester is synthetic
The carboxylate bishydroxyethyl terephthalate has two kinds of synthesis techniques
PTA direct esterification method: 2490g terephthalic acid, 1209g ethylene glycol are joined in the reactor, nitrogen pressure is to 0.35MPa, be warming up to 230 ℃ and begin to carry out esterification, water outlet, reach theoretical aquifer yield and finish esterification, pressure is reduced to normal pressure, and this moment, temperature rose to 255 ℃, obtained carboxylate.
Under the stirring action of reactor stirrer, in carboxylate, add 1.0g polycondensation catalyst antimonous oxide, 0.4g stablizer trimethyl phosphite 99, and then add above-mentioned inorganic long after glow luminous material/glycolic suspension, ethylene glycol wherein is constantly evaporation in the interpolation process, collect after being condensed into liquid, keep temperature not descend in the interpolation process, after adding finishes, interior temperature rise to 268 ℃, begin to be decompressed to 2.6KPa, carry out prepolymerization reaction, during interior temperature rise to 285 ℃, pressure is reduced to 80Pa, carries out polycondensation, determines to reach that nitrogen extrudes material after the required viscosity according to the reactor motor power, through cooling, pelletizing promptly makes inorganic long after glow luminous material content and is 4% energy-accumulating luminous polyester slice.
The mensuration of the limiting viscosity of energy-accumulating luminous polyester slice, fusing point, glycol ether, moisture content is pressed GB/T14190-93 fiber polyester chip analytical procedure and is measured result such as table 1
The energy-accumulating luminous polyester slice test result of table 1
Limiting viscosity fusing point glycol ether end carboxyl moisture %
dl/g ℃ ％ mol/t
0.638 259 2.0 25 0.3
With the section of the luminous polyester after the above-mentioned polymerization, in vacuum drum, carry out drying, drying temperature is 140 ℃, vacuum tightness 40Pa, 10 hours time of drying, the water ratio of section is got dry good section melt-spinning less than 30PPm, can produce the luminous polyester fiber.
When the content of luminescent material less than 6% the time, the luminous polyester section has better spinnability, content is greater than 6% o'clock, the spinning property variation, content can't spinning greater than 9% when above.
The present invention will be further described to use several embodiment below again, is not limited to this several embodiment certainly.
Embodiment 2. is as described in the embodiment 1, and different is
1, the modulation of inorganic long after glow luminous material/glycolic suspension
Take by weighing 900g ethylene glycol and join in the material-compound tank, stir situation under add the 86.4g luminescent material, poured grinding in ball grinder then into 40 minutes, promptly get luminescent material/glycolic suspension,
2, energy-accumulating luminous polyester is synthetic
DMT method: with 2910g dimethyl terephthalate (DMT), 2325g ethylene glycol and catalyst acetic acid magnesium 0.62g, manganese acetate 0.60g, be warming up to 175 ℃, pressure is to carry out transesterification reaction under the normal pressure, is warming up to 215 ℃ gradually, methyl alcohol among the DMT is cemented out by ethylene glycol, the methyl alcohol quantity of distillate reaches 95% o'clock of theoretical value, and transesterification reaction finishes, and obtains carboxylate, continue to be warming up to 255 ℃, steam excessive ethylene glycol and remaining methyl alcohol, collect, separate with system through condensation.
Luminescent material content is 3% energy-accumulating luminous polyester.
Embodiment 3. is as described in the embodiment 2, and different is:
Take by weighing 960g ethylene glycol and join in the material-compound tank, stir situation under add the 144g luminescent material, poured grinding in ball grinder then into 30 minutes, promptly get luminescent material/glycolic suspension.The method that all the other press the energy-accumulating luminous polyester of embodiment 2 preparation promptly gets luminescent material content and is 5% energy-accumulating luminous polyester.
Embodiment 4. is as described in the embodiment 2, and different is:
Taking by weighing 1200g ethylene glycol joins in the material-compound tank, stir situation under add the 172.8g luminescent material, poured grinding in ball grinder then into 35 minutes, promptly get luminescent material/glycolic suspension, the method that all the other press the energy-accumulating luminous polyester of embodiment 2 preparation promptly gets luminescent material content and is 6% energy-accumulating luminous polyester.
Claims (10)
1. the preparation method of an energy-accumulating luminous polyester, comprise that reaction monomers carries out esterification or transesterification reaction, polycondensation in the presence of catalyzer, stablizer, it is characterized in that, reaction monomers is fibre-grade pure terephthalic acid or dimethyl terephthalate (DMT) and ethylene glycol, and the unit for uniform suspension that ethylene glycol and luminescent material are mixed with adds in the reaction system.
2. the preparation method of energy-accumulating luminous polyester as claimed in claim 1 is characterized in that, described luminescent material/glycolic suspension is to finish the back interpolation in esterification or transesterification reaction.
3. the preparation method of energy-accumulating luminous polyester as claimed in claim 1, it is characterized in that, described luminescent material/glycolic suspension can be to join reaction system in esterification or transesterification reaction stage, also can be to join reaction system in the polycondensation stage.
4. the preparation method of energy-accumulating luminous polyester as claimed in claim 1, it is characterized in that, described luminescent material is rare-earth activated long after glow luminous material, and it can be any long after glow luminous material or its mixture in alkali earth metal aluminate, silicate, the aluminosilicate.
5. as the preparation method of claim 1 or 4 described energy-accumulating luminous polyester, it is characterized in that the median size of described luminescent material is 1～10 micron.
6. as the preparation method of claim 1 or 4 described energy-accumulating luminous polyester, it is characterized in that the median size of described luminescent material is 1～3 micron.
7. as the preparation method of claim 1 or 4 described energy-accumulating luminous polyester, it is characterized in that the consumption of described luminescent material is 0.1～9% by the weight percent calculating of polyester.
8. as the preparation method of claim 1 or 4 described energy-accumulating luminous polyester, it is characterized in that the consumption of described luminescent material calculates to being 2～8% by the weight percent of polyester.
9. as the preparation method of claim 1 or 4 described energy-accumulating luminous polyester, it is characterized in that the consumption of described luminescent material is 3～6% by the weight percent calculating of polyester.
10. as the preparation method of claim 1 or 4 described energy-accumulating luminous polyester, it is characterized in that, specifically comprise the steps:
(1) in material-compound tank, adds ethylene glycol, under condition of stirring, add inorganic long after glow luminous material and be made into slurries, pour grinding in ball grinder then into, be dispersed into uniform suspension;
(2) pure terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol, catalyzer, stablizer are joined in the reaction, heat up and carry out esterification or transesterification reaction;
(3) after esterification or transesterification reaction finish, inorganic long after glow luminous material/the glycolic suspension of step (1) is joined in the reactant under non-pressurized situation, free ethylene glycol volatilization back is collected and is separated with reaction system, contain the atomic reactant of luminescent material and carry out polycondensation through heating up, reducing pressure, determine to reach discharging after the required viscosity according to the reactor motor power, promptly make energy-accumulating luminous polyester slice of the present invention through cooling, granulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021351112A CN1175021C (en) | 2002-06-13 | 2002-06-13 | Prepn of energy-accumulating luminous polyester |
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| CNB021351112A CN1175021C (en) | 2002-06-13 | 2002-06-13 | Prepn of energy-accumulating luminous polyester |
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| CN1175021C true CN1175021C (en) | 2004-11-10 |
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| CNB021351112A Expired - Fee Related CN1175021C (en) | 2002-06-13 | 2002-06-13 | Prepn of energy-accumulating luminous polyester |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294190C (en) * | 2003-08-06 | 2007-01-10 | 东华大学 | Long persistence luminous polyamide and preparation process thereof |
| CN100338171C (en) * | 2004-10-27 | 2007-09-19 | 中国石油化工股份有限公司 | Long persistence luminous thermoplastic plastics composition and method of making the same |
| CN100348690C (en) * | 2004-10-27 | 2007-11-14 | 中国石油化工股份有限公司 | Luminous polyethylene terephthalate compostition and its preparation method |
| EP2409833A1 (en) * | 2010-07-23 | 2012-01-25 | Saint-Gobain Glass France | Laminated glazing for head-up display |
| EP2546319A1 (en) * | 2011-07-13 | 2013-01-16 | Koninklijke Philips Electronics N.V. | High efficiency plastic light conversion components by incorporation of phosphor in a polymer by adding to monomers before polymerisation |
| CN102493017A (en) * | 2011-12-08 | 2012-06-13 | 江南大学 | Rare-earth silicate blue long-afterglow polyester fiber and preparation method thereof |
| CN103374209B (en) * | 2012-04-13 | 2016-08-03 | 中国石油天然气股份有限公司 | Luminous poly terephthalic acid 1,3 propylene glycol ester composite material |
| CN115094534B (en) * | 2022-08-08 | 2024-07-02 | 浙江理工大学 | Preparation method of luminous polyester fiber |
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