CN103242594B - Polyalcohol hydrogel microballoon and preparation method thereof - Google Patents
Polyalcohol hydrogel microballoon and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of polyalcohol hydrogel microballoon and preparation method thereof, preparation method provided by the invention adopts a step emulsion polymerization that Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer are carried out copolymerization, obtains having the polyalcohol hydrogel microballoon of photoluminescent property after the multipolymer with temperature sensitive response obtained and rare earth compounding being reacted.Method provided by the invention obtains the polyalcohol hydrogel with Thermo-sensitive by single stage method letex polymerization, then this polyalcohol hydrogel and rare earth compounding is reacted, and can obtain desired product, and simple, the consuming time shortening of the method technique, production cost is lower.And polyalcohol hydrogel microballoon provided by the invention had both had the character of temperature response, there is again excellent fluorescent optics character, for multiple response intelligent material, and dispersed and be easy to carry out controlled self-assembly on hydrophilic base material in water, in the field such as optical material, biomedicine, there is important value.
Description
Technical field
The present invention relates to polymer arts, particularly relate to a kind of polyalcohol hydrogel microballoon and preparation method thereof.
Background technology
Intelligent material has can perception respond environment, as electricity, light, stress, strain, chemistry or nuclear radiation etc., and there is the type material of function executive capability, it can respond extraneous change, according to way selection and the control response of setting, react sensitiveer, in time and appropriate, after outside stimulus is eliminated, virgin state can be returned to rapidly.Although the history of intelligent material research and development is not long, because the performance of its uniqueness is not only used widely in industrial and agricultural production and daily life, and developing high-tech is played an important role.
In recent years, the research work of intelligent material is unprecedentedly active, wherein has the with the fastest developing speed of the novel high polymer hydrogel of intelligent behavior.This kind of macromolecule hydrogel energy perception ambient environmental conditions, as the change of temperature, soda acid, pressure, sound wave, electric field, magnetic field and light wave, simultaneously externally work done, its solvability, volume, shape, configuration etc. can with foreign objects rationality or chemical irritation reciprocally response change.Chemical irritation, as pH, metabolite, ion change the molecular force between polymer segment and solute; Another kind of physical property stimulation such as temperature, light, shearing force, pressure or electric field change kinetics energy and the Intermolecular Forces of segment.External stimulus changes the ionization power of polymer system, hydrogen bond or hydrophobic forces, thus causes reversible microphase-separated or self-assembly.This kind of sensitive intelligent response functional materials is applied all to some extent in medicament slow release, bioseparation, protein purification, industrial coating, oil-exploration, biology and membrane science, viscosity variation and emulsion-stabilizing etc.Due to their importance in scientific research and industrial production, be devoted to study various types of stimulus responsive polymers systematic research and get more and more.
Eighties of last century the nineties rises, the preparation of complex function hydrogel microsphere and construct micro-/micro-nano structure surface patterning technique and more and more paid close attention to, and becomes the important component part in numerous modern science and technology field.Hydrogel microsphere in the past for the assembling of aqueous phase micro-patterning has two kinds: one to be nano level microgel usually, be polymerized primarily of hydrogel monomer, but this microgel is dispersed in water, wetting ability is extremely strong, from polymerization system, washing is separated very difficult, is unfavorable for carrying out controlled patterning assembling; Two is adopt seeded emulsion polymerization two-step approach first to synthesize the hydrophobic seed microballoon of hard, core shell hydrogel glue microballoon is prepared again at the soft responsiveness aquagel shell of external sheath, but the preparation of two-step approach polymerization core shell hydrogel glue microballoon, purge process are loaded down with trivial details, expend time in length, production cost is higher, is unfavorable for application.
Summary of the invention
The object of the present invention is to provide a kind of polyalcohol hydrogel microballoon with photoluminescent property and preparation method thereof, procedure provided by the invention is simple, controlled, consuming time short.
The invention provides polyalcohol hydrogel microballoon, comprise the multipolymer with temperature sensitive response and the rare earth compounding being compounded in described multipolymer outside;
Described multipolymer is Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization monomer copolymerization are obtained by reacting;
Described rare earth compounding is rare earth chloride, oxalic acid compounds and pyridine compounds and their are obtained by reacting.
Preferably, described rare earth chloride is EuCl
3, TbCl
3, ErCl
3, SmCl
3and TmCl
3in one or more;
Described oxalic acid compounds is one or more in oxalic acid, ammonium oxalate and oxaminic acid;
Described soluble pyridinium compounds is one or more in picolinic acid, 2-picolinic acid, quinolinic acid and 3,4-pyridine dicarboxylic acid.
Preferably, described Thermo-sensitive polymerization single polymerization monomer is one or more in NIPA, N, N-acrylamide, vinyl caprolactam and the different acrylamide of 2-carboxyl;
Described hard hydrophobic polymeric monomer is one or more in vinylbenzene, fluorostyrene, glycidyl methacrylate and methyl methacrylate;
Described electronegative functional polymerization single polymerization monomer is one or more in methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid and fumaric acid.
Preferably, the mass ratio of the multipolymer and described rare earth compounding described in temperature sensitive response is (0.01 ~ 1): (1 ~ 30).
Preferably, the particle diameter of polyalcohol hydrogel microballoon is 80nm ~ 650nm.
The invention provides a kind of preparation method of polyalcohol hydrogel microballoon, comprise the following steps:
A) rare earth chloride, oxalic acid compounds and soluble pyridinium compounds are dissolved in water, add basic cpd wherein, the pH value of regulator solution is 6.5 ~ 7.0, obtains rare earth compounding;
B) by Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer mixing, add initiator wherein, carry out copolymerization, obtain the multipolymer with temperature sensitive response;
C) multipolymer with temperature sensitive response that the rare earth compounding described step a) obtained and described step b) obtain mixes, and obtains polyalcohol hydrogel microballoon after reaction;
The not order restriction of described step a) and step b).
Preferably, described rare earth chloride is EuCl
3, TbCl
3, ErCl
3, SmCl
3and TmCl
3in one or more;
Described oxalic acid compounds is one or more in oxalic acid, ammonium oxalate and oxaminic acid;
Described soluble pyridinium compounds is one or more in picolinic acid, 2-picolinic acid, quinolinic acid and 3,4-pyridine dicarboxylic acid.
Preferably, the mol ratio of described rare earth chloride, oxalic acid compounds and soluble pyridinium compounds is 1:(1 ~ 5): (1 ~ 5).
Preferably, described Thermo-sensitive polymerization single polymerization monomer is one or more in NIPA, N, N-acrylamide, vinyl caprolactam and the different acrylamide of 2-carboxyl;
Described hard hydrophobic polymeric monomer is one or more in vinylbenzene, fluorostyrene, glycidyl methacrylate and methyl methacrylate;
Described electronegative functional polymerization single polymerization monomer is one or more in methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid and fumaric acid.
Preferably, the mass ratio of described Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer is (0.5 ~ 8): (1.5 ~ 10): (0.1 ~ 3).
Preferably, in described step b), the temperature of copolymerization is 65 DEG C ~ 80 DEG C;
In described step b), the time of copolymerization is 5 hours ~ 10 hours.
Preferably, the temperature of reacting in described step c) is 30 DEG C ~ 65 DEG C;
The time of reacting in described step c) is 1 hour ~ 4 hours.
The invention provides a kind of polyalcohol hydrogel microballoon and preparation method thereof, preparation method provided by the invention comprises the following steps: a) rare earth chloride, oxalic acid compounds and soluble pyridinium compounds are dissolved in water, add basic cpd wherein, the pH value of regulator solution is 6.5 ~ 7.0, obtains rare earth compounding; B) by Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer mixing, add initiator wherein, carry out copolymerization, obtain the multipolymer with temperature sensitive response; C) multipolymer with temperature sensitive response that the rare earth compounding described step a) obtained and described step b) obtain mixes, and obtains the polyalcohol hydrogel microballoon with photoluminescent property after reaction; The not order restriction of described step a) and step b).Method provided by the invention is reacted with rare earth chloride and oxalic acid compounds and soluble pyridinium compounds, obtains the rare earth compounding with photoluminescent property; Adopt single stage method letex polymerization that Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer are carried out copolymerization, obtain the polyalcohol hydrogel with temperature response; Then the rare earth compounding obtained and polyalcohol hydrogel are reacted, obtain and not only there is fluorescence response, but also there is the polyalcohol hydrogel micro-sphere structure of temperature response.Method provided by the invention obtains the polyalcohol hydrogel with Thermo-sensitive by single stage method letex polymerization, then this polyalcohol hydrogel and rare earth compounding is reacted, and can obtain desired product.Simple, the consuming time shortening of method technique provided by the invention, production cost is lower.
Polyalcohol hydrogel microballoon provided by the invention comprises the multipolymer with temperature sensitive response and the rare earth compounding being compounded in described multipolymer outside; Described multipolymer is Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization monomer copolymerization are obtained by reacting; Described rare earth compounding is rare earth chloride, oxalic acid compounds and pyridine compounds and their are obtained by reacting.Polyalcohol hydrogel microballoon provided by the invention had both had the character of temperature response, there is again excellent fluorescent optics character, for multiple response intelligent material, and the multipolymer of polyalcohol hydrogel microballoon that the present invention obtains has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, can be dispersed and be easy to carry out controllability assembling on hydrophilic base material in water, in the field such as optical material, biomedicine, there is important value.Experimental result shows, polyalcohol hydrogel microballoon provided by the invention shows the character of good fluorescence with temperature regulation and control response, and namely can complete self-assembly under the condition of fixed temperature and humidity, obtains the assembling pattern of sequential 2 D.
Accompanying drawing explanation
Fig. 1 is the rare earth compounding fluorescent spectrum curve at different temperatures that the embodiment of the present invention 1 obtains;
Fig. 2 is the stereoscan photograph of the polyalcohol hydrogel microballoon that the embodiment of the present invention 1 obtains;
Fig. 3 is the photoluminescent property temperature response curve of the polyalcohol hydrogel microballoon that the embodiment of the present invention 1 obtains;
Fig. 4 is the stereoscan photograph of the patterning assembling that the embodiment of the present invention 1 obtains;
Fig. 5 is that the polyalcohol hydrogel Nano microsphere that the embodiment of the present invention 1 obtains piles up the sequential 2 D assembling fluorescence photo obtained in water.
Embodiment
The invention provides polyalcohol hydrogel microballoon, comprise the multipolymer with temperature sensitive response and the rare earth compounding being compounded in described multipolymer outside;
Described multipolymer is Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization monomer copolymerization are obtained by reacting;
Described rare earth compounding is rare earth chloride, oxalic acid compounds and pyridine compounds and their are obtained by reacting.
The invention provides a kind of polyalcohol hydrogel microballoon, comprise the multipolymer with temperature sensitive response and the rare earth compounding being compounded in described multipolymer outside.In the present invention, described multipolymer is Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization monomer reaction obtain, and this multipolymer has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic; Rare earth compounding is compounded in the outside of multipolymer, obtains having photoluminescent property and temperature sensitive controlled intelligent response polyalcohol hydrogel Nano microsphere.Polyalcohol hydrogel microballoon provided by the invention is multiple response intelligent material, has important value in the field such as optical material, biomedicine.
Polyalcohol hydrogel microballoon provided by the invention comprises the multipolymer with temperature sensitive response.The multipolymer in the present invention with temperature sensitive response is Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization monomer copolymerization are obtained by reacting.This multipolymer with temperature sensitive response has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, makes the polyalcohol hydrogel microballoon obtained have good mechanical stability, and easily carries out self-assembly.In the present invention, the preparation method described in the multipolymer of temperature sensitive response preferably includes following steps:
By Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer mixing, add initiator wherein, carry out copolymerization, obtain the multipolymer with temperature sensitive response.
Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer preferably mix by the present invention in water, obtain mixed monomer solution after deoxygenation; Described mixed monomer solution is heated, adds initiator wherein and carry out copolymerization, obtain the multipolymer with temperature sensitive response.The present invention does not have special restriction to the method that described Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer mix in water, can add Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer in water.The mixing solutions obtained stirs after preferably described Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer being mixed in water by the present invention, and passes into nitrogen discharge oxygen wherein, obtains mixed monomer solution.In the present invention, described Thermo-sensitive polymerization single polymerization monomer is preferably NIPA (NIPAM), N, one or more in N-acrylamide (DEAAM), vinyl caprolactam (VCL) and the different acrylamide of 2-carboxyl (CIPAAM), be more preferably NIPA (NIPAM), N, one in N-acrylamide (DEAAM), vinyl caprolactam (VCL) and the different acrylamide of 2-carboxyl (CIPAAM), most preferably be NIPA (NIPAM) or N, N-acrylamide (DEAAM); Described hard hydrophobic polymeric monomer is preferably one or more in vinylbenzene (St), fluorostyrene (F-St), glycidyl methacrylate (GMA) or methyl methacrylate (MMA), be more preferably the one in vinylbenzene (St), fluorostyrene (F-St), glycidyl methacrylate (GMA) or methyl methacrylate (MMA), most preferably be vinylbenzene (St) or fluorostyrene (F-St); Described electronegative functional monomer is preferably one or more in methacrylic acid (HMA), vinylformic acid (AA), methylene-succinic acid (IA), toxilic acid (Maleic acid) and fumaric acid (Fumaric acid), is more preferably the one in methacrylic acid (HMA), vinylformic acid (AA), methylene-succinic acid (IA), toxilic acid (Maleicacid) and fumaric acid (Fumaric acid).In the present invention, the mass ratio of described Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer is preferably (0.5 ~ 8): (1.5 ~ 10): (0.1 ~ 3), be more preferably (1 ~ 6): (3 ~ 7): (0.5 ~ 2), be more preferably (2 ~ 5): (4 ~ 6): (1 ~ 1.5);
The method of the present invention to the stirring described in technique scheme does not have special restriction, adopt the technical scheme of stirring well known to those skilled in the art, in the present invention, the temperature of described stirring is preferably room temperature, the speed of described stirring is preferably 200 revs/min ~ 400 revs/min, is more preferably 250 revs/min ~ 350 revs/min; The present invention does not have special restriction to the described mode passing into nitrogen, adopt the technical scheme of logical nitrogen deoxygenation well known to those skilled in the art, in the present invention, described in pass into nitrogen time be preferably 10 minutes ~ 50 minutes, be more preferably 15 minutes ~ 40 minutes.
After obtaining mixed monomer solution, described mixed monomer solution heats by the present invention, carries out copolymerization after adding initiator wherein, obtains the multipolymer with temperature sensitive response.In the present invention, described initiator is preferably persulfuric acid compounds, peroxyboric acid compounds or percarbonic acid compounds, is more preferably Potassium Persulphate (K
2s
2o
8), ammonium persulphate ((NH
4)
2s
2o
8), Sodium peroxoborate (NaBO
34H
2o), SPC-D (2Na
2cO
33H
2o
2) and Sodium Persulfate (Na
2s
2o
8) in one or more.In the present invention, the mass ratio of described initiator and described Thermo-sensitive polymerization single polymerization monomer is preferably (0.05 ~ 0.5): (0.5 ~ 8), is more preferably (0.1 ~ 0.4): (1 ~ 6), most preferably is (0.2 ~ 0.3): (2 ~ 5).The present invention preferably adds initiator solution in described mixed monomer solution, carries out copolymerization.In the present invention, the mass concentration of described initiator solution is preferably (0.005 ~ 0.5) g/mL, is more preferably (0.01 ~ 0.04) g/mL, most preferably is (0.02 ~ 0.03) g/mL.After adding initiator, mixed monomer solution becomes milky emulsion gradually by clarifying.In the present invention, the temperature of described heating mixed monomer solution is preferably 65 DEG C ~ 80 DEG C, is more preferably 70 DEG C ~ 75 DEG C;
The present invention, after add initiator in mixed monomer solution, preferably keeps above-mentioned Heating temperature to carry out copolymerization, obtains the multipolymer with temperature sensitive response.The present invention preferably stirs in the process of carrying out copolymerization, the method of the present invention to described stirring does not have special restriction, adopt the technical scheme of stirring well known to those skilled in the art, in the present invention, the speed of described stirring is preferably 200 revs/min ~ 400 revs/min, is more preferably 250 revs/min ~ 350 revs/min.In the present invention, the time of described copolymerization is preferably 5 hours ~ 10 hours, is more preferably 6 hours ~ 9 hours, most preferably is 7 hours ~ 8 hours.
After completing described copolymerization, the present invention the reaction product obtained is down to room temperature and carry out filtering, centrifugal and washing.The present invention to described filtration, centrifugal and washing method there is no special restriction, adopt filtration well known to those skilled in the art, centrifugal and washing technical scheme.The present invention preferably with distilled water to the filtration product obtained centrifugal and washing 2 ~ 4 times, obtain the multipolymer with temperature response.
Polyalcohol hydrogel microballoon provided by the invention comprises the rare earth compounding being compounded in described multipolymer outside, and described rare earth compounding is rare earth chloride, oxalic acid compounds and pyridine compounds and their are obtained by reacting.In the present invention, the preparation method of described rare earth compounding preferably includes following steps:
Rare earth chloride, oxalic acid compounds and soluble pyridinium compounds are dissolved in water, add basic cpd wherein, the pH value of regulator solution is 6.5 ~ 7.0, obtains rare earth compounding.
Rare earth chloride containing crystal water, oxalic acid compounds and soluble pyridinium compounds preferably dissolve by the present invention in water, slowly drip the basic cpd aqueous solution wherein, adjust and keep the pH value of solution to be 6.5 ~ 7.0, obtaining rare earth compounding.In the present invention, described rare earth chloride is preferably EuCl
3, TbCl
3, ErCl
3, SmCl
3and TmCl
3in one or more, be more preferably EuCl
3, TbCl
3, SmCl
3and TmCl
3in one or more.When described rare earth chloride is EuCl
3time, the described rare earth chloride containing crystal water is preferably EuCl
36H2O, when described rare earth chloride is TbCl
3time, the described rare earth chloride containing crystal water is preferably TbCl
36H2O, when described rare earth chloride is ErCl
3time, the described rare earth chloride containing crystal water is preferably ErCl
36H
2o, when described rare earth chloride is SmCl
3time, the described rare earth chloride containing crystal water is preferably SmCl
36H
2o, when described rare earth chloride is TmCl
3time, the described rare earth chloride containing crystal water is preferably TmCl
36H
2o.In the present invention, described oxalic acid compounds is preferably one or more in oxalic acid (Oxalic acid), oxamide (Oxamide) and oxaminic acid (Oxamic acid); Described soluble pyridinium compounds be preferably in picolinic acid (Picolinic acid), 2-picolinic acid (2-Picolinic acid), quinolinic acid (Quinolinic acid) and cinchomeronic acid (Cinchomeronic acid) one or more; The kind of the present invention to described basic cpd does not have special restriction, the basic cpd for adjust ph well known to those skilled in the art can be adopted, in the present invention, described basic cpd is preferably oxyhydroxide, be more preferably sodium hydroxide, most preferably be aqueous sodium hydroxide solution; The volumetric molar concentration of described aqueous sodium hydroxide solution is preferably 0.01mol/L ~ 3mol/L, is more preferably 0.05mol/L ~ 2mol/L;
The speed of the present invention to described dropping alkaline compound solution does not have special restriction, and those skilled in the art according to the experience of adjusted to ph, can select suitable rate of addition.In the present invention, the mol ratio of described rare-earth chlorination compound, oxalic acid compounds and soluble pyridinium compounds is preferably 1:(1 ~ 5): (1 ~ 5), is more preferably 1:2:1.
In the present invention, the mass ratio of the multipolymer and described rare earth compounding described in temperature sensitive response is preferably (0.01 ~ 1): (1 ~ 30), is more preferably (0.02 ~ 0.08): (2 ~ 25).
The inner casing of polyalcohol hydrogel microballoon provided by the invention is the multipolymer with temperature sensitive response, rare earth compounding is compounded in the outside of described multipolymer, the described multipolymer with temperature sensitive response has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, can realize controlled self-assembly; And described rare earth compounding has very strong fluorescent emission performance, therefore, polyalcohol hydrogel microballoon provided by the invention had both had temperature response character, there is again excellent fluorescent optics characteristic, be that a kind of multiple response can only material, in the field such as optical material, biomedicine, there is important value.The particle diameter of polyalcohol hydrogel microballoon provided by the invention is preferably 80nm ~ 650nm.
The invention provides a kind of preparation method of polyalcohol hydrogel microballoon, comprise the following steps:
A) rare earth chloride, oxalic acid compounds and soluble pyridinium compounds are dissolved in water, add basic cpd wherein, the pH value of regulator solution is 6.5 ~ 7.0, obtains rare earth compounding;
B) by Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer mixing, add initiator wherein, carry out copolymerization, obtain the multipolymer with temperature sensitive response;
C) multipolymer with temperature sensitive response that the rare earth compounding described step a) obtained and described step b) obtain mixes, and obtains polyalcohol hydrogel microballoon after reaction;
The not order restriction of described step a) and step b).
Method provided by the invention adopts single stage method letex polymerization that Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer are carried out copolyreaction, obtains the microballoon with inner hard stability and outside hydrogel strongly hydrophilic dual structure; And then rare earth compounding and this microballoon are reacted, rare earth compounding compound is entered microballoon outside, obtain there is photoluminescent property and temperature sensitive controlled can only responsive polymer hydrogel Nano microsphere.Procedure provided by the invention is simply controlled, and shortening consuming time, reduces production cost.
The present invention is preferably according to the rare earth compounding that the method preparing rare earth compounding described in technique scheme prepares, preferably preparing the multipolymer with temperature sensitive response according to preparing the method with the multipolymer of temperature sensitive response described in technique scheme, not repeating them here.In the present invention, the process of the multipolymer prepared rare earth compounding and have temperature sensitive response does not sequentially limit.
Obtain rare earth compounding and there is temperature sensitive response multipolymer after, described rare earth compounding mixes with the multipolymer with temperature sensitive response by the present invention, obtains polyalcohol hydrogel microballoon after reaction.The multipolymer with temperature sensitive response obtained preferably joins and prepares in the reaction product of rare earth compounding by the present invention, and pass into nitrogen protection, stirring reaction obtains polyalcohol hydrogel microballoon.The method of the present invention to described stirring does not have special restriction, adopts the technical scheme of stirring well known to those skilled in the art, and in the present invention, described stirring is preferably magnetic agitation.The temperature of described reaction is preferably 30 DEG C ~ 65 DEG C, is more preferably 35 DEG C ~ 60 DEG C, most preferably is 40 DEG C ~ 55 DEG C; The time of described reaction is preferably 1 hour ~ 4 hours, is more preferably 2 hours ~ 3 hours.
The present invention preferably complete rare earth compounding and there is temperature sensitive response the reaction of multipolymer after, preferably the reaction product distilled water obtained is carried out centrifuge washing, obtains polyalcohol hydrogel microballoon dispersion emulsion.The method of the present invention to described centrifuge washing does not have special restriction, adopts the technical scheme of centrifuge washing well known to those skilled in the art, and in the present invention, the number of times of described centrifuge washing is preferably 2 ~ 4 times.
Polyalcohol hydrogel microballoon provided by the invention has controlled self-assembly behavior, preferably carries out self-assembly to polyalcohol hydrogel microballoon in accordance with the following methods, obtains having fluorescence sequential 2 D pattern:
Mixing solutions monocrystalline silicon piece being placed in the vitriol oil and hydrogen peroxide boils, cool the hydrophilic substrate that post rinsing obtains for assembling pattern;
The mask plate of predetermined pattern is placed on described substrate, then carries out hydrophobic pattern exposure-processed;
The polyalcohol hydrogel microballoon that preparation method described in polyalcohol hydrogel microballoon described in technique scheme or technique scheme obtains is placed on the substrate after exposure-processed, carries out self-assembly.
The present invention preferably adopts monocrystalline silicon piece as the substrate of self-assembly, and the size of the present invention to described monocrystalline silicon piece does not have special restriction, and those skilled in the art according to the needs of scientific research, production or other purposes, can select the monocrystalline silicon piece of suitable dimension.In the present invention, the diameter of described monocrystalline silicon piece is preferably 75mm ~ 150mm.In the present invention, the described vitriol oil is known to the skilled person the vitriol oil in meaning, can buy commercially available vitriol oil commodity; The mass concentration of described hydrogen peroxide is preferably 25% ~ 35%, is more preferably 30%, directly can buy commercially available hydrogen peroxide commodity and use; The volume of described mixing solutions is preferably 100mL ~ 300mL, is more preferably 120mL ~ 280mL, most preferably is 150mL ~ 250mL; In the present invention, the volume ratio of the described vitriol oil and hydrogen peroxide is preferably (5 ~ 8): (2 ~ 5), most preferably are 7:3.In the present invention, described in time of boiling be preferably 10 minutes ~ 30 minutes, be more preferably 15 minutes ~ 25 minutes.The monocrystalline silicon piece boiled preferably is cooled to room temperature by the present invention, then preferably carries out ultrasonic cleaning with deionized water, chloroform and ethanol, preferably dries up with nitrogen, obtains the hydrophilic substrate for assembling pattern.The method of the present invention to described ultrasonic cleaning does not have special restriction, adopts ultrasonic technical scheme well known to those skilled in the art; Those skilled in the art can according to the consumption of the size Selection ultrasonic cleaning deionized water of the monocrystalline silicon piece adopted, chloroform and ethanol, and in the present invention, the volume of described deionized water is preferably 10mL ~ 30mL, is more preferably 15mL ~ 25mL; The volume of described chloroform is preferably 10mL ~ 30mL, is more preferably 15mL ~ 25mL; The volume of described ethanol is preferably 10mL ~ 30mL, is more preferably 15mL ~ 25mL.
After obtaining the substrate for assembling pattern, the mask plate of predetermined pattern is placed on described substrate by the present invention, then carries out hydrophobic pattern exposure-processed.The present invention does not have special restriction to described mask plate, and those skilled in the art can select suitable mask plate according to required pattern.The present invention preferably adopts ultraviolet exposure machine to carry out hydrophobic pattern exposure-processed to described hydrophilic substrate, obtains hydrophobe substrate.The power of the ultraviolet lamp that described exposure-processed adopts is preferably 350W, and the time of described exposure-processed is preferably 30s ~ 150s, is more preferably 40s ~ 140s, most preferably is 50s ~ 130s.
After completing described exposure-processed, the substrate after exposure-processed preferably cuts by the present invention.In the present invention, the length of the substrate after described cutting is preferably 5mm ~ 50mm, is more preferably 10mm ~ 45mm, most preferably is 15mm ~ 40mm; The money of the substrate after described cutting is preferably 5mm ~ 50mm, is more preferably 10mm ~ 45mm, most preferably is 15mm ~ 40mm.
After completing the cutting to substrate, the polyalcohol hydrogel microballoon that described in the polyalcohol hydrogel microballoon that technique scheme obtains by the present invention or technique scheme, preparation method obtains is placed on the substrate after exposure-processed, the present invention preferably the direct polyalcohol hydrogel microballoon that preparation process is obtained dispersion emulsion drip on hydrophobe substrate, carry out self-assembly, the hydrogel of described polyalcohol hydrogel microballoon outside shows strong wetting ability, along with the volatilization of moisture, microballoon self-assembly in the hydrophilic region of substrate, obtains the orderly pattern of fluorescence large-area two-dimensional.Dropping preferably has the substrate of polyalcohol hydrogel microballoon dispersion emulsion to be placed in climatic chamber to carry out self-assembly by the present invention, and in the present invention, the temperature of described self-assembly is preferably 2 DEG C ~ 30 DEG C, is more preferably 5 DEG C ~ 25 DEG C; The relative humidity of described self-assembly is preferably 60% ~ 95%RH, is more preferably 65% ~ 90%RH, most preferably is 70% ~ 85%RH.
The invention provides a kind of polyalcohol hydrogel microballoon and preparation method thereof, polyalcohol hydrogel microballoon provided by the invention comprises the multipolymer with temperature sensitive response and the rare earth compounding being compounded in described multipolymer outside; Described multipolymer is Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization monomer copolymerization are obtained by reacting; Described rare earth compounding is rare earth chloride, oxalic acid compounds and pyridine compounds and their are obtained by reacting.Polyalcohol hydrogel microballoon provided by the invention had both had the character of temperature response, there is again excellent fluorescent optics character, for multiple response intelligent material, and the multipolymer of polyalcohol hydrogel microballoon that the present invention obtains has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, can be dispersed and be easy to carry out controllability assembling on hydrophilic base material in water, in the field such as optical material, biomedicine, there is important value.
Preparation method provided by the invention comprises the following steps: a) rare earth chloride, oxalic acid compounds and soluble pyridinium compounds are dissolved in water, add basic cpd wherein, and the pH value of regulator solution is 6.5 ~ 7.0, obtains rare earth compounding; B) by Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer mixing, add initiator wherein, carry out copolymerization, obtain the multipolymer with temperature sensitive response; C) multipolymer with temperature sensitive response that the rare earth compounding described step a) obtained and described step b) obtain mixes, and obtains the polyalcohol hydrogel microballoon with photoluminescent property after reaction; The not order restriction of described step a) and step b).Method provided by the invention is reacted with rare earth chloride and oxalic acid compounds and soluble pyridinium compounds, obtains the rare earth compounding with photoluminescent property; Adopt single stage method letex polymerization that Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer are carried out copolymerization, obtain the polyalcohol hydrogel with temperature response; Then the rare earth compounding obtained and polyalcohol hydrogel are reacted, obtain and not only there is fluorescence response, but also there is the polyalcohol hydrogel micro-sphere structure of temperature response.Method provided by the invention obtains the polyalcohol hydrogel with Thermo-sensitive by single stage method letex polymerization, then this polyalcohol hydrogel and rare earth compounding is reacted, and can obtain desired product.Simple, the consuming time shortening of method technique provided by the invention, production cost is lower.
In order to further illustrate the present invention, below in conjunction with embodiment, polyalcohol hydrogel microballoon provided by the invention and preparation method thereof being described in detail, but they can not being interpreted as limiting the scope of the present invention.
The model of ultraviolet exposure machine is MDA-400M in the following embodiments.
Embodiment 1
Take 0.0366g EuCl
36H
2o, 0.018g oxamide and 0.0139g picolinic acid, be 1:2:1 Homogeneous phase mixing in redistilled water in molar ratio, slowly drip the NaOH aqueous solution that volumetric molar concentration is 0.5mol/L wherein, adjust and keep the pH value of solution to be 6.5 ~ 7.0, obtaining 30mL rare earth compounding Eu (Oxamide)
2the Picolinic aqueous solution; The rare earth compounding obtained is carried out fluorometric investigation by the present invention, result as shown in Figure 1, Fig. 1 is the rare earth compounding fluorescent spectrum curve at different temperatures that the embodiment of the present invention 1 obtains, the fluorescent spectrum curve obtained at 25 DEG C, 30 DEG C, 35 DEG C and 40 DEG C respectively, as seen from Figure 1, rare earth compounding prepared by the present invention has stable photoluminescent property, the fluorescent spectrum curve obtained under differing temps overlaps, and this illustrates that the photoluminescent property of rare earth compounding prepared by the present invention is not by the impact of temperature.
The Eu (Oxamide) that the present invention will obtain
2the Picolinic aqueous solution carries out fluorometric investigation, and result shows, the Eu (Oxamide) that the present invention obtains
2the Picolinic aqueous solution has very strong fluorescence emission spectrum;
In the reactor containing 150mL distilled water, add 2.5g NIPA, 4g St and 1g HMA, at room temperature stirs with the speed of 300 revs/min, then in the mixing solutions obtained, leads to nitrogen deoxygenation 20 minutes; The anaerobic mixing solutions obtained is warming up to 70 DEG C, then to adding 10mL containing 0.15g Na
2s
2o
8aqueous solution initiated polymerization, solution becomes milky emulsion gradually by clarifying, keep temperature 70 C, stirring velocity 300 revs/min, reacts 8 hours, is then down to room temperature and filters, obtaining polymer emulsion; By polymer emulsion distilled water centrifugal and washed product 3 times repeatedly, finally obtain PS/(PNIPAM-MA) polyalcohol hydrogel Nano microsphere emulsion 100mL;
Add 7mL PS/(PNIPAM-MA in the reactor) microballoon emulsion, then add 2mLEu (Oxamide)
2the Picolinic aqueous solution, adds distilled water and makes the cumulative volume of mixing solutions be 20mL, pass into nitrogen protection; magnetic agitation; react 2 hours at 34 DEG C, with distilled water centrifuge washing 3 times repeatedly, obtain and there is photoluminescent property and temperature sensitive controlled Eu (Oxamide)
2picolinic-PS/(PNIPAM-MA) dispersion emulsion 15mL; The polyalcohol hydrogel microballoon obtained is carried out sem test analysis by the present invention, result as shown in Figure 2, Fig. 2 is the stereoscan photograph of the polyalcohol hydrogel microballoon that the embodiment of the present invention 1 obtains, as seen from Figure 2, microspherulite diameter is about 318nm, has some polyalcohol hydrogel segments between microballoon; The polyalcohol hydrogel microballoon obtained is carried out fluorescence property test by the present invention, result as shown in Figure 3, Fig. 3 is the photoluminescent property temperature response curve of the polyalcohol hydrogel microballoon that the embodiment of the present invention 1 obtains, curve a ~ f is respectively the fluorescent spectrum curve obtained at 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C and 50 DEG C, as seen from Figure 3, the polyalcohol hydrogel microballoon that prepared by the present invention shows the character of good fluorescence with temperature regulation and control response.
Using diameter be the monocrystalline silicon piece of 90mm as substrate, in 98% vitriol oil and 30% hydrogen peroxide (volume ratio 7:3) mixing solutions, (150mL) boils 20 minutes; Carry out ultrasonic rinsing with 15mL deionized water, 15mL chloroform and 15mL ethanol respectively by after monocrystalline silicon piece cool to room temperature, then dry up the silicon chip obtaining surface hydrophilic with nitrogen; Choose the mask plate (length and width is 178mm) of required pattern, use ultraviolet exposure machine to carry out hydrophobic pattern exposure-processed to silicon chip, UV lamp power is 350W, and the treatment time is 50 seconds;
After completing exposure-processed, patterned substrate is cut by the present invention: long for 10mm, wide be 10mm; The Eu (Oxamide) that technique scheme is obtained
2picolinic-PS/ (PNIPAM-MA) emulsion 0.8mL drips in hydrophobe pattern wafers, in climatic chamber, control envrionment temperature 10 DEG C, relative humidity is 60%RH, impel microballoon outside hydrogel performance strongly hydrophilic, along with the volatilization of moisture, microballoon is assembled in on-chip hydrophilic region, obtains the orderly pattern of fluorescence large-area two-dimensional.The pattern obtained is carried out sem test by the present invention, result as shown in Figure 4, Fig. 4 is the stereoscan photograph of the patterning assembling that the embodiment of the present invention 1 obtains, as seen from Figure 4, in polyalcohol hydrogel microballoon provided by the invention, the outside hydrogel segment of microballoon shows as wetting ability, carries out aggregately stacked, form orderly pattern at hydrophilic region; The present invention carries out photoluminescent property detection by assembling the pattern obtained, result as shown in Figure 5, Fig. 5 is that the polyalcohol hydrogel Nano microsphere that the embodiment of the present invention 1 obtains piles up the sequential 2 D assembling fluorescence photo obtained in water, can see obvious two-dimensional and periodic fluorescent bands by Fig. 5, this fluorescent bands is red.
Embodiment 2:
Take 0.0187g TbCl
36H
2o, 0.089g Oxamic acid, 0.0836g Cinchomeronicacid, 1:2:1 Homogeneous phase mixing in redistilled water in molar ratio, slowly drip the NaOH aqueous solution that volumetric molar concentration is 0.1mol/L wherein, adjust and keep solution ph to be 6.5 ~ 7.0, obtaining 25mLTb (Oxamic)
2the Cinchomeronic aqueous solution;
The Tb (Oxamic) that the present invention will obtain
2the Cinchomeronic aqueous solution carries out fluorometric investigation, and result shows, Tb (Oxamic) prepared by the present invention
2the Cinchomeronic aqueous solution has very hyperfluorescenceZeng Yongminggaoyingguang emmission spectrum;
In the reactor containing 200mL distilled water, add 5g VCL, 8g GMA and 1.5g Maleicacid, stir with the speed of 350 revs/min under room temperature, logical nitrogen deoxygenation 30 minutes in the mixing solutions obtained; The anaerobic mixing solutions obtained is warming up to 75 DEG C, then adds 10mL wherein containing 0.1gNaBO
34H
2the aqueous solution initiated polymerization of O, solution becomes milky emulsion gradually by clarifying, and keep temperature 75 DEG C, stirring velocity 350 revs/min, reacts 7 hours, be then down to room temperature and filter, obtaining polymer emulsion.By polymer emulsion distilled water centrifugal and washed product 3 times repeatedly, finally obtain PGMA/(PVCL-Maleic) polyalcohol hydrogel Nano microsphere emulsion 150mL;
PGMA/ (PVCL-Maleic) the polyalcohol hydrogel Nano microsphere that the present invention prepares has good temperature-sensing property;
Add PGMA/ (PVCL-Maleic) microballoon emulsion prepared by 8mL technique scheme in the reactor, then add Tb (Oxamic) prepared by technique scheme wherein
2cinchomeronic aqueous solution 4mL, then add distilled water wherein and make cumulative volume be 20mL, pass into nitrogen protection; magnetic agitation; react 3 hours at 30 DEG C, with distilled water centrifuge washing 3 times repeatedly, obtain and there is photoluminescent property and temperature sensitive controlled Tb (Oxamic)
2cinchomeronic-PGMA/(PVCL-Maleic) dispersion emulsion 20mL, microspherulite diameter is about 389nm;
Using diameter be the monocrystalline silicon piece of 100mm as substrate, in 98% vitriol oil and 30% hydrogen peroxide (volume ratio 7:3) mixing solutions, (200mL) boils 25 minutes; Carry out ultrasonic rinsing by after monocrystalline silicon piece cool to room temperature respectively with 20mL deionized water, 20mL chloroform and 20mL ethanol, then dry up the silicon chip obtaining surface hydrophilic with nitrogen; Choose the mask plate (length and width is 178mm) of required pattern, use ultraviolet exposure machine to carry out hydrophobic pattern exposure-processed to silicon chip, UV lamp power 350W, the time of exposure-processed is 80 seconds;
After completing exposure-processed, patterned substrate is cut by the present invention: long for 25mm, wide be 15mm; Tb (Oxamic) prepared by technique scheme
2cinchomeronic-PGMA/ (PVCL-Maleic) emulsion 1.5mL drips in hydrophobe pattern wafers, in climatic chamber, control envrionment temperature 2 DEG C, relative humidity is 95%RH, impel microballoon outside hydrogel performance strongly hydrophilic, along with the volatilization of moisture, microballoon is assembled in on-chip hydrophilic region, obtains the orderly pattern of fluorescence large-area two-dimensional.
Embodiment 3:
Take 0.0037g SmCl
36H
2o, 0.0018g Oxamide and 0.0012g2-Picolinic, 1:2:1 Homogeneous phase mixing in redistilled water in molar ratio, slowly drip the NaOH aqueous solution that volumetric molar concentration is 0.01mol/L wherein, adjust and keep solution ph to be 6.5 ~ 7.0, obtain Sm (Oxamide)
2(2-Picolinic) aqueous solution 10mL;
The Sm (Oxamide) that the present invention will obtain
2(2-Picolinic) aqueous solution carries out fluorometric investigation, and result shows, Sm (Oxamide) prepared by the present invention
2(2-Picolinic) aqueous solution has very hyperfluorescenceZeng Yongminggaoyingguang transmitting;
In the reactor containing 80mL distilled water, add 0.5g DEAAM, 1.5g F-St and 0.1gAA, stir with the speed of 400 revs/min under room temperature, logical nitrogen deoxygenation 15 minutes in the mixing solutions obtained; The anaerobic mixing solutions obtained is warming up to 65 DEG C, then adds 10mL wherein containing 0.5gK
2s
2o
8aqueous solution initiated polymerization, solution becomes milky emulsion gradually by clarifying, keep temperature 65 DEG C, stirring velocity 400 revs/min, reacts 5 hours, is then down to room temperature and filters, obtaining polymer emulsion.By polymer emulsion distilled water centrifugal and washed product 2 times repeatedly, finally obtain PFSt/ (PDEAAM-AA) polyalcohol hydrogel Nano microsphere emulsion 30mL;
PFSt/ (PDEAAM-AA) polyalcohol hydrogel that the present invention prepares
Add PFSt/ (PDEAAM-AA) microballoon emulsion prepared by 5mL technique scheme in the reactor, and then add Sm (Oxamide) prepared by technique scheme wherein
2(2-Picolinic) aqueous solution 1mL, then add distilled water wherein and make cumulative volume be 20mL, pass into nitrogen protection; magnetic agitation; react 1 hour at 65 DEG C, with distilled water centrifuge washing 2 times repeatedly, obtain and there is photoluminescent property and temperature sensitive controlled Sm (Oxamide)
2(2-Picolinic)-PFSt/ (PDEAAM-AA) dispersion emulsion 5mL, microspherulite diameter is about 97nm;
Using diameter be the monocrystalline silicon piece of 75mm as substrate, in 98% vitriol oil and 30% hydrogen peroxide (volume ratio 7:3) mixing solutions, (100mL) boils 10 minutes; Carry out ultrasonic rinsing by after monocrystalline silicon piece cool to room temperature respectively with 10mL deionized water, 10mL chloroform and 10mL ethanol, then dry up the silicon chip obtaining surface hydrophilic with nitrogen;
Choose the mask plate (length and width is 178mm) of required pattern, use ultraviolet exposure machine to carry out hydrophobic pattern exposure-processed to silicon chip, UV lamp power is 350W, and the time of exposure-processed is 30 seconds;
After completing exposure-processed, patterned substrate is cut by the present invention: long 5mm, wide 5mm.Sm (Oxamide) prepared by technique scheme
2(2-Picolinic)-PFSt/ (PDEAAM-AA) emulsion 0.5mL drips in hydrophobe pattern wafers, in climatic chamber, control envrionment temperature 20 DEG C, relative humidity is 85%RH, impel microballoon outside hydrogel performance strongly hydrophilic, along with the volatilization of moisture, microballoon is assembled in on-chip hydrophilic region, obtains the orderly pattern of fluorescence large-area two-dimensional.
Embodiment 4:
Take 0.384g TmCl
36H
2o, 0.18g Oxalic acid and 0.167g Quinolinic acid, 1:2:1 Homogeneous phase mixing in redistilled water in molar ratio, slowly drip the NaOH aqueous solution that volumetric molar concentration is 3mol/L wherein, adjust and keep the pH value of solution to be 6.5 ~ 7.0, obtain Tm (Oxalic)
2quinolinic aqueous solution 50mL;
The present invention detects the Tm (Oxalic) obtained
2the fluorescence property of the Quinolinic aqueous solution, result shows, the Tm (Oxalic) that the present invention prepares
2the Quinolinic aqueous solution has very hyperfluorescenceZeng Yongminggaoyingguang and launches;
In the reactor containing 250mL distilled water, add 8g CIPAAM, 10g MMA and 3g IA, at room temperature stir with the speed of 200 revs/min, logical nitrogen deoxygenation 40 minutes in the mixing solutions obtained; The anaerobic mixing solutions obtained is warming up to 80 DEG C, then adds 10mL wherein containing 0.05g (NH
4)
2s
2o
8aqueous solution initiated polymerization, solution becomes milky emulsion gradually by clarifying, keep temperature 80 DEG C, stirring velocity 200 revs/min, reacts 10 hours, is then down to room temperature and filters, obtaining polymer emulsion.By polymer emulsion distilled water centrifugal and washed product 4 times repeatedly, finally obtain PMMA/ (PCIPAAM-IA) polyalcohol hydrogel Nano microsphere emulsion 200mL;
PMMA/ (PCIPAAM-IA) the polyalcohol hydrogel Nano microsphere that the present invention prepares has good temperature-sensing property;
Add PMMA/ (PCIPAAM-IA) microballoon emulsion prepared by 10mL technique scheme in the reactor, in reaction vessel, then add Tm (Oxalic) prepared by technique scheme
2quinolinic aqueous solution 5mL, then add distilled water wherein and make cumulative volume be 20mL, pass into nitrogen protection; magnetic agitation; react 4 hours at 50 DEG C, with distilled water centrifuge washing 4 times repeatedly, obtain and there is photoluminescent property and temperature sensitive controlled Tm (Oxalic)
2quinolinic-PMMA/ (PCIPAAM-IA) dispersion emulsion 30mL, microspherulite diameter is about 602nm;
Using diameter be the monocrystalline silicon piece of 150mm as substrate, in 98% vitriol oil and 30% hydrogen peroxide (volume ratio 7:3) mixing solutions, (300mL) boils 30 minutes; Carry out ultrasonic rinsing by after monocrystalline silicon piece cool to room temperature respectively with 30mL deionized water, 30mL chloroform and 30mL ethanol, then dry up the silicon chip obtaining surface hydrophilic with nitrogen;
Choose the mask plate (length and width is 178mm) of required pattern, use ultraviolet exposure machine to carry out hydrophobic pattern exposure-processed to silicon chip, UV lamp power is 350W, and the time of exposure-processed is 150 seconds;
After completing exposure-processed, patterned substrate is cut by the present invention: long 50mm, wide 50mm.Tm (Oxalic) prepared by technique scheme
2quinolinic-PMMA/ (PCIPAAM-IA) emulsion 5mL drips in hydrophobe pattern wafers, in climatic chamber, control envrionment temperature 30 DEG C, relative humidity is 70%RH, impel microballoon outside hydrogel performance strongly hydrophilic, along with the volatilization of moisture, microballoon is assembled in on-chip hydrophilic region, obtains the orderly pattern of fluorescence large-area two-dimensional.
As seen from the above embodiment, the invention provides a kind of polyalcohol hydrogel microballoon and preparation method thereof, polyalcohol hydrogel microballoon provided by the invention comprises the multipolymer with temperature sensitive response and the rare earth compounding being compounded in described multipolymer outside; Described multipolymer is Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization monomer copolymerization are obtained by reacting; Described rare earth compounding is rare earth chloride, oxalic acid compounds and pyridine compounds and their are obtained by reacting.Polyalcohol hydrogel microballoon provided by the invention had both had the character of temperature response, there is again excellent fluorescent optics character, for multiple response intelligent material, and the multipolymer of polyalcohol hydrogel microballoon that the present invention obtains has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, can be dispersed and be easy to carry out controllability assembling on hydrophilic base material in water, in the field such as optical material, biomedicine, there is important value.
Preparation method provided by the invention comprises the following steps: a) rare earth chloride, oxalic acid compounds and soluble pyridinium compounds are dissolved in water, add basic cpd wherein, and the pH value of regulator solution is 6.5 ~ 7.0, obtains rare earth compounding; B) by Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer mixing, add initiator wherein, carry out copolymerization, obtain the multipolymer with temperature sensitive response; C) multipolymer with temperature sensitive response that the rare earth compounding described step a) obtained and described step b) obtain mixes, and obtains the polyalcohol hydrogel microballoon with photoluminescent property after reaction; The not order restriction of described step a) and step b).Method provided by the invention is reacted with rare earth chloride and oxalic acid compounds and soluble pyridinium compounds, obtains the rare earth compounding with photoluminescent property; Adopt single stage method letex polymerization that Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer are carried out copolymerization, obtain the polyalcohol hydrogel with temperature response; Then the rare earth compounding obtained and polyalcohol hydrogel are reacted, obtain and not only there is fluorescence response, but also there is the polyalcohol hydrogel micro-sphere structure of temperature response.Method provided by the invention obtains the polyalcohol hydrogel with Thermo-sensitive by single stage method letex polymerization, then this polyalcohol hydrogel and rare earth compounding is reacted, and can obtain desired product.Simple, the consuming time shortening of method technique provided by the invention, production cost is lower.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (12)
1. polyalcohol hydrogel microballoon, comprises the multipolymer with temperature sensitive response and the rare earth compounding being compounded in described multipolymer outside;
Described multipolymer adopts single stage method letex polymerization that Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer are carried out copolyreaction and obtains;
Described rare earth compounding is rare earth chloride, oxalic acid compounds and pyridine compounds and their are obtained by reacting.
2. polyalcohol hydrogel microballoon according to claim 1, is characterized in that, described rare earth chloride is EuCl
3, TbCl
3, ErCl
3, SmCl
3and TmCl
3in one or more;
Described oxalic acid compounds is one or more in oxalic acid, ammonium oxalate and oxaminic acid;
Described soluble pyridinium compounds is one or more in picolinic acid, 2-picolinic acid, quinolinic acid and 3,4-pyridine dicarboxylic acid.
3. polyalcohol hydrogel microballoon according to claim 1, is characterized in that, described Thermo-sensitive polymerization single polymerization monomer is one or more in NIPA, N, N-acrylamide, vinyl caprolactam and the different acrylamide of 2-carboxyl;
Described hard hydrophobic polymeric monomer is one or more in vinylbenzene, fluorostyrene, glycidyl methacrylate and methyl methacrylate;
Described electronegative functional polymerization single polymerization monomer is one or more in methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid and fumaric acid.
4. polyalcohol hydrogel microballoon according to claim 1, is characterized in that, described in there is the mass ratio of the multipolymer of temperature sensitive response and described rare earth compounding for (0.01 ~ 1): (1 ~ 30).
5. polyalcohol hydrogel microballoon according to claim 1, is characterized in that, the particle diameter of polyalcohol hydrogel microballoon is 80nm ~ 650nm.
6. a preparation method for polyalcohol hydrogel microballoon, comprises the following steps:
A) rare earth chloride, oxalic acid compounds and soluble pyridinium compounds are dissolved in water, add basic cpd wherein, the pH value of regulator solution is 6.5 ~ 7.0, obtains rare earth compounding;
B) by Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer mixing, add initiator wherein, carry out copolymerization, obtain the multipolymer with temperature sensitive response;
C) rare earth compounding described step a) obtained and described step b) multipolymer with temperature sensitive response that obtains mixes, and obtains polyalcohol hydrogel microballoon after reaction;
Described step a) and step b) not order restriction.
7. preparation method according to claim 6, is characterized in that, described rare earth chloride is EuCl
3, TbCl
3, ErCl
3, SmCl
3and TmCl
3in one or more;
Described oxalic acid compounds is one or more in oxalic acid, ammonium oxalate and oxaminic acid;
Described soluble pyridinium compounds is one or more in picolinic acid, 2-picolinic acid, quinolinic acid and 3,4-pyridine dicarboxylic acid.
8. preparation method according to claim 6, is characterized in that, the mol ratio of described rare earth chloride, oxalic acid compounds and soluble pyridinium compounds is 1:(1 ~ 5): (1 ~ 5).
9. preparation method according to claim 6, is characterized in that, described Thermo-sensitive polymerization single polymerization monomer is one or more in NIPA, N, N-acrylamide, vinyl caprolactam and the different acrylamide of 2-carboxyl;
Described hard hydrophobic polymeric monomer is one or more in vinylbenzene, fluorostyrene, glycidyl methacrylate and methyl methacrylate;
Described electronegative functional polymerization single polymerization monomer is one or more in methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid and fumaric acid.
10. the preparation method according to claim 6 or 9 any one, it is characterized in that, the mass ratio of described Thermo-sensitive polymerization single polymerization monomer, hard hydrophobic polymeric monomer and electronegative functional polymerization single polymerization monomer is (0.5 ~ 8): (1.5 ~ 10): (0.1 ~ 3).
11. preparation methods according to claim 6 or 9 any one, is characterized in that, described step b) in the temperature of copolymerization be 65 DEG C ~ 80 DEG C;
Described step b) in time of copolymerization be 5 hours ~ 10 hours.
12. preparation methods according to claim 6, is characterized in that, described step c) in reaction temperature be 30 DEG C ~ 65 DEG C;
Described step c) in reaction time be 1 hour ~ 4 hours.
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