A kind of preparation method of self-healing property aquagel fibreTechnical field
The present invention relates to intellectual material field more particularly to a kind of preparation methods of self-healing property aquagel fibre.
Background technique
Hydrogel (Hydrogel) is the gel using water as decentralized medium.Water soluble polymer with cross-linked networkIt is middle to introduce a part of hydrophobic grouping and hydrophilic residue, hydrophilic residue and water molecules, hydrone is connected to netted inside, andThe cross-linked polymer of hydrophobic residue water-swellable.It is a kind of macromolecule network system, property is soft, it is able to maintain certain shape,A large amount of water can be absorbed.PVA hydrogel has good non-toxic and biocompatibility, can be applied in daily life, veryTo be applied to biomedicine in.
Usually there is the disadvantages of gel strength is low, poor toughness and absorption speed are slow in hydrogel, be unable to satisfy the requirement used.So reinforcing the workability of hydrogel come mechanical performances such as strength and toughnesses for enhancing hydrogel by the way of crosslinking, open upThe use scope of hydrogel is opened up, the mode of crosslinking can be divided into physical crosslinking and chemical crosslinking two major classes.And be only physical crosslinking orChemical crosslinking cannot all obtain the hydrogel of rationality intensity, so double cross-linking patterns have been included into the design thinking range of hydrogelIt is interior.
Fiber applications are extensive, can be made into filament, the end of a thread and the rope made of hemp, and papermaking or while knitting felt can also be made into fibrous layer；SimultaneouslyAlso it is commonly used to manufacture unclassified stores, and collectively constitutes composite material with unclassified stores, there is great purposes in human lives,The use of fiber generally requires fiber and has certain intensity, and the hydrogel for passing through double cross connection can be competent at this " fabric ".
The self-reparing capability of material is broadly divided into two major classes, and the selfreparing of foreign aid's property and intrinsic selfreparing, foreign aid's property are reviewed one's lessons by oneselfIt is repairing monomer or adhesive and realize selfreparing by material package again, repairing performance is limited.So we gradually willSight shifts to intrinsic self-repair material.Wish what self-repair material itself can be received by the special role self-regeneration of itselfDamage.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation methods of self-healing property aquagel fibre.This hairIn bright method, using the water-setting with very good mechanical properties of the physical-chemical double cross linked method preparation of the method for the present invention preparationGlue fiber, intensity, toughness with higher, high transparency, it is more standby be cut off after self-reparing capability, improve materialDurability.The present invention uses process for copolymerization, realizes chemical crosslinking, then the method for taking repeatedly freeze-thaw makes waterThere is crystallite area inside gel, realizes physical crosslinking.Had using the aquagel fibre of the method for the present invention preparation goodMechanical performance, high transparency, self-regeneration.
The specific technical proposal of the invention is: a kind of preparation method of self-healing property aquagel fibre, comprising the following steps:
Step 1), polyethylene dissolving alcohol: polyvinyl alcohol is added in deionized water, heating water bath is to 70-80 DEG C, by acutely stirringMixing dissolves polyvinyl alcohol, is then allowed to stand after polyvinyl alcohol is completely dissolved, and obtains poly-vinyl alcohol solution, for use.
Polyvinyl alcohol is due to having certain degree of polymerization, so needing under conditions of certain liter gentle agitation, promotesSolvent molecule is spread into polymer, and polyvinyl alcohol is allowed to be swollen and dissolve.
Acrylamide and acrylic acid are added into poly-vinyl alcohol solution by step 2), in mass ratio (40:60)-(30:70), stirIt mixes uniformly, ultrasonic disperse, for use.
Potassium peroxydisulfate is added by 600-700mg/ml and presses solution gross mass 1.5-2.5% addition N, N- methylene for step 3)Bisacrylamide.
It joined crosslinking agent when reaction, so that obtained polymer has certain chemical bond degree of cross linking, have certain strongDegree.Reaction time is unsuitable too short or too long, and the reaction time, the too short degree of polymerization was not high, and the condition of fiber applications is not achieved in intensity, andReaction time can not be too long, and reaction time too long meeting can not become so that the right high and excessively high degree of cross linking of polymer polySpinning solution carries out wet spinning, or has carried out spinning but fiber can really up to the mark in time, does not have flexibility or fiber is firmly crisp easily broken.
Step 4) pours into step 3) acquired solution in three-neck flask, and logical nitrogen is caught up with except oxygen, causes at 55-65 DEG CAcrylamide and acrylic acid are copolymerized conjunction, reaction time 4-6h；
Step 5), using syringe by reaction solution implantation quality score be 1-3% sodium hydrate aqueous solution in solidificating fiber,Natural air drying is taken out after placing 4-8h, obtains aquagel fibre；
Step 6), to after completion of the reaction, aquagel fibre be freezed 3-5h at -80 DEG C to -60 DEG C, take out, solve at room temperatureFreeze 10-14h, thaw after freezing 6h at -80 to -60 DEG C, reciprocal 3 times, forms crystallite area point physical crosslinking, finally obtain certainlyMore property aquagel fibre.
In the prior art, compare the method for lacking and hydrogel being prepared as fiber, be primarily due to conventional hydrogels intensity,Toughness is poor, less meets the application positioning of fiber.And the present invention greatly improves hydrogel using the method for double cross connectionMechanical performance, so that aquagel fibre is prepared into for reality.And containing a large amount of in prepared by the method hydrogelHydrogen bond realize the self-regeneration of aquagel fibre.
In the methods of the invention, using N, N- methylene-bisacrylamide makes polymer molecule be cross-linked with each other, and usesThe method of freeze-thaw repeatedly forms crystallite area node between polyvinyl alcohol molecule, polymer molecule is allowed to be linked to be netNetwork structure forms physics cross-linked structure, greatly enhances the performance of crosslinking, enhance the mechanical performance of fiber, and physicsThe dynamic reversible characteristic of cross-linked network enables hydrogel to carry out selfreparing under the harsh conditions of general non-cryogenic.Conductive water-settingIts fracture port can be carried out docking and carry out selfreparing, the fibre after reparation by glue fiber when fracture having occurred when applying as conducting wireDimension still has certain mechanical strength and electric conductivity, it is not necessary to change and substitute circuit.
In the present invention, fiber flexibility, toughness, preferable intensity, electrically conductive, transparent and self-regeneration performance.
Preferably, in step 1), the M of the polyvinyl alcoholw=89000-98000, percent alcoholysis > 99%.
Preferably, in step 1), mixing time 1-3h.
Preferably, the ultrasonic disperse time is 20-40min in step 2), ultrasonic 5min suspends 3min.
Ultrasonic disperse wants ultrasonic 5min pause 3min, avoids heat accumulation when ultrasound, is surpassed before initiator is addedSound dispersion, can only carry out mechanical stirring after adding initiator and crosslinking agent, inevitable heat production when ultrasound is avoided to send outRaw premature polymerization.Polymerization reaction will have free radical just to can be carried out, and then cause chain reaction, polymerization inhibitor meeting of the oxygen as reaction(free radical attack oxygen-oxygen bond forms the intermediate of similar peroxide) is quenched in the free radical made, thus prevent reaction continue intoRow, not can be carried out polymerization or needs using more initiators.
Preferably, carrying out rousing nitrogen 30min to solution before reaction, driving the oxygen incorporated in solution out of in step 4).
The copolymer chain that free radical polymerization generates mutually is tangled by intermolecular hydrogen bonding effect, forms physical crosslinkingCrosslinking points.This is one of physical crosslinking physical crosslinking point.It is polyvinyl alcohol in low temperature cold repeatedly there are also a kind of crosslinking pointsFreeze and make polyvinyl alcohol chain generate certain orientation during thawing, and form the cross-linked microcrystalline area of physics, forms crosslinkingNetwork.
It is compared with the prior art, the beneficial effects of the present invention are:
1, the method for the present invention selects polyvinyl alcohol as raw material, and having good non-toxic and biocompatibility is as fiberExcellent selection.
2, the aquagel fibre of the method for the present invention preparation has excellent mechanical performance, is that conventional hydrogels material cannotIt realizes, by way of being chemically crosslinked and being physical crosslinking two kinds of crosslinking methods and deposit hydrogel has been reached and be prepared into fiberCondition.
3, preparation process of the present invention is simple, environmental-friendly, energy-efficient, and gained conductive fiber is contained abundant by itselfStrong hydrogen bonding be provided with self-repairing capability, strengthen the injury resistant ability of material, conductive fiber breakage need not substitute, directly willFracture, which contacts with each other, may wait for self-regeneration.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1:
Step 1: polyethylene dissolving alcohol: polyvinyl alcohol 1.2g being added in 6.8ml deionized water, is placed in water-bath environmentHeating water bath is carried out to 75 DEG C, by being vigorously stirred stirring 2h polyvinyl alcohol is dissolved in deionized water, is then allowed to standPolyvinyl alcohol to be confirmed is stand-by after being completely dissolved.
Step 2: 0.85g acrylamide and 1.85g propylene is added in polyvinyl alcohol uniform solution obtained in step 1Acid is uniformly dispersed in the two in the poly-vinyl alcohol solution with certain viscosity by churned mechanically effect, ultrasoundDisperse 40min, ultrasonic 5min suspends 3min, for use.
Step 3: in two solution of above-mentioned steps be added potassium peroxydisulfate (650mg/ml) as reaction carry out initiator andThe crosslinking agent that the N,N methylene bis acrylamide of 55.6mg is chemically crosslinked as hydrogel.
Step 4: solution made from step 3 is poured into bottle, logical nitrogen is caught up with except oxygen, causes acrylamide at 60 DEG CConjunction, reaction time 4h are copolymerized with acrylic acid.
Step 5: being frozen into the sodium hydrate aqueous solution for the use of syringe being 2% by reaction solution implantation quality scoreFiber takes out natural air drying after 6h to be placed.
Step 6: aquagel fibre is placed in low temperature refrigerator to after completion of the reaction, 4h is freezed under the conditions of -70 DEG C, is takenOut, thaw 12h at room temperature, then is placed in refrigerator and thaws after freezing 6h, reciprocal 3 times, can form crystallite area point physical crosslinking, mostThe aquagel fibre that chemical-physical double cross connection has self-healing property is obtained eventually.
Embodiment 2:
Step 1: polyethylene dissolving alcohol: polyvinyl alcohol 1.2g being added in 6.8ml deionized water, is placed in water-bath environmentHeating water bath is carried out to 75 DEG C, by being vigorously stirred stirring 2h polyvinyl alcohol is dissolved in deionized water, is then allowed to standPolyvinyl alcohol to be confirmed is stand-by after being completely dissolved.
Step 2: 0.992g acrylamide and 1.668g third is added in polyvinyl alcohol uniform solution obtained in step 1Olefin(e) acid is uniformly dispersed in the two in the poly-vinyl alcohol solution with certain viscosity by churned mechanically effect, surpassesSound disperses 20min, and ultrasonic 5min suspends 3min, for use.
Step 3: in two solution of above-mentioned steps be added potassium peroxydisulfate (650mg/ml) as reaction carry out initiator andThe crosslinking agent that the N,N methylene bis acrylamide of 55.6mg is chemically crosslinked as hydrogel；
Step 4: solution made from step 3 is poured into bottle, logical nitrogen is caught up with except oxygen, causes acrylamide and third at 60 DEG COlefin(e) acid is copolymerized conjunction, reaction time 5h.
Step 5: being frozen into the sodium hydrate aqueous solution for the use of syringe being 2% by reaction solution implantation quality scoreFiber takes out natural air drying after 6h to be placed.
Step 6: aquagel fibre is placed in low temperature refrigerator to after completion of the reaction, 4h is freezed under the conditions of -70 DEG C, is takenOut, thaw 12h at room temperature, then is placed in refrigerator and thaws after freezing 6h, reciprocal 3 times, can form crystallite area point physical crosslinking, mostThe aquagel fibre that chemical-physical double cross connection has self-healing property is obtained eventually.
Embodiment 3:
Step 1: polyethylene dissolving alcohol: polyvinyl alcohol 1.2g being added in 6.8ml deionized water, is placed in water-bath environmentHeating water bath is carried out to 75 DEG C, by being vigorously stirred stirring 2h polyvinyl alcohol is dissolved in deionized water, is then allowed to standPolyvinyl alcohol to be confirmed is stand-by after being completely dissolved.
Step 2: 0.834g acrylamide and 1.946g third is added in polyvinyl alcohol uniform solution obtained in step 1Olefin(e) acid is uniformly dispersed in the two in the poly-vinyl alcohol solution with certain viscosity by churned mechanically effect, surpassesSound disperses 30min, and ultrasonic 5min suspends 3min, for use.
Step 3: in above-mentioned steps two) initiator of potassium peroxydisulfate (650mg/ml) as reaction progress is added in solutionThe crosslinking agent being chemically crosslinked with the N,N methylene bis acrylamide of 55.6mg as hydrogel；
Step 4: solution made from step 3 is poured into bottle, logical nitrogen is caught up with except oxygen, causes acrylamide and third at 60 DEG COlefin(e) acid is copolymerized conjunction, reaction time 6h.
Step 5: being frozen into the sodium hydrate aqueous solution for the use of syringe being 2% by reaction solution implantation quality scoreFiber takes out natural air drying after 6h to be placed.
Step 6: aquagel fibre is placed in low temperature refrigerator to after completion of the reaction, 4h is freezed under the conditions of -70 DEG C, is takenOut, thaw 12h at room temperature, then is placed in refrigerator and thaws after freezing 6h, reciprocal 3 times, can form crystallite area point physical crosslinking, mostThe aquagel fibre that chemical-physical double cross connection has self-healing property is obtained eventually.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present inventionMethod therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present inventionTechnical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention sideThe protection scope of case.