CN108484923A - Supermolecule polymer and preparation method thereof based on lipoic acid class compound - Google Patents
Supermolecule polymer and preparation method thereof based on lipoic acid class compound Download PDFInfo
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- CN108484923A CN108484923A CN201810232611.7A CN201810232611A CN108484923A CN 108484923 A CN108484923 A CN 108484923A CN 201810232611 A CN201810232611 A CN 201810232611A CN 108484923 A CN108484923 A CN 108484923A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The present invention relates to a kind of supermolecule polymer and preparation method thereof based on lipoic acid or/and its derivative.The supermolecule polymer is mainly obtained by lipoic acid or/and its derivative, crosslinking agent and source of iron after hot melt mixes.The molar ratio of wherein lipoic acid or/and its derivative, crosslinking agent and source of iron is 2:(0.1~1.5):(0.01~1)；The lipoic acid or/and its derivative are selected from：One or more kinds of mixtures in compound shown in Formulas I；The crosslinking agent is the hydrocarbon compound containing unsaturated carbon carbon bond, and the source of iron is made of molysite with the organic solvent that can dissolve molysite.The stretchable degree of supermolecule polymer provided by the invention is more than 150 times, and it can supper-fast selfreparing at ambient temperature.In Formulas I, R1For hydrogen or C1~C4Linear or branched alkyl group, R2For hydrogen or carboxyl, the integer that n is 1~5.
Description
Technical field
The present invention relates to a kind of supermolecule polymers and preparation method thereof, specifically, be related to it is a kind of based on lipoic acid or/
With the supermolecule polymer of its derivative and preparation method thereof.
Background technology
Supermolecule polymer refers to the interaction self assembly of small molecule monomer or low polymer by non-covalent bond
Made of polymer.The factors such as acid-base value, temperature and illumination can lead to the dissociation and recombination of the non-covalent bond of supermolecule polymer,
With invertibity, therefore, supermolecule polymer, which is a kind of, to be state in recent years as the intellectual material of selfreparing and self-healing
One of inside and outside research hotspot.
Supermolecule polymer application field is extensive, such as the intellectual material being modified, electronic device and biomaterial etc..Closely
Nian Lai is quickly grown in biology and the application study of biomedical sector, including with the relevant application of cell, organizational project,
Drug delivery, immunological regulation and wound healing etc..
2016, Bao Zhenan et al. was obtained by the introducing crosslinked complex in dimethyl silicone polymer (PDMS) chain
A kind of stretchable 100 times, can room temperature selfreparing in 48 hours elastomer (A highly stretchable autonomous
Self-healing elastomer, Nat.Chem.2016,8,618-624.).Used crosslinking complex is by 2,6- pyridines
Diamide ligand forms, it is coordinated by three kinds of different interactions and the center Fe (III).
The shortcomings of the prior art is that the monomer or low polymer for preparing supermolecule polymer seldom (need certainly
System).Therefore, it is that the present invention needs the skill solved to prepare the supermolecule polymer with excellent properties using existing known compound
Art problem.
Invention content
The present inventor has found through extensive and in-depth study：It uses lipoic acid or derivatives thereof for monomer, is equipped with
The crosslinking agent and iron ion source of particular types and specific quantity can obtain a kind of super under conditions of not adding solvent through heat fusing method
Molecularly Imprinted Polymer.After testing, the stretchable degree of gained supermolecule polymer is more than 150 times, and it can be ultrafast at ambient temperature
Fast selfreparing (being no more than one minute).
A purpose of the invention is, provides a kind of supermolecule polymer based on lipoic acid or/and its derivative.
The supermolecule polymer is made by the following preparation method of key step：
Under solvent-free conditions, by lipoic acid or/and its derivative, crosslinking agent and source of iron target is obtained after hot melt mixes
Object；
Wherein, the molar ratio of lipoic acid or/and its derivative, crosslinking agent and source of iron is 2:(0.1~1.5):(0.01~
1), (molal quantity of source of iron is in terms of the molal quantity of iron ion)；
The lipoic acid or/and its derivative are selected from：(containing two kinds) mixing one or more kinds of in compound shown in Formulas I
Object；
The crosslinking agent is the hydrocarbon compound containing unsaturated carbon carbon bond, and the source of iron is by molysite and can dissolve having for molysite
Solvent forms；
In Formulas I, R1For hydrogen or C1~C4Linear or branched alkyl group, R2For hydrogen or carboxyl (- COOH), the integer that n is 1~5.
It is another object of the present invention to provide a kind of method preparing above-mentioned supermolecule polymer.
The method has main steps that：Under solvent-free conditions, lipoic acid or/and its derivative are placed in stirring
It in the reaction vessel of device, stirs and heats, again by above-mentioned molar ratio after lipoic acid or/and the fusing of its derivative, to described
Crosslinking agent and source of iron are sequentially added in reaction vessel, after being stirred at least 3 minutes, stop heating, object is obtained after cooling.
Description of the drawings
Fig. 1 are the outside drawing of supermolecule polymer prepared by the embodiment of the present invention 1；
Fig. 2 are the rheological property curve of supermolecule polymer prepared by the embodiment of the present invention 2；
Fig. 3 are the structural characterization figure of supermolecule polymer prepared by the embodiment of the present invention 3；
Wherein, A is the structural schematic diagram of polymer, and B is the infrared spectrogram of polymer, and C is the Raman spectrum of polymer
Figure；
Fig. 4 are the self-healing performance figure of supermolecule polymer prepared by the embodiment of the present invention 4；
Wherein, A is the self-healing micro-image of supermolecule polymer, stretchings of the B for supermolecule polymer initially and after self-healing
Curve；
Fig. 5 are the underwater self-healing performance figure of supermolecule polymer prepared by the embodiment of the present invention 5；
Wherein, A is the cutting drawing of supermolecule polymer, and B is the underwater self-healing performance performance figure of supermolecule polymer.
Fig. 6 are stretching and the resilience performance figure of supermolecule polymer prepared by the embodiment of the present invention 6：
Wherein, A is the initial graph of supermolecule polymer, and B is the tensile diagram of supermolecule polymer, and C is supermolecule polymer
The figure discharged after stretching, D are the tensile property curve of supermolecule polymer, and E is the resilience performance curve of supermolecule polymer.
Specific implementation mode
In a preferred technical solution of the invention, the lipoic acid or/and its derivative are compound shown in Formulas I,
The integer that wherein n is 1~3.
In presently preferred technical solution, crosslinking agent used is substituted benzene, the substituent group of the substituted benzene
For vinyl or C1~C3Alkyl-substituted vinyl；
The crosslinking agent that the present invention recommends is styrene, divinylbenzene or 1,3- bis- (1- methyl ethylenes) benzene
(DIB)。
In a further preferred technical solution of the present invention, the molysite can be ferric sulfate, iron chloride, ferric nitrate or/
And ferric stearate；The organic solvent is acetone, ethyl alcohol or methanol.
The method provided by the invention for preparing supermolecule polymer of the present invention, has main steps that：In solvent-free item
Under part, lipoic acid or/and its derivative are placed in the reaction vessel with agitating device, stir and heat that (oil bath temperature is
70 DEG C~200 DEG C), the molar ratio as previously described after lipoic acid or/and the fusing of its derivative is added into the reaction vessel
Crosslinking agent, after, continue stirring 5 minutes~8 minutes, then iron is added into the reaction vessel in molar ratio as previously described
Source, after, it is stirred for 3 minutes~5 minutes, stops heating, object is obtained after cooling.
The present invention has following features：
1, the raw material used in the present invention is beneficial to human body, and bio-compatible derives from a wealth of sources, cheap and easy to get, has industry feasible
Property；
2, the present invention is not necessarily to solvent, rapid reaction, process is simple and safe, no using the method for directly heating melt raw material
Generate the industrial pollution such as waste water, waste residue.Entire preparation process is simple, and low production cost, quantitative yield meets Green Chemistry
It is required that；
3, there is supermolecule polymer provided by the invention room temperature and underwater self-healing property, high elongation (can stretch 150 times
More than) and excellent thermo-responsive (can be under thermostimulation, solid-liquid conversion times can be 10 times or more).
In addition, supermolecule polymer provided by the invention has good biocompatibility (and being free of solvent), in biology
Medical field is with a wide range of applications.
Below by embodiment, the present invention is further elaborated, and purpose, which is only that, is best understood from present disclosure.
Therefore, the cited case does not limit the scope of the invention.
The preparation of supermolecule polymer
Embodiment 1
10g lipoic acid powder is placed in the reactor with agitating device, oil bath heating to lipoic acid powder melts, and opens
Begin to stir.Then plus in bis- (1- methyl ethylenes) benzene (DIB) to the reactor of 6g (60wt%) 1,3-, continue heating stirring 5
Minute.It adds in the acetone soln to the reactor of 0.1g iron chloride, continues heating stirring 3 minutes, stop heating, be cooled to
Room temperature is to get supermolecule polymer -1.
Embodiment 2~8
Outside the type and monomer of change monomer and crosslinking agent, the molar ratio of crosslinking agent and source of iron, remaining step and condition
It is same as Example 1, different supermolecule polymers are respectively obtained, table 1 is referred to.
Table 1
The appearance of supermolecule polymer provided by the invention is shown in Fig. 1 (by taking supermolecule polymer -1 as an example)；What is provided is super
Molecularly Imprinted Polymer rheological property curve is shown in Fig. 2 (by taking supermolecule polymer -2 as an example)；And the supermolecule polymer structure provided
Characterization is shown in Fig. 3 (by taking supermolecule polymer -3 as an example).
The test of supermolecule polymer self-healing (conjunction) performance, tensile property and thermal response property
Embodiment 9
1, the test of self-healing (conjunction) performance
(1) supermolecule polymer of the present invention (for supermolecule polymer -4) for taking one section of strip, will with scissors
It cuts into two sections and against putting together, is placed on glass slide, and the figure for being damaged polymer is recorded with 100 × power microscope
Picture observes its self-healing performance with 100 × power microscope again after 50 hours, record；
The supermolecule polymer of the present invention (for supermolecule polymer -4) for taking one section of strip, is cut with scissors
It is cut into two sections and against putting together, places 1 minute, polymer is placed on clamp of tensile machine for two sections, with the speed of 100mm/min
Degree is stretched, its tensile property is observed.
In Fig. 4, A is the self-healing micro-image (1 minute) of supermolecule polymer -4, and B is the initial of supermolecule polymer -4
With the stress strain curve after self-healing；
(2) supermolecule polymer of the present invention (for supermolecule polymer -5) for taking one section of thick strip, uses scissors
Two sections are cut to, puts it into water and against putting together, observes its self-healing performance, referring to Fig. 5, (wherein, A is
The cutting drawing of supermolecule polymer, B are the underwater self-healing performance performance figure of supermolecule polymer).
Above-mentioned experiment shows that supermolecule polymer -4 has excellent air and underwater self-healing (conjunction) performance.
2, tensile property is tested
The supermolecule polymer of the present invention (by taking supermolecule polymer -6 as an example) for taking one section of strip, grasps poly-
Two sections of object is closed, it is 1cm to make polymer initial length.Slow smoothly strained polymer, observes its tensile property, is stretched to 50cm
Slow smoothly release polymers again after above, observe its resilience performance；
The supermolecule polymer of the present invention (by taking supermolecule polymer -6 as an example) for taking one section of strip, by polymer two
Section is placed on clamp of tensile machine, is stretched with the speed of 100mm/min, observes its tensile property；
The supermolecule polymer of the present invention (by taking supermolecule polymer -6 as an example) for taking one section of strip, by polymer two
Section is placed on clamp of tensile machine, is carried out cyclic tension with the speed of 100mm/min, is observed its resilience performance.
A is the initial graph of supermolecule polymer -6 in Fig. 6, and B is the tensile diagram of supermolecule polymer -6, and C is poly- for supermolecule
The figure discharged after object -6 stretches is closed, D is the tensile property curve of supermolecule polymer -6, and E is the rebound of supermolecule polymer -6
Performance curve.
By A it is found that the initial length of supermolecule polymer -6 is 1cm, by B it is found that supermolecule polymer -6 is uniformly drawn
50cm or more is extended to, by C it is found that the supermolecule polymer -6 after being released is 5 times of initial length, by D it is found that the oversubscription
The extensibility of sub- polymer -6 up to 15000% or more, by E it is found that the supermolecule polymer -6 can 200% extensibility
Lower repeatedly cycle, it was demonstrated that its excellent draftability and resilience.
3, thermo-responsive is tested
The first supermolecule polymer of the present invention for forming elastomer is melted under 70 DEG C of oil bath heatings, is then stopped
Only heating is cooled to room temperature, and polymer is converted into elastic state from molten state again.
Therefore, the supermolecule polymer has excellent thermal response property：Solid-liquid can be achieved under thermostimulation to turn
It changes.
Claims (7)
1. a kind of supermolecule polymer, which is characterized in that the supermolecule polymer is by the following preparation method system of key step
：
Under solvent-free conditions, by lipoic acid or/and its derivative, crosslinking agent and source of iron object is obtained after hot melt mixes；
Wherein, the molar ratio of lipoic acid or/and its derivative, crosslinking agent and source of iron is 2:(0.1~1.5):(0.01~1)；
The lipoic acid or/and its derivative are selected from：One or more kinds of mixtures in compound shown in Formulas I；
The crosslinking agent is the hydrocarbon compound containing unsaturated carbon carbon bond, and the source of iron is by molysite and can dissolve the organic molten of molysite
Agent forms；
In Formulas I, R1For hydrogen or C1~C4Linear or branched alkyl group, R2For hydrogen or carboxyl, the integer that n is 1~5.
2. supermolecule polymer as described in claim 1, which is characterized in that the wherein described lipoic acid or/and its derivative are
The integer that compound shown in Formulas I, wherein n are 1~3.
3. supermolecule polymer as claimed in claim 1 or 2, which is characterized in that crosslinking agent is used in wherein：Substituted benzene；Institute
The substituent group for stating substituted benzene is vinyl or C1~C3Alkyl-substituted vinyl.
4. supermolecule polymer as claimed in claim 3, which is characterized in that the wherein described crosslinking agent is：Styrene, divinyl
Base benzene or 1,3- bis- (1- methyl ethylenes) benzene.
5. supermolecule polymer as claimed in claim 1 or 2, which is characterized in that molysite is used in wherein：Ferric sulfate, chlorination
Iron, ferric nitrate or/and ferric stearate.
6. supermolecule polymer as claimed in claim 1 or 2, which is characterized in that organic solvent wherein used is acetone, ethyl alcohol
Or methanol.
7. a kind of method preparing supermolecule polymer as claimed in claim 1 or 2, has main steps that：In solvent-free item
Under part, lipoic acid or/and its derivative are placed in the reaction vessel with agitating device, stirs and heats, wait for lipoic acid or/
Molar ratio as described in claim 1 or 2 after being melted with its derivative, crosslinking agent is added into the reaction vessel, after,
Continue stirring 5 minutes~8 minutes, then source of iron is added into the reaction vessel for molar ratio as described in claim 1 or 2, it is complete
Bi Hou is stirred for 3 minutes~5 minutes, stops heating, object is obtained after cooling.
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