CN103374120B - A kind of preparation method of luminous polyethylene terephthalate - Google Patents
A kind of preparation method of luminous polyethylene terephthalate Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of luminous polyethylene terephthalate; By ethylene glycol, terephthalic acid and the nano luminescent agent-ethylene glycol colloidal sol polymerization through macromolecular compound modification, obtain luminous polyethylene terephthalate; Nano luminescent agent is 0.1 ~ 10% of polyethylene terephthalate weight; Nano luminescent agent is 1 ~ 10% of nano luminescent agent-ethylene glycol sol weight; Macromolecular compound is 0.1 ~ 5% of nano luminescent agent-ethylene glycol sol weight; The limiting viscosity of this polyethylene terephthalate is 0.55 ~ 0.75dL/g, and under visible light illumination, in the dark luminescence continues more than 12 hours to the fabric of the fiber obtained; Its fabric is after 20 standard wash under the identical radiation of visible light time, and in the dark luminescence continues more than 12 hours.
Description
Technical field:
The present invention relates to the preparation method of a kind of polyethylene terephthalate (PET) matrix material, in particular to a kind of nano luminescent agent-ethylene glycol colloidal sol added in the preparation process of PET through macromolecular compound modification, synthesis has the preparation method of the PET composite material of illumination effect.
Background technology:
Polyethylene terephthalate (PET) fiber is since industrialization, just the premium properties such as, rebound resilience good, photostabilization good, wear resistance good, good heat resistance high with its modulus is subject to the weaving favor of people in the industry and the welcome of human consumer, Application Areas constantly expands, and demand increases gradually.
Luminous polyethylene terephthalate is a kind of photic light storage type self luminous material, realizes the function of automatic luminous by absorbing various visible ray.Its outstanding feature is after absorbing daytime, storing various visible ray, in the dark sustainable luminous more than 12 hours.
Patent 138876A describes a kind of method preparing luminous polyethylene terephthalate, is the suspension adding ethylene glycol luminous agent in the building-up process of polyester, prepares luminous polyethylene terephthalate.The shortcoming of this preparation method is the suspension instability of ethylene glycol luminous agent, luminous agent can be caused to disperse in the polyester uneven, thus cause the spinning property of luminous polyethylene terephthalate poor.
What the patent of invention of patent 94107601.6 adopted is add luminescent material before spinning, and then heating and melting in extrusion machine, makes luminescent material be scattered in polymer melt, extrude the luminescent fibre being processed into and having luminous effect through extrusion machine from spinning mouth.This kind of technology is difficult to ensure that luminescent material is uniformly dispersed in the polymer completely, and the indexs such as the end breakage rate of luminescent fibre and intensity are bad.
Luminous agent-ethylene glycol the colloidal sol through macromolecular compound modification and other auxiliary agent is added in the building-up process of polyethylene terephthalate, poliester chip and fiber is made to have luminescent properties, under dark condition, there are good mark, instruction, decorative effect, the value of fabric can be improved.
Summary of the invention:
The object of this invention is to provide a kind of nano luminescent agent-ethylene glycol colloidal sol added in preparation process through macromolecular compound modification, the preparation method with the PET composite material of illumination effect of synthesis.
Luminous polyethylene terephthalate of the present invention is by ethylene glycol, terephthalic acid and the nano luminescent agent-ethylene glycol colloidal sol polymerization through macromolecular compound modification, obtains luminous polyethylene terephthalate.
The nano luminescent agent that the particle diameter accounting for reaction mixture gross weight 0.1 ~ 10% is 1nm ~ 1um is added in esterification stage of polyethylene terephthalate, rough vacuum polycondensation or high vacuum polycondensation stage; The nano luminescent agent particle that wherein particle diameter is greater than 760nm accounts for less than 5% of luminous agent total amount.
Described agent-ethylene glycol the colloidal sol of the nano luminescent through macromolecular compound modification refers to and carries out modification with macromolecular compound to the colloidal sol that nano luminescent agent particle-ethylene glycol is formed, the macromolecular chain of macromolecular compound is grafted to inorganic nano-particle sub-surface, thus the chance of the mutual collision weakened between nano luminescent agent particle and reunion, play the effect controlling nano luminescent agent particle aggregation, make nano luminescent agent particle even, stable dispersion in colloidal sol.The yttrium aluminum garnet that described nano luminescent agent is selected from zinc phosphate, strontium aluminate, the europkium-activated yttrium aluminum garnet of trivalent, divalence europkium-activated chlorine strontium phosphate, cerium activate, bivalent manganese activates and the coactivated yttrium oxysulfide of divalent europium, one or more mixture in the europkium-activated calcium chlorate magnesium of divalence.Described macromolecular compound refers to one or more the mixture in polyoxyethylene glycol, polyvinyl alcohol.
The temperature of reaction in esterification stage is 200 ~ 290 DEG C, and reaction pressure is 0.1 ~ 0.5MPa, and the reaction times is 60 ~ 180 minutes; Rough vacuum multi-stage polycondensation temperature of reaction is 200 ~ 290 DEG C, and pressure reduces to 1000Pa gradually by normal pressure, and the reaction times is 10 ~ 90 minutes; High vacuum stage of Fig polycondensation temperature is 250 ~ 300 DEG C, and reaction system vacuum tightness is 50 ~ 100Pa, and the reaction times is 60 ~ 150 minutes.
Nano luminescent agent is 0.1 ~ 10% of luminous polyethylene terephthalate weight;
Nano luminescent agent is 1 ~ 10% of nano luminescent agent-ethylene glycol sol weight.
Macromolecular compound is 0.1 ~ 5% of nano luminescent agent-ethylene glycol sol weight.
In the building-up process of the matrix material of luminous polyethylene terephthalate, nano luminescent agent-ethylene glycol colloidal sol through macromolecular compound modification is joined in the polymerization system of PET, obtain the matrix material be made up of PET and luminous agent, with the fabric that the fiber that this matrix material spins is made into, there is absorption visible ray, performance that in the dark can be luminous.And illumination effect is lasting, washable, wear-resisting.
The present invention be using pure terephthalic acid (PTA), ethylene glycol (EG), nano luminescent agent-ethylene glycol colloidal sol as raw material, prepare luminous polyethylene terephthalate matrix material.Innovative point of the present invention carries out modification by with macromolecular compound to nano luminescent agent-ethylene glycol colloidal sol, improve the stability of nano luminescent agent-ethylene glycol colloidal sol, ensure that nano luminescent agent exists with nano-form in colloidal sol, then the nano luminescent of the mistake through macromolecular compound modification agent-ethylene glycol colloidal sol is joined in the polymerization system of polyester, nano luminescent agent is uniformly dispersed in the polyester, the good spinnability of polymkeric substance.Illumination effect is lasting, washable, wear-resisting.
The limiting viscosity of this luminous poliester chip is 0.55 ~ 0.75dL/g, the fabric of the luminous pet fiber of preparation after radiation of visible light, in the dark sustainable luminous more than 12 hours.Its fabric is substantially constant through 20 standard continuous illumination times.
The present invention be using pure terephthalic acid (PTA), ethylene glycol (EG), through the nano luminescent agent-ethylene glycol colloidal sol of macromolecular compound modification as raw material, prepare luminous polyethylene terephthalate matrix material.Innovative point of the present invention joins in the polymerization system of polyethylene terephthalate by the nano luminescent agent-ethylene glycol colloidal sol through macromolecular compound modification, nano luminescent agent is uniformly dispersed in polyethylene terephthalate, illumination effect is lasting, washable, wear-resisting.
The limiting viscosity of this luminous poliester chip is 0.55 ~ 0.75dL/g, the fabric of the luminous pet fiber of preparation after radiation of visible light, in the dark sustainable luminous more than 12 hours.Its fabric illumination effect after 20 standard wash is substantially constant.
Embodiment
Except as otherwise noted, all in embodiment numbers and percentage ratio are all for benchmark with the weight of PTA.
Embodiment 1
Be equipped with in the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator at one and add 1000 grams of pure terephthalic acids (PTA), 250 grams of ethylene glycol (EG), 280 grams of Nano strontium aluminate-ethylene glycol colloidal sol (wherein strontium aluminates 19 grams, ethylene glycol is 260 grams, polyoxyethylene glycol 1 gram), esterification reaction temperature is 250 DEG C, and reaction pressure is 0.26MPa, and the reaction times is 110 minutes.The product of above-mentioned esterification technique obtains luminous PET composite material through polycondensating process again.Wherein, rough vacuum multi-stage polycondensation temperature of reaction is 260 DEG C, and pressure reduces to 1000Pa gradually by normal pressure, and the reaction times is 30 minutes, and high vacuum stage of Fig polycondensation temperature is 275 DEG C, and reaction system vacuum tightness is 55Pa, and the reaction times is 82 minutes.
The polymer chips fusing point obtained is 245 DEG C, and limiting viscosity is 0.65dL/g, and under visible light illumination, in the dark luminescence continues more than 12 hours to the fabric of the fiber obtained.Its fabric is after 20 standard wash under the identical radiation of visible light time, and in the dark luminescence continues more than 12 hours.
Embodiment 2
Be equipped with in the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator at one and add 1000 grams of pure terephthalic acids (PTA), 300 grams of ethylene glycol (EG), 230 grams of trivalent europkium-activated yttrium aluminum garnet-ethylene glycol colloidal sol (wherein europkium-activated yttrium aluminum garnets of trivalent 18 grams, ethylene glycol is 210 grams, polyvinyl alcohol 2 grams), esterification reaction temperature is 245 DEG C, and reaction pressure is 0.25MPa, and the reaction times is 120 minutes.The product of above-mentioned esterification technique, again through polycondensating process, obtains luminous PET composite material.Wherein, rough vacuum multi-stage polycondensation temperature of reaction is 255 DEG C, and pressure reduces to 1000Pa gradually by normal pressure, and the reaction times is 25 minutes, and high vacuum stage of Fig polycondensation temperature is 280 DEG C, and reaction system vacuum tightness is 50Pa, and the reaction times is 90 minutes.
The polymer chips fusing point obtained is 246 DEG C, and limiting viscosity is 0.66dL/g, and under visible light illumination, in the dark luminescence continues more than 12 hours to the fabric of the fiber obtained.Its fabric is after 20 standard wash under the identical radiation of visible light time, and in the dark luminescence continues more than 12 hours.
Embodiment 3
Be equipped with in the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator at one and add 1000 grams of pure terephthalic acids (PTA), 250 grams of ethylene glycol (EG), 280 grams of nanometer divalence europkium-activated chlorine strontium phosphate-ethylene glycol colloidal sol (wherein europkium-activated chlorine strontium phosphates of nanometer divalence 19.5 grams, ethylene glycol is 260 grams, polyoxyethylene glycol 0.5 gram), esterification reaction temperature is 250 DEG C, and reaction pressure is 0.25MPa, and the reaction times is 90 minutes.The product of above-mentioned esterification technique, again through polycondensating process, obtains luminous PET composite material.Wherein, rough vacuum multi-stage polycondensation temperature of reaction is 200 ~ 240 DEG C, and pressure reduces to 1000Pa gradually by normal pressure, and the reaction times is 30 minutes, and high vacuum stage of Fig polycondensation temperature is 285 DEG C, and reaction system vacuum tightness is 50Pa, and the reaction times is 78 minutes.
The polymer chips fusing point obtained is 245 DEG C, and limiting viscosity is 0.64dL/g, and under visible light illumination, in the dark luminescence continues more than 12 hours to the fabric of the fiber obtained.Its fabric is after 20 standard wash under the identical radiation of visible light time, and in the dark luminescence continues more than 12 hours.
Embodiment 4
Be equipped with in the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator at one and add 1000 grams of pure terephthalic acids (PTA), 400 grams of ethylene glycol (EG), 115 grams of nanometer bivalent manganeses activate and divalent europium coactivated yttrium oxysulfide-ethylene glycol colloidal sol (the wherein activation of nanometer bivalent manganese and coactivated yttrium oxysulfide of divalent europium 3 grams, ethylene glycol is 110 grams, polyvinyl alcohol 2 grams), esterification reaction temperature is 230 DEG C, reaction pressure is 0.1 ~ 0.25MPa, and the reaction times is 125 minutes.The product of above-mentioned esterification technique, again through polycondensating process, obtains luminous PET composite material.Wherein, rough vacuum multi-stage polycondensation temperature of reaction is 250 DEG C, and pressure reduces to 1000Pa gradually by normal pressure, and the reaction times is 30 minutes, and high vacuum stage of Fig polycondensation temperature is 270 DEG C, and reaction system vacuum tightness is 50Pa, and the reaction times is 84 minutes.
The polymer chips fusing point obtained is 246 DEG C, and limiting viscosity is 0.64dL/g, and under visible light illumination, in the dark luminescence continues more than 12 hours to the fabric of the fiber obtained.Its fabric is after 20 standard wash under the identical radiation of visible light time, and in the dark luminescence continues more than 12 hours.
Embodiment 5
Be equipped with in the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator at one and add 1000 grams of pure terephthalic acids (PTA), 400 grams of ethylene glycol (EG), 135 grams of nanometer zinc phosphate-ethylene glycol colloidal sol (wherein zinc phosphates 20 grams, ethylene glycol is 110 grams, polyoxyethylene glycol 5 grams), esterification reaction temperature is 250 DEG C, and reaction pressure is 0.25MPa, and the reaction times is 115 minutes.The product of above-mentioned esterification technique, again through polycondensating process, obtains luminous PET composite material.Wherein, rough vacuum multi-stage polycondensation temperature of reaction is 260 DEG C, and pressure reduces to 1000Pa gradually by normal pressure, and the reaction times is 25 minutes, and high vacuum stage of Fig polycondensation temperature is 270 DEG C, and reaction system vacuum tightness is 50Pa, and the reaction times is 69 minutes.
The polymer chips fusing point obtained is 246 DEG C, and limiting viscosity is 0.63, and under visible light illumination, in the dark luminescence continues more than 12 hours to the fabric of the fiber obtained.Its fabric is after 20 standard wash under the identical radiation of visible light time, and in the dark luminescence continues more than 12 hours.
Claims (1)
1. the preparation method of a luminous polyethylene terephthalate; It is characterized in that: by ethylene glycol, terephthalic acid and the nano luminescent agent-ethylene glycol colloidal sol polymerization through macromolecular compound modification, obtain luminous polyethylene terephthalate;
The temperature of reaction in esterification stage is 200 ~ 290 DEG C, and reaction pressure is 0.1 ~ 0.5MPa, and the reaction times is 60 ~ 180 minutes; Rough vacuum multi-stage polycondensation temperature of reaction is 200 ~ 290 DEG C, and pressure reduces to 1000Pa gradually by normal pressure, and the reaction times is 10 ~ 90 minutes; High vacuum stage of Fig polycondensation temperature is 250 ~ 300 DEG C, and reaction system vacuum tightness is 50 ~ 100Pa, and the reaction times is 60 ~ 150 minutes;
Described nano luminescent agent-ethylene glycol colloidal sol refers to the colloidal sol that nano luminescent agent and ethylene glycol through macromolecular compound modification are formed;
Described macromolecular compound refers to one or more the mixture in polyoxyethylene glycol, polyvinyl alcohol;
The yttrium aluminum garnet that described nano luminescent agent is zinc phosphate, strontium aluminate, the europkium-activated yttrium aluminum garnet of trivalent, divalence europkium-activated chlorine strontium phosphate, cerium activate, bivalent manganese activates and the coactivated yttrium oxysulfide of divalent europium, one or more mixture in the europkium-activated calcium chlorate magnesium of divalence;
Described nano luminescent agent is 0.1 ~ 10% of polyethylene terephthalate weight;
Described nano luminescent agent is 1 ~ 10% of nano luminescent agent-ethylene glycol sol weight;
Described macromolecular compound is 0.1 ~ 5% of nano luminescent agent-ethylene glycol sol weight.
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| CN106337209A (en) * | 2016-09-10 | 2017-01-18 | 巢湖市鼎盛渔具有限公司 | High-density polyethylene light-emitting fiber for weaving fishing net |
| CN107325498B (en) * | 2017-07-06 | 2019-03-26 | 青岛大学 | A kind of PET base europium complexing hybrid luminescent materials 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 |
Citations (4)
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| CN1431070A (en) * | 2003-01-21 | 2003-07-23 | 武汉大学 | Method for preparing water-soluble nano particles |
| CN1978312A (en) * | 2005-12-05 | 2007-06-13 | 北京航空航天大学 | Inorganic oxide sol modified by using high molecular compound stabilizer and its preparing method |
| CN101899144A (en) * | 2009-05-27 | 2010-12-01 | 中国石油天然气股份有限公司 | Method for preparing flame-retardant luminous polyethylene glycol terephthalate |
| CN102076784A (en) * | 2008-05-08 | 2011-05-25 | 3M创新有限公司 | Surface-modified nanoparticles |
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| US20080001124A1 (en) * | 2006-06-29 | 2008-01-03 | Idemitsu Kosan Co., Ltd. | Fluorescent composition and fluorescence conversion substrate using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431070A (en) * | 2003-01-21 | 2003-07-23 | 武汉大学 | Method for preparing water-soluble nano particles |
| CN1978312A (en) * | 2005-12-05 | 2007-06-13 | 北京航空航天大学 | Inorganic oxide sol modified by using high molecular compound stabilizer and its preparing method |
| CN102076784A (en) * | 2008-05-08 | 2011-05-25 | 3M创新有限公司 | Surface-modified nanoparticles |
| CN101899144A (en) * | 2009-05-27 | 2010-12-01 | 中国石油天然气股份有限公司 | Method for preparing flame-retardant luminous polyethylene glycol terephthalate |
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