CN109467628A - A kind of preparation method of composite nano-polymers particle - Google Patents
A kind of preparation method of composite nano-polymers particle Download PDFInfo
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- CN109467628A CN109467628A CN201811260043.8A CN201811260043A CN109467628A CN 109467628 A CN109467628 A CN 109467628A CN 201811260043 A CN201811260043 A CN 201811260043A CN 109467628 A CN109467628 A CN 109467628A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F116/14—Monomers containing only one unsaturated aliphatic radical
- C08F116/16—Monomers containing no hetero atoms other than the ether oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/10—Homopolymers or copolymers of unsaturated ethers
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
Abstract
The present invention relates to a kind of preparation methods of composite nano-polymers particle.For the present invention using poly(N-isopropylacrylamide) ionic microgel as nano-reactor, glycidyl methacrylate is model monomer, prepares the composite nano-polymers particle by dispersin polymerization.Basic step includes: synthesis poly(N-isopropylacrylamide) ionic microgel;By microgel dispersion in anhydrous methanol, glycidyl methacrylate model monomer is added, initiator is added after being warming up to setting value;According to monomer additional amount, the adjustment reaction time controls polymerization reaction;To after reaction through the cooling composite nano-polymers particle for being centrifuged acquisition different-grain diameter.Compared with prior art, the present invention uses ionic microgel for nano-reactor, has developed a kind of new process for preparing size tunable, composite nano-polymers particle with excellent temperature-sensing property.The simple and reliable process, has a good application prospect.
Description
Technical field
The present invention relates to a kind of preparation methods of composite nano-polymers particle, in particular with poly- (N- isopropyl propylene
Amide) method that ionic microgel prepares composite nanoparticle, belong to dispersin polymerization technical field.
Background technique
Polymer nano-particle has a wide range of applications in numerous areas: such as photon crystal material, the color in anti-forgery ink
Backing material, the carrier in drug delivery system and the template for preparing porous material etc. in spectrum separation.Common polymer
The preparation method of nanoparticle mainly has emulsion polymerization and dispersin polymerization, wherein dispersin polymerization is due to that can prepare high solids content
Product, more by the favor of industry.
In recent years, the dispersion polymerization systems for being particle-stabilised dose to polymer nano-particle are studied more and more.It is poly- at this
In zoarium system, the main function of stabilizer is to prevent polymer nano-particle from reuniting.So far, for dispersion polymerization systems
Particle-stabilised dose mainly has Nano particles of silicon dioxide and poly(N-isopropylacrylamide) microgel.Such as in the dispersion of styrene
In polymerization, they can replace surfactant molecule, prevent the polystyrene nanoparticle generated from reuniting, play physics
The effect of barrier.In this case, the polymerization reaction of styrene occurs particle-stabilised dose of outside, and this method preparation gathers
Styrene nanoparticle surface is often adsorbed with particle-stabilised dose, influences subsequent applications.Furthermore, it was reported that pass through hydrophilic and hydrophobic
Effect adjusts the variation of water content in the hardness and dispersion polymerization systems of poly(N-isopropylacrylamide) microgel, can
In particle-stabilised dose of internal-response, composite nano-polymers particle (Langmuir, 2017,34 (11): 3420- are prepared
3425).It is worth noting that the composite nanoparticle of this method preparation is usually the polystyrene nanoparticle of octopus shape, and
Do not have temperature-sensing property, however, how using poly(N-isopropylacrylamide) ionic microgel preparation have size tunable,
The composite nano-polymers particle of temperature-sensing property has not yet to see report.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide a kind of systems of composite nano-polymers particle
Preparation Method is the nano-reactor using ionic poly(N-isopropylacrylamide) microgel as polymer reaction, and preparation is poly-
Close the new process of object composite nanoparticle.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention relates to a kind of preparation methods of composite nano-polymers particle, with poly(N-isopropylacrylamide) ion
Type microgel is nano-reactor, and it is compound by dispersin polymerization to prepare the polymer with the polymerisable monomer containing epoxy group
Nanoparticle.
Preferably, the polymerisable monomer containing epoxy group includes glycidyl methacrylate, allyl contracting
Water glycerin ether, phenyl glycidyl ether, tetrahydrophthalic acid 2-glycidyl ester or 1,2- epoxy group -5- hexene.
It is furthermore preferred that the polymerisable monomer containing epoxy group is glycidyl methacrylate.Of the invention
In system, preferably using poly(N-isopropylacrylamide) ionic microgel as nano-reactor, methyl propenoic acid glycidyl
Ester is model monomer, and it is compound to obtain poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) by dispersin polymerization
Nanoparticle.
Preferably, the partial size of the poly(N-isopropylacrylamide) ionic microgel is 250~750nm.
Preferably, the poly(N-isopropylacrylamide) ionic microgel is using n-isopropyl acrylamide as master
Monomer, 1- vinyl imidazole are caused by water-soluble free radical as co-monomer, Isosorbide-5-Nitrae-dibromobutane as crosslinking agent in water
Agent causes precipitation polymerization reaction and obtains.
More specifically include the following steps: for n-isopropyl acrylamide, 1- vinyl imidazole and 1,4- dibromobutane to be added
It in reaction vessel equipped with water, is passed through nitrogen and eliminates and be warming up to 60~80 DEG C in container after oxygen, constant temperature 10~30 minutes, be added
Initiator azo diisobutyl amidine hydrochloride, according to addition quantitative response 4~24 hours of monomer, centrifugation obtained poly- (N- isopropyl
Acrylamide) ionic microgel.
Preferably, the n-isopropyl acrylamide, 1- vinyl imidazole, Isosorbide-5-Nitrae-dibromobutane molar ratio are 40:3:1
~10:2:1.
Preferably, the mass ratio of the n-isopropyl acrylamide and water is 1:100~1:800.
Preferably, the mass ratio of the n-isopropyl acrylamide and water-soluble free radical initiator is 100:1~1000:
1。
Preferably, the dispersin polymerization be by microgel inside quaternary ammonium salt and the polymerisable monomer containing epoxy group
Epoxy group interaction, and then ring-opening polymerisation.
The ring-opening polymerisation is that the acid condition that quaternary ammonium structure provides in the microgel and the microgel carry
Hydrone deposit the ring-opening polymerisation carried out at ambient.
Preferably, the dispersin polymerization includes the following steps:
S1, by the poly(N-isopropylacrylamide) ionic microgel dispersion in anhydrous methanol, addition contain ring
The polymerisable monomer of oxygen groups, under inert atmosphere conditions in 60~90 DEG C constant temperature 30~60 minutes;
S2, it is added initiator for reaction 8~48 hours, cooling centrifugation is to get the composite nano-polymers particle.
More specifically include the following steps: the poly(N-isopropylacrylamide) ionic microgel dispersion in no water beetle
In alcohol and it is packed into reaction vessel, the polymerisable monomer (such as glycidyl methacrylate) containing epoxy group is added, is passed through
Nitrogen eliminates in container and system is warming up to 60~90 DEG C after oxygen, constant temperature 30~two isobutyl of initiator azo is added after sixty minutes
Nitrile reacts 8~48 hours according to the additional amount of glycidyl methacrylate, obtains the poly- methyl-prop after cooling centrifugation
Olefin(e) acid ethylene oxidic ester/poly(N-isopropylacrylamide) composite nanoparticle.
Preferably, the polymerisable monomer containing epoxy group and poly(N-isopropylacrylamide) ionic microgel
Molar ratio be 1:1~50:1;The molar ratio of the initiator and the polymerisable monomer containing epoxy group is 1:100~1:
10000。
Preferably, the partial size of the composite nano-polymers particle is 280~960nm.
Glycidyl methacrylate model monomer used in the present invention contains the high epoxy group of reactivity,
It is anti-that SN1 nucleophilic displacement of fluorine can occur under the acid condition that quaternary ammonium structure provides in poly(N-isopropylacrylamide) ion microgel
It should make epoxy ring-opening.The hydrone carried in poly(N-isopropylacrylamide) ion microgel serves as nucleopilic reagent to attract
The carbon atom of epoxy group.The substance containing carboxyl newly formed after ring-opening reaction can be seeped by the electrostatic interaction of carboxyl and quaternary ammonium
Thoroughly into microgel.Therefore, it is micro- solidifying to be likely to occur in poly(N-isopropylacrylamide) ion for the polymerization of this substance containing carboxyl
The inside of glue, microgel plays the role of micro-nano reactor at this time, finally obtains composite nano-polymers particle.Due to poly-
(n-isopropyl acrylamide) ion microgel has Thermo-sensitive, therefore obtained polymethylacrylic acid within the scope of 25~65 DEG C
Ethylene oxidic ester/poly(N-isopropylacrylamide) composite nanoparticle also has corresponding Thermo-sensitive.Secondly, simple is poly-
Repulsion of (n-isopropyl acrylamide) ion microgel during partial size increases with temperature and declined, between quaternary ammonium structure
Effect has inhibiting effect to partial size reduction, keeps its temperature sensitive linearity curve more gentle;In comparison, polymethyl acid glycidyl
Ester/poly(N-isopropylacrylamide) composite nanoparticle charge density decreases, and partial size increases with temperature and declined
Become apparent from.
Compared with prior art, the present invention has a characteristic that
1, the present invention has developed a kind of using ionic poly(N-isopropylacrylamide) microgel as polymer reaction
Nano-reactor prepares the new process of composite nano-polymers particle, the simple and reliable process, before having good industrialization
Scape;
2, the mechanism of composite nano-polymers particle preparation method prepared by the present invention is the season inside by microgel
The interaction of the epoxy group of ammonium salt and reaction monomers, and then the ring-opening polymerisation under water and acid condition;
3, using glycidyl methacrylate as model monomer, the polymethylacrylic acid prepared through the invention shrinks sweet
Grease-poly(N-isopropylacrylamide) composite nanoparticle has the characteristics that size tunable, temperature sensitive function admirable.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings:
Fig. 1 is the reaction route figure of 1 poly(N-isopropylacrylamide) ion microgel of embodiment in the present invention;
Fig. 2 is the scanning electron microscope (SEM) photograph of 2 poly(N-isopropylacrylamide) ion microgel of embodiment in the present invention;
Fig. 3 is the transmission electron microscope picture of 3 poly(N-isopropylacrylamide) ion microgel of embodiment in the present invention;
Fig. 4, which is that 4 poly (glycidyl methacrylate)s of embodiment/poly(N-isopropylacrylamide) is compound in the present invention, to be received
The scanning electron microscope (SEM) photograph of rice corpuscles;
Fig. 5, which is that 5 poly (glycidyl methacrylate)s of embodiment/poly(N-isopropylacrylamide) is compound in the present invention, to be received
The scanning electron microscope (SEM) photograph of rice corpuscles;
Fig. 6, which is that 6 poly (glycidyl methacrylate)s of embodiment/poly(N-isopropylacrylamide) is compound in the present invention, to be received
The transmission electron microscope picture of rice corpuscles;
Fig. 7 is the transmission electron microscope picture of 1 polystyrene nanoparticle of comparative example in the present invention;
Fig. 8 is 3 poly(N-isopropylacrylamide) ion microgel of embodiment, 6 polymethyl of embodiment in the present invention
1 polystyrene nanoparticle of acid glycidyl ester/poly(N-isopropylacrylamide) composite nanoparticle and comparative example it is temperature sensitive
Linearity curve.Wherein (1) is polystyrene nanoparticle, and (2) are poly(N-isopropylacrylamide) ion microgel, and (3) are poly-
Glycidyl methacrylate/poly(N-isopropylacrylamide) composite nanoparticle;
Fig. 9 is 3 poly(N-isopropylacrylamide) ion microgel of embodiment, 6 polymethyl of embodiment in the present invention
The X-ray of 1 polystyrene nanoparticle of acid glycidyl ester/poly(N-isopropylacrylamide) composite nanoparticle and comparative example
Photoelectron spectroscopy figure;Wherein (1) is polystyrene nanoparticle, and (2) are poly(N-isopropylacrylamide) ion microgel,
It (3) is poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle;
Figure 10 is 3 poly(N-isopropylacrylamide) ion microgel of embodiment, 6 polymethyl of embodiment in the present invention
In Fu of 1 polystyrene nanoparticle of acid glycidyl ester/poly(N-isopropylacrylamide) composite nanoparticle and comparative example
Leaf transformation infrared spectrum;Wherein (1) is polystyrene nanoparticle, and (2) are poly(N-isopropylacrylamide) ion microgel,
It (3) is poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
The present embodiment is related to a kind of preparation method of poly(N-isopropylacrylamide) ion microgel, and reaction route is such as
Shown in Fig. 1, specifically comprise the following steps:
It weighs n-isopropyl acrylamide 452mg to be dissolved in 290mL deionized water, the Isosorbide-5-Nitrae-two of 72 μ L is added into solution
The 1- vinyl imidazole of bromobutane, 56 μ L.During system is warming up to 60 DEG C, it is stirred with the rate of 1000rpm, and
It is passed through nitrogen 30 minutes or so.After temperature is stablized, in 10mL water simultaneously by the azo diisobutyl amidine hydrochloride salt of 50mg
It is injected into initiated polymerization in above-mentioned solution.About 1 hour stopping nitrogen being bubbled after system becomes cloudy.Polymerization reaction 6
Hour, then cool to room temperature that reaction was completed.After reaction stops, the lotion containing poly(N-isopropylacrylamide) is existed
It is centrifuged 40 minutes under the revolving speed of 10000rpm.Then supernatant is removed, the microgel ultrasonic disperse that centrifugation is obtained is in no water beetle
It in alcohol, and is centrifuged 40 minutes under the revolving speed of 4000rpm, this centrifugation-dispersion process repeats three times.Poly- (the N- that will be finally obtained
N-isopropylacrylamide) be dispersed in it is spare in anhydrous methanol.
The partial size of the present embodiment poly(N-isopropylacrylamide) ion microgel is 300nm.
Embodiment 2
The present embodiment is related to a kind of preparation method of poly(N-isopropylacrylamide) ion microgel, specifically includes as follows
Step:
It weighs n-isopropyl acrylamide 904mg to be dissolved in 190mL deionized water, the Isosorbide-5-Nitrae-of 144 μ L is added into solution
The 1- vinyl imidazole of dibromobutane, 112 μ L.During system is warming up to 70 DEG C, stirred with the rate of 1200rpm
It mixes, and is passed through nitrogen 30 minutes or so.After temperature is stablized, by the azo diisobutyl amidine hydrochloride salt of 100mg in 10mL
In water and it is injected into initiated polymerization in above-mentioned solution.About 1 hour stopping nitrogen being bubbled after system becomes cloudy.Polymerization
Reaction 12 hours, then cools to room temperature that reaction was completed.After reaction stops, by the lotion containing poly(N-isopropylacrylamide)
It is centrifuged 40 minutes under the revolving speed of 10000rpm.Then supernatant is removed, the microgel ultrasonic disperse that centrifugation is obtained is anhydrous
It in methanol, and is centrifuged 40 minutes under the revolving speed of 4000rpm, this centrifugation-dispersion process repeats three times.It is poly- by what is finally obtained
(n-isopropyl acrylamide) is dispersed in spare in anhydrous methanol.
The partial size of the present embodiment poly(N-isopropylacrylamide) ion microgel is 570nm, which sweeps
It is as shown in Figure 2 to retouch electron microscope.As shown in Figure 2, the microgel obtained is that spherical and particle diameter distribution is relatively narrow.
Embodiment 3
The present embodiment is related to a kind of preparation method of poly(N-isopropylacrylamide) ion microgel, specifically includes as follows
Step:
It weighs n-isopropyl acrylamide 1356mg to be dissolved in 390mL deionized water, the Isosorbide-5-Nitrae-of 216 μ L is added into solution
The 1- vinyl imidazole of dibromobutane, 168 μ L.During system is warming up to 75 DEG C, stirred with the rate of 1500rpm
It mixes, and is passed through nitrogen 30 minutes or so.After temperature is stablized, by the azo diisobutyl amidine hydrochloride salt of 150mg in 10mL
In water and it is injected into initiated polymerization in above-mentioned solution.About 1 hour stopping nitrogen being bubbled after system becomes cloudy.Polymerization
Reaction 18 hours, then cools to room temperature that reaction was completed.After reaction stops, by the lotion containing poly(N-isopropylacrylamide)
It is centrifuged 40 minutes under the revolving speed of 9000rpm.Then supernatant is removed, the microgel ultrasonic disperse that centrifugation is obtained is in no water beetle
It in alcohol, and is centrifuged 40 minutes under the revolving speed of 4000rpm, this centrifugation-dispersion process repeats three times.Poly- (the N- that will be finally obtained
N-isopropylacrylamide) be dispersed in it is spare in anhydrous methanol.
The partial size of the present embodiment poly(N-isopropylacrylamide) ion microgel is about 750nm, the ion microgel
Transmission electron microscope picture is as shown in Figure 3.From the figure 3, it may be seen that the obscurity boundary of Microgels, illustrates that particle is softer.
Embodiment 4
The present embodiment is related to a kind of poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nano-granule
The preparation method of son, specifically comprises the following steps:
By the poly(N-isopropylacrylamide) ion microgel dispersion in embodiment 1 in 100mL anhydrous methanol, Xiang Qi
The glycidyl methacrylate of 0.5mL and the azodiisobutyronitrile of 30mg are added in middle 50mL dispersion liquid.By system liter
Temperature is stirred to during 65 DEG C with the rate of 250rpm, and is bubbled 30 minutes with nitrogen, about 1 hour after temperature is stablized
Stop nitrogen being bubbled, polymerization reaction 12 hours, then cools to room temperature that reaction was completed.After reaction stops, poly- methyl-prop will be contained
Olefin(e) acid ethylene oxidic ester/poly(N-isopropylacrylamide) composite nanoparticle methanol dispersion liquid is under the revolving speed of 2000rpm
Centrifugation 40 minutes.Poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nano-granule that centrifugation is obtained
Sub- ultrasonic disperse is fitted into bag filter and dialyses in deionized water three days in absolute methanol solution, replaces deionization daily
Water.Finally obtain pure poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle.
The present embodiment poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle partial size
About 540nm, scanning electron microscope (SEM) photograph are as shown in Figure 4.As shown in Figure 4, the partial size of composite nanoparticle is obvious compared with Microgels
Increase, drying rear surface has the fold similar to PNIPAM ion microgel.
Embodiment 5
The present embodiment is related to a kind of poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nano-granule
The preparation method of son, specifically comprises the following steps:
By the poly(N-isopropylacrylamide) ion microgel dispersion in embodiment 2 in 100mL anhydrous methanol, Xiang Qi
The azodiisobutyronitrile of the middle glycidyl methacrylate that 0.75mL is added and 45mg.System is being warming up to 80 DEG C of processes
In, it being stirred with the rate of 350rpm, and be bubbled 30 minutes with nitrogen, about 1 hour stopping nitrogen being bubbled after temperature is stablized,
Polymerization reaction 18 hours, then cool to room temperature that reaction was completed.After reaction stops, polymethyl acid glycidyl will be contained
Ester/poly(N-isopropylacrylamide) composite nanoparticle methanol dispersion liquid is centrifuged 40 minutes under the revolving speed of 2000rpm.It will
Obtained poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle ultrasonic disperse is centrifuged in nothing
It in water beetle alcoholic solution, and is fitted into bag filter and dialyses in deionized water three days, replace deionized water daily.It finally obtains pure
Poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle.
The present embodiment poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle partial size
About 790nm, scanning electron microscope (SEM) photograph are as shown in Figure 5.As shown in Figure 5, the partial size of the composite nanoparticle obtained is with used
The increase of the mole of the increase and glycidyl methacrylate of the partial size of microgel and increase.
Embodiment 6
The present embodiment is related to a kind of poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nano-granule
The preparation method of son, specifically comprises the following steps:
By the poly(N-isopropylacrylamide) ion microgel dispersion in embodiment 3 in 100mL anhydrous methanol, Xiang Qi
The glycidyl methacrylate of 1.0mL and the azodiisobutyronitrile of 50mg are added in middle 30mL dispersion liquid.By system liter
Temperature is stirred to during 70 DEG C with the rate of 350rpm, and is bubbled 30 minutes with nitrogen, about 1 hour after temperature is stablized
Stop nitrogen being bubbled, polymerization reaction 24 hours, then cools to room temperature that reaction was completed.After reaction stops, poly- methyl-prop will be contained
Olefin(e) acid ethylene oxidic ester/poly(N-isopropylacrylamide) composite nanoparticle methanol dispersion liquid is under the revolving speed of 2000rpm
Centrifugation 40 minutes.Poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nano-granule that centrifugation is obtained
Sub- ultrasonic disperse is fitted into bag filter and dialyses in deionized water three days in absolute methanol solution, replaces deionization daily
Water.Finally obtain pure poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle.
The present embodiment poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle partial size
About 960nm, transmission electron microscope picture are as shown in Figure 6.It will be appreciated from fig. 6 that the nanoparticle be poly (glycidyl methacrylate)/
Poly(N-isopropylacrylamide) composite nanoparticle.
Embodiment 7
The present embodiment is related to a kind of poly allyl glycidylether/poly(N-isopropylacrylamide) composite nanoparticle
Preparation method specifically comprises the following steps:
By the poly(N-isopropylacrylamide) ion microgel dispersion in embodiment 3 in 100mL anhydrous methanol, Xiang Qi
The allyl glycidyl ether of 0.8mL and the azodiisobutyronitrile of 50mg are added in middle 30mL dispersion liquid.It is warming up to by system
It during 70 DEG C, is stirred with the rate of 350rpm, and is bubbled 30 minutes with nitrogen, stopped within about 1 hour after temperature is stablized
Nitrogen is bubbled, and polymerization reaction 24 hours, then cools to room temperature that reaction was completed.After reaction stops, it shrinking containing polyallyl
Glycerin ether/poly(N-isopropylacrylamide) composite nanoparticle methanol dispersion liquid is centrifuged 40 points under the revolving speed of 2000rpm
Clock.Poly allyl glycidylether/poly(N-isopropylacrylamide) composite nanoparticle ultrasonic disperse that centrifugation obtains is existed
It in absolute methanol solution, and is fitted into bag filter and dialyses in deionized water three days, replace deionized water daily.It finally obtains pure
Net poly allyl glycidylether/poly(N-isopropylacrylamide) composite nanoparticle.
The present embodiment obtains with glycidyl methacrylate being monomer using allyl glycidyl ether as monomer
When similar composite nanoparticle, partial size is about 810nm.
Comparative example 1
This comparative example is related to a kind of preparation method of polystyrene nanoparticle, specifically comprises the following steps:
By the poly(N-isopropylacrylamide) ion microgel dispersion in embodiment 3 in 100mL anhydrous methanol, Xiang Qi
The styrene of 0.84mL and the azodiisobutyronitrile of 50mg are added in middle 30mL dispersion liquid.System is being warming up to 70 DEG C of processes
In, it being stirred with the rate of 350rpm, and be bubbled 30 minutes with nitrogen, about 1 hour stopping nitrogen being bubbled after temperature is stablized,
Polymerization reaction 24 hours, then cool to room temperature that reaction was completed.After reaction stops, by the methanol containing polystyrene nanoparticle
Dispersion liquid is centrifuged 40 minutes under the revolving speed of 2000rpm.The polystyrene nanoparticle ultrasonic disperse that centrifugation is obtained is anhydrous
It in methanol solution, and is fitted into bag filter and dialyses in deionized water three days, replace deionized water daily.Finally obtain when it is pure
Net polystyrene nanoparticle, the composite nanoparticle obtained different from the use of when containing epoxy-functional monomers.
The partial size of this comparative example polystyrene nanoparticle is 580nm.Its transmission electron microscope picture is as shown in fig. 7, can by Fig. 7
Know, polystyrene nanoparticle sharpness of border illustrates that particle is harder.
3 poly(N-isopropylacrylamide) ion microgel of embodiment, 6 poly (glycidyl methacrylate) of embodiment/
The Thermo-sensitive curve comparison of poly(N-isopropylacrylamide) composite nanoparticle and this comparative example polystyrene nanoparticle is such as
Shown in Fig. 8, as shown in Figure 8, poly (glycidyl methacrylate)/poly(N-isopropylacrylamide) composite nanoparticle has
Thermo-sensitive similar with poly(N-isopropylacrylamide) ion microgel, and polystyrene nanoparticle does not have Thermo-sensitive,
Illustrate the Nomenclature Composition and Structure of Complexes of the composite nanoparticle.
In addition, the shrink of 3 poly(N-isopropylacrylamide) ion microgel of embodiment, 6 polymethylacrylic acid of embodiment is sweet
Grease/poly(N-isopropylacrylamide) composite nanoparticle and this comparative example polystyrene nanoparticle x-ray photoelectron
Energy spectrum diagram and Fourier transform infrared spectrogram difference are as shown in Figure 9 and Figure 10.As shown in Figure 9, polymethyl acid glycidyl
Ester/poly(N-isopropylacrylamide) composite nanoparticle and poly(N-isopropylacrylamide) ion microgel all contain N member
Element, O element and Br element, and polystyrene nanoparticle contains only C element;As shown in Figure 10, polymethylacrylic acid shrinks sweet
Grease/poly(N-isopropylacrylamide) composite nanoparticle and poly(N-isopropylacrylamide) ion microgel all contain acyl
The characteristic peak of amine key and ester bond disappears in the characteristic peak of composite nanoparticle epoxy group, illustrates sweet in Glycidyl methacrylate
Ring-opening reaction has occurred during polymerizeing in grease, further demonstrates the Nomenclature Composition and Structure of Complexes of the composite nanoparticle.
Specific embodiments of the present invention are described above.It should be pointed out that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of preparation method of composite nano-polymers particle, which is characterized in that with poly(N-isopropylacrylamide) ion
Type microgel is nano-reactor, and it is compound by dispersin polymerization to prepare the polymer with the polymerisable monomer containing epoxy group
Nanoparticle.
2. the preparation method of composite nano-polymers particle as described in claim 1, which is characterized in that described to contain epoxy group
The polymerisable monomer of group includes glycidyl methacrylate, allyl glycidyl ether, phenyl glycidyl ether, tetrahydro neighbour
Phthalic acid 2-glycidyl ester or 1,2- epoxy group -5- hexene.
3. the preparation method of composite nano-polymers particle as claimed in claim 2, which is characterized in that described to contain epoxy group
The polymerisable monomer of group is glycidyl methacrylate.
4. the preparation method of composite nano-polymers particle as described in claim 1, which is characterized in that poly- (the N- isopropyl
Base acrylamide) ionic microgel partial size be 250~750nm.
5. the preparation method of composite nano-polymers particle as described in claim 1, which is characterized in that poly- (the N- isopropyl
Base acrylamide) ionic microgel be using n-isopropyl acrylamide as main monomer, 1- vinyl imidazole as co-monomer,
1,4- dibromobutane causes precipitation polymerization reaction by water-soluble free radical initiator in water as crosslinking agent and obtains.
6. the preparation method of composite nano-polymers particle as claimed in claim 5, which is characterized in that the N- isopropyl third
Acrylamide, 1- vinyl imidazole, 1,4- dibromobutane molar ratio be 40:3:1~10:2:1.
7. the preparation method of composite nano-polymers particle as described in claim 1, which is characterized in that the dispersin polymerization is
It is interacted by the epoxy group of the quaternary ammonium salt inside microgel and the polymerisable monomer containing epoxy group, and then open loop is poly-
It closes.
8. the preparation method of composite nano-polymers particle as claimed in claim 1 or 7, which is characterized in that the dispersion is poly-
Conjunction includes the following steps:
S1, by the poly(N-isopropylacrylamide) ionic microgel dispersion in anhydrous methanol, addition contain epoxy group
Group polymerisable monomer, under inert atmosphere conditions in 60~90 DEG C constant temperature 30~60 minutes;
S2, it is added initiator for reaction 8-48 hours, cooling centrifugation is to get the composite nano-polymers particle.
9. the preparation method of composite nano-polymers particle as claimed in claim 8, which is characterized in that described to contain epoxy group
The polymerisable monomer of group and the molar ratio of poly(N-isopropylacrylamide) ionic microgel are 1:1~50:1;The initiation
The molar ratio of agent and the polymerisable monomer containing epoxy group is 1:100~1:10000.
10. the preparation method of composite nano-polymers particle as described in claim 1, which is characterized in that the polymer is multiple
The partial size for closing nanoparticle is 280~960nm.
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