CN103242594A - Polymer hydrogel microspheres and preparation method thereof - Google Patents
Polymer hydrogel microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention provides polymer hydrogel microspheres and a preparation method thereof. The preparation method comprises the following steps of: carrying out copolymerization reaction on a thermosensitive polymerized monomer, a hard hydrophobic polymerized monomer and a polymerized monomer with negative electricity functionality by adopting a one-step emulsion polymerization method; and reacting the obtained polymer with thermosensitive response with a rare earth complex to obtain the polymer hydrogel microspheres with fluorescence properties. According to the method, a polymer hydrogel with thermosensitivity is obtained through one-step method emulsion polymerization, and then the polymer hydrogel is used for reacting with the rare earth complex to obtain the needed product, so that the method is simple in process, the consumed time is shortened, and the production cost is relatively low. Moreover, the polymer hydrogel microspheres provided by the invention have a property of temperature response and good fluorescence optical properties, are intelligent materials with multi-responsiveness, can be uniformly dispersed in water, can be controllably and automatically assembled on a hydrophilic base material easily, and have important values in the fields of optical materials, biological medicine and the like.
Description
Technical field
The present invention relates to polymer arts, relate in particular to a kind of polyalcohol hydrogel microballoon and preparation method thereof.
Background technology
Intelligent material is but that environment is had the perception response, as electricity, light, stress, strain, chemistry or nuclear radiation etc., and the type material with function executive capability, it can respond extraneous the variation, select and control response according to the mode of setting, reaction is relatively sensitiveer, timely and appropriate, after outside stimulus is eliminated, can return to virgin state rapidly.Though the history of intelligent material research and development is not long, owing to its particular performances not only is being used widely aspect industrial and agricultural production and the 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 novel high polymer hydrogel with the fastest developing speed of intelligent behavior.This family macromolecule hydrogel energy perception ambient environmental conditions, variation as temperature, soda acid, pressure, sound wave, electric field, magnetic field and light wave, work done simultaneously externally, its solvability, volume, shape, configuration etc. can be with the foreign objects rational faculty or chemical irritations and reciprocal response change.Chemical irritation changes the molecular force between polymer segment and solute as pH, metabolite, ion; Another kind of physical property stimulates kinetics energy and the Intermolecular Forces that changes segment as temperature, light, shearing force, pressure or electric field.External stimulus changes ionization power, hydrogen bond or the hydrophobic interaction power of polymer system, thereby causes reversible microphase-separated or self-assembly.The intelligent response functional materials of this class sensitivity is all used to some extent at medicament slow release, bioseparation, protein purification, industrial coating, oil-exploration, biology and aspects such as membrane science, viscosity variation and emulsion-stabilizing.Owing to their importance in scientific research and industrial production, it is more and more to be devoted to study various types of stimulus responsive polymers systematic researches.
The eighties of last century the nineties rises, and the preparation of complex function hydrogel microsphere and construct little/micro-nano structure patterned surface technology and more and more paid close attention to becomes the important component part in numerous modern science and technology field.The hydrogel microsphere that in the past was used for the assembling of water micro-patterning has two kinds usually: the one, and the nano level microgel, mainly formed by the hydrogel monomer polymerization, yet this microgel evenly disperses in water, wetting ability is extremely strong, it is very difficult to wash separation from polymerization system, is unfavorable for carrying out controlled patterning assembling; The 2nd, adopt the earlier synthetic hydrophobic seed microballoon of hard of seeded emulsion polymerization two-step approach, coat soft responsiveness aquagel shell at skin again and prepare the nucleocapsid hydrogel microsphere, yet preparation, the purge process of two-step approach polymerization nucleocapsid hydrogel microsphere are loaded down with trivial details, length expends time in, production cost is higher, is unfavorable for using.
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, simple, controlled, the consuming time weak point of procedure provided by the invention.
The invention provides the polyalcohol hydrogel microballoon, comprise the multipolymer with temperature sensitive response and the rare earth compounding that is compounded in described multipolymer outside;
Described multipolymer is that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer copolymerization reaction obtain;
Described rare earth compounding is that rare earth chloride, oxalic acid compounds and pyridine compounds and their reaction obtain.
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 the oxaminic acid;
Described water-soluble pyridine compounds and their is one or more in picolinic acid, 2-picolinic acid, quinolinic acid and 3, the 4-pyridine dicarboxylic acid.
Preferably, described temperature sensitive property polymerization single polymerization monomer is N-N-isopropylacrylamide, N, one or more in N-diethyl acrylamide, ethene hexanolactam and the 2-carboxyl isopropyl alkene acid amides;
The hydrophobic polymerization single polymerization monomer of described hard is one or more in vinylbenzene, fluorostyrene, glycidyl methacrylate and the methyl methacrylate;
Described electronegative functional polymerization monomer is one or more in methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid and the fumaric acid.
Preferably, the mass ratio of described multipolymer with temperature sensitive response and described rare earth compounding 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, may further comprise the steps:
A) rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their are dissolved in water, to wherein adding basic cpd, the pH value of regulator solution is 6.5～7.0, obtains rare earth compounding;
B) temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are mixed, to wherein adding initiator, carry out copolymerization, obtain having the multipolymer of temperature sensitive response;
C) rare earth compounding that described step a) is obtained mixes with the multipolymer with temperature sensitive response that described step b) obtains, and obtains the polyalcohol hydrogel microballoon after the reaction;
Described step a) and step b) do not have sequence limit.
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 the oxaminic acid;
Described water-soluble pyridine compounds and their is one or more in picolinic acid, 2-picolinic acid, quinolinic acid and 3, the 4-pyridine dicarboxylic acid.
Preferably, the mol ratio of described rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their is 1:(1～5): (1～5).
Preferably, described temperature sensitive property polymerization single polymerization monomer is N-N-isopropylacrylamide, N, one or more in N-diethyl acrylamide, ethene hexanolactam and the 2-carboxyl isopropyl alkene acid amides;
The hydrophobic polymerization single polymerization monomer of described hard is one or more in vinylbenzene, fluorostyrene, glycidyl methacrylate and the methyl methacrylate;
Described electronegative functional polymerization monomer is one or more in methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid and the fumaric acid.
Preferably, the mass ratio of described temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer is (0.5～8): (1.5～10): (0.1～3).
Preferably, the temperature of copolymerization is 65 ℃～80 ℃ in the described step b);
The time of copolymerization is 5 hours～10 hours in the described step b).
Preferably, the temperature of reacting in the described step c) is 30 ℃～65 ℃;
The time of reacting in the 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 may further comprise the steps: a) rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their are dissolved in water, to wherein adding basic cpd, the pH value of regulator solution is 6.5～7.0, obtains rare earth compounding; B) temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are mixed, to wherein adding initiator, carry out copolymerization, obtain having the multipolymer of temperature sensitive response; C) rare earth compounding that described step a) is obtained mixes with the multipolymer with temperature sensitive response that described step b) obtains, and obtains having the polyalcohol hydrogel microballoon of photoluminescent property after the reaction; Described step a) and step b) do not have sequence limit.Method provided by the invention obtains having the rare earth compounding of photoluminescent property with rare earth chloride and oxalic acid compounds and the reaction of water-soluble pyridine compounds and their; Adopt the single stage method letex polymerization that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are carried out copolymerization, obtain having the polyalcohol hydrogel of temperature response; Then with the rare earth compounding that obtains and polyalcohol hydrogel reaction, obtained not only having fluorescence response, but also had the polyalcohol hydrogel micro-sphere structure of temperature response.The polyalcohol hydrogel that method provided by the invention obtains having temperature sensitive property by the single stage method letex polymerization with this polyalcohol hydrogel and rare earth compounding reaction, can obtain desired product again.Simple, the consuming time shortening of method technology provided by the invention, production cost is lower.
Polyalcohol hydrogel microballoon provided by the invention comprises the multipolymer with temperature sensitive response and is compounded in the rare earth compounding of described multipolymer outside; Described multipolymer is that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer copolymerization reaction obtain; Described rare earth compounding is that rare earth chloride, oxalic acid compounds and pyridine compounds and their reaction obtain.Polyalcohol hydrogel microballoon provided by the invention had both had the character of temperature response, has good fluorescent optics character again, be the multiple response intelligent material, and the multipolymer of the polyalcohol hydrogel microballoon that the present invention obtains has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, can in water, evenly disperse and be easy to carry out the controllability assembling at hydrophilic base material, have important value in fields such as optical material, biomedicines.Experimental result shows that polyalcohol hydrogel microballoon provided by the invention shows good fluorescence with the character of temperature adjusting response, and namely can finish self-assembly under the condition of fixed temperature and humidity, obtains the assembling pattern of sequential 2 D.
Description of drawings
The fluorescent spectrum curve of rare earth compounding under differing temps that Fig. 1 obtains for the embodiment of the invention 1;
The stereoscan photograph of the polyalcohol hydrogel microballoon that Fig. 2 obtains for the embodiment of the invention 1;
The photoluminescent property temperature response curve of the polyalcohol hydrogel microballoon that Fig. 3 obtains for the embodiment of the invention 1;
The stereoscan photograph of the patterning assembling that Fig. 4 obtains for the embodiment of the invention 1;
The polyalcohol hydrogel Nano microsphere that Fig. 5 obtains for the embodiment of the invention 1 is piled up the sequential 2 D assembling fluorescence photo that obtains in water.
Embodiment
The invention provides the polyalcohol hydrogel microballoon, comprise the multipolymer with temperature sensitive response and the rare earth compounding that is compounded in described multipolymer outside;
Described multipolymer is that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer copolymerization reaction obtain;
Described rare earth compounding is that rare earth chloride, oxalic acid compounds and pyridine compounds and their reaction obtain.
The invention provides a kind of polyalcohol hydrogel microballoon, comprise the multipolymer with temperature sensitive response and the rare earth compounding that is compounded in described multipolymer outside.In the present invention, described multipolymer is that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard 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 the multiple response intelligent material, has important value in fields such as optical material, biomedicines.
Polyalcohol hydrogel microballoon provided by the invention comprises the multipolymer with temperature sensitive response.Described multipolymer with temperature sensitive response is that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer copolymerization reaction obtain in the present invention.This multipolymer with temperature sensitive response has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, makes the polyalcohol hydrogel microballoon that obtains have mechanical stability preferably, and carries out self-assembly easily.In the present invention, described preparation method with multipolymer of temperature sensitive response preferably includes following steps:
Temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are mixed, to wherein adding initiator, carry out copolymerization, obtain having the multipolymer of temperature sensitive response.
The present invention preferably mixes temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer in water, obtain mixed monomer solution behind the deoxygenation; With described mixed monomer solution heating, carry out copolymerization to wherein adding initiator, obtain having the multipolymer of temperature sensitive response.The present invention does not have special restriction to the method that described temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer mix in water, can add temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer in water.The present invention after preferably described temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer being mixed in water stirs the mixing solutions that obtains, and feeds nitrogen discharge oxygen wherein, obtains mixed monomer solution.In the present invention, described temperature sensitive property polymerization single polymerization monomer is preferably N-N-isopropylacrylamide (NIPAM), N, in N-diethyl acrylamide (DEAAM), ethene hexanolactam (VCL) and the 2-carboxyl isopropyl alkene acid amides (CIPAAM) one or more, more preferably N-N-isopropylacrylamide (NIPAM), N, a kind of in N-diethyl acrylamide (DEAAM), ethene hexanolactam (VCL) and the 2-carboxyl isopropyl alkene acid amides (CIPAAM), most preferably be N-N-isopropylacrylamide (NIPAM) or N, N-diethyl acrylamide (DEAAM); The hydrophobic polymerization single polymerization monomer of described hard is preferably one or more in vinylbenzene (St), fluorostyrene (F-St), glycidyl methacrylate (GMA) or the methyl methacrylate (MMA), more preferably a kind of in vinylbenzene (St), fluorostyrene (F-St), glycidyl methacrylate (GMA) or the methyl methacrylate (MMA) most preferably is 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 the fumaric acid (Fumaric acid), more preferably a kind of in methacrylic acid (HMA), vinylformic acid (AA), methylene-succinic acid (IA), toxilic acid (Maleic acid) and the fumaric acid (Fumaric acid).In the present invention, the mass ratio of described temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer is preferably (0.5～8): (1.5～10): (0.1～3), more preferably (1～6): (3～7): (0.5～2), more preferably (2～5): (4～6): (1～1.5);
The present invention does not have special restriction to the described stirring method of technique scheme, adopt the technical scheme of stirring well known to those skilled in the art to get final product, in the present invention, the temperature of described stirring is preferably room temperature, the speed of described stirring is preferably 200 rev/mins～400 rev/mins, more preferably 250 rev/mins～350 rev/mins; The present invention does not have special restriction to the mode of described feeding nitrogen, adopt the technical scheme of logical nitrogen deoxygenation well known to those skilled in the art to get final product, in the present invention, the time of described feeding nitrogen is preferably 10 minutes～and 50 minutes, more preferably 15 minutes～40 minutes.
After obtaining mixed monomer solution, the present invention heats described mixed monomer solution, carries out copolymerization after wherein adding initiator, obtains having the multipolymer of temperature sensitive response.In the present invention, described initiator is preferably persulfuric acid compounds, peroxyboric acid compounds or percarbonic acid compounds, 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 temperature sensitive property polymerization single polymerization monomer is preferably (0.05～0.5): (0.5～8), 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, carry out copolymerization.In the present invention, the mass concentration of described initiator solution is preferably (0.005～0.5) g/mL, and 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 clarification.In the present invention, the temperature of described heating mixed monomer solution is preferably 65 ℃～80 ℃, more preferably 70 ℃～75 ℃;
The present invention preferably keeps above-mentioned Heating temperature to carry out copolymerization add initiator in mixed monomer solution after, obtains having the multipolymer of temperature sensitive response.The present invention preferably stirs in the process of carrying out copolymerization, the present invention does not have special restriction to described stirring method, adopt the technical scheme of stirring well known to those skilled in the art to get final product, in the present invention, the speed of described stirring is preferably 200 rev/mins～400 rev/mins, more preferably 250 rev/mins～350 rev/mins.In the present invention, the time of described copolymerization is preferably 5 hours～and 10 hours, more preferably 6 hours～9 hours, most preferably be 7 hours～8 hours.
After finishing described copolymerization, the present invention the reaction product that obtains is down to room temperature and filter, centrifugal and the washing.The present invention does not have special restriction to described filtration, method centrifugal and washing, adopts filtration well known to those skilled in the art, technical scheme centrifugal and washing to get final product.The present invention preferably with distilled water centrifugal and washing 2～4 times to the filtration product that obtains, obtains having the multipolymer of temperature response.
Polyalcohol hydrogel microballoon provided by the invention comprises the rare earth compounding that is compounded in described multipolymer outside, and described rare earth compounding is that rare earth chloride, oxalic acid compounds and pyridine compounds and their reaction obtain.In the present invention, the preparation method of described rare earth compounding preferably includes following steps:
Rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their are dissolved in water, and to wherein adding basic cpd, the pH value of regulator solution is 6.5～7.0, obtains rare earth compounding.
Rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their that the present invention preferably will contain crystal water dissolve in water, and slowly to wherein dripping the basic cpd aqueous solution, adjusting and keeping the pH value of solution is 6.5～7.0, obtains 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, EuCl more preferably
3, TbCl
3, SmCl
3And TmCl
3In one or more.When described rare earth chloride is EuCl
3The time, the described rare earth chloride that contains crystal water is preferably EuCl
36H2O is when described rare earth chloride is TbCl
3The time, the described rare earth chloride that contains crystal water is preferably TbCl
36H2O is when described rare earth chloride is ErCl
3The time, the described rare earth chloride that contains crystal water is preferably ErCl
36H
2O is when described rare earth chloride is SmCl
3The time, the described rare earth chloride that contains crystal water is preferably SmCl
36H
2O is when described rare earth chloride is TmCl
3The time, the described rare earth chloride that contains 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 the oxaminic acid (Oxamic acid); Described water-soluble pyridine compounds and their is preferably one or more in picolinic acid (Picolinic acid), 2-picolinic acid (2-Picolinic acid), quinolinic acid (Quinolinic acid) and the cinchomeronic acid (Cinchomeronic acid); The present invention does not have special restriction to the kind of described basic cpd, can adopt the basic cpd for adjusting pH value well known to those skilled in the art to get final product, in the present invention, described basic cpd is preferably oxyhydroxide, more preferably sodium hydroxide most preferably is aqueous sodium hydroxide solution; The volumetric molar concentration of described aqueous sodium hydroxide solution is preferably 0.01mol/L～3mol/L, more preferably 0.05mol/L～2mol/L;
The present invention does not have special restriction to the speed of described dropping alkaline compound solution, and those skilled in the art can select suitable rate of addition according to the experience of adjusting the pH value.In the present invention, the mol ratio of described rare-earth chlorination compound, oxalic acid compounds and water-soluble pyridine compounds and their is preferably 1:(1～5): (1～5), more preferably 1:2:1.
In the present invention, described have the multipolymer of temperature sensitive response and the mass ratio of described rare earth compounding is preferably (0.01～1): (1～30), 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 dual structure that described multipolymer with temperature sensitive response has 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, has good fluorescent optics characteristic again, be that a kind of multiple response can only material, have significant values in fields such as optical material, biomedicines.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, may further comprise the steps:
A) rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their are dissolved in water, to wherein adding basic cpd, the pH value of regulator solution is 6.5～7.0, obtains rare earth compounding;
B) temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are mixed, to wherein adding initiator, carry out copolymerization, obtain having the multipolymer of temperature sensitive response;
C) rare earth compounding that described step a) is obtained mixes with the multipolymer with temperature sensitive response that described step b) obtains, and obtains the polyalcohol hydrogel microballoon after the reaction;
Described step a) and step b) do not have sequence limit.
Method provided by the invention adopts the single stage method letex polymerization that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are carried out copolyreaction, obtains having the microballoon of inner hard stability and outside hydrogel strongly hydrophilic dual structure; And then rare earth compounding and this microballoon reacted, enter the microballoon outside with rare earth compounding is compound, obtain having photoluminescent property and temperature sensitive controlled can only responsive polymer hydrogel Nano microsphere.Procedure simple controllable provided by the invention, shortening consuming time has reduced production cost.
The rare earth compounding that the present invention preferably prepares according to the described method for preparing rare earth compounding of technique scheme, preferably the method that has a multipolymer of temperature sensitive response according to the described preparation of technique scheme prepares the multipolymer with temperature sensitive response, does not repeat them here.In the present invention, the preparation rare earth compounding does not have sequence limit with the process with multipolymer of temperature sensitive response.
After obtaining rare earth compounding and having the multipolymer of temperature sensitive response, the present invention mixes described rare earth compounding with the multipolymer with temperature sensitive response, obtain the polyalcohol hydrogel microballoon after the reaction.The multipolymer with temperature sensitive response that the present invention preferably will obtain joins in the reaction product of preparation rare earth compounding, feeds nitrogen protection, and stirring reaction obtains the polyalcohol hydrogel microballoon.The present invention does not have special restriction to described stirring method, adopts the technical scheme of stirring well known to those skilled in the art to get final product, and in the present invention, described stirring is preferably magnetic agitation.The temperature of described reaction is preferably 30 ℃～65 ℃, more preferably 35 ℃～60 ℃, most preferably is 40 ℃～55 ℃; The time of described reaction is preferably 1 hour～and 4 hours, more preferably 2 hours～3 hours.
The present invention preferably after the reaction of finishing rare earth compounding and the multipolymer with temperature sensitive response, preferably carries out centrifuge washing with the reaction product that obtains with distilled water, obtains polyalcohol hydrogel microballoon dispersion emulsion.The present invention does not have special restriction to the method for described centrifuge washing, adopts the technical scheme of centrifuge washing well known to those skilled in the art to get final product, 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 in accordance with the following methods the polyalcohol hydrogel microballoon is carried out self-assembly, obtains having fluorescence sequential 2 D pattern:
Placing the mixing solutions of the vitriol oil and hydrogen peroxide to boil, cool off post rinsing monocrystalline silicon piece obtains for the hydrophilic substrate of assembling pattern;
The mask plate of predetermined pattern is placed on the described substrate, carry out the hydrophobic pattern exposure-processed then;
The polyalcohol hydrogel microballoon that the described polyalcohol hydrogel microballoon of technique scheme or the described preparation method of technique scheme are obtained places on the substrate after the exposure-processed, carries out self-assembly.
The present invention preferably adopts monocrystalline silicon piece as the substrate of self-assembly, and the present invention does not have special restriction to the size of described monocrystalline silicon piece, and those skilled in the art can select the monocrystalline silicon piece of suitable dimension according to the needs of scientific research, production or other purposes.In the present invention, the diameter of described monocrystalline silicon piece is preferably 75mm～150mm.In the present invention, the described vitriol oil is the vitriol oil on the meaning as well known to those skilled in the art, can buy commercially available vitriol oil commodity; The mass concentration of described hydrogen peroxide is preferably 25%～35%, and more preferably 30%, can directly buy commercially available hydrogen peroxide commodity and use; The volume of described mixing solutions is preferably 100mL～300mL, and 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, the described time of boiling is preferably 10 minutes～and 30 minutes, more preferably 15 minutes～25 minutes.The monocrystalline silicon piece that the present invention preferably will boil is cooled to room temperature, preferably carries out ultrasonic cleaning with deionized water, chloroform and ethanol then, preferably dries up with nitrogen, obtains the hydrophilic substrate for the assembling pattern.The present invention does not have special restriction to the method for described ultrasonic cleaning, adopts ultrasonic technical scheme well known to those skilled in the art to get final product; Those skilled in the art can be according to size Selection ultrasonic cleaning deionized water, chloroform and the consumption of ethanol of the monocrystalline silicon piece that adopts, and in the present invention, the volume of described deionized water is preferably 10mL～30mL, more preferably 15mL～25mL; The volume of described chloroform is preferably 10mL～30mL, more preferably 15mL～25mL; The volume of described ethanol is preferably 10mL～30mL, more preferably 15mL～25mL.
After obtaining the substrate for the assembling pattern, the present invention places the mask plate of predetermined pattern on the described substrate, carries out the hydrophobic pattern exposure-processed then.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 the uv-exposure machine that described hydrophilic substrate is carried out the hydrophobic pattern exposure-processed, obtains close and distant water base.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, and more preferably 40s～140s most preferably is 50s～130s.
After finishing described exposure-processed, the present invention preferably cuts the substrate after the exposure-processed.In the present invention, the length of the substrate after the described cutting is preferably 5mm～50mm, and more preferably 10mm～45mm most preferably is 15mm～40mm; The money of the substrate after the described cutting is preferably 5mm～50mm, and more preferably 10mm～45mm most preferably is 15mm～40mm.
After finishing the cutting to substrate, the polyalcohol hydrogel microballoon that the polyalcohol hydrogel microballoon that the present invention obtains technique scheme or the described preparation method of technique scheme obtain places on the substrate after the exposure-processed, the dispersion emulsion of the preferred polyalcohol hydrogel microballoon that directly preparation process is obtained of the present invention drips on close and distant water base, carry out self-assembly, the hydrogel of described polyalcohol hydrogel microballoon outside shows strong wetting ability, volatilization along with moisture, microballoon self-assembly in the hydrophilic region of substrate obtains the orderly pattern of fluorescence large-area two-dimensional.The present invention preferably has dropping the substrate of polyalcohol hydrogel microballoon dispersion emulsion to place to carry out self-assembly in the climatic chamber, and in the present invention, the temperature of described self-assembly is preferably 2 ℃～30 ℃, more preferably 5 ℃～25 ℃; The relative humidity of described self-assembly is preferably 60%～95%RH, and 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 is compounded in the rare earth compounding of described multipolymer outside; Described multipolymer is that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer copolymerization reaction obtain; Described rare earth compounding is that rare earth chloride, oxalic acid compounds and pyridine compounds and their reaction obtain.Polyalcohol hydrogel microballoon provided by the invention had both had the character of temperature response, has good fluorescent optics character again, be the multiple response intelligent material, and the multipolymer of the polyalcohol hydrogel microballoon that the present invention obtains has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, can in water, evenly disperse and be easy to carry out the controllability assembling at hydrophilic base material, have important value in fields such as optical material, biomedicines.
Preparation method provided by the invention may further comprise the steps: a) rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their are dissolved in water, to wherein adding basic cpd, the pH value of regulator solution is 6.5～7.0, obtains rare earth compounding; B) temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are mixed, to wherein adding initiator, carry out copolymerization, obtain having the multipolymer of temperature sensitive response; C) rare earth compounding that described step a) is obtained mixes with the multipolymer with temperature sensitive response that described step b) obtains, and obtains having the polyalcohol hydrogel microballoon of photoluminescent property after the reaction; Described step a) and step b) do not have sequence limit.Method provided by the invention obtains having the rare earth compounding of photoluminescent property with rare earth chloride and oxalic acid compounds and the reaction of water-soluble pyridine compounds and their; Adopt the single stage method letex polymerization that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are carried out copolymerization, obtain having the polyalcohol hydrogel of temperature response; Then with the rare earth compounding that obtains and polyalcohol hydrogel reaction, obtained not only having fluorescence response, but also had the polyalcohol hydrogel micro-sphere structure of temperature response.The polyalcohol hydrogel that method provided by the invention obtains having temperature sensitive property by the single stage method letex polymerization with this polyalcohol hydrogel and rare earth compounding reaction, can obtain desired product again.Simple, the consuming time shortening of method technology provided by the invention, production cost is lower.
In order to further specify the present invention, below in conjunction with embodiment polyalcohol hydrogel microballoon provided by the invention and preparation method thereof is described in detail, but they can not be interpreted as restriction to protection domain of the present invention.
The model of uv-exposure machine is MDA-400M in the following embodiments.
Embodiment 1
Take by weighing 0.0366g EuCl
36H
2O, 0.018g oxamide and 0.0139g picolinic acid, be that 1:2:1 evenly mixes in redistilled water in molar ratio, slowly to wherein dripping the NaOH aqueous solution that volumetric molar concentration is 0.5mol/L, adjusting and keeping the pH value of solution is 6.5～7.0, obtains 30mL rare earth compounding Eu (Oxamide)
2The Picolinic aqueous solution; The present invention carries out fluorometric investigation with the rare earth compounding that obtains, the result as shown in Figure 1, the fluorescent spectrum curve of rare earth compounding under differing temps that Fig. 1 obtains for the embodiment of the invention 1, it is respectively the fluorescent spectrum curve that under 25 ℃, 30 ℃, 35 ℃ and 40 ℃, obtains, as seen from Figure 1, the rare earth compounding of the present invention's preparation has stable fluorescence character, the fluorescent spectrum curve that obtains under the differing temps overlaps, and the photoluminescent property of the rare earth compounding of this explanation the present invention preparation is not subjected to Temperature Influence.
The present invention is with the Eu (Oxamide) that obtains
2The Picolinic aqueous solution carries out fluorometric investigation, and the result shows, the Eu that the present invention obtains (Oxamide)
2The Picolinic aqueous solution has very strong fluorescence emission spectrum;
Add 2.5g N-N-isopropylacrylamide in the reactor that contains 150mL distilled water, 4g St and 1g HMA at room temperature stir with 300 rev/mins speed, then logical nitrogen deoxygenation 20 minutes in the mixing solutions that obtains; The anaerobic mixing solutions that obtains is warming up to 70 ℃, contains 0.15g Na to adding 10mL again
2S
2O
8Aqueous solution initiated polymerization, solution becomes milky emulsion gradually by clarification, keeps 70 ℃ of temperature, 300 rev/mins of stirring velocitys were reacted 8 hours, were down to room temperature then and filtered, and obtained polymer emulsion; Polymer emulsion with distilled water centrifugal and washed product 3 times repeatedly, is finally obtained PS/(PNIPAM-MA) polyalcohol hydrogel Nano microsphere emulsion 100mL;
In reactor, add 7mL PS/(PNIPAM-MA) the microballoon emulsion, add 2mL Eu (Oxamide) then
2The Picolinic aqueous solution, adding distilled water, to make the cumulative volume of mixing solutions be 20mL, feeds nitrogen protection, magnetic agitation 34 ℃ of reactions 2 hours down, with distilled water centrifuge washing 3 times repeatedly, has obtained having photoluminescent property and temperature sensitive controlled Eu (Oxamide)
2Picolinic-PS/(PNIPAM-MA) dispersion emulsion 15mL; The present invention carries out the sem test analysis with the polyalcohol hydrogel microballoon that obtains, the result as shown in Figure 2, the stereoscan photograph of the polyalcohol hydrogel microballoon that Fig. 2 obtains for the embodiment of the invention 1, as seen from Figure 2, microspherulite diameter is about 318nm, and some polyalcohol hydrogel segments are arranged between the microballoon; The present invention carries out the fluorescence property test with the polyalcohol hydrogel microballoon that obtains, the result as shown in Figure 3, the photoluminescent property temperature response curve of the polyalcohol hydrogel microballoon that Fig. 3 obtains for the embodiment of the invention 1, curve a～f is respectively the fluorescent spectrum curve that obtains under 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃, as seen from Figure 3, the polyalcohol hydrogel microballoon of the present invention's preparation has shown good fluorescence with the character of temperature adjusting response.
With diameter be the monocrystalline silicon piece of 90mm as substrate, (150mL) boiled 20 minutes in 98% vitriol oil and 30% hydrogen peroxide (volume ratio 7:3) mixing solutions; To carry out ultrasonic rinsing with 15mL deionized water, 15mL chloroform and 15mL ethanol respectively behind the monocrystalline silicon piece cool to room temperature, dry up the silicon chip that obtains surface hydrophilic with nitrogen then; Choose the mask plate (length and width is 178mm) of required pattern, use the uv-exposure machine that silicon chip is carried out the hydrophobic pattern exposure-processed, UV lamp power is 350W, and the treatment time is 50 seconds;
After finishing exposure-processed, the present invention cuts patterned substrate: length is 10mm, the wide 10mm of being; The Eu (Oxamide) that technique scheme is obtained
2Picolinic-PS/ (PNIPAM-MA) emulsion 0.8mL drips on close and distant water patterns substrate, be 60%RH in 10 ℃ of climatic chamber inner control envrionment temperatures, relative humidity, impel the outside hydrogel performance of microballoon strongly hydrophilic, volatilization along with moisture, microballoon is assembled in on-chip hydrophilic region, obtains the orderly pattern of fluorescence large-area two-dimensional.The present invention carries out sem test with the pattern that obtains, the result as shown in Figure 4, the stereoscan photograph of the patterning assembling that Fig. 4 obtains for the embodiment of the invention 1, as seen from Figure 4, in the polyalcohol hydrogel microballoon provided by the invention, the outside hydrogel segment of microballoon shows as wetting ability, carries out aggregately stacked at hydrophilic region, forms orderly pattern; The pattern that the present invention obtains assembling carries out photoluminescent property and detects, the result as shown in Figure 5, the polyalcohol hydrogel Nano microsphere that Fig. 5 obtains for the embodiment of the invention 1 is piled up the sequential 2 D assembling fluorescence photo that obtains in water, can see tangible two-dimensional and periodic fluorescence band by Fig. 5, this fluorescence band is red.
Embodiment 2:
Take by weighing 0.0187g TbCl
36H
2O, 0.089g Oxamic acid, 0.0836g Cinchomeronic acid, 1:2:1 evenly mixes in redistilled water in molar ratio, slowly to wherein dripping the NaOH aqueous solution that volumetric molar concentration is 0.1mol/L, adjusting and keeping the pH value of solution value is 6.5～7.0, obtains 25mL Tb (Oxamic)
2The Cinchomeronic aqueous solution;
The present invention is with the Tb (Oxamic) that obtains
2The Cinchomeronic aqueous solution carries out fluorometric investigation, and the result shows, the Tb (Oxamic) of the present invention's preparation
2The Cinchomeronic aqueous solution has very hyperfluorescence emmission spectrum;
Add 5g VCL, 8g GMA and 1.5g Maleic acid in the reactor that contains 200mL distilled water, the speed with 350 rev/mins under the room temperature stirs, and leads to the nitrogen deoxygenation 30 minutes in the mixing solutions that obtains; The anaerobic mixing solutions that obtains is warming up to 75 ℃, contains 0.1g NaBO to wherein adding 10mL again
34H
2The aqueous solution initiated polymerization of O, solution becomes milky emulsion gradually by clarification, keeps 75 ℃ of temperature, and 350 rev/mins of stirring velocitys were reacted 7 hours, were down to room temperature then and filtered, and obtained polymer emulsion.Polymer emulsion with distilled water centrifugal and washed product 3 times repeatedly, is finally obtained PGMA/(PVCL-Maleic) polyalcohol hydrogel Nano microsphere emulsion 150mL;
The PGMA/ that the present invention prepares (PVCL-Maleic) polyalcohol hydrogel Nano microsphere has temperature-sensing property preferably;
PGMA/ (PVCL-Maleic) the microballoon emulsion that adds the preparation of 8mL technique scheme in reactor is again to the Tb (Oxamic) that wherein adds the technique scheme preparation
2Cinchomeronic aqueous solution 4mL, to make cumulative volume be 20mL to wherein adding distilled water again, feeds nitrogen protection; magnetic agitation; 30 ℃ of down reactions 3 hours, with distilled water centrifuge washing 3 times repeatedly, photoluminescent property and temperature sensitive controlled Tb (Oxamic) have been obtained having
2Cinchomeronic-PGMA/(PVCL-Maleic) dispersion emulsion 20mL, microspherulite diameter is about 389nm;
With diameter be the monocrystalline silicon piece of 100mm as substrate, (200mL) boiled 25 minutes in 98% vitriol oil and 30% hydrogen peroxide (volume ratio 7:3) mixing solutions; To carry out ultrasonic rinsing respectively with 20mL deionized water, 20mL chloroform and 20mL ethanol behind the monocrystalline silicon piece cool to room temperature, dry up the silicon chip that obtains surface hydrophilic with nitrogen then; Choose the mask plate (length and width is 178mm) of required pattern, use the uv-exposure machine that silicon chip is carried out the hydrophobic pattern exposure-processed, UV lamp power 350W, the time of exposure-processed is 80 seconds;
After finishing exposure-processed, the present invention cuts patterned substrate: length is 25mm, the wide 15mm of being; Tb (Oxamic) with the technique scheme preparation
2Cinchomeronic-PGMA/ (PVCL-Maleic) emulsion 1.5mL drips on close and distant water patterns substrate, be 95%RH in 2 ℃ of climatic chamber inner control envrionment temperatures, relative humidity, impel the outside hydrogel performance of microballoon strongly hydrophilic, volatilization along with moisture, microballoon is assembled in on-chip hydrophilic region, obtains the orderly pattern of fluorescence large-area two-dimensional.
Embodiment 3:
Take by weighing 0.0037g SmCl
36H
2O, 0.0018g Oxamide and 0.0012g2-Picolinic, 1:2:1 evenly mixes in redistilled water in molar ratio, slowly to wherein dripping the NaOH aqueous solution that volumetric molar concentration is 0.01mol/L, adjusting and keeping the pH value of solution value is 6.5～7.0, obtains Sm (Oxamide)
2(2-Picolinic) aqueous solution 10mL;
The present invention is with the Sm (Oxamide) that obtains
2(2-Picolinic) aqueous solution carries out fluorometric investigation, and the result shows, the Sm (Oxamide) of the present invention's preparation
2(2-Picolinic) aqueous solution has very hyperfluorescence emission;
Add 0.5g DEAAM, 1.5g F-St and 0.1g AA in the reactor that contains 80mL distilled water, the speed with 400 rev/mins under the room temperature stirs, and leads to the nitrogen deoxygenation 15 minutes in the mixing solutions that obtains; The anaerobic mixing solutions that obtains is warming up to 65 ℃, contains 0.5g K to wherein adding 10mL again
2S
2O
8Aqueous solution initiated polymerization, solution becomes milky emulsion gradually by clarification, keeps 65 ℃ of temperature, 400 rev/mins of stirring velocitys were reacted 5 hours, were down to room temperature then and filtered, and obtained polymer emulsion.Polymer emulsion with distilled water centrifugal and washed product 2 times repeatedly, is finally obtained PFSt/ (PDEAAM-AA) polyalcohol hydrogel Nano microsphere emulsion 30mL;
The PFSt/ that the present invention prepares (PDEAAM-AA) polyalcohol hydrogel
PFSt/ (PDEAAM-AA) the microballoon emulsion that in reactor, adds the preparation of 5mL technique scheme, and then to the Sm (Oxamide) that wherein adds the technique scheme preparation
2(2-Picolinic) aqueous solution 1mL, to make cumulative volume be 20mL to wherein adding distilled water again, feeds nitrogen protection; magnetic agitation; 65 ℃ of down reactions 1 hour, with distilled water centrifuge washing 2 times repeatedly, photoluminescent property and temperature sensitive controlled Sm (Oxamide) have been obtained having
2(2-Picolinic)-and PFSt/ (PDEAAM-AA) dispersion emulsion 5mL, microspherulite diameter is about 97nm;
With diameter be the monocrystalline silicon piece of 75mm as substrate, (100mL) boiled 10 minutes in 98% vitriol oil and 30% hydrogen peroxide (volume ratio 7:3) mixing solutions; To carry out ultrasonic rinsing respectively with 10mL deionized water, 10mL chloroform and 10mL ethanol behind the monocrystalline silicon piece cool to room temperature, dry up the silicon chip that obtains surface hydrophilic with nitrogen then;
Choose the mask plate (length and width is 178mm) of required pattern, use the uv-exposure machine that silicon chip is carried out the hydrophobic pattern exposure-processed, UV lamp power is 350W, and the time of exposure-processed is 30 seconds;
After finishing exposure-processed, the present invention cuts patterned substrate: long 5mm, wide 5mm.Sm (Oxamide) with the technique scheme preparation
2(2-Picolinic)-PFSt/ (PDEAAM-AA) emulsion 0.5mL drips on close and distant water patterns substrate, be 85%RH in 20 ℃ of climatic chamber inner control envrionment temperatures, relative humidity, impel the outside hydrogel performance of microballoon strongly hydrophilic, volatilization along with moisture, microballoon is assembled in on-chip hydrophilic region, obtains the orderly pattern of fluorescence large-area two-dimensional.
Embodiment 4:
Take by weighing 0.384g TmCl
36H
2O, 0.18g Oxalic acid and 0.167g Quinolinic acid, 1:2:1 evenly mixes in redistilled water in molar ratio, slowly to wherein dripping the NaOH aqueous solution that volumetric molar concentration is 3mol/L, adjusting and keeping the pH value of solution is 6.5～7.0, obtains Tm (Oxalic)
2Quinolinic aqueous solution 50mL;
The present invention detects the Tm (Oxalic) that obtains
2The fluorescence property of the Quinolinic aqueous solution, the result shows, the Tm that the present invention prepares (Oxalic)
2The Quinolinic aqueous solution has very hyperfluorescence emission;
Add 8g CIPAAM, 10g MMA and 3g IA in the reactor that contains 250mL distilled water, at room temperature stir with 200 rev/mins speed, logical nitrogen deoxygenation is 40 minutes in the mixing solutions that obtains; The anaerobic mixing solutions that obtains is warming up to 80 ℃, contains 0.05g (NH to wherein adding 10mL again
4)
2S
2O
8Aqueous solution initiated polymerization, solution becomes milky emulsion gradually by clarification, keeps 80 ℃ of temperature, 200 rev/mins of stirring velocitys were reacted 10 hours, were down to room temperature then and filtered, and obtained polymer emulsion.Polymer emulsion with distilled water centrifugal and washed product 4 times repeatedly, is finally obtained PMMA/ (PCIPAAM-IA) polyalcohol hydrogel Nano microsphere emulsion 200mL;
The PMMA/ that the present invention prepares (PCIPAAM-IA) polyalcohol hydrogel Nano microsphere has good temperature-sensing property;
PMMA/ (PCIPAAM-IA) the microballoon emulsion that adds the preparation of 10mL technique scheme in reactor adds the Tm (Oxalic) that technique scheme prepares then in reaction vessel
2Quinolinic aqueous solution 5mL, to make cumulative volume be 20mL to wherein adding distilled water again, feeds nitrogen protection, magnetic agitation 50 ℃ of reactions 4 hours down, with distilled water centrifuge washing 4 times repeatedly, has obtained having photoluminescent property and temperature sensitive controlled Tm (Oxalic)
2Quinolinic-PMMA/ (PCIPAAM-IA) dispersion emulsion 30mL, microspherulite diameter is about 602nm;
With diameter be the monocrystalline silicon piece of 150mm as substrate, (300mL) boiled 30 minutes in 98% vitriol oil and 30% hydrogen peroxide (volume ratio 7:3) mixing solutions; To carry out ultrasonic rinsing respectively with 30mL deionized water, 30mL chloroform and 30mL ethanol behind the monocrystalline silicon piece cool to room temperature, dry up the silicon chip that obtains surface hydrophilic with nitrogen then;
Choose the mask plate (length and width is 178mm) of required pattern, use the uv-exposure machine that silicon chip is carried out the hydrophobic pattern exposure-processed, UV lamp power is 350W, and the time of exposure-processed is 150 seconds;
After finishing exposure-processed, the present invention cuts patterned substrate: long 50mm, wide 50mm.Tm (Oxalic) with the technique scheme preparation
2Quinolinic-PMMA/ (PCIPAAM-IA) emulsion 5mL drips on close and distant water patterns substrate, be 70%RH in 30 ℃ of climatic chamber inner control envrionment temperatures, relative humidity, impel the outside hydrogel performance of microballoon strongly hydrophilic, volatilization along with 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 is compounded in the rare earth compounding of described multipolymer outside; Described multipolymer is that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer copolymerization reaction obtain; Described rare earth compounding is that rare earth chloride, oxalic acid compounds and pyridine compounds and their reaction obtain.Polyalcohol hydrogel microballoon provided by the invention had both had the character of temperature response, has good fluorescent optics character again, be the multiple response intelligent material, and the multipolymer of the polyalcohol hydrogel microballoon that the present invention obtains has the dual structure of inner hard stability and outside hydrogel strongly hydrophilic, can in water, evenly disperse and be easy to carry out the controllability assembling at hydrophilic base material, have important value in fields such as optical material, biomedicines.
Preparation method provided by the invention may further comprise the steps: a) rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their are dissolved in water, to wherein adding basic cpd, the pH value of regulator solution is 6.5～7.0, obtains rare earth compounding; B) temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are mixed, to wherein adding initiator, carry out copolymerization, obtain having the multipolymer of temperature sensitive response; C) rare earth compounding that described step a) is obtained mixes with the multipolymer with temperature sensitive response that described step b) obtains, and obtains having the polyalcohol hydrogel microballoon of photoluminescent property after the reaction; Described step a) and step b) do not have sequence limit.Method provided by the invention obtains having the rare earth compounding of photoluminescent property with rare earth chloride and oxalic acid compounds and the reaction of water-soluble pyridine compounds and their; Adopt the single stage method letex polymerization that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are carried out copolymerization, obtain having the polyalcohol hydrogel of temperature response; Then with the rare earth compounding that obtains and polyalcohol hydrogel reaction, obtained not only having fluorescence response, but also had the polyalcohol hydrogel micro-sphere structure of temperature response.The polyalcohol hydrogel that method provided by the invention obtains having temperature sensitive property by the single stage method letex polymerization with this polyalcohol hydrogel and rare earth compounding reaction, can obtain desired product again.Simple, the consuming time shortening of method technology provided by the invention, production cost is lower.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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. the polyalcohol hydrogel microballoon comprises the multipolymer with temperature sensitive response and the rare earth compounding that is compounded in described multipolymer outside;
Described multipolymer is that temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer copolymerization reaction obtain;
Described rare earth compounding is that rare earth chloride, oxalic acid compounds and pyridine compounds and their reaction obtain.
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 the oxaminic acid;
Described water-soluble pyridine compounds and their is one or more in picolinic acid, 2-picolinic acid, quinolinic acid and 3, the 4-pyridine dicarboxylic acid.
3. polyalcohol hydrogel microballoon according to claim 1 is characterized in that, described temperature sensitive property polymerization single polymerization monomer is N-N-isopropylacrylamide, N, one or more in N-diethyl acrylamide, ethene hexanolactam and the 2-carboxyl isopropyl alkene acid amides;
The hydrophobic polymerization single polymerization monomer of described hard is one or more in vinylbenzene, fluorostyrene, glycidyl methacrylate and the methyl methacrylate;
Described electronegative functional polymerization monomer is one or more in methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid and the fumaric acid.
4. polyalcohol hydrogel microballoon according to claim 1 is characterized in that, the mass ratio of described multipolymer with temperature sensitive response and described rare earth compounding is (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. the preparation method of a polyalcohol hydrogel microballoon may further comprise the steps:
A) rare earth chloride, oxalic acid compounds and water-soluble pyridine compounds and their are dissolved in water, to wherein adding basic cpd, the pH value of regulator solution is 6.5～7.0, obtains rare earth compounding;
B) temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer are mixed, to wherein adding initiator, carry out copolymerization, obtain having the multipolymer of temperature sensitive response;
C) rare earth compounding that described step a) is obtained mixes with the multipolymer with temperature sensitive response that described step b) obtains, and obtains the polyalcohol hydrogel microballoon after the reaction;
Described step a) and step b) do not have sequence limit.
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 the oxaminic acid;
Described water-soluble pyridine compounds and their is one or more in picolinic acid, 2-picolinic acid, quinolinic acid and 3, the 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 water-soluble pyridine compounds and their is 1:(1～5): (1～5).
9. preparation method according to claim 6 is characterized in that, described temperature sensitive property polymerization single polymerization monomer is N-N-isopropylacrylamide, N, one or more in N-diethyl acrylamide, ethene hexanolactam and the 2-carboxyl isopropyl alkene acid amides;
The hydrophobic polymerization single polymerization monomer of described hard is one or more in vinylbenzene, fluorostyrene, glycidyl methacrylate and the methyl methacrylate;
Described electronegative functional polymerization monomer is one or more in methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid and the fumaric acid.
10. according to claim 6 or 9 any described preparation methods, it is characterized in that the mass ratio of described temperature sensitive property polymerization single polymerization monomer, the hydrophobic polymerization single polymerization monomer of hard and electronegative functional polymerization monomer is (0.5～8): (1.5～10): (0.1～3).
11. according to claim 6 or 9 any described preparation methods, it is characterized in that the temperature of copolymerization is 65 ℃～80 ℃ in the described step b);
The time of copolymerization is 5 hours～10 hours in the described step b).
12. preparation method according to claim 6 is characterized in that, the temperature of reacting in the described step c) is 30 ℃～65 ℃;
The time of reacting in the described step c) is 1 hour～4 hours.
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