CN103467648B - A kind of ultralow second-order transition temperature mix europium fluorine Si acrylate red fluorescence agent and preparation method thereof - Google Patents
A kind of ultralow second-order transition temperature mix europium fluorine Si acrylate red fluorescence agent and preparation method thereof Download PDFInfo
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- CN103467648B CN103467648B CN201310364752.1A CN201310364752A CN103467648B CN 103467648 B CN103467648 B CN 103467648B CN 201310364752 A CN201310364752 A CN 201310364752A CN 103467648 B CN103467648 B CN 103467648B
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Abstract
What <b> the invention discloses a kind of ultralow second-order transition temperature mixes the agent of europium fluorine Si acrylate red fluorescence, and it is characterized in that, its chemical structural formula is: </b>
this fluorescent agent number-average molecular weight of <b/><b> is </b><bGreatT.Gre aT.GT15000-20000g/mol</b>LEss T.LTssT.LTb>, wherein, </b><bGreatT.Gre aT.GTa</b><bGrea tT.GreaT.GT, </b><bGreatT.Gre aT.GTb</b><bGrea tT.GreaT.GT, </b><bGreatT.Gre aT.GTn</b><bGrea tT.GreaT.GT is the repeat number of segment, be the integer being more than or equal to </b><bGreatT.Gre aT.GT1</b><bGrea tT.GreaT.GT, </b><bGreatT.Gre aT.GTR in structural formula
1</b><bGreatT.Gre aT.GT and </b><bGreatT.Gre aT.GTR
2</b><bGreatT.Gre aT.GT is acrylic ester monomer.This luminous agent shows the very strong intensity that glows, and has the good characteristics of luminescence and stability, and the extremely frigid zones that is used as preferably resists cold road markings material.The present invention provides the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of above-mentioned ultralow second-order transition temperature simultaneously, the method is free from environmental pollution, product yield is high, reaching </b><bGreatT.Gre more than aT.GT90%</b><bGr eatT.GreaT.GT, is a kind of very good red fluorescence agent preparation method.</b>
Description
Technical field
The invention belongs to luminescent material technical field, what be specifically related to a kind of ultralow second-order transition temperature mixes europium fluorine Si acrylate red fluorescence agent and preparation method thereof.
Background technology
It is narrow, bright in luster that the rare earth luminescent material 4f orbital energy level abundant because rare earth ion contains shows photoluminescent band, absorbs excitation energy ability strong, the feature that efficiency of conversion is high.Rare earth ion generally presents trivalent in crystal, is the most stable a kind of state, and the luminescence observed in visible and IR regions, mainly from transition between energy level in 4f configuration, is line spectrum.Due to rare earth element there is the 4f shell that do not fill up and 4f electronics outer field
5s
2,
5p
6the characteristic of screening of nucleus, makes rare earth element have extremely complicated line spectrum.Except lanthanon, the complicacy of spectrum is that any other element can not be compared.
Many rare earth ions have abundant energy level and their the transition characteristic of 4f electronics, make rare earth become a huge luminous treasure-house, for new and high technology provides the luminescent material of a lot of superior performance.Europium is exactly a kind of typical rare earth red light material, and europium material has stronger Eu
3+characteristic fluorescence, and have that purity of color is high, chemical stability good and in theory, the most sub-efficiency can reach the advantage such as 100%, become the study hotspot in rare earth photoelectricity functional material.The luminescence of europium material mainly comes from Eu
3+'s
5d
0-
7d
2characteristic emission peak, its emission peak is positioned at about 617nm, and does not change with the difference of part.
Europium ion, as the effective luminescence center of one, is widely used in inorganic and luminous organic material.But there is the problem such as machine-shaping difficulty, price height in europium inorganic materials; Europium organic molecule title complex then existence and stability difference etc. problem, these factors limit europium luminescent material and apply more widely.Because rare earth material cost is high, bring difficulty to its widespread use.Therefore, synthesis good luminous performance, cheap rare-earth luminescent material just becomes the target that people pursue.The feature such as due to macromolecular material itself, there is good stability and source is wide, forming process is easy, if europium is incorporated in polymer matrix and makes photoluminescence rareearth polymer material, the fluorescence that photoluminescence rareearth polymer material sends existing rare earth luminescence intensity is high, the feature of pure color, have again the advantage that needed for macromolecular LED title complex, excitation energy is low, fluorescence efficiency is high, content of rare earth is few and price is more cheap, its application prospect will be very wide.
With vinylformic acid or esters of acrylic acid for the acrylic ester emulsion that main raw material synthesizes is the macromolecular material that a kind of cementability is strong, film-forming properties is high, there is excellent film-forming properties, corrosion-resistant, chemical-resistant resistance, good oil-proofness and weathering resistance, and abundant raw material source, produce easy to implement.Containing Si-O key in silicone molecules, greatly, the structure of Si-O key has obvious polarity, can play shielding effect to organic radical for silicon and oxygen electronegativity, the destruction to polymer molecular chain such as reduction oxygen molecule, thus give its excellent thermotolerance, oxygen resistence, weather resistance.Fluorine element is as the maximum element of electronegativity, and polarizability is low, and C-F bond energy is up to 460KJ/mol; The shielding protection effect of F atom to C-C key skeleton of C-F key makes fluoro-resin have very high unreactiveness just.Through the characteristic of fluorinated silicone modified acrylate material by all or part of absorption fluorine silicon materials, show as the features such as excellent weathering resistance, weather resistance, chemical proofing, preservative property, insulativity, noninflammability, non-adhesive, stain resistance and low temperature flexibility are good.
So far, have ultralow second-order transition temperature and adopt the rare earth luminescent material of fluorinated silicone modified acylate dope europium to there is no people and relate to, the present invention will make up both at home and abroad in the vacancy of this research field, and the research and probe for rare earth luminescent material goes out a new road.Due to the soft monomer adopted in the chemical stability of the brilliance of fluorine atom and Siliciumatom, weathering resistance, resistant of high or low temperature and the present invention, what the present invention prepared mix the agent of europium fluorine Si acrylate red fluorescence will have very low second-order transition temperature, this red fluorescence agent simultaneously can effectively by near ultraviolet excitation, and it goes out to show the very strong intensity that glows at 618nm.
Summary of the invention
The present invention seeks to: what provide a kind of ultralow second-order transition temperature mixes the agent of europium fluorine Si acrylate red fluorescence, this luminous agent shows the very strong intensity that glows, and there is the good characteristics of luminescence and stability, the extremely frigid zones that is used as preferably resists cold road markings material.
Technical scheme of the present invention is: a kind of ultralow second-order transition temperature mix the agent of europium fluorine Si acrylate red fluorescence, its chemical structural formula is:
This fluorescent agent number-average molecular weight is 15000-20000g/mol, and wherein, a, b, n are the repeat number of segment, and be the integer being more than or equal to 1, in structural formula, R1 and R2 is acrylic ester monomer.
Further, R described in the present invention
1and R
2be two kinds of different esters of acrylic acid soft monomers, described esters of acrylic acid soft monomer refers to the one in ethyl propenoate, n-butyl acrylate, isobutyl acrylate, Isooctyl acrylate monomer, n-octyl, vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate.
Another object of the present invention is to provide a kind of preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of above-mentioned ultralow second-order transition temperature, the method is free from environmental pollution, and product yield is high, reaches more than 90%, be a kind of very good red fluorescence agent preparation method, it comprises the following steps:
(1) get the part of the mixture of two kinds of acrylic ester monomers, cationic emulsifier, nonionic emulsifying agent, initiator and water, stir and regulate the front pH value of polymerization, at N by pH value regulator
2atmosphere, temperature T
1=75 ~ 80 DEG C, and under the condition of Keep agitation, reaction for some time, obtain the seed emulsion of micro-blueness;
(2) get the mixture of two kinds of acrylic ester monomers, cationic emulsifier, nonionic emulsifying agent, initiator and water in step (1) remainder, pre-emulsification is carried out with whole silane coupling agents and trifluoro propyl trimethylammonium cyclotrisiloxane, then pre-emulsion is dripped in the progressive suddenly seed emulsion that (1) obtains, add silane hydrolyzate inhibitor, at temperature T after dropwising to reaction system in dropping process simultaneously
2for some time is reacted at=81 ~ 86 DEG C;
(3) after reaction terminates, by emulsion cool to room temperature, by pH value regulator, emulsion is adjusted to pH=7 ~ 7.5, then filters emulsion with 200 mesh filter screens, obtain cationic Emulsion;
(4) europium sesquioxide is dissolved in dust technology obtains europium nitrate solution, europium nitrate solution is instilled mixing and stirring in the cationic Emulsion that step (3) obtains by ampoule tube, put into vacuum drying oven again to dry, what obtain ultralow second-order transition temperature mixes the agent of europium fluorine Si acrylate red fluorescence.
Further, in above-mentioned preparation method each component (part can be gram or kilogram) content is as follows by mass:
Two kinds of acrylic ester monomers totally 25 ~ 45 parts, and the mass values between them is 0.5 ~ 2, silane coupling agent 1 ~ 3 part, trifluoro propyl trimethylammonium cyclotrisiloxane 1 ~ 20 part, cationic emulsifier 1 ~ 3 part, nonionic emulsifying agent 0.5 ~ 2 part, initiator 0.2 ~ 0.5 part, 70 ~ 130 parts, water;
In described step (1), cationic emulsifier is the one in Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide; Nonionic emulsifying agent is the one in polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether, water-based ethoxy base class non-ionic type fluorocarbon surfactant;
In described step (2), silane coupling agent is t etram-ethyltetravinylcyclotetrasiloxane, the one in vinyl triethoxyl siloxanes, vinyl trimethoxy siloxanes; Initiator is the one in ammonium persulphate, Potassium Persulphate.
Further, in above-mentioned preparation method, in described step (1), " part " described in " part of the mixture of two kinds of acrylic ester monomers, cationic emulsifier, nonionic emulsifying agent, initiator and water " is 1/5 ~ 1/4 of above amount of the mixture;
Further, in above-mentioned preparation method, described pH value regulator is selected from: one or more the mixture in Glacial acetic acid, sodium hydroxide, sodium bicarbonate, ammoniacal liquor.
Further, in above-mentioned preparation method, in described step (2), pre-emulsified method is for using high-shear machine pre-emulsification, and the pre-emulsified time is 5 ~ 15 minutes.
Further, in above-mentioned preparation method, the time of described " pre-emulsion being dripped the seed emulsion that progressive rapid (1) obtains " is 1 ~ 3 hour.
Further, in above-mentioned preparation method, in described step (2), the quality of described silane hydrolyzate inhibitor is 1% ~ 5% of silane coupling agent and trifluoro propyl trimethylammonium cyclotrisiloxane total amount, and this silane hydrolyzate inhibitor is selected from one or more the mixture in ethylene glycol, methyl alcohol, ethanol, glycerol.
Further, in above-mentioned preparation method, at temperature T in described step (2)
2the time of lower reaction is 4 ~ 6 hours.
The test of mixing the agent of europium fluorine Si acrylate red fluorescence of the ultralow second-order transition temperature prepared by aforesaid method is measured by following method:
1. the mensuration of second-order transition temperature: get 2 ~ 4mg fluorescent agent solid Q20 differential scanning calorimeter (TA instrument company of the U.S.) and measure its second-order transition temperature.
2. the mensuration of emmission spectrum and excitation spectrum: the luminescence at room temperature testing this fluorescent agent with ultraviolet lamp, spectrum Dongwoo, DM701 type spectrometer (photomultiplier is Hamamatsu, R928 type) is measured, resolving power 0.02nm; Excitation spectrum at room temperature adopts Perkin-ElmerLS-50B type spectrophotometer measurement, and resolving power is 0.1nm.
3. the mensuration of extinction curve: at room temperature use CW-488nm (chopper) line argon ion (Ar
+) laser excitation sample, the face being placed on spectrometer with a spectral filter is filtered the laser rays of dispersion, transmit after detector, monochromator (ActonResearchCorp.Pro-750) and photomultiplier (HamamastuR928) are amplified, be delivered to registering instrument and oscilloscope respectively, to record fluorescence spectrum and to measure fluorescence lifetime.
Advantage of the present invention is:
1. first fluorin radical, silicon group are incorporated in acrylic ester polymer by the present invention, prepare fluorine Si acrylate copolymer, are then doped into by europium in this fluorine Si acrylate, and what obtain ultralow second-order transition temperature mixes the agent of europium fluorine Si acrylate red fluorescence.This red fluorescence agent has the second-order transition temperature of less than-50 DEG C, and this red fluorescence agent can effectively by near ultraviolet excitation, it goes out to show the very strong intensity that glows at 618nm, there is the good characteristics of luminescence and stability, compare existing fluorescent agent, the extremely frigid zones that is used as preferably resists cold road markings material.
2. the present invention provides the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of above-mentioned ultralow second-order transition temperature simultaneously, and the method is free from environmental pollution, and product yield is high, reaches more than 90%, is a kind of very good red fluorescence agent preparation method.
Accompanying drawing explanation
Fig. 1 is the DSC graphic representation of the red fluorescence agent that embodiment 1 prepares;
The utilizing emitted light spectrogram of Fig. 2 to be red fluorescence agent supervisory wavelength that embodiment 1 prepares be 395nm;
The exciting light spectrogram of Fig. 3 to be red fluorescence agent supervisory wavelength that embodiment 1 prepares be 618nm;
The extinction curve figure of Fig. 4 to be red fluorescence agent supervisory wavelength that embodiment 1 prepares be 355nm.
Table 1 mixes europium fluorine Si acrylate red fluorescence agent second-order transition temperature for the ultralow second-order transition temperature in each embodiment.
Embodiment
Embodiment: the present invention is described in further detail below in conjunction with embodiment, but the present invention is not limited to embodiment:
Embodiment 1
By 1/5 of the mixture of two kinds of acrylic ester monomers (n-butyl acrylate+Isooctyl acrylate monomer), compound emulsifying agent (cetyl trimethylammonium bromide+fatty alcohol-polyoxyethylene ether), initiator ammonium persulfate and water, under 80 DEG C of conditions, react 0.5h, obtain the seed emulsion of micro-blueness, then by two kinds of acrylic ester monomers (n-butyl acrylate+Isooctyl acrylate monomer), compound emulsifying agent (cetyl trimethylammonium bromide+fatty alcohol-polyoxyethylene ether), the remainder of the mixture of initiator and water, and whole silane coupling agent (specifically selecting vinyl trimethoxy siloxanes in the present embodiment) and trifluoro propyl trimethylammonium cyclotrisiloxane carry out high speed shear pre-emulsification 10min, then instill lentamente in above-mentioned seed emulsion, 4h is reacted under 85 DEG C of conditions, after cooling, pH to 7.5 is regulated with ammoniacal liquor, obtain Emulsion, 3g europium sesquioxide is dissolved in 100ml dust technology and obtains europium nitrate solution, instilled in Emulsion by ampoule tube, mixed solution is stirred 12h, and the vacuum drying oven putting into 80 DEG C dries 24h, and what obtain ultralow second-order transition temperature mixes the agent of europium fluorine Si acrylate red fluorescence.
Cetyl trimethylammonium bromide in above-mentioned compound emulsifying agent: the mass ratio of fatty alcohol-polyoxyethylene ether is 2:1; N-butyl acrylate: the mass ratio of Isooctyl acrylate monomer is 2:1; The consumption of trifluoro propyl trimethylammonium cyclotrisiloxane is 1% of two kinds of acrylic ester monomer summations; Vinyl trimethoxy siloxanes is 5% of two kinds of acrylic ester monomers and trifluoro propyl trimethylammonium cyclotrisiloxane summation.
Embodiment 2
By 1/5 of the mixture of two kinds of acrylic ester monomers (n-butyl acrylate+Isooctyl acrylate monomer), compound emulsifying agent (cetyl trimethylammonium bromide+fatty alcohol-polyoxyethylene ether), initiator ammonium persulfate and water, under 80 DEG C of conditions, react 0.5h, obtain the seed emulsion of micro-blueness, then by two kinds of acrylic ester monomers (n-butyl acrylate+Isooctyl acrylate monomer), compound emulsifying agent (cetyl trimethylammonium bromide+fatty alcohol-polyoxyethylene ether), the remainder of the mixture of initiator and water, and whole silane coupling agent (specifically selecting vinyl trimethoxy siloxanes in the present embodiment) and trifluoro propyl trimethylammonium cyclotrisiloxane carry out high speed shear pre-emulsification 10min, then instill lentamente in above-mentioned seed emulsion, 4h is reacted under 85 DEG C of conditions, after cooling, pH to 7.5 is regulated with ammoniacal liquor, obtain Emulsion, 4g europium sesquioxide is dissolved in 100ml dust technology and obtains europium nitrate solution, instilled in Emulsion by ampoule tube, mixed solution is stirred 12h, and the vacuum drying oven putting into 80 DEG C dries 24h, and what obtain ultralow second-order transition temperature mixes the agent of europium fluorine Si acrylate red fluorescence.
Cetyl trimethylammonium bromide in above-mentioned compound emulsifying agent: fatty alcohol-polyoxyethylene ether mass ratio is 2:1; N-butyl acrylate: the mass ratio of Isooctyl acrylate monomer is 2:1; The consumption of trifluoro propyl trimethylammonium cyclotrisiloxane is 5% of two kinds of acrylic ester monomer summations; Vinyl trimethoxy siloxanes is 5% of two kinds of acrylic ester monomers and trifluoro propyl trimethylammonium cyclotrisiloxane summation.
Embodiment 3
By 1/5 of the mixture of two kinds of acrylic ester monomers (n-butyl acrylate+Isooctyl acrylate monomer), compound emulsifying agent (cetyl trimethylammonium bromide+water-based ethoxy base class non-ionic type fluorocarbon surfactant), initiator ammonium persulfate and water, under 80 DEG C of conditions, react 0.5h, obtain the seed emulsion of micro-blueness; Then by the remainder of the mixture of two kinds of acrylic ester monomers (n-butyl acrylate+Isooctyl acrylate monomer), compound emulsifying agent (cetyl trimethylammonium bromide+water-based ethoxy base class non-ionic type fluorocarbon surfactant), initiator and water, and whole silane coupling agent (specifically selecting vinyl triethoxyl siloxanes in the present embodiment) and trifluoro propyl trimethylammonium cyclotrisiloxane carry out high speed shear pre-emulsification 10min, then instill in above-mentioned seed emulsion lentamente.Under 85 DEG C of conditions, react 4h, after cooling, regulate pH to 7.5 with ammoniacal liquor, obtain Emulsion; 5g europium sesquioxide is dissolved in 100ml dust technology and obtains europium nitrate solution, instilled in Emulsion by ampoule tube, mixed solution is stirred 12h, and the vacuum drying oven putting into 80 DEG C dries 24h, and what obtain ultralow second-order transition temperature mixes the agent of europium fluorine Si acrylate red fluorescence.
Cetyl trimethylammonium bromide in above-mentioned compound emulsifying agent: water-based ethoxy base class non-ionic type fluorocarbon surfactant mass ratio is 2:1; N-butyl acrylate: the mass ratio of Isooctyl acrylate monomer is 2:1; The consumption of trifluoro propyl trimethylammonium cyclotrisiloxane is 10% of two kinds of acrylic ester monomer summations; Vinyl triethoxyl siloxanes is 5% of two kinds of acrylic ester monomers and trifluoro propyl trimethylammonium cyclotrisiloxane summation.
Embodiment 4
By 2.2 kilograms of n-butyl acrylates and Isooctyl acrylate monomer, a certain amount of cetyl trimethylammonium bromide and water-based ethoxy base class non-ionic type fluorocarbon surfactant, initiator, water join in the reactor of 50L, open nitrogen protection, under stirring, be heated to 80 DEG C, until emulsion becomes micro-blueness; Again remaining 9.1 kilograms of n-butyl acrylates and Isooctyl acrylate monomer, 6.5 kilograms of trifluoro propyl trimethylammonium cyclotrisiloxane and vinyl triethoxyl siloxanes, cetyl trimethylammonium bromide and water-based ethoxy base class non-ionic type fluorocarbon surfactant, initiator, water are carried out high speed shear pre-emulsification 15min, instilled in 3 hours in reactor, 85 DEG C are warming up to after all dripping off, continuation insulation reaction stirred after 5 hours is down to room temperature, after regulating pH to 7.5 with ammoniacal liquor, discharging is filtered, and obtains Emulsion; 300g europium sesquioxide is dissolved in 1500ml dust technology and obtains europium nitrate solution, instilled in Emulsion by ampoule tube, mixed solution is stirred 12h, the vacuum drying oven putting into 80 DEG C dries 24h, and what obtain the ultralow second-order transition temperature produced in enormous quantities mixes the agent of europium fluorine Si acrylate red fluorescence.
Cetyl trimethylammonium bromide in above-mentioned compound emulsifying agent: water-based ethoxy base class non-ionic type fluorocarbon surfactant mass ratio is 2:1; N-butyl acrylate: the mass ratio of Isooctyl acrylate monomer is 2:1; The consumption of trifluoro propyl trimethylammonium cyclotrisiloxane is 50% of two kinds of acrylic ester monomer summations; Vinyl triethoxyl siloxanes is 5% of two kinds of acrylic ester monomers and trifluoro propyl trimethylammonium cyclotrisiloxane summation.
The europium fluorine Si acrylate red fluorescence agent of mixing of the ultralow second-order transition temperature that above embodiment prepares is determined as follows:
1. the mensuration of second-order transition temperature: get 2 ~ 4mg fluorescent agent solid Q20 differential scanning calorimeter (TA instrument company of the U.S.) and measure its second-order transition temperature.
2. the mensuration of emmission spectrum and excitation spectrum: the luminescence at room temperature testing this fluorescent agent with ultraviolet lamp, spectrum Dongwoo, DM701 type spectrometer (photomultiplier is Hamamatsu, R928 type) is measured, resolving power 0.02nm; Excitation spectrum at room temperature adopts Perkin-ElmerLS-50B type spectrophotometer measurement, and resolving power is 0.1nm.
3. the mensuration of extinction curve: at room temperature use CW-488nm (chopper) line argon ion (Ar
+) laser excitation sample, the face being placed on spectrometer with a spectral filter is filtered the laser rays of dispersion, transmit after detector, monochromator (ActonResearchCorp.Pro-750) and photomultiplier (HamamastuR928) are amplified, be delivered to registering instrument and oscilloscope respectively, to record fluorescence spectrum and to measure fluorescence lifetime.
The second-order transition temperature mixing the agent of europium fluorine Si acrylate red fluorescence of the ultralow second-order transition temperature in the various embodiments described above is as shown in the table:
| Embodiment | Second-order transition temperature (DEG C) |
| 1 | -51.5 |
| 2 | -53.3 |
| 3 | -57.7 |
| 4 | -61.4 |
The europium fluorine Si acrylate red fluorescence agent of mixing of the ultralow second-order transition temperature prepared for embodiment 1 is analyzed as follows:
The DSC curve of composition graphs 1 can be found out, the second-order transition temperature mixing the agent of europium fluorine Si acrylate red fluorescence of this ultralow second-order transition temperature is low reaches-51.5 DEG C, and this shows that this red fluorescence agent is suitable for being used as extremely frigid zones and resists cold road markings material.
As can be seen from the emmission spectrum in Fig. 2, under the exciting of 395nm near-ultraviolet light, due to
5d
0→
7f
2transition of electron, this red fluorescence agent shows very strong ruddiness in the position of 618nm wavelength, illustrates that this red fluorescence agent can send ruddiness effectively.
The exciting light spectrogram of Fig. 3 to be this look fluorescent agent supervisory wavelength be 618nm, as can be seen from the figure, this excitation spectrum is made up of many narrow and broad peaks, at the strong peak of 398nm be wherein by
7f
0→
5l
6that transfer transport causes and be in 467nm place set up a stronger peak be by
7f
0→
5d
2transfer transport causes, and the light emitting region at these two peaks mates with near ultraviolet region and thus can be used in remote illumination very much.
Fig. 4 is the extinction curve of this red fluorescence agent under 355nm excites, and this extinction curve presents single index characteristic, by formula
calculate its fall time, wherein I is the luminous intensity when time t, and fall time is 0.43ms, and so short fall time can be applied in White-light LED illumination.
Certain above-described embodiment is just exemplifying of illustrating that technical conceive of the present invention and feature do and non exhaustive, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All modifications done according to the spirit of main technical schemes of the present invention, all should be encompassed within protection scope of the present invention.
Claims (10)
1. ultralow second-order transition temperature mix the agent of europium fluorine Si acrylate red fluorescence, it is characterized in that, its chemical structural formula is:
This fluorescent agent number-average molecular weight is 15000-20000g/mol, and wherein, a, b, n are the repeat number of segment, are the integer being more than or equal to 1, R in structural formula
1and R
2be acrylic ester monomer.
2. a kind of ultralow second-order transition temperature according to claim 1 mix the agent of europium fluorine Si acrylate red fluorescence, it is characterized in that, described R
1and R
2be two kinds of different esters of acrylic acid soft monomers, described esters of acrylic acid soft monomer refers to the one in ethyl propenoate, n-butyl acrylate, isobutyl acrylate, Isooctyl acrylate monomer, n-octyl, vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate.
3. the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of a kind of ultralow second-order transition temperature as described in claim 1 ~ 2 any one, is characterized in that comprising the following steps:
(1) get the part of the mixture of two kinds of acrylic ester monomers, cationic emulsifier, nonionic emulsifying agent, initiator and water, stir and regulate the front pH value of polymerization, at N by pH value regulator
2atmosphere, temperature T
1=75 ~ 80 DEG C, and under the condition of Keep agitation, reaction for some time, obtain the seed emulsion of micro-blueness;
(2) remainder of the mixture of two kinds of acrylic ester monomers, cationic emulsifier, nonionic emulsifying agent, initiator and water in step (1) is got, and whole silane coupling agents and trifluoro propyl trimethylammonium cyclotrisiloxane carry out pre-emulsification, then pre-emulsion is dripped in the progressive suddenly seed emulsion that (1) obtains, add silane hydrolyzate inhibitor, at temperature T after dropwising to reaction system in dropping process simultaneously
2for some time is reacted at=81 ~ 86 DEG C;
(3) after reaction terminates, by emulsion cool to room temperature, by pH value regulator, emulsion is adjusted to pH=7 ~ 7.5, then filters emulsion with 200 mesh filter screens, obtain cationic Emulsion;
(4) europium sesquioxide is dissolved in dust technology obtains europium nitrate solution, europium nitrate solution is instilled mixing and stirring in the cationic Emulsion that step (3) obtains by ampoule tube, put into vacuum drying oven again to dry, what obtain ultralow second-order transition temperature mixes the agent of europium fluorine Si acrylate red fluorescence.
4. the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of a kind of ultralow second-order transition temperature according to claim 3, it is characterized in that, each component by mass content is as follows:
Two kinds of acrylic ester monomers totally 25 ~ 45 parts, and the mass values between them is 0.5 ~ 2, silane coupling agent 1 ~ 3 part, trifluoro propyl trimethylammonium cyclotrisiloxane 1 ~ 20 part, cationic emulsifier 1 ~ 3 part, nonionic emulsifying agent 0.5 ~ 2 part, initiator 0.2 ~ 0.5 part, 70 ~ 130 parts, water;
In described step (1), cationic emulsifier is the one in Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide; Nonionic emulsifying agent is the one in polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether, water-based ethoxy base class non-ionic type fluorocarbon surfactant;
In described step (2), silane coupling agent is t etram-ethyltetravinylcyclotetrasiloxane, the one in vinyl triethoxyl siloxanes, vinyl trimethoxy siloxanes; Initiator is the one in ammonium persulphate, Potassium Persulphate.
5. the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of a kind of ultralow second-order transition temperature according to claim 3, it is characterized in that, in step (1), " part " described in " part of the mixture of two kinds of acrylic ester monomers, cationic emulsifier, nonionic emulsifying agent, initiator and water " is 1/5 ~ 1/4 of above amount of the mixture.
6. the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of a kind of ultralow second-order transition temperature according to claim 3, it is characterized in that, in step (1), described pH value regulator is selected from: one or more the mixture in Glacial acetic acid, sodium hydroxide, sodium bicarbonate, ammoniacal liquor.
7. the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of a kind of ultralow second-order transition temperature according to claim 3, it is characterized in that, in step (2), pre-emulsified method is for using high-shear machine pre-emulsification, and the pre-emulsified time is 5 ~ 15 minutes.
8. the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of a kind of ultralow second-order transition temperature according to claim 3, it is characterized in that, in step (2), the time of described " pre-emulsion being dripped the seed emulsion that progressive rapid (1) obtains " is 1 ~ 3 hour.
9. the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of a kind of ultralow second-order transition temperature according to claim 3, it is characterized in that, in step (2), the quality of described silane hydrolyzate inhibitor is 1% ~ 5% of silane coupling agent and trifluoro propyl trimethylammonium cyclotrisiloxane total amount, and this silane hydrolyzate inhibitor is selected from one or more the mixture in ethylene glycol, methyl alcohol, ethanol, glycerol.
10. the preparation method mixing the agent of europium fluorine Si acrylate red fluorescence of a kind of ultralow second-order transition temperature according to claim 3, is characterized in that, in step (2), at temperature T
2the time of lower reaction is 4 ~ 6 hours.
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| JP2006071525A (en) * | 2004-09-03 | 2006-03-16 | Konica Minolta Medical & Graphic Inc | Radiation image conversion panel and its manufacturing method |
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| JP2006071525A (en) * | 2004-09-03 | 2006-03-16 | Konica Minolta Medical & Graphic Inc | Radiation image conversion panel and its manufacturing method |
| CN103242479A (en) * | 2013-05-22 | 2013-08-14 | 南通福伦利新材料有限公司 | Fluorosilicone acrylates copolymer emulsion as well as preparation method and application thereof |
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| "A novel thermally stable Eu(III) complex-modified acrylate nano-polymer and its luminescence properties";Lin Xu et al.;《Journal of Nanoparticle Research》;Springer;20130706;第15卷(第8期);第2页实验部分，第5页右栏第1段，图7 * |
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