CN101085422A - Method of preparing temperature sensitive nano microcapsule by using small molecule hydrocarbon as template - Google Patents
Method of preparing temperature sensitive nano microcapsule by using small molecule hydrocarbon as template Download PDFInfo
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- CN101085422A CN101085422A CN 200710069316 CN200710069316A CN101085422A CN 101085422 A CN101085422 A CN 101085422A CN 200710069316 CN200710069316 CN 200710069316 CN 200710069316 A CN200710069316 A CN 200710069316A CN 101085422 A CN101085422 A CN 101085422A
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Abstract
The invention relates to the making of nanometer microcapsule. It uses organic small mole hydrocarbon drop as the template, using fine lotion polymer, polymerizing the temperature sensitive monomer, polymer monomer and coupling monomer, using the coupling monomer to form into coupling shell, dropping with extra monomers of the above to form into temperature sensitive nanometer capsule. It is simple, effective, stable to get 100-100 nanometer temperature sensitive capsule, being able to adjust the size of he capsule through adjusting the environmental temperature, further controlling the loading and release. It can be used as the catalyst loading, protein and other active matter control and release.
Description
Technical field
The present invention relates to a kind of preparation method of capsule of nano, being specifically related to a kind of is the method that template prepares temperature sensitive nano microcapsule with the small molecule hydrocarbon.
Background technology
Temperature sensing polymer is to environmental change, and variations in temperature especially can intelligent and reversibly response.Therefore, (Heskins M, Guillet J E.J Macromol Sci Chem, 1969 after finding the responsive to temperature characteristic of linear poly N-isopropyl acrylamide in 1969,2:1441), the research for this base polymer is one of the focus in polymer science field always.Near the phase transition phenomenon that temperature sensing polymer can show minimum critical solution temperature (LCST), generally believe that reason that the phase transition phenomenon appears in temperature sensing polymer is because the hydrogen bond that forms between the hydrophilic radical on the temperature sensing polymer macromolecular chain and the water is destroyed when being higher than minimum critical phase transition temperature, make the dehydration of temperature sensing polymer molecule, thereby make complete dissolved state (the become random coil structure) dehydration of temperature sensing polymer when being lower than minimum critical solution temperature be shrunk to graininess.Present many scholars structurized temperature sensing polymer particle that begins one's study is such as temperature-sensitive nano level (micron order) particle of nucleocapsid or loose structure etc.N-N-isopropylacrylamide and cinnamic copolymer nuclear have been synthesized by the emulsifier-free emulsion polymerization method, seeded emulsion polymerization by the N-N-isopropylacrylamide coats one deck poly-N-isopropyl acrylamide shell on nuclear again, the temperature sensitive property of success synthesizing micron-grade core-shell particles (Xiao X C, Chu L Y, Chen W M, Wang S, Xie R.Langmuir, 2004,20:5247).With the copolymer of kayexalate physical crosslinking allylamine and N-N-isopropylacrylamide the temperature sensitive property particle of loose structure (Chen B, Gao C Y., Macromol Rapid Commun, 2005,26:1657).Up to the present, by miniemulsion and the seeded emulsion polymerization method for preparing the temperature-sensitive nano capsule that combines report is not arranged also.
In order to prepare capsule of nano, patent and document reported than multi-method, as sacrificing template, big molecule self-assembly method, directly polymerization and self-assembly method layer by layer.They also have been widely used in various occasions, as the industries such as coating, paint, papermaking, leather, cosmetics such as white plastic pigment, uvioresistant additive and feel modifier as paint and water paint; Another important use is an encapsulation function compound therein, makes the macromolecular material with slow-release function, is applied to occasions such as pharmacy, medical diagnosis, biotechnology.Especially now successfully the material of biologically actives such as cell, DNA is coated wherein, have breakthrough application and occur.
The method for preparing capsule of nano, having of having proposed is following several:
(1) utilize the hydrophilic block copolymer of the hydrophobic end of an end to be self-assembled into micella, and on water-wet side, introduce the unit have siloxanes, utilize the hydrolysis-condensation effect of siloxanes again, form capsule of nano (the Kyougmoo Koh of hydridization, Kohji Ohno, Yoshinobu Tsujii, et al.Angew Chem Int Ed, 2003,42:4197);
(2) utilize polystyrene to be template, outside template, utilize the method for self assembly layer by layer, connect multi-layer polyelectrolyte and inorganic nano-particle, remove template by chemical extraction or calcining method then, obtain Nano capsule (Caruso F, Caruso RA, Mohwald H.Science, 1998,282:1111);
(3) utilize emulsion polymerisation, outside polymer template, form the shell that one deck is formed by styrene and double bond containing siloxanyl monomers copolymerization, wherein in emulsion polymerization process siloxy group also hydrolysis-condensation become inorganic network, get rid of the nuclear template then, obtain Nano capsule (Tissot I, Novat C, Lefebvre F, et al.Macromolecules, 2001,34:5737);
(4) utilize the New Emulsion polymerization, original position encapsulation small molecule hydrocarbon, synthetic microcapsules (US4,973,670,1990; McDonald C J, Bouck K J, Chaput A B, et al.Macromolecules, 200,33:1593); With the hexadecane is template, mini-emulsion polymerization styrene one-step method prepare Nano capsule (Tiarks, F, Landfester K, Antonietti M.Langmuir, 2001,17:908); With the normal octane is template, styrene and the combined polymerization of 3-methacryl trimethoxy silicon propyl ester miniemulsion prepare the inorganic-organic hybridization nano capsule (NiK F, Shan G R, Weng Z X.Macromolecules, 2006,39:2529).
For method (1), need block polymer synthesis with active free radical polymerization elder generation, carry out self assembly then, utilize the hydrolysis-condensation reaction to form inorganic phase, remove hydrophobic polymer core again, step is more relatively, and has the limited problem of packaging efficiency; For method (2), utilize the self assembly layer by layer of polyelectrolyte, also need to remove the step of template, and because the polyelectrolyte particulate easily flocculates, needs to carry out under extremely low concentration, can not stable dispersion in solvent, so its range of application also is restricted; For method (3), though synthetic easier, relatively very difficult for the removal of polymer template, and the polymer of removing is also cumbersome with separating of microcapsules; For method (4), preparation process is the easiest, only needs single step reaction just can obtain microcapsules, and the removal of small molecule hydrocarbon class template is convenient, is the good method of preparation microcapsules.The present invention will be on the basis of the method, and the preparation temperature sensitive nano microcapsule does not have the report that utilizes the synthetic temperature sensitive nano microcapsule of this method at present as yet.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide a kind of novel be the method for preparing temperature sensitive nano microcapsule of template with the small molecule hydrocarbon, preparation process is simple, can stably obtain the temperature sensitive property of nanoscale capsule, and capsule can produce intelligence and reversible response to the variation of environment temperature, has wide practical use.
For achieving the above object, the inventor finds through further investigation, adopt the mini-emulsion polymerization method, before the polymerization temperature sensitive monomer, comonomer, cross-linking monomer and small molecule hydrocarbon being mixed together, being dispersed into miniemulsion, is template with the small molecule hydrocarbon, directly polymerization obtains capsule of nano, by continuing to drip the mixed aqueous solution of adding temperature sensitive monomer and water-soluble cross-linked monomer, on capsule of nano, form the shell of one deck temperature sensing polymer then, finally obtain temperature sensitive nano microcapsule.In the process of synthesis of nano microcapsules, by control prescription and polymerizing condition, the shell that contains the temperature sensitive monomer unit is coated on the small molecule hydrocarbon drop interface, form capsule of nano.This method need not to remove the step of template, greatly simplifies the preparation process of microcapsules.
The present invention elder generation in water, is mixed emulsifiers dissolve with temperature sensitive monomer, comonomer, cross-linking monomer, small molecule hydrocarbon and co-stabilizer, join in the above-mentioned aqueous solution, with ultrasonic wave above-mentioned mixed liquor is disperseed, and obtains stable miniemulsion; Above-mentioned miniemulsion is heated to 40～80 ℃, adds the water soluble starter initiated polymerization.In the system that water soluble starter causes, initator is decomposed into elementary free radical in water, according to the difference of initiator type, and elementary free radical positively chargeable, negative electrical charge or big molecule hydrophilic chain.Elementary free radical or oligomer free radical because electrostatic interaction or steric effect, and are trapped within the drop surface in diffusing into the process of drop, make the drop surface become main polymerization place, and monomer is constantly replenished from drop inside.Because polymer is mutually incompatible with monomer droplet, along with reaction is carried out, the new polymer that forms is separated out on the drop surface rapidly.Temperature sensitive monomer is a hydrophilic monomer, so has the more oligomer free radical that is formed by temperature sensitive monomer in the polymerization system.Polymerization temperature is generally greater than LCST, and therefore temperature sensitive property oligomer free radical reaches after the critical chain length and can separate out and dripped by monomer liquid and to catch from water.Although temperature sensing polymer shows hydrophobicity more than LCST, still less than the polymer of small molecule hydrocarbon and formation, under the effect of thermodynamics motive force, the temperature sensing polymer free radical tends to be distributed on the drop outer surface its hydrophobicity.Thermodynamics motive force, electrostatic interaction or (with) under the acting in conjunction of steric effect, the oligomer free radical of aqueous phase and dead polymers can be adsorbed by drop, the drop surface becomes main polymerization place, most of polymer is looked unfamiliar and is separated out at drip gauge.Interfacial tension between polymer phase and the water is less than the interfacial tension of small molecule hydrocarbon and water, so entering the polymer of the radical polymerization formation of drop inside also can overlay on the surface of small molecule hydrocarbon drop from the drop diffusion inside under the effect of thermodynamics motive force to drip gauge bread, form stable network structure by copolymerization simultaneously, finally obtain the capsule of nano that shell contains the temperature sensitive monomer unit with cross-linking monomer.
After the system conversion ratio reaches 90%, add water soluble starter, and begin to drip the mixed aqueous solution of adding temperature sensitive monomer and water-soluble cross-linked monomer.The homopolymers of the temperature sensitive monomer that forms in the former miniemulsion system and copolymer can improve the compatibility of temperature sensing polymer and Nano capsule shell, so the oligomer that the second stage temperature sensitive monomer forms tends to be adsorbed by Nano capsule and coat in the Nano capsule outside; Polymer generation graft reaction on part temperature sensitive monomer and the Nano capsule, above-mentioned two processes finally all can obtain temperature sensitive nano microcapsule.
The method that the present invention adopts is: the monomer that participates in reaction comprises at least a temperature sensitive monomer, at least a comonomer and at least a cross-linking monomer, the total consumption of monomer is meant the gross mass of temperature sensitive monomer, comonomer, cross-linking monomer, but does not comprise and add temperature sensitive monomer and water-soluble cross-linked monomer;
This method comprises the following steps:
(1) with emulsifiers dissolve in water, obtain the aqueous solution of emulsifying agent, the ratio of total consumption of monomer and water is 0.0025: 1～0.5: 1, the emulsifying agent consumption is 1%～20% of the total consumption of monomer;
(2) temperature sensitive monomer is mixed with small molecule hydrocarbon, co-stabilizer, comonomer, cross-linking monomer, join in the solution that step (1) obtains, above-mentioned mixed liquor is disperseed, obtain stable miniemulsion with ultrasonic wave;
Wherein, the small molecule hydrocarbon consumption is 40%～360% of the total consumption of monomer, the consumption of co-stabilizer is 3%～25% of a small molecule hydrocarbon consumption, the temperature sensitive monomer consumption is 2%～20% of the total consumption of monomer, the comonomer consumption is 50%～97% of the total consumption of monomer, and amount ofthe cross-linking monomer is 1%～40% of a monomer total amount;
(3) adjustment to 40～80 of the emulsion that step (2) is obtained ℃, under inert gas shielding, add water soluble starter and carry out mini-emulsion polymerization, the water soluble starter consumption is 3%～25% of the total consumption of monomer, react after 120～600 minutes, obtain the capsule of nano that the shell polymer contains the temperature sensitive monomer unit;
(4) after the system conversion ratio reaches more than 90%, add water soluble starter and drip the mixed aqueous solution add temperature sensitive monomer and water-soluble cross-linked monomer, the dropping time was controlled in 30～240 minutes, after adding monomer solution and dripping, was incubated 3～20 hours;
Wherein, the consumption of adding temperature sensitive monomer is 2～15 times of the middle temperature sensitive monomer of step (2), water-soluble cross-linked monomer consumption is to add 10%～50% of temperature sensitive monomer, the ratio of adding total consumption of monomer and water is 0.05: 1～0.5: 1, add the total consumption of monomer and be meant the gross mass of adding temperature sensitive monomer and water-soluble cross-linked monomer, adding the water soluble starter consumption is to add 0.5%～10% of the total consumption of monomer;
Described temperature sensitive monomer is at least a in caprolactam or the following structural formula with adding temperature sensitive monomer:
R in the structural formula (1)
1, R
2Be H, C
2～C
5Aliphatic chain, and R
1, R
2Can not be H simultaneously, R
3Be H, CH
3
R in the structural formula (2)
1Be C
1～C
5Aliphatic chain, R
2, R
3Be H, CH
3
Described comonomer structure is at least a in the following structural formula:
In the structural formula (3), R
1Be H, CH
3Perhaps C
2H
5, R
2Be phenyl, substituted-phenyl, Cl, CN, alkyl ether or OCOCH
3
In the structural formula (4), R
1Be H, CH
3Perhaps C
2H
5, X is C
1～C
12Aliphatic chain or the C of hydroxyl
1～C
12Aliphatic chain;
Described cross-linking monomer structure is at least a in the following structural formula:
In the structural formula (5), R is phenyl ring, C
nH
2n, n=0～8 wherein;
Described water-soluble cross-linked monomer is at least a in structural formula (6), formula (7), the formula (8).
Among the present invention, described small molecule hydrocarbon is at least a in the alkane of cycloalkane, aromatic hydrocarbon or 5～14 carbon.
Among the present invention, described co-stabilizer is C
12～C
18Aliphatic hydrocarbon, C
12～C
18Fatty alcohol, structural formula (9) or structural formula (10) at least a:
In the structural formula (9), R
1Be H, CH
3, C
2H
5, X is C
12～C
18Aliphatic chain;
In the structural formula (10), R
1Be H, CH
3, CF
3, m=0～17, R
fBe C
nH
jF
2n+1-jFluoro fat (n=1～18, j=0～34), and m+n=12～18.
Among the present invention, described emulsifying agent is organic carboxylate, organic sulfate, organic sulfonate, organic phosphate anionic emulsifier, the organic quaternary ammonium salt cationic emulsifier, at least a in amphoteric ion type emulsifying agent or polyoxyethylene ester, APEO, the polyoxyethylene amine nonionic emulsifier.
Among the present invention, described water-soluble water soluble starter is at least a in hydrogen peroxide, persulfate, cationic diazo salt, polyethylene glycol azo macromole evocating agent, the water soluble oxidized reduction initiating system; The reducing substances that is added in the described water soluble oxidized reduction initiating system is at least a in primary amine, secondary amine, tertiary amine alcohol, sulphite, thiosulfate, the ferrous salt.
Considering that the monomer hydrophily is excessive causes secondary nucleation easily, is difficult to obtain the Nano capsule of hollow structure, so consumption that must the control temperature sensitive monomer in the prescription of mini-emulsion polymerization, reduces the quantity of secondary nucleation.Temperature sensitive monomer consumption in the system should be controlled in 2.5%～20% scope of the total consumption of monomer.
Consider that capsule of nano must have sufficient mechanical strength to keep the certain structure form, therefore must add a certain amount of cross-linking monomer in the system, cross-linking monomer can be hydrophobic divinylbenzene, also can be hydrophilic N, N '-methylene diacrylamine etc.The used in amounts of cross-linking monomer is controlled in 1%～40% scope.
Total consumption of monomer and water ratio are 0.0025: 1～0.5: 1.
Small molecule hydrocarbon is at least a in alkane (as pentane, octane, dodecane etc.), cycloalkane (as cyclohexane) or the aromatic hydrocarbon (benzene, toluene etc.) of 5～14 carbon among the present invention, and consumption is 40%～360% of the total consumption of monomer.
Co-stabilizer is at least a in the alcohol (as hexadecanol etc.), structural formula (9) (as lauryl methacrylate etc.), structural formula (10) (as methacrylic acid perfluoro capryl ethyl ester etc.) of the alkane (as hexadecane etc.) of 12～18 carbon, 12～18 carbon among the present invention, and consumption is 3%～25% of a small molecule hydrocarbon consumption.
Emulsifying agent among the present invention can select for use ionic emulsifying agent (as anionic emulsifier lauryl sodium sulfate, dodecyl sodium sulfate, cationic emulsifier softex kw etc., amphion emulsifying agent dodecyl dimethyl Propylamino sulfonic acid etc.) or nonionic emulsifier (as TWEEN series, SPAN series, OP series etc.) or their mixture, consumption is 1%～20% of the total consumption of monomer.
Water-soluble peroxide initiator of the optional usefulness of initator (as potassium peroxydisulfate, Ammonium Persulfate 98.5 etc.) or water soluble oxidized reduction initiating system are (as systems such as persulfate and triethanolamine, tetramethyl two ethylenediamines, morphine quinolines, hydrogen peroxide and ferrous sulfate system) or the water-soluble cationic azo-initiator (as 2,2 '-azo (2-amidine propane) dichloride hydrogen etc.) at least a in, consumption is 3% ~ 25% of the total consumption of monomer.
Consider that system stability and elementary free radical and oligomer free radical are trapped within the ratio on the drop interface, emulsifying agent of selecting for use and initator must couplings, cationic initator can with cationic or (with) nonionic emulsifier uses simultaneously; The nonionic initator then can use simultaneously with single ionic and nonionic emulsifier, also can with ionic and the composite use of nonionic emulsifier; The anionic initator can with anionic or (with) nonionic emulsifier uses simultaneously.
The invention has the beneficial effects as follows:
Preparation process of the present invention is simple, can stably obtain the temperature-sensitive nano hollow capsules, and the penetration property of capsule can have wider range of application by the reversible adjusting of variation of environment temperature.The hollow capsules that the present invention obtains can be widely used in catalyst and load with; The control of medicine, protein and other bioactivator discharges; Also can load the particle of nanoscale; Fields such as the loading of other reagent and control release.
The specific embodiment
Describe the present invention in detail below by specific embodiment, wherein the data of embodiment 1～3 are as shown in table 1, and the data of embodiment 4～6 are shown in Table 2.
Embodiment 1:
Take by weighing emulsifying agent dodecyl sodium sulfate 0.53g, add in the 1000g water, obtain emulsifier solution.Octane 10g, hexadecane 0.6g, N-N-isopropylacrylamide 0.3g, styrene 2g, divinylbenzene 0.5g are mixed, join in the mentioned emulsifier aqueous solution, above-mentioned mixed liquor is disperseed, obtain stable emulsion with ultrasonic wave; Adjustment to 80 ℃ under nitrogen protection, adds potassium peroxydisulfate 0.25g and causes, reaction 120min.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 106.5nm under 25 ℃ of conditions; Its hydrodynamics diameter is 102.4nm under 40 ℃ of conditions, and particle does not have temperature sensitive property substantially.With its form of transmission electron microscopy observation, be the capsule of hollow structure.Add potassium peroxydisulfate 0.05g, drip 4.5gN-N-isopropylacrylamide, 0.45g allylamine and the formulated aqueous solution of 95g water, dripped off in 0.5 hour, drip off back insulation 3 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 419.5nm under 25 ℃ of conditions; Its hydrodynamics diameter is 140.3nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, particle still is a hollow capsules.
Embodiment 2:
Take by weighing emulsifying agent softex kw 8g, obtain emulsifier solution in the adding 1000g water.Octane 200g, hexadecane 12g, caprolactam 6g, styrene 60g, divinylbenzene 40g are mixed, join in the mentioned emulsifier aqueous solution, above-mentioned mixed liquor is disperseed, obtain stable emulsion with ultrasonic wave; Adjustment to 60 ℃ under nitrogen protection, adds 2, and 2 '-azo (2-amidine propane) dihydrochloride 5g causes, reaction 240min.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 134.2nm under 25 ℃ of conditions; Its hydrodynamics diameter is 129.5nm under 40 ℃ of conditions, and particle does not have temperature sensitive property substantially.With its form of transmission electron microscopy observation, be the capsule of hollow structure.Add potassium peroxydisulfate 0.1g, drip 12g caprolactam, 6g tartaric acid diacrylamine and the formulated aqueous solution of 100g water, dripped off in 2 hours, drip off back insulation 20 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 335.6nm under 25 ℃ of conditions; Its hydrodynamics diameter is 140.5nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, particle still is a hollow capsules.
Embodiment 3:
Take by weighing emulsifier op-10 70g, add in the 1000g water, obtain emulsifier solution.With pentane 200g, hexadecanol 50g, vinyl isobutyramide 12g, styrene 440g, N, N '-methylene diacrylamine 4.6g mixes, and joins in the above-mentioned aqueous solution that contains emulsifying agent, with ultrasonic wave above-mentioned mixed liquor is disperseed, and obtains stable emulsion; Adjustment to 50 ℃ under nitrogen protection, adds potassium peroxydisulfate 10g, and sodium sulfite 5g causes, reaction 260min.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 150.3nm under 25 ℃ of conditions; Its hydrodynamics diameter is 147.6nm under 40 ℃ of conditions, and particle does not have temperature sensitive property substantially.With its form of transmission electron microscopy observation, be the capsule of hollow structure.Add potassium peroxydisulfate 5g, ethamine 2.5g drips 60g vinyl isobutyramide, 20gN, and the N '-methylene diacrylamine and the formulated aqueous solution of 160g water dripped off in 3 hours, drips off back insulation 20 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 470.6nm under 25 ℃ of conditions; Its hydrodynamics diameter is 168.5nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, particle still is a hollow capsules.
Embodiment 4:
Take by weighing emulsifier sodium lauryl sulfate 0.63g, add in the 1000g water, obtain emulsifier solution.With cyclohexane 100g, methacrylic acid perfluoro capryl ethyl ester 3g, N-N-isopropylacrylamide 8g, methyl methacrylate 50g, divinylbenzene 5g mixes, join in the above-mentioned aqueous solution that contains emulsifying agent, above-mentioned mixed liquor is disperseed, obtain stable emulsion with ultrasonic wave; Adjustment to 40 ℃ under nitrogen protection, adds potassium peroxydisulfate 10g, and triethanolamine 5g causes, reaction 600min.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 95.8nm under 25 ℃ of conditions; Its hydrodynamics diameter is 92.3nm under 40 ℃ of conditions, and particle does not have temperature sensitive property substantially.With its form of transmission electron microscopy observation, be the microcapsules of hollow structure.Add potassium peroxydisulfate 1g, diethylamine 0.5g drips 32gN-N-isopropylacrylamide, 8gN, and the N '-methylene diacrylamine and the formulated aqueous solution of 200g water dripped off in 2 hours, drips off back insulation 10 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 374.6nm under 25 ℃ of conditions; Its hydrodynamics diameter is 129.5nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, still be the capsule of hollow.
Embodiment 5:
Take by weighing emulsifier sodium lauryl sulfate 5g, OP-10 5g obtains emulsifier solution in the adding 1000g water.With toluene 100g, hexadecane 10g, N-N-isopropylacrylamide 8g, acrylonitrile 80g, divinylbenzene 15g mixes, and joins in the above-mentioned aqueous solution that contains emulsifying agent, with ultrasonic wave above-mentioned mixed liquor is disperseed, and obtains stable emulsion; Adjustment to 50 ℃ under nitrogen protection, adds hydrogen peroxide 10g, and sodium thiosulfate 5g causes, reaction 210min.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 105.9nm under 25 ℃ of conditions; Its hydrodynamics diameter is 98.3nm under 40 ℃ of conditions, and particle does not have temperature sensitive property substantially.With its form of transmission electron microscopy observation, be the microcapsules of hollow structure.Add potassium peroxydisulfate 3g, ferrous sulfate 1.5g drips 80gN-N-isopropylacrylamide, 30gN, and the N '-methylene diacrylamine and the formulated aqueous solution of 500g water dripped off in 2 hours, drips off back insulation 20 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 568.3nm under 25 ℃ of conditions; Its hydrodynamics diameter is 145.2nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, still be the capsule of hollow.
Embodiment 6:
Take by weighing emulsifier op-10 10g, add in the 1000g water, obtain emulsifier solution.With octane 100g, hexadecane 10g, caprolactam 30g, styrene 80g, divinylbenzene 50g mixes, and joins in the above-mentioned aqueous solution that contains emulsifying agent, with ultrasonic wave above-mentioned mixed liquor is disperseed, and obtains stable emulsion; Adjustment to 75 ℃ under nitrogen protection, adds polyethylene glycol 800 azo macromole evocating agent 24g and causes, reaction 260min.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 230.2nm under 25 ℃ of conditions; Its hydrodynamics diameter is 185.2nm under 40 ℃ of conditions, and particle has certain temperature sensitive property.With its form of transmission electron microscopy observation, be the microcapsules of hollow structure.Add polyethylene glycol 800 azo macromole evocating agent 7.5g, drip 60g caprolactam, 15gN, the N '-methylene diacrylamine and the formulated aqueous solution of 300g water dripped off in 4 hours, dripped off back insulation 20 hours, cessation reaction.Measure particle size with dynamic light scattering particle diameter instrument: its hydrodynamics diameter is 682.3nm under 25 ℃ of conditions; Its hydrodynamics diameter is 223.2nm under 40 ℃ of conditions, and particle shows tangible temperature sensitive property.With its form of transmission electron microscopy observation, still be the capsule of hollow.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention and principal character.Therefore, no matter from which point, above-mentioned experimental program of the present invention all can only be thought can not limit the present invention to explanation of the present invention, claim has been pointed out scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, in implication suitable and any variation in the scope, all should think to be included in the scope of claims with claims of the present invention.
Claims (5)
1, a kind of is the method that template prepares temperature sensitive nano microcapsule with the small molecule hydrocarbon, it is characterized in that, the monomer that participates in reaction comprises at least a temperature sensitive monomer, at least a comonomer and at least a cross-linking monomer, the total consumption of monomer is meant the gross mass of temperature sensitive monomer, comonomer, cross-linking monomer, but does not comprise and add temperature sensitive monomer and water-soluble cross-linked monomer;
This method comprises the following steps:
(1) with emulsifiers dissolve in water, obtain the aqueous solution of emulsifying agent, the ratio of total consumption of monomer and water is 0.0025: 1～0.5: 1, the emulsifying agent consumption is 1%～20% of the total consumption of monomer;
(2) temperature sensitive monomer is mixed with small molecule hydrocarbon, co-stabilizer, comonomer, cross-linking monomer, join in the solution that step (1) obtains, above-mentioned mixed liquor is disperseed, obtain stable miniemulsion with ultrasonic wave;
Wherein, the small molecule hydrocarbon consumption is 40%～360% of the total consumption of monomer, the consumption of co-stabilizer is 3%～25% of a small molecule hydrocarbon consumption, the temperature sensitive monomer consumption is 2%～20% of the total consumption of monomer, the comonomer consumption is 50%～97% of the total consumption of monomer, and amount ofthe cross-linking monomer is 1%～40% of a monomer total amount;
(3) adjustment to 40～80 of the emulsion that step (2) is obtained ℃, under inert gas shielding, add water soluble starter and carry out mini-emulsion polymerization, the water soluble starter consumption is 3%～25% of the total consumption of monomer, react after 120～600 minutes, obtain the capsule of nano that the shell polymer contains the temperature sensitive monomer unit;
(4) after the system conversion ratio reaches more than 90%, add water soluble starter and drip the mixed aqueous solution add temperature sensitive monomer and water-soluble cross-linked monomer, the dropping time was controlled in 30～240 minutes, after adding monomer solution and dripping, was incubated 3～20 hours;
Wherein, the consumption of adding temperature sensitive monomer is 2～15 times of the middle temperature sensitive monomer of step (2), water-soluble cross-linked monomer consumption is to add 10%～50% of temperature sensitive monomer, the ratio of adding total consumption of monomer and water is 0.05: 1～0.5: 1, add the total consumption of monomer and be meant the gross mass of adding temperature sensitive monomer and water-soluble cross-linked monomer, adding the water soluble starter consumption is to add 0.5%～10% of the total consumption of monomer;
Described temperature sensitive monomer is at least a in caprolactam or the following structural formula with adding temperature sensitive monomer:
R in the structural formula (1)
1, R
2Be H, C
2～C
5Aliphatic chain, and R
1, R
2Can not be H simultaneously, R
3Be H, CH
3
R in the structural formula (2)
1Be C
1～C
5Aliphatic chain, R
2, R
3Be H, CH
3
Described comonomer structure is at least a in the following structural formula:
In the structural formula (3), R
1Be H, CH
3Perhaps C
2H
5, R
2Be phenyl, substituted-phenyl, Cl, CN, alkyl ether or OCOCH
3
In the structural formula (4), R
1Be H, CH
3Perhaps C
2H
5, X is C
1～C
12Aliphatic chain or the C of hydroxyl
1～C
12Aliphatic chain;
Described cross-linking monomer structure is at least a in the following structural formula:
In the structural formula (5), R is phenyl ring, C
nH
2n, n=0～8 wherein;
Described water-soluble cross-linked monomer is at least a in structural formula (6), formula (7), the formula (8).
According to the claim 1 described method for preparing temperature sensitive nano microcapsule, it is characterized in that 2, described small molecule hydrocarbon is at least a in the alkane of cycloalkane, aromatic hydrocarbon or 5～14 carbon.
3, according to the claim 1 described method for preparing temperature sensitive nano microcapsule, it is characterized in that described co-stabilizer is C
12～C
18Aliphatic hydrocarbon, C
12～C
18Fatty alcohol, structural formula (9) or structural formula (10) at least a:
In the structural formula (9), R
1Be H, CH
3, C
2H
5, X is C
12～C
18Aliphatic chain;
In the structural formula (10), R
1Be H, CH
3, CF
3, m=0～17, R
fBe C
nH
jF
2n+1-jFluoro fat (n=1～18, j=0～34), and m+n=12～18.
4, according to the claim 1 described method for preparing temperature sensitive nano microcapsule, it is characterized in that, described emulsifying agent is organic carboxylate, organic sulfate, organic sulfonate, organic phosphate anionic emulsifier, the organic quaternary ammonium salt cationic emulsifier, at least a in amphoteric ion type emulsifying agent or polyoxyethylene ester, APEO, the polyoxyethylene amine nonionic emulsifier.
5, according to the claim 1 described method for preparing temperature sensitive nano microcapsule, it is characterized in that described water soluble starter is at least a in hydrogen peroxide, persulfate, cationic diazo salt, polyethylene glycol azo macromole evocating agent, the water soluble oxidized reduction initiating system; The reducing substances that is added in the described water soluble oxidized reduction initiating system is at least a in primary amine, secondary amine, tertiary amine alcohol, sulphite, thiosulfate, the ferrous salt.
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