CN108079916A - Nanometer-sized microcapsules, polymer matrix self-healing composite material and preparation method - Google Patents
Nanometer-sized microcapsules, polymer matrix self-healing composite material and preparation method Download PDFInfo
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- CN108079916A CN108079916A CN201711405493.7A CN201711405493A CN108079916A CN 108079916 A CN108079916 A CN 108079916A CN 201711405493 A CN201711405493 A CN 201711405493A CN 108079916 A CN108079916 A CN 108079916A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/188—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using encapsulated compounds
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Abstract
The invention discloses nanometer-sized microcapsules, polymer matrix self-healing composite material and preparation methods, belong to functional material preparation and composite material high performance technology field.Microcapsules are prepared as：Styrene, oleic acid and deionized water are mixed, add in potassium persulfate, heats up and polystyrene spheres is made；It is mixed with deionized water, adds in the homogeneous mixture solotion of phenol, hexamethylenetetramine and deionized water, heated up and phenolic resin package polystyrene spheres are made；Toluene is added in, silane coupling agent is added in after lower stirring, is heated up, the hollow phenolic resin ball that surface is modified is made in stirring；Toluene is added in, stirring removes extra toluene solution, mixed with dicyclopentadiene, heats up, stirring, and the self-healing capsule of phenolic resin package renovation agent dicyclopentadiene is made.The method of the present invention controls capsule shape characteristic, capsule size, wall thickness etc. well, and the self-healing microcapsules are added in epoxy resin-base, not only has toughening effect to material, also achieves self-healing function.
Description
Technical field
The invention belongs to functional material preparation and composite material high performance technology fields, and in particular to a kind of polymer matrix
The preparation method of self-healing composite material nanometer-sized microcapsules.
Background technology
Polymer composites are more and more wider in the utilization of aerospace field, but in use and its surrounding environment
Under the influence of, the internal appearance for inevitably having micro-crack.The appearance and propagation of micro-crack make material structure degenerate, under performance
Drop, influences its service life.However, the crackle of polymer is usually all hidden in its deeper inside, and because technical office
It is sex-limited, on many matrixes as so crack split etc. it is tiny it is impaired usually be not easy to be noticeable, there are larger security risks.For this
A problem is inspired by organism self-healing function, it is proposed that self-healing material concept.Self-healing material is as a kind of new intelligence
Energy material can imitate life system, and the dual property with self diagnosis and self-healing.When material generates damage, self-healing
Material can make certain in the case of no external help and respond and complete self healing.
Method according to matter and energy supply is different, polymer matrix self-healing material be developing progressively in-situ type healing and
Filling type two kinds of systems of healing.The i.e. intrinsic formula healing of in-situ type healing, refers under conditions of any extraneous reparation medium is not added,
Material can be issued in external influence is born from main healing, i.e., the molecular structure for the reversible chemical reaction having by composite material itself
The forms such as design or the diffusion of macromolecular.But this system has stringent basal body structure requirement, and self-healing function is only special
It tells on matrix, and usually needs to apply outside energy and stimulation, other conventional composites can not be by this method
Realize self-healing function, this system is not presently available extensive use.Filling type healing is the healing of foreign aid's type, refers to and is polymerizeing
Additional renovation agent is filled in object matrix, make material that can independently be discharged after being damaged and diffuses to entire crackle, finally according to certain
Kind mechanism makes the self-regeneration of crackle bonding realization material.Since this method requires not for the chemical constitution of matrix in itself
Height, although adding additional renovation agent compared with in-situ type healing system, it has still obtained extensively should in general polymer material
With with better universality.It is micro- that the main research at present of filling type healing system concentrates on liquid core fibre, microcapsules, three-dimensional
The healing form such as blood vessel, carbon nanotubes.
Microcapsule-type polymer matrix self-healing material has for other polymers base self-healing material：Healing effect
The advantages that rate is high, and structural requirement is low, and preparation method is simple.Industrial metaplasia is more being expected to just because of microcapsule-type self-healing material
It is with the obvious advantage in terms of production, therefore it becomes the hot spot of current application study.But current existing self-healing microcapsules preparation side
Fado is in-situ polymerization, interfacial polymerization, and capsule size is larger (grain size is much in 1 μm, is 1~500 μm), shows poor
Capsule pattern and wall thickness control, and influence self-healing efficiency.
The content of the invention
The present invention provides a kind of new polymer matrix self-healing composite material with receiving for microcapsule-type self-healing material
The preparation method of meter level microcapsules, this method first prepare microcapsule shell, then reversely filling renovation agent, reach control capsule very well
The features such as shape characteristic, capsule size, wall thickness, reaches with self-healing function purpose.
Technical scheme：
A kind of preparation method of polymer matrix self-healing composite material nanometer-sized microcapsules, step are as follows：
(1) polystyrene (PS) microballoon is prepared
Styrene, oleic acid and deionized water are mixed, stir 1h, potassium persulfate (KPS) is added in, is warming up to 70 DEG C, stirs
Mix reaction 5h.After reaction, it is cooled to room temperature, centrifuge washing, polystyrene (PS) ball is made.
(2) phenolic resin embedding polystyrene (PS@PF) ball is prepared
Polystyrene spheres solution is taken to be mixed with deionized water, ultrasonic disperse 10min.Add in phenol, hexamethylenetetramine with
The homogeneous mixture solotion of deionized water after ultrasonic disperse 10min, solution is poured into reaction kettle and is warming up to 160 DEG C, reacts 4h.
After reaction, phenolic resin package polystyrene spheres are made in centrifuge washing.
(3) preparation of hollow phenolic resin (PF) ball and surface are modified
Above-mentioned obtained solution is added in into toluene, is stirred at 50 DEG C, silane coupling agent (KH-550) is added in after 6h, is warming up to
90 DEG C, stir 15-20h.After reaction, the hollow phenolic resin ball that surface is modified is made in centrifuge washing.
(4) preparation of phenolic resin embedding dicyclopentadiene (DCPD@PF)
Above-mentioned solution is centrifuged, addition toluene, after ultrasonic disperse 10min, stir 0.5h.It is more that removal is centrifuged again
Remaining toluene solution, and mixed with dicyclopentadiene, 40 DEG C are warming up to, stirs 15-20h.After reaction, centrifuge washing again,
The self-healing capsule of package renovation agent dicyclopentadiene is made.
The present invention provides self-healing microcapsules made from a kind of above-mentioned preparation method.
Further, in the above-mentioned technical solutions, capsule wall is phenolic resin, and capsule renovation agent is bicyclic penta 2
Alkene.
Further, in the above-mentioned technical solutions, self-healing microcapsules be spheric granules, a diameter of 300nm~800nm.
The present invention provides a kind of self-healing microcapsule composite material, includes above-mentioned self-healing microcapsules.
The present invention provides the preparation method of above-mentioned self-repairing microcapsule composite material, comprises the following steps：
Take catalyst and ethanol solution 1:3 mixing, by mixed solution and self-healing microcapsules according to claim 6
It is added to by 5~10wt% in the mixed solution of resin and acetone, after ultrasonic disperse, vacuumizes 90 DEG C of heating 5min, removal is molten
Ethyl alcohol and acetone in liquid.Then resin and 593 curing agent weight ratios 4 are pressed:1 adds in 593 curing agent, is poured into mold, 30 DEG C
Reaction for 24 hours, obtains the epoxy resin composite material with self-healing function.
Further, in the above-mentioned technical solutions, the resin is epoxy resin E51 or phenolic resin.
Further, in the above-mentioned technical solutions, the catalyst is Ge Labu catalyst Grubbs or tungsten hexachloride
WCl6。
The present invention works as template with polystyrene spheres, first prepares the phenolic resin microcapsules outer wall of certain size requirement, then
Reversely filling renovation agent, realizes the efficient preparation of self-healing microcapsules, substantially increases the control to microcapsules pattern and size
System, and nanometer-sized microcapsules can be prepared, compactness, covering property are good.Capsule is added in the self-healing prepared after basis material to answer
Condensation material triggers capsules break after impaired, discharges renovation agent, achievees the purpose that repair crack, has corresponding self-healing effect
Fruit.
Description of the drawings
Fig. 1 is that the phenolic resin of embodiment 1 embeds the microscopic appearance scanning electron microscope (SEM) photograph (SEM) of polystyrene spheres (PS@PF).
Fig. 2 is the microscopic appearance transmission electron microscope picture (TEM) of the hollow phenolic resin ball (PF) of embodiment 1.
Fig. 3 (a) is that the nanometer self-healing microcapsules of embodiment 1 impregnate infrared spectrogram (FTIR) after toluene.
Fig. 3 (b) is that the nanometer self-healing microcapsules of embodiment 1 impregnate infrared spectrogram (FTIR) after acetone.
Specific embodiment
Below in conjunction with attached drawing and technical solution, the specific embodiment further illustrated the present invention.
Self-healing composite material and the fracture toughness of original material and self-healing efficiency such as following table are obtained by case study on implementation：
Embodiment 1
(1) preparation of polystyrene (PS) ball
3mL styrene, 0.1g oleic acid and 140mL deionized waters are added in there-necked flask, are placed on constant temperature blender with magnetic force
Upper 800r/min stirs 1h.Then 0.2g potassium persulfates (KPS) are added in, there-necked flask transposition heat collecting type heated at constant temperature magnetic force is stirred
It mixes and 70 DEG C is warming up in device, nitrogen protection is stirred to react 5h.After reaction, it is cooled to room temperature, is centrifuged in desk centrifuge
Washing four times, wherein second is washed with ethyl alcohol, remaining is washed with deionized three times, and polystyrene (PS) ball is made, presses
60mg/mL is scattered in aqueous solution.
(2) preparation of phenolic resin embedding polystyrene (PS@PF) ball
1.5mL polystyrene spheres solution is taken to mix with 60mL deionized waters to add in beaker, is positioned over ultrasonic cleaner
Middle ultrasonic disperse 10min.Then 0.282g phenol is added in, 0.21g hexamethylenetetramines are mixed with the uniform of 20mL deionized waters
Solution after ultrasonic disperse 10min, solution is poured into the reaction kettle that capacity is 120mL.It repeats the above steps, by two reactions
Kettle, which is positioned in electric drying oven with forced convection, is warming up to 160 DEG C, reacts 4h.After reaction, with deionized water centrifuge washing 3 times,
It is washed 1 time with ethyl alcohol again, phenolic resin package polystyrene spheres is made, is scattered in ethanol solution and stores.
Fig. 1 is shown in prepared phenolic resin package polystyrene spheres (PS@PF) surface topography and thermogravimetric analysis.Statistics indicate that institute
It is uniform to obtain Product size, the smooth densification in surface, good dispersion, thick spherical shell is about 50nm, and thermal stable temperature is 250 DEG C, and phenolic aldehyde
Resin successfully wraps up polystyrene spheres.
(3) preparation of hollow phenolic resin (PF) ball and surface are modified
Above-mentioned obtained solution is poured into there-necked flask addition 100mL toluene, be positioned in magnetic stirring apparatus 50 DEG C,
It is stirred under 800r/min, 3mL silane coupling agents (KH-550) is added in after 6h, be warming up to 90 DEG C, stir 15-20h.Reaction terminates
Afterwards, centrifuge washing four times, wherein being washed with deionized for the second time, remaining is washed three times with ethyl alcohol, and the sky that surface is modified is made
Heart phenolic resin ball, is scattered in ethyl alcohol and stores.
The hollow phenolic resin microspheres that prepared surface is modified are shown in Fig. 2.
(4) preparation of phenolic resin embedding dicyclopentadiene (DCPD@PF)
The hollow phenolic resin ball solution being modified to above-mentioned scattered surface in ethanol centrifuges, and adds in 6mL first
Benzene, in beaker after ultrasonic disperse 10min, the 800r/min stirrings 0.5h under magnetic agitation effect.It centrifuges again afterwards
It is mixed except extra toluene solution, and with 20g dicyclopentadienes in there-necked flask, is warming up to 40 DEG C, stir 15-20h.Reaction terminates
Afterwards, centrifuge again, and, the self-healing capsule of package renovation agent dicyclopentadiene is made with ethyl alcohol centrifuge washing once.
Fig. 3 is the infrared analysis figure that obtained microcapsules impregnate toluene, acetone respectively, statistics indicate that microcapsules successfully wrap up
Renovation agent dicyclopentadiene and capsule compactness, covering property are good.
(5) preparation of self-healing epoxy resin composite material
Take WCl6 and ethanol solution 1:3 mixing, mixed solution and the self-healing capsule of above-mentioned preparation are added to by 5wt%
In the mixed solution of epoxy resin E51 and acetone, after ultrasonic disperse 5min, 90 DEG C of heating are vacuumized with circulating water type vacuum pump
5min removes ethyl alcohol and acetone in solution.Then by resin and curing agent than 4:1 adds in curing agent 593, is poured into mold,
30 DEG C of reactions for 24 hours, obtain the epoxy resin composite material with self-healing function.
According to ASTM D5045 standards, to the self-healing composite material Three Points Bending Specimen of pure resin and addition microcapsules into
Row fracture toughness research, the results showed that, self-healing microcapsules prepared by the 5wt% present invention are added in resin matrix, material breaks
It splits toughness to be significantly improved, and self-healing efficiency reaches 38.1%, effectively reaches to crackle self-healing requirement.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited；Although with reference to foregoing reality
Example is applied the present invention is described in detail, it for those of ordinary skill in the art, still can be to foregoing implementation
Technical solution recorded in example modifies or carries out equivalent substitution to which part technical characteristic；And these are changed or replace
It changes, the essence of appropriate technical solution is not made to depart from the spirit and scope of claimed technical solution of the invention.
Claims (8)
1. a kind of preparation method of polymer matrix self-healing composite material nanometer-sized microcapsules, step are as follows：
(1) styrene, oleic acid and deionized water are mixed, adds in potassium persulfate, be warming up to 70 DEG C, be stirred to react, be made poly-
Styrene ball；
(2) polystyrene spheres solution is taken to be mixed with deionized water, adds in the uniformly mixed of phenol, hexamethylenetetramine and deionized water
Solution is closed, is warming up to 160 DEG C, reacts and phenolic resin package polystyrene spheres is made；
(3) above-mentioned obtained phenolic resin package polystyrene spheres are added in into toluene, silane coupling agent are added in after stirring 6h at 50 DEG C,
90 DEG C are warming up to, stirs 15-20h, the hollow phenolic resin ball that surface is modified is made；
(4) the hollow phenolic resin ball being modified above-mentioned surface adds in toluene, stirs 0.5h, removes extra toluene solution, and double
Cyclopentadiene mixes, and is warming up to 40 DEG C, stirs 15-20h, and the self-healing rubber alloy of phenolic resin package renovation agent dicyclopentadiene is made
Capsule.
2. self-healing microcapsules made from preparation method as described in claim 1.
3. self-healing microcapsules according to claim 2, which is characterized in that capsule wall is phenolic resin, and capsule is repaiied
Multiple agent is dicyclopentadiene.
4. self-healing microcapsules according to claim 2, which is characterized in that self-healing microcapsules be spheric granules, diameter
For 300nm~800nm.
5. a kind of self-healing microcapsule composite material, which is characterized in that include the self-healing microcapsules described in claim 2.
6. the preparation method of self-repairing microcapsule composite material as claimed in claim 5, which is characterized in that including following step
Suddenly：
Take catalyst and ethanol solution 1:Mixed solution and self-healing microcapsules according to claim 2 are pressed 5 by 3 mixing
~10wt% is added in the mixed solution of resin and acetone, after ultrasonic disperse, is vacuumized 90 DEG C of heating 5min, is removed in solution
Ethyl alcohol and acetone.Then by resin and curing agent than 4:1 adds in 593 curing agent, is poured into mold, and 30 DEG C of reactions for 24 hours, obtain
Epoxy resin composite material with self-healing function.
7. the preparation method of self-healing microcapsule composite material according to claim 6, which is characterized in that the resin
For epoxy resin or phenolic resin.
8. the preparation method of self-healing microcapsule composite material according to claim 5, which is characterized in that the catalyst
For Ge Labu catalyst Grubbs or tungsten hexachloride WCl6。
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| CN101269311A (en) * | 2008-04-25 | 2008-09-24 | 哈尔滨工业大学 | Polymer group composite material self-repairing nano-scale capsule and preparation method thereof |
| CN102492174A (en) * | 2011-11-30 | 2012-06-13 | 哈尔滨工业大学 | Urea resin wrapped dicyclopentadiene nanometer microcapsule, and synthetic method and application thereof |
| US20120207921A1 (en) * | 2011-02-14 | 2012-08-16 | Space Administration | Elongated Microcapsules and their Formation |
| KR20130051127A (en) * | 2011-11-09 | 2013-05-20 | 엘지이노텍 주식회사 | Self-healing material comprising microcapsule, method for self-healing using the same |
| CN105174770A (en) * | 2014-05-29 | 2015-12-23 | 纳米及先进材料研发院有限公司 | Self-healing material and preparation process thereof |
| CN107224945A (en) * | 2017-06-26 | 2017-10-03 | 西北工业大学 | It is a kind of using phenolic resin be wall material solids as emulsifying agent dicyclopentadiene microcapsule and preparation method |
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2017
- 2017-12-22 CN CN201711405493.7A patent/CN108079916B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215407A (en) * | 2008-01-18 | 2008-07-09 | 中山大学 | High temperature self-restoring fibre enhancement epoxy composite material and preparation method thereof |
| CN101269311A (en) * | 2008-04-25 | 2008-09-24 | 哈尔滨工业大学 | Polymer group composite material self-repairing nano-scale capsule and preparation method thereof |
| US20120207921A1 (en) * | 2011-02-14 | 2012-08-16 | Space Administration | Elongated Microcapsules and their Formation |
| KR20130051127A (en) * | 2011-11-09 | 2013-05-20 | 엘지이노텍 주식회사 | Self-healing material comprising microcapsule, method for self-healing using the same |
| CN102492174A (en) * | 2011-11-30 | 2012-06-13 | 哈尔滨工业大学 | Urea resin wrapped dicyclopentadiene nanometer microcapsule, and synthetic method and application thereof |
| CN105174770A (en) * | 2014-05-29 | 2015-12-23 | 纳米及先进材料研发院有限公司 | Self-healing material and preparation process thereof |
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