CN106519154A - Linear temperature sensitive polymers and a preparing method thereof - Google Patents
Linear temperature sensitive polymers and a preparing method thereof Download PDFInfo
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- CN106519154A CN106519154A CN201610957659.5A CN201610957659A CN106519154A CN 106519154 A CN106519154 A CN 106519154A CN 201610957659 A CN201610957659 A CN 201610957659A CN 106519154 A CN106519154 A CN 106519154A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Temperature sensitive polymers having a structure shown as a formula (I) are provided. Glycol is adopted as a core and is reacted with an acetylating agent to obtain an initiator, then the initiator and temperature sensitive monomers are subjected to atom transfer radical polymerization to obtain the active temperature sensitive polymers with uniform chain length and controllable molecular weights, and finally tails ends of the polymers are subjected to azidation to obtain the temperature sensitive polymers the tails ends of which are azido. Compared with the prior art, the polymers are characterized by being simple, convenient and easy to implement. The number and lengths of arms are controllable. Structures of the polymers can be flexibly adjusted so that modification is convenient. The polymers have good temperature sensitivity and a using temperature range close to the environment temperature and have a good application prospect.
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 modal one kind 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 mid portion.Responsive to temperature type linear polymer is one
Class itself is capable of the slight change of ambient temperature to external world and is responded, and produces the change of corresponding physical arrangement and chemical property
The family macromolecule being even mutated.The temperature that aqueous solutions of polymers occurs phase in version is referred to as lowest critical solution temperature (LCST).
Line style temperature sensing polymer is due to can occur larger change in volume near critical temperature so as in medicine, biological, cosmetic
The fields such as product, sensor are widely used, therefore the unique structure of line style temperature sensing polymer is received widely with performance
Concern.By introducing functional group in temperature sensing polymer end so as to can be with more other functional group reactionses, widening which should
With field and value.
Traditional radical polymerization is easily caused the molecular weight of polymer, molecular weight distribution, chain structure due to wayward
And end degree of functionality is out of control, even there is sometimes the reactions such as branched, crosslinking, so as to having a strong impact on high molecular performance and making
Use scope.In recent years, with the development of Controlled/Living Radical Polymerization technology, the synthesis of polymer is more prone to, species
It is more.Wherein ATRP reactions it is easily operated, the advantages of mild condition (not needing strict eliminating water, deoxygenation), while and having concurrently
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-
Compound is modified, therefore has broad application prospects in terms of Molecular Design.
The content of the invention
Present invention solves the technical problem that being to provide the line style temperature sensing polymer that a kind of end has azido, this Shen
The polymer that please be provided has Thermo-sensitive and end has 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 polymerized by temperature sensitive monomer and is formed, and the temperature sensitive monomer is selected from NIPA, N- propyl group acryloyls
Amine, N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, the positive propionic acid amide. of N- vinyls, N- second
Thiazolinyl caprolactam, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-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 various.
Preferably, the R is hydrogen or methyl, and the temperature sensitive monomer is selected from NIPA, N- propyl group propylene
Amide, N, one or more in N- acrylamides, N- vinyls 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 method of described temperature sensing polymer, comprises the following steps：
A), under noble gases 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 shielding, will be the initiator, temperature sensitive monomer, catalyst and complexant anti-in a solvent
Should, obtain the active temperature sensing polymer with formula IV structure；The temperature sensitive monomer is selected from NIPA, N-
Propylacrylamide, N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, N- vinyls are just
Propionic acid amide., N- caprolactams, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-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
One or more in amide；
C), the active temperature sensing polymer is reacted in a solvent with Hydrazoic acid,sodium salt, obtains the temperature with formula I structure
Sensitive polymer；
Wherein, R is methyl or hydrogen；
N is 10～100；
A is polymerized by temperature sensitive monomer and is formed, and the temperature sensitive monomer is selected from NIPA, N- propyl group acryloyls
Amine, N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, the positive propionic acid amide. of N- vinyls, N- second
Thiazolinyl caprolactam, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-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 various.
Preferably, 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-methyl propionyl chlorides, 2- chloro-2-methyl propionyl bromides, 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, step A) in, the mol ratio of the ethylene glycol, acid binding agent and acylating agent is 1：(2.1～2.5)：
(2.1～2.5).
Preferably, step B) in, the catalyst is selected from Cu-lyt., cuprous bromide, Cuprous sulfocyanate and hexafluoro
One or more during phosphoric acid is cuprous；The complexant is selected from tetramethylethylenediamine, N, N, N ', N ", N, " two sub- second of-pentamethyl
Base triamine, 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triens, three-(2- methylaminoethyls) amine and three-(2- ethylamino second
Base) one or more in amine；The solvent is the mixed solvent of DMF and deionized water.
Preferably, step B) in, the mol ratio of the initiator, temperature sensitive monomer, catalyst and complexant is 1：
(20～200)：(0.5～4)：(0.5～4).
Preferably, the active temperature sensing polymer and the mol ratio of the Hydrazoic acid,sodium salt are 1：(2～20).
This application provides a kind of temperature sensing polymer with formula I structure, its with ethylene glycol as core, by with acyl
Agent is reacted, and has obtained initiator, then has passed through atom transfer radical polymerization with temperature sensitive monomer with initiator, has obtained
The active temperature sensing polymer that chain length is homogeneous, molecular weight is controllable；Finally by active polymer ends Azide, obtain 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 thing end, and which can occur intermolecular cycloaddition reaction, efficiently can introduce new by click-reaction
Functional group or polymer segment, are further to build novel block polymer, dendritic and three-dimensional network polymer
Material provides approach.
Description of the drawings
Fig. 1 is step 1 in the embodiment of the present invention 1) the middle initiator for preparing1H-NMR spectrum；
Fig. 2 is the line style temperature sensing polymer that 1) embodiment of the present invention is prepared1H-NMR spectrum；
Fig. 3 is the gel permeation chromatography spectrogram of the line style temperature sensing polymer that 1) embodiment of the present invention is prepared；
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 embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limit.
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 polymerized by temperature sensitive monomer and is formed, and the temperature sensitive monomer is selected from NIPA, N- propyl group acryloyls
Amine, N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, the positive propionic acid amide. of N- vinyls, N- second
Thiazolinyl caprolactam, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-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 various.
This application provides a kind of new polymer, which is the line style Thermo-sensitive polymerization that azido group is contained in a kind of end
Thing.
On temperature responsive polymer chain, generally have 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 group on macromolecular chain can form hydrogen bond with hydrone, now
Macromolecule-hydrone interaction force is more than macromolecule-macromolecule interaction force, and its hydrophilic accounts for leading, at macromolecular chain
In extended configuration；And during temperature rising, the hydrogen bond between macromolecule and water constantly weakens, while the hydrophobic work between macromolecular chain
With gradually strengthening；When temperature is higher than lower critical solution temperature (lower critical solutiontemperature, LCST)
When, the hydrophobic interaction between macromolecule-macromolecule is in turn more than the interaction force between macromolecule-hydrone, now high
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, the A in the temperature sensing polymer preferably by NIPA,
N- propylacrylamides, N, N- acrylamides or N- vinyl Isopropamides are polymerized to be formed, the Thermo-sensitive polymerization for obtaining
Thing 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 method of above-mentioned temperature sensing polymer, comprises the following steps：
A), under noble gases 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 shielding, will be the initiator, temperature sensitive monomer, catalyst and complexant anti-in a solvent
Should, obtain the active temperature sensing polymer with formula IV structure；The temperature sensitive monomer is selected from NIPA, N-
Propylacrylamide, N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, N- vinyls are just
Propionic acid amide., N- caprolactams, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-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
One or more in amide；
C), the active temperature sensing polymer is reacted in a solvent with Hydrazoic acid,sodium salt, obtains the temperature with formula I structure
Sensitive polymer；
Wherein, R is methyl or hydrogen；
N is 10～100；
A is polymerized by temperature sensitive monomer and is formed, and the temperature sensitive monomer is selected from NIPA, N- propyl group acryloyls
Amine, N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, the positive propionic acid amide. of N- vinyls, N- second
Thiazolinyl caprolactam, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-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 various.
During temperature sensing polymer is prepared, the application is prepared for initiator first, will ethylene glycol, acid binding agent,
Catalyst is reacted 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 noble gases 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, is kept 1～2h of low temperature, then is slowly increased to room temperature, is reacted 6～24h, is obtained initiator.
The reaction equation of above-mentioned reaction is as follows：
During initiator is prepared, hydroxyl is reacted with carboxylic acid halides, generates ester group and halogen acids, and the presence of halogen acids affects
The yield of reaction, it is therefore desirable to the acid in course of reaction is removed using acid binding agent so as to generate complex salt, to improve the receipts of reaction
Rate.Herein described acid binding agent is acid binding agent well known to those skilled in the art, in this regard, the application has no particular limits, is shown
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-methyl propionyl chlorides, 2- chloro-2-methyl propionyl bromides, 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 DMAP；The preferred dichloromethane of the solvent or second
Nitrile.Preferably, the mol ratio of 1, the 3- dihydroxy adamantines, acid binding agent and acylating agent is preferably 1：(2.1～
2.5)：(2.1～2.5).
In order to obtain pure initiator, after above-mentioned reaction, the product for obtaining preferably is washed by the application successively
Wash, 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 Jing decompression rotary evaporations after washing are removed.It is described cross chromatographic column be
Neutral alumina chromatographic column, solvent are 1 for the ratio of ethyl acetate and normal hexane: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 and complexant are reacted in a solvent, obtain tying with formula IV
The active temperature sensing polymer of structure；The temperature sensitive monomer is selected from NIPA, N- propylacrylamides, N- rings third
Base acrylamide, N, N- acrylamides, N- vinyl Isopropamides, the positive propionic acid amide. of N- vinyls, N- vinyls are in oneself
Amide, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-N '-positive Propylpiperazine, N- (2,2- dimethyl-
- 5 alcohol of 1,3- dioxanes) one or more in-acrylamide and N- (- 5 alcohol of 2- ethyoxyl -1,3- dioxanes)-acrylamide；
In order that reaction carries 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 instead
Mouth rubber closure is sealed, and after evacuation-logical nitrogen 3 times, under nitrogen protection, rapidly joins catalyst, evacuation-logical nitrogen
3 times, react 2～6 hours at 20～60 DEG C, obtain active temperature sensing polymer.Above-mentioned course of reaction is specially：
During active temperature sensing polymer is prepared, with the initiator, the temperature sensitive monomer there occurs that atom turns
Move radical polymerization.The Main Function of herein described complexant is to increase dissolubility and adjustment of the catalyst in organic faciess and urges
The oxidation-reduction potential of agent, so that catalyst reaches activity needed for reaction, and is kinetically being matched with ATRP reactions；
Specifically it is exactly in reversible passivation reaction, make balance be partial to significantly the direction for generating dormancy kind, to obtain relatively low spike
Concentration, it is to avoid irreversible terminating reaction；Ensure constant number of free radical, all polymer chains is increased with identical speed,
Make polymer unification.So as to obtain the polymer with 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, example, and 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)
One or more, more preferably 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, and this application is had no particular limits,
Example, the catalyst be preferably selected from Cu-lyt., cuprous bromide, Cuprous sulfocyanate and hexafluorophosphoric acid it is cuprous in one kind or
It is various, more preferably cuprous bromide.The temperature sensitive monomer be preferably selected from NIPA, N- propylacrylamides,
N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, the positive propionic acid amide. of N- vinyls, N- ethylene
Base caprolactam, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-N '-positive Propylpiperazine, N- (2,2- bis-
Methyl isophthalic acid, -5 alcohol of 3- dioxanes) one kind in-acrylamide and N- (- 5 alcohol of 2- ethyoxyl -1,3- dioxanes)-acrylamide or
It is various, more preferably NIPA, N- propylacrylamides, N, N- acrylamides, N- vinyl isopropyls
One or more of amide and N- caprolactams；The solvent is that DMF is molten with the mixing of deionized water
Agent.The mol ratio of the initiator, temperature sensitive monomer, catalyst and complexant is 1: (20～200)：(0.5～4)：(0.5～
4)。
In order to obtain pure active temperature sensing polymer, the product for obtaining after reacting, is preferably added four by the application
Hydrogen furan dilutes, and stirring terminates polymerization in atmosphere；Again with tetrahydrofuran as eluent, by silica gel-neutral alumina color
Spectrum post removes catalyst, after rotary evaporation removes solvent, then Jing precipitations, filtration and vacuum drying successively, obtain active temperature
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 strata is neutral alumina, lower floor is silica gel, highly than for 1:3；Precipitant used by the precipitation is ether, stone
Oily ether mixed solvent or normal hexane, ether, petroleum ether mixed solvent ratio are 1:1～3 (V/V), wherein with 1:2 is optimal.
The application obtains temperature sensing polymer finally with active temperature sensing polymer as raw material with reaction of sodium azide.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 active temperature sensing polymer is preferably 1 with the mol ratio of the Hydrazoic acid,sodium salt:2～1:20, more preferably 1:10.
After reaction terminates, by the purification of products for obtaining, specially：
Reactant liquor is added in bag filter, first water was changed per 6 hours, dialysed 48～96 hours；Through rotary evaporation
After removing solvent, then Jing precipitations, filtration and vacuum drying successively, obtain the line style temperature sensing polymer for containing azido in end.
In said process, the rotary evaporation is to be removed by the organic solvent Jing decompression rotary evaporations of chromatographic column；It is described
After being precipitated as rotary evaporation product with tetrahydrofuran dissolving after, be dropwise added dropwise in a large amount of cold normal hexane, repeat this
Operation 2～3 times.
The preparation method of the present invention is simple to operate, and reaction condition is gentle, and as the application adopts atom transferred free radical
Polymerization, is easily controlled the brachium of line temperature sensing polymer, and molecular weight distribution is narrower, and adjustable in relative broad range；Originally simultaneously
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, is further to build novel topological structure, such as block polymer, dendritic and three-dimensional network polymerization
Thing material provides precisely efficiently approach.
For a further understanding of the present invention, the temperature sensing polymer provided to the present invention with reference to embodiment 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.Will be 2- bromine isobutyl acylbromides (20.70g, 90mmol) little 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 12 hours.After reaction terminates,
By the product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*
3) wash successively.Organic layer rotary evaporation after washing is removed into solvent；Dissolved using ethyl acetate again, cross neutral alumina
Post, with ethyl acetate：Normal hexane 1:2 (V/V) are eluent, and after rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to
In ice ethanol, and 12 hours are stood at 0 DEG C, filtered with funnel, and with cold washing with alcohol (10ml), under room temperature, in vacuum
It is dried in drying baker, obtains two-(2- bromine isobutyl acyloxy) ethylene glycol initiator of white crystal.Fig. 1 is work prepared by the step
For the initiator of core1H-NMR spectrum, solvent be deuterochloroform (referred to as：d-CDCl3)；
By NIPA 4g, two-(2- bromine isobutyl acyloxy) ethylene glycol 0.1272g of initiator, three (2- diformazans
Amino-ethyl) amine 0.1629g, during addition has the reaction bulb of Teflon stir.Add N,N-dimethylformamide 10ml
With deionized water 5ml, stirring, fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere
In, cuprous bromide catalyst 0.1018g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react
Under the conditions of 25 DEG C of temperature, stirring reaction 2 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, in air, stirring 1 is little
When.With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product
Dissolve by solvent of tetrahydrofuran, be slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml is precipitation in precipitant.Decompression
The product of filtration is vacuum dried through 40 DEG C, obtains white solid powder activity temperature sensing polymer.
Polymer is pressed into 1 with sodium azide：10 mol ratio is dissolved in N, between N- dimethyl in amide, 60 DEG C, and under stirring condition,
Reaction 48 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 150ml normal hexane.The product of filtration under diminished pressure obtains white solid through 40 DEG C of vacuum drying
Powder, which has formula (I5) structure.Result of the test 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 be heavy water (referred to as：D2O)；Fig. 3
Gel permeation chromatography spectrogram for temperature sensing polymer manufactured in the present embodiment is (referred to as：), 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
Ethylene glycol (2.5g, 40mmol) is added the solution containing pyridine (6.636g, 84mmol) and tetrahydrofuran 30ml
In, 30min is stirred under condition of ice bath.By 2- bromine isobutyl acylbromides (19.32g, 84mmol) by constant pressure funnel at 1 hour
Inside it is slowly added to, continues to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 24 hours.After reaction terminates, will
The product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*3)
Wash successively.Organic layer rotary evaporation after washing is removed into solvent.Dissolved with ethyl acetate, cross neutral alumina column, with second
Acetoacetic ester：Normal hexane 1:2 (V/V) are eluent.After rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to ice ethanol
In, and 24 hours are stood at 0 DEG C.Filtered with funnel, and with cold washing with alcohol (10ml).Under room temperature, in vacuum drying oven
In be dried to obtain two-(2- bromine isobutyl acyloxy) ethylene glycol initiator of white crystal.
By NIPA 4g, two-(2- bromine isobutyl acyloxy) ethylene glycol 0.0640g of initiator, three (2- diformazans
Amino-ethyl) amine 0.1626g, during addition has the reaction bulb of Teflon stir.Add N,N-dimethylformamide 10ml
With deionized water 10ml, stirring, fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere
In, cuprous bromide catalyst 0.1018g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react
Under the conditions of temperature 60 C, stirring reaction 6 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, in air, stirring 1 is little
When.With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product
Dissolve by solvent of tetrahydrofuran, be slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml is precipitation in precipitant.Decompression
The product of filtration is vacuum dried through 40 DEG C, obtains white solid powder activity temperature sensing polymer.
Polymer is pressed into 1 with sodium azide：2 mol ratio is dissolved in N, between N- dimethyl in amide, 80 DEG C, and under stirring condition,
Reaction 96 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 150ml normal hexane.The product of filtration under diminished pressure obtains white solid through 40 DEG C of vacuum drying
Powder temperature sensing polymer.Result of the test shows that the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment is 32 DEG C.
Embodiment 3
Ethylene glycol (2.5g, 40mmol) is added the solution containing pyridine (7.9g, 100mmol) and tetrahydrofuran 30ml
In, 30min is stirred under condition of ice bath.Will be 2- bromine isobutyl acylbromides (23.19g, 100mmol) little 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 6 hours.After reaction terminates,
By the product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*
3) wash successively.Organic layer rotary evaporation after washing is removed into solvent.Dissolved with ethyl acetate, cross neutral alumina column, with
Ethyl acetate：Normal hexane 1:2 (V/V) are eluent.After rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.Filtered with funnel, and with cold washing with alcohol (10ml).Under room temperature, in vacuum drying
Two-(2- bromine isobutyl acyloxy) ethylene glycol initiator of white crystal is dried to obtain in case.
By NIPA 1g, two-(2- bromine isobutyl acyloxy) ethylene glycol 0.1590g of initiator, three (2- diformazans
Amino-ethyl) amine 0.0508g add have Teflon stir reaction bulb in.Add N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere,
Cuprous bromide catalyst 0.0318g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react temperature
Under the conditions of 20 DEG C of degree, stirring reaction 2 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, stir 1 hour in air.
With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product with
Tetrahydrofuran is dissolved for solvent, is slowly dropped to ether：Petroleum ether=1:1 (V/V) 50ml is precipitation in precipitant.Filtration under diminished pressure
Product through 40 DEG C be vacuum dried, obtain white solid powder activity temperature sensing polymer.
Polymer is pressed into 1 with sodium azide：20 mol ratio is dissolved in N, between N- dimethyl in amide, 40 DEG C, and under stirring condition,
Reaction 24 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 50ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains white solid
Powder temperature sensing polymer.Result of the test 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.Will be 2- bromine isobutyl acylbromides (16.32g, 71mmol) little 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 16 hours.After reaction terminates,
By the product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*
3) wash successively.Organic layer rotary evaporation after washing is removed into solvent.Dissolved with ethyl acetate, cross neutral alumina column, with
Ethyl acetate：Normal hexane 1:2 (V/V) are eluent.After rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.Filtered with funnel, and with cold washing with alcohol (10ml).Under room temperature, in vacuum drying
Two-(2- bromine isobutyl acyloxy) ethylene glycol of white crystal initiator is dried to obtain in case.
By NIPA 4g, two-(2- bromine isobutyl acyloxy) ethylene glycol 0.0848g of initiator, three (2- diformazans
Amino-ethyl) amine 0.2545g add have Teflon stir reaction bulb in.Add N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere,
Cuprous bromide catalyst 0.1593g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react temperature
Under the conditions of 30 DEG C of degree, stirring reaction 4 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, stir 1 hour in air.
With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product with
Tetrahydrofuran is dissolved for solvent, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml is precipitation in precipitant.Reduced pressure
The product of filter is vacuum dried through 40 DEG C, obtains white solid powder activity temperature sensing polymer.
Polymer is pressed into 1 with sodium azide：10 mol ratio is dissolved in N, between N- dimethyl in amide, 50 DEG C, and under stirring condition,
Reaction 48 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains white solid
Body powder temperature sensing polymer.Result of the test 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.Will be 2- bromine isobutyl acylbromides (13.8g, 60mmol) little 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 12 hours.After reaction terminates,
By the product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*
3) wash successively.Organic layer rotary evaporation after washing is removed into solvent.Dissolved with ethyl acetate, cross neutral alumina column, with
Ethyl acetate：Normal hexane 1:2 (V/V) are eluent.After rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.Filtered with funnel, and with cold washing with alcohol (10ml).Under room temperature, in vacuum drying
It is dried in case, obtains two-(2- bromine isobutyl acyloxy) ethylene glycol of white crystal initiator.
By NIPA 4g, two-(2- bromine isobutyl acyloxy) ethylene glycol 0.2120g of initiator, three (2- diformazans
Amino-ethyl) amine 0.1355g add have Teflon stir reaction bulb in.Add N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere,
Cuprous bromide catalyst 0.0848g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react temperature
Under the conditions of 40 DEG C of degree, stirring reaction 5 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, stir 1 hour in air.
With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product with
Tetrahydrofuran is dissolved for solvent, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml is precipitation in precipitant.Reduced pressure
The product of filter is vacuum dried through 40 DEG C, obtains white solid powder activity temperature sensing polymer.
Polymer is pressed into 1 with sodium azide：5 mol ratio is dissolved in N, between N- dimethyl in amide, 70 DEG C, and under stirring condition,
Reaction 72 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains white solid
Body powder temperature sensing polymer.Result of the test shows that the LCST of temperature sensing polymer aqueous solution manufactured in the present embodiment is 32 DEG C.
Embodiment 6
Ethylene glycol (2.5g, 40mmol) is added the solution containing pyridine (6.636g, 84mmol) and tetrahydrofuran 30ml
In, 30min is stirred under condition of ice bath.By 2- bromine isobutyl acylbromides (19.32g, 84mmol) by constant pressure funnel at 1 hour
Inside it is slowly added to, continues to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 24 hours.After reaction terminates, will
The product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*3)
Wash successively.Organic layer rotary evaporation after washing is removed into solvent.Dissolved with ethyl acetate, cross neutral alumina column, with second
Acetoacetic ester：Normal hexane 1:2 (V/V) are eluent.After rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to ice ethanol
In, and 24 hours are stood at 0 DEG C.Filtered with funnel, and with cold washing with alcohol (10ml).Under room temperature, in vacuum drying oven
Middle drying, obtains two-(2- bromine isobutyl acyloxy) ethylene glycol of white crystal initiator.
By N- propyl Methacrylamides 4g, two-(2- bromine isobutyl acyloxy) ethylene glycol 0.1273g of initiator, three (2- diformazans
Amino-ethyl) amine 0.1626g, during addition has the reaction bulb of Teflon stir.Add N,N-dimethylformamide 10ml
With deionized water 10ml, stirring, fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere
In, cuprous bromide catalyst 0.1018g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react
Under the conditions of temperature 60 C, stirring reaction 6 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, in air, stirring 1 is little
When.With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product
Dissolve by solvent of tetrahydrofuran, be slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml is precipitation in precipitant.Decompression
The product of filtration is vacuum dried through 40 DEG C, obtains white solid powder activity temperature sensing polymer.
Polymer is pressed into 1 with sodium azide：2 mol ratio is dissolved in N, between N- dimethyl in amide, 80 DEG C, and under stirring condition,
Reaction 96 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, is obtained with formula
(Ⅰ6) structure temperature sensing polymer white solid powder.Result of the test shows, temperature sensing polymer water manufactured in the present embodiment
The LCST of solution is 25 DEG C.
Embodiment 7
Ethylene glycol (2.5g, 40mmol) is added the solution containing pyridine (7.9g, 100mmol) and tetrahydrofuran 30ml
In, 30min is stirred under condition of ice bath.Will be 2- bromine isobutyl acylbromides (23.19g, 100mmol) little 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 6 hours.After reaction terminates,
By the product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*
3) wash successively.Organic layer rotary evaporation after washing is removed into solvent.Dissolved with ethyl acetate, cross neutral alumina column, with
Ethyl acetate：Normal hexane 1:2 (V/V) are eluent.After rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.Filtered with funnel, and with cold washing with alcohol (10ml).Under room temperature, in vacuum drying
It is dried in case, obtains two-(2- bromine isobutyl acyloxy) ethylene glycol of white crystal initiator.
By N, N- acrylamide 4g, initiator two-(2- bromine isobutyl acyloxy) ethylene glycol 0.1132g, three (2- bis-
Methylaminoethyl) amine 0.1447g add have Teflon stir reaction bulb in.Add N,N-dimethylformamide 10ml
With deionized water 5ml, stirring, fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere
In, cuprous bromide catalyst 0.0906g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react
Under the conditions of 25 DEG C of temperature, stirring reaction 2 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, in air, stirring 1 is little
When.With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product
Dissolve by solvent of tetrahydrofuran, be slowly dropped to ether：Petroleum ether=1:1 (V/V) 50ml is precipitation in precipitant.Reduced pressure
The product of filter is vacuum dried through 40 DEG C, obtains white solid powder activity temperature sensing polymer.
Polymer is pressed into 1 with sodium azide：20 mol ratio is dissolved in N, between N- dimethyl in amide, 40 DEG C, and under stirring condition,
Reaction 24 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 50ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, is obtained with formula
(Ⅰ7) structure temperature sensing polymer white solid powder.Result of the test 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.Will be 2- bromine isobutyl acylbromides (16.32g, 71mmol) little 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 16 hours.After reaction terminates,
By the product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*
3) wash successively.Organic layer rotary evaporation after washing is removed into solvent.Dissolved with ethyl acetate, cross neutral alumina column, with
Ethyl acetate：Normal hexane 1:2 (V/V) are eluent.After rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.Filtered with funnel, and with cold washing with alcohol (10ml).Under room temperature, in vacuum drying
It is dried in case, obtains two-(2- bromine isobutyl acyloxy) ethylene glycol of white crystal initiator.
By N- vinylisobutyramide 4g, two-(2- bromine isobutyl acyloxy) ethylene glycol 0.1273g of initiator, three (2- diformazans
Amino-ethyl) amine 0.1626g add have Teflon stir reaction bulb in.Add N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere,
Cuprous bromide catalyst 0.1018g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react temperature
Under the conditions of 60 DEG C of degree, stirring reaction 6 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, stir 1 hour in air.
With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product with
Tetrahydrofuran is dissolved for solvent, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml is precipitation in precipitant.Reduced pressure
The product of filter is vacuum dried through 40 DEG C, obtains white solid powder activity temperature sensing polymer.
Polymer is pressed into 1 with sodium azide：10 mol ratio is dissolved in N, between N- dimethyl in amide, 50 DEG C, and under stirring condition,
Reaction 48 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, is obtained with formula
(Ⅰ8) structure temperature sensing polymer white solid powder.Result of the test 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.Will be 2- bromine isobutyl acylbromides (13.8g, 60mmol) little 1 by constant pressure funnel
When it is interior be slowly added to, continue to keep low temperature 1～2 hour.Then room temperature is gradually increased to, continues reaction 12 hours.After reaction terminates,
By the product for obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*
3) wash successively.Organic layer rotary evaporation after washing is removed into solvent.Dissolved with ethyl acetate, cross neutral alumina column, with
Ethyl acetate：Normal hexane 1:2 (V/V) are eluent.After rotary evaporation, the dissolving of product Jing dichloromethane is slowly dropped to ice second
In alcohol, and 12 hours are stood at 0 DEG C.Filtered with funnel, and with cold washing with alcohol (10ml).Under room temperature, in vacuum drying
It is dried in case, obtains two-(2- bromine isobutyl acyloxy) ethylene glycol of white crystal.
By N- caprolactam 4g, two-(2- bromine isobutyl acyloxy) ethylene glycol 0.1035g of initiator, three (2- diformazans
Amino-ethyl) amine 0.1322g add have Teflon stir reaction bulb in.Add N,N-dimethylformamide 10ml and
Deionized water 5ml, stirring fully dissolve.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere,
Cuprous bromide catalyst 0.0828g is rapidly added, while evacuation-logical nitrogen 3 times.Under nitrogen or argon, react temperature
Under the conditions of 40 DEG C of degree, stirring reaction 5 hours.After reaction terminates, plus the tetrahydrofuran dilution of 15ml, stir 1 hour in air.
With tetrahydrofuran as solvent, catalyst is removed by aluminium oxide-silicagel column.Rotary evaporation removes unnecessary solvent, crude product with
Tetrahydrofuran is dissolved for solvent, is slowly dropped to ether：Petroleum ether=1:2 (V/V) 200ml is precipitation in precipitant.Reduced pressure
The product of filter is vacuum dried through 40 DEG C, obtains white solid powder activity temperature sensing polymer.
Polymer and sodium azide are dissolved in into N by 1: 10 mol ratio, between N- dimethyl in amide, 60 DEG C, under stirring condition,
Reaction 72 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, one was changed per 6 hours
Secondary water, dialyses two days, removes unreacted sodium azide.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrofuran as molten
Agent is dissolved, and precipitates in being slowly dropped to 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, is obtained with formula
(Ⅰ9) structure temperature sensing polymer white solid powder.Result of the test 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 help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improve and modification is also fallen in the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope for causing.
Claims (9)
1. a kind of temperature sensing polymer with formula I structure,
Wherein, R is methyl or hydrogen；
N is 10～100；
A is polymerized by temperature sensitive monomer and is formed, the temperature sensitive monomer selected from NIPA, N- propylacrylamides,
N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, the positive propionic acid amide. of N- vinyls, N- ethylene
Base caprolactam, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-N '-positive Propylpiperazine, N- (2,2- bis-
Methyl isophthalic acid, -5 alcohol of 3- dioxanes) one kind in-acrylamide and N- (- 5 alcohol of 2- ethyoxyl -1,3- dioxanes)-acrylamide or
It is various.
2. temperature sensing polymer according to claim 1, it is characterised in that the R is hydrogen or methyl, the Thermo-sensitive list
Body is selected from NIPA, N- propylacrylamides, N, N- acrylamides, N- vinyls Isopropamide and N-
One or more in caprolactam.
3. temperature sensing polymer according to claim 1, it is characterised in that the number-average molecular weight of the temperature sensing polymer
For 2000～20000g/mol, PDI ＜ 1.3.
4. the preparation method of the temperature sensing polymer described in claim 1, comprises the following steps：
A), under noble gases and anhydrous condition, by ethylene glycol, acid binding agent, catalyst and the acylating agent with formula II structure
React in a solvent, obtain the initiator with formula III structure；
B), under inert gas shielding, the initiator, temperature sensitive monomer, catalyst and complexant are reacted in a solvent, is obtained
To the active temperature sensing polymer with formula IV structure；The temperature sensitive monomer is selected from NIPA, N- propyl group
Acrylamide, N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, the positive propionyl of N- vinyls
Amine, N- caprolactams, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-N '-positive Propylpiperazine,
N- (- 5 alcohol of 2,2- dimethyl -1,3- dioxanes)-acrylamides and N- (- 5 alcohol of 2- ethyoxyl -1,3- dioxanes)-acrylamide
In one or more；
C), the active temperature sensing polymer is reacted in a solvent with Hydrazoic acid,sodium salt, obtains the Thermo-sensitive with formula I structure
Polymer；
Wherein, R is methyl or hydrogen；
N is 10～100；
A is polymerized by temperature sensitive monomer and is formed, the temperature sensitive monomer selected from NIPA, N- propylacrylamides,
N- cyclopropyl acrylamides, N, N- acrylamides, N- vinyl Isopropamides, the positive propionic acid amide. of N- vinyls, N- ethylene
Base caprolactam, NVP, N- acryloyl group pyrrolidines, N- acryloyl group-N '-positive Propylpiperazine, N- (2,2- bis-
Methyl isophthalic acid, -5 alcohol of 3- dioxanes) one kind in-acrylamide and N- (- 5 alcohol of 2- ethyoxyl -1,3- dioxanes)-acrylamide or
It is various.
5. preparation method according to claim 4, it is characterised in that step A) in, the acid binding agent be pyridine or
Triethylamine；The catalyst is DMAP；The solvent is dichloromethane or acetonitrile, and the acylating agent is selected from 2-
The bromo- 2- methyl propionyl bromide of bromo- 2- methyl propionyl chloride, 2-, 2- chloro-2-methyl propionyl chlorides, 2- chloro-2-methyl propionyl bromides, chloro second
Acyl chlorides, chloroacetyl bromine, bromo acetyl bromide, bromoacetyl chlorine, 2 bromo propionyl bromide, 2- bromo propionyl chloros, 2- chlorine propionyl bromide or 2- chlorine
Propionyl chloride.
6. preparation method according to claim 4, it is characterised in that step A) in, the ethylene glycol, acid binding agent with
The mol ratio of acylating agent is 1：(2.1～2.5)：(2.1～2.5).
7. preparation method according to claim 4, it is characterised in that step B) in, the catalyst is selected from chlorination
One or more during cuprous, cuprous bromide, Cuprous sulfocyanate and hexafluorophosphoric acid are cuprous；The complexant is selected from tetramethyl second two
Amine, N, N, N ', N ", N, "-five methyl diethylentriamine, 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triens, three-(2- first
Amino-ethyl) one or more in amine and three-(2- ethylaminoethyls) amine；The solvent be DMF with go
The mixed solvent of ionized water.
8. preparation method according to claim 4, it is characterised in that step B) in, the initiator, Thermo-sensitive list
The mol ratio of body, catalyst and complexant is 1：(20～200)：(0.5～4)：(0.5～4).
9. preparation method according to claim 4, it is characterised in that the active temperature sensing polymer and the Azide
The mol ratio of sodium is 1：(2～20).
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| CN109694479A (en) * | 2018-12-29 | 2019-04-30 | 广东工业大学 | A kind of supramolecular materials and Subjective and Objective Self-Assembled and preparation method thereof |
| CN114149600A (en) * | 2021-12-27 | 2022-03-08 | 河南中医药大学 | Preparation method and application of temperature-responsive hydrogel |
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| CN101490108A (en) * | 2006-08-09 | 2009-07-22 | 赢创罗姆有限责任公司 | Process for preparing acid-terminated ATRP products |
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| CN109694479A (en) * | 2018-12-29 | 2019-04-30 | 广东工业大学 | A kind of supramolecular materials and Subjective and Objective Self-Assembled and preparation method thereof |
| 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 |
| CN114149600A (en) * | 2021-12-27 | 2022-03-08 | 河南中医药大学 | Preparation method and application of temperature-responsive hydrogel |
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| CN106519154B (en) | 2018-08-10 |
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