CN105949368B - A kind of multiple response amphipathic polymer particle and preparation method thereof - Google Patents
A kind of multiple response amphipathic polymer particle and preparation method thereof Download PDFInfo
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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
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The present invention provides a kind of preparation methods of the amphipathic polymer particle with multiple response, belong to novel high polymer material field.The present invention be using acrylic acid, acrylate, substituted acrylamide as comonomer, using water as reaction medium, initiator effect under, by an environmental-friendly step surfactant- free emulsion polymerization be made with temperature, pH, salt response amphipathic polymer particle.The amphipathic polymer diameter of particle is uniform, and lotion can make organic solvent（O）And water（W）Form stable oil-in-water（O/W）Or Water-In-Oil（W/O）Lotion has the multiple responses such as temperature sensitivity, pH responses and brine sensitivity, is with a wide range of applications in fields such as solid surfactant, biomedicine, intelligent coatings, environment-responsive materials.
Description
Technical field
The invention belongs to polymeric material fields, are related to a kind of preparation of amphipathic polymer particle；More particularly to a kind of tool
There is the preparation of the multiple responses amphipathic polymer particle such as pH, temperature, ionic strength, be mainly used for solid surfactant, life
The fields such as object medicine, intelligent coatings, environment-responsive material.
Background technology
Amphipathic particle is that a kind of Surface Physical Chemistry property has anisotropy or the asymmetric particle of structure.It is excellent
Physical and chemical performance shown in the fields such as chemistry, biomedicine, sensor, solid surfactant, intelligent coatings
Huge application prospect.The property and function of amphipathic polymer particle depend on its pattern and chemical characteristic, such as in fluid boundary,
Pattern anisotropy is the key factor for determining its configuration and the interaction of latex intergranular.Some amphipathic polymer particles are made
For solid surfactant, by changing its pattern and amphipathic, outside stimulus is responded, such as temperature, light, pH, ion
The stimulation of intensity etc., and then its characteristic and function also change, the amphipathic polymer particle as with multiple response.Surface
The amphipathic polymer particle of multiple response or the good chemical material of one kind rolled into a ball with carboxylate radical or amine foundation, pass through surface
Functional group and other nanoparticles are compound, can be used to synthesize the advanced polymer composites with excellent properties, organic and inorganic
Composite material can be applied to the fields such as solid surfactant, drug delivery, display technology, environment-responsive material.
Amphipathic polymer particle with multiple response causes it solely because of its special appearance and the anisotropy of chemical property
Special stimulating responsive, and these performances do not observe in isotropic homogeneous particle.Up to the present, multiple sound
The amphipathic polymer particle research answered has obtained remarkable progress, has different synthetic methods, and such as selective modification, lotion are gathered
Conjunction, wet chemistry synthesis, self assembly etc..Such as a kind of nanoparticle with pH sensibility（Patent of invention CN102294212A）；One
Kind is for medicine controlled releasing and the temperature response type polymer particles of genophore（Patent of invention CN104629059A）.Some have
It needs to add in crosslinking agent in the amphipathic polymer particle building-up process of stimuli responsive, and needs to be swollen, also need to sometimes organic
Solvent-induced phase separation.However, at present in amphipathic polymer microparticle technologies of the synthesis with stimuli responsive, partial reaction needs
Solvent, this can damage to environment.There are the shortcomings of building-up process complexity, low yield for part preparation method.
The content of the invention
The present invention seeks to parts in view of the shortcomings of the prior art, and providing a kind of simple, efficient, environmentally friendly prepare has
The method of multiple response amphipathic polymer particle.
First, there is the preparation of multiple response amphipathic polymer particle
The present invention is using acrylic acid and its derivative acrylate and substituted acrylamide as comonomer, using water as solvent,
Under initiator effect, it is made using a simple and environmental-friendly step surfactant- free emulsion polymerization with pH, temperature, ionic strength
Etc. responses amphipathic polymer particle.Its synthetic method is as follows：
Part initiator solution is first added in reaction medium, is warming up to 55 ~ 95 DEG C, stirs 5 ~ 30 min；Then stirring
The mixture of lower addition comonomer and remaining initiator solution are mixed, continuing stirring at 55 ~ 95 DEG C makes it the reaction was complete, obtains
The lotion of amphipathic polymer particle with multiple response centrifuges, obtains the amphipathic polymer particle with multiple response.
In the mixture of the comonomer, the mass ratio of three classes monomeric acrylic, acrylate and substituted acrylamide
For 1: 0.5 : 0.1 ~ 1: 8: 0.6；Wherein, acrylic acid is acrylic or methacrylic acid；Acrylate is acrylic acid
At least two in methyl esters, methyl methacrylate, butyl acrylate, butyl methacrylate；Substituted acrylamide is N, N-
At least one of acrylamide, n-isopropyl acrylamide.
The rate of addition of the mixture of the comonomer is 10 ~ 50 d/min, and time for adding is 0.5 ~ 2 h.
The initiator ammonium persulfate or potassium peroxydisulfate, total dosage are the 0.15% ~ 3% of comonomer gross mass.Wherein
The amount for adding in initiator for the first time is the 1/6 ~ 1/3 of initiator total amount.
2nd, the microscopic appearance and structural characterization of multiple response amphipathic polymer particle
1st, macroscopic view and microscopic appearance
Fig. 1 is the scanning electron microscope of the multiple response amphipathic polymer particle prepared（SEM）Figure（a）And transmission electron microscope
（TEM）Figure（b）.From SEM figures as can be seen that polymer particles are the ball-type pattern of uniform particle sizes, average grain diameter is 350 ~ 400
Between nm.From TEM as can be seen that polymer particles are the ball-type pattern of uniform particle sizes, average grain diameter is about 350 nm, with SEM
Data it is basically identical.Polymer particles also can be seen from TEM as two-sided structure, the similar hemisphere face of property is close to each other, and
The different hemisphere face of property is mutually become estranged, and this two-sided microballoon is one of its amphiphilic form of expression.
2nd, infrared spectrum analysis
Fig. 2 is the infrared absorption spectrum of the amphipathic polymer particle prepared.As can be seen that 2959 cm-1With 2875 cm-1
It is the stretching vibration absworption peak of saturation C-H, 1383 cm-1It is the bending vibration absworption peak of saturation C-H；1733 cm-1Locate for ester C=
The stretching vibration absworption peak of O, 1265 cm-1With 1167 cm-1It is the antisymmetry of C-O-C and symmetrical stretching vibration feature in ester group
Peak.Since there are stronger hydrogen bond action, C=O in amido bond is moved to low frequency, 1636 cm in polymer-1Place is flexible for it
Vibration absorption peak.1453 cm-1Place is carboxylate radical（-COO-）Symmetrical stretching vibration peak in conjugated system.Infrared spectrogram explanation,
Monomeric acrylic, acrylate and substituted acrylamide have both participated in polymerisation.
3rd, the amphipathic and emulsifiability test of amphipathic polymer particle
In order to evaluate the amphipathic of polymer particles, the dispersity of polymer particles in water is tested.Fig. 3 is multiple
The emulsifiability of response amphipathic polymer corpuscle emulsion.With water as solvent, white emulsion can be made in polymer particles（Figure
a1）, thus with dispersiveness and emulsifiability well；It is heated to 70 DEG C（Scheme a2）, lotion is without significant change, while in grease
There is good emulsibility at interface（Scheme a3）, illustrate that double-sided polymerization object particle is a kind of solid surfactant of stabilization, existing parent
Water end (W.E.), and have hydrophobic end.Therefore, which can make organic solvent（O）And water（W）Form stable oil-in-water
（O/W）Or Water-In-Oil（W/O）Lotion.
4th, the multiple response test of amphipathic polymer particle
1st, pH responses
In order to evaluate the relation of amphipathic polymer particle and pH, the emulsification of polymer particles in different pH environment is tested
Property.Fig. 4 be emulsifiability of the corpuscle emulsion of amphipathic polymer containing multiple response under different pH, wherein b1、b2、b3Respectively
PH 6.7, pH 11.4, pH 2.3 amphipathic polymer particle emulsifiability figure.The result shows that change the pH value of solution,
The emulsibility of particle can be changed.Illustrate that it has good emulsibility in neutral and alkaline environment（b2, b3）；In acyclic acidic
There is no emulsibility in border（Scheme b1）.Therefore the amphipathic polymer particle has certain pH responses.
2nd, salt response
In order to evaluate the relation of amphipathic polymer particle and salinity, polymer particles in different salinity environment are tested
Emulsibility.Fig. 5 be emulsifiability of the corpuscle emulsion of amphipathic polymer containing multiple response in different salinity, wherein c1、
c2、c3It is that concentration is 0.03 mol/L respectively（M）, 0.10 M, the amphipathic polymer particle emulsifiability figure of 0.30 M.As a result table
Bright, the concentration of salting liquid has larger impact to the emulsibility of amphipathic polymer particle.When the concentration of salting liquid is relatively low, polymer
The lotion that particle is stablized is O/W（c1）；Increase the concentration of salting liquid, phase transition occurs for the lotion that polymer particles are stablized, and is formed
W/O lotions（c2）；Continue the concentration of increase salting liquid, the emulsifying capacity of polymer particles is deteriorated（c3）.Therefore the amphipathic polymer
Particle has certain salinity response.Fig. 5 also illustrates that in the salting liquid of various concentration, polymer particles are in grease circle
Face shows different emulsifiabilities.Therefore, polymer particles are two-sided and with amphipathic.
3rd, the relation of diameter of particle and temperature
In order to evaluate the relation of amphipathic polymer particle and temperature, the pass of emulsion particle diameter and temperature under different temperatures is tested
System（Fig. 6）.As can be seen that room temperature（20℃~25℃）Under, the polymer particles in aqueous solution, average grain diameter for 460 nm ~
470 nm（The grain size is higher than SEM, the TEM measured under drying regime and surveys numerical value, is because having portion swells or adhesion）, work as breast
After liquid temperature degree is increased to 35 DEG C, average grain diameter mutation is to 800 nm, when temperature further rises to 50 DEG C, average grain diameter variation compared with
It is small, still between 800 ~ 830 nm.Illustrate to raise with temperature, during more than 35 DEG C, polymer grain size significantly increases.When temperature drops
After low, average grain diameter is reduced to original numerical value.Therefore, which has temperature-responsive.
In conclusion the present invention with acrylic acid, acrylate and substituted acrylamide etc. for monomer, by a step without soap breast
Liquid polymerization is prepared for a kind of amphipathic nature polyalcohol particle with multiple response.There is the based fine particles excellent pH to respond
Property, Thermo-sensitive and ionic strength response, and emulsifying capacity is controllable.Solid surfactant, biomedicine, electronics,
The fields such as environment-responsive material are with a wide range of applications.In addition, the present invention with distillation water as solvent, be not added with emulsifier and
Crosslinking agent, Environmental Safety；It is simple for process, efficient, clean using a step surfactant- free emulsion polymerization synthetic technology, be conducive to industry
Change.
Description of the drawings
Fig. 1 is that the SEM and TEM of multiple response amphipathic polymer particle scheme.
Fig. 2 is the infrared absorpting light spectra of multiple response amphipathic polymer particle.
Fig. 3 is the emulsifiability figure of multiple response amphipathic polymer corpuscle emulsion.
Fig. 4 be emulsifiability figure of the multiple response amphipathic polymer corpuscle emulsion under different pH, wherein b1、b2、b3Point
It Wei not pH 6.7, pH 11.4, the amphipathic polymer particle emulsifiability figure of pH 2.3.
Fig. 5 be emulsifiability figure of the multiple response amphipathic polymer corpuscle emulsion in different salinity, wherein c1、c2、
c3It is that concentration is 0.03 M, 0.10 M, the amphipathic polymer particle emulsifiability figure of 0.30 M respectively.
Fig. 6 is the temperature of multiple response amphipathic polymer particle and the relational graph of grain size.
Specific embodiment
The preparation of amphipathic polymer particle of the present invention is described further below by specific embodiment.
Embodiment 1
In the reactor equipped with blender, condenser pipe and dropping funel, 30 mL water are added in, 90 DEG C are warming up under stirring.
The mixture of acrylic acid, acrylate and substituted acrylamide is laid in dropping funel（The mass ratio of three is 1:0.5:
0.1）.4 mL, 1 mg/mL ammonium persulfate aqueous solutions are first added in the reactor, and 25 min are stirred at 90 DEG C.Then, stirring
The lower 1 mg/mL ammonium persulfate aqueous solutions of mixture and 16 mL that 10 g comonomers are added dropwise simultaneously, control rate of addition, are added dropwise
1.0 h of time.After being added dropwise, maintaining to continue at 90 DEG C to stir 3 h makes that the reaction was complete, obtains the breast of amphipathic polymer particle
Liquid centrifuges, obtains the amphipathic polymer particle with multiple response.
Temperature-responsive：The polymer particles are the ball-type pattern of uniform particle sizes, and the polymer particles are average at 25 DEG C
Grain size is 460 nm；It increases the temperature at 35 DEG C, average grain diameter increases to 800 nm；When further increasing the temperature to 50 DEG C,
Average grain diameter only slightly variation, about 830 nm.After temperature reduces, grain size is decreased to original numerical value therewith.
PH responses：In the weakly acidic pH environment of pH=6.7, water and toluene can be made to form stable O/W lotions；PH=
In 2.3 sour environment, polymer particles lose emulsifying capacity, water and toluene layering；In the alkaline environment of pH=11.4, gather
Close the emulsibility enhancing of object particle.Therefore, illustrate that amphipathic polymer particle has certain pH responses.
Salt response：When NaCl concentration is 0.03 M in aqueous solution, the lotion that polymer particles are stablized is O/W； NaCl
Concentration when increasing to 0.1 M, phase transition occurs for the lotion that polymer particles are stablized, and forms W/O lotions, and the concentration of NaCl increases
During to 0.3 M, the emulsifying capacity of particle is deteriorated.
Embodiment 2
In the reactor equipped with blender, condenser pipe and dropping funel, 60 mL water are added in, 85 DEG C are warming up under stirring.
The mixture of acrylic acid, acrylate and substituted acrylamide comonomer is laid in dropping funel（The mass ratio of three is
1:2:0.2）.6 mL, 1 mg/mL ammonium persulfate aqueous solutions are first added in, 15 min are stirred at 85 DEG C.Then drip simultaneously under stiring
Add the 1 mg/mL ammonium persulfate aqueous solutions of mixture and 17 mL of 15 g comonomers, control rate of addition, time for adding is
1.5 h.After being added dropwise, maintaining to continue at 85 DEG C to stir 2 h makes that the reaction was complete, obtains the lotion of amphipathic polymer particle, from
The heart separates, and obtains the amphipathic polymer particle with multiple response.The pattern of the polymer particles, pH responses, salt response
Etc. similar to Example 1.
Embodiment 3
In the reactor equipped with blender, condenser pipe and dropping funel, 80 mL water are added in, 75 DEG C are warming up under stirring.
The mixture of acrylic acid, acrylate and substituted acrylamide comonomer is laid in dropping funel（The mass ratio of three is
1:5:0.3）.7 mL, 1 mg/mL persulfate aqueous solutions are first added in the reactor, and 25 min are stirred at 75 DEG C.Then, exist
The lower 1 mg/mL ammonium persulfate aqueous solutions of mixture and 25 mL that 25 g comonomers are added dropwise simultaneously of stirring, control rate of addition,
2 h of time for adding.After being added dropwise, maintaining to continue at 75 DEG C to stir 2 h makes that the reaction was complete, obtains the amphiphilic with multiple response
The lotion of polymer particles further centrifuges, obtains the amphipathic polymer particle with multiple response.The polymer particles
Pattern, pH responses, salt response etc. it is similar to Example 1.
Embodiment 4
In the reactor equipped with blender, condenser pipe and dropping funel, 45 mL water are added in, 92 DEG C are warming up under stirring.
The mixture of acrylic acid, acrylate and substituted acrylamide comonomer is laid in dropping funel（The mass ratio of three is 1
: 8 : 0.6）.4 mL 1mg/mL ammonium persulfate aqueous solutions are first added in the reactor, and 15 min are stirred at 92 DEG C.Then, exist
The lower 1 mg/mL ammonium persulfate aqueous solutions of mixture and 14 mL that 8 g comonomers are added dropwise simultaneously of stirring, control rate of addition,
50 min of time for adding.After being added dropwise, maintaining to continue at 92 DEG C to stir 1.5 h makes that the reaction was complete, obtains with multiple response
Amphipathic polymer particle lotion, further centrifuge, obtain the amphipathic polymer particle with multiple response.The polymerization
Pattern, pH responses, the salt response of object particle etc. are similar to Example 1.
Claims (4)
1. a kind of preparation method with multiple response amphipathic polymer particle is with acrylic acid, acrylate, substitution propylene
Amide is comonomer, and water is reaction medium, initiator effect under, by a step surfactant- free emulsion polymerization be made with pH,
The amphipathic polymer particle of temperature, salt response；
Specifically preparation process is：Part initiator solution is first added in reaction medium, is warming up to 55 ~ 95 DEG C, stirring 5 ~ 30
min；Then the mixture of comonomer and remaining initiator solution are added under stiring, and continuing stirring at 55 ~ 95 DEG C makes it
The reaction was complete, obtains the lotion of the amphipathic polymer particle with multiple response, centrifuges, obtains two with multiple response
Close polymer particles；
In the comonomer, acrylic acid is acrylic or methacrylic acid；Acrylate is methyl acrylate, methacrylic acid
At least two in methyl esters, butyl acrylate, butyl methacrylate；Substituted acrylamide is N, N- acrylamides,
At least one of n-isopropyl acrylamide, and the mass ratio of monomeric acrylic, acrylate, substituted acrylamide is 1:
0.5:0.1~ 1:8:0.6。
2. there is the preparation method of multiple response amphipathic polymer particle as described in claim 1, it is characterised in that：Initiator
For ammonium persulfate or potassium peroxydisulfate, total dosage is the 0.15% ~ 3% of comonomer gross mass.
3. there is the preparation method of multiple response amphipathic polymer particle as described in claim 1, it is characterised in that：For the first time
The amount for adding in initiator is the 1/3 ~ 1/6 of initiator total amount.
4. there is the preparation method of multiple response amphipathic polymer particle as described in claim 1, it is characterised in that：Copolymerization is single
The rate of addition of the mixture of body is 10 ~ 50 d/min, and time for adding is 0.5 ~ 2 h.
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| CN104645357A (en) * | 2015-01-31 | 2015-05-27 | 湖北大学 | MRI (magnetic resonance imaging) contrast agent as well as preparation method and application thereof |
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| CN101838375A (en) * | 2010-04-23 | 2010-09-22 | 东华大学 | Temperature and pH stimuli-responsive intelligent polymer microcapsule and preparation thereof |
| CN104645357A (en) * | 2015-01-31 | 2015-05-27 | 湖北大学 | MRI (magnetic resonance imaging) contrast agent as well as preparation method and application thereof |
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