CN104387534A - Graft polyethylene blue-light-conversion resin and preparation method thereof, and light conversion film - Google Patents
Graft polyethylene blue-light-conversion resin and preparation method thereof, and light conversion film Download PDFInfo
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- CN104387534A CN104387534A CN201410734497.XA CN201410734497A CN104387534A CN 104387534 A CN104387534 A CN 104387534A CN 201410734497 A CN201410734497 A CN 201410734497A CN 104387534 A CN104387534 A CN 104387534A
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Abstract
The invention discloses a graft polyethylene blue-light-conversion resin and a preparation method thereof, and a light conversion film, belonging to the technical field of high polymer materials. The graft polyethylene blue-light-conversion resin solves the technical problem of short light conversion service life in the light conversion film in the prior art. The preparation method comprises the following steps: using N-allyl-4-methoxy-1,8-naphthoyl imine as a functional monomer; carrying out pre-irradiation treatment on the polyethylene resin by using beta rays; and adding the polyethylene resin subjected to pre-irradiation treatment and the functional monomer into a reactor, grafting, cooling, and granulating to obtain the graft polyethylene blue-light-conversion resin. The graft polyethylene blue-light-conversion resin and the polyethylene resin or ethylene-vinyl acetate copolymer are subjected to mixed film blowing to obtain the light conversion film. After the light conversion film is subjected to accelerated induction at 60 DEG C for 22 days, the blue fluorescence accounts for 53-76% of the initial intensity.
Description
Technical field
The present invention relates to a kind of grafted polyethylene and turn blue light resin and preparation method thereof and light-converting film, belong to technical field of polymer materials.
Background technology
Optical transfer agricultural film is a kind of agricultural plastic film realizing light transition function by adding light-converting agent, it can convert 400-500nm royal purple light or 600-700nm blood orange light to by the 300-400nm near-ultraviolet light of plant pest, or non-absorbent for plant 500-580nm yellow green light is converted to blood orange light.Polyethylene is widely used as optical transfer agricultural film base material, and relative to other agriculture light compensation methods, light-converting film has great price and promotion advantage.Light-converting agent can be divided three classes: inorganic rare earth class, rare earth compounding class, fluorochrome class light-converting agent.Its light-converting agent of product that current studies in China is promoted is essentially rare earth class, and price is higher.Though wherein mineral-type good light stability, bad with Compatibility in Plastics, bad dispersibility, to turning light transmittance efficiency and film thickness has larger restriction; Easily there is photodissociation in rare earth compounding class, turns the light life-span short.Also there is life-span short problem in the fluorescence dye class of current employing, but more there is prospect cost aspect than rare earth class, and organic molecular structure type is many, and the selection of structure also has very large space.Therefore, by by fluorochrome class light-converting agent and polycthylene graftedly reduce its transfer ability, high to the existing light-converting agent price of solution, consistency is bad and turn the light life-span plastic sheeting for farm use that affects such as short and turn the significant and actual application value of the problem of light.
It is high that 1,8-naphthoyl imide compounds has fluorescence quantum yield, and Stokes shift is large, the advantages such as light, heat and chemical stability are good, and the deriving method on 4-position and imide is flexible.But push away very greatly-La conjugated system owing to existing in its molecular structure, poor with compatible polyolefin, as adopted physics to add, its goods in use for some time monomer easily move, ooze out, and turn light function and are difficult to keep.
Summary of the invention
The object of the invention is to solve light-converting film in prior art and turn light life-span short technical problem, provide a kind of grafted polyethylene to turn blue light resin and preparation method thereof and light-converting film.
The invention provides a kind of grafted polyethylene and turn blue light resin, pre-irradiation polyvinyl resin molecular chain is grafted with N-allyl group-4-methoxyl group-1,8-naphthalimide, and percentage of grafting mass percent is 0.1-0.4%;
Described pre-irradiation polyvinyl resin adopts following method to obtain: adopt rumbatron as irradiation source, in air atmosphere, carry out pre-irradiation with β ray to polyvinyl resin, pre-irradiation time 0.125s, pre-irradiation dosage range is 5kGy-80kGy;
Described polyvinyl resin is Low Density Polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer;
The structural formula of described N-allyl group-4-methoxyl group-1,8-naphthalimide is as follows:
The present invention also provides a kind of grafted polyethylene to turn the preparation method of blue light resin, comprises the following steps:
(1) in air atmosphere, adopt rumbatron as irradiation source, carry out pre-irradiation with β ray to polyvinyl resin, pre-irradiation time 0.125s, pre-irradiation dosage range is 5kGy-80kGy, obtains pre-irradiation polyvinyl resin;
Described polyvinyl resin is Low Density Polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer;
(2) by the N-allyl group-4-methoxyl group-1 of 0.6-3 weight part, the pre-irradiation polyvinyl resin of 8-naphthalimide and 97-99.4 weight part adds in reactor, at 150-225 DEG C of reaction 0.9-9.5min, obtain reaction product, reaction product, through cooling, granulation, obtains grafted polyethylene and turns blue light resin;
The structural formula of described N-allyl group-4-methoxyl group-1,8-naphthalimide is as follows:
Preferably, described reactor is Banbury mixer, single screw extrusion machine or twin screw extruder.
The present invention also provides and adopts above-mentioned grafted polyethylene to turn the standby light-converting film of blue light resin-made, and this light-converting film turns after blue light resin mixes with the polyvinyl resin of 75-92.5 weight part through the grafted polyethylene of 7.5-25 weight part, and blown film obtains;
Or turning after blue light resin mixes with the ethylene-vinyl acetate copolymer of 85 weight parts through the grafted polyethylene of 15 weight parts, blown film obtains;
Described polyvinyl resin is Low Density Polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer.
Preferably, the UV-light of 300-400nm can be converted into the royal purple light of 400-500nm by described light-converting film.
Preferably, the thickness of described light-converting film is 0.10mm.
Preferably, in described light-converting film, the mass percent content of N-allyl group-4-methoxyl group-1,8-naphthalimide is 0.15%.
Preferably, in described ethylene-vinyl acetate copolymer, the mass percent content of vinyl acetate between to for plastic is 5%-18%.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention adopts pre-irradiation and crosslinking technology, in air atmosphere, pre-irradiation is carried out to polyvinyl resin, the polyvinyl resin of pre-irradiation produces polymeric peroxide on its molecular chain, using the polymeric peroxide produced on polyethylene molecular chain as initiator, crosslinking technology is adopted to have reactive behavior and the function monomer (N-allyl group-4-methoxyl group-1 turning blue light, 8-naphthalimide) be grafted on the polyethylene molecular chain of pre-irradiation, this function monomer is bonded together with covalent chemical bond and polyethylene molecular chain, because the polyethylene through pre-irradiation is connected with covalent linkage with this function monomer, can not migration precipitation, therefore this graft resin has and long-actingly turns blue light function,
2, grafted polyethylene of the present invention turns blue light resin and will have reactive behavior and have the function monomer turning blue light and be grafted on the polyethylene molecular chain of pre-irradiation, overcome the shortcoming of the invalid losses such as conventional light-converting agent migration, and because function monomer used contains allyl group, so in pre-irradiation polyvinyl resin and function monomer polypropylene fusion graft process, inhibit homopolymerization and the chainpropagation of function monomer, avoid naphthalimide parent too near and the quenching of fluorescence that produces, also inhibits the degraded of pre-irradiation polyvinyl resin in grafting process or crosslinking reaction simultaneously;
3, light-converting film of the present invention has and long-actingly turns blue light action, and through 60 DEG C of inductions, after the 22 day, turn the light-converting film of blue light resin containing grafted polyethylene, the percentage ratio that blue (purple) look fluorescence accounts for initial strength is 53-76%.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of N-allyl group-4-methoxyl group-1,8-naphthalimide prepared by the embodiment of the present invention 1;
Fig. 2 is the partial enlarged drawing of Fig. 1;
Fig. 3 is the partial enlarged drawing of Fig. 1;
Fig. 4 is the partial enlarged drawing of Fig. 1;
Fig. 5 is ultraviolet-visible absorption spectra figure and the fluorescent emission spectrogram of light-converting film prepared by the embodiment of the present invention 1.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just to further illustrate the features and advantages of the present invention instead of limiting to the claimed invention.
A kind of grafted polyethylene turns blue light resin, and pre-irradiation polyvinyl resin molecular chain is grafted with N-allyl group-4-methoxyl group-1,8-naphthalimide, and percentage of grafting mass percent is 0.1-0.4%;
Wherein, N-allyl group-4-methoxyl group-1,8-naphthalimide is function monomer, and its structural formula is as follows:
Pre-irradiation polyvinyl resin adopts following method to obtain: adopt rumbatron as irradiation source, in air atmosphere, carry out pre-irradiation with β ray to polyvinyl resin, the pre-irradiation time is 0.125s, and pre-irradiation dosage range is 5kGy-80kGy;
Polyvinyl resin is Low Density Polyethylene or linear low density polyethylene, and linear low density polyethylene can be ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer.
Above-mentioned grafted polyethylene turns the preparation method of blue light resin, comprises the following steps:
(1) in air atmosphere, adopt rumbatron as irradiation source, carry out pre-irradiation with β ray to polyvinyl resin, the pre-irradiation time is 0.125s, and pre-irradiation dosage range is 5kGy-80kGy, obtains pre-irradiation polyvinyl resin;
Wherein, polyvinyl resin is Low Density Polyethylene or linear low density polyethylene, and linear low density polyethylene can be ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer;
(2) by the N-allyl group-4-methoxyl group-1 of 0.6-3 weight part, the pre-irradiation polyvinyl resin of 8-naphthalimide and 97-99.4 weight part adds in reactor, at 150-225 DEG C of reaction 0.9-9.5min, obtain reaction product, reaction product, through cooling, granulation, obtains grafted polyethylene and turns blue light resin;
Wherein, reactor can adopt Banbury mixer or screw extrusion press, and screw extrusion press is that single screw extrusion machine or twin screw extruder all can.If employing Banbury mixer, rotor speed can be 60rpm, if adopt screw extrusion press, screw speed is 15rpm or 30rpm.
Adopt above-mentioned grafted polyethylene to turn the standby light-converting film of blue light resin-made, this light-converting film turns after blue light resin mixes with the polyvinyl resin of 75-92.5 weight part through the grafted polyethylene of 7.5-25 weight part, and blown film obtains; Or turning after blue light resin mixes with the ethylene-vinyl acetate copolymer of 85 weight parts through the grafted polyethylene of 15 weight parts, blown film obtains.
Wherein, polyvinyl resin is Low Density Polyethylene or linear low density polyethylene, and linear low density polyethylene can be ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer; In ethylene-vinyl acetate copolymer, vinyl acetate between to for plastic mass percent content is 5%-18%.Light-converting film thickness can be 0.1mm.The UV-light of 300-400nm can be converted into the royal purple light of 400-500nm by this light-converting film, and in light-converting film, the mass percent content of N-allyl group-4-methoxyl group-1,8-naphthalimide is preferably 0.15%.
The invention provides a kind of above-mentioned N-allyl group-4-methoxyl group-1, the preparation method of 8-naphthalimide, but be not limited thereto, step is as follows: by chloro-for 4-1, 8-naphthalic anhydride, allylamine hydrochloride, methyl alcohol, acid binding agent joins in reaction unit, under nitrogen protection, under Keep agitation, stirring velocity 50-60r/min, be heated to 65 DEG C of backflows, after backflow 2 ~ 5h, stop heating, after question response system is cooled to 40-45 DEG C, add sodium methylate and catalyzer, under nitrogen protection, be heated to 65 DEG C of backflows, and under continuous stirring, stirring velocity 50-60r/min, reaction 1.5 ~ 5h, after reaction terminates, solution after reaction is poured into water, add the hcl acidifying of 2mol/L, wherein, methyl alcohol (original bulk): water: the volume ratio of hydrochloric acid is 1: (1-2.4): (1-2.4), after suction filtration, obtain solid, use the salt acid elution solid one to three time of 50-100mL 2mol/L again, wash with water again to neutrality, be dried to constant weight, with methyl alcohol or ethyl alcohol recrystallization, obtain function monomer N-allyl group-4-methoxyl group-1, 8-naphthalimide, productive rate (mass percent) is 70.1-90.3%,
Wherein, chloro-1, the 8-naphthalic anhydride of 4-: allylamine hydrochloride: acid binding agent: sodium methylate: the mol ratio of catalyzer is 1: (1-1.5): (0.6-2): (7-10): (0.1-0.3); The concentration of chloro-1, the 8-naphthalic anhydride of 4-in methyl alcohol is 130-215mmol/L; Acid binding agent is triethylamine, pyridine, sodium carbonate or salt of wormwood; Catalyzer is copper sulfate or cupric sulfate pentahydrate; In laboratory, reaction unit can adopt the there-necked flask that agitator, thermometer, reflux condensing tube, nitrogen ingress pipe and heating unit are housed.
In the embodiment of the present invention, the detection method of every detection is as follows:
1, N-allyl group-4-methoxyl group-1,8-naphthalimide
1hNMR test condition:
Nuclear-magnetism sample is obtained by silica gel column chromatography, eluent: petrol ether/ethyl acetate=3.5/1, and ultraviolet 365nm develops the color, R
f=0.27.After collecting product frac, rotary evaporation removes desolventizing, 80 DEG C of vacuum-drying 10h.With the deuterated dimethyl sulfoxide (DMSO) containing tetramethylsilane for solvent, quantity of solvent: 0.5mL; Measured by BrukerAV600 nuclear magnetic resonance analyser (600MHz), sample size: 10mg; Test condition: temperature: 298K, spectrum width: 5387.931Hz, accumulative frequency: 4, sampling time: 1.1404692s.
2, the measuring method of the ultraviolet-visible absorption spectroscopy of light-converting film:
Test sample is cut into the print of 50mm × 15mm (long × wide).Absorption spectrum is recorded by PerkinElmerLambda 900UV/VIS/NIR spectrophotometer, does blank, sweep limit 200-760nm with air.
3, the measuring method of fluorescence emission spectrum:
Test sample is cut into the print of 50mm × 15mm (long × wide).Fluorescence emission spectrum is by HITACHIF-7000 fluorescent spectrophotometer assay, and excitation wavelength 358nm, photomultiplier (PMT) voltage 700V, excitation-emission slit is 2.5nm, sweep velocity 1200nm/min, wavelength region 380-600nm.
4, the testing method of percentage of grafting:
Mix with function monomer with ethene-butene-1 copolymer (butylene mass percent content is 5%), obtain mixture, in mixture, the mass percent content of function monomer is respectively 0.02%, 0.04%, 0.06%, 0.08%, 0.10%, 0.15%, 0.20%, 0.26% and 0.60%; The mixture vulcanizing press of difference in functionality monomer content is molded into the thick film of 0.1mm, with the absorption spectrum of ultraviolet-visible pectrophotometer film that difference brake monomer content is different under similarity condition; By the absorbance A at characteristic absorption peaks (358nm) place of film absorption spectrum
358with the absorbance A at ethylene-butene copolymer baseline absorbance (450nm) place
450do ratio, i.e. A
358/ A
450, use A
358/ A
450typical curve equation is obtained: y=0.1012x-0.13297, R with the mass percent linear regression of function monomer
2=0.9855, wherein y is the mass percent of function monomer, and x is A
358/ A
450.The reason that polyethylene produces baseline absorbance in UV-visible region is: the loss of incident light that in polyethylene, the scattering of light of crystallite causes, i.e. this baseline absorbance non-absorbing but light scattering loss; Be due to butylene mass percent content be 5% ethene-butene-1 copolymer, Low Density Polyethylene, hexene mass relative content is the ethene-1-hexene copolymer of 8%, octene mass percent content is that the light scattering loss produced in UV-visible region of the ethylene-l-octane copolymer of 9% is consistent, therefore adopt butylene mass percent content be 5% ethene-Ding 1-alkene copolymer mix with the function monomer of different content, tested by ultraviolet, obtain the typical curve surveying percentage of grafting;
Adopt the grafted polyethylene of dissolving precipitated method to preparation to turn blue light resin to purify, in 500mL round-bottomed flask, add grafted polyethylene prepared by 5g turn blue light resin, add 300mL toluene again, heating for dissolving, grafted polyethylene to be prepared turns after blue light resin dissolves completely, through nickel screen filtered while hot in acetone or alcohol solution, precipitate.Unreacted function monomer and function monomer homopolymer are dissolved in acetone or alcohol, and filtered by throw out, wash, dry 48h in the vacuum drying oven of 60 DEG C, the grafted polyethylene being purifying turns blue light resin; The grafted polyethylene of purifying is turned blue light resin mold and is pressed into the thick film of 0.1mm, with ultraviolet-visible pectrophotometer with typical curve similarity condition under survey absorption spectrum, and try to achieve A
358/ A
450, bring typical curve equation into and draw percentage of grafting.
5, the testing method of fluorescence retention rate:
To the light-converting film of blue light resin be turned containing grafted polyethylene or turn the light-converting film of Blue light agent containing the commercialization of equal in quality percentage ratio, being placed in 60 DEG C accelerates on drip instrument, do condensation induction, separated in time, after general 6-7 days, fluorometric investigation is done in sampling, and each sample is evenly got three places and surveyed fluorescence, get the mean value of three maximum emission peak fluorescence intensities, different time fluorescent emission peak intensity and initial fluorescence emission peak strength ratio are fluorescence retention rate intensity percentage ratio.
The present invention is further illustrated below in conjunction with embodiment.In embodiment adopt material all by commercially available, wherein, the producer that commercialization turns Blue light agent is Zhangjiakou Ai Ke fine chemistry industry limited liability company.
Embodiment 1
(1) by chloro-for 4.3mmol 4-1, 8-naphthalic anhydride, 5.16mmol allylamine hydrochloride, 33mL methyl alcohol, 8.60mmol pyridine joins and agitator is housed, thermometer, reflux condensing tube, in the 100mL there-necked flask of nitrogen ingress pipe and heating unit, pass into nitrogen, be heated to 65 DEG C reflux and stir, stirring velocity 50r/min, after backflow 2h, stop heating, close nitrogen, after question response system is cooled to 40 DEG C, add 30.1mmol sodium methylate and 0.43mmol cupric sulfate pentahydrate, pass into nitrogen again, be heated to 65 DEG C reflux and stir 1.5h, stirring velocity 50r/min, reaction system is poured in 50mL water quencher after reaction terminates, add the 2mol/l hcl acidifying of 50mL, suction filtration, the 2mol/l salt pickling of the solid 50mL obtained once, wash with water again to neutrality, be dried to constant weight, function monomer N-allyl group-4-methoxyl group-1 is obtained after drying with ethyl alcohol recrystallization, 8-naphthalimide, function monomer productive rate mass percent is 76.2%,
(2) by ethene-1-hexene copolymer, hexene mass relative content is 8%, under air atmosphere, and Accelerating electron apparatus carries out pre-irradiation with β ray, and pre-irradiation dosage is 12kGy, irradiation time 0.125s;
(3) above-mentioned functions monomer and pre-irradiation ethene-1-hexene copolymer are joined in Banbury mixer, the weight part of pre-irradiation ethene-1-hexene copolymer is 99.4, the weight part of function monomer is 0.6, and temperature of reaction controls at 225 DEG C, rotor speed 60rpm, reaction times 7min, reaction terminates rear compressing tablet, cooling, granulation, obtain grafted polyethylene and turn blue light resin, percentage of grafting mass percent is 0.15%;
(4) Low Density Polyethylene grafted polyethylene of 25 weight parts being turned blue light resin and 75 weight parts mixes rear, blown film, obtains the light-converting film turning blue light resin containing grafted polyethylene that thickness is 0.10mm; Simultaneously by the ethene-1-hexene copolymer of 24.85 weight parts, hexene mass relative content is the Low Density Polyethylene of 8%, 75 weight parts, turns Blue light agent mix with the commercialization of 0.15 weight part, blown film, obtains the light-converting film turning Blue light agent containing commercialization that thickness is 0.10mm;
Test through fluorescence retention rate: the light-converting film turning blue light resin containing grafted polyethylene, fluorescence retention rate intensity percentage ratio is respectively the 3rd day the 76%, ten day the 60%, the 16 day the 56%, the 22 day 55%; Containing the commercial light-converting film turning Blue light agent, fluorescence retention rate intensity percentage ratio is respectively the 3rd day the 59%, ten day the 51%, the 16 day the 42%, the 22 day 39%.Contrasted by comparative example 1 and embodiment 1, can find out, compared with the light-converting film turning blue light resin of the present invention turns the light-converting film of Blue light agent with the commercialization containing equal in quality percentage ratio, there is higher fluorescence retention rate containing grafted polyethylene.
Fig. 1 is N-allyl group-4-methoxyl group-1, the 8-naphthalimide of preparation in embodiment 1
1hNMR spectrogram, Fig. 2-4 is the partial enlarged drawing of Fig. 1, as can be seen from Fig. 1-4,
1h NMR (600MHz, DMSO-d
6,δ): 8.56 (d, J=8.3Hz, 1H, Ar H), 8.51 (d, J=7.2Hz, 1H, Ar H), 8.48 (d, J=8.3Hz, 1H, Ar H), 7.83 (t, J=7.8Hz, 1H, Ar H), 7.35 (d, J=8.3Hz, 1H, Ar H), 5.94 (ddd, J=22.5,10.4,5.3Hz, 1H; CH=), 5.16 – 5.09 (m, 2H; CH
2=), 4.65 (d, J=5.2Hz, 2H; CH
2), 4.14 (s, 3H; CH
3).Illustrate that the present invention has prepared N-allyl group-4-methoxyl group-1,8-naphthalimide really.
Fig. 5 is ultraviolet-visible absorption spectra figure and the fluorescence emission spectrogram of light-converting film prepared by the embodiment of the present invention 1.As can be seen from Figure 5, the UV-light of 300-400nm can be converted into the royal purple light of 400-500nm by light-converting film of the present invention.
Embodiment 2
(1) by chloro-for 8.67mmol 4-1, 8-naphthalic anhydride, 13.00mmol allylamine hydrochloride, 41.4mL methyl alcohol, 14.38mmol triethylamine joins and agitator is housed, thermometer, reflux condensing tube, in the 100mL there-necked flask of nitrogen ingress pipe and heating unit, pass into nitrogen, be heated to 65 DEG C reflux and stir, stirring velocity 60r/min, after backflow 5h, stop heating, close nitrogen, after question response system is cooled to 45 DEG C, add 86.7mmol sodium methylate and 1.07mmol copper sulfate, pass into nitrogen again, be heated to 65 DEG C reflux and stir 4h, stirring velocity 60r/min, reaction system is poured in 82.8mL water quencher after reaction terminates, add the 2mol/l hcl acidifying of 82.8mL, suction filtration, the 2mol/l salt pickling of the solid 100mL obtained once, wash with water again to neutrality, be dried to constant weight, function monomer N-allyl group-4-methoxyl group-1 is obtained after drying by recrystallizing methanol, 8-naphthalimide, function monomer productive rate mass percent is 90.3%,
(2) by ethylene-l-octane copolymer, octene mass percent content is 9%, and in air atmosphere, Accelerating electron apparatus carries out pre-irradiation with β ray, pre-irradiation dosage is 50kGy, irradiation time 0.125s;
(3) above-mentioned functions monomer and pre-irradiation ethylene-l-octane copolymer are joined in Banbury mixer, the weight part of pre-irradiation ethylene-l-octane copolymer is 97, the weight part of function monomer is 3, and temperature of reaction controls at 190 DEG C, rotor speed 60rpm, reaction times 7min, reaction terminates rear compressing tablet, cooling, granulation, obtain grafted polyethylene and turn blue light resin, percentage of grafting mass percent is 0.40%;
(4) the butylene mass percent grafted polyethylene of 5 weight parts being turned blue light resin and 95 weight parts be 5% ethene-butene-1 copolymer mix after, blown film, obtains the light-converting film turning blue light resin containing grafted polyethylene that thickness is 0.10mm; Simultaneously by the ethylene-l-octane copolymer of 4.85 weight parts, octene mass percent content is 9%, the butylene mass percent content of 95 weight parts is the ethene-butene-1 copolymer of 5%, turn Blue light agent with the commercialization of 0.15 weight part to mix, blown film, obtains the light-converting film turning Blue light agent containing commercialization that thickness is 0.10mm.
Test through fluorescence retention rate: the light-converting film turning blue light resin containing grafted polyethylene, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 90%, ten day the 83%, the 16 day the 78%, the 22 day 76%; Containing the commercial light-converting film turning Blue light agent, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 55%, ten day the 49%, the 16 day the 44%, the 22 day 42%.
Embodiment 3
(1) by chloro-for 12.9mmol 4-1, 8-naphthalic anhydride, 16.8mmol allylamine hydrochloride, 80mL methyl alcohol, 9.65mmol salt of wormwood joins and agitator is housed, thermometer, reflux condensing tube, in the 250mL there-necked flask of nitrogen ingress pipe and heating unit, pass into nitrogen, be heated to 65 DEG C reflux and stir, stirring velocity 55r/min, after backflow 3h, stop heating, close nitrogen, after question response system is cooled to 42 DEG C, add 117.4mmol sodium methylate and 3.87mmol copper sulfate, pass into nitrogen again, be heated to 65 DEG C reflux and stir 2h, stirring velocity 55r/min, reaction system is poured in 192mL water quencher after reaction terminates, add the 2mol/l hcl acidifying of 192mL, suction filtration, the 2mol/l salt pickling of the solid 100mL obtained twice, wash with water again to neutrality, be dried to constant weight, function monomer N-allyl group-4-methoxyl group-1 is obtained after drying by recrystallizing methanol, 8-naphthalimide, function monomer productive rate mass percent 84.8%,
(2) by Low Density Polyethylene, in air atmosphere, Accelerating electron apparatus carries out pre-irradiation with β ray, pre-irradiation dosage is 5kGy, irradiation time 0.125s;
(3) above-mentioned functions monomer and pre-irradiation ldpe resin are joined in Banbury mixer, the weight part of pre-irradiation ldpe resin is 99.4, the weight part of function monomer is 0.6, and temperature of reaction controls at 190 DEG C, rotor speed 60rpm, reaction times 9.5min, reaction terminates rear compressing tablet, cooling, granulation, obtain grafted polyethylene and turn blue light resin, percentage of grafting mass percent is 0.10%;
(4) the hexene mass relative content grafted polyethylene of 25 weight parts being turned blue light resin and 75 weight parts be 8% ethene-1-hexene copolymer mix after, blown film, obtains the light-converting film turning blue light resin containing grafted polyethylene that thickness is 0.10mm; Simultaneously by the Low Density Polyethylene of 24.85 weight parts, the hexene mass relative content of 75 weight parts is the ethene-1-hexene copolymer of 8%, turn Blue light agent with the commercialization of 0.15 weight part to mix, blown film, obtain the light-converting film turning Blue light agent containing commercialization that thickness is 0.10mm.
Test through fluorescence retention rate: the light-converting film turning blue light resin containing grafted polyethylene, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 71%, ten day the 56%, the 16 day the 55%, the 22 day 53%; Containing the commercial light-converting film turning Blue light agent, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 56%, ten day the 53%, the 16 day the 41%, the 22 day 40%.
Embodiment 4
(1) by chloro-for 43.0mmol 4-1, 8-naphthalic anhydride, 47.3mmol allylamine hydrochloride, 240mL methyl alcohol, 64.5mmol triethylamine joins and agitator is housed, thermometer, reflux condensing tube, in the 500mL there-necked flask of nitrogen ingress pipe and heating unit, pass into nitrogen, be heated to 65 DEG C reflux and stir, stirring velocity 50r/min, after backflow 3h, stop heating, close nitrogen, after question response system is cooled to 45 DEG C, add 391.2mmol sodium methylate and 5.16mmol copper sulfate, pass into nitrogen again, be heated to 65 DEG C reflux and stir 3h, stirring velocity 60r/min, reaction system is poured in 240mL water quencher after reaction terminates, add the 2mol/l hcl acidifying of 576mL, suction filtration, the 2mol/l salt pickling of the solid 100mL obtained three times, wash with water again to neutrality, be dried to constant weight, function monomer N-allyl group-4-methoxyl group-1 is obtained after drying by recrystallizing methanol, 8-naphthalimide, function monomer productive rate mass percent 82.6%,
(2) by ethene-butene-1 copolymer, butylene mass percent content is 5%, and in air atmosphere, Accelerating electron apparatus carries out pre-irradiation with β ray, pre-irradiation dosage is 60kGy, irradiation time 0.125s;
(3) above-mentioned functions monomer and pre-irradiation ethene-butene-1 copolymer are joined in Banbury mixer, the weight part of pre-irradiation ethene-butene-1 copolymer is 98, the weight part of function monomer is 2, and temperature of reaction controls at 190 DEG C, rotor speed 60rpm, reaction times 7min, reaction terminates rear compressing tablet, cooling, granulation, obtain grafted polyethylene and turn blue light resin, percentage of grafting mass percent is 0.33%;
(4) the octene mass percent content grafted polyethylene of 7.5 weight parts being turned blue light resin and 92.5 weight parts be 9% ethylene-l-octane copolymer mix after, blown film, obtains the light-converting film turning blue light resin containing grafted polyethylene that thickness is 0.10mm; Simultaneously by the ethene-butene-1 copolymer of 7.35 weight parts, butylene mass percent content is 5%, the octene mass percent content of 92.5 weight parts is the ethylene-l-octane copolymer of 9%, turn Blue light agent with the commercialization of 0.15 weight part to mix, blown film, obtains the light-converting film turning Blue light agent containing commercialization that thickness is 0.10mm.
Test through fluorescence retention rate: the light-converting film turning blue light resin containing grafted polyethylene, fluorescence retention rate intensity percentage ratio is respectively the 3rd day the 87%, ten day the 78%, the 16 day the 73%, the 22 day 71%; Containing the commercial light-converting film turning Blue light agent, fluorescence retention rate intensity percentage ratio is respectively the 3rd day the 54%, ten day the 50%, the 16 day the 43%, the 22 day 38%.
Embodiment 5
(1) by chloro-for 21.5mmol 4-1, 8-naphthalic anhydride, 21.5mmol allylamine hydrochloride, 100mL methyl alcohol, 12.9mmol sodium carbonate joins and agitator is housed, thermometer, reflux condensing tube, in the 250mL there-necked flask of nitrogen ingress pipe and heating unit, pass into nitrogen, be heated to 65 DEG C reflux and stir, stirring velocity 60r/min, after backflow 2.5h, stop heating, close nitrogen, after question response system is cooled to 45 DEG C, add 172.1mmol sodium methylate and 4.30mmol cupric sulfate pentahydrate, pass into nitrogen again, be heated to 65 DEG C reflux and stir 5h, stirring velocity 60r/min, reaction system is poured in 240mL water quencher after reaction terminates, add the 2mol/l hcl acidifying of 100mL, suction filtration, the 2mol/l salt pickling of the solid 50mL obtained three times, wash with water again to neutrality, be dried to constant weight, function monomer N-allyl group-4-methoxyl group-1 is obtained after drying with ethyl alcohol recrystallization, 8-naphthalimide, function monomer productive rate mass percent is 70.1%,
(2) by ethene-butene-1 copolymer, butylene mass percent content is 5%, and in air atmosphere, Accelerating electron apparatus carries out pre-irradiation with β ray, pre-irradiation dosage is 80kGy irradiation time 0.125s;
(3) above-mentioned functions monomer and pre-irradiation ethene-butene-1 copolymer are mixed in the hopper joining SHJ20 single screw extrusion machine, pre-irradiation ethene-butene-1 copolymer weight part is 99, the weight part of function monomer is 1, SHJ20 single screw extrusion machine is 170 DEG C from spout to die head Ge Duan district temperature, 200 DEG C, 210 DEG C, 210 DEG C, screw speed is at 15rpm, extrusion reaction time 0.9min, check rod, cooling, granulation, obtain grafted polyethylene and turn blue light resin, percentage of grafting mass percent 0.19%;
(4) the vinyl acetate between to for plastic mass percent content grafted polyethylene of 15 weight parts being turned blue light resin and 85 weight parts be 5% ethylene-vinyl acetate copolymer mix after, blown film, obtain the light-converting film turning blue light resin containing grafted polyethylene that thickness is 0.10mm; Simultaneously by the ethene-butene-1 copolymer of 14.85 weight parts, butylene mass percent content is 5%, the vinyl acetate between to for plastic mass percent content of 85 weight parts is the ethylene-vinyl acetate copolymer of 5%, turn Blue light agent with the commercialization of 0.15 weight part to mix, blown film, obtains the light-converting film turning Blue light agent containing commercialization that thickness is 0.10mm.
Test through fluorescence retention rate: the light-converting film turning blue light resin containing grafted polyethylene, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 75%, ten day the 67%, the 16 day the 65%, the 22 day 60%; Containing the commercial light-converting film turning Blue light agent, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 54%, ten day the 50%, the 16 day the 48%, the 22 day 41%.
Embodiment 6
(1) by chloro-for 43.0mmol 4-1, 8-naphthalic anhydride, 51.6mmol allylamine hydrochloride, 200mL methyl alcohol, 65.9mmol sodium carbonate joins and agitator is housed, thermometer, reflux condensing tube, in the 500mL there-necked flask of nitrogen ingress pipe and heating unit, pass into nitrogen, be heated to 65 DEG C reflux and stir, stirring velocity 55r/min, after backflow 3h, stop heating, close nitrogen, after question response system is cooled to 40 DEG C, add 395.2mmol sodium methylate and 5.16mmol cupric sulfate pentahydrate, pass into nitrogen again, be heated to 65 DEG C reflux and stir 2h, stirring velocity 60r/min, reaction system is poured in 200mL water quencher after reaction terminates, add the 2mol/l hcl acidifying of 200mL, suction filtration, the 2mol/l salt pickling of the solid 100mL obtained twice, wash with water again to neutrality, be dried to constant weight, function monomer N-allyl group-4-methoxyl group-1 is obtained after drying with ethyl alcohol recrystallization, 8-naphthalimide, function monomer productive rate mass percent is 76.6%,
(2) by ethene-butene-1 copolymer, butylene mass percent content is 5%, and in air atmosphere, Accelerating electron apparatus carries out pre-irradiation with β ray, pre-irradiation dosage is 30kGy irradiation time 0.125s;
(3) above-mentioned functions monomer and pre-irradiation ethene-butene-1 copolymer are mixed in the hopper joining SHJ30 response type twin screw extruder, pre-irradiation ethene-butene-1 copolymer weight part is 99, the weight part of function monomer is 1, SHJ30 response type twin screw extruder is 150 DEG C from spout to die head Ge Duan district temperature, 170 DEG C, 190 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 200 DEG C, screw speed is at 30rpm, extrusion reaction time 1.4min, check rod, cooling, granulation, obtain grafted polyethylene and turn blue light resin, percentage of grafting mass percent 0.26%,
(4) the vinyl acetate between to for plastic mass percent content grafted polyethylene of 15 weight parts being turned blue light resin and 85 weight parts be 18% ethylene-vinyl acetate copolymer mix after, blown film, obtain the light-converting film turning blue light resin containing grafted polyethylene that thickness is 0.10mm; Be the ethylene-butene copolymer of 5% by the butylene mass percent of 14.85 weight parts simultaneously, the vinyl acetate between to for plastic mass percent content of 85 weight parts is the ethylene-vinyl acetate copolymer of 18%, turn Blue light agent with the commercialization of 0.15 weight part to mix, blown film, obtains the light-converting film turning Blue light agent containing commercialization that thickness is 0.10mm.
Test through fluorescence retention rate: the light-converting film turning blue light resin containing grafted polyethylene, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 81%, ten day the 73%, the 16 day the 68%, the 22 day 65%; Containing the commercial light-converting film turning Blue light agent, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 55%, ten day the 53%, the 16 day the 50%, the 22 day 42%.
Embodiment 7
(1) by chloro-for 43.0mmol 4-1, 8-naphthalic anhydride, 51.6mmol allylamine hydrochloride, 220mL methyl alcohol, 55.9mmol sodium carbonate joins and agitator is housed, thermometer, reflux condensing tube, in the 500mL there-necked flask of nitrogen ingress pipe and heating unit, pass into nitrogen, be heated to 65 DEG C reflux and stir, stirring velocity 50r/min, after backflow 3h, stop heating, close nitrogen, after question response system is cooled to 42 DEG C, add 395.2mmol sodium methylate and 8.6mmol cupric sulfate pentahydrate, pass into nitrogen again, be heated to 65 DEG C reflux and stir 2.5h, stirring velocity 50r/min, reaction system is poured in 220mL water quencher after reaction terminates, add the 2mol/l hcl acidifying of 220mL, suction filtration, the 2mol/l salt pickling of the solid 100mL obtained twice, wash with water again to neutrality, be dried to constant weight, function monomer N-allyl group-4-methoxyl group-1 is obtained after drying with ethyl alcohol recrystallization, 8-naphthalimide, function monomer productive rate mass percent is 77.8%,
(2) by Low Density Polyethylene, in air atmosphere, Accelerating electron apparatus carries out pre-irradiation with β ray, pre-irradiation dosage is 20kGy, irradiation time 0.125s;
(3) above-mentioned functions monomer and pre-irradiation Low Density Polyethylene are mixed in the hopper joining SHJ30 response type twin screw extruder, pre-irradiation Low Density Polyethylene weight part is 99, the weight part of function monomer is 1, SHJ30 response type twin screw extruder is 150 DEG C from spout to die head Ge Duan district temperature, 165 DEG C, 180 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 190 DEG C, 195 DEG C, screw speed is at 30rpm, extrusion reaction time 1.4min, check rod, cooling, granulation, obtain grafted polyethylene and turn blue light resin, percentage of grafting mass percent 0.22%,
(4) the vinyl acetate between to for plastic mass percent content grafted polyethylene of 15 weight parts being turned blue light resin and 85 weight parts be 12% ethylene-vinyl acetate copolymer mix after, blown film, obtain the light-converting film turning blue light resin containing grafted polyethylene that thickness is 0.10mm; Simultaneously by the Low Density Polyethylene of 14.85 weight parts, the vinyl acetate between to for plastic mass percent content of 85 weight parts is the ethylene-vinyl acetate copolymer of 12%, turn Blue light agent with the commercialization of 0.15 weight part to mix, blown film, obtain the light-converting film turning Blue light agent containing commercialization that thickness is 0.10mm.
Test through fluorescence retention rate: the light-converting film turning blue light resin containing grafted polyethylene, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 78%, ten day the 71%, the 16 day the 66%, the 22 day 63%; Containing the commercial light-converting film turning Blue light agent, fluorescence retention rate intensity percentage ratio is respectively the 4th day the 54%, ten day the 51%, the 16 day the 50%, the 22 day 41%.
Obviously, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (8)
1. grafted polyethylene turns a blue light resin, it is characterized in that, pre-irradiation polyvinyl resin molecular chain is grafted with N-allyl group-4-methoxyl group-1,8-naphthalimide, and percentage of grafting mass percent is 0.1-0.4%;
Described pre-irradiation polyvinyl resin adopts following method to obtain: adopt rumbatron as irradiation source, in air atmosphere, carry out pre-irradiation with β ray to polyvinyl resin, pre-irradiation time 0.125s, pre-irradiation dosage range is 5kGy-80kGy;
Described polyvinyl resin is Low Density Polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer;
The structural formula of described N-allyl group-4-methoxyl group-1,8-naphthalimide is as follows:
2. grafted polyethylene turns a preparation method for blue light resin, it is characterized in that, comprises the following steps:
(1) in air atmosphere, adopt rumbatron as irradiation source, carry out pre-irradiation with β ray to polyvinyl resin, pre-irradiation time 0.125s, pre-irradiation dosage range is 5kGy-80kGy, obtains pre-irradiation polyvinyl resin;
Described polyvinyl resin is Low Density Polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer;
(2) by the N-allyl group-4-methoxyl group-1 of 0.6-3 weight part, the pre-irradiation polyvinyl resin of 8-naphthalimide and 97-99.4 weight part adds in reactor, at 150-225 DEG C of reaction 0.9-9.5min, obtain reaction product, reaction product, through cooling, granulation, obtains grafted polyethylene and turns blue light resin;
The structural formula of described N-allyl group-4-methoxyl group-1,8-naphthalimide is as follows:
3. a kind of grafted polyethylene according to claim 2 turns the preparation method of blue light resin, it is characterized in that, described reactor is Banbury mixer, single screw extrusion machine or twin screw extruder.
4. adopt grafted polyethylene according to claim 1 to turn the standby light-converting film of blue light resin-made, it is characterized in that, this light-converting film turns after blue light resin mixes with the polyvinyl resin of 75-92.5 weight part through the grafted polyethylene of 7.5-25 weight part, and blown film obtains;
Or turning after blue light resin mixes with the ethylene-vinyl acetate copolymer of 85 weight parts through the grafted polyethylene of 15 weight parts, blown film obtains;
Described polyvinyl resin is Low Density Polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer or ethylene-l-octane copolymer.
5. light-converting film according to claim 4, is characterized in that, the UV-light of 300-400nm can be converted into the royal purple light of 400-500nm by described light-converting film.
6. light-converting film according to claim 4, is characterized in that, the thickness of described light-converting film is 0.10mm.
7. light-converting film according to claim 4, is characterized in that, in described light-converting film, the mass percent content of N-allyl group-4-methoxyl group-1,8-naphthalimide is 0.15%.
8. light-converting film according to claim 4, is characterized in that, in described ethylene-vinyl acetate copolymer, the mass percent content of vinyl acetate between to for plastic is 5%-18%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096676A (en) * | 2018-07-13 | 2018-12-28 | 中国科学院长春应用化学研究所 | One kind is polycthylene grafted to turn light stream drop film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0728745A1 (en) * | 1995-02-21 | 1996-08-28 | Bayer Ag | 1,8-Naphthalimid derivates, process for their preparation and their use as intermediates |
| CN101203567A (en) * | 2005-06-07 | 2008-06-18 | 西巴特殊化学品控股有限公司 | Scratch resistant polyolefin |
-
2014
- 2014-12-05 CN CN201410734497.XA patent/CN104387534A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0728745A1 (en) * | 1995-02-21 | 1996-08-28 | Bayer Ag | 1,8-Naphthalimid derivates, process for their preparation and their use as intermediates |
| CN101203567A (en) * | 2005-06-07 | 2008-06-18 | 西巴特殊化学品控股有限公司 | Scratch resistant polyolefin |
Non-Patent Citations (3)
| Title |
|---|
| IVO GRABCHEV, ET AL.: "Copolymerization and photostabilization of methylmethacrylate with 1,8-naphthalimide fluorescent brighteners", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 * |
| J. Z. WU, ET AL.: "Surface Modification of Low-Density Polyethylene Films by UV-Induced Graft Copolymerization with a Fluorescent Monomer", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 殷敬华 等: "《高分子材料的反应加工》", 30 April 2008, 科学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096676A (en) * | 2018-07-13 | 2018-12-28 | 中国科学院长春应用化学研究所 | One kind is polycthylene grafted to turn light stream drop film and preparation method thereof |
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