CN103374209B - A kind of luminous poly terephthalic acid 1,3 propylene glycol ester composite - Google Patents
A kind of luminous poly terephthalic acid 1,3 propylene glycol ester composite Download PDFInfo
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- CN103374209B CN103374209B CN201210109161.5A CN201210109161A CN103374209B CN 103374209 B CN103374209 B CN 103374209B CN 201210109161 A CN201210109161 A CN 201210109161A CN 103374209 B CN103374209 B CN 103374209B
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Abstract
The present invention relates to a kind of luminous poly terephthalic acid 1, the composite of 3 propylene glycol esters, by 1,3 propylene glycol, p-phthalic acid and nano luminescent agent 1,3 propylene glycol colloidal sol polymerizations, the reaction temperature in esterification stage is 200～290 DEG C, and reaction pressure is 0.1～0.5MPa, and the response time is 60～180 minutes；Coarse vacuum multi-stage polycondensation reaction temperature is 200～290 DEG C, and pressure is gradually reduced to 1000Pa by normal pressure, and the response time is 10～90 minutes；High vacuum stage of Fig polycondensation reaction temperature is 250～300 DEG C, and reaction system vacuum is 50～100Pa, and the response time is 60～150 minutes；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 composite of a kind of poly terephthalic acid 1,3 propylene glycol ester (PTT), add nano luminescent agent colloidal sol particularly to a kind of in the preparation process of PTT, synthesis has the PTT composite of illumination effect.
Background technology:
Polyethylene terephthalate (PTT) fiber is since industrialization, just, the premium properties such as resilience good, light resistance good, wearability good, heat-resist high with its modulus is by the weaving favor of people in the industry and welcoming of consumer, application constantly expands, and demand is gradually increased.
Luminous poly terephthalic acid 1,3 propylene glycol ester is a kind of photic light storage type self luminous material, realizes the function of automatic luminous by absorbing various visible rays.Its outstanding feature be daytime absorb, store various visible ray after, the most 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, the luminous polyethylene terephthalate of preparation.The shortcoming of this preparation method is that the suspension of ethylene glycol luminous agent is unstable, luminous agent can be caused to disperse in the polyester uneven, thus causes the spinnability of luminous polyethylene terephthalate poor.
The patent of invention of patent 94107601.6 uses interpolation luminescent material before spinning, then adds heat fusing in extruder, makes luminescent material be scattered in polymer melt, is extruded and processed into the luminescent fibre with luminous effect through extruder from spinning mouth.This kind of technology is difficult to ensure that luminescent material is completely dispersed uniformly in the polymer, and the index such as the end breakage rate of luminescent fibre and intensity is bad.
Luminous agent-1,3 propylene glycol colloidal sols and other auxiliary agent is added in poly terephthalic acid 1, the building-up process of 3 propylene glycol esters, make poly terephthalic acid 1,3 propylene glycol esters sections and fiber have luminescent properties, have good mark, instruction, decorative effect, can improve the value of fabric under dark condition.
Summary of the invention:
A kind of method that it is an object of the invention to provide Nano sol prepares poly terephthalic acid 1, the 3 propylene glycol ester composite of luminescence.
The preparation method of luminous poly terephthalic acid 1,3 propylene glycol ester of the present invention is by 1,3 propylene glycol, p-phthalic acid and nano luminescent agent-1,3 propylene glycol colloidal sol polymerizations, obtains poly terephthalic acid 1,3 propylene glycol ester of luminescence；Wherein:
At poly terephthalic acid 1, the esterification stage of 3 propylene glycol esters, coarse vacuum polycondensation reaction or fine vacuum polycondensation reaction stage add account for reactant mixture gross weight 0.1～10% particle diameter be the anti-luminous agent of nanometer of 1nm～1um；Wherein the particle diameter nano luminescent agent particle more than 760nm accounts for less than the 5% of luminous agent total amount.
Described nano luminescent agent-1,3 propylene glycol colloidal sols refer to nano luminescent agent particle and 1, the colloidal sol that 3 propylene glycol are formed, one or more the mixture in yttrium-aluminium-garnet, bivalent manganese activation and the coactivated yttrium oxysulfide of divalent europium, bivalence europkium-activated chloric acid calcium and magnesium that described luminous agent activates selected from zinc phosphate, strontium aluminate, the europkium-activated yttrium-aluminium-garnet of trivalent, bivalence europkium-activated chlorine strontium phosphate, cerium.
The reaction temperature in esterification stage is 200～290 DEG C, and reaction pressure is 0.1～0.5MPa, and the response time is 60～180 minutes；Coarse vacuum multi-stage polycondensation reaction temperature is 200～290 DEG C, and pressure is gradually reduced to 1000Pa by normal pressure, and the response time is 10～90 minutes；High vacuum stage of Fig polycondensation reaction temperature is 250～300 DEG C, and reaction system vacuum is 50～100Pa, and the response time is 60～150 minutes.
Nano luminescent agent is the 0.1～10% of luminous poly terephthalic acid 1,3 propylene glycol ester weight；
Nano luminescent agent is nano luminescent agent-1, the 1～10% of 3 propylene glycol sol weight.
At luminous poly terephthalic acid 1, in the building-up process of the composite of 3 propylene glycol esters, by nano luminescent agent-1,3 propylene glycol colloidal sols join in the polymerization system of PET, obtain the composite being made up of PTT with luminous agent, the fabric that the fiber spinned with this composite is made into has an absorption visible ray, performance that in the dark can be luminous.And illumination effect is lasting, washable, wear-resisting.
The present invention is by p-phthalic acid (PTA), 1,3 propylene glycol (PDO), nano luminescent agent-1, and 3 propylene glycol colloidal sols, as raw material, prepare poly terephthalic acid 1, the 3 propylene glycol ester composite of luminescence.The innovative point of the present invention is by nano luminescent agent-1, and 3 propylene glycol colloidal sols join in the polymerization system of polyester, and nano luminescent agent is uniformly dispersed in the polyester, the good spinnability of polymer.Illumination effect is lasting, washable, wear-resisting.
This luminescence poly terephthalic acid 1,3 propylene glycol ester section intrinsic viscosity be 0.55～0.75dL/g, the fabric of luminous poly terephthalic acid 1,3 propylene glycol ester fiber of preparation after radiation of visible light, the most sustainable luminous more than 12 hours.Its fabric was basically unchanged through 20 standard continuous illumination times.
This luminescence poly terephthalic acid 1,3 propylene glycol ester section intrinsic viscosity be 0.55～0.75dL/g, the fabric of luminous poly terephthalic acid 1,3 propylene glycol ester fiber of preparation after radiation of visible light, the most sustainable luminous more than 12 hours.Its fabric illumination effect after 20 standard wash is basically unchanged.
Detailed description of the invention
Except as otherwise noted, in embodiment, all of parts and percentages is all on the basis of the weight of PTA.
Embodiment 1
One equipped with the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator in add 1000 grams of p-phthalic acids (PTA), 250 gram 1,3 propylene glycol (PDO), 280 grams of Nano strontium aluminate-1, and 3 propylene glycol colloidal sols (wherein strontium aluminate 20 grams, 1,3 propylene glycol are 260 grams), esterification reaction temperature is 250 DEG C, and reaction pressure is 0.26MPa, and the response time is 110 minutes.The product of above-mentioned esterification technique obtains the PTT composite of luminescence again through polycondensating process.Wherein, coarse vacuum multi-stage polycondensation reaction temperature is 260 DEG C, and pressure is gradually reduced to 1000Pa by normal pressure, and the response time is 30 minutes, and high vacuum stage of Fig polycondensation reaction temperature is 275 DEG C, and reaction system vacuum is 55Pa, and the response time is 82 minutes.
The polymer chips fusing point obtained is 245 DEG C, and intrinsic 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
One equipped with the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator in add 1000 grams of p-phthalic acids (PTA), 300 gram 1,3 propylene glycol (PDO), 230 grams of europkium-activated yttrium-aluminium-garnet-1 of trivalent, and 3 propylene glycol colloidal sols (the wherein europkium-activated yttrium-aluminium-garnet of trivalent 20 grams, 1,3 propylene glycol are 210 grams), esterification reaction temperature is 245 DEG C, and reaction pressure is 0.25MPa, and the response time is 120 minutes.The product of above-mentioned esterification technique through polycondensating process, obtains the PTT composite of luminescence again.Wherein, coarse vacuum multi-stage polycondensation reaction temperature is 255 DEG C, and pressure is gradually reduced to 1000Pa by normal pressure, and the response time is 25 minutes, and high vacuum stage of Fig polycondensation reaction temperature is 280 DEG C, and reaction system vacuum is 50Pa, and the response time is 90 minutes.
The polymer chips fusing point obtained is 246 DEG C, and intrinsic 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
One equipped with the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator in add 1000 grams of p-phthalic acids (PTA), 250 gram 1,3 propylene glycol (PDO), 280 grams of nanometer bivalence europkium-activated chlorine strontium phosphate-1, and 3 propylene glycol colloidal sols (wherein nanometer bivalence europkium-activated chlorine strontium phosphate 20 grams, 1,3 propylene glycol are 260 grams), esterification reaction temperature is 250 DEG C, and reaction pressure is 0.25MPa, and the response time is 90 minutes.The product of above-mentioned esterification technique through polycondensating process, obtains the PTT composite of luminescence again.Wherein, coarse vacuum multi-stage polycondensation reaction temperature is 200～240 DEG C, and pressure is gradually reduced to 1000Pa by normal pressure, and the response time is 30 minutes, and high vacuum stage of Fig polycondensation reaction temperature is 285 DEG C, and reaction system vacuum is 50Pa, and the response time is 78 minutes.
The polymer chips fusing point obtained is 245 DEG C, and intrinsic 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
One equipped with the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator in add 1000 grams of p-phthalic acids (PTA), 400 gram 1,3 propylene glycol (PDO), 115 grams of nanometer bivalent manganeses activate and the coactivated yttrium oxysulfide-1 of divalent europium, (wherein nanometer bivalent manganese activates and the coactivated yttrium oxysulfide of divalent europium 5 grams 3 propylene glycol colloidal sols, 1,3 propylene glycol are 110 grams), esterification reaction temperature is 230 DEG C, reaction pressure is 0.1～0.25MPa, and the response time is 125 minutes.The product of above-mentioned esterification technique through polycondensating process, obtains the PTT composite of luminescence again.Wherein, coarse vacuum multi-stage polycondensation reaction temperature is 250 DEG C, and pressure is gradually reduced to 1000Pa by normal pressure, and the response time is 30 minutes, and high vacuum stage of Fig polycondensation reaction temperature is 270 DEG C, and reaction system vacuum is 50Pa, and the response time is 84 minutes.
The polymer chips fusing point obtained is 246 DEG C, and intrinsic 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
One equipped with the 5L stainless steel cauldron of nitrogen inlet, condensate outlet and agitator in add 1000 grams of p-phthalic acids (PTA), 400 gram 1,3 propylene glycol (PDO), 112 grams of nanometer zinc phosphate-1, and 3 propylene glycol colloidal sols (wherein zinc phosphate 25 grams, 1,3 propylene glycol are 110 grams), esterification reaction temperature is 250 DEG C, and reaction pressure is 0.25MPa, and the response time is 115 minutes.The product of above-mentioned esterification technique through polycondensating process, obtains the PTT composite of luminescence again.Wherein, coarse vacuum multi-stage polycondensation reaction temperature is 260 DEG C, and pressure is gradually reduced to 1000Pa by normal pressure, and the response time is 25 minutes, and high vacuum stage of Fig polycondensation reaction temperature is 270 DEG C, and reaction system vacuum is 50Pa, and the response time is 69 minutes.
The polymer chips fusing point obtained is 246 DEG C, and intrinsic 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. a luminous poly terephthalic acid 1,3 propylene glycol ester composite；It is characterized in that: by 1,3 propylene glycol, right
Phthalic acid and nano luminescent agent-1,3 propylene glycol colloidal sol polymerizations, obtain poly terephthalic acid 1,3 propylene glycol ester of luminescence；
Described nano luminescent agent-1,3 propylene glycol colloidal sol refers to the colloidal sol that nano luminescent agent is formed with 1,3 propylene glycol；
Described luminous agent is zinc phosphate, strontium aluminate, the europkium-activated yttrium-aluminium-garnet of trivalent, bivalence europkium-activated chlorine phosphorus
Yttrium-aluminium-garnet, bivalent manganese activation and the coactivated yttrium oxysulfide of divalent europium, bivalence that acid strontium, cerium activate are europkium-activated
One or more mixture in chloric acid calcium and magnesium；
Described nano luminescent agent is the 0.1～10% of poly terephthalic acid 1,3 propylene glycol ester weight；
Described nano luminescent agent is the 1～10% of nano luminescent agent-1,3 propylene glycol sol weight；
The particle diameter of described nano luminescent agent is 1nm～1 μm, wherein the particle diameter nano luminescent agent particle more than 760nm
Account for less than the 5% of nano luminescent agent total amount；
The reaction temperature in esterification stage is 200～290 DEG C, and reaction pressure is 0.1～0.5MPa, and the response time is
60～180 minutes；Coarse vacuum multi-stage polycondensation reaction temperature is 200～290 DEG C, and pressure is gradually reduced to 1000Pa by normal pressure,
Response time is 10～90 minutes；High vacuum stage of Fig polycondensation reaction temperature is 250～300 DEG C, reaction system vacuum
Being 50～100Pa, the response time is 60～150 minutes.
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| CN201210109161.5A CN103374209B (en) | 2012-04-13 | 2012-04-13 | A kind of luminous poly terephthalic acid 1,3 propylene glycol ester composite |
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| CN201210109161.5A CN103374209B (en) | 2012-04-13 | 2012-04-13 | A kind of luminous poly terephthalic acid 1,3 propylene glycol ester composite |
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| CN103374209B true CN103374209B (en) | 2016-08-03 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388176A (en) * | 2002-06-13 | 2003-01-01 | 济南正昊化纤新材料有限公司 | Prepn of energy-accumulating luminous polyester |
| 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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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388176A (en) * | 2002-06-13 | 2003-01-01 | 济南正昊化纤新材料有限公司 | Prepn of energy-accumulating luminous polyester |
| 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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