CN106928672A - With hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability and preparation method thereof - Google Patents
With hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability and preparation method thereof Download PDFInfo
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Abstract
It is the invention discloses the structure with hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability and preparation method thereof, the polymer moieties of the hybrid cross-linked network of polycaprolactone
Description
Technical field
It is with the two-way shape note of heat/magnetic response specifically the present invention relates to the preparation field of crosslinked polymer network
Recall hybrid cross-linked network of the polycaprolactone of function and self-healing capability and preparation method thereof, the hybrid cross-linked network of polycaprolactone can
As the medical material with memory function, aeronautical material, degradable material, sensor etc..
Background technology
Shape-memory material (shape memory materials, SMMs) be it is a kind of be rapidly developed in recent years it is new
Type intellectual material, it initially originates from marmem, afterwards in order to adapt to wider application demand, shape memory ceramics
(shape memory ceramics, SMCs) and shape-memory polymer (shape memory polymers, SMPs) also phase
After being developed.Wherein SMPs is so that deformation quantity is big, the processing of light weight, structural behaviour easy-regulating, easy-formation, the low advantage of cost
Cause the extensive concern in the world, relevant research is also developed rapidly.
Shape memory behavior refers to the product with original shape, after deformation and fixing, by external condition
Stimulate, the phenomenon for making it return to original shape.Current shape memory high molecule material, according to the difference of incentive condition, can divide
It is thermic induction type, electroluminescent induction type, photic induction type, mangneto induction type etc..Conventional shape-memory polymer is being replied
Later, it is necessary to figuration could drive second reply, also referred to as one-way shape memory polymer again.It is repeatedly many for needing
The secondary field for using, this material is greatly limited.And in order to adapt to wider application demand, one kind is new to be had
The bidirectional shape memory polymer of reversible Shape memory behavior is developed.
Semi-crystalline polymer cross-linked network is the important kind of bidirectional shape memory polymer.According to bidirectional shape memory
The structure of semi-crystalline polymer cross-linked network is analyzed, it is known that semi-crystalline polymer cross-linked network refers to semi-crystalline polymer chain
Section exists with tridimensional network, and segment has crystallization-melting reversible transition.By this kind of polymer in constant external force condition
Under, segment can be induced along stress direction and crystallized, and show the phenomenon of decrease temperature crystalline induction elongation；Polymer chain is heated simultaneously
Section melting, shows the phenomenon that the melting induction that heats up is shunk.Therefore a kind of semi-crystalline polymer cross-linked network is designed, is answered constant
By changing temperature-driven segment crystallization-melting transition under the conditions of power, bidirectional shape memory function can be showed.
Polycaprolactone (PCL) is a kind of aliphatic polyester for being widely used in medical material, field of medicine release, and
PCL is equally a kind of semi-crystalline polymer, and its good crystallizing power makes it be successfully applied in bidirectional shape memory material.
Poly-cage modle oligomeric silsesquioxane (POSS) that Mather et al. designs triggers caprolactone (CL) open loop that POSS-PCL is obtained
Diol, is crosslinked by end and PCL-POSS Chemical Physics crosslinking dual network is obtained；Pandini et al. pass through sol gel
Prepare the PCL cross-linked networks of different gel contents, proposes the two-way shape of gel content and crystallization situation to semi-crystalline polymer
Shape memory performance has tremendous influence；The PCL networks of crosslinking are made base material by Leng et al., are loaded with Fe3O4Nano particle
Multi-walled carbon nano-tubes (Fe3O4@C) make filler, the shape-memory material with many stimuli responsives and bidirectional reversible behavior is obtained
Deng.Although above-mentioned crosslinked polymer network embodies preferable bidirectional shape memory ability, this irreversible covalent cross-linking net
Network structure causes that the processing and forming mode of material is greatly limited, it is difficult to which satisfaction is widely applied demand.It will be apparent that should
Technology be difficult and meanwhile meet bidirectional shape memory, can reprocess, many requirements such as many stimuli responsives.
Catechol, also referred to as catechol, are the compounds formed after two ortho-hydrogens of benzene are optionally substituted by a hydroxyl group.It is produced
It is small point used extensively in food, medicine, agricultural chemicals while existing in poison, insect, tealeaves in vegetable and fruit
Son.In organic chemistry, catechol and its derivative caused scientists and widely discussed past in 20 years, and it can be with
Ferroso-ferric oxide is formed to be stablized and reversible coordinate bond.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided with heat/magnetic response bidirectional shape memory function
And the hybrid cross-linked network of polycaprolactone of self-healing capability, the hybrid cross-linked network of the polycaprolactone be it is a kind of it is new, while having
Heat/magnetic response bidirectional shape memory function, can re-workability and hypocrystalline polycaprolactone hydridization the advantages of self-healing capability hand over
Networking network.
It is above-mentioned new with heat/magnetic response bidirectional shape memory function and self-healing it is a further object of the present invention to provide preparing
The preparation method of the hybrid cross-linked network of polycaprolactone of conjunction ability.
The present invention is achieved through the following technical solutions：With heat/magnetic response bidirectional shape memory function and self-healing capability
The hybrid cross-linked network of polycaprolactone, be have selected when MOLECULE DESIGN is carried out with very excellent biocompatibility and biology can
The polycaprolactone of degradability is used as the PCL hydridization of bidirectional shape memory function and self-healing capability with heat/magnetic response
The basic composition segment of cross-linked network；End group modification is carried out to polymer segment by catechol group, then with ferroso-ferric oxide
Nano particle be coordinated obtain with heat/magnetic response bidirectional shape memory function, can re-workability and self-healing capability
The hybrid cross-linked networks of hypocrystalline PCL：
The structure of the polymer moieties of the hybrid cross-linked network of polycaprolactone is
PCL represents pla-pcl segment in formula, and number-average molecular weight is 2000~10000g/mol, and it is different that R represents coupling agent two
Hydrocarbyl portion in cyanate.
It is further of the present invention with heat/magnetic response bidirectional shape memory function and self-healing to be better achieved
The hybrid cross-linked network of polycaprolactone of ability：The structure of the hybrid cross-linked network of pla-pcl is
In formulaRepresenting the polymer moieties of the hybrid cross-linked network of polycaprolactone, number-average molecular weight is 2000~
10000g/mol,Represent magnetic ferroferric oxide nanometer particle part in the hybrid cross-linked network of polycaprolactone.
It is further of the present invention with heat/magnetic response bidirectional shape memory function and self-healing to be better achieved
The hybrid cross-linked network of polycaprolactone of ability：The ferroferric oxide nano granules content of the hybrid cross-linked network of pla-pcl is
5~30wt%, gel content is 70~100%；The hybrid cross-linked network uni-directional shape memory fixed rate R of pla-pclfFor
70~100%, shape memory response rate RrIt is 70~100%；The hybrid cross-linked network bi-directional shape memory of pla-pcl is returned
Multiple rate RrecIt is 70~100%, the hybrid cross-linked network of polycaprolactone 10 hours remediation efficiencies at 100 DEG C can reach 85~
95%.
It is further of the present invention with heat/magnetic response bidirectional shape memory function and self-healing to be better achieved
The hybrid cross-linked network of polycaprolactone of ability：Hydrocarbyl portion is diphenylmethane diisocyanates in the coupling agent diisocyanate
Ester, XDI, toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate or the isocyanide of hexa-methylene two
Any one of hydrocarbyl portion in acid esters.
Preparation with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability
Method, the polycaprolactone blocked using catechol group is coordination cross-linked with ferroferric oxide nano granules, the preparation method bag
Include step in detail below：
1) polycaprolactone of catechol group end-blocking is prepared；
2) the modified ferroferric oxide nano granules of oleic acid moieties are prepared；
3) the hybrid cross-linked network of pla-pcl is prepared.
It is further of the present invention with heat/magnetic response bidirectional shape memory function and self-healing to be better achieved
The preparation method of the hybrid cross-linked network of polycaprolactone of ability, the step 1) including step in detail below：
1.1) by terminal hydroxy group polycaprolactone vaccum dewatering, stirring is then heated up under inert gas shielding to after melting, plus
Enter the DMF dissolvings of purifying；It is preferred to heat up stirring under nitrogen or argon to after melting, add the DMF dissolvings of purifying；
1.2) add and be calculated as 1 with terminal hydroxy group polycaprolactone molal quantity：2.0~3.0 coupling agent diisocyanate to reaction
In, catalyst (tin catalyst) is added in 2~5h of reaction at 60~80 DEG C；It is preferably added dibutyl tin laurate or pungent
The tin class such as sour stannous makees catalyst；
1.3) take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.0~3.0 dopamine hydrochloride is first dissolved in DMF, plus
Enter activator activation, be then added in reaction, 8~12h is reacted at 40~50 DEG C, precipitation is dried, and obtains catechol group
The polycaprolactone of end-blocking, is then stored in dry environment with standby；It is preferably added the triethylamine activation of purifying or adds carbonic acid
The conventional acid binding agent such as potassium (drying regime) is activated, and is then added in reaction, and 8~12h is reacted at 40~50 DEG C, finally by
Water shield solution or hydrochloric acid solution are precipitated, and are dried, and obtain the polycaprolactone of catechol group end-blocking；Preferably used when being precipitated
The aqueous solution of watery hydrochloric acid is precipitated, and further preferred use methanol solution is precipitated
It is further of the present invention with heat/magnetic response bidirectional shape memory function and self-healing to be better achieved
The preparation method of the hybrid cross-linked network of polycaprolactone of ability：The M of described terminal hydroxy group polycaprolactonenIt is 2000~10000g/
Mol, structural formula is：
Wherein, 7<n<43.
It is further of the present invention with heat/magnetic response bidirectional shape memory function and self-healing to be better achieved
The preparation method of the hybrid cross-linked network of polycaprolactone of ability：The coupling agent diisocyanate is diphenylmethane diisocyanates
Ester, XDI, toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate or the isocyanide of hexa-methylene two
Any one in acid esters.
It is further of the present invention with heat/magnetic response bidirectional shape memory function and self-healing to be better achieved
The preparation method of the hybrid cross-linked network of polycaprolactone of ability：The step 2) including step in detail below：
2.1) by FeCl24H2O and FeCl36H2O with mol ratio 1:2 is soluble in water, adds solution total mass ratio 3%
The enuatrol of~5% content, stirring and dissolving under inert gas shielding, agitating mode is preferably mechanical agitation, but is not limited to machinery
Stirring means, are then, more than or equal to addition ammoniacal liquor (25~28%w/w) under 800r/min, to keep 30~90min in rotating speed；It is excellent
Choosing by FeCl24H2O and FeCl36H2O with mol ratio 1:2 is soluble in water, adds solution total mass ratio 3%~5% to contain
The enuatrol of amount, the stirring and dissolving under the inert gas shielding such as nitrogen or argon gas, agitating mode is preferably mechanical agitation, but does not limit
In mechanical agitation methods, be then preferably added in the case where preferred rotating speed is 800~1000r/min consumption for 15mL ammoniacal liquor (25~
28%w/w), 30~90min is kept；
2.2) by step 2.1) reaction solution precipitated, separated after, washing, dry, obtain black powder；It is preferred to
Step 2.1) reaction solution in add acetone precipitation, after centrifugation, then by acetone, ethanol wash after spontaneously dry, it is excellent
Choosing washing three times, obtains black powder；Precipitating reagent, separate mode, detergent are common selection, but are not limited to this kind of selection.
2.3) by step 2.2) gained black powder is added to the water, and adds the oil of the content of aqueous solution total mass ratio 3%~5%
Sour sodium, dissolving, dispersion continues to be stirred under inert gas shielding (preferably using ultrasonic disperse) after 10~60min, excellent
The mechanical agitation under the protection of the inert gas such as nitrogen or/and argon gas of choosing, agitating mode is preferably mechanical agitation, but is not limited to
Mechanical agitation methods, rotating speed after reaction solution is precipitated, separate, is washed more than or equal to 30~90min is stirred under 800r/min
Wash, dry；30~90min under 800~1000r/min of preferred rotating speed, adds acetone precipitation, centrifugation, then by third
Spontaneously dried after ketone, ethanol washing, spontaneously dried after preferably washing three times, obtain four modified oxidations three of black oleic acid moieties
Iron nano-particle, is then stored in dry environment with standby.Precipitating reagent, separate mode, detergent are common selection, but are not limited to
This kind of selection.
It is further of the present invention with heat/magnetic response bidirectional shape memory function and self-healing to be better achieved
The preparation method of the hybrid cross-linked network of polycaprolactone of ability：The step 3) prepare the hybrid cross-linked network of pla-pcl and be specially
By step 1) obtained by catechol group end-blocking polycaprolactone and step 2) obtained by the modified ferroso-ferric oxide of oleic acid moieties
Nano particle is according to mass ratio 20:1~20:6 proportioning is dissolved in organic solvent, and preferred organic solvent uses soluble polymer
Conventional volatile organic solvent, by after dispersion, being poured into grinding tool, solvent flashing film forming；
More preferably：The step 3) prepare the hybrid cross-linked network of pla-pcl and be specially step 1) obtained by youngster
The polycaprolactone of tea phenol group end capping and step 2) obtained by the modified ferroferric oxide nano granules of oleic acid moieties according to quality
Than 20:1~20:6 proportioning is dissolved in chloroform, after dispersion, is poured into grinding tool, solvent flashing film forming；The step dispersing mode
Preferably ultrasonic disperse, grinding tool are preferably polytetrafluoroethylene (PTFE) grinding tool, but are not limited to this kind of selection.
The present invention compared with prior art, with advantages below and beneficial effect：
1st, because the hybrid cross-linked network of polycaprolactone that the present invention is provided is with good biocompatibility, biodegradation
Property, the polycaprolactone of high crystalline and low melting point make polymer segment, made with the ferroferric oxide nano granules of bio-compatible
Crosslinking points, thus it is not only that shape memory functional material field adds a kind of alternative new varieties, and the cross-linked network
Network has biocompatibility；Simultaneously as the introducing of ferroferric oxide nano granules causes that there is the material magnetic and magnetic heat to ring
Ying Xing, has widened its application field.
2nd, because the hybrid cross-linked network of polycaprolactone that the present invention is provided is with polycaprolactone as polymer segment, with four oxygen
Change three iron nano-particles and make crosslinking points, be connected with nano particle by polymer by catechol group and make hybrid cross-linked network；Cause
For catechol group and ferroferric oxide nano granules are present as a kind of reversible coordination, therefore the cross-linked network has certainly
Healing ability and cycling processability, so as to widen the application field of the shape-memory material significantly.
3rd, molecular weight and polymer and four oxidations three of polymer segment can be regulated and controled due to the method that the present invention is provided
The content of iron nano-particle, thus different thermal transition temperatures can be obtained, different magnetic, the biodegradable shape of magnetic thermal effect
Memory material, so as to widen the application field of the shape-memory material significantly.
4th, preparation method is simple, the maturation that the present invention is provided, technique is easily controllable.
5th, be incorporated into catechol group in polymer by the present invention, the stronger coordination ability using it with ferroso-ferric oxide
Form dynamic crosslinking network, due to the invertibity of coordinate bond, make the cross-linked network that there is self-healing capability and can reprocessabilty
Feature.
Specific embodiment
The present invention is described in further detail with reference to embodiment, but embodiments of the present invention not limited to this.
Embodiment 1：
The present invention proposes the polycaprolactone hydridization with heat/magnetic response bidirectional shape memory function and self-healing capability and hands over
Networking network, the polycaprolactone with very excellent biocompatibility and biodegradability is have selected when MOLECULE DESIGN is carried out
It is used as basic group of the hybrid cross-linked networks of the PCL of bidirectional shape memory function and self-healing capability with heat/magnetic response
Into segment；End group modification is carried out to polymer segment by catechol group, then is coordinated with ferroferric oxide nano granules
Obtain with heat/magnetic response bidirectional shape memory function, can re-workability and self-healing capability hypocrystalline PCL it is hybrid cross-linked
Network：
The structure of the polymer moieties of the hybrid cross-linked network of polycaprolactone is
PCL represents pla-pcl segment in formula, and number-average molecular weight is 2000~10000g/mol, and it is different that R represents coupling agent two
Hydrocarbyl portion in cyanate.
Embodiment 2：
The present embodiment is further optimized on the basis of above-described embodiment, further for institute of the present invention is better achieved
State with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability：It is described to gather
The structure of the hybrid cross-linked network of lactone is
In formulaRepresenting the polymer moieties of the hybrid cross-linked network of polycaprolactone, number-average molecular weight is 2000~
10000g/mol,Represent magnetic ferroferric oxide nanometer particle part in the hybrid cross-linked network of polycaprolactone.
Embodiment 3：
The present embodiment is further optimized on the basis of any of the above-described embodiment, and further is that this hair is better achieved
It is bright described with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability：It is described
The ferroferric oxide nano granules content of the hybrid cross-linked network of pla-pcl is 5~30wt%, and gel content is 70~100%；
The hybrid cross-linked network uni-directional shape memory fixed rate R of pla-pclfIt is 70~100%, shape memory response rate RrFor 70~
100%；The hybrid cross-linked network bi-directional shape memory response rate R of pla-pclrecIt is 70~100%, polycaprolactone hydridization is handed over
Networking network 10 hours remediation efficiencies at 100 DEG C can reach 85~95%.
Embodiment 4：
The present embodiment is further optimized on the basis of any of the above-described embodiment, and further is that this hair is better achieved
It is bright described with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability：It is described
Hydrocarbyl portion is different '-diphenylmethane diisocyanate, XDI, toluene two in coupling agent diisocyanate
Cyanate, dicyclohexyl methyl hydride diisocyanate or in hexamethylene diisocyanate hydrocarbyl portion any one.
Embodiment 5：
The present embodiment is further optimized on the basis of any of the above-described embodiment, with the two-way shape note of heat/magnetic response
Recall the preparation method of the hybrid cross-linked network of the polycaprolactone of function and self-healing capability, gathered in oneself using what catechol group was blocked
Ester is coordination cross-linked with ferroferric oxide nano granules, and the preparation method includes step in detail below：
1) polycaprolactone of catechol group end-blocking is prepared；
2) the modified ferroferric oxide nano granules of oleic acid moieties are prepared；
3) the hybrid cross-linked network of pla-pcl is prepared.
Embodiment 6：
The present embodiment is further optimized on the basis of any of the above-described embodiment, and further is that this hair is better achieved
The bright described preparation with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability
Method, the step 1) including step in detail below：
1.1) by terminal hydroxy group polycaprolactone vaccum dewatering, stirring is then heated up under nitrogen protection to after melting, add pure
The DMF dissolvings of change；It is preferred by terminal hydroxy group polycaprolactone under 100 DEG C of temperature conditionss vaccum dewatering；
1.2) add and be calculated as 1 with terminal hydroxy group polycaprolactone molal quantity：2.0~3.0 coupling agent diisocyanate to reaction
In, add dibutyl tin laurate to make catalyst, it is preferably added 5 drop dibutyl tin laurates and makees catalyst, in 60~
2~5h is reacted at 80 DEG C；
1.3) take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.0~3.0 dopamine hydrochloride is first dissolved in DMF, plus
Enter the triethylamine activation of purifying, be then added in reaction, 8~12h is reacted at 40~50 DEG C, it is heavy finally by methanol solution
Form sediment, dry, obtain the polycaprolactone of catechol group end-blocking, be then stored in dry environment with standby.
Embodiment 7：
The present embodiment is further optimized on the basis of any of the above-described embodiment, and further is that this hair is better achieved
The bright described preparation with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability
Method：The M of described terminal hydroxy group polycaprolactonenIt is 2000~10000g/mol, structural formula is：
Wherein, 7<n<43.
Embodiment 8：
The present embodiment is further optimized on the basis of any of the above-described embodiment, and further is that this hair is better achieved
The bright described preparation with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability
Method：The coupling agent diisocyanate is '-diphenylmethane diisocyanate, XDI, toluene diisocyanate
Any one in acid esters, dicyclohexyl methyl hydride diisocyanate or hexamethylene diisocyanate.
Embodiment 9：
The present embodiment is further optimized on the basis of any of the above-described embodiment, and further is that this hair is better achieved
The bright described preparation with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability
Method：The step 2) including step in detail below：
2.1) by FeCl2·4H2O and FeCl3·6H2O is with mol ratio 1:2 is soluble in water, adds solution total mass ratio 3%
The enuatrol of~5% content, the lower mechanical agitation dissolving of nitrogen protection, then adds 15mL in the case where rotating speed is 800~1000r/min
Ammoniacal liquor (25~28%w/w), keeps 30~90min；
2.2) to step 2.1) reaction solution in add acetone precipitation, then centrifugation washs three by acetone, ethanol
Spontaneously dried after secondary, obtain black powder；
2.3) by step 2.2) gained black powder is added to the water, and adds the oil of the content of aqueous solution total mass ratio 3%~5%
Sour sodium, dissolving, mechanical agitation under nitrogen protection is continued after 10~60min of ultrasound, 30 under 800~1000r/min of rotating speed~
90min, adds acetone precipitation, centrifugation, is spontaneously dried after then washing three times by acetone, ethanol, obtains black oleic acid
Group modified ferroferric oxide nano granules, are then stored in dry environment with standby.
Embodiment 10：
The present embodiment is further optimized on the basis of any of the above-described embodiment, and further is that this hair is better achieved
The bright described preparation with the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability
Method：The step 3) prepare the hybrid cross-linked network of pla-pcl and be specially step 1) obtained by catechol group end-blocking it is poly-
Caprolactone and step 2) obtained by the modified ferroferric oxide nano granules of oleic acid moieties according to mass ratio 20:1~20:6 match somebody with somebody
Than being dissolved in chloroform, in after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE) grinding tool, solvent flashing film forming.
Embodiment 11：
The present embodiment is further optimized on the basis of any of the above-described embodiment, first by MnIt is the end hydroxyl of 2800g/mol
Base polycaprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, adds with terminal hydroxy group
Polycaprolactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate adds di lauric dibutyl in reaction
Tin makees catalyst, in reacting 2.0h at 80 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first molten
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 12h is reacted at 40 DEG C, it is molten finally by methyl alcohol
Liquid precipitate, dries, and obtains the polycaprolactone of catechol end-blocking.The polycaprolactone and oil acidification four modified oxygen that catechol is blocked
Change three iron nano-particles according to mass ratio 20:1 proportioning is dissolved in chloroform, by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE)
In grinding tool, solvent flashing film forming.The gel content of products therefrom is 83.19%, and one-way shape memory fixed rate is 99.74%,
One-way shape memory response rate is 95.07%, and bidirectional shape memory response rate is 93.87%.
Embodiment 12：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 2800g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate is made in reaction, adding dibutyl tin laurate
Catalyst, in reacting 2.0h at 80 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first dissolved in
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 12h is reacted at 40 DEG C, finally by methanol solution
Precipitation, dries, and obtains the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked and oil acidification four modified oxidations
Three iron nano-particles are according to mass ratio 20:3 proportioning is dissolved in chloroform, is ground by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE)
In tool, solvent flashing film forming.The gel content of products therefrom is 87.66%, and one-way shape memory fixed rate is 98.57%, single
It is 97.99% to shape memory response rate, bidirectional shape memory response rate is 97.69%.
Embodiment 13：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 2800g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate is made in reaction, adding dibutyl tin laurate
Catalyst, in reacting 2.0h at 80 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first dissolved in
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 12h is reacted at 40 DEG C, finally by methanol solution
Precipitation, dries, and obtains the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked and oil acidification four modified oxidations
Three iron nano-particles are according to mass ratio 20:6 proportioning is dissolved in chloroform, is ground by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE)
In tool, solvent flashing film forming.The gel content of products therefrom is 92.80%, and one-way shape memory fixed rate is 99.29%, single
It is 95.97% to shape memory response rate, bidirectional shape memory response rate is 89.94%.
Embodiment 14：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 4900g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate is made in reaction, adding dibutyl tin laurate
Catalyst, in reacting 3.5h at 70 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first dissolved in
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 10h is reacted at 45 DEG C, finally by methanol solution
Precipitation, dries, and obtains the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked and oil acidification four modified oxidations
Three iron nano-particles are according to mass ratio 20:1 proportioning is dissolved in chloroform, is ground by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE)
In tool, solvent flashing film forming.The gel content of products therefrom is 80.73%, and one-way shape memory fixed rate is 99.71%, single
It is 93.29% to shape memory response rate, bidirectional shape memory response rate is 91.76%.
Embodiment 15：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 4900g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate is made in reaction, adding dibutyl tin laurate
Catalyst, in reacting 3.5h at 70 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first dissolved in
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 8h is reacted at 50 DEG C, it is heavy finally by methanol solution
Form sediment, dry, obtain the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked and oil acidification four modified oxidations three
Iron nano-particle is according to mass ratio 20:3 proportioning is dissolved in chloroform, by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE) grinding tool
In, solvent flashing film forming.The gel content of products therefrom is 85.10%, and one-way shape memory fixed rate is 99.47%, unidirectionally
Shape memory response rate is 96.83%, and bidirectional shape memory response rate is 92.80%.
Embodiment 16：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 4900g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate is made in reaction, adding dibutyl tin laurate
Catalyst, in reacting 3.5h at 70 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first dissolved in
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 10h is reacted at 45 DEG C, finally by methanol solution
Precipitation, dries, and obtains the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked and oil acidification four modified oxidations
Three iron nano-particles are according to mass ratio 20:6 proportioning is dissolved in chloroform, is ground by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE)
In tool, solvent flashing film forming.The gel content of products therefrom is 88.05%, and one-way shape memory fixed rate is 99.15%, single
It is 96.50% to shape memory response rate, bidirectional shape memory response rate is 89.71%.
Embodiment 17：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 6100g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate is made in reaction, adding dibutyl tin laurate
Catalyst, in reacting 5.0h at 60 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first dissolved in
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 12h is reacted at 40 DEG C, finally by methanol solution
Precipitation, dries, and obtains the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked and oil acidification four modified oxidations
Three iron nano-particles are according to mass ratio 20:1 proportioning is dissolved in chloroform, is ground by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE)
In tool, solvent flashing film forming.The gel content of products therefrom is 77.18%, and one-way shape memory fixed rate is 99.67%, single
It is 94.92% to shape memory response rate, bidirectional shape memory response rate is 92.21%.
Embodiment 18：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 6100g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate is made in reaction, adding dibutyl tin laurate
Catalyst, in reacting 5.0h at 60 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first dissolved in
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 8h is reacted at 50 DEG C, it is heavy finally by methanol solution
Form sediment, dry, obtain the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked and oil acidification four modified oxidations three
Iron nano-particle is according to mass ratio 20:3 proportioning is dissolved in chloroform, by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE) grinding tool
In, solvent flashing film forming.The gel content of products therefrom is 88.42%, and one-way shape memory fixed rate is 99.35%, unidirectionally
Shape memory response rate is 95.84%, and bidirectional shape memory response rate is 93.52%.
Embodiment 19：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 6100g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.2 coupling agent hexamethylene diisocyanate is made in reaction, adding dibutyl tin laurate
Catalyst, in reacting 5.0h at 60 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.5 dopamine hydrochloride is first dissolved in
In DMF, the triethylamine activation of purifying is added, be then added in reaction, 8h is reacted at 50 DEG C, it is heavy finally by methanol solution
Form sediment, dry, obtain the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked and oil acidification four modified oxidations three
Iron nano-particle is according to mass ratio 20:6 proportioning is dissolved in chloroform, by after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE) grinding tool
In, solvent flashing film forming.The gel content of products therefrom is 89.79%, and one-way shape memory fixed rate is 99.01%, unidirectionally
Shape memory response rate is 96.43%, and bidirectional shape memory response rate is 92.19%.
Embodiment 20：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 2800g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.4 coupling agent toluene di-isocyanate(TDI) is catalyzed in reaction, adding dibutyl tin laurate
Agent, in reacting 3.5h at 70 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.8 dopamine hydrochloride is first dissolved in DMF,
The triethylamine activation of purifying is added, is then added in reaction, 10h is reacted at 40 DEG C, precipitated finally by methanol solution, done
It is dry, obtain the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked is received with oil acidification modified ferroso-ferric oxide
Rice grain is according to mass ratio 20:1 proportioning is dissolved in chloroform, in after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE) grinding tool, is waved
Hair solvent film forming.The gel content of products therefrom is 78.26%, and one-way shape memory fixed rate is 98.63%, unidirectional shape note
It is 98.02% to recall response rate, and bidirectional shape memory response rate is 86.43%.
Embodiment 21：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 4900g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.4 coupling agent toluene di-isocyanate(TDI) is catalyzed in reaction, adding dibutyl tin laurate
Agent, in reacting 3.5h at 70 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.8 dopamine hydrochloride is first dissolved in DMF,
The triethylamine activation of purifying is added, is then added in reaction, 10h is reacted at 40 DEG C, precipitated finally by methanol solution, done
It is dry, obtain the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked is received with oil acidification modified ferroso-ferric oxide
Rice grain is according to mass ratio 20:3 proportioning is dissolved in chloroform, in after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE) grinding tool, is waved
Hair solvent film forming.The gel content of products therefrom is 83.62%, and one-way shape memory fixed rate is 99.33%, unidirectional shape note
It is 98.45% to recall response rate, and bidirectional shape memory response rate is 89.78%.
Embodiment 22：
The present embodiment is further optimized on the basis of embodiment 1-10, first by MnFor the terminal hydroxy group of 6100g/mol gathers
Caprolactone vacuumizes 2~3h of water removal at 100 DEG C, adds the DMF of purifying to dissolve under nitrogen protection, and addition gathers oneself with terminal hydroxy group
Lactone molal quantity is calculated as 1：2.4 coupling agent toluene di-isocyanate(TDI) is catalyzed in reaction, adding dibutyl tin laurate
Agent, in reacting 3.5h at 70 DEG C；Take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.8 dopamine hydrochloride is first dissolved in DMF,
The triethylamine activation of purifying is added, is then added in reaction, 10h is reacted at 40 DEG C, precipitated finally by methanol solution, done
It is dry, obtain the polycaprolactone of catechol end-blocking.The polycaprolactone that catechol is blocked is received with oil acidification modified ferroso-ferric oxide
Rice grain is according to mass ratio 20:6 proportioning is dissolved in chloroform, in after ultrasonic disperse, being poured into polytetrafluoroethylene (PTFE) grinding tool, is waved
Hair solvent film forming.The gel content of products therefrom is 88.74%, and one-way shape memory fixed rate is 98.67%, unidirectional shape note
It is 98.38% to recall response rate, and bidirectional shape memory response rate is 87.94%.
The above, is only presently preferred embodiments of the present invention, not does any formal limitation to the present invention, it is every according to
Any simple modification, the equivalent variations made to above example according to technical spirit of the invention, each fall within protection of the invention
Within the scope of.
Claims (10)
1. there is the hybrid cross-linked network of heat/polycaprolactone of magnetic response bidirectional shape memory function and self-healing capability, its feature
It is：The structure of the polymer moieties of the hybrid cross-linked network of polycaprolactone is
PCL represents pla-pcl segment in formula, and number-average molecular weight is 2000~10000g/mol, and R represents the isocyanic acid of coupling agent two
Hydrocarbyl portion in ester.
2. the polycaprolactone with heat/magnetic response bidirectional shape memory function and self-healing capability according to claim 1
Hybrid cross-linked network, it is characterised in that：The structure of the hybrid cross-linked network of pla-pcl is
In formulaThe polymer moieties of the hybrid cross-linked network of polycaprolactone are represented,Represent the friendship of polycaprolactone hydridization
Magnetic ferroferric oxide nanometer particle part in networking network.
3. the polycaprolactone with heat/magnetic response bidirectional shape memory function and self-healing capability according to claim 2
Hybrid cross-linked network, it is characterised in that：The ferroferric oxide nano granules content of the hybrid cross-linked network of pla-pcl be 5~
30wt%, gel content is 70~100%.
4. poly- with heat/magnetic response bidirectional shape memory function and self-healing capability according to claim 1 or 2 or 3
The hybrid cross-linked network of caprolactone, it is characterised in that：Hydrocarbyl portion is the isocyanide of diphenyl-methane two in the coupling agent diisocyanate
Acid esters, XDI, toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate or hexa-methylene two are different
Any one of hydrocarbyl portion in cyanate.
5. as claimed in claim 1 or 2 or 3 or 4 poly- with heat/magnetic response bidirectional shape memory function and self-healing capability
The preparation method of the hybrid cross-linked network of caprolactone, the polycaprolactone and ferroferric oxide nano granules blocked using catechol group
It is coordination cross-linked, it is characterised in that the preparation method includes step in detail below：
1) polycaprolactone of catechol group end-blocking is prepared；
2) the modified ferroferric oxide nano granules of oleic acid moieties are prepared；
3) the hybrid cross-linked network of pla-pcl is prepared.
6. the polycaprolactone with heat/magnetic response bidirectional shape memory function and self-healing capability according to claim 5
The preparation method of hybrid cross-linked network, it is characterised in that：The step 1) including step in detail below：
1.1) by terminal hydroxy group polycaprolactone vaccum dewatering, stirring is then heated up under inert gas shielding to after melting, is added pure
The DMF dissolvings of change；
1.2) add and be calculated as 1 with terminal hydroxy group polycaprolactone molal quantity：2.0~3.0 coupling agent diisocyanate in reaction, plus
Enter catalyst, in 2~5h of reaction at 60~80 DEG C；
1.3) take terminal hydroxy group polycaprolactone molal quantity and be calculated as 1:2.0~3.0 dopamine hydrochloride is first dissolved in DMF, is added and is lived
Agent is activated, and is then added in reaction, and 8~12h is reacted at 40~50 DEG C, and precipitation is dried, and obtains catechol group end-blocking
Polycaprolactone.
7. the polycaprolactone hydridization with heat/magnetic response bidirectional shape memory function and self-healing capability described in claim 6
The preparation method of cross-linked network, it is characterised in that：Described terminal hydroxy group polycaprolactone MnIt is 2000~10000g/mol, structural formula
For：
Wherein, 7<n<43.
8. the polycaprolactone with heat/magnetic response bidirectional shape memory function and self-healing capability according to claim 6
The preparation method of hybrid cross-linked network, it is characterised in that：The coupling agent diisocyanate is '-diphenylmethane diisocyanate, benzene
Dimethylene diisocyanate, toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate or hexamethylene diisocyanate
In any one.
9. the polycaprolactone with heat/magnetic response bidirectional shape memory function and self-healing capability according to claim 5
The preparation method of hybrid cross-linked network, it is characterised in that：The step 2) including step in detail below：
2.1) by FeCl24H2O and FeCl36H2O with mol ratio 1:2 is soluble in water, and addition solution total mass ratio 3%~
Then the enuatrol of 5% content, stirring and dissolving under inert gas shielding adds ammoniacal liquor in the case where rotating speed is more than or equal to 800r/min
(25~28%w/w), keeps 30~90min；
2.2) by step 2.1) reaction solution precipitated, separated after, washing, dry, obtain black powder；
2.3) by step 2.2) gained black powder is added to the water, and adds the oleic acid of the content of aqueous solution total mass ratio 3%~5%
Sodium, dissolving continues to be stirred under inert gas shielding after 10~60min of dispersion, and rotating speed is stirred under being more than or equal to 800r/min
30~90min is mixed, after reaction solution is precipitated, separate, washing, is dried, obtain four modified oxidations three of black oleic acid moieties
Iron nano-particle.
10. according to claim any one of 5-9 with heat/magnetic response bidirectional shape memory function and self-healing capability
The preparation method of the hybrid cross-linked network of polycaprolactone, it is characterised in that：The step 3) prepare the hybrid cross-linked network of pla-pcl
Specially by step 1) obtained by catechol group end-blocking polycaprolactone and step 2) obtained by modified four oxygen of oleic acid moieties
Change three iron nano-particles according to mass ratio 20:1~20:6 proportioning is dissolved in organic solvent, by after dispersion, being poured into grinding tool
In, solvent flashing film forming.
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| WO2022039676A1 (en) * | 2020-08-21 | 2022-02-24 | Nanyang Technological University | Induction heating-cured adhesives |
| US11643574B2 (en) | 2021-05-28 | 2023-05-09 | Cohesys Inc. | Adhesive devices and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107275121A (en) * | 2017-07-12 | 2017-10-20 | 广东工业大学 | A kind of ultracapacitor with self-healing and preparation method thereof |
| CN108341940A (en) * | 2018-02-12 | 2018-07-31 | 贵州大学 | A kind of preparation method of the efficiently long chain branching polylactic without gel |
| CN108341940B (en) * | 2018-02-12 | 2020-05-12 | 贵州大学 | Preparation method of efficient gel-free long-chain branched polylactic acid |
| WO2022039676A1 (en) * | 2020-08-21 | 2022-02-24 | Nanyang Technological University | Induction heating-cured adhesives |
| US11643574B2 (en) | 2021-05-28 | 2023-05-09 | Cohesys Inc. | Adhesive devices and uses thereof |
| CN113831706A (en) * | 2021-08-19 | 2021-12-24 | 常州大学 | High-toughness polycaprolactone remodelable shape memory material and preparation method thereof |
| CN113831706B (en) * | 2021-08-19 | 2022-05-31 | 常州大学 | High-toughness polycaprolactone remodelable shape memory material and preparation method thereof |
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