CN106519154B - Linear temperature sensing polymer and preparation method thereof - Google Patents
Linear temperature sensing polymer and preparation method thereof Download PDFInfo
- Publication number
- CN106519154B CN106519154B CN201610957659.5A CN201610957659A CN106519154B CN 106519154 B CN106519154 B CN 106519154B CN 201610957659 A CN201610957659 A CN 201610957659A CN 106519154 B CN106519154 B CN 106519154B
- Authority
- CN
- China
- Prior art keywords
- temperature sensing
- solvent
- polymer
- sensing polymer
- reaction
- 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
- 0 CC(C)NC(C(CC(C)(C)C(C)(C)C)C(C)(C)*)=O Chemical compound CC(C)NC(C(CC(C)(C)C(C)(C)C)C(C)(C)*)=O 0.000 description 2
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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
Landscapes
- 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 ethylene glycol 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 linear temperature sensing polymer and its system
Preparation Method.
Background technology
Linear polymer structure is the most common type in macromolecule topological structure.Due to there are two free ends,
So that linear macromolecule chain end has larger degree of freedom relative to chain middle section.Responsive to temperature type linear polymer is one
Class itself can respond the slight change of ambient temperature, generate the variation of corresponding physical arrangement and chemical property
An even family macromolecule of mutation.The temperature that phase transition occurs for aqueous solutions of polymers is known as lowest critical solution temperature (LCST).
Line style temperature sensing polymer makes it in medicine, biology, makeup since larger volume change can occur near critical-temperature
The fields such as product, sensor are widely used, therefore the unique structure of line style temperature sensing polymer receives widely with performance
Concern.By introducing functional group in temperature sensing polymer end, make it that can widen it with other more functional group reactions and answer
With field and value.
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 polymer is more prone to, type
More.The advantages that wherein ATRP reacts easily operated, mild condition (not needing stringent water removal, deoxygenation), while having concurrently again
The characteristics of living polymerization, however, it would be possible to make all free yl polymerizating monomers carry out controllable/" activity " polymerization, and effectively to poly-
It closes object to be modified, therefore has broad application prospects in terms of Molecular Design.
Invention content
Present invention solves the technical problem that being to provide a kind of line style temperature sensing polymer 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 10~100；
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- ethyoxyl -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 2000~20000g/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 ethylene glycol, 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 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- ethyoxyl -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 10~100；
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- ethyoxyl -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 ethylene glycol, acid binding agent and acylating agent is 1：(2.1~2.5)：
(2.1~2.5).
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：
(20~200)：(0.5~4)：(0.5~4).
Preferably, the molar ratio of the active temperature sensing polymer and the sodium azide is 1：(2~20).
This application provides a kind of temperature sensing polymers with formula (I) structure, using ethylene glycol as core, by with acyl
Agent is reacted, and 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；Finally by active polymer ends Azide, obtains end and contain
The temperature sensing polymer of azido.This application provides a kind of polymer with Thermo-sensitive, further, the polymerization of the application
Azido functional group is contained in object end, and intermolecular cycloaddition reaction can occur, and can efficiently be introduced newly by click-reaction
Functional group or polymer segment, for further structure novel block polymer, dendritic and three-dimensional network polymer
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) the line style temperature sensing polymer for preparing1H-NMR spectrum；
Fig. 3 be the embodiment of the present invention 1) prepare line style temperature sensing polymer gel permeation chromatography spectrogram；
Fig. 4 is the linear temperature sensing polymer infrared spectrum 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 10~100；
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- ethyoxyl -1,3- dioxanes)-acrylamide
Or it is a variety of.
This application provides a kind of novel polymer, are a kind of line style Thermo-sensitive 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 2000~20000g/mol, PDI ＜ 1.3；Institute
The number-average molecular weight for stating temperature sensing polymer is more preferably 4000~13000g/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 ethylene glycol, 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 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- ethyoxyl -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 10~100；
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- ethyoxyl -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 ethylene glycol, acid binding agent,
Catalyst reacts in a solvent with the acylating agent with formula (II) structure, obtains the initiator with formula (III) structure；In order to anti-
Should be abundant, the process for preparing initiator is specially：
Under inert gas and anhydrous condition, ethylene glycol, acid binding agent are mixed with catalyst, under condition of ice bath, by acyl
Agent is added dropwise in said mixture, keeps 1~2h of low temperature, then be slowly increased to room temperature, and reaction 6~for 24 hours, obtain initiator.
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 preferredChoosingFrom 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 preferred dichloromethane of the solvent or second
Nitrile.Preferably, the molar ratio of 1, the 3- dihydroxy adamantines, acid binding agent and acylating agent is preferably 1：(2.1~
2.5)：(2.1~2.5).
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- ethyoxyl -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- ethyoxyl -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: (20~200)：(0.5~4)：(0.5~
4)。
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：
In above process, 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 1:2~1:20, more preferably 1:10.
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 line temperature sensing polymer be easy to control, molecular weight distribution is relatively narrow, and adjustable in wider range；Simultaneously originally
The polymer of azido functional group is contained in the prepared end of invention, and generable intermolecular cycloaddition reaction 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
Ethylene glycol (2.5g, 40mmol) is added to molten containing triethylamine (9.18g, 90mmol) and dichloromethane 75ml
In liquid, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (20.70g, 90mmol) is small 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 12 hours.After reaction,
By obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*
3) it washs successively.Organic layer rotary evaporation after washing is removed into solvent；It uses ethyl acetate to dissolve again, crosses neutral alumina
Column, with ethyl acetate：N-hexane 1:2 (V/V) are eluent, and after rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to
In ice ethyl alcohol, and 12 hours are stood at 0 DEG C, is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml), at room temperature, in vacuum
It is dry in drying box, obtain white crystal two-(2- bromine isobutyls acyloxy) ethylene glycol initiator.Fig. 1 is work prepared by the step
For the initiator of core1H-NMR spectrum, solvent are that deuterochloroform (is referred to as：d-CDCl3)；
By n-isopropyl acrylamide 4g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.1272g, three (2- diformazans
Amino-ethyl) amine 0.1629g, being added has in the reaction bulb of Teflon stir.N,N-dimethylformamide 10ml is added
With deionized water 5ml, stirring is fully dissolved.Under stiring, after vacuumizing-leading to nitrogen 3 times.Atmosphere is protected in nitrogen or argon gas
In, it is rapidly added cuprous bromide catalyst 0.1018g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, it reacts
Under the conditions of 25 DEG C of temperature, it is stirred to react 2 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, it is small that 1 is stirred in air
When.Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product
It is dissolved by solvent of tetrahydrofuran, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.Decompression
The product of filtering obtains white solid powder activity temperature sensing polymer by 40 DEG C of vacuum drying.
Polymer and Sodium azide are pressed 1：10 molar ratio is dissolved in N, between N- dimethyl in amide, 60 DEG C, and under stirring condition,
Reaction 48 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 150ml n-hexanes and is precipitated.The product being filtered under diminished pressure obtains white solid by 40 DEG C of vacuum drying
Powder, with formula (I5) structure.Test result shows that the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment is 32
℃。
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
The solution containing pyridine (6.636g, 84mmol) and tetrahydrofuran 30ml is added in ethylene glycol (2.5g, 40mmol)
In, stir 30min under condition of ice bath.By 2- bromine isobutyl acylbromides (19.32g, 84mmol) by constant pressure funnel at 1 hour
It is inside slowly added to, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 24 hours.After reaction, will
Obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*3)
It washs successively.Organic layer rotary evaporation after washing is removed into solvent.It is dissolved with ethyl acetate, neutral alumina column is crossed, with second
Acetoacetic ester：N-hexane 1:2 (V/V) are eluent.After rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to ice ethyl alcohol
In, and stand 24 hours at 0 DEG C.It is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml).At room temperature, in vacuum drying chamber
In be dried to obtain white crystal two-(2- bromine isobutyls acyloxy) ethylene glycol initiator.
By n-isopropyl acrylamide 4g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.0640g, three (2- diformazans
Amino-ethyl) amine 0.1626g, being added has in the reaction bulb of Teflon stir.N,N-dimethylformamide 10ml is added
With deionized water 10ml, stirring is fully dissolved.Under stiring, after vacuumizing-leading to nitrogen 3 times.Atmosphere is protected in nitrogen or argon gas
In, it is rapidly added cuprous bromide catalyst 0.1018g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, it reacts
Under the conditions of temperature 60 C, it is stirred to react 6 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, it is small that 1 is stirred in air
When.Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product
It is dissolved by solvent of tetrahydrofuran, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.Decompression
The product of filtering obtains white solid powder activity temperature sensing polymer by 40 DEG C of vacuum drying.
Polymer and Sodium azide are pressed 1：2 molar ratio is dissolved in N, between N- dimethyl in amide, 80 DEG C, and under stirring condition,
Reaction 96 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 150ml n-hexanes and is precipitated.The product being filtered under diminished pressure obtains white solid by 40 DEG C of vacuum drying
Powder temperature sensing polymer.Test result shows that the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment is 32 DEG C.
Embodiment 3
The solution containing pyridine (7.9g, 100mmol) and tetrahydrofuran 30ml is added in ethylene glycol (2.5g, 40mmol)
In, stir 30min under condition of ice bath.2- bromine isobutyl acylbromides (23.19g, 100mmol) is small 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 6 hours.After reaction,
By obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*
3) it washs successively.Organic layer rotary evaporation after washing is removed into solvent.It is dissolved with ethyl acetate, crosses neutral alumina column, with
Ethyl acetate：N-hexane 1:2 (V/V) are eluent.After rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml).At room temperature, it is being dried in vacuo
White crystal two-(2- bromine isobutyls acyloxy) ethylene glycol initiator is dried to obtain in case.
By n-isopropyl acrylamide 1g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.1590g, three (2- diformazans
Amino-ethyl) amine 0.0508g addition has in the reaction bulb of Teflon stir.Be added N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring are 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 0.0318g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, reaction temperature
Under the conditions of 20 DEG C of degree, it is stirred to react 2 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.
Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product with
Tetrahydrofuran dissolves for solvent, is slowly dropped to ether：Petroleum ether=1:1 (V/V) 50ml is to be precipitated in precipitating reagent.It is filtered under diminished pressure
Product by 40 DEG C vacuum drying, obtain white solid powder activity temperature sensing polymer.
Polymer and Sodium azide are pressed 1：20 molar ratio is dissolved in N, between N- dimethyl in amide, 40 DEG C, and under stirring condition,
Reaction 24 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 50ml n-hexanes and is precipitated.The product being filtered under diminished pressure obtains white solid by 40 DEG C of vacuum drying
Powder temperature sensing polymer.Test result shows that the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment is 32 DEG C.
Embodiment 4
Ethylene glycol (2.0g, 32.3mmol) is added molten containing pyridine (5.606g, 71mmol) and tetrahydrofuran 50ml
In liquid, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (16.32g, 71mmol) is small 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 16 hours.After reaction,
By obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*
3) it washs successively.Organic layer rotary evaporation after washing is removed into solvent.It is dissolved with ethyl acetate, crosses neutral alumina column, with
Ethyl acetate：N-hexane 1:2 (V/V) are eluent.After rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml).At room temperature, it is being dried in vacuo
White crystal initiator two-(2- bromine isobutyls acyloxy) ethylene glycol is dried to obtain in case.
By n-isopropyl acrylamide 4g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.0848g, three (2- diformazans
Amino-ethyl) amine 0.2545g addition has in the reaction bulb of Teflon stir.Be added N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring are 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 0.1593g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, reaction temperature
Under the conditions of 30 DEG C of degree, it is stirred to react 4 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.
Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product with
Tetrahydrofuran dissolves for solvent, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.It depressurized
The product of filter obtains white solid powder activity temperature sensing polymer by 40 DEG C of vacuum drying.
Polymer and Sodium azide are pressed 1：10 molar ratio is dissolved in N, between N- dimethyl in amide, 50 DEG C, and under stirring condition,
Reaction 48 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 150ml n-hexanes and is precipitated.It is solid to obtain white by 40 DEG C of vacuum drying for the product being filtered under diminished pressure
Body powder temperature sensing polymer.Test result shows that the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment is 32 DEG C.
Embodiment 5
Ethylene glycol (1.55g, 25mmol) is added molten containing triethylamine (6.072g, 60mmol) and tetrahydrofuran 50ml
In liquid, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (13.8g, 60mmol) is small 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 12 hours.After reaction,
By obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*
3) it washs successively.Organic layer rotary evaporation after washing is removed into solvent.It is dissolved with ethyl acetate, crosses neutral alumina column, with
Ethyl acetate：N-hexane 1:2 (V/V) are eluent.After rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml).At room temperature, it is being dried in vacuo
It is dry in case, obtain white crystal initiator two-(2- bromine isobutyls acyloxy) ethylene glycol.
By n-isopropyl acrylamide 4g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.2120g, three (2- diformazans
Amino-ethyl) amine 0.1355g addition has in the reaction bulb of Teflon stir.Be added N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring are 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 0.0848g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, reaction temperature
Under the conditions of 40 DEG C of degree, it is stirred to react 5 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.
Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product with
Tetrahydrofuran dissolves for solvent, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.It depressurized
The product of filter obtains white solid powder activity temperature sensing polymer by 40 DEG C of vacuum drying.
Polymer and Sodium azide are pressed 1：5 molar ratio is dissolved in N, between N- dimethyl in amide, 70 DEG C, and under stirring condition,
Reaction 72 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 150ml n-hexanes and is precipitated.It is solid to obtain white by 40 DEG C of vacuum drying for the product being filtered under diminished pressure
Body powder temperature sensing polymer.Test result shows that the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment is 32 DEG C.
Embodiment 6
The solution containing pyridine (6.636g, 84mmol) and tetrahydrofuran 30ml is added in ethylene glycol (2.5g, 40mmol)
In, stir 30min under condition of ice bath.By 2- bromine isobutyl acylbromides (19.32g, 84mmol) by constant pressure funnel at 1 hour
It is inside slowly added to, continues to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 24 hours.After reaction, will
Obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*3)
It washs successively.Organic layer rotary evaporation after washing is removed into solvent.It is dissolved with ethyl acetate, neutral alumina column is crossed, with second
Acetoacetic ester：N-hexane 1:2 (V/V) are eluent.After rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to ice ethyl alcohol
In, and stand 24 hours at 0 DEG C.It is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml).At room temperature, in vacuum drying chamber
Middle drying obtains white crystal initiator two-(2- bromine isobutyls acyloxy) ethylene glycol.
By N- propyl Methacrylamide 4g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.1273g, three (2- diformazans
Amino-ethyl) amine 0.1626g, being added has in the reaction bulb of Teflon stir.N,N-dimethylformamide 10ml is added
With deionized water 10ml, stirring is fully dissolved.Under stiring, after vacuumizing-leading to nitrogen 3 times.Atmosphere is protected in nitrogen or argon gas
In, it is rapidly added cuprous bromide catalyst 0.1018g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, it reacts
Under the conditions of temperature 60 C, it is stirred to react 6 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, it is small that 1 is stirred in air
When.Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product
It is dissolved by solvent of tetrahydrofuran, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.Decompression
The product of filtering obtains white solid powder activity temperature sensing polymer by 40 DEG C of vacuum drying.
Polymer and Sodium azide are pressed 1：2 molar ratio is dissolved in N, between N- dimethyl in amide, 80 DEG C, and under stirring condition,
Reaction 96 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 150ml n-hexanes and is precipitated.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying with formula
(Ⅰ6) structure temperature sensing polymer white solid powder.Test result shows temperature sensing polymer water manufactured in the present embodiment
The LCST of solution is 25 DEG C.
Embodiment 7
The solution containing pyridine (7.9g, 100mmol) and tetrahydrofuran 30ml is added in ethylene glycol (2.5g, 40mmol)
In, stir 30min under condition of ice bath.2- bromine isobutyl acylbromides (23.19g, 100mmol) is small 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 6 hours.After reaction,
By obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*
3) it washs successively.Organic layer rotary evaporation after washing is removed into solvent.It is dissolved with ethyl acetate, crosses neutral alumina column, with
Ethyl acetate：N-hexane 1:2 (V/V) are eluent.After rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml).At room temperature, it is being dried in vacuo
It is dry in case, obtain white crystal initiator two-(2- bromine isobutyls acyloxy) ethylene glycol.
By N, N- acrylamide 4g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.1132g, three (2- bis-
Methylaminoethyl) amine 0.1447g addition has in the reaction bulb of Teflon stir.N,N-dimethylformamide 10ml is added
With deionized water 5ml, stirring is fully dissolved.Under stiring, after vacuumizing-leading to nitrogen 3 times.Atmosphere is protected in nitrogen or argon gas
In, it is rapidly added cuprous bromide catalyst 0.0906g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, it reacts
Under the conditions of 25 DEG C of temperature, it is stirred to react 2 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, it is small that 1 is stirred in air
When.Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product
It is dissolved by solvent of tetrahydrofuran, is slowly dropped to ether：Petroleum ether=1:1 (V/V) 50ml is to be precipitated in precipitating reagent.It depressurized
The product of filter obtains white solid powder activity temperature sensing polymer by 40 DEG C of vacuum drying.
Polymer and Sodium azide are pressed 1：20 molar ratio is dissolved in N, between N- dimethyl in amide, 40 DEG C, and under stirring condition,
Reaction 24 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 50ml n-hexanes and is precipitated.The product being filtered under diminished pressure is obtained by 40 DEG C of vacuum drying with formula
(Ⅰ7) structure temperature sensing polymer white solid powder.Test result shows temperature sensing polymer water manufactured in the present embodiment
The LCST of solution is 33 DEG C.
Embodiment 8
Ethylene glycol (2.0g, 32.3mmol) is added molten containing pyridine (5.606g, 71mmol) and tetrahydrofuran 50ml
In liquid, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (16.32g, 71mmol) is small 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 16 hours.After reaction,
By obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*
3) it washs successively.Organic layer rotary evaporation after washing is removed into solvent.It is dissolved with ethyl acetate, crosses neutral alumina column, with
Ethyl acetate：N-hexane 1:2 (V/V) are eluent.After rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml).At room temperature, it is being dried in vacuo
It is dry in case, obtain white crystal initiator two-(2- bromine isobutyls acyloxy) ethylene glycol.
By N- vinylisobutyramide 4g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.1273g, three (2- diformazans
Amino-ethyl) amine 0.1626g addition has in the reaction bulb of Teflon stir.Be added N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring are 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, reaction temperature
Under the conditions of 60 DEG C of degree, it is stirred to react 6 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.
Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product with
Tetrahydrofuran dissolves for solvent, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.It depressurized
The product of filter obtains white solid powder activity temperature sensing polymer by 40 DEG C of vacuum drying.
Polymer and Sodium azide are pressed 1：10 molar ratio is dissolved in N, between N- dimethyl in amide, 50 DEG C, and under stirring condition,
Reaction 48 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 150ml n-hexanes and is precipitated.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 temperature sensing polymer water manufactured in the present embodiment
The LCST of solution is 39 DEG C.
Embodiment 9
Ethylene glycol (1.55g, 25mmol) is added molten containing triethylamine (6.072g, 60mmol) and tetrahydrofuran 50ml
In liquid, 30min is stirred under condition of ice bath.2- bromine isobutyl acylbromides (13.8g, 60mmol) is small 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1~2 hour.Then it is gradually increased to room temperature, the reaction was continued 12 hours.After reaction,
By obtained product 5% sodium bicarbonate solution (100ml*3), saturated salt solution (100ml*3), deionized water (100ml*
3) it washs successively.Organic layer rotary evaporation after washing is removed into solvent.It is dissolved with ethyl acetate, crosses neutral alumina column, with
Ethyl acetate：N-hexane 1:2 (V/V) are eluent.After rotary evaporation, product is dissolved through dichloromethane, is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.It is filtered with funnel, cold ethyl alcohol is used in combination to wash (10ml).At room temperature, it is being dried in vacuo
It is dry in case, obtain white crystal two-(2- bromine isobutyls acyloxy) ethylene glycol.
By N- caprolactam 4g, initiator two-(2- bromine isobutyls acyloxy) ethylene glycol 0.1035g, three (2- diformazans
Amino-ethyl) amine 0.1322g addition has in the reaction bulb of Teflon stir.Be added N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring are 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 0.0828g, while vacuumizing-leading to nitrogen 3 times.Under nitrogen or argon, reaction temperature
Under the conditions of 40 DEG C of degree, it is stirred to react 5 hours.After reaction, add the tetrahydrofuran of 15ml to dilute, stirred 1 hour in air.
Using tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes extra solvent, crude product with
Tetrahydrofuran dissolves for solvent, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml are to be precipitated in precipitating reagent.It depressurized
The product of filter obtains white solid powder activity temperature sensing polymer by 40 DEG C of vacuum drying.
Polymer and Sodium azide are dissolved in N by 1: 10 molar ratio, between N- dimethyl in amide, 60 DEG C, under stirring condition,
Reaction 72 hours.After reaction, reaction solution is added in the bag filter of activation, using deionized water as solvent, changes one within every 6 hours
Secondary water dialyses two days, removes unreacted Sodium azide.Rotary evaporation removes extra solvent, and crude product is molten with tetrahydrofuran
Agent is dissolved, and is slowly dropped in 150ml n-hexanes and is precipitated.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 temperature sensing polymer water manufactured in the present embodiment
The LCST of 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 10~100；
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 2000~20000g/mol, polymer dispersity index ＜ 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 ethylene glycol, acid binding agent, catalyst and the acylating agent with formula (II) structure
It reacts 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 10~100；
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 ethylene glycol, acid binding agent with
The molar ratio of acylating agent is 1：(2.1~2.5)：(2.1~2.5).
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 and three-(2- methylaminoethyls) amine
In it is one or more；The solvent is the mixed solvent of n,N-Dimethylformamide and deionized water.
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：(20~200)：(0.5~4)：(0.5~4).
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：(2~20).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610957659.5A CN106519154B (en) | 2016-10-27 | 2016-10-27 | Linear temperature sensing polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610957659.5A CN106519154B (en) | 2016-10-27 | 2016-10-27 | Linear temperature sensing polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106519154A CN106519154A (en) | 2017-03-22 |
| CN106519154B true CN106519154B (en) | 2018-08-10 |
Family
ID=58325533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610957659.5A Active CN106519154B (en) | 2016-10-27 | 2016-10-27 | Linear temperature sensing polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106519154B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694479B (en) * | 2018-12-29 | 2021-05-28 | 广东工业大学 | Supermolecular material and host-guest self-assembly hydrogel and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100517101B1 (en) * | 2002-07-31 | 2005-09-27 | 한국과학기술연구원 | Dual Stimuli-Responsive Hydrogels and Their Synthetic Methods |
| DE102006037352A1 (en) * | 2006-08-09 | 2008-02-14 | Evonik Röhm Gmbh | Process for the preparation of acid-terminated ATRP products |
| CN103992452B (en) * | 2014-05-13 | 2016-08-17 | 同济大学 | A kind of star block copolymer possessing sugar, temperature, the triple sensitivity of pH and preparation method thereof |
-
2016
- 2016-10-27 CN CN201610957659.5A patent/CN106519154B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106519154A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106496387A (en) | Four arm temperature sensing polymers and preparation method thereof | |
| CN106366225B (en) | Six arm temperature sensing polymers and preparation method thereof | |
| Lee et al. | ATRP synthesis of amphiphilic random, gradient, and block copolymers of 2-(dimethylamino) ethyl methacrylate and n-butyl methacrylate in aqueous media | |
| CN110003481B (en) | Preparation method of eight-arm hetero-arm star polymer | |
| CN103214680B (en) | Preparation method and application method of novel amphipathic copolymerization network | |
| 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 | |
| Liu et al. | Preparation of thermoresponsive polymers bearing amino acid diamide derivatives via RAFT polymerization | |
| Hou et al. | Synthesis of poly (2-hydroxyethyl methacrylate) end-capped with asymmetric functional groups via atom transfer radical polymerization | |
| CN103261236B (en) | Curable compositions with moisture-urable functionality clusters near the chain ends | |
| CN106519154B (en) | Linear temperature sensing polymer and preparation method thereof | |
| CN103936947B (en) | A kind of preparation method of dual photosynthesis-carbon dioxide response block copolymer | |
| Ayres et al. | Synthesis of hydrophilic polar supports based on poly (dimethylacrylamide) via copper-mediated radical polymerization from a cross-linked polystyrene surface: potential resins for oligopeptide solid-phase synthesis | |
| Zhao et al. | Synthesis of Poly (methyl acrylate) Grafted onto Silica Particles by Z‐supported RAFT Polymerization | |
| CN106496388A (en) | Four arm temperature sensing polymer of adamantyl and preparation method thereof | |
| CN102344524B (en) | Water-soluble click-reaction hyperbranched polymer | |
| CN107236067B (en) | Adamantyl both arms temperature sensing polymer and preparation method thereof | |
| CN104628948A (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 | |
| CN109134769A (en) | A kind of producing high-molecular method of imide fluorescent dye | |
| CN111253536A (en) | Polypropylene triblock copolymer responding to temperature and pH and preparation method thereof | |
| CN110003410B (en) | Six-arm star copolymer and preparation method thereof | |
| CN101955561A (en) | Vinyl alcohol series polymer | |
| EP1688440A1 (en) | Novel hyperbranched polymer | |
| CN106117401A (en) | A kind of novel method being prepared ferrocene-based polymer by controllable type polyacrylonitrile resin | |
| CN105418844B (en) | A kind of preparation method of hydroxyl liquid rubber | |
| WO2011154977A1 (en) | 'process for the preparation of colesevelam hydrochloride" |
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 |