CN106366225B - Six arm temperature sensing polymers and preparation method thereof - Google Patents
Six arm temperature sensing polymers and preparation method thereof Download PDFInfo
- Publication number
- CN106366225B CN106366225B CN201610957656.1A CN201610957656A CN106366225B CN 106366225 B CN106366225 B CN 106366225B CN 201610957656 A CN201610957656 A CN 201610957656A CN 106366225 B CN106366225 B CN 106366225B
- Authority
- CN
- China
- Prior art keywords
- temperature sensing
- solvent
- polymer
- temperature
- sensing polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
This application provides a kind of temperature sensing polymers with formula (I) structure; it is using dipentaerythritol as core; it is reacted with acylating agent by it; obtain initiator; again by initiator and temperature sensitive monomer by atom transfer radical polymerization, the active temperature sensing polymer that chain length is uniform, molecular weight is controllable has been obtained；The end of polymer is finally subjected to Azide, obtains the temperature sensing polymer for having azido to end.Compared with prior art, the polymer of the application has the characteristics that easy easily implementation, and arm number, brachium are controllable, flexible structure is adjustable, facilitate modification, while it has excellent application prospect with good Thermo-sensitive and close to the use scope of environment temperature.
Description
Technical field
The invention belongs to polymer chemistry and technical field of material chemistry, more particularly to a kind of six arm temperature sensing polymers and its system
Preparation Method.
Background technology
Multi-arm star polymer is that one kind is connected to by covalent bond on core by a plurality of polymeric arms, and is collectively constituted with core
A kind of polymer with star topology；Since its spherical branched structure of special three-dimensional and characteristic, star polymer become
One of the hot spot of polymeric material field research.Star polymer has more terminal functional groups, can be by modifying
To the polymer of different structure and performance.Responsive to temperature type star polymer is that one kind itself can be to the thin of ambient temperature
Microvariations responds, and generates the variation even family macromolecule of mutation of corresponding physical arrangement and chemical property.Polymer
The temperature that phase transition occurs for aqueous solution is known as lowest critical solution temperature (LCST).Star temperature sensing polymer is due in stagnation temperature
Nearby larger volume change can occur for degree, it is made to be widely used in the fields such as medicine, biology, cosmetics, sensor,
Therefore, the unique structure of star temperature sensing polymer has received widespread attention with performance.By in temperature sensing polymer end
Functional group is introduced, makes it that can widen its application field and value with other more functional group reactions.
Traditional free radical polymerization is easy to cause the molecular weight of polymer, molecular weight distribution, chain structure due to being difficult to control
And end degree of functionality is out of control, the reactions such as branched, crosslinking even occurs sometimes, to seriously affect high molecular performance and make
Use range.In recent years, with the development of Controlled/Living Radical Polymerization technology, the synthesis of star-type polymer is more prone to, kind
Class is also more.The advantages that wherein ATRP reacts easily operated, mild condition (not needing stringent water removal, deoxygenation), while again
The characteristics of having living polymerization concurrently, however, it would be possible to make all free yl polymerizating monomers carry out controllable/" activity " polymerization, and effectively
Polymer is modified, therefore is had broad application prospects in terms of Molecular Design.
Invention content
Present invention solves the technical problem that being to provide a kind of six arm temperature sensing polymers of the end with azido, this Shen
The polymer that please be provided is with Thermo-sensitive and end is with azido group.
In view of this, this application provides a kind of temperature sensing polymer with formula (I) structure,
Wherein, R is methyl or hydrogen；
N is 5~100；
A is polymerize by temperature sensitive monomer to be formed, and the temperature sensitive monomer is selected from n-isopropyl acrylamide, N- propyl acryloyls
Amine, N- cyclopropyl acrylamide, N, N- acrylamides, N- vinyl Isopropamide, the positive propionamide of N- vinyl, N- second
Alkenyl caprolactam, n-vinyl pyrrolidone, N- acryloyl groups pyrrolidines, N- acryloyl groups-N '-positive Propylpiperazine, N- (2,2-
- 5 alcohol of dimethyl -1,3- dioxanes) one kind in-acrylamide and N- (- 5 alcohol of 2- ethyoxyls -1,3- dioxanes)-acrylamide
Or it is a variety of.
Preferably, the R is hydrogen or methyl, and the temperature sensitive monomer is selected from n-isopropyl acrylamide, N- propyl propylene
Amide, N, it is one or more in N- acrylamides, N- vinyl Isopropamide and N- caprolactams.
Preferably, the number-average molecular weight of the temperature sensing polymer is 3000~50000g/mol, PDI ＜ 1.3.
Present invention also provides the preparation methods of the temperature sensing polymer, include the following steps：
A), under inert gas and anhydrous condition, by dipentaerythritol, acid binding agent, catalyst and there is formula (II) structure
Acylating agent react in a solvent, obtain the initiator with formula (III) structure；
B), under inert gas protection, the initiator, temperature sensitive monomer, catalyst and complexant is anti-in a solvent
It answers, obtains the active temperature sensing polymer with formula (IV) structure；The temperature sensitive monomer is selected from n-isopropyl acrylamide, N-
Propylacrylamide, N- cyclopropyl acrylamide, N, N- acrylamides, N- vinyl Isopropamide, N- vinyl are just
Propionamide, N- caprolactams, n-vinyl pyrrolidone, N- acryloyl groups pyrrolidines, N- acryloyl groups-N '-positive third
Piperazine, N- (- 5 alcohol of 2,2- dimethyl -1,3- dioxanes)-acrylamides and N- (- 5 alcohol of 2- ethyoxyls -1,3- dioxanes)-propylene
It is one or more in amide；
C), the active temperature sensing polymer is reacted in a solvent with sodium azide, obtains the temperature with formula (I) structure
Sensitive polymer；
Wherein, R is methyl or hydrogen；
N is 5~100；
A is polymerize by temperature sensitive monomer to be formed, and the temperature sensitive monomer is selected from n-isopropyl acrylamide, N- propyl acryloyls
Amine, N- cyclopropyl acrylamide, N, N- acrylamides, N- vinyl Isopropamide, the positive propionamide of N- vinyl, N- second
Alkenyl caprolactam, n-vinyl pyrrolidone, N- acryloyl groups pyrrolidines, N- acryloyl groups-N '-positive Propylpiperazine, N- (2,2-
- 5 alcohol of dimethyl -1,3- dioxanes) one kind in-acrylamide and N- (- 5 alcohol of 2- ethyoxyls -1,3- dioxanes)-acrylamide
Or it is a variety of.
Preferably, the step A) in, the acid binding agent is pyridine or triethylamine；The catalyst is 4- dimethylaminos
Pyridine；The solvent is dichloromethane or acetonitrile, and the acylating agent is selected from the bromo- 2- methyl propionyl chlorides of 2-, the bromo- 2- methyl propionyl of 2-
Bromine, 2- chloro-2-methyls propionyl chloride, 2- chloro-2-methyls propionyl bromide, chloro-acetyl chloride, chloroacetyl bromine, bromo acetyl bromide, bromo
Chloroacetic chloride, 2 bromo propionyl bromide, 2- bromo propionyl chloros, 2- chlorine propionyl bromide or 2- chlorpromazine chlorides.
Preferably, the step A) in, the molar ratio of the dipentaerythritol, acid binding agent and acylating agent is 1：(6.1~
6.5)：(6.1~6.5).
Preferably, the step B) in, the catalyst is selected from stannous chloride, cuprous bromide, cuprous sulfocyanide and hexafluoro
It is one or more during phosphoric acid is cuprous；The complexant is selected from tetramethylethylenediamine, N, N, N ', N ", N, " the sub- second of-pentamethyl two
Base triamine, 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triens, three-(2- methylaminoethyls) amine and three-(2- ethylamino second
Base) it is one or more in amine；The solvent is the mixed solvent of n,N-Dimethylformamide and deionized water.
Preferably, the step B) in, the initiator, temperature sensitive monomer, the molar ratio of catalyst and complexant are 1：
(30~500)：(0.5~12)：(0.5~12).
Preferably, the molar ratio of the active temperature sensing polymer and the sodium azide is 1：(6~36).
This application provides a kind of temperature sensing polymers with formula (I) structure to pass through using dipentaerythritol as core
It is reacted with acylating agent, has obtained initiator, then obtained by atom transfer radical polymerization with initiator and temperature sensitive monomer
The active temperature sensing polymer that chain length is uniform, molecular weight is controllable is arrived；Finally by active polymer ends Azide, end is obtained
Temperature sensing polymer containing azido.This application provides a kind of polymer with Thermo-sensitive, further, the application's
Polymer ends contain azido functional group, have a plurality of segment, intermolecular to have larger space, polymer is to the anti-of temperature
Answer more sensitive, Thermo-sensitive is good, and intermolecular cycloaddition reaction can also occur, and new official can be efficiently introduced by click-reaction
Energy group or polymer segment, for further structure novel block polymer, dendritic and three-dimensional network polymeric material
Material provides approach.
Description of the drawings
Fig. 1 is the initiator prepared in step 1) in the embodiment of the present invention 11H-NMR spectrum；
Fig. 2 is the embodiment of the present invention 1) six arm star temperature sensing polymers for preparing1H-NMR spectrum；
Fig. 3 be the embodiment of the present invention 1) prepare six arm star temperature sensing polymers gel permeation chromatography spectrogram；
Fig. 4 is six arm star temperature sensing polymer infrared spectrums before and after end Azide prepared by the embodiment of the present invention 1.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of temperature sensing polymer with formula (I) structure,
Wherein, R is methyl or hydrogen；
N is 5~100；
A is polymerize by temperature sensitive monomer to be formed, and the temperature sensitive monomer is selected from n-isopropyl acrylamide, N- propyl acryloyls
Amine, N- cyclopropyl acrylamide, N, N- acrylamides, N- vinyl Isopropamide, the positive propionamide of N- vinyl, N- second
Alkenyl caprolactam, n-vinyl pyrrolidone, N- acryloyl groups pyrrolidines, N- acryloyl groups-N '-positive Propylpiperazine, N- (2,2-
- 5 alcohol of dimethyl -1,3- dioxanes) one kind in-acrylamide and N- (- 5 alcohol of 2- ethyoxyls -1,3- dioxanes)-acrylamide
Or it is a variety of.
This application provides a kind of novel polymer, are a kind of six arm Thermo-sensitives that azido group is contained in end polymerizations
Object.
On temperature responsive polymer chain, usually has a certain proportion of hydrophilic functional groups (such as ester group, amide groups) concurrently and dredge
Water functional group (alkane group).When the temperature is low, the hydrophilic radical on macromolecular chain can form hydrogen bond with hydrone, at this time
Macromolecule-hydrone interaction force be more than macromolecule-macromolecule interaction force, hydrophily account for it is leading, at macromolecular chain
In extended configuration；And when temperature raising, the hydrogen bond between macromolecule and water constantly weakens, while the hydrophobic work between macromolecular chain
Reinforced with gradual；When temperature is higher than lower critical solution temperature (lower critical solutiontemperature, LCST)
When, the hydrophobic effect between macromolecule-macromolecule is more than the interaction force between macromolecule-hydrone in turn, high at this time
The hydrophobicity of strand occupies leading, and performance macroscopically is then that a large amount of water in polymeric colloid are discharged, and gel is sent out therewith
It is raw to shrink.
In the application, preferably, A in the temperature sensing polymer preferably by n-isopropyl acrylamide,
N- propylacrylamides, N, N- acrylamides or N- vinyl Isopropamides polymerize to be formed, obtained Thermo-sensitive polymerization
Object has formula (I1), formula (I2), formula (I3) or formula (I4) shown in structure；
The number-average molecular weight of herein described temperature sensing polymer is preferably 3000~50000g/mol, PDI ＜ 1.3；Institute
The number-average molecular weight for stating temperature sensing polymer is more preferably 6000~25000g/mol, and PDI is 1.2~1.0.
Present invention also provides the preparation methods of above-mentioned temperature sensing polymer, include the following steps：
A), under inert gas and anhydrous condition, by dipentaerythritol, acid binding agent, catalyst and there is formula (II) structure
Acylating agent react in a solvent, obtain the initiator with formula (III) structure；
B), under inert gas protection, the initiator, temperature sensitive monomer, catalyst and complexant is anti-in a solvent
It answers, obtains the active temperature sensing polymer with formula (IV) structure；The temperature sensitive monomer is selected from n-isopropyl acrylamide, N-
Propylacrylamide, N- cyclopropyl acrylamide, N, N- acrylamides, N- vinyl Isopropamide, N- vinyl are just
Propionamide, N- caprolactams, n-vinyl pyrrolidone, N- acryloyl groups pyrrolidines, N- acryloyl groups-N '-positive third
Piperazine, N- (- 5 alcohol of 2,2- dimethyl -1,3- dioxanes)-acrylamides and N- (- 5 alcohol of 2- ethyoxyls -1,3- dioxanes)-propylene
It is one or more in amide；
C), the active temperature sensing polymer is reacted in a solvent with sodium azide, obtains the temperature with formula (I) structure
Sensitive polymer；
Wherein, R is methyl or hydrogen；
N is 5~100；
A is polymerize by temperature sensitive monomer to be formed, and the temperature sensitive monomer is selected from n-isopropyl acrylamide, N- propyl acryloyls
Amine, N- cyclopropyl acrylamide, N, N- acrylamides, N- vinyl Isopropamide, the positive propionamide of N- vinyl, N- second
Alkenyl caprolactam, n-vinyl pyrrolidone, N- acryloyl groups pyrrolidines, N- acryloyl groups-N '-positive Propylpiperazine, N- (2,2-
- 5 alcohol of dimethyl -1,3- dioxanes) one kind in-acrylamide and N- (- 5 alcohol of 2- ethyoxyls -1,3- dioxanes)-acrylamide
Or it is a variety of.
During preparing temperature sensing polymer, the application is prepared for initiator first, i.e., by dipentaerythritol, tie up acid
Agent, catalyst react in a solvent with the acylating agent with formula (II) structure, obtain the initiator with formula (III) structure；In order to
Reaction is abundant, and the process for preparing initiator is specially：
Under inert gas and anhydrous condition, dipentaerythritol, acid binding agent are mixed with catalyst, under condition of ice bath,
Acylating agent is added dropwise in said mixture, keeps 1~2h of low temperature, then be slowly increased to room temperature, reaction 6~for 24 hours, caused
Agent.
The reaction equation of above-mentioned reaction is as follows：
During preparing initiator, hydroxyl is reacted with carboxylic acid halides, generates ester group and halogen acids, and the presence of halogen acids influences
The yield of reaction, it is therefore desirable to using the acid in acid binding agent removal reaction process, it be made to generate complex salt, to improve the receipts of reaction
Rate.Herein described acid binding agent is that acid binding agent well known to those skilled in the art shows in this regard, the application is not particularly limited
Example, the acid binding agent is preferably selected from pyridine or triethylamine.
The acylating agent is the raw material with the glycol reaction, it is preferred that the acylating agent is preferably selected from the bromo- 2- first of 2-
The bromo- 2- methyl propionyl bromide of base propionyl chloride, 2-, 2- chloro-2-methyls propionyl chloride, 2- chloro-2-methyls propionyl bromide, chloro-acetyl chloride, chlorine
For acetyl bromide, bromo acetyl bromide, bromoacetyl chlorine, 2 bromo propionyl bromide, 2- bromo propionyl chloros, 2- chlorine propionyl bromide or 2- chlorpromazine chlorides；
More preferably 2- bromine isobutyl acylbromides.The catalyst is preferably 4-dimethylaminopyridine；The solvent be preferably dichloromethane or
Acetonitrile.Preferably, the molar ratio of 1, the 3- dihydroxy adamantines, acid binding agent and acylating agent is preferably 1：(6.1~
6.5)：(6.1~6.5).
Pure initiator in order to obtain, after above-mentioned reaction, the application preferably washes obtained product successively
It washs, rotary evaporation, cross chromatographic column, rotary evaporation and drying.The washing is followed successively by 5% sodium bicarbonate solution, saturated common salt
Water and deionized water；The rotary evaporation is that the organic solvent after washing is removed through depressurizing rotary evaporation.It is described cross chromatographic column be
Neutral alumina chromatographic column, solvent are that the ratio of ethyl acetate and n-hexane is 1:2(V/V).
The application carries out the preparation of active temperature sensing polymer, i.e., then using initiator as reaction raw materials：In indifferent gas
Under body protection, the initiator, temperature sensitive monomer, catalyst are reacted in a solvent with complexant, obtains tying with formula (IV)
The active temperature sensing polymer of structure；The temperature sensitive monomer is selected from n-isopropyl acrylamide, N- propylacrylamides, N- rings third
Base acrylamide, N, N- acrylamides, N- vinyl Isopropamide, the positive propionamide of N- vinyl, N- vinyl are in oneself
Amide, n-vinyl pyrrolidone, N- acryloyl groups pyrrolidines, N- acryloyl groups-N '-positive Propylpiperazine, N- (2,2- dimethyl-
- 5 alcohol of 1,3- dioxanes) it is one or more in-acrylamide and N- (- 5 alcohol of 2- ethyoxyls -1,3- dioxanes)-acrylamide；
In order to make reaction carry out more abundant, above-mentioned reaction is specially：
Above-mentioned initiator, temperature sensitive monomer, complexant and solvent are added in dry anhydrous and oxygen-free reaction bulb, with anti-
Mouthful rubber stopper is sealed, and after vacuumizing-leading to nitrogen 3 times, under nitrogen protection, rapidly joins catalyst, vacuumize-lead to nitrogen
It 3 times, is reacted 2~6 hours at 20~60 DEG C, obtains active temperature sensing polymer.Above-mentioned reaction process is specially：
During preparing active temperature sensing polymer, the temperature sensitive monomer has occurred atom with the initiator and turns
Move free radical polymerization.The main function of herein described complexant is to increase solubility and adjustment of the catalyst in organic phase to urge
The oxidation-reduction potential of agent so that catalyst reaches activity needed for reaction, and matches kinetically being reacted with ATRP；
Specifically it is exactly that balance is made to be biased to generate the direction of suspend mode kind significantly in reversible passivation reaction, to obtain relatively low reactive species
Concentration avoids irreversible termination from reacting；Ensure constant number of free radical, all polymer chains made to increase with identical rate,
Make polymer unification.To obtain that there is the polymer of predetermined molecular weight, Narrow Molecular Weight Distribution and structure-controllable.The application institute
It is complexant well known to those skilled in the art to state complexant, and exemplary, the complexant is preferably selected from tetramethylethylenediamine
(TMEDA), N, N, N ', N ", N "-five methyl diethylentriamine (PMDETA), 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triethylenes
Tetramine (HMTETA), three-(2- methylaminoethyls) amine (Me6- TREN) and three-(2- ethylaminoethyls) amine (Et6TREN in)
It is one or more, more preferable three-(2- methylaminoethyls) amine (Me6- TREN) or N, N, N ', N ", N " ,-pentamethyl diethylidene
Triamine (PMDETA).The catalyst is catalyst well known to those skilled in the art, is not particularly limited to this application,
It is exemplary, the catalyst be preferably selected from stannous chloride, cuprous bromide, cuprous sulfocyanide and hexafluorophosphoric acid it is cuprous in one kind or
It is a variety of, more preferably cuprous bromide.The temperature sensitive monomer be preferably selected from n-isopropyl acrylamide, N- propylacrylamides,
N- cyclopropyl acrylamide, N, N- acrylamides, N- vinyl Isopropamide, the positive propionamide of N- vinyl, N- ethylene
Base caprolactam, n-vinyl pyrrolidone, N- acryloyl groups pyrrolidines, N- acryloyl groups-N '-positive Propylpiperazine, N- (2,2- bis-
Methyl-1, -5 alcohol of 3- dioxanes)-acrylamide and one kind in N- (- 5 alcohol of 2- ethyoxyls -1,3- dioxanes)-acrylamide or
It is a variety of, more preferably n-isopropyl acrylamide, N- propylacrylamides, N, N- acrylamides, N- vinyl isopropyls
Amide and N- caprolactams are one or more；The solvent is molten for the mixing of n,N-Dimethylformamide and deionized water
Agent.The initiator, temperature sensitive monomer, the molar ratio of catalyst and complexant are 1：(30~500)：(0.5~12)：(0.5~
12)。
Obtained product after reacting, is preferably added four by pure active temperature sensing polymer in order to obtain, the application
Hydrogen furans dilutes, and stirring terminates polymerization in air；Again using tetrahydrofuran as eluent, pass through silica gel-neutral alumina color
It composes column and removes catalyst, after rotary evaporation removes solvent, then obtain active temperature through precipitating, filtering and be dried in vacuo successively
Sensitive polymer.
In above-mentioned purification process, in the silica gel-neutral alumina chromatographic column silica gel and neutral alumina be 200~
300 mesh, and upper layer is neutral alumina, lower layer is silica gel, highly than being 1:3；Precipitating reagent used in the precipitation is ether, stone
Oily ether mixed solvent or n-hexane, ether, petroleum ether mixed solvent ratio are 1:1~3 (V/V), wherein with 1:2 be best.
The application, with reaction of sodium azide, obtains temperature sensing polymer finally using active temperature sensing polymer as raw material.On
The reaction equation for stating reaction is as follows：
During above-mentioned mistake, the temperature of the reaction is preferably 40~80 DEG C, and time of the reaction is preferably 24~
96h；The molar ratio of the activity temperature sensing polymer and the sodium azide is preferably 1:6~1:36, more preferably 1:18.
After reaction, the purification of products that will be obtained, specially：
Reaction solution is added in bag filter, first water is changed within every 6 hours, is dialysed 48~96 hours；By rotary evaporation
After removing solvent, then the line style temperature sensing polymer for containing azido in end is obtained through precipitating, filtering and be dried in vacuo successively.
In the above process, the rotary evaporation is to be removed by the organic solvent of chromatographic column through depressurizing rotary evaporation；It is described
Be precipitated as by after rotary evaporation product dissolved with tetrahydrofuran after, be added dropwise to dropwise in a large amount of cold n-hexanes, repeat this
Operation 2~3 times.
The preparation method of the present invention is easy to operate, and reaction condition is mild, and since the application uses atom transferred free radical
Polymerization, makes the brachium of temperature sensing polymer be easy to control, molecular weight distribution is relatively narrow, and adjustable in wider range；This hair simultaneously
The polymer of azido functional group is contained in bright prepared end, has a plurality of segment, intermolecular to have larger space, polymerization
Object is more sensitive to the reaction of temperature, and Thermo-sensitive is good, and intermolecular cycloaddition reaction can also occur for azido group, is synthesis triazole
The classical way of nitrogen heterocycles；Azido functional group in macromolecule can efficiently by click-reaction introduce new functional group or
Polymer segment polymerize for further structure novel topological structure, such as block polymer, dendritic and three-dimensional network
Object material provides precisely efficiently approach.
For a further understanding of the present invention, with reference to embodiment to temperature sensing polymer provided by the invention and its preparation
Method is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Dipentaerythritol (2.55g, 10mmol) is added and contains triethylamine (6.19g, 61mmol) and dichloromethane 50ml
Solution in, stir 30min under condition of ice bath.2- bromine isobutyl acylbromides (14.07g, 61mmol) are passed through into constant pressure funnel
It is slowly added in 1 hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 12 hours.Reaction knot
Shu Hou, by obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water
(100ml*3) is washed successively.Organic layer rotary evaporation after washing is removed into solvent, is used in combination dichloromethane to dissolve, is slowly added dropwise
Into ice ether, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, true
It is dry in empty drying box, obtain white crystal initiator.Fig. 1 is the initiator as core prepared by the step1H-NMR is composed
Figure, solvent are that deuterochloroform (is referred to as：d-CDCl3)；
By n-isopropyl acrylamide 4g, initiator 0.1353g, three (2- dimethylaminoethyls) amine 0.1626g additions have
In the reaction bulb of Teflon stir.N,N-Dimethylformamide 10ml and deionized water 5ml is added, stirring is fully molten
Solution.Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalyst
0.1018g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, under the conditions of 30 DEG C of reaction temperature, 2 are stirred to react
Hour.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：18 molar ratio is dissolved in N, between N- dimethyl in amide, in 60 DEG C of stirring conditions
Under, it reacts 48 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
White solid powder, with formula (I5) structure.Test result shows temperature sensing polymer aqueous solution manufactured in the present embodiment
LCST is 32 DEG C.
Fig. 2 is temperature sensing polymer manufactured in the present embodiment1H-NMR spectrum, solvent are that heavy water (is referred to as：D2O)；Fig. 3
For the gel permeation chromatography spectrogram (abbreviation of temperature sensing polymer manufactured in the present embodiment：GPC), mobile phase is tetrahydrofuran, mark
Sample is polystyrene；Fig. 4 is the linear temperature sensing polymer infrared spectrum before and after end Azide manufactured in the present embodiment.
Embodiment 2
Dipentaerythritol (2.55g, 10mmol) is added and contains pyridine (5.135g, 65mmol) and tetrahydrofuran 100ml
Solution in, stir 30min under condition of ice bath.2- bromine isobutyl acylbromides (14.95g, 65mmol) are passed through into constant pressure funnel
It is slowly added in 1 hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 24 hours.Reaction knot
Shu Hou, by obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water
(100ml*3) is washed successively.Organic layer rotary evaporation after washing is removed into solvent, is used in combination dichloromethane to dissolve, is slowly added dropwise
Into ice ether, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, true
It is dry in empty drying box, obtain white crystal initiator.
By n-isopropyl acrylamide 1g, initiator 0.3363g, three (2- dimethylaminoethyls) amine 0.0.0337g additions
In the reaction bulb for having Teflon stir.N,N-Dimethylformamide 5ml and deionized water 5ml is added, stirring is fully molten
Solution.Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalyst
0.0211g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, under the conditions of 20 DEG C of reaction temperature, 2 are stirred to react
Hour.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 50ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：36 molar ratio is dissolved in N, between N- dimethyl in amide, in 40 DEG C of stirring conditions
Under, it reacts 48 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
White solid powder temperature sensing polymer.Test result shows the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment
It is 32 DEG C.
Embodiment 3
Dipentaerythritol (3g, 11.8mmol) is added containing pyridine (5.97g, 76mmol) and dichloromethane 100ml
In solution, 30min is stirred under condition of ice bath.By 2- bromine isobutyl acylbromides (17.37g, 76mmol) by constant pressure funnel 1
It is slowly added in hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 24 hours.Reaction terminates
Afterwards, with 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*3) washes successively
It washs.Organic layer rotary evaporation after washing is removed into solvent, is used in combination dichloromethane to dissolve, is slowly dropped in ice ether, and 0
12 hours are stood at DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, dry in vacuum drying chamber, it obtains
To white crystal initiator.
By n-isopropyl acrylamide 4g, initiator 0.2029, three (2- dimethylaminoethyls) amine 0.1625g additions have poly-
In the reaction bulb of tetrafluoroethene stirrer.N,N-Dimethylformamide 10ml and deionized water 5ml is added, stirring is fully dissolved.
Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalyst
0.1018g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, under the conditions of 40 DEG C of reaction temperature, 4 are stirred to react
Hour.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：12 molar ratio is dissolved in N, between N- dimethyl in amide, in 50 DEG C of stirring conditions
Under, it reacts 72 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
White solid powder temperature sensing polymer.Test result shows the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment
It is 32 DEG C.
Embodiment 4
Dipentaerythritol (2.55g, 10mmol) is added and contains triethylamine (6.375g, 63mmol) and tetrahydrofuran
In the solution of 100ml, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (14.49g, 63mmol) are passed through into constant pressure addition
Funnel is slowly added in 1 hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 12 hours.Instead
After answering, by obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionization
Water (100ml*3) washs successively.Organic layer rotary evaporation after washing is removed into solvent, dichloromethane is used in combination to dissolve, is slowly dripped
It is added in ice ether, and 12 hours is stood at 0 DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, exist
It is dry in vacuum drying chamber, obtain white crystal initiator.
By n-isopropyl acrylamide 4g, initiator 0.0812g, three (2- dimethylaminoethyls) amine 0.1951g additions have
In the reaction bulb of Teflon stir.N,N-Dimethylformamide 15ml and deionized water 7.5ml is added, stirs, fully
Dissolving.Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalysis
Agent 0.1221g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, it under the conditions of 60 DEG C of reaction temperature, is stirred to react
6 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：6 molar ratio is dissolved in N, between N- dimethyl in amide, in 80 DEG C of stirring conditions
Under, it reacts 96 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
White solid powder temperature sensing polymer.Test result shows the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment
It is 32 DEG C.
Embodiment 5
Dipentaerythritol (2.55g, 10mmol) is added and contains triethylamine (6.375g, 64mmol) and tetrahydrofuran
In the solution of 100ml, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (14.72g, 64mmol) are passed through into constant pressure addition
Funnel is slowly added in 1 hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 12 hours.Instead
After answering, by obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionization
Water (100ml*3) washs successively.Organic layer rotary evaporation after washing is removed into solvent, dichloromethane is used in combination to dissolve, is slowly dripped
It is added in ice ether, and 12 hours is stood at 0 DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, exist
It is dry in vacuum drying chamber, obtain white crystal initiator.
By n-isopropyl acrylamide 4g, initiator 0.4058g, three (2- dimethylaminoethyls) amine 0.1626g additions have
In the reaction bulb of Teflon stir.N,N-Dimethylformamide 10ml and deionized water 5ml is added, stirring is fully molten
Solution.Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalyst
0.1018g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, under the conditions of 50 DEG C of reaction temperature, 3 are stirred to react
Hour.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：24 molar ratio is dissolved in N, between N- dimethyl in amide, in 80 DEG C of stirring conditions
Under, it reacts 48 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
White solid powder temperature sensing polymer.
Embodiment 6
Dipentaerythritol (2.55g, 10mmol) is added and contains pyridine (5.135g, 65mmol) and tetrahydrofuran 100ml
Solution in, stir 30min under condition of ice bath.2- bromine isobutyl acylbromides (14.95g, 65mmol) are passed through into constant pressure funnel
It is slowly added in 1 hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 24 hours.Reaction knot
Shu Hou, by obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water
(100ml*3) is washed successively.Organic layer rotary evaporation after washing is removed into solvent, is used in combination dichloromethane to dissolve, is slowly added dropwise
Into ice ether, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, true
It is dry in empty drying box, obtain white crystal initiator.
By propyl Methacrylamide 4g, initiator 0.1353g, three (2- dimethylaminoethyls) amine 0.1626g additions have poly-
In the reaction bulb of tetrafluoroethene stirrer.N,N-Dimethylformamide 5ml and deionized water 5ml is added, stirring is fully dissolved.
Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalyst
0.1018g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, under the conditions of 60 DEG C of reaction temperature, 4 are stirred to react
Hour.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 50ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：6 molar ratio is dissolved in N, between N- dimethyl in amide, in 80 DEG C of stirring conditions
Under, it reacts 48 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
With formula (I6) structure white solid powder temperature sensing polymer.Test result shows that Thermo-sensitive manufactured in the present embodiment is poly-
The LCST for closing object aqueous solution is 25 DEG C.
Embodiment 7
Dipentaerythritol (3g, 11.8mmol) is added containing pyridine (5.97g, 76mmol) and dichloromethane 100ml
In solution, 30min is stirred under condition of ice bath.By 2- bromine isobutyl acylbromides (17.37g, 76mmol) by constant pressure funnel 1
It is slowly added in hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 24 hours.Reaction terminates
Afterwards, by obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water
(100ml*3) is washed successively.Organic layer rotary evaporation after washing is removed into solvent, is used in combination dichloromethane to dissolve, is slowly added dropwise
Into ice ether, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, true
It is dry in empty drying box, obtain white crystal initiator.
By N, N- acrylamide 4g, initiator 0.1203, three (2- dimethylaminoethyls) amine 0.1447g, which are added, to be had
In the reaction bulb of Teflon stir.N,N-Dimethylformamide 10ml and deionized water 5ml is added, stirring is fully molten
Solution.Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalyst
0.0905g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, under the conditions of 70 DEG C of reaction temperature, 4 are stirred to react
Hour.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：18 molar ratio is dissolved in N, between N- dimethyl in amide, in 40 DEG C of stirring conditions
Under, it reacts 24 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
With (I7) structure white solid powder temperature sensing polymer.Test result shows Thermo-sensitive polymerization manufactured in the present embodiment
The LCST of object aqueous solution is 33 DEG C.
Embodiment 8
Dipentaerythritol (2.55g, 10mmol) is added and contains triethylamine (6.375g, 63mmol) and tetrahydrofuran
In the solution of 100ml, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (14.49g, 63mmol) are passed through into constant pressure addition
Funnel is slowly added in 1 hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 12 hours.Instead
After answering, by obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionization
Water (100ml*3) washs successively.Organic layer rotary evaporation after washing is removed into solvent, dichloromethane is used in combination to dissolve, is slowly dripped
It is added in ice ether, and 12 hours is stood at 0 DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, exist
It is dry in vacuum drying chamber, obtain white crystal initiator.
By N- vinylisobutyramide 4g, initiator 0.1353g, three (2- dimethylaminoethyls) amine 0.1626g additions have
In the reaction bulb of Teflon stir.N,N-Dimethylformamide 15ml and deionized water 7.5ml is added, stirs, fully
Dissolving.Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalysis
Agent 0.1018g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, it under the conditions of 60 DEG C of reaction temperature, is stirred to react
6 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：18 molar ratio is dissolved in N, between N- dimethyl in amide, in 60 DEG C of stirring conditions
Under, it reacts 72 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
With formula (I8) structure temperature sensing polymer white solid powder.Test result shows that Thermo-sensitive manufactured in the present embodiment is poly-
The LCST for closing object aqueous solution is 39 DEG C.
Embodiment 9
Dipentaerythritol (2.55g, 10mmol) is added and contains triethylamine (6.375g, 64mmol) and tetrahydrofuran
In the solution of 100ml, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (14.72g, 64mmol) are passed through into constant pressure addition
Funnel is slowly added in 1 hour, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 12 hours.Instead
After answering, by obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionization
Water (100ml*3) washs successively.Organic layer rotary evaporation after washing is removed into solvent, dichloromethane is used in combination to dissolve, is slowly dripped
It is added in ice ether, and 12 hours is stood at 0 DEG C.It is filtered with funnel, cold ether is used in combination to wash (10ml).At room temperature, exist
It is dry in vacuum drying chamber, obtain white crystal initiator.
By N- caprolactam 4g, initiator 0.1101g, three (2- dimethylaminoethyls) amine 0.1323g additions have
In the reaction bulb of Teflon stir.N,N-Dimethylformamide 10ml and deionized water 5ml is added, stirring is fully molten
Solution.Under stiring, after vacuumizing-leading to nitrogen 3 times.In nitrogen or argon gas protection atmosphere, it is rapidly added cuprous bromide catalyst
0.0828g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, under the conditions of 30 DEG C of reaction temperature, 4 are stirred to react
Hour.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.Using tetrahydrofuran as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes extra solvent, and crude product is dissolved by solvent of tetrahydrofuran, is delayed
Slowly it is added drop-wise to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.The product being filtered under diminished pressure is dry by 40 DEG C of vacuum
It is dry, obtain white solid powder activity temperature sensing polymer.
Polymer and sodium azide are pressed 1：18 molar ratio is dissolved in N, between N- dimethyl in amide, in 60 DEG C of stirring conditions
Under, it reacts 48 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, every 6 hours
A water is changed, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes extra solvent, and crude product is with tetrahydrochysene furan
It mutters and is dissolved for solvent, be slowly dropped in 150ml n-hexanes and precipitate.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying
With formula (I9) structure temperature sensing polymer white solid powder.Test result shows that Thermo-sensitive manufactured in the present embodiment is poly-
The LCST for closing object aqueous solution is 32 DEG C.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest range caused.
Claims (9)
1. one kind having the temperature sensing polymer of formula (I) structure,
Wherein, R is methyl or hydrogen；
N is 5~100；
A is polymerize by temperature sensitive monomer to be formed, the temperature sensitive monomer be selected from n-isopropyl acrylamide, N- propylacrylamides,
N- cyclopropyl acrylamide, N, one in N- acrylamides, N- caprolactams and n-vinyl pyrrolidone
Kind is a variety of.
2. temperature sensing polymer according to claim 1, which is characterized in that the R is hydrogen or methyl, the Thermo-sensitive list
Body is in n-isopropyl acrylamide, N- propylacrylamides, N, N- acrylamides and N- caprolactams
It is one or more.
3. temperature sensing polymer according to claim 1, which is characterized in that the number-average molecular weight of the temperature sensing polymer
For 3000~50000g/mol, PDI ＜ 1.3.
4. the preparation method of temperature sensing polymer described in claim 1, includes the following steps：
A), under inert gas and anhydrous condition, by dipentaerythritol, acid binding agent, catalyst and the acyl with formula (II) structure
Agent is reacted in a solvent, obtains the initiator with formula (III) structure；
B), under inert gas protection, the initiator, temperature sensitive monomer, catalyst are reacted in a solvent with complexant, is obtained
To the active temperature sensing polymer with formula (IV) structure；The temperature sensitive monomer is selected from n-isopropyl acrylamide, N- propyl
Acrylamide, N- cyclopropyl acrylamide, N, N- acrylamides, N- caprolactams and N- ethenyl pyrrolidones
It is one or more in ketone；
C), the active temperature sensing polymer is reacted in a solvent with sodium azide, obtains the Thermo-sensitive with formula (I) structure
Polymer；
Wherein, R is methyl or hydrogen；
N is 5~100；
X is Cl or Br；
A is polymerize by temperature sensitive monomer to be formed, the temperature sensitive monomer be selected from n-isopropyl acrylamide, N- propylacrylamides,
N- cyclopropyl acrylamide, N, one in N- acrylamides, N- caprolactams and n-vinyl pyrrolidone
Kind is a variety of.
5. preparation method according to claim 4, which is characterized in that the step A) in, the acid binding agent be pyridine or
Triethylamine；The catalyst is 4-dimethylaminopyridine；The solvent is dichloromethane or acetonitrile, and the acylating agent is selected from 2-
Bromo- 2- methyl propionyl chloride, the bromo- 2- methyl propionyl bromides of 2-, 2- chloro-2-methyls propionyl chloride, chloro-acetyl chloride, bromo acetyl bromide, bromine
For chloroacetic chloride, 2 bromo propionyl bromide, 2- bromo propionyl chloros or 2- chlorpromazine chlorides.
6. preparation method according to claim 4, which is characterized in that the step A) in, the dipentaerythritol ties up acid
The molar ratio of agent and acylating agent is 1：(6.1~6.5)：(6.1~6.5).
7. preparation method according to claim 4, which is characterized in that the step B) in, the catalyst is selected from chlorination
It is one or more in cuprous, cuprous bromide and cuprous sulfocyanide；The complexant is selected from tetramethylethylenediamine, N, N, N ', N ",
N, "-five methyl diethylentriamine, 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triens, three-(2- methylaminoethyls) amine and
It is one or more in three-(2- ethylaminoethyls) amine；The solvent is the mixing of n,N-Dimethylformamide and deionized water
Solvent.
8. preparation method according to claim 4, which is characterized in that the step B) in, the initiator, Thermo-sensitive list
The molar ratio of body, catalyst and complexant is 1：(30~500)：(0.5~12)：(0.5~12).
9. preparation method according to claim 4, which is characterized in that the activity temperature sensing polymer and the Azide
The molar ratio of sodium is 1：(6~36).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610957656.1A CN106366225B (en) | 2016-10-27 | 2016-10-27 | Six arm temperature sensing polymers and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610957656.1A CN106366225B (en) | 2016-10-27 | 2016-10-27 | Six arm temperature sensing polymers and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106366225A CN106366225A (en) | 2017-02-01 |
| CN106366225B true CN106366225B (en) | 2018-08-10 |
Family
ID=57893654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610957656.1A Active CN106366225B (en) | 2016-10-27 | 2016-10-27 | Six arm temperature sensing polymers and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106366225B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016324B (en) * | 2018-01-10 | 2021-08-17 | 中国石油化工股份有限公司 | High-temperature-resistant water-based drilling fluid shear strength improving agent and preparation method thereof |
| CN109705371B (en) * | 2018-12-29 | 2021-05-11 | 广东工业大学 | Supramolecular material, six-arm star-shaped cross-linked hydrogel and preparation method thereof |
| CN109705372B (en) * | 2018-12-29 | 2021-08-13 | 广东工业大学 | Supramolecular material, hydrogel and preparation method thereof |
| CN109721738B (en) * | 2018-12-29 | 2021-04-16 | 广东工业大学 | Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787105A (en) * | 2010-02-10 | 2010-07-28 | 东南大学 | Preparation method of network interpenetrating functional aquagel |
-
2016
- 2016-10-27 CN CN201610957656.1A patent/CN106366225B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787105A (en) * | 2010-02-10 | 2010-07-28 | 东南大学 | Preparation method of network interpenetrating functional aquagel |
Non-Patent Citations (2)
| Title |
|---|
| AMA-m-P( AA-co-NVP) 共聚物水凝胶的合成与溶胀性能研究;刘明凯，梁成峰，郭建维;《合成材料老化与应用》;20110630;第40卷(第3期);第14-16页 * |
| KATJA JANKOVA, MELANIA BEDNAREK,SØREN HVILSTED.Star Polymers by ATRP of Styrene and Acrylates Employing Multifunctional Initiators.《Journal of Polymer Science: Part A: Polymer Chemistry》.2005,第43卷(第17期),第3748-3759页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106366225A (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106366225B (en) | Six arm temperature sensing polymers and preparation method thereof | |
| CN106496387A (en) | Four arm temperature sensing polymers and preparation method thereof | |
| CN103214680B (en) | Preparation method and application method of novel amphipathic copolymerization network | |
| CN106633087B (en) | Miscellaneous arm star polymer of a kind of eight arms and preparation method thereof | |
| Chen et al. | Synthesis of linear amphiphilic tetrablock quaterpolymers with dual stimulus response through the combination of ATRP and RAFT by a click chemistry site transformation approach | |
| CN106519154B (en) | Linear temperature sensing polymer and preparation method thereof | |
| CN107446146A (en) | A kind of hydrogel for possessing photochromic characteristic and preparation method thereof | |
| Hou et al. | Synthesis of poly (2-hydroxyethyl methacrylate) end-capped with asymmetric functional groups via atom transfer radical polymerization | |
| CN106496388A (en) | Four arm temperature sensing polymer of adamantyl and preparation method thereof | |
| CN109705290B (en) | Temperature-responsive side-chain photosensitive block copolymer and preparation method thereof | |
| CN107236067B (en) | Adamantyl both arms temperature sensing polymer and preparation method thereof | |
| CN102344524B (en) | Water-soluble click-reaction hyperbranched polymer | |
| CN104628948B (en) | Acrylate-type poly-chain transfer agent as well as preparation method and application of poly-chain transfer agent in preparation of columnar polymer brush | |
| CN101402713B (en) | Process for producing hydrogel with optical activity | |
| CN110003410B (en) | Six-arm star copolymer and preparation method thereof | |
| CN101955561A (en) | Vinyl alcohol series polymer | |
| CN111253536A (en) | Polypropylene triblock copolymer responding to temperature and pH and preparation method thereof | |
| JP5083556B2 (en) | Living radical polymerization initiator and method for producing polymer | |
| CN107383377B (en) | Cyclic polycaprolactone-polyethylene glycol amphiphilic block copolymer, and preparation and application thereof | |
| EP1688440A1 (en) | Novel hyperbranched polymer | |
| CN107674158B (en) | Temperature-sensitive hydrogel with hyperbranched structure and preparation method and application thereof | |
| CN106117401A (en) | A kind of novel method being prepared ferrocene-based polymer by controllable type polyacrylonitrile resin | |
| CN105085844A (en) | Diblock copolymer for oil-water separation with temperature control wetting property and preparing method thereof | |
| CN103980398A (en) | Self-assembly with perylene derivative or analog as fluorescent chromogenic end group and preparation method thereof | |
| CN101724125A (en) | Hydrophobic association polymer with cation surface active monomer and synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |