CN108164636A - A kind of preparation method of pH response types copolymer nano hydrogel - Google Patents
A kind of preparation method of pH response types copolymer nano hydrogel Download PDFInfo
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- 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
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- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- 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
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Abstract
The present invention relates to a kind of preparation methods of pH response types copolymer nano hydrogel, the monomer pair that hydrogen bond action or positive and negative charge effect can mutually occur is added in the aqueous dispersions containing hydrophobic initiator and surfactant, and adds in crosslinking agent and obtained pH response type copolymer nano hydrogels is reacted under oxygen-free environment and 40~80 DEG C of temperature conditions；When surfactant is ionic surfactant, the interaction between monomer pair is that reaction system pH is 1.5~3.0 when hydrogen bond action and reaction start；When surfactant is nonionic surface active agent, the interaction between monomer pair is acted on for positive and negative charge.This method can be made simultaneously containing weak acid unit and the nano-hydrogel of weak base unit or other active function groups, widened the type of pH response type nano hydrogels；Product has been made in pure water phase in the present invention, without using a large amount of organic solvents；Preparation flow of the present invention is simple, efficient, of low cost, conducive to large-scale production.
Description
Technical field
The invention belongs to nano-hydrogel fields, are related to a kind of preparation method of pH response types copolymer nano hydrogel.
Background technology
PH response type nano hydrogels are that a kind of structure snd size are changed with medium pH changes, have crosslinking knot
The polymer nano-particle of structure, size is generally between 1nm~1000nm.PH response type nano hydrogels, usually only contain
Single weak acid or weak base component.Since its size is small, large specific surface area, transient response is good and active function groups enrich
(such as carboxyl, amido), pH response type nano hydrogels can be widely applied to medicament slow release, medical diagnosis, biosensor, micro-
The fields such as reactor and catalyst carrier.
At present using Macromolecular self-assembly method, can be easy to that pH response type nano hydrogels are made, in Journal
Polymer Micelles with Crosslinked Ionic Cores For in of Controlled Release
It has been recorded in mono- texts of Delivery of Anticancer Drugs using Macromolecular self-assembly method synthesis pH response type nanos
The method of hydrogel, but its preparation concentration is very low, is not suitable for industrial-scale production.
Emulsion polymerisation process has the advantages that efficient, easy and is easy to large-scale production.Use reverse micro emulsion at present more
Polymerization prepares pH response type nano hydrogels, the A Tumor- in Angewandte Chemie International
Acidity-Activated Charge-Conversional Nanogel as an Intelligent Vehicle for
Conversed phase micro emulsion copolymerization synthesis is described in mono- texts of Promoted Tumoral-Cell Uptake and Drug Delivery
The method of pH response type nano hydrogels.In addition, precipitation polymerization (Huang JS, Wan SR, Guo M, Yan
HS.Preparation of Narrow or Mono-disperse Crosslinked Poly((meth)acrylic
acid)/Iron Oxide Magnetic Microspheres[J].Journal of Materials Chemistry
2006,16,4535-4541), distillation-precipitation polymerization and reflux-precipitation polymerization process can also be used to prepare monodispersed pH sound
Type nano-hydrogel is answered, although above method efficiency is higher, these methods use organic solvent as reaction medium, can be right
Environment brings detrimental effect.Therefore a kind of environment amenable pH response type nanos hydrogel preparation method quarter is developed not allow
It is slow.But due to pH sensitive monomers and its water solubility of polymer, using existing aqueous phase emulsion polymerization technique, the pH of generation is responded
Type polymer is difficult to be nucleated, thus macroscopic hydrogel can only be prepared, and the pH response type hydrogels of nanoscale can not be made
Particle.
Therefore a kind of great realistic meaning of preparation method of the simple pH response type nanos hydrogel of preparation flow is developed.
Invention content
The purpose of the present invention is be directed to the prior art prepares the deficiency that environment is unfriendly and economy is bad, one kind is provided
Environmentally friendly, preparation flow is simple and the preparation method of the good pH response type nanos hydrogel of economy.
To achieve the above object, the present invention adopts the following technical scheme that：
Hydrogen bond action or positive and negative can mutually be occurred by being added in the aqueous dispersions containing hydrophobic initiator and surfactant
The monomer pair of charge effect, and add in crosslinking agent reacted under oxygen-free environment and 40~80 DEG C of temperature conditions be made pH response types be total to
Polymers nano-hydrogel.
The present invention ensures that polymerisation slowly carries out by adding in hydrophobic initiator.The reaction of the present invention need to be in oxygen-free environment
Lower progress, this is because the reaction monomer between and crosslinking agent is Raolical polymerizable, reactivity kind free radical meeting
It is reacted with oxygen, so as to terminate polymerisation.Reaction temperature is too low, and decomposition of initiator rate is too slow, leads to polymerization rate
Too slow, monomer conversion is low；Reaction temperature is excessively high, and decomposition of initiator rate is too fast, causes polymerization rate too fast, reactant
The instantaneous concentration of the copolymer generated in system is excessively high, causes its rapid aggregation and has little time to capture enough surfactants, from
And macroscopic view precipitation occurs.
As preferred technical solution：
A kind of preparation method of pH response types copolymer nano hydrogel as described above, the surfactant are ion
During type surfactant, the interaction between monomer pair be when hydrogen bond action and reaction start reaction system pH be 1.5~
3.0；When surfactant is nonionic surface active agent, the interaction between monomer pair is acted on for positive and negative charge.
For hydrogen bond action monomer to reaction system, such as using nonionic surface active agent, non-ionic surface is lived
Property agent contained by hydroxyl and ehter bond hydrogen bond can be also formed between hydrogen-bond donor monomer, on the one hand, can and hydrogen bond receptor monomer shape
Into competition, it is unfavorable for the formation of copolymer hydrogen bond complex, on the other hand, will also result under surfactant stabilizing power
Drop.Reaction system pH when starting further for reaction, pH is relatively low, and the hydrogen bond action monomer between and its copolymer is too strong, a side
The size of the copolymer complex of face generation is larger, and on the other hand, the aggregation velocity between complex compound is too fast, leads to copolymer network
It closes object aggregation to be difficult to capture enough surfactants from reaction system in time, so as to which macroscopical precipitation have occurred；PH higher,
Hydrogen bond action of the monomer to monomer between and its copolymer is excessively weak, on the one hand causes generation size smaller, structurally loose
Copolymer complex, on the other hand, cause to be difficult to generate hydrophobic complex compound between copolymer segment, be finally difficult to obtain unimodal
The nano-hydrogel dispersion liquid of distribution, the conversion ratio of monomer are relatively low.For positive and negative charge effect monomer to reaction system, such as
Using ionic surfactant, also with monomer positive and negative charge can occur for surfactant, and one side surfactant is with correspondence
Monomer generates competition, is unfavorable for the formation of copolymer positive and negative charge effect complex compound, on the other hand will also result in surfactant
The decline of stabilizing power eventually leads to the copolymer nano hydrogel for being difficult to that stable dispersion and even structure is prepared.
A kind of preparation method of pH response types copolymer nano hydrogel as described above, is as follows：
(1) hydrophobic initiator and surfactant are dispersed in deionized water；
(2) monomer pair and crosslinking agent are added in, is reacted under oxygen-free environment and 40~80 DEG C of temperature conditions；
(3) surfactant is added in 1.0 hours again after the start of the reaction the reaction was continued 3~6h, pH response types are made
Copolymer nano hydrogel；
After adding in surfactant again, monomer is to a concentration of 20~80g/L in reaction system；It is described to add in surface again
The quality of activating agent accounts for the 75~80% of the total addition of surfactant.
Such as disposable addition surfactant, can cause successively to be nucleated causes particle size distribution wide；This programme is by dividing
Secondary addition surfactant can effectively avoid such case.The time of addition surfactant cannot be long again, otherwise unit
The surfactant added in time is sufficient to compensate for stablizing the surfactant that nano-hydrogel particle is consumed, and easily leads to and receives
The rice mutual coalescence of hydrogel particle is so as to occur macroscopical precipitation.The front and rear surfactant added in twice is without identical, as long as energy
Enough meet the needs of monomer pair.Then polymerization rate is too fast to excessive concentration for monomer in reaction system, in reaction system
The instantaneous concentration of the copolymer of generation is excessively high, causes its rapid aggregation and has little time to capture enough surfactants, so as to send out
Raw macroscopic view precipitation；Concentration is too low, and the relative molecular mass of the copolymer generated in reaction system is too small, it is difficult to generate hydrophobic and cause
Close copolymer complex, cause to be difficult to be stablized and grain size be Unimodal Distribution copolymer nano hydrogel dispersion liquid.It is first
Secondary addition surfactant is excessive, and it is wide to easily cause nano-hydrogel particle diameter distribution；It is very few that surfactant is added in for the first time, again
Before adding surfactant, coalescence probability increases between the nano-hydrogel particle generated in system, can cause to generate size very
Even there is macroscopical sediment in big nano-hydrogel.
A kind of preparation method of pH response types copolymer nano hydrogel as described above, is as follows：
(1) hydrophobic initiator and surfactant are dispersed in deionized water；
(2) monomer pair and crosslinking agent are added in, 3~6h is reacted under oxygen-free environment and 40~80 DEG C of temperature conditions, pH is made
Response type copolymer nano hydrogel；React a concentration of 20~70g/L of monomer pair in system when starting.
A kind of preparation method of pH response types copolymer nano hydrogel as described above, the oxygen-free environment for nitrogen or
Ar gas environment；The monomer is 0.9~1.1 to the molar ratio for including monomer A and monomer B, the monomer A and monomer B：1, work as list
The molar ratio of body A and monomer B is 1：1, it can match between the functional group between co-polymer, act on completely, one of which list two-by-two
During body excess, the functional group of institute's band will be superfluous, and superfluous functional group's number can excessively lead to complex structure compactness and dredge
Aqueous decline, and part water solubility copolymer is generated, so as to cause the copolymer for being difficult to be stablized and grain size is Unimodal Distribution
Nano-hydrogel dispersion liquid；Addition moisture dissipates after the addition monomer pair and crosslinking agent refer to uniform mix monomer pair and crosslinking agent
In liquid, so as to form uniform cross-linked structure inside nanoparticle with the uniform nano-hydrogel of obtained stable structure.
A kind of preparation method of pH response types copolymer nano hydrogel as described above, total matter of the surfactant
Measure 10~30% for monomer to quality；The quality of the hydrophobic initiator is monomer to the 1.0~3.5% of quality；The friendship
The quality for joining agent is monomer to the 10~25% of quality；
The surfactant is ionic surfactant or nonionic surface active agent；
The hydrophobic initiator is the hydrophobic initiator of azo or the hydrophobic initiator of organic peroxide class；
The crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate or N, N '-methylene-bisacrylamide.
A kind of preparation method of pH response types copolymer nano hydrogel as described above, the anionic surface activity
Agent is selected from neopelex, one kind of Aerosol OT and lauryl sodium sulfate or two kinds；
The cationic surface active agent is alkyl quaternary ammonium salts cationic surface active agent, specially dodecyl three
Ammonio methacrylate, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyl trimethyl ammonium bromide and ten
One kind in six alkyl trimethyl ammonium bromides or two kinds；
The nonionic surface active agent is selected from O-20, O-15, AEO-15, AEO-7, OP-15, OP-20, OP-30, spits
Temperature -20, Tween-40, one kind of Tween-60 and Tween-80 or two kinds；
The hydrophobic initiator of azo is azodiisobutyronitrile, azobisisoheptonitrile or azo-bis-iso-dimethyl；
The hydrophobic initiator of organic peroxide class is benzoyl peroxide or the benzoyl peroxide tert-butyl ester.
A kind of preparation method of pH response types copolymer nano hydrogel as described above, the monomer is to being selected from band carboxyl
The alpha-olefin and alpha-olefin with amide groups, the alpha-olefin with carboxyl and hydroxyl alpha-olefin, alpha-olefin and band with carboxyl
The alpha-olefin of pyrrolidone-base, the alpha-olefin with carboxyl and the alpha-olefin with amido and the alpha-olefin with carboxyl and with pyridyl group
Alpha-olefin in a pair more than；Protection scope of the present invention is not limited merely to this, as long as the work for the monomer pair that reaction adds in
With type such as it is all unanimously hydrogen bond action or is all positive and negative charge effect, monomer pair can arbitrarily combines according to actual demand, in addition
Two kinds of substances of above-mentioned monomer pair can add in simultaneously to react, and also can successively add in, but successively add in may cause it is obtained
Nano-hydrogel structure is uneven；The monomer of hydrogen bond action can mutually occur to for made from reactant in nano-hydrogel
Simultaneously containing weak acid unit (such as carboxyl) and other active function groups (such as hydroxyl, amide groups, pyrrolidone-base), with can be mutual
Occur the monomer of positive and negative charge effect to for made from reactant in nano-hydrogel simultaneously containing weak acid unit (such as carboxyl) and
Weak base unit (such as amido, pyridyl group) has only widened pH responses containing single weak acid or weak base unit compared with the prior art
The type of type nano-hydrogel.
A kind of preparation method of pH response types copolymer nano hydrogel as described above, the alpha-olefin with carboxyl and
Alpha-olefin with amide groups is more than a pair in methacrylic acid and acrylamide and acrylic acid and acrylamide；
The alpha-olefin with carboxyl and hydroxyl alpha-olefin are selected from acrylic acid and hydroxyethyl methacrylate and first
It is more than a pair in base acrylic acid and hydroxyethyl methacrylate；
The alpha-olefin with carboxyl and the alpha-olefin with pyrrolidone-base be selected from acrylic acid and vinyl pyrrolidone with
And more than a pair in methacrylic acid and vinyl pyrrolidone；
The alpha-olefin with carboxyl and the alpha-olefin with amido are selected from acrylic acid and vinylamine, methacrylic acid and ethylene
In amine, acrylic acid and methacrylic acid -2- dimethylamine ethyl ester and methacrylic acid and methacrylic acid -2- dimethylamine ethyl esters
It is more than a pair；
The alpha-olefin with carboxyl and the alpha-olefin with pyridyl group are selected from acrylic acid and 4-vinylpridine, metering system
In acid and 4-vinylpridine, acrylic acid and 2- vinylpyridines and methacrylic acid and 2- vinylpyridines it is a pair of with
On.
A kind of preparation method of pH response types copolymer nano hydrogel as described above, the pH response types copolymer are received
The mean hydrodynamic diameter (dispersion pH be in 4 deionized water) of gel particle is 60~300nm in rice hydrogel, polydispersion
Property coefficient is that 0.10~0.30, pH response type copolymer nano hydrogels are dispersed in gel particle when in the deionized water that pH is 7
Mean hydrodynamic diameter the ratio between mean hydrodynamic diameter of gel particle when in the deionized water that pH is 4 is dispersed in it
It is 1.9~5.81:1, copolymer nano hydrogel pH responses obtained are good.
Reaction principle：
Due to the pH dependences that hydrogen bond action or positive and negative charge act on, by gathering with hydrogen bond action or positive and negative charge effect
The nanoparticle that object forms physical blending or chemical blend is closed, shows significant pH responses, such as by big in aqueous solution
Molecular template polymerization crosslinking hydroxyethyl cellulose-polymethylacrylic acid nanoparticle obtained, gelatin-polyacrylic acid nano
Microballoon, glucan-g- polyacrylic acid nano microballoons etc..In matrix polymerization method, being previously added in polymerization system can be with
Hydrogen bond occurs for the polymer of in-situ polymerization generation or the macromolecular template of positive and negative charge effect, rush form it into hydrophobic polymerization
Object-complex formers；The Micelle-like Nano-structure of Two of hydrophobic complex compound is stable in the presence of instead by template molecule excessive in absorption system
It answers in system.
The prior art precipitates combined polymerization methacrylic acid in ethanol medium and acrylamide prepares copolymer microsphere, system
Product size it is larger, mean hydrodynamic diameter is micron order scale, can not meet nanoscale in more than 300nm
Use demand, environmentally protective idea of development is not met as medium yet using organic solvent.It can be in ethanol medium
Synthesize poly- (methacrylic acid-acrylic amide) microballoon be critical to be known as two, first, ethyl alcohol is the poor solvent of polyacrylamide；
Second is that can form methacrylic acid-acrylic amide complex small droplet in ethanol medium, such as changing aqueous medium into can not synthesize
Copolymer microsphere.
The present invention selects the monomer that hydrogen bond action or positive and negative charge effect can occur to being used for aqueous phase emulsion polymerization first
In method, the polymerization behavior of Specific Interactions (hydrogen bond action or positive and negative charge act on) regulation and control monomer pair is utilized so that in situ raw
Into copolymer between hydrophobic copolymer complex generated by hydrogen bond or positive and negative charge effect, so as to facilitate copolymer nano water
The nucleation of gel and growth；Secondly, by the way that polymeric reaction condition is controlled to generate the larger copolymer of relative molecular weight, promote original position
The copolymer of generation, which interacts, to form that size is smaller and the hydrophobic complex compound of compact structure, and introduces surfactant, surely
Fixed hydrophobic copolymer complex aggregation is to obtain the sediment of stable nano-hydrogel dispersion liquid rather than macroscopic view, finally
The product of nanoscale is made；Finally using with monomer to premixing by the way of add in crosslinking agent, formed inside nanoparticle
Uniform cross-linked structure is finally successfully realized pH response type copolymer nano water so as to which the nano-hydrogel of stable structure be made
Preparation of the gel in pure water phase.
Advantageous effect：
(1) preparation method of a kind of pH response types copolymer nano hydrogel of the invention, can be made and contain weak acid simultaneously
Unit and the nano-hydrogel of weak base unit or other active function groups only contain single weak acid or weak compared with the prior art
The nano-hydrogel of alkali unit has widened the type of pH response type nano hydrogels；
(2) preparation method of a kind of pH response types copolymer nano hydrogel of the invention, pH has been made in pure water phase
Response type copolymer nano hydrogel, it is environmentally friendly without using a large amount of organic solvents；
(3) preparation method of a kind of pH response types copolymer nano hydrogel of the invention, preparation flow is simple, efficiency
It is high, of low cost, conducive to large-scale production, great application prospect.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of preparation method of pH response types copolymer nano hydrogel, first by hydrophobic initiator azobisisoheptonitrile and table
Face activating agent neopelex is dispersed in deionized water, uniform mix monomer pair and crosslinking agent divinyl
It carries out reaction 3h after benzene in addition dispersion liquid at nitrogen environment and 40 DEG C and pH response type copolymer nano hydrogels is made,
In, the gross mass of surfactant is monomer to the 10% of quality, and the quality of hydrophobic initiator is monomer to the 1.0% of quality,
The quality of crosslinking agent is monomer to the 10% of quality, and system pH is 2 when reaction starts, and monomer is single to a concentration of 20g/L in system
Body centering includes the monomer A of hydrogen bond action and monomer B can occur each other, and monomer A is acrylamide, and monomer B is metering system
Acid, the molar ratio of monomer A and monomer B is 0.9：1.
PH response types copolymer nano hydrogel obtained is characterized, characterization step is as follows：
(1) pH response types copolymer nano hydrogel dispersion liquid dialysis purification obtained is obtained using deionized water
The copolymer nano hydrogel dispersion liquid of purifying is analysed, dispersion liquid is divided equally and obtains dispersion liquid I and dispersion liquid II；
(2) pH value of dispersion liquid I is adjusted to 4, and it is 0.1mg/ to be diluted to dispersion fluid solid content with the pH deionized waters for being 4
ML measures the average grain diameter and polydispersity coefficient of gel particle using Malvern DTS1060 light scattering particle instrument；
(3) pH value of dispersion liquid II is adjusted to 7, and is diluted to dispersion fluid solid content with the pH deionized waters for being 7 and is
0.1mg/mL measures the average grain diameter and polydispersity coefficient of gel particle using Malvern DTS1060 light scattering particle instrument.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 300nm, polydispersity coefficient 0.24；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 970nm, polydispersity coefficient 0.28, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 3.23 times, shows good pH responses.
Embodiment 2
A kind of preparation method of pH response types copolymer nano hydrogel, first by hydrophobic two isobutyric acid diformazan of initiator azo
Ester and surfactant Aerosol OT are dispersed in deionized water, uniformly disperse monomer pair and crosslinking
Addition aqueous dispersions carry out reaction 6h at ar gas environment and 70 DEG C and pH response types are made after agent ethylene glycol dimethacrylate
Copolymer nano hydrogel, wherein, the gross mass of surfactant is monomer to the 20% of quality, and the quality of hydrophobic initiator is
Monomer is to the 2.3% of quality, and the quality of crosslinking agent is monomer to the 25% of quality, and system pH is 1.5 when reaction starts, in system
Monomer is to a concentration of 70g/L, and for monomer to including the monomer A of hydrogen bond action and monomer B can occur each other, monomer A is acryloyl
Amine, monomer B are acrylic acid, and the molar ratio of monomer A and monomer B is 1：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 180nm, polydispersity coefficient 0.20；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 630nm, polydispersity coefficient 0.30, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 3.5 times, shows good pH responses.
Embodiment 3
A kind of preparation method of pH response types copolymer nano hydrogel, first by hydrophobic initiator azodiisobutyronitrile and table
Face activating agent O-20 is dispersed in deionized water, uniform mix monomer pair and crosslinking agent N, N '-methylene-bisacrylamide
Addition aqueous dispersions carry out reaction 4.5h at oxygen-free environment nitrogen environment and 60 DEG C and pH response type copolymer nano water are made afterwards
Gel, wherein, the gross mass of surfactant is monomer to the 30% of quality, and the quality of hydrophobic initiator is monomer to quality
3.5%, the quality of crosslinking agent is monomer to the 18% of quality, when reaction starts in system monomer to a concentration of 50g/L, monomer pair
Monomer A and monomer B, monomer A including positive and negative charge effect can occur each other are methacrylic acid, and monomer B is vinylamine, single
The molar ratio of body A and monomer B is 1.1：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 60nm, polydispersity coefficient 0.30；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of grain is 348nm, polydispersity coefficient 0.25, it is seen that when the pH value of medium increases to 7 by 4,
The grain size of copolymer nano gel increases 5.8 times, shows good pH responses.
Embodiment 4
A kind of preparation method of pH response types copolymer nano hydrogel, first by hydrophobic initiator benzoyl peroxide and table
Face activating agent lauryl sodium sulfate is dispersed in deionized water, uniform mix monomer pair and cross-linker divinylbenzene
Aqueous dispersions are added in afterwards and carry out reaction 1h at nitrogen environment and 80 DEG C, and it is anti-to add surfactant sodium dodecyl base benzene sulfonic acid sodium salt
Answer 6h that pH response type copolymer nano hydrogels are made, wherein, the gross mass of surfactant is monomer to the 25% of quality, is dredged
The quality of water initiator for monomer to the 1.5% of quality, the quality of the surfactant added in again accounts for the total matter of surfactant
The 78% of amount, the quality of crosslinking agent are monomer to the 15% of quality, and system pH is 3.0 when reaction starts, and adds in surface again and lives
Property agent after for monomer to a concentration of 20g/L, monomer is single to including the monomer A of hydrogen bond action and monomer B can occur each other in system
Body A is acrylic acid, and monomer B is hydroxyethyl methacrylate, and the molar ratio of monomer A and monomer B is 1.05：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 200nm, polydispersity coefficient 0.10；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 996nm, polydispersity coefficient 0.15, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 4.98 times, shows good pH responses.It lives with the disposable surface that adds in
Property agent compare, add in surfactant in two times and significantly reduce the polydispersity coefficient of product.
Comparative example 1
A kind of preparation method of pH response types copolymer aquagel, experimental procedure is substantially the same manner as Example 4, and difference exists
In monomer to the molar ratio on addition opportunity and monomer；Monomer B is only added in when this comparative example starts, monomer A is added after half an hour
It is reacted with crosslinking agent, the molar ratio of monomer A and monomer B is 1：10.The final hydrogel that macroscopic view is made, it is right with embodiment 4
Than finding, the hydrogel of nanoscale has successfully been made in the present invention.
Comparative example 2
A kind of preparation method of pH response types copolymer aquagel, experimental procedure is substantially the same manner as Example 4, and difference exists
In monomer to not adding in together, when beginning, only adds in monomer B, and monomer A is added after half an hour and crosslinking agent is reacted.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 350nm, polydispersity coefficient 0.33；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle is 1856nm, polydispersity coefficient 0.66, and for multi-modal.It can be seen that this comparison
The structure of gel particle is uneven made from example, and when gel particle swells in alkaline medium, the homopolymer of monomer B will
Separate out causes multi-modal from gel particle.It compares and finds with embodiment 4, nano-hydrogel grain produced by the present invention
Diameter is small and even structure.
Comparative example 3
A kind of preparation method of pH response types copolymer aquagel, experimental procedure is substantially the same manner as Example 4, and difference exists
In the molar ratio of monomer A and monomer B be 1：10.The final hydrogel that macroscopic view is made, compares with embodiment 4 and finds, the present invention into
The hydrogel of nanoscale has been made in work(.
Comparative example 4
A kind of preparation method of pH response types copolymer aquagel, experimental procedure is substantially the same manner as Example 4, and difference exists
The 90% of surfactant gross mass is accounted in the quality of the surfactant added in again.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 414nm, polydispersity coefficient 0.25, and is bimodal distribution, except the nanometer of stock size
Hydrogel peak, the also big particle peak there are size in the micron-scale.It compares and finds with embodiment 4, the addition of initial surfactant
Measure it is very few, the average grain diameter of the copolymer nano hydrogel of preparation significantly increase and in system there are a small amount of size in the micron-scale
Bulky grain.
Comparative example 5
A kind of preparation method of pH response types copolymer aquagel, experimental procedure is substantially the same manner as Example 4, and difference exists
The 50% of surfactant gross mass is accounted in the quality of the surfactant added in again.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 167nm, polydispersity coefficient 0.44, and is bimodal distribution.It compares and sends out with embodiment 4
Existing, initial surfactant additive amount is excessive, and the average grain diameter of the copolymer nano hydrogel of preparation becomes smaller, but its polydispersion
Property coefficient significantly increases, and illustrates that dimensional homogeneity significantly deteriorates.
Embodiment 5
A kind of preparation method of pH response types copolymer nano hydrogel, first by the hydrophobic tertiary fourth of initiator benzoyl peroxide
Ester and surfactant hexadecyltrimethylammonium chloride are dispersed in deionized water, uniform mix monomer pair and crosslinking
Aqueous dispersions are added in after agent N, N '-methylene-bisacrylamide and carry out reaction 0.2h at ar gas environment and 50 DEG C, add table
PH response type copolymer nano hydrogels are made in face activating agent dodecyl trimethyl ammonium chloride reaction 4h, wherein, surface-active
The gross mass of agent is monomer to the 16% of quality, and the quality of hydrophobic initiator is monomer to the 1.8% of quality, the table added in again
The quality of face activating agent accounts for the 79% of surfactant gross mass, and the quality of crosslinking agent is monomer to the 19% of quality, and reaction is opened
System pH is 2.2 during the beginning, and monomer is to a concentration of 80g/L in system after addition surfactant again, and monomer is to including each other
The monomer A of hydrogen bond action and monomer B enough occurs, monomer A is acrylic acid, and monomer B is vinyl pyrrolidone, monomer A and monomer B
Molar ratio be 0.95：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 200nm, polydispersity coefficient 0.25；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 606nm, polydispersity coefficient 0.21, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 3.03 times, shows good pH responses.
Embodiment 6
A kind of preparation method of pH response types copolymer nano hydrogel, first by hydrophobic two isobutyric acid diformazan of initiator azo
Ester and surfactant octadecyltrimethylammonium chloride are dispersed in deionized water, uniform mix monomer pair and crosslinking
Aqueous dispersions are added in after agent ethylene glycol dimethacrylate and carry out reaction 0.1h at nitrogen environment and 70 DEG C, add surface
The reaction was continued that pH response type copolymer nano hydrogels are made in 5h for activating agent dodecyl trimethyl ammonium bromide, wherein, surface is lived
Property agent gross mass be monomer to the 10% of quality, the quality of hydrophobic initiator is monomer to the 2.5% of quality, the table added in afterwards
The quality of face activating agent accounts for the 77% of surfactant gross mass, and the quality of crosslinking agent is monomer to the 12% of quality, and reaction is opened
System pH is 2.4 during the beginning, and monomer is to a concentration of 70g/L in system after addition surfactant again, and monomer is to including each other
The monomer A of hydrogen bond action and monomer B enough occurs, monomer A is acrylic acid, and monomer B is vinyl pyrrolidone, monomer A and monomer B
Molar ratio be 1.1：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 180nm, polydispersity coefficient 0.22；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 504nm, polydispersity coefficient 0.28, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 2.8 times, shows good pH responses.
Embodiment 7
A kind of preparation method of pH response types copolymer nano hydrogel, first by the hydrophobic tertiary fourth of initiator benzoyl peroxide
Ester and surfactant sodium dodecyl base trimethylammonium bromide are dispersed in deionized water, uniform mix monomer pair and crosslinking
Dispersion liquid is added in after agent N, N '-methylene-bisacrylamide and carries out reaction 0.5h at nitrogen environment and 78 DEG C, adds surface
PH response type copolymer nano hydrogels are made in lammonium bromide reaction 3.5h, wherein, surface-active
The gross mass of agent is monomer to the 25% of quality, and the quality of hydrophobic initiator is monomer to the 1.6% of quality, the table added in again
The quality of face activating agent accounts for the 79% of surfactant gross mass, and the quality of crosslinking agent is monomer to the 12% of quality, and reaction is opened
System pH is 2.0 during the beginning, and monomer is to a concentration of 50g/L in system after addition surfactant again, and monomer is to including each other
The monomer A of hydrogen bond action and monomer B enough occurs, monomer A is acrylamide, and monomer B is mole of acrylic acid, monomer A and monomer B
Than being 1.03：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 250nm, polydispersity coefficient 0.18；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 504nm, polydispersity coefficient 0.28, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 2.8 times, shows good pH responses.
Embodiment 8
A kind of preparation method of pH response types copolymer nano hydrogel, first by hydrophobic two isobutyric acid diformazan of initiator azo
Ester and surfactant A EO-7 are dispersed in deionized water, uniform mix monomer pair and crosslinking agent dimethacrylate
Dispersion liquid is added in after glycol ester and carries out reaction 0.7h at ar gas environment and 55 DEG C, adds surfactant O-15 reactions 6h
PH response type copolymer nano hydrogels are made, wherein, the gross mass of surfactant is monomer to the 25% of quality, hydrophobic to draw
Send out agent quality for monomer to the 2.6% of quality, the quality of the surfactant added in again accounts for surfactant gross mass
77%, the quality of crosslinking agent is monomer to the 19% of quality, adds in after surfactant in system monomer again to a concentration of
55g/L, monomer are acrylic acid to including the monomer A of positive and negative charge effect and monomer B, monomer A can occur each other, and monomer B is
4-vinylpridine, the molar ratio of monomer A and monomer B is 1：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 240nm, polydispersity coefficient 0.20；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 717nm, polydispersity coefficient 0.26, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 2.99 times, shows good pH responses.
Embodiment 9
A kind of preparation method of pH response types copolymer nano hydrogel, basic step is same as Example 7, and difference exists
In the monomer that it is added in further including acrylic acid and vinyl pyrrolidone, wherein monomeric acrylic and monomer vinyl pyrrolidines
The molar ratio of ketone is 1.02：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 120nm, polydispersity coefficient 0.20；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 228nm, polydispersity coefficient 0.21, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 1.9 times, shows good pH responses.
Embodiment 10
A kind of preparation method of pH response types copolymer nano hydrogel, basic step is same as Example 7, and difference exists
In the monomer that it is added in further including acrylic acid and hydroxyethyl methacrylate, wherein monomeric acrylic and monomer methacrylic acid
The molar ratio of hydroxyl ethyl ester is 1：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 210nm, polydispersity coefficient 0.20；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 630nm, polydispersity coefficient 0.26, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 3 times, shows good pH responses.
Embodiment 11
A kind of preparation method of pH response types copolymer nano hydrogel, basic step is same as Example 7, and difference exists
In the monomer of its addition to further including acrylamide and methacrylic acid, wherein monomeric acrylamide and monomer methacrylic acid
Molar ratio is 1.06：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 260nm, polydispersity coefficient 0.18；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 935nm, polydispersity coefficient 0.24, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 3.6 times, shows good pH responses.
Embodiment 12
A kind of preparation method of pH response types copolymer nano hydrogel, basic step is same as Example 8, and difference exists
In the monomer that it is added in further including methacrylic acid and 2- vinylpyridines, wherein monomer methacrylic acid and monomer 2- ethylene
The molar ratio of yl pyridines is 0.92：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 140nm, polydispersity coefficient 0.20；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 700nm, polydispersity coefficient 0.24, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 5 times, shows good pH responses.
Embodiment 13
A kind of preparation method of pH response types copolymer nano hydrogel, basic step is same as Example 8, and difference exists
In the monomer that it is added in further including acrylic acid and methacrylic acid -2- dimethylamine ethyl esters, wherein monomeric acrylic and monomer first
The molar ratio of base acrylic acid -2- dimethylamine ethyl esters is 1.02：1.
Its characterizing method is same as Example 1.
Characterization is it is found that pH response types copolymer nano hydrogel obtained is dispersed in gel in the deionized water that pH is 4
The mean hydrodynamic diameter of grain is 200nm, polydispersity coefficient 0.22；It is dispersed in gel in the deionized water that pH is 7
The mean hydrodynamic diameter of particle be 600nm, polydispersity coefficient 0.25, it is seen that when the pH value of medium increases to 7 by 4
When, the grain size of copolymer nano gel increases 3 times, shows good pH responses.
Embodiment 14~18
A kind of preparation method of pH response types copolymer nano hydrogel, step and parameter are substantially the same manner as Example 6,
Difference is the performance parameter of its surfactant added in twice, monomer A, monomer B and product, and wherein surfactant 1 is
The surfactant being dissolved in deionized water, the surfactant that surfactant 2 is added in for second, average hydrodynamic
The mean hydrodynamic diameter of gel particle in a diameter of product nano-hydrogel, polydispersity coefficient are more points of gel particle
Dissipate property coefficient, ratio refer to product be dispersed in pH be 7 deionized water in when gel particle mean hydrodynamic diameter and its
It is dispersed in the ratio between mean hydrodynamic diameter of gel particle when in the deionized water that pH is 4.
Embodiment 19~23
A kind of preparation method of pH response types copolymer nano hydrogel, step and parameter are substantially the same manner as Example 7,
Difference is the performance parameter of its surfactant added in twice, monomer A, monomer B and product, and wherein surfactant 1 is
The surfactant being dissolved in deionized water, the surfactant that surfactant 2 is added in for second, average hydrodynamic
The mean hydrodynamic diameter of gel particle in a diameter of product nano-hydrogel, polydispersity coefficient are more points of gel particle
Dissipate property coefficient, ratio refer to product be dispersed in pH be 7 deionized water in when gel particle mean hydrodynamic diameter and its
It is dispersed in the ratio between mean hydrodynamic diameter of gel particle when in the deionized water that pH is 4.
Embodiment 24~32
A kind of preparation method of pH response types copolymer nano hydrogel, step and parameter are substantially the same manner as Example 8,
Difference is the performance parameter of its surfactant added in twice, monomer A, monomer B and product, and wherein surfactant 1 is
The surfactant being dissolved in deionized water, the surfactant that surfactant 2 is added in for second, average hydrodynamic
The mean hydrodynamic diameter of gel particle in a diameter of product nano-hydrogel, polydispersity coefficient are more points of gel particle
Dissipate property coefficient, ratio refer to product be dispersed in pH be 7 deionized water in when gel particle mean hydrodynamic diameter and its
It is dispersed in the ratio between mean hydrodynamic diameter of gel particle when in the deionized water that pH is 4.
Claims (10)
1. a kind of preparation method of pH response types copolymer nano hydrogel, it is characterized in that：Containing hydrophobic initiator and surface work
Property agent aqueous dispersions in add in the monomer pair that hydrogen bond action or positive and negative charge effect can mutually occur, and add in crosslinking agent and exist
It is reacted under oxygen-free environment and 40~80 DEG C of temperature conditions and pH response type copolymer nano hydrogels is made.
A kind of 2. preparation method of pH response types copolymer nano hydrogel according to claim 1, which is characterized in that institute
When stating surfactant as ionic surfactant, the interaction between monomer pair is anti-when being hydrogen bond action and reaction beginning
It is 1.5~3.0 to answer system pH；When surfactant is nonionic surface active agent, the interaction between monomer pair is just
Negative electrical charge acts on.
A kind of 3. preparation method of pH response types copolymer nano hydrogel according to claim 2, which is characterized in that tool
Body step is as follows：
(1) hydrophobic initiator and surfactant are dispersed in deionized water；
(2) monomer pair and crosslinking agent are added in, is reacted under oxygen-free environment and 40~80 DEG C of temperature conditions；
(3) surfactant is added in 1.0 hours again after the start of the reaction the reaction was continued 3~6h, the copolymerization of pH response types is made
Object nano-hydrogel；
After adding in surfactant again, monomer is to a concentration of 20~80g/L in reaction system；It is described to add in surface-active again
The quality of agent accounts for the 75~80% of the total addition of surfactant.
A kind of 4. preparation method of pH response types copolymer nano hydrogel according to claim 2, which is characterized in that tool
Body step is as follows：
(1) hydrophobic initiator and surfactant are dispersed in deionized water；
(2) monomer pair and crosslinking agent are added in, 3~6h is reacted under oxygen-free environment and 40~80 DEG C of temperature conditions, pH responses are made
Type copolymer nano hydrogel；React a concentration of 20~70g/L of monomer pair in system when starting.
A kind of 5. preparation method of pH response types copolymer nano hydrogel according to claim 1, which is characterized in that institute
Oxygen-free environment is stated as nitrogen or ar gas environment；The monomer is to including mole of monomer A and monomer B, the monomer A and monomer B
Than being 0.9~1.1：1；The addition monomer pair and crosslinking agent add in aqueous dispersions after referring to uniform mix monomer pair and crosslinking agent
In.
A kind of 6. preparation method of pH response types copolymer nano hydrogel according to claim 1, which is characterized in that institute
The gross mass for stating surfactant is monomer to the 10~30% of quality；The quality of the hydrophobic initiator is monomer to quality
1.0~3.5%；The quality of the crosslinking agent is monomer to the 10~25% of quality；
The surfactant is anionic surfactant, cationic surface active agent or non-ionic surfactant
Agent；
The hydrophobic initiator is the hydrophobic initiator of azo or the hydrophobic initiator of organic peroxide class；
The crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate or N, N '-methylene-bisacrylamide.
A kind of 7. preparation method of pH response types copolymer nano hydrogel according to claim 6, which is characterized in that institute
It states anionic surfactant and is selected from neopelex, Aerosol OT and lauryl sodium sulfate
One kind or two kinds；
The cationic surface active agent is alkyl quaternary ammonium salts cationic surface active agent, specially trimethyl
Ammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyl trimethyl ammonium bromide and hexadecane
One kind in base trimethylammonium bromide or two kinds；
The nonionic surface active agent be selected from O-20, O-15, AEO-15, AEO-7, OP-15, OP-20, OP-30, tween-
20th, one kind of Tween-40, Tween-60 and Tween-80 or two kinds；
The hydrophobic initiator of azo is azodiisobutyronitrile, azobisisoheptonitrile or azo-bis-iso-dimethyl；
The hydrophobic initiator of organic peroxide class is benzoyl peroxide or the benzoyl peroxide tert-butyl ester.
A kind of 8. preparation method of pH response types copolymer nano hydrogel according to claim 1, which is characterized in that institute
State monomer to be selected from the alpha-olefin with the carboxyl and alpha-olefin with amide groups, the alpha-olefin with carboxyl and hydroxyl alpha-olefin,
Alpha-olefin with carboxyl is with the alpha-olefin with pyrrolidone-base, the alpha-olefin with carboxyl and the alpha-olefin with amido and with carboxyl
Alpha-olefin and alpha-olefin with pyridyl group in a pair more than.
A kind of 9. preparation method of pH response types copolymer nano hydrogel according to claim 8, which is characterized in that institute
It states the alpha-olefin with carboxyl and the alpha-olefin with amide groups is selected from methacrylic acid and acrylamide and acrylic acid and acryloyl
It is more than a pair in amine；
The alpha-olefin with carboxyl and hydroxyl alpha-olefin are selected from acrylic acid and hydroxyethyl methacrylate and methyl-prop
It is more than a pair in olefin(e) acid and hydroxyethyl methacrylate；
The alpha-olefin with carboxyl is selected from acrylic acid and vinyl pyrrolidone and first with the alpha-olefin with pyrrolidone-base
It is more than a pair in base acrylic acid and vinyl pyrrolidone；
The alpha-olefin with carboxyl and the alpha-olefin with amido be selected from acrylic acid and vinylamine, methacrylic acid and vinylamine,
One in acrylic acid and methacrylic acid -2- dimethylamine ethyl ester and methacrylic acid and methacrylic acid -2- dimethylamine ethyl esters
To more than；
The alpha-olefin with carboxyl and the alpha-olefin with pyridyl group be selected from acrylic acid and 4-vinylpridine, methacrylic acid and
It is more than a pair in 4-vinylpridine, acrylic acid and 2- vinylpyridines and methacrylic acid and 2- vinylpyridines.
10. a kind of preparation method of pH response types copolymer nano hydrogel according to claim 1, which is characterized in that
In the pH response types copolymer nano hydrogel mean hydrodynamic diameter of gel particle be 60~300nm, polydispersity
Coefficient is that 0.10~0.30, pH response type copolymer nano hydrogels are dispersed in gel particle when in the deionized water that pH is 7
The ratio between mean hydrodynamic diameter of gel particle is when mean hydrodynamic diameter is dispersed in it in deionized water that pH is 4
1.9~5.8:1.
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