CN108677381A - Left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane of a kind of Quadrupolar hydrogen bond crosslinking and preparation method thereof - Google Patents
Left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane of a kind of Quadrupolar hydrogen bond crosslinking and preparation method thereof Download PDFInfo
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- CN108677381A CN108677381A CN201810406786.5A CN201810406786A CN108677381A CN 108677381 A CN108677381 A CN 108677381A CN 201810406786 A CN201810406786 A CN 201810406786A CN 108677381 A CN108677381 A CN 108677381A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
Abstract
The present invention provides left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane of a kind of Quadrupolar hydrogen bond crosslinking and preparation method thereof, and preparation method is：Levorotatory lactide, stannous octoate and tetraethylene glycol are added in reaction bulb, under vacuum conditions after heating reaction, obtain D-lactic acid soft material；After polytetramethylene glycol is added to dextrorotation lactide, stannous octoate is added, under vacuum conditions after heating reaction, obtains L-lactic acid soft material；After the two is added to chloroform dissolving, Quadrupolar hydrogen bond crosslinking agent is added, under vacuum conditions heating copolymerization, obtains Quadrupolar hydrogen bond and be crosslinked left-handed dextrorotation polylactic acid intelligent soft material；It is finally dissolved in and is evenly stirred until and is completely dissolved in the tetrahydrofuran solvent containing chloroform, obtain spinning solution, Quadrupolar hydrogen bond, which is prepared, through electrostatic spinning is crosslinked left-handed L-lactic acid intelligent soft material nano fibrous membrane.Intelligent soft material nano fibrous membrane prepared by the present invention has stretchable, tear-proof and self-regeneration and good biocompatibility.
Description
Technical field
The invention belongs to textile material technical fields, and in particular to a kind of left-handed dextrorotation polylactic acid intelligence of Quadrupolar hydrogen bond crosslinking
Soft material nano fibrous membrane and preparation method thereof.
Background technology
Intelligent soft material is a kind of new function material that can perceive outside stimulus, have can bear large deformation, have it is good
The features such as good bioaffinity, compatibility, cheap lightweight.Selfreparing intelligent soft material can be to polymer material in use
The micro-crack generated by the factors such as machinery, chemistry, light and heat carries out spontaneous reparation, which can be no external world
Conditional stimulus is either completed under environmental stimuli, and safety, service life and the low maintenance cost of intelligent soft material are improved.
Currently, selfreparing composition polymer is divided into thermoplastic material and thermosets, thermal plastic high polymer according to structure
Internal structure is in chain, and selfreparing, thermosetting are carried out by modes such as thermal diffusion, sovent diffusion, photoinduction, chain recombination and reversible keys
Property macromolecule inside in netted, there is good high temperature resistant solvent resistance, it usually needs by by the means such as consolidant reality
Existing selfreparing.Printed fabric disclosed in Chinese patent CN 205890013U, the printed fabric include base, the upper bed of material and ink
Dope layer, super lubricious containing SLIPS selfreparings on the printing ink paint layer, the SLIPS selfreparings are super lubricious to be
It is made using nano ventilated material, lubricant is contained in nano-micro structure, therefore form hydrophobic surface, and by SLIPS selfreparings
It is super it is lubricious be more bonded with ink coating, improve the colorfulness of printing ink paint layer, stereovision and securely.Chinese patent
A kind of capsule of nano material and preparation method thereof with self-regeneration and wear-resisting functions disclosed in CN 104131469B, packet
It includes fabric matrix made of fiber and is coated on that fiber is outer, thickness is nano level wall material, therefore is formed using fiber as core, wall material
For the capsule of nano structure of capsule sheath, which is that modification of chitosan crosslinks obtained by the reaction gather with trithiocarbonate
The mixture of object or the polymer and gelatin is closed, specific preparation method is：Chitosan is dissolved in acetic acid, persulfuric acid is added
Ammonium, N react under the action of N '-methylene-bisacrylamides and acrylic acid, modified chitosan are obtained, then by modified shell
After trithiocarbonate, ether, azodiisobutyronitrile mixing are added in glycan, recycled through multiple freeze thaw-degassing, in nitrogen
Atmosphere encloses lower heating and thermal insulation and handles to obtain cross-linked polymer, then cross-linked polymer is added in the lotion containing gelatin, finally
Two water and calcium chloride reaction are added, obtain microcapsule dressing agent, microcapsule dressing agent is subjected to encapsulated arrangement to fabric matrix,
Satinage is carried out again obtains the textile with self-regeneration and wear-resisting functions.Textile prepared by this method utilizes two
Silica improves the wearability of textile, realizes self-healing properties using the group modified chitosan molecule of selfreparing, extends material
Service life.By the above-mentioned prior art it is found that by adhering to selfreparing intelligent layer in fiber or web surface, weaving is assigned
Product self-healing properties, but at present self-repair material textile is stretchable, studied in terms of tear-proof and self-regeneration not at
It is ripe.
Invention content
The technical problem to be solved in the present invention is to provide a kind of Quadrupolar hydrogen bonds to be crosslinked left-handed dextrorotation polylactic acid intelligent soft material
Polytetramethylene glycol and tetraethylene glycol are added separately to levorotatory lactide and dextrorotation third are handed over by nano fibrous membrane and preparation method thereof
In ester, under the action of stannous octoate catalyst, prepared by heating in vacuum reaction respectively obtains l-lactic acid soft material and dextrorotation
Polylactic acid soft material, then by l-lactic acid soft material and dextrorotation polylactic acid soft material Quadrupolar hydrogen bond crosslinking agent effect
Under, heating in vacuum is obtained by the reaction Quadrupolar hydrogen bond and is crosslinked left-handed dextrorotation polylactic acid intelligent soft material, is finally crosslinked Quadrupolar hydrogen bond left
Rotation dextrorotation polylactic acid intelligent soft material is that intelligent soft material nano fibrous membrane is prepared through electrostatic spinning in raw material, the intelligence softwood
Material nano fibrous membrane maintains original biocompatibility, and has stretchable, the performance of tear-proof and self-regeneration.
In order to solve the above technical problems, the technical scheme is that：
A kind of poly- left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane of Quadrupolar hydrogen bond crosslinking, which is characterized in that described
It is poly- l-lactic acid soft material and poly- dextrorotation that Quadrupolar hydrogen bond crosslinking, which gathers left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane,
The spinning solution that polylactic acid soft material is prepared through Quadrupolar hydrogen bond cross-linking agents is obtained through electrostatic spinning.
As a preferred embodiment of the above technical solution, a kind of Quadrupolar hydrogen bond crosslinking gathers left-handed dextrorotation polylactic acid intelligence softwood
Expect the preparation method of nano fibrous membrane, it is characterised in that：Include the following steps：
(1) levorotatory lactide, stannous octoate and tetraethylene glycol are added in reaction bulb, under vacuum conditions heating reaction
Afterwards, it after chloroform dissolves, is recrystallized with ethyl alcohol, obtains l-lactic acid soft material；
(2) polytetramethylene glycol is added to dextrorotation lactide after mixing, stannous octoate catalyst is added, true
Under Altitude after heating reaction, after chloroform dissolves, is recrystallized with ethyl alcohol, obtain dextrorotation polylactic acid soft material；
(3) dextrorotation polylactic acid soft material prepared by the l-lactic acid soft material and step (2) prepared step (1) is added
To after being dissolved in chloroform, Quadrupolar hydrogen bond crosslinking agent is added, under vacuum conditions heating copolymerization, dissolution filter precipitation is dry, obtains
Quadrupolar hydrogen bond is crosslinked left-handed dextrorotation polylactic acid intelligent soft material；
(4) Quadrupolar hydrogen bond prepared by step (3) left-handed dextrorotation polylactic acid intelligent soft material is crosslinked to be dissolved in containing chloroform
It is evenly stirred until and is completely dissolved in tetrahydrofuran solvent, obtain spinning solution, it is poly- that Quadrupolar hydrogen bond crosslinking is prepared through electrostatic spinning
Left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane.
As a preferred embodiment of the above technical solution, in the step (1), levorotatory lactide, stannous octoate and tetraethylene glycol matter
Amount is than being 70-75:0.1-0.2：1.5-1.7.
As a preferred embodiment of the above technical solution, in the step (1), the vacuum degree for heating reaction is 0.001-0.005Pa,
2-4h first is heated at 100-120 DEG C, then heats to 150-160 DEG C, time 18-20h.
As a preferred embodiment of the above technical solution, in the step (2), polytetramethylene glycol, dextrorotation lactide and octanoic acid
The mass ratio of stannous is 2-3:65-70:0.1-0.2.
As a preferred embodiment of the above technical solution, in the step (2), the vacuum degree for heating reaction is 0.001-0.003Pa,
3-6h first is heated at 110-120 DEG C, then heats to 140-150 DEG C, time 18-20h.
As a preferred embodiment of the above technical solution, in the step (3), l-lactic acid soft material, dextrorotation polylactic acid softwood
The mass ratio of material and Quadrupolar hydrogen bond crosslinking agent is 0.2-0.5:0.9-0.95：0.01-0.05.
As a preferred embodiment of the above technical solution, in the step (3), the vacuum degree for heating copolymerization is 0.001-0.005Pa,
0.5h first is heated at 50-60 DEG C, then heats to 95-100 DEG C, time 2h.
As a preferred embodiment of the above technical solution, in the step (4), in the tetrahydrofuran solvent containing chloroform tetrahydrofuran and
The volume ratio of chloroform is 1-3:0.5-1.
As a preferred embodiment of the above technical solution, in the step (4), the condition of electrostatic spinning is：Voltage is 13-15kV,
The flow of spinning solution is 0.4-0.6mL/h, and it is 15cm to receive distance.
Compared with prior art, the invention has the advantages that：
(1) raw material of nano fibrous membrane prepared by the present invention is polylactic acid intelligent soft material, the polylactic acid intelligent soft material
It is that polytetramethylene glycol and tetraethylene glycol are added separately in levorotatory lactide and dextrorotation lactide, in stannous octoate catalyst
Under the action of, prepared by heating in vacuum reaction respectively obtains l-lactic acid soft material and dextrorotation polylactic acid soft material, the polylactic acid
Contain polytetramethylene glycol and tetraethylene glycol flexible polymer chain in material, in Poly L-lactic acid structural unit and poly- L-lactic acid knot
On the basis of structure unit can form stereoscopic composite by the stronger Van der Waals force of molecule interchain under certain condition, four are being utilized
Deuterium bond crosslinking agent acts on, and further increases the combination between Poly L-lactic acid structural unit and poly- L-lactic acid structural unit
Power is prepared Quadrupolar hydrogen bond and is crosslinked left-handed dextrorotation polylactic acid intelligent soft material.Quadrupolar hydrogen bond crosslinking prepared by the present invention is left-handed
Dextrorotation polylactic acid intelligent soft material on the basis of ensureing biocompatibility, improves poly- compared with conventional poly-lactic acid material
The heat resistance and mechanical performance of lactate material, and it is raw material system that Quadrupolar hydrogen bond, which is crosslinked left-handed dextrorotation polylactic acid intelligent soft material,
The viscosity and uniformity of standby spinning solution further increase, and reduce the difficulty of electrostatic spinning, and be prepared into through electrostatic spinning
There is stretchable, the performance of tear-proof and self-regeneration to intelligent soft material nano fibrous membrane.
(2) the Quadrupolar hydrogen bond crosslinking that prepared by the present invention gathers left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane by electrostatic
Spining technology is combined with intelligent soft material technology, improves the mechanical property of the nano fibrous membrane of electrostatic spinning, improves nanofiber
Film volume is stretchable and tear resistance, and the self-repair material due to containing in nanofiber, assigns reviewing one's lessons by oneself for nano fibrous membrane
Renaturation energy improves nano composite membrane suitable application area range, can meet the requirement of intelligent textile.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
(1) it is 70 according to the mass ratio of levorotatory lactide, stannous octoate and tetraethylene glycol:0.1：1.5, by levorotatory lactide,
Stannous octoate and tetraethylene glycol are added in reaction bulb, under the vacuum environment of 0.001Pa, are first heated 2h at 100 DEG C, are then risen
To 150 DEG C, time 18h is recrystallized after chloroform dissolves with ethyl alcohol temperature, obtains l-lactic acid soft material.
(2) it is 2 according to the mass ratio of polytetramethylene glycol, dextrorotation lactide and stannous octoate:65:0.1, it is sub- by poly- four
Methyl glycol is added to dextrorotation lactide after mixing, and stannous octoate catalyst is added, under the vacuum environment of 0.001Pa,
3h first is heated at 110 DEG C, then heats to 140 DEG C, time 18h is recrystallized after chloroform dissolves with ethyl alcohol, obtains the right side
Revolve polylactic acid soft material.
(3) by weight, 0.2 part of l-lactic acid soft material and 0.9 part of dextrorotation polylactic acid soft material are added
To after being dissolved in 20 parts of chloroforms, 0.01 part of Quadrupolar hydrogen bond crosslinking agent is added, under the vacuum environment of 0.001Pa, first 50
0.5h is heated at DEG C, then heats to 95 DEG C, time 2h, dissolution filter precipitation is dry, obtains Quadrupolar hydrogen bond and is crosslinked the left-handed right side
Revolve polylactic acid intelligent soft material.
(4) Quadrupolar hydrogen bond is crosslinked the volume ratio that left-handed dextrorotation polylactic acid intelligent soft material is dissolved in tetrahydrofuran and chloroform
It is 1:0.5 in the mixed solvent, which is evenly stirred until, to be completely dissolved, and the spinning solution of 8wt% is obtained, and is 13kV, the stream of spinning solution in voltage
Amount is 0.4mL/h, and it is 15cm to receive distance, and the poly- left-handed dextrorotation polylactic acid intelligence of Quadrupolar hydrogen bond crosslinking is prepared through electrostatic spinning
Soft material nano fibrous membrane.
Embodiment 2：
(1) it is 75 according to the mass ratio of levorotatory lactide, stannous octoate and tetraethylene glycol:0.2：1.7, by levorotatory lactide,
Stannous octoate and tetraethylene glycol are added in reaction bulb, under the vacuum environment of 0.005Pa, are first heated 4h at 120 DEG C, are then risen
To 160 DEG C, time 20h is recrystallized after chloroform dissolves with ethyl alcohol temperature, obtains l-lactic acid soft material.
(2) it is 3 according to the mass ratio of polytetramethylene glycol, dextrorotation lactide and stannous octoate:70:0.2, it is sub- by poly- four
Methyl glycol is added to dextrorotation lactide after mixing, and stannous octoate catalyst is added, under the vacuum environment of 0.005Pa,
6h first is heated at 120 DEG C, then heats to 150 DEG C, time 20h is recrystallized after chloroform dissolves with ethyl alcohol, obtains the right side
Revolve polylactic acid soft material.
(3) by weight, 0.5 part of l-lactic acid soft material and 0.95 part of dextrorotation polylactic acid soft material are added
To after being dissolved in 30 parts of chloroforms, 0.05 part of Quadrupolar hydrogen bond crosslinking agent is added, under the vacuum environment of 0.005Pa, first 60
0.5h is heated at DEG C, then heats to 100 DEG C, time 2h, dissolution filter precipitation is dry, and it is left-handed to obtain Quadrupolar hydrogen bond crosslinking
Dextrorotation polylactic acid intelligent soft material.
(4) Quadrupolar hydrogen bond is crosslinked the volume ratio that left-handed dextrorotation polylactic acid intelligent soft material is dissolved in tetrahydrofuran and chloroform
It is 3:1 in the mixed solvent, which is evenly stirred until, to be completely dissolved, and the spinning solution of 12wt% is obtained, and is 15kV, the stream of spinning solution in voltage
Amount is 0.6mL/h, and it is 15cm to receive distance, and the poly- left-handed dextrorotation polylactic acid intelligence of Quadrupolar hydrogen bond crosslinking is prepared through electrostatic spinning
Soft material nano fibrous membrane.
Embodiment 3：
(1) it is 72 according to the mass ratio of levorotatory lactide, stannous octoate and tetraethylene glycol:0.12：1.6, by levorotatory lactide,
Stannous octoate and tetraethylene glycol are added in reaction bulb, under the vacuum environment of 0.003Pa, are first heated 3h at 105 DEG C, are then risen
To 155 DEG C, time 19h is recrystallized after chloroform dissolves with ethyl alcohol temperature, obtains l-lactic acid soft material.
(2) it is 2.5 according to the mass ratio of polytetramethylene glycol, dextrorotation lactide and stannous octoate:68:0.13, it will gather
Tetramethylene glycol is added to dextrorotation lactide after mixing, stannous octoate catalyst is added, in the vacuum environment of 0.002Pa
Under, 4h first is heated at 115 DEG C, then heats to 145 DEG C, time 19h is recrystallized after chloroform dissolves with ethyl alcohol, is obtained
Dextrorotation polylactic acid soft material.
(3) by weight, 0.4 part of l-lactic acid soft material and 0.92 part of dextrorotation polylactic acid soft material are added
To after being dissolved in 25 parts of chloroforms, 0.03 part of Quadrupolar hydrogen bond crosslinking agent is added, under the vacuum environment of 0.003Pa, first 55
0.5h is heated at DEG C, then heats to 98 DEG C, time 2h, dissolution filter precipitation is dry, obtains Quadrupolar hydrogen bond and is crosslinked the left-handed right side
Revolve polylactic acid intelligent soft material.
(4) Quadrupolar hydrogen bond is crosslinked the volume ratio that left-handed dextrorotation polylactic acid intelligent soft material is dissolved in tetrahydrofuran and chloroform
It is 1.5:0.7 in the mixed solvent, which is evenly stirred until, to be completely dissolved, and the spinning solution of 11wt% is obtained, and is 14.5kV, spinning in voltage
The flow of liquid is 0.45mL/h, and it is 15cm to receive distance, and it is poly- that the poly- left-handed dextrorotation of Quadrupolar hydrogen bond crosslinking is prepared through electrostatic spinning
Lactic acid intelligent soft material nano fibrous membrane.
Embodiment 4：
(1) it is 71 according to the mass ratio of levorotatory lactide, stannous octoate and tetraethylene glycol:0.17：1.65, left-handed third is handed over
Ester, stannous octoate and tetraethylene glycol are added in reaction bulb, under the vacuum environment of 0.002Pa, first heat 2.5h at 115 DEG C,
155 DEG C are then heated to, time 19.5h is recrystallized after chloroform dissolves with ethyl alcohol, obtains l-lactic acid soft material.
(2) it is 2.4 according to the mass ratio of polytetramethylene glycol, dextrorotation lactide and stannous octoate:65:0.13, it will gather
Tetramethylene glycol is added to dextrorotation lactide after mixing, stannous octoate catalyst is added, in the vacuum environment of 0.004Pa
Under, 3.5h first is heated at 115 DEG C, then heats to 147 DEG C, time 18.5h is recrystallized after chloroform dissolves with ethyl alcohol,
Obtain dextrorotation polylactic acid soft material.
(3) by weight, 0.3 part of l-lactic acid soft material and 0.91 part of dextrorotation polylactic acid soft material are added
To after being dissolved in 27 parts of chloroforms, 0.03 part of Quadrupolar hydrogen bond crosslinking agent is added, under the vacuum environment of 0.002Pa, first 57
0.5h is heated at DEG C, then heats to 98 DEG C, time 2h, dissolution filter precipitation is dry, obtains Quadrupolar hydrogen bond and is crosslinked the left-handed right side
Revolve polylactic acid intelligent soft material.
(4) Quadrupolar hydrogen bond is crosslinked the volume ratio that left-handed dextrorotation polylactic acid intelligent soft material is dissolved in tetrahydrofuran and chloroform
It is 2.5:0.8 in the mixed solvent, which is evenly stirred until, to be completely dissolved, and the spinning solution of 9.5wt% is obtained, and is 13.5kV, spinning in voltage
The flow of liquid is 0.55mL/h, and it is 15cm to receive distance, and it is poly- that the poly- left-handed dextrorotation of Quadrupolar hydrogen bond crosslinking is prepared through electrostatic spinning
Lactic acid intelligent soft material nano fibrous membrane.
Embodiment 5：
(1) it is 70 according to the mass ratio of levorotatory lactide, stannous octoate and tetraethylene glycol:0.2：1.5, by levorotatory lactide,
Stannous octoate and tetraethylene glycol are added in reaction bulb, under the vacuum environment of 0.005Pa, are first heated 4h at 100 DEG C, are then risen
To 150 DEG C, time 20h is recrystallized after chloroform dissolves with ethyl alcohol temperature, obtains l-lactic acid soft material.
(2) it is 2 according to the mass ratio of polytetramethylene glycol, dextrorotation lactide and stannous octoate:70:0.1, it is sub- by poly- four
Methyl glycol is added to dextrorotation lactide after mixing, and stannous octoate catalyst is added, under the vacuum environment of 0.005Pa,
6h first is heated at 110 DEG C, then heats to 140 DEG C, time 20h is recrystallized after chloroform dissolves with ethyl alcohol, obtains the right side
Revolve polylactic acid soft material.
(3) by weight, 0.2 part of l-lactic acid soft material and 0.95 part of dextrorotation polylactic acid soft material are added
To after being dissolved in 20 parts of chloroforms, 0.05 part of Quadrupolar hydrogen bond crosslinking agent is added, under the vacuum environment of 0.001Pa, first 60
0.5h is heated at DEG C, then heats to 95 DEG C, time 2h, dissolution filter precipitation is dry, obtains Quadrupolar hydrogen bond and is crosslinked the left-handed right side
Revolve polylactic acid intelligent soft material.
(4) Quadrupolar hydrogen bond is crosslinked the volume ratio that left-handed dextrorotation polylactic acid intelligent soft material is dissolved in tetrahydrofuran and chloroform
It is 3:0.5 in the mixed solvent, which is evenly stirred until, to be completely dissolved, and the spinning solution of 12wt% is obtained, and is 13kV in voltage, spinning solution
Flow is 0.6mL/h, and it is 15cm to receive distance, and Quadrupolar hydrogen bond crosslinking, which is prepared, through electrostatic spinning gathers left-handed dextrorotation polylactic acid intelligence
It can soft material nano fibrous membrane.
Embodiment 6：
(1) it is 75 according to the mass ratio of levorotatory lactide, stannous octoate and tetraethylene glycol:0.1：1.7, by levorotatory lactide,
Stannous octoate and tetraethylene glycol are added in reaction bulb, under the vacuum environment of 0.001Pa, are first heated 2h at 120 DEG C, are then risen
To 160 DEG C, time 18h is recrystallized after chloroform dissolves with ethyl alcohol temperature, obtains l-lactic acid soft material.
(2) it is 3 according to the mass ratio of polytetramethylene glycol, dextrorotation lactide and stannous octoate:65:0.2, it is sub- by poly- four
Methyl glycol is added to dextrorotation lactide after mixing, and stannous octoate catalyst is added, under the vacuum environment of 0.001Pa,
3h first is heated at 120 DEG C, then heats to 150 DEG C, time 18h is recrystallized after chloroform dissolves with ethyl alcohol, obtains the right side
Revolve polylactic acid soft material.
(3) by weight, 0.5 part of l-lactic acid soft material and 0.9 part of dextrorotation polylactic acid soft material are added
To after being dissolved in 30 parts of chloroforms, 0.01 part of Quadrupolar hydrogen bond crosslinking agent is added, under the vacuum environment of 0.005Pa, first 50
0.5h is heated at DEG C, then heats to 100 DEG C, time 2h, dissolution filter precipitation is dry, and it is left-handed to obtain Quadrupolar hydrogen bond crosslinking
Dextrorotation polylactic acid intelligent soft material.
(4) Quadrupolar hydrogen bond is crosslinked the volume ratio that left-handed dextrorotation polylactic acid intelligent soft material is dissolved in tetrahydrofuran and chloroform
It is 1:1 in the mixed solvent, which is evenly stirred until, to be completely dissolved, and the spinning solution of 8wt% is obtained, and is 15kV, the flow of spinning solution in voltage
For 0.4mL/h, it is 15cm to receive distance, and it is intelligently soft that the poly- left-handed dextrorotation polylactic acid of Quadrupolar hydrogen bond crosslinking is prepared through electrostatic spinning
Material nano tunica fibrosa.
After testing, the Quadrupolar hydrogen bond crosslinking that prepared by embodiment 1-6 gathers left-handed dextrorotation polylactic acid intelligent soft material nanofiber
The result of film and prior art polylactic acid nano fiber film is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | The prior art | |
| Fracture strength (MPa) | 2.6 | 3.4 | 2.9 | 3.0 | 3.1 | 2.8 | 2.1 |
| Elongation at break (%) | 28 | 30 | 32 | 31 | 30 | 29 | 24 |
| It can elasticity recovery modulus (MPa) | 0.76 | 0.89 | 0.81 | 0.79 | 0.83 | 0.86 | 0.16 |
| The time required to self-healing (h) | 12 | 9 | 10 | 11.5 | 9.5 | 10.5 | -- |
As seen from the above table, the Quadrupolar hydrogen bond crosslinking that prepared by the present invention gathers left-handed dextrorotation polylactic acid intelligent soft material nanofiber
The mechanical property and toughness of film significantly improve, and have stretchable tear resistance, can be to micro gap after standing a period of time
Self-healing is carried out, it is functional good.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of Quadrupolar hydrogen bond is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane, it is characterised in that：The quadruple
The left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane of hydrogen bond crosslinks is l-lactic acid soft material and dextrorotation polylactic acid softwood
Expect that the spinning solution being prepared through Quadrupolar hydrogen bond cross-linking agents is obtained through electrostatic spinning.
2. a kind of Quadrupolar hydrogen bond described in claim 1 is crosslinked the preparation of left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Method, which is characterized in that include the following steps：
(1) levorotatory lactide, stannous octoate and tetraethylene glycol are added in reaction bulb, under vacuum conditions after heating reaction, warp
After chloroform dissolving, is recrystallized with ethyl alcohol, obtain l-lactic acid soft material；
(2) polytetramethylene glycol is added to dextrorotation lactide after mixing, stannous octoate catalyst is added, in vacuum ring
Under border after heating reaction, after chloroform dissolves, is recrystallized with ethyl alcohol, obtain dextrorotation polylactic acid soft material；
(3) dextrorotation polylactic acid soft material prepared by l-lactic acid soft material and step (2) prepared by step (1) is added to chlorine
In imitative after dissolving, Quadrupolar hydrogen bond crosslinking agent is added, under vacuum conditions heating copolymerization, dissolution filter precipitation is dry, obtains quadruple
The left-handed dextrorotation polylactic acid intelligent soft material of hydrogen bond crosslinks；
(4) Quadrupolar hydrogen bond prepared by step (3) is crosslinked left-handed dextrorotation polylactic acid intelligent soft material and is dissolved in the tetrahydrochysene containing chloroform
It is evenly stirred until and is completely dissolved in THF solvent, obtain spinning solution, Quadrupolar hydrogen bond, which is prepared, through electrostatic spinning is crosslinked the left-handed right side
Revolve polylactic acid intelligent soft material nano fibrous membrane.
3. a kind of Quadrupolar hydrogen bond according to claim 2 is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Preparation method, it is characterised in that：In the step (1), the mass ratio of levorotatory lactide, stannous octoate and tetraethylene glycol is 70-75:
0.1-0.2：1.5-1.7.
4. a kind of Quadrupolar hydrogen bond according to claim 2 is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Preparation method, it is characterised in that：In the step (1), the vacuum degree for heating reaction is 0.001-0.005Pa, first in 100-120
2-4h is heated at DEG C, then heats to 150-160 DEG C, time 18-20h.
5. a kind of Quadrupolar hydrogen bond according to claim 2 is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Preparation method, it is characterised in that：In the step (2), polytetramethylene glycol, dextrorotation lactide and stannous octoate mass ratio
For 2-3:65-70:0.1-0.2.
6. a kind of Quadrupolar hydrogen bond according to claim 2 is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Preparation method, it is characterised in that：In the step (2), the vacuum degree for heating reaction is 0.001-0.003Pa, first in 110-120
3-6h is heated at DEG C, then heats to 140-150 DEG C, time 18-20h.
7. a kind of Quadrupolar hydrogen bond according to claim 2 is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Preparation method, it is characterised in that：In the step (3), l-lactic acid soft material, dextrorotation polylactic acid soft material and Quadrupolar hydrogen bond
The mass ratio of crosslinking agent is 0.2-0.5:0.9-0.95：0.01-0.05.
8. a kind of Quadrupolar hydrogen bond according to claim 2 is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Preparation method, it is characterised in that：In the step (3), the vacuum degree for heating copolymerization is 0.001-0.005Pa, first at 50-60 DEG C
Lower heating 0.5h then heats to 95-100 DEG C, time 2h.
9. a kind of Quadrupolar hydrogen bond according to claim 2 is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Preparation method, it is characterised in that：In the step (4), the volume of tetrahydrofuran and chloroform in the tetrahydrofuran solvent containing chloroform
Than for 1-3:0.5-1.
10. a kind of Quadrupolar hydrogen bond according to claim 2 is crosslinked left-handed dextrorotation polylactic acid intelligent soft material nano fibrous membrane
Preparation method, it is characterised in that：In the step (4), the condition of electrostatic spinning is：Voltage is 13-15kV, the stream of spinning solution
Amount is 0.4-0.6mL/h, and it is 15cm to receive distance.
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| CN109912945A (en) * | 2018-11-19 | 2019-06-21 | 江苏科技大学 | A kind of poly-lactic acid in high molecular weight material and preparation method thereof |
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| CZ308409B6 (en) * | 2013-02-26 | 2020-08-05 | Elmarco S.R.O. | Preparation for the administration of at least one biologically and / or pharmaceutically active substance |
| CN104831416B (en) * | 2015-03-25 | 2017-03-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of prolamine-modified polylactic acid regenerated yarn fibre yarn |
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| US10603230B2 (en) * | 2016-11-09 | 2020-03-31 | Nano And Advanced Materials Institute Limited | Low friction core-shell nanofibrous membranes for delivery of active ingredients to the wet skin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109912945A (en) * | 2018-11-19 | 2019-06-21 | 江苏科技大学 | A kind of poly-lactic acid in high molecular weight material and preparation method thereof |
| CN109912945B (en) * | 2018-11-19 | 2021-04-30 | 江苏科技大学 | High-molecular-weight polylactic acid material and preparation method thereof |
| CN112898636A (en) * | 2021-02-18 | 2021-06-04 | 陕西科技大学 | Preparation method of self-healing cellulose-based plastic |
| CN112898636B (en) * | 2021-02-18 | 2022-02-18 | 陕西科技大学 | Preparation method of self-healing cellulose-based plastic |
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