CN106366225A - Six-arm thermosensitive polymer and preparation method thereof - Google Patents
Six-arm thermosensitive polymer and preparation method thereof Download PDFInfo
- Publication number
- CN106366225A CN106366225A CN201610957656.1A CN201610957656A CN106366225A CN 106366225 A CN106366225 A CN 106366225A CN 201610957656 A CN201610957656 A CN 201610957656A CN 106366225 A CN106366225 A CN 106366225A
- Authority
- CN
- China
- Prior art keywords
- acrylamide
- solvent
- polymer
- temperature sensing
- vinyl
- 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.)
- Granted
Links
- 0 *C(*)(*)C(N)=O Chemical compound *C(*)(*)C(N)=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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application provides a thermosensitive polymer having a structure as shown in formula (I). The thermosensitive polymer takes dipentaerythritol as a core, and is prepared by enabling the dipentaerythritol to react with an acylating agent so as to obtain an initiator, then carrying out atom transfer radical polymerization on the initiator and a thermosensitive monomer to obtain an active thermosensitive polymer with uniform chain length and controllable molecular weight, and finally, carrying out an azido reaction on the tail end of the polymer to obtain the thermosensitive polymer having an azide group at the tail end. Compared with the prior art, the polymer provided by the application has the characteristics of being simple, convenient and easy to implement, has controllable arm number and arm length, and is flexible and adjustable in structure and convenient to modify; furthermore, the thermosensitive polymer has good thermosensitivity and a use scope close to environment temperature, thus having good application prospect.
Description
Technical field
The invention belongs to polymer chemistry and technical field of material chemistry, particularly to a kind of six arm temperature sensing polymers and its system
Preparation Method.
Background technology
Multi-arm star polymer is that one kind is connected on core by covalent bond by a plurality of polymeric arms, and collectively constitutes with core
Have and the one of star topology birds of the same feather flock together compound；Due to its spherical branched structure of special three-dimensional and characteristic, star polymer becomes
One of focus of polymeric material field research.Star polymer has more terminal functional groups, can be by modifying
Polymer to different structure and performance.Responsive to temperature type star polymer is that a class itself is capable of the thin of ambient temperature to external world
Microvariations responds, and produces change even a family macromolecule of mutation of corresponding physical arrangement and chemical property.Polymer
Aqueous solution occurs the temperature of phase in version to be referred to as lowest critical solution temperature (lcst).Star temperature sensing polymer is due in stagnation temperature
Degree nearby can occur larger change in volume so as to be widely used in medicine, the field such as biology, cosmetics, sensor,
Therefore, the unique structure of star temperature sensing polymer is of great interest with performance.By in temperature sensing polymer end
Introduce functional group so as to its application and value can be widened with other functional group reactionses more.
Traditional radical polymerization, due to wayward, is easily caused the molecular weight of polymer, molecular weight distribution, chain structure
And end degree of functionality is out of control, sometimes even there is the reaction such as branched, crosslinked, thus 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 star-type polymer is more prone to, and plants
Class is also more.Wherein atrp reaction easily operated, the advantages of mild condition (not needing strict eliminating water, deoxygenation), again simultaneously
Have the feature of living polymerization concurrently however, it would be possible to make all free yl polymerizating monomers carry out controlled/" active " polymerization, and effectively
Polymer is modified, therefore has broad application prospects in terms of Molecular Design.
Content of the invention
Present invention solves the technical problem that being the six arm temperature sensing polymers providing a kind of end to have azido, this Shen
The polymer that please provide has Thermo-sensitive and end has azido group.
In view of this, this application provides one kind has the temperature sensing polymer of formula () structure,
Wherein, r is methyl or hydrogen；
N is 5～100；
A is formed by temperature sensitive monomer polymerization, and described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n- propyl group acryloyl
Amine, n- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, the positive propionic acid amide. of n- vinyl, n- second
Thiazolinyl caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine, n- (2,2-
Dimethyl -1,3- dioxanes -5 alcohol) one of-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide
Or it is multiple.
Preferably, described r is hydrogen or methyl, and described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n- propyl group propylene
Amide, n, one or more of n- acrylamide, n- vinyl Isopropamide and n- caprolactam.
Preferably, the number-average molecular weight of described temperature sensing polymer is 3000～50000g/mol, pdi ＜ 1.3.
Present invention also provides the preparation method of described temperature sensing polymer, comprise the following steps:
A), under noble gases and anhydrous condition, by Bis(pentaerythritol), acid binding agent, catalyst and have formula () structure
Acylating agent react in a solvent, obtain the initiator with formula () structure；
B), under inert gas shielding, will be anti-in a solvent to described initiator, temperature sensitive monomer, catalyst and complexant
Should, obtain the active temperature sensing polymer with formula () structure；Described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n-
Propylacrylamide, n- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, n- vinyl are just
Propionic acid amide., n- caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive third
Piperazine, n- (2,2- dimethyl -1,3- dioxanes -5 alcohol)-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-propylene
One or more of amide；
C), described activity temperature sensing polymer is reacted in a solvent with Hydrazoic acid,sodium salt, obtain the temperature with formula () structure
Sensitive polymer；
Wherein, r is methyl or hydrogen；
N is 5～100；
A is formed by temperature sensitive monomer polymerization, and described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n- propyl group acryloyl
Amine, n- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, the positive propionic acid amide. of n- vinyl, n- second
Thiazolinyl caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine, n- (2,2-
Dimethyl -1,3- dioxanes -5 alcohol) one of-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide
Or it is multiple.
Preferably, in described step a), described acid binding agent is pyridine or triethylamine；Described catalyst is 4- dimethylamino
Pyridine；Described solvent is dichloromethane or acetonitrile, and described acylating agent is selected from 2- bromo- 2- methyl propionyl chloride, 2- bromo- 2- methyl propionyl
Bromine, 2- chloro-2-methyl propionyl chloride, 2- chloro-2-methyl propionyl bromide, chloro-acetyl chloride, chloroacetyl bromine, bromo acetyl bromide, bromo
Chloroacetic chloride, 2 bromo propionyl bromide, 2- bromo propionyl chloro, 2- chlorine propionyl bromide or 2- chlorpromazine chloride.
Preferably, in described step a), the mol ratio of described Bis(pentaerythritol), acid binding agent and acylating agent be 1:(6.1～
6.5): (6.1～6.5).
Preferably, in described step b), described catalyst is selected from Cu-lyt., cuprous bromide, Cuprous sulfocyanate and hexafluoro
Phosphoric acid is one or more of cuprous；Described 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- methylaminoethyl) amine and three-(2- ethylamino second
One or more of base) amine；Described solvent is n, the mixed solvent of n- dimethylformamide and deionized water.
Preferably, in described step b), the mol ratio of described initiator, temperature sensitive monomer, catalyst and complexant is 1:
(30～500): (0.5～12): (0.5～12).
Preferably, described activity temperature sensing polymer and the mol ratio of described Hydrazoic acid,sodium salt are 1:(6～36).
This application provides one kind has the temperature sensing polymer of formula () structure, it is passed through with Bis(pentaerythritol) as core
Reacted with acylating agent, obtained initiator, then atom transfer radical polymerization is passed through with temperature sensitive monomer with initiator, obtained
Arrive the active temperature sensing polymer that chain length is homogeneous, molecular weight is controlled；Finally by active polymer ends Azide, obtain end
Temperature sensing polymer containing azido.This application provides a kind of polymer with Thermo-sensitive, further, the application's
Polymer ends contain azido functional group, have a plurality of segment, intermolecular have larger space, and polymer is anti-to temperature
Should be more sensitive, Thermo-sensitive is good, and it also can occur intermolecular cycloaddition reaction, efficiently can introduce new official by click-reaction
Can roll into a ball or polymer segment, for building novel block polymer, dendritic and three-dimensional network polymeric material further
Material provides approach.
Brief description
Fig. 1 is step 1 in the embodiment of the present invention 1) the middle initiator prepared1H-nmr spectrogram；
Fig. 2 is the embodiment of the present invention 1) six arm star temperature sensing polymers of preparing1H-nmr spectrogram；
Fig. 3 is the embodiment of the present invention 1) the gel permeation chromatography spectrogram of six arm star temperature sensing polymers prepared；
Fig. 4 is six arm star temperature sensing polymer infrared spectrums before and after the end Azide of the embodiment of the present invention 1 preparation.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment, the preferred embodiment of the invention is described, 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 one kind has the temperature sensing polymer of formula () structure,
Wherein, r is methyl or hydrogen；
N is 5～100；
A is formed by temperature sensitive monomer polymerization, and described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n- propyl group acryloyl
Amine, n- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, the positive propionic acid amide. of n- vinyl, n- second
Thiazolinyl caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine, n- (2,2-
Dimethyl -1,3- dioxanes -5 alcohol) one of-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide
Or it is multiple.
This application provides a kind of new polymer, it is the six arm Thermo-sensitive polymerizations 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 (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, simultaneously 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 more than the interaction force between macromolecule-hydrone in turn, 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
Raw contraction.
In the application, preferably, a in described temperature sensing polymer preferably by n- N-isopropylacrylamide,
N- propylacrylamide, n, n- acrylamide or the polymerization of n- vinyl Isopropamide are formed, the Thermo-sensitive polymerization obtaining
Thing have formula (1), formula (2), formula (3) or formula (4) shown in structure；
The number-average molecular weight of herein described temperature sensing polymer is preferably 3000～50000g/mol, pdi ＜ 1.3；Institute
The number-average molecular weight stating temperature sensing polymer is more preferably 6000～25000g/mol, and pdi is 1.2～1.0.
Present invention also provides the preparation method of above-mentioned temperature sensing polymer, comprise the following steps:
A), under noble gases and anhydrous condition, by Bis(pentaerythritol), acid binding agent, catalyst and have formula () structure
Acylating agent react in a solvent, obtain the initiator with formula () structure；
B), under inert gas shielding, will be anti-in a solvent to described initiator, temperature sensitive monomer, catalyst and complexant
Should, obtain the active temperature sensing polymer with formula () structure；Described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n-
Propylacrylamide, n- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, n- vinyl are just
Propionic acid amide., n- caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive third
Piperazine, n- (2,2- dimethyl -1,3- dioxanes -5 alcohol)-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-propylene
One or more of amide；
C), described activity temperature sensing polymer is reacted in a solvent with Hydrazoic acid,sodium salt, obtain the temperature with formula () structure
Sensitive polymer；
Wherein, r is methyl or hydrogen；
N is 5～100；
A is formed by temperature sensitive monomer polymerization, and described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n- propyl group acryloyl
Amine, n- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, the positive propionic acid amide. of n- vinyl, n- second
Thiazolinyl caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine, n- (2,2-
Dimethyl -1,3- dioxanes -5 alcohol) one of-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide
Or it is multiple.
During preparing temperature sensing polymer, the application is prepared for initiator first, will Bis(pentaerythritol), tie up acid
Agent, catalyst and have the acylating agent of formula () structure and react in a solvent, obtain the initiator with formula () structure；In order to
Reaction fully, the described process preparing initiator particularly as follows:
Under noble gases and anhydrous condition, Bis(pentaerythritol), acid binding agent are mixed with catalyst, under condition of ice bath,
Acylating agent is added dropwise in said mixture, keeps low temperature 1～2h, then be slowly increased to room temperature, react 6～24h, caused
Agent.
The reaction equation of above-mentioned reaction is as follows:
During preparing initiator, hydroxyl is reacted with carboxylic acid halides, generates ester group and halogen acids, the presence impact of halogen acids
The yield of reaction is it is therefore desirable to remove the acid in course of reaction so as to generate complex salt using acid binding agent, 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, shows
Example, described acid binding agent is preferably selected from pyridine or triethylamine.
Described acylating agent is raw material with described glycol reaction it is preferred that described acylating agent is preferably selected from 2- bromo- 2- first
Base propionyl chloride, 2- bromo- 2- methyl propionyl bromide, 2- chloro-2-methyl propionyl chloride, 2- chloro-2-methyl propionyl bromide, chloro-acetyl chloride, chlorine
For acetyl bromide, bromo acetyl bromide, bromoacetyl chlorine, 2 bromo propionyl bromide, 2- bromo propionyl chloro, 2- chlorine propionyl bromide or 2- chlorpromazine chloride；
More preferably 2- bromine isobutyl acylbromide.Described catalyst is preferably DMAP；Described solvent be preferably dichloromethane or
Acetonitrile.Preferably, the mol ratio of described 1,3- dihydroxy adamantine, acid binding agent and acylating agent be preferably 1:(6.1～
6.5): (6.1～6.5).
In order to obtain pure initiator, after above-mentioned reaction, the product obtaining preferably is washed by the application successively
Wash, rotary evaporation, cross chromatographic column, rotary evaporation and drying.Described washing is followed successively by 5% sodium bicarbonate solution, saturated common salt
Water and deionized water；Described rotary evaporation is that the organic solvent after washing removes through decompression rotary evaporation.Described cross chromatographic column be
Neutral alumina chromatographic column, solvent is 1:2 (v/v) for the ratio of ethyl acetate and normal hexane.
The application and then using initiator as reaction raw materials, carries out the preparation of active temperature sensing polymer it may be assumed that in indifferent gas
Under body protection, described initiator, temperature sensitive monomer, catalyst and complexant are reacted in a solvent, obtain tying with formula ()
The active temperature sensing polymer of structure；Described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n- propylacrylamide, n- ring third
Base acrylamide, n, oneself is interior for n- acrylamide, n- vinyl Isopropamide, the positive propionic acid amide. of n- vinyl, n- vinyl
Amide, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine, n- (2,2- dimethyl-
1,3- dioxanes -5 alcohol) one or more of-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide；
In order that reaction carry out more abundant, above-mentioned reaction particularly as follows:
Above-mentioned initiator, temperature sensitive monomer, complexant and solvent are added in dry anhydrous and oxygen-free reaction bulb, with anti-
Mouthful 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 particularly as follows:
During the active temperature sensing polymer of preparation, with described initiator, described temperature sensitive monomer there occurs that atom turns
Move radical polymerization.The Main Function of herein described complexant is to increase dissolubility in organic faciess for the catalyst and adjustment is urged
The oxidation-reduction potential of agent, so that catalyst reaches activity needed for reaction, and is matched kinetically being reacted with atrp；
It is exactly specifically to make balance significantly be partial to the direction generating dormancy kind, to obtain relatively low spike in reversible passivation reaction
Concentration, it is to avoid irreversible terminating reaction；Ensure constant number of free radical, so that all polymer chains is increased with identical speed,
Make polymer unification.Thus obtaining the polymer with predetermined molecular weight, Narrow Molecular Weight Distribution and structure-controllable.The application institute
Stating complexant is complexant well known to those skilled in the art, example, and described 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- methylaminoethyl) amine (me6- tren) and three-(2- ethylaminoethyl) amine (et6Tren in)
One or more, more preferably three-(2- methylaminoethyl) amine (me6- tren) or n, n, n ', n ", n " and ,-pentamethyl diethylidene
Triamine (pmdeta).Described catalyst is catalyst well known to those skilled in the art, and this application is had no particular limits,
Example, described catalyst be preferably selected from Cu-lyt., cuprous bromide, Cuprous sulfocyanate and hexafluorophosphoric acid one of cuprous or
Multiple, more preferably cuprous bromide.Described temperature sensitive monomer be preferably selected from n- N-isopropylacrylamide, n- propylacrylamide,
N- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, the positive propionic acid amide. of n- vinyl, n- ethylene
Base caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine, n- (2,2- bis-
Methyl isophthalic acid, 3- dioxanes -5 alcohol) one of-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide or
Multiple, more preferably n- N-isopropylacrylamide, n- propylacrylamide, n, n- acrylamide, n- vinyl isopropyl
Amide and one or more of n- caprolactam；Described solvent is n, and n- dimethylformamide is molten with the mixing of deionized water
Agent.The mol ratio of described initiator, temperature sensitive monomer, catalyst and complexant is 1:(30～500): (0.5～12): (0.5～
12).
In order to obtain pure active temperature sensing polymer, the product obtaining after reacting, is preferably added four by the application
Hydrogen furan dilutes, and stirring terminates polymerization in atmosphere；Again with oxolane as eluent, by silica gel-neutral alumina color
Spectrum post removes catalyst, removes after solvent through rotary evaporation, more successively through precipitation, filtration and vacuum drying, obtains activity temperature
Sensitive polymer.
In above-mentioned purification process, in described 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, and aspect ratio is 1:3；Described precipitation precipitant used is ether, stone
Oily ether mixed solvent or normal hexane, ether, petroleum ether mixed solvent ratio are 1:1～3 (v/v), are optimal wherein with 1:2.
The application, finally with active temperature sensing polymer as raw material, with reaction of sodium azide, obtains temperature sensing polymer.On
The reaction equation stating reaction is as follows:
During above-mentioned mistake, the temperature of described reaction is preferably 40～80 DEG C, and time of described reaction is preferably 24～
96h；Described activity temperature sensing polymer is preferably 1:6～1:36, more preferably 1:18 with the mol ratio of described Hydrazoic acid,sodium salt.?
After reaction terminates, by the purification of products obtaining, particularly as follows:
Reactant liquor is added in bag filter, changes within every 6 hours first water, dialyse 48～96 hours；Through rotary evaporation
After removing solvent, more successively through precipitation, filtration and vacuum drying, obtain the line style temperature sensing polymer containing azido in end.
In said process, described rotary evaporation is to be removed through decompression rotary evaporation by the organic solvent of chromatographic column；Described
Be precipitated as by after rotary evaporation product with oxolane dissolving after, be dropwise added dropwise in normal hexane cold in a large number, repeat this
Operation 2～3 times.
The preparation method of the present invention is simple to operate, and reaction condition is gentle, and because the application adopts atom transferred free radical
Polymerization, makes the brachium of temperature sensing polymer be easily controlled, molecular weight distribution is narrower, and adjustable in relative broad range；Simultaneously this
The polymer of azido functional group is contained in bright prepared end, has a plurality of segment, intermolecular have larger space, polymerization
Thing is more sensitive to the reaction of temperature, and Thermo-sensitive is good, and azido group also can occur 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, for building novel topological structure further, 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 present invention being provided 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
Bis(pentaerythritol) (2.55g, 10mmol) is added and contains triethylamine (6.19g, 61mmol) and dichloromethane 50ml
Solution in, under condition of ice bath stir 30min.2- bromine isobutyl acylbromide (14.07g, 61mmol) is passed through constant pressure funnel
It was slowly added in 1 hour, continue to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 12 hours.Reaction knot
Shu Hou, by the product 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 solvent, and with dichloromethane dissolving, is slowly added dropwise
To in ice ether, and stand 12 hours at 0 DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature, true
It is dried in empty drying baker, obtain white crystal initiator.Fig. 1 is the initiator as core of this step preparation1H-nmr composes
Figure, solvent is for deuterochloroform (referred to as: d-cdcl3)；
N- N-isopropylacrylamide 4g, initiator 0.1353g, three (2- dimethylaminoethyl) amine 0.1626g is added to be had
In the reaction bulb of Teflon stir.Add n, n- dimethylformamide 10ml and deionized water 5ml, stir, fully molten
Solution.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere, it is rapidly added cuprous bromide catalyst
0.1018g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 30 DEG C of reaction temperature, stirring reaction 2
Hour.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 200ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:18, in amide between n- dimethyl, in 60 DEG C of stirring conditions
Under, react 48 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains
White solid powder, its have formula (5) structure.Result of the test shows, temperature sensing polymer aqueous solution manufactured in the present embodiment
Lcst is 32 DEG C.
Fig. 2 is temperature sensing polymer manufactured in the present embodiment1H-nmr spectrogram, solvent is for heavy water (referred to as: d2o)；Fig. 3
Gel permeation chromatography spectrogram (referred to as: gpc) for temperature sensing polymer manufactured in the present embodiment, mobile phase is oxolane, mark
Sample is polystyrene；Fig. 4 is the linear temperature sensing polymer infrared spectrum before and after the Azide of end manufactured in the present embodiment.
Embodiment 2
Bis(pentaerythritol) (2.55g, 10mmol) is added and contains pyridine (5.135g, 65mmol) and oxolane 100ml
Solution in, under condition of ice bath stir 30min.2- bromine isobutyl acylbromide (14.95g, 65mmol) is passed through constant pressure funnel
It was slowly added in 1 hour, continue to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 24 hours.Reaction knot
Shu Hou, by the product 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 solvent, and with dichloromethane dissolving, is slowly added dropwise
To in ice ether, and stand 12 hours at 0 DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature, true
It is dried in empty drying baker, obtain white crystal initiator.
N- N-isopropylacrylamide 1g, initiator 0.3363g, three (2- dimethylaminoethyl) amine 0.0.0337g is added
Have in the reaction bulb of Teflon stir.Add n, n- dimethylformamide 5ml and deionized water 5ml, stir, fully molten
Solution.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere, it is rapidly added cuprous bromide catalyst
0.0211g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 20 DEG C of reaction temperature, stirring reaction 2
Hour.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 50ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:36, in amide between n- dimethyl, in 40 DEG C of stirring conditions
Under, react 48 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml 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, the lcst of temperature sensing polymer aqueous solution manufactured in the present embodiment
For 32 DEG C.
Embodiment 3
Bis(pentaerythritol) (3g, 11.8mmol) is added containing pyridine (5.97g, 76mmol) and dichloromethane 100ml
In solution, stir 30min under condition of ice bath.2- bromine isobutyl acylbromide (17.37g, 76mmol) is passed through constant pressure funnel 1
It is slowly added in hour, continue to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 24 hours.Reaction terminates
Afterwards, with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionized water (100ml*3) is washed successively
Wash.Organic layer rotary evaporation after washing is removed solvent, and with dichloromethane dissolving, is slowly dropped in ice ether, and 0
12 hours are stood at DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature, it is dried in vacuum drying oven, obtains
To white crystal initiator.
By n- N-isopropylacrylamide 4g, initiator 0.2029, three (2- dimethylaminoethyl) amine 0.1625g addition has poly-
In the reaction bulb of tetrafluoroethene stirrer.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, it is rapidly added cuprous bromide catalyst
0.1018g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 40 DEG C of reaction temperature, stirring reaction 4
Hour.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 200ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:12, in amide between n- dimethyl, in 50 DEG C of stirring conditions
Under, react 72 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml 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, the lcst of temperature sensing polymer aqueous solution manufactured in the present embodiment
For 32 DEG C.
Embodiment 4
Bis(pentaerythritol) (2.55g, 10mmol) is added and contains triethylamine (6.375g, 63mmol) and oxolane
In the solution of 100ml, stir 30min under condition of ice bath.2- bromine isobutyl acylbromide (14.49g, 63mmol) is passed through constant pressure addition
Funnel was slowly added in 1 hour, continued to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 12 hours.Instead
After should terminating, by the product obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionization
Water (100ml*3) washs successively.Organic layer rotary evaporation after washing is removed solvent, and with dichloromethane dissolving, slowly drips
It is added in ice ether, and stand 12 hours at 0 DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature,
It is dried in vacuum drying oven, obtain white crystal initiator.
N- N-isopropylacrylamide 4g, initiator 0.0812g, three (2- dimethylaminoethyl) amine 0.1951g is added to be had
In the reaction bulb of Teflon stir.Add n, n- dimethylformamide 15ml and deionized water 7.5ml, stir, fully
Dissolving.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere, it is rapidly added cuprous bromide catalysis
Agent 0.1221g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 60 DEG C of reaction temperature, stirring reaction
6 hours.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 200ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:6, in amide between n- dimethyl, in 80 DEG C of stirring conditions
Under, react 96 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml 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, the lcst of temperature sensing polymer aqueous solution manufactured in the present embodiment
For 32 DEG C.
Embodiment 5
Bis(pentaerythritol) (2.55g, 10mmol) is added and contains triethylamine (6.375g, 64mmol) and oxolane
In the solution of 100ml, stir 30min under condition of ice bath.2- bromine isobutyl acylbromide (14.72g, 64mmol) is passed through constant pressure addition
Funnel was slowly added in 1 hour, continued to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 12 hours.Instead
After should terminating, by the product obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionization
Water (100ml*3) washs successively.Organic layer rotary evaporation after washing is removed solvent, and with dichloromethane dissolving, slowly drips
It is added in ice ether, and stand 12 hours at 0 DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature,
It is dried in vacuum drying oven, obtain white crystal initiator.
N- N-isopropylacrylamide 4g, initiator 0.4058g, three (2- dimethylaminoethyl) amine 0.1626g is added to be had
In the reaction bulb of Teflon stir.Add n, n- dimethylformamide 10ml and deionized water 5ml, stir, fully molten
Solution.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere, it is rapidly added cuprous bromide catalyst
0.1018g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 50 DEG C of reaction temperature, stirring reaction 3
Hour.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 200ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:24, in amide between n- dimethyl, in 80 DEG C of stirring conditions
Under, react 48 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains
White solid powder temperature sensing polymer.
Embodiment 6
Bis(pentaerythritol) (2.55g, 10mmol) is added and contains pyridine (5.135g, 65mmol) and oxolane 100ml
Solution in, under condition of ice bath stir 30min.2- bromine isobutyl acylbromide (14.95g, 65mmol) is passed through constant pressure funnel
It was slowly added in 1 hour, continue to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 24 hours.Reaction knot
Shu Hou, by the product 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 solvent, and with dichloromethane dissolving, is slowly added dropwise
To in ice ether, and stand 12 hours at 0 DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature, true
It is dried in empty drying baker, obtain white crystal initiator.
By propyl Methacrylamide 4g, initiator 0.1353g, three (2- dimethylaminoethyl) amine 0.1626g addition has poly-
In the reaction bulb of tetrafluoroethene stirrer.Add n, n- dimethylformamide 5ml and deionized water 5ml, stirring, fully dissolve.
Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere, it is rapidly added cuprous bromide catalyst
0.1018g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 60 DEG C of reaction temperature, stirring reaction 4
Hour.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 50ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:6, in amide between n- dimethyl, in 80 DEG C of stirring conditions
Under, react 48 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains
Have formula (6) structure white solid powder temperature sensing polymer.Result of the test shows, Thermo-sensitive manufactured in the present embodiment gathers
The lcst of compound aqueous solution is 25 DEG C.
Embodiment 7
Bis(pentaerythritol) (3g, 11.8mmol) is added containing pyridine (5.97g, 76mmol) and dichloromethane 100ml
In solution, stir 30min under condition of ice bath.2- bromine isobutyl acylbromide (17.37g, 76mmol) is passed through constant pressure funnel 1
It is slowly added in hour, continue to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 24 hours.Reaction terminates
Afterwards, by the product 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 solvent, and with dichloromethane dissolving, is slowly added dropwise
To in ice ether, and stand 12 hours at 0 DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature, true
It is dried in empty drying baker, obtain white crystal initiator.
By n, n- acrylamide 4g, initiator 0.1203, three (2- dimethylaminoethyl) amine 0.1447g adds to be had
In the reaction bulb of Teflon stir.Add n, n- dimethylformamide 10ml and deionized water 5ml, stir, fully molten
Solution.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere, it is rapidly added cuprous bromide catalyst
0.0905g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 70 DEG C of reaction temperature, stirring reaction 4
Hour.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 200ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:18, in amide between n- dimethyl, in 40 DEG C of stirring conditions
Under, react 24 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains
Have (7) structure white solid powder temperature sensing polymer.Result of the test shows, Thermo-sensitive polymerization manufactured in the present embodiment
The lcst of thing aqueous solution is 33 DEG C.
Embodiment 8
Bis(pentaerythritol) (2.55g, 10mmol) is added and contains triethylamine (6.375g, 63mmol) and oxolane
In the solution of 100ml, stir 30min under condition of ice bath.2- bromine isobutyl acylbromide (14.49g, 63mmol) is passed through constant pressure addition
Funnel was slowly added in 1 hour, continued to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 12 hours.Instead
After should terminating, by the product obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionization
Water (100ml*3) washs successively.Organic layer rotary evaporation after washing is removed solvent, and with dichloromethane dissolving, slowly drips
It is added in ice ether, and stand 12 hours at 0 DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature,
It is dried in vacuum drying oven, obtain white crystal initiator.
N- vinylisobutyramide 4g, initiator 0.1353g, three (2- dimethylaminoethyl) amine 0.1626g is added to be had
In the reaction bulb of Teflon stir.Add n, n- dimethylformamide 15ml and deionized water 7.5ml, stir, fully
Dissolving.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere, it is rapidly added cuprous bromide catalysis
Agent 0.1018g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 60 DEG C of reaction temperature, stirring reaction
6 hours.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 200ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:18, in amide between n- dimethyl, in 60 DEG C of stirring conditions
Under, react 72 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains
Have formula (8) structure temperature sensing polymer white solid powder.Result of the test shows, Thermo-sensitive manufactured in the present embodiment gathers
The lcst of compound aqueous solution is 39 DEG C.
Embodiment 9
Bis(pentaerythritol) (2.55g, 10mmol) is added and contains triethylamine (6.375g, 64mmol) and oxolane
In the solution of 100ml, stir 30min under condition of ice bath.2- bromine isobutyl acylbromide (14.72g, 64mmol) is passed through constant pressure addition
Funnel was slowly added in 1 hour, continued to keep low temperature 1～2 hour.Then it is gradually increased to room temperature, continue reaction 12 hours.Instead
After should terminating, by the product obtaining with 5% sodium bicarbonate solution (100ml*3), saturated aqueous common salt (100ml*3), deionization
Water (100ml*3) washs successively.Organic layer rotary evaporation after washing is removed solvent, and with dichloromethane dissolving, slowly drips
It is added in ice ether, and stand 12 hours at 0 DEG C.Filtered with funnel, and wash (10ml) with cold ether.Under room temperature,
It is dried in vacuum drying oven, obtain white crystal initiator.
N- caprolactam 4g, initiator 0.1101g, three (2- dimethylaminoethyl) amine 0.1323g is added to be had
In the reaction bulb of Teflon stir.Add n, n- dimethylformamide 10ml and deionized water 5ml, stir, fully molten
Solution.Under agitation, after evacuation-logical nitrogen 3 times.In nitrogen or argon protection atmosphere, it is rapidly added cuprous bromide catalyst
0.0828g, evacuation-logical nitrogen 3 times simultaneously.Under nitrogen or argon, under the conditions of 30 DEG C of reaction temperature, stirring reaction 4
Hour.After reaction terminates, plus the oxolane dilution of 15ml, stir 1 hour in the air.With oxolane as solvent, pass through
Aluminium oxide-silicagel column removes catalyst.Rotary evaporation removes unnecessary solvent, and crude product is dissolved with oxolane for solvent, delays
Slowly it is added drop-wise to ether: petroleum ether=1:2 (v/v) 200ml is to precipitate in precipitant.The product of filtration under diminished pressure is done through 40 DEG C of vacuum
Dry, obtain white solid powder activity temperature sensing polymer.
Polymer and Hydrazoic acid,sodium salt are dissolved in n by the mol ratio of 1:18, in amide between n- dimethyl, in 60 DEG C of stirring conditions
Under, react 48 hours.After reaction terminates, reactant liquor is added in the bag filter of activation, with deionized water as solvent, every 6 hours
Change a water, dialyse two days, remove unreacted Hydrazoic acid,sodium salt.Rotary evaporation removes unnecessary solvent, and crude product is with tetrahydrochysene furan
Mutter and dissolve for solvent, be slowly dropped to precipitation in 150ml normal hexane.The product of filtration under diminished pressure is vacuum dried through 40 DEG C, obtains
Have formula (9) structure temperature sensing polymer white solid powder.Result of the test shows, Thermo-sensitive manufactured in the present embodiment gathers
The lcst of compound aqueous 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 it is 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 modify and also fall in the protection domain of the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention.
Multiple modifications to these embodiments will be apparent from 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
It is not intended to be limited to the embodiments shown herein, and be to fit to and principles disclosed herein and features of novelty phase one
The scope the widest causing.
Claims (9)
1. one kind has the temperature sensing polymer of formula () structure,
Wherein, r is methyl or hydrogen；
N is 5～100；
A by temperature sensitive monomer polymerization is formed, described temperature sensitive monomer selected from n- N-isopropylacrylamide, n- propylacrylamide,
N- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, the positive propionic acid amide. of n- vinyl, n- ethylene
Base caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine, n- (2,2- bis-
Methyl isophthalic acid, 3- dioxanes -5 alcohol) one of-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide or
Multiple.
2. temperature sensing polymer according to claim 1 it is characterised in that described r be hydrogen or methyl, described Thermo-sensitive list
Body is selected from n- N-isopropylacrylamide, n- propylacrylamide, n, n- acrylamide, n- vinyl Isopropamide and n-
One or more of caprolactam.
3. temperature sensing polymer according to claim 1 is it is characterised in that the number-average molecular weight of described temperature sensing polymer
For 3000～50000g/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 Bis(pentaerythritol), acid binding agent, catalyst and the acyl with formula () structure
Agent is reacted in a solvent, obtains the initiator with formula () structure；
B), under inert gas shielding, described initiator, temperature sensitive monomer, catalyst and complexant are reacted in a solvent, obtains
To the active temperature sensing polymer with formula () structure；Described temperature sensitive monomer is selected from n- N-isopropylacrylamide, n- propyl group
Acrylamide, n- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, the positive propionyl of n- vinyl
Amine, n- caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine,
N- (2,2- dimethyl -1,3- dioxanes -5 alcohol)-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide
One or more of；
C), described activity temperature sensing polymer is reacted in a solvent with Hydrazoic acid,sodium salt, obtain the Thermo-sensitive with formula () structure
Polymer；
Wherein, r is methyl or hydrogen；
N is 5～100；
A by temperature sensitive monomer polymerization is formed, described temperature sensitive monomer selected from n- N-isopropylacrylamide, n- propylacrylamide,
N- cyclopropyl acrylamide, n, n- acrylamide, n- vinyl Isopropamide, the positive propionic acid amide. of n- vinyl, n- ethylene
Base caprolactam, n- vinyl pyrrolidone, n- acryloyl group pyrrolidine, n- acryloyl group-n '-positive Propylpiperazine, n- (2,2- bis-
Methyl isophthalic acid, 3- dioxanes -5 alcohol) one of-acrylamide and n- (2- ethyoxyl -1,3- dioxanes -5 alcohol)-acrylamide or
Multiple.
5. preparation method according to claim 4 is it is characterised in that in described step a), described acid binding agent be pyridine or
Triethylamine；Described catalyst is DMAP；Described solvent is dichloromethane or acetonitrile, and described acylating agent is selected from 2-
Bromo- 2- methyl propionyl chloride, 2- bromo- 2- methyl propionyl bromide, 2- chloro-2-methyl propionyl chloride, 2- chloro-2-methyl propionyl bromide, chloro second
Acyl chlorides, chloroacetyl bromine, bromo acetyl bromide, bromoacetyl chlorine, 2 bromo propionyl bromide, 2- bromo propionyl chloro, 2- chlorine propionyl bromide or 2- chlorine
Propionyl chloride.
6. preparation method according to claim 4 is it is characterised in that in described step a), described Bis(pentaerythritol), ties up acid
Agent is 1:(6.1～6.5 with the mol ratio of acylating agent): (6.1～6.5).
7. preparation method according to claim 4 is it is characterised in that in described step b), described catalyst is selected from chlorination
Cuprous, cuprous bromide, Cuprous sulfocyanate and hexafluorophosphoric acid are one or more of cuprous；Described 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 of amine and three-(2- ethylaminoethyl) amine；Described solvent be n, n- dimethylformamide with go
The mixed solvent of ionized water.
8. preparation method according to claim 4 is it is characterised in that in described step b), described initiator, Thermo-sensitive list
The mol ratio of body, catalyst and complexant is 1:(30～500): (0.5～12): (0.5～12).
9. preparation method according to claim 4 is it is characterised in that described activity temperature sensing polymer and described Azide
The mol ratio of sodium is 1:(6～36).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610957656.1A CN106366225B (en) | 2016-10-27 | 2016-10-27 | Six arm temperature sensing polymers and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610957656.1A CN106366225B (en) | 2016-10-27 | 2016-10-27 | Six arm temperature sensing polymers and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106366225A true CN106366225A (en) | 2017-02-01 |
| CN106366225B CN106366225B (en) | 2018-08-10 |
Family
ID=57893654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610957656.1A Active CN106366225B (en) | 2016-10-27 | 2016-10-27 | Six arm temperature sensing polymers and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106366225B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705372A (en) * | 2018-12-29 | 2019-05-03 | 广东工业大学 | A kind of supramolecular materials and hydrogel and preparation method thereof |
| CN109705371A (en) * | 2018-12-29 | 2019-05-03 | 广东工业大学 | Supramolecular materials, hydrogel of six arm stars crosslinking and preparation method thereof |
| CN109721738A (en) * | 2018-12-29 | 2019-05-07 | 广东工业大学 | Supramolecular materials, self-healing temperature-sensitive hydrogel and preparation method thereof |
| CN110016324A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of high-temperature resistant water base drilling fluid extracting and cutting agent and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787105A (en) * | 2010-02-10 | 2010-07-28 | 东南大学 | Preparation method of network interpenetrating functional aquagel |
-
2016
- 2016-10-27 CN CN201610957656.1A patent/CN106366225B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787105A (en) * | 2010-02-10 | 2010-07-28 | 东南大学 | Preparation method of network interpenetrating functional aquagel |
Non-Patent Citations (3)
| Title |
|---|
| KATJA JANKOVA, MELANIA BEDNAREK,SØREN HVILSTED: "Star Polymers by ATRP of Styrene and Acrylates Employing Multifunctional Initiators", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
| 刘明凯，梁成峰，郭建维: "AMA-m-P( AA-co-NVP) 共聚物水凝胶的合成与溶胀性能研究", 《合成材料老化与应用》 * |
| 李青山主编: "《材料科学与工程实验教程 高分子分册》", 31 August 2012 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016324A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of high-temperature resistant water base drilling fluid extracting and cutting agent and preparation method thereof |
| CN110016324B (en) * | 2018-01-10 | 2021-08-17 | 中国石油化工股份有限公司 | High-temperature-resistant water-based drilling fluid shear strength improving agent and preparation method thereof |
| CN109705372A (en) * | 2018-12-29 | 2019-05-03 | 广东工业大学 | A kind of supramolecular materials and hydrogel and preparation method thereof |
| CN109705371A (en) * | 2018-12-29 | 2019-05-03 | 广东工业大学 | Supramolecular materials, hydrogel of six arm stars crosslinking and preparation method thereof |
| CN109721738A (en) * | 2018-12-29 | 2019-05-07 | 广东工业大学 | Supramolecular materials, self-healing temperature-sensitive hydrogel and preparation method thereof |
| CN109721738B (en) * | 2018-12-29 | 2021-04-16 | 广东工业大学 | Supramolecular material, self-healing temperature-sensitive hydrogel and preparation method thereof |
| CN109705371B (en) * | 2018-12-29 | 2021-05-11 | 广东工业大学 | Supramolecular material, six-arm star-shaped cross-linked hydrogel and preparation method thereof |
| CN109705372B (en) * | 2018-12-29 | 2021-08-13 | 广东工业大学 | Supramolecular material, hydrogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106366225B (en) | 2018-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106496387A (en) | Four arm temperature sensing polymers and preparation method thereof | |
| CN106366225A (en) | Six-arm thermosensitive polymer and preparation method thereof | |
| CN106633087B (en) | Miscellaneous arm star polymer of a kind of eight arms and preparation method thereof | |
| CN103980440A (en) | Semi-interpenetrating intelligent hydrogel and preparation method and application thereof | |
| CN103524519B (en) | Camptothecin prodrug monomer and polymeric prodrug amphipathic molecules thereof as well as preparation method and application of camptothecin prodrug monomer and polymeric prodrug amphipathic molecules | |
| CN107446146A (en) | A kind of hydrogel for possessing photochromic characteristic and preparation method thereof | |
| CN105085846B (en) | A kind of block copolymer and preparation method thereof | |
| CN105131170A (en) | Nanogel modified by ionic liquid and loaded with chiral catalyst and preparing method and application thereof | |
| CN106519154B (en) | Linear temperature sensing polymer and preparation method thereof | |
| CN106496388A (en) | Four arm temperature sensing polymer of adamantyl and preparation method thereof | |
| CN107383239A (en) | A kind of N pyridines urea groups chitosan quaternary ammonium salt and its preparation method and application | |
| JP2023539664A (en) | Porous resin for solid phase synthesis and its manufacturing method | |
| CN108395499A (en) | A kind of preparation method of the bionical cohesive hydrogel system of amino acid | |
| CN104628948B (en) | Acrylate-type poly-chain transfer agent as well as preparation method and application of poly-chain transfer agent in preparation of columnar polymer brush | |
| KR20050056288A (en) | Acrylamides monomer and thermoresponsive acrylamides polymer prepared by using same | |
| CN107236067B (en) | Adamantyl both arms temperature sensing polymer and preparation method thereof | |
| CN104761693A (en) | Self-assembly method of galactose-containing thermo-sensitive copolymer | |
| CN110003410B (en) | Six-arm star copolymer and preparation method thereof | |
| CN107674158B (en) | Temperature-sensitive hydrogel with hyperbranched structure and preparation method and application thereof | |
| CN107383377B (en) | Cyclic polycaprolactone-polyethylene glycol amphiphilic block copolymer, and preparation and application thereof | |
| CN103980398A (en) | Self-assembly with perylene derivative or analog as fluorescent chromogenic end group and preparation method thereof | |
| CN104804142A (en) | Multi-responsive HPC (hydroxy propyl cellulose) grafted copolymer as well as preparation method and application thereof | |
| CN105418844B (en) | A kind of preparation method of hydroxyl liquid rubber | |
| CN101280069A (en) | Preparation of cross linker for synthesizing amphipathic gel and application of the cross linker | |
| CN111533865B (en) | Anti-protein-adsorption self-cleaning block copolymer, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |