CN106279552A - A kind of fluorescence rubber particle and preparation method thereof - Google Patents
A kind of fluorescence rubber particle and preparation method thereof Download PDFInfo
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- CN106279552A CN106279552A CN201510312455.1A CN201510312455A CN106279552A CN 106279552 A CN106279552 A CN 106279552A CN 201510312455 A CN201510312455 A CN 201510312455A CN 106279552 A CN106279552 A CN 106279552A
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Abstract
The present invention relates to rubber materials, disclose a kind of fluorescence rubber particle and preparation method thereof.Described fluorescence rubber particle is the rubber particles that grafted with maleic anhydride and/or maleic acid obtain on the rubber particles have cross-linked structure.Fluorescence rubber particle excitation spectrum in its fluorescence spectrum and emission spectrum that the present invention provides all occur in that red shift, are respectively provided with the fluorescent effect of excellence in wider wave-length coverage.
Description
Technical field
The present invention relates to rubber materials, in particular it relates to a kind of fluorescence rubber particle and a kind of fluorescence rubber
The preparation method of micelle.
Background technology
Fluorescent material is closely bound up with the daily life of the mankind, and is widely used in dyestuff, photooxidation
The numerous areas such as agent, anti-counterfeiting mark, Optical Bleaching Agent, chemistry and bioanalysis.Development in recent years is got up
Fluorescence Chemical Sensor and molecular signal system more make the application of fluorescent material have to carry significantly
Height and expansion, it has wide in terms of materia medica, physiology, environmental science, information science technology
Application prospect.
Fluorescent material refers to store outside energy, and converts it into as light under dark surrounds
One class material of energy.Fluorescent material is divided into inorganic fluorescent material and organic fluorescence materials.Wherein, inorganic glimmering
Representative in luminescent material is rare-earth luminescent material, has fluorescent material constantly to occur subsequently, such as CRT
Fluorescent material, lamp phosphor, Field emission displays (FED) fluorescent material etc..Organic fluorescence materials is then
Being widely used in weaving, coloring plastic and printing color, it can be divided three classes according to material structure: tool
Have rigid structure aromatic fused ring compound, have conjugated structure Intramolecular charge transfer and certain
A little metal organic complexes, wherein, have conjugated structure Intramolecular charge transfer and have preferably
Radiative decay ability.
At present fluorescence composite material be usually in the way of metal complex is by coordination polymerization metal from
Son connection obtains fluorescence property on the organic material, and this reaction will be in High Temperature High Pressure and certain urging
Agent or vacuum or anhydrous under the conditions of reaction prepare, operating procedure is complicated, and preparation cost is high,
Material itself does not have excellent processability, and range of application is restricted.
In order to overcome the drawbacks described above of existing fluorescence composite material, need exploitation one at present badly and can prepare
Have wide range of applications and do not affect the fluorescent material of the performance that even can improve matrix material.
Summary of the invention
It is an object of the invention to provide a kind of new fluorescence rubber particle and the system of this fluorescence rubber particle
Preparation Method.
Specifically, the invention provides a kind of fluorescence rubber particle, described fluorescence rubber particle is for have
The rubber particles that on the rubber particles of cross-linked structure, grafted with maleic anhydride and/or maleic acid obtain.
Present invention also offers the preparation method of a kind of fluorescence rubber particle, the method is included in has crosslinking
Grafted with maleic anhydride and/or maleic acid on the rubber particles of structure.
The present inventor finds after further investigation, when on the rubber particles with cross-linked structure
After grafted with maleic anhydride and/or maleic acid, the rubber particles obtained has fluorescent effect, and
And excitation spectrum and the emission spectrum in its fluorescence spectrum all occurs in that red shift, therefore at wider wavelength
In the range of be respectively provided with excellence fluorescent effect, widened its range.Additionally, this fluorescence rubber particle
Preparation method simple, it is adaptable to the preparation of various fluorescence rubber particles, and prepared fluorescence rubber
Particle can apply to the modification of various basic material (such as plastics, rubber, coating etc.), holds the most very much
Easily prepare composite fluorescent material.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1-a is the emission spectrum figure of the fluorescence rubber particle that embodiment 1 prepares；
Fig. 1-b is the exciting light spectrogram of the fluorescence rubber particle that embodiment 1 prepares；
Fig. 2-a is the emission spectrum figure of the fluorescence rubber particle that comparative example 1 prepares；
Fig. 2-b is the exciting light spectrogram of the fluorescence rubber particle that comparative example 1 prepares.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The fluorescence rubber particle that the present invention provides is the suitable fourth of grafting on the rubber particles have cross-linked structure
The rubber particles that enedioic acid acid anhydride and/or maleic acid obtain.
The fluorescence rubber particle that the present invention provides is a kind of grafting on the rubber particles have cross-linked structure
Modified monomer maleic anhydride and/or maleic acid and the rubber particles that obtains, it is in fluorescence spectrum
Excitation spectrum and the peak wavelength of emission spectrum all occur in that red shift.In the present invention, described at fluorescence
Excitation spectrum and the peak wavelength of emission spectrum in spectrum occur that red shift refers to relative to not grafting
There is the rubber particles of the cross-linked structure excitation spectrum in fluorescence spectrum and the peak wavelength of emission spectrum
For.The direction that red shift is directed to wavelength bigger is moved.The present invention to described fluorescence rubber particle glimmering
Excitation spectrum and the amplitude of the peak wavelength red shift of emission spectrum in light spectrum the most specially limit, preferably
Ground, relative to excitation spectrum in fluorescence spectrum of the rubber particles with cross-linked structure of not grafting and
For the peak wavelength of emission spectrum, described fluorescence rubber particle excitation spectrum in fluorescence spectrum and send out
Penetrate the peak wavelength at least 1nm of red shift independently of one another of spectrum, preferably red shift at least 5nm, preferably red shift
At least 10nm, further preferred red shift at least 20nm, more preferably red shift at least 30nm, the reddest
Move to few 50nm.
The fluorescence rubber particle provided according to the present invention, although as long as having the rubber of cross-linked structure toward described in
The fluorescence rubber particle of acquisition just can be made after grafted with maleic anhydride and maleic acid on particle
There is red shift in excitation spectrum and the peak wavelength of emission spectrum in fluorescence spectrum, and have good
Fluorescence property, but in order to make described fluorescence rubber particle have more preferable fluorescence property, it is preferable that described
In fluorescence rubber particle, total percent grafting of maleic anhydride and maleic acid is more than 0.1%, preferably
It is more than 1%, more preferably more than 5%, most preferably more than 10%.
The fluorescence rubber particle provided according to the present invention, it is preferable that described in there is the rubber grain of cross-linked structure
The mean diameter of son is 0.02-1 μm, more preferably 0.05-0.5 μm, particularly preferably 0.05-0.2 μm.
Correspondingly, the mean diameter of the final fluorescence rubber particle obtained is preferably also 0.02-1 μm, more preferably
0.05-0.5 μm, particularly preferably 0.05-0.2 μm.
The gel content of the described rubber particles with cross-linked structure is not particularly limited by the present invention, example
As, described in there is cross-linked structure the gel content of rubber particles can be more than 60 weight %, preferably
It is more than 75 weight %, more than particularly preferably 80 weight %.In the present invention, described gel content
Be this area for characterizing a kind of Common Parameters of rubber cross degree, it is according to public in CN1402752A
The method opened records.
The kind of the described rubber particles with cross-linked structure is not particularly limited by the present invention, such as,
Can be selected from natural rubber, butadiene-styrene rubber, carboxylic styrene-butadiene rubber, nitrile rubber, carboxy terminated nitrile rubber,
Polybutadiene rubber, silicone rubber, neoprene, acrylate rubber, butadiene-styrene-vinyl pyridine rubber, isoprene rubber,
Butyl rubber, thiorubber., Acrylester Butadiene Rubber, polyurethane rubber, fluorubber and ethylene-
At least one in vinyl acetate rubber, is preferably selected from butadiene-styrene rubber, carboxylic styrene-butadiene rubber, butyronitrile rubber
At least one in glue, carboxy terminated nitrile rubber, acrylate rubber and butadiene-styrene-vinyl pyridine rubber, is more preferably selected from
At least one in carboxylic styrene-butadiene rubber, acrylate rubber and butadiene-styrene-vinyl pyridine rubber.
The described rubber particles with cross-linked structure can be commercially available, it is also possible to according to this area skill
Known to art, various methods prepare.Such as, have described in the rubber particles of cross-linked structure can be by
The international patent application WO01/40356 submitted for 18th in JIUYUE in 2000 according to applicant of the present invention is (excellent
First power 1999 days December 3 days) and applicant of the present invention submit June 15 calendar year 2001
Full sulfuration prepared by international patent application WO01/98395 (priority date on June 15th, 2000)
Powdered rubber.Additionally, the example of described fully vulcanized powder rubber includes but not limited to: form of finely divided powder, mehtod sky
So rubber form of finely divided powder, mehtod butadiene-styrene rubber form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, form of finely divided powder, mehtod butyronitrile
Rubber, form of finely divided powder, mehtod carboxy terminated nitrile rubber, form of finely divided powder, mehtod polybutadiene rubber, form of finely divided powder, mehtod silicon
Rubber, form of finely divided powder, mehtod neoprene, form of finely divided powder, mehtod acrylate rubber, form of finely divided powder, mehtod butylbenzene pyrrole
Rubber, form of finely divided powder, mehtod isoprene rubber, form of finely divided powder, mehtod butyl rubber, form of finely divided powder, mehtod thiorubber.,
Form of finely divided powder, mehtod Acrylester Butadiene Rubber, form of finely divided powder, mehtod polyurethane rubber, form of finely divided powder, mehtod fluorine
At least one in rubber, form of finely divided powder, mehtod ethylene vinyl acetate rubber etc., is preferably and entirely vulcanizes powder
End butadiene-styrene rubber, form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, Vulcanized Powdered Nitrile Rubber, form of finely divided powder, mehtod
In carboxy terminated nitrile rubber, form of finely divided powder, mehtod acrylate rubber and form of finely divided powder, mehtod butadiene-styrene-vinyl pyridine rubber at least
One, most preferably form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, form of finely divided powder, mehtod acrylate rubber and full sulfur
Change at least one in powder butadiene-styrene-vinyl pyridine rubber.The gel content of described fully vulcanized powder rubber is preferably 60
More than weight %, more than more preferably 75 weight %, more than particularly preferably 80 weight %.Described entirely
The mean diameter of sulfide powder rubber is preferably 0.02-1 μm, more preferably 0.05-0.5 μm, particularly preferably
0.05-0.2μm.Additionally, each microgranule in described fully vulcanized powder rubber is homogeneous, the most singly
Individual microgranule is the most all homogenizing, does not find to divide under the observation of existing microtechnique in microgranule
The most homogeneous phenomenons such as layer, split-phase.This rubber particles with cross-linked structure is by by corresponding rubber
Latex cross-linking radiation and by fixing for rubber particles particle diameter.
Have described in additionally, cross-linked structure rubber particles can also for according to applicant of the present invention in
The cross-linked powdery rubber prepared by Chinese patent application CN1353131A that on November 3rd, 2000 submits
Glue.The example of described cross-linked powdered rubber includes but not limited to: cross-linked powdery butadiene-styrene rubber and/or friendship
Connection type powder polybutadiene rubber.This cross-linked powdered rubber is a kind of with cross-linking type synthetic rubber latex
For raw material, the powdered rubber that drying obtains, its mean diameter is 0.05-0.3 μm, gel content and work
Gel content for the cross-linking type synthetic rubber latex of raw material keeps consistent, and more than preferably 80 weight %,
More than more preferably 85 weight %.This cross-linked powdered rubber is not required to add interleaving agent and can freely flow
Dynamic.Each microgranule in this cross-linked powdered rubber is homogeneous, and the most single microgranule is in composition
It is all homogenizing, under the observation of existing microtechnique, in microgranule, does not find that layering, split-phase etc. are the most homogeneous
Phenomenon.
The preparation method of the fluorescence rubber particle that the present invention provides is included in the rubber grain with cross-linked structure
Grafted with maleic anhydride and/or maleic acid on son.
According to the preparation method of the fluorescence rubber particle that the present invention provides, although as long as there is toward described in crosslinking
The glimmering of acquisition just can be made after grafted with maleic anhydride and maleic acid on the rubber particles of structure
There is red shift in the peak wavelength of light rubber particles excitation spectrum in fluorescence spectrum and emission spectrum, and
There is good fluorescence property, but in order to make described fluorescence rubber particle have more preferable fluorescence property, excellent
Selection of land, in described fluorescence rubber particle, total percent grafting of maleic anhydride and maleic acid is 0.1%
Above, preferably more than 1%, more preferably more than 5%, most preferably more than 10%.
The present invention is to grafted with maleic anhydride on the rubber particles have cross-linked structure and/or maleic
The mode of diacid is not particularly limited, it is preferred to use following two mode is carried out:
(1-1) there is the rubber particles of cross-linked structure containing maleic anhydride and/or along fourth by described
The solution of enedioic acid soaks so that described in have the rubber particles of cross-linked structure swelling, then carry out
Graft polymerization reaction, is finally dried the graft polymerization reaction product obtained；Or,
(1-2) by the rubber latex containing cross-linking radiation and maleic anhydride and/or maleic acid
Solution carry out graft polymerization reaction, finally the graft polymerization reaction product obtained is dried.
Wherein, when using mode (1-1) grafted with maleic anhydride and/or maleic acid, adopted
The mean diameter of the rubber particles with cross-linked structure be preferably 0.02-1 μm, more preferably
0.05-0.5 μm, particularly preferably 0.05-0.2 μm.Correspondingly, the fluorescence rubber particle finally obtained
Mean diameter is preferably also 0.02-1 μm, more preferably 0.05-0.5 μm, particularly preferably 0.05-0.2 μm.
Additionally, the gel content of the rubber particles with cross-linked structure used can be more than 60 weight %,
It is preferably more than 75 weight %, more than particularly preferably 80 weight %.
In mode (1-1), in the described solution containing maleic anhydride and/or maleic acid
Solvent can be existing various can to dissolve maleic anhydride and maleic acid and enable to
There is the solvent that the rubber particles of cross-linked structure is swelling, for example, it is possible to selected from acetone, water, dehydrated alcohol,
At least one in ether, ethyl acetate, chloroform, oxolane, N-Methyl pyrrolidone etc..Additionally,
As long as the consumption of described solvent enables to maleic anhydride and maleic acid dissolves and makes to have
The rubber particles of cross-linked structure is the most swelling, and therefore not to repeat here.
The condition soaked described in mode (1-1) is not particularly limited, as long as can make by the present invention
The rubber particles described in get with cross-linked structure occurs swelling, so that maleic anhydride and/or suitable fourth
Enedioic acid enters in the cross-linked network structure of this rubber particles, all can know these those skilled in the art
Know, do not repeat.
Kind and the preparation method described in additionally, with the rubber particles of cross-linked structure have had been described above
Described, therefore not to repeat here.
When using mode (1-2) grafted with maleic anhydride and/or maleic acid, the spoke used
Elastomer latex according to crosslinking can be above-mentioned international patent application WO01/40356 (priority date 1999
On December 3) disclosed in irradiated crosslinking after, be spray-dried after rubber latex, specifically
Natural rubber latex styrene butadiene rubber latex carboxylic styrene-butadiene rubber latex, nitrile rubber glue can be selected from
Breast, carboxy terminated nitrile rubber latex, polybutadiene rubber latex, silicone rubber latex, Neoprene latex,
Acrylate rubber latex, butadiene-styrene-vinyl pyridine rubber latex, isoprene rubber latex, butyl rubber latex, polysulfide
Rubber latex, Acrylester Butadiene Rubber latex, polyurethane rubber latex, fluoroelastomer latex and second
At least one in alkene-vinyl acetate rubber latex, is preferably selected from styrene butadiene rubber latex Carboxy
Rubber latex, nitrile rubber latex, carboxy terminated nitrile rubber latex, acrylate rubber latex and butylbenzene pyrrole
At least one in rubber latex, is more preferably selected from carboxylic styrene-butadiene rubber latex, acrylate rubber glue
At least one in breast and butadiene-styrene-vinyl pyridine rubber latex.Additionally, consolidating of the rubber latex of described cross-linking radiation contains
Measure typically 20-70 weight %, preferably 30-60 weight %, more preferably 40-50 weight %.
Additionally, the graft polymerization reaction of mode (1-2) can not use crosslinking coagent, it is possible to use
Crosslinking coagent.Described crosslinking coagent can be selected from simple function group crosslinking coagent, two functional group's crosslinking coagents,
Any one in trifunctional crosslinking coagent, the above crosslinking coagent of four-functional group crosslinking coagent and five functional groups
Kind.The example of described simple function group crosslinking coagent includes but not limited to: (methyl) 1-Octyl acrylate, (first
Base) Isooctyl acrylate monomer, at least one in (methyl) glycidyl acrylate；Described two senses
Group crosslinking coagent example include but not limited to: 1,4-butanediol two (methyl) acrylate, 1,6-oneself two
Alcohol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl)
At least one in acrylate, neopentyl glycol two (methyl) acrylate, divinylbenzene；Described
The example of trifunctional crosslinking coagent includes but not limited to: trimethylolpropane tris (methyl) acrylate
And/or tetramethylolmethane three (methyl) acrylate；The example of described four-functional group crosslinking coagent include but not
It is limited to: tetramethylolmethane four (methyl) acrylate and/or ethoxyquin tetramethylolmethane four (methyl) acrylic acid
Ester；The example of the described five above crosslinking coagents of functional group includes but not limited to: dipentaerythritol five (methyl)
Acrylate.In this article, described (methyl) acrylate refers to acrylate and/or methacrylic acid
Ester.These crosslinking coagents can be applied in combination in any way, as long as they contribute to entering of cross-linking reaction
Row.Additionally, the addition of described crosslinking coagent is generally the 0.1-10 weight of dry glue weight in latex
%, preferably 0.5-9 weight %, more preferably 0.7-7 weight %.
The kind of solvent in solution described in mode (1-2) is not particularly limited by the present invention, permissible
For water or existing various water-soluble solvent, wherein, the kind of described water-soluble solvent can be all this
These those skilled in the art all can be known, therefore not to repeat here by the conventional selection in field.Additionally, institute
As long as stating the carrying out of the consumption beneficially graft polymerization reaction of solvent, therefore not to repeat here.
Additionally, by the solution containing rubber latex and grafted monomers through graft polymerization reaction, the most after drying
The fluorescence rubber particle obtained also has the full sulfuration disclosed in above-mentioned international patent application WO01/40356
The characteristic of powdered rubber.That is, the gel content of this fluorescence rubber particle is preferably more than 60 weight %,
More than more preferably 75 weight %, more than particularly preferably 80 weight %.This fluorescence rubber particle is logical
Cross and corresponding rubber latex carried out cross-linking radiation and rubber particles particle diameter is fixed, its particle diameter with
The particle diameter of the latex particle in starting rubber latex is consistent.Rubber particles (latex in starting rubber latex
Particle) mean diameter be generally 0.02-1 μm, preferably 0.05-0.5 μm, more preferably 0.05-0.2 μm.
The mean diameter of the rubber particles with cross-linked structure after irradiated crosslinking is the most also 0.02-1 μm, excellent
Elect 0.05-0.5 μm, more preferably 0.05-0.2 μm as.The average particle of the fluorescence rubber particle finally given
Footpath is the most also 0.02-1 μm, preferably 0.05-0.5 μm, more preferably 0.05-0.2 μm.
In mode (1-1) and (1-2), the consumption of described maleic anhydride and maleic acid makes
In the fluorescence rubber particle that must finally give, total percent grafting of maleic anhydride and maleic acid is preferred
Be more than 0.1%, more preferably more than 1%, more preferably more than 5%, most preferably 10% with
On.
The mode of graft polymerization reaction in mode (1-1) and (1-2) is not particularly limited by the present invention,
Can carry out to use existing various modes, it is preferred to use radiation grafting copolymerization reacts, more preferably high energy
X ray irradiation x graft polymerization reaction.Wherein, the spoke that described high-energy ray irradiation graft polymerization reaction is used
The source of penetrating is preferably cobalt source, ultraviolet or high-energy electron accelerator, particularly preferably cobalt source.The meter of irradiation used
The atmosphere that amount and irradiation process are used all does not has any restriction, as long as it is smooth to enable to grafted monomers
It is grafted on the elastomer latex of rubber particles or the cross-linking radiation with cross-linked structure and makes to finally give
The gel content of rubber particles reach more than 60 weight %, preferably reach more than 75 weight %, more excellent
Choosing reaches more than 80 weight %, and such as, the dosage of irradiation can be 0.1-30Mrad, is preferably
0.5-20Mrad。
The method and apparatus that the product that described graft polymerization reaction obtains is dried is not had spy by the present invention
Do not limit, can be any drying means of the prior art and drying equipment, it is preferred to use spray dried
Dry method is dried, and concrete operations those skilled in the art all can know, therefore not to repeat here.
Hereinafter will be described the present invention by embodiment.
Experimental data in following example and comparative example following instrument and equipment and assay method measure:
The test instrunment of the fluorescence spectrum of fluorescence rubber particle is: fluorescence spectrophotometer (F-7000FL
Spectrophotometer), test mode is length scanning (Wavelength scan), the pattern of test
There are two kinds: launch (Emission) and excite (Excitation).
Embodiment 1
Fluorescence rubber particle that this embodiment provides for the present invention is described and preparation method thereof.
By 5g maleic anhydride (Tianjin recovery development in science and technology company limited, fusing point is 52-54 DEG C)
Be dissolved in 50mL acetone, by Carboxy powdered rubber (middle petrochemical industry Beijing Chemical Research Institute produce,
The trade mark is VP201, and mean diameter is 90nm, and gel content is 91 weight %) add in above-mentioned solution,
Wherein maleic anhydride is 10:100 with the weight ratio of Carboxy powdered rubber, swelling at 30 DEG C
Using cobalt source to carry out radiation grafting copolymerization reaction after 72 hours, irradiation dose used is 12kGy, and irradiation connects
Branch polyreaction is dried to obtain fluorescence Carboxy powdered rubber after completing.Afterwards by gained fluorescence rubber powder
End carries out fluorescence steady state test, obtains emission spectrum Fig. 1-a and excitation spectrum Fig. 1-b of sample, and
Peak wavelength and the red shift amplitude thereof of its percent grafting, excitation spectrum and emission spectrum are shown in Table 1.From Fig. 1-a
In it can be seen that the transmitting light peak value of this sample is at 450nm.It can be seen that this sample from Fig. 1-b
Exciting light peak value between 330-370nm.
Comparative example 1
This comparative example is for fluorescence rubber particle that reference is described and preparation method thereof.
Prepare fluorescence rubber particle according to the method for embodiment 1, except for the difference that, be added without maleic acid
Acid anhydride, carries out fluorescence steady state test by gained fluorescence rubber particle, obtain sample emission spectrum Fig. 2-a and
Excitation spectrum Fig. 2-b.It can be seen that the transmitting light peak value of this sample is at 395nm from Fig. 2-a.From
It can be seen that the exciting light peak value of this sample is between 310-330nm in Fig. 2-b.
Embodiment 2
Fluorescence rubber particle that this embodiment provides for the present invention is described and preparation method thereof.
Fluorescence rubber particle is prepared, except for the difference that, by acetone same volume according to the method for embodiment 1
Water substitute, maleic anhydride obtains maleic acid after being dissolved in water, and Carboxy powdered rubber
Addition makes maleic acid be 15:100 with the weight ratio of Carboxy powdered rubber, through fluorescence spectrum
Method is verified, prepared fluorescence rubber particle has a fluorescence property, and its percent grafting, excitation spectrum and
Peak wavelength and the red shift amplitude thereof of emission spectrum are shown in Table 1.
Embodiment 3
Fluorescence rubber particle that this embodiment provides for the present invention is described and preparation method thereof.
Fluorescence rubber particle is prepared, except for the difference that, by Carboxy powder rubber according to the method for embodiment 1
(middle petrochemical industry Beijing Chemical Research Institute produces the acrylate powder rubber of glue identical weight part, and the trade mark is
VP301, mean diameter is 200nm, and gel content is 91 weight %) substitute, test through fluorescent spectrometry
Card, prepared fluorescence rubber particle has fluorescence property, and its percent grafting, excitation spectrum and transmitting
Peak wavelength and the red shift amplitude thereof of spectrum are shown in Table 1.
Comparative example 2
This comparative example is for fluorescence rubber particle that reference is described and preparation method thereof.
Prepare fluorescence rubber particle according to the method for embodiment 3, except for the difference that, be added without maleic acid
Acid anhydride, carries out fluorescence steady state test by gained fluorescence rubber particle, its excitation spectrum and the peak value of generation spectrum
Wavelength is shown in Table 1.
Embodiment 4
Fluorescence rubber particle that this embodiment provides for the present invention is described and preparation method thereof.
Fluorescence rubber particle is prepared, except for the difference that, by Carboxy powder rubber according to the method for embodiment 1
(middle petrochemical industry Beijing Chemical Research Institute produces the butylbenzene pyrrole powdered rubber of glue identical weight part, and the trade mark is
VP701, mean diameter is 200nm, and gel content is 91 weight %) substitute, test through fluorescent spectrometry
Card, prepared fluorescence rubber particle has fluorescence property, and its percent grafting, excitation spectrum and transmitting
Peak wavelength and the red shift amplitude thereof of spectrum are shown in Table 1.
Comparative example 3
This comparative example is for fluorescence rubber particle that reference is described and preparation method thereof.
Prepare fluorescence rubber particle according to the method for embodiment 4, except for the difference that, be added without maleic acid
Acid anhydride, carries out fluorescence steady state test by gained fluorescence rubber particle, its excitation spectrum and the peak value of emission spectrum
Wavelength is shown in Table 1.
Embodiment 5
Fluorescence rubber particle that this embodiment provides for the present invention is described and preparation method thereof.
Fluorescence rubber particle is prepared, except for the difference that, by acetone same volume according to the method for embodiment 4
Water substitute, maleic anhydride obtains maleic acid after being dissolved in water, and Carboxy powdered rubber
Addition makes maleic acid be 15:100 with the weight ratio of Carboxy powdered rubber, through fluorescence spectrum
Method is verified, prepared fluorescence rubber particle has a fluorescence property, and its percent grafting, excitation spectrum and
Peak wavelength and the red shift amplitude thereof of emission spectrum are shown in Table 1.
Embodiment 6
Fluorescence rubber particle that this embodiment provides for the present invention is described and preparation method thereof.
By the commercially available styrene-butadiene latex (Qilu Petrochemical produces, and the trade mark is db-50) that solid content is 45 weight %
5kg is placed in a container, and under agitation dropping Isooctyl acrylate monomer 75g, after being added dropwise to complete, continues to stir
Mixing 1 hour, afterwards with cobalt-60 radiosterilize, irradiation dose is 2.5Mrad, and close rate is 50Gy/min,
To the styrene-butadiene latex of cross-linking radiation, its solid content is 45 weight %, and mean diameter is 100nm, gel
Content is 87 weight %.
By 15g maleic anhydride (Tianjin recovery development in science and technology company limited, fusing point is 52-54 DEG C)
It is dissolved in 100mL deionized water, obtains the aqueous solution of maleic acid.Then by this maleic two
Aqueous acid interpolation is in the styrene-butadiene latex of above-mentioned cross-linking radiation of 45 weight % to 200g solid content,
And be uniformly mixed, then carrying out radiation grafting copolymerization reaction, irradiation dose used is 20kGy, spoke
Fluorescence butylbenzene powdered rubber it is dried to obtain according to graft polymerization reaction after completing.Gained fluorescence rubber particle is entered
Row fluorescence steady state test, this fluorescence rubber particle has fluorescence property, and its percent grafting, excitation spectrum
It is shown in Table 1 with the peak wavelength of emission spectrum.
Comparative example 4
This comparative example is for fluorescence rubber particle that reference is described and preparation method thereof.
By commercially available styrene-butadiene latex that 200g solid content is 45 weight %, (Qilu Petrochemical produces, and the trade mark is
Db-50) carrying out irradiation, irradiation dose is 20kGy, and gained fluorescence rubber particle is carried out fluorescence stable state
Test, the peak wavelength of its excitation spectrum and emission spectrum is shown in Table 1.
Table 1
As can be seen from the above results, when being grafted maleic acid on the rubber particles have cross-linked structure
After acid anhydride and/or maleic acid, the rubber particles obtained has fluorescent effect, and in its fluorescence spectrum
In excitation spectrum and emission spectrum all occur in that red shift, be therefore respectively provided with excellent in wider wave-length coverage
Different fluorescent effect, has widened its range.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. a fluorescence rubber particle, it is characterised in that described fluorescence rubber particle is for have crosslinking
The rubber particles that on the rubber particles of structure, grafted with maleic anhydride and/or maleic acid obtain.
Fluorescence rubber particle the most according to claim 1, wherein, described fluorescence rubber particle exists
Excitation spectrum and the peak wavelength of emission spectrum in fluorescence spectrum have maleic acid compared to non-grafted
The rubber particles of acid anhydride and/or maleic acid excitation spectrum in fluorescence spectrum and the peak value of emission spectrum
The wavelength at least 1nm of red shift independently of one another, preferably red shift at least 5nm, preferably red shift at least 10nm,
Further preferably red shift at least 20nm, more preferably at least red shift 30nm, most preferably at least red shift 50nm.
Fluorescence rubber particle the most according to claim 1, wherein, in described fluorescence rubber particle
Total percent grafting of maleic anhydride and maleic acid is more than 0.1%, preferably more than 1%, and more excellent
Elect more than 5% as, most preferably more than 10%.
4. according to the fluorescence rubber particle described in any one in claim 1-3, wherein, described tool
The mean diameter of the rubber particles of crosslinking structure is 0.02-1 μm, preferably 0.05-0.5 μm, more preferably
For 0.05-2 μm.
5. according to the fluorescence rubber particle described in any one in claim 1-3, wherein, described tool
The gel content of the rubber particles of crosslinking structure is more than 60 weight %, more than preferably 75 weight %,
More than more preferably 80 weight %.
6. according to the fluorescence rubber particle described in any one in claim 1-3, wherein, described tool
The rubber particles of crosslinking structure selected from natural rubber, butadiene-styrene rubber, carboxylic styrene-butadiene rubber, nitrile rubber,
Carboxy terminated nitrile rubber, polybutadiene rubber, silicone rubber, neoprene, acrylate rubber, butylbenzene pyrrole
Rubber, isoprene rubber, butyl rubber, thiorubber., Acrylester Butadiene Rubber, polyurethane rubber
At least one in glue, fluorubber and ethylene vinyl acetate rubber.
7. a preparation method for fluorescence rubber particle, the method is included in the rubber with cross-linked structure
Grafted with maleic anhydride and/or maleic acid on particle.
Method the most according to claim 7, wherein, maleic two in described fluorescence rubber particle
Total percent grafting of anhydride and maleic acid is more than 0.1%, preferably more than 1%, more preferably 5%
Above, most preferably more than 10%.
9. according to the method described in claim 7 or 8, wherein, there is the rubber grain of cross-linked structure
On son, the mode of grafted with maleic anhydride and/or maleic acid includes:
(1-1) there is the rubber particles of cross-linked structure containing maleic anhydride and/or along fourth by described
The solution of enedioic acid soaks so that described in have the rubber particles of cross-linked structure swelling, then carry out
Graft polymerization reaction, is finally dried the graft polymerization reaction product obtained；Or,
(1-2) by the rubber latex containing cross-linking radiation and maleic anhydride and/or maleic acid
Solution carry out graft polymerization reaction, finally the graft polymerization reaction product obtained is dried.
Method the most according to claim 9, wherein, described in there is the rubber particles of cross-linked structure
Mean diameter be 0.02-1 μm, preferably 0.05-0.5 μm, more preferably 0.05-2 μm.
11. methods according to claim 9, wherein, described in there is the rubber particles of cross-linked structure
Gel content be more than 60 weight %, more than preferably 75 weight %, more preferably 80 weight % with
On.
12. methods according to claim 9, wherein, described in there is the rubber particles of cross-linked structure
Selected from natural rubber, butadiene-styrene rubber, carboxylic styrene-butadiene rubber, nitrile rubber, carboxy terminated nitrile rubber, poly-fourth
Diene rubber, silicone rubber, neoprene, acrylate rubber, butadiene-styrene-vinyl pyridine rubber, isoprene rubber, fourth
Base rubber, thiorubber., Acrylester Butadiene Rubber, polyurethane rubber, fluorubber and ethylene-second
At least one in alkene acetas rubber.
13. methods according to claim 9, wherein, described elastomer latex is selected from natural rubber latex
Breast styrene butadiene rubber latex carboxylic styrene-butadiene rubber latex, nitrile rubber latex, carboxy terminated nitrile rubber latex,
Polybutadiene rubber latex, silicone rubber latex, Neoprene latex, acrylate rubber latex, butylbenzene
Pyrrole rubber latex, isoprene rubber latex, butyl rubber latex, thiorubber. latex, acrylate-fourth
Diene rubber latex, polyurethane rubber latex, fluoroelastomer latex and ethylene vinyl acetate rubber latex
In at least one.
14. methods according to claim 9, wherein, the grafting described in (1-1) and (1-2)
Polyreaction is radiation grafting copolymerization reaction, preferably high-energy ray irradiation graft polymerization reaction.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87108108A (en) * | 1986-10-29 | 1988-08-24 | 三井石油化学工业株式会社 | Thermoplastic elastomer composition |
| WO2007004762A1 (en) * | 2005-06-30 | 2007-01-11 | Cheil Industries Inc. | Polycarbonate resin composition with good light reflectance |
| CN101020734A (en) * | 2007-03-14 | 2007-08-22 | 四川大学 | Grafting modification process of regenerating waste butyl rubber |
| CN102174131A (en) * | 2011-02-17 | 2011-09-07 | 福建师范大学 | Rubber with fluorescence response to pH value and preparation method thereof |
| CN102174153A (en) * | 2011-02-11 | 2011-09-07 | 福建师范大学 | Method for preparing covalence-coordination co-crosslinking elastomer |
| CN103333377A (en) * | 2013-07-26 | 2013-10-02 | 武汉工程大学 | Water-swelling nitrile rubber and preparation method thereof |
| CN103509159A (en) * | 2013-09-23 | 2014-01-15 | 北京石油化工学院 | Grafting modification method for solution-polymerized styrene-butadiene rubber with low gel rate |
-
2015
- 2015-06-09 CN CN201510312455.1A patent/CN106279552A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87108108A (en) * | 1986-10-29 | 1988-08-24 | 三井石油化学工业株式会社 | Thermoplastic elastomer composition |
| WO2007004762A1 (en) * | 2005-06-30 | 2007-01-11 | Cheil Industries Inc. | Polycarbonate resin composition with good light reflectance |
| CN101020734A (en) * | 2007-03-14 | 2007-08-22 | 四川大学 | Grafting modification process of regenerating waste butyl rubber |
| CN102174153A (en) * | 2011-02-11 | 2011-09-07 | 福建师范大学 | Method for preparing covalence-coordination co-crosslinking elastomer |
| CN102174131A (en) * | 2011-02-17 | 2011-09-07 | 福建师范大学 | Rubber with fluorescence response to pH value and preparation method thereof |
| CN103333377A (en) * | 2013-07-26 | 2013-10-02 | 武汉工程大学 | Water-swelling nitrile rubber and preparation method thereof |
| CN103509159A (en) * | 2013-09-23 | 2014-01-15 | 北京石油化工学院 | Grafting modification method for solution-polymerized styrene-butadiene rubber with low gel rate |
Non-Patent Citations (2)
| Title |
|---|
| 廖双泉等: "《天然橡胶改性与应用》", 30 June 2007, 中国农业大学出版社 * |
| 朱根娣: "《现代检验医学仪器分析技术及应用》", 28 February 2005, 上海科学技术文献出版社 * |
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