CN104527083A - Method for preparing self-healing composite material by employing electrospinning method - Google Patents
Method for preparing self-healing composite material by employing electrospinning method Download PDFInfo
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- CN104527083A CN104527083A CN201410778882.4A CN201410778882A CN104527083A CN 104527083 A CN104527083 A CN 104527083A CN 201410778882 A CN201410778882 A CN 201410778882A CN 104527083 A CN104527083 A CN 104527083A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
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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
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Abstract
The invention provides a method for preparing a self-healing composite material by employing an electrospinning method. The method comprises the following steps: dissolving a spinnable polymer and a liquid healing agent into a volatile solvent, carrying out electrospinning, and curing the obtained spinnable polymer/healing agent composite fiber with a curing agent dilute solution at a room temperature, so as to obtain the spinnable polymer/healing agent composite fiber with a shell layer on the surface; dissolving the spinnable polymer and a curing agent into the volatile solvent, and carrying out electrostatic spinning, so as to obtain the spinnable polymer/healing agent composite fiber; stacking two composite fibers to form a fiber film; pouring a curable resin material; and repeatedly paving the film, pouring resin, and curing, so as to obtain the self-healing composite material; when the composite material generates a micro-crack, the internal fiber cracks; and the healing agent blocked in a fiber micropore and the curing agent blocked in another fiber micropore are released on the crack part and react under the heated condition, thus achieving self-healing, so that the material can become a self-repairing artificial material with an application prospect.
Description
Technical field
The invention belongs to functional material preparation field, be specifically related to a kind of method utilizing method of electrostatic spinning to prepare self-healing composite.
Background technology
Polymeric material and its composite have application widely at high-technology field because of the performance of its excellence.These materials in use inevitably produce damage, macroscopic view damage or the damage of microcosmic all can cause material mechanical performance to decline, reduction service life, even can cause unpredictable loss.Although the crackle that adopt traditional artificial recovery technique as gluingly subsidized, resin injection etc. can produce composite material surface or other macroscopic failures are repaired, maintenance material property is played a role, but the destruction occurring in material internal especially earlier damage is usually that the even existing various characterizing method of naked eyes is all difficult to detect, repairs and do not know where to begin especially.By the inspiration of healing automatically after organism damage, the concept that scientists proposes " self-repair material ".Self-repair material is such class smart material: the visible or invisible crackle caused to external world, material can be repaired automatically or under environmental stimuli, micro-crack is healed substantially, the key property maintaining material can be continued, extend the service life of material.Bionical selfreparing Objective Concept the eighties in last century proposes, and correlative study in last decade development rapidly.Whether use renovation agent according to self-repair procedure, the selfreparing of polymeric material (comprising polymer matrix composite) can be divided into foreign aid's type and the large class of Intrinsical two.The selfreparing of foreign aid's type refers to by means of additional renovation agent to realize the self-healing properties of material, mainly comprise heeling-in microencapsulation renovation agent and the large class of heeling-in doughnut renovation agent two, be contain the microcapsules of liquid renovation agent or liquid core fibre by heeling-in in matrix material and obtain, the compatibility of admixture and matrix material during preparation, will be considered.These two kinds of self-repair material processing technologys are day by day ripe, and material category also increases gradually, show certain application potential in the self-healing field of polymeric material.But generally common self-repair material preparation process is still more loaded down with trivial details, operation relative difficulty, even relate to complicated chemical reaction, and cost of manufacture is higher.The most important thing is the microcapsules with self-healing function that obtain or fiber size bigger than normal, thus reduce the mechanical property of composite.
Summary of the invention
Technical problem solved by the invention how to prepare self-healing composite by simple method, do not affect the mechanical property of composite while realizing the self-healing performance of composite.
In order to solve the problems of the technologies described above, the invention provides a kind of method utilizing method of electrostatic spinning to prepare self-healing composite.
The method utilizing method of electrostatic spinning to prepare self-healing composite provided by the present invention, comprises following:
1) spinnable polymer and liquid consolidant are dissolved in volatile solvent, obtain the blend solution of spinnable polymer and consolidant; Then the blend solution of described spinnable polymer and consolidant is carried out electrostatic spinning, obtain spinnable polymer/consolidant composite fibre; Finally make described spinnable polymer/consolidant composite fibre quickly through curing agent weak solution, at room temperature solidify, the consolidant of described spinnable polymer/consolidant composite fibre outer surface and curing agent are reacted, thus obtains spinnable polymer/consolidant composite fibre that there is shell on surface;
2) spinnable polymer and described curing agent are dissolved in volatile solvent, obtain the blend solution of spinnable polymer and curing agent; Then the blend solution of described spinnable polymer and curing agent is carried out electrostatic spinning, obtain spinnable polymer/curing agent composite fibre;
3) spinnable polymer of shell/consolidant composite fibre and described spinnable polymer/curing agent composite fibre is had on described surface to stack formation tunica fibrosa, cast curable resin materials, repeat above-mentioned plastic film mulch, resin-cast process, obtain fiber/resin composite, by gained composite material solidification, obtain described self-healing composite.
In said method, described spinnable polymer is of the same race or not similar polymers, that described polymer is Prof. Du Yucang or natural polymer, and described polymer is selected from following at least one: polystyrene (molecular weight is 10000-250000), polyacrylonitrile (molecular weight is 10000-150000), polyurethane (molecular weight is 10000-80000), polyvinyl alcohol-poly (propylene carbonate) (molecular weight is 10000-100000), polyvinyl alcohol (molecular weight is 12000-300000), polycaprolactone (molecular weight is 10000-80000), lactic acid caprolactone copolymer (molecular weight is 20000-120000), poly (glycolide-co-lactide) (molecular weight is 100000-450000), polylactide (molecular weight is 80000-240000), polyethylene glycol (molecular weight is 5000-20000), polymethyl methacrylate (molecular weight is 35000-250000), polyvinylpyrrolidone (molecular weight is 500000-1200000), polyaniline (molecular weight is 20000-100000), polyether sulfone (molecular weight is 50000-100000), PLA (molecular weight 150000-500000), polyethylene glycol oxide (molecular weight is 100000-600000), polyvinyl chloride (molecular weight is 50000-120000), shitosan (molecular weight is 200000-500000), Kynoar (molecular weight is 400000-600000), polyimides (molecular weight is 40000-60000), polyamide (molecular weight is 5000-20000) and polypropylene (molecular weight is 80000-150000).
Said method step 1) in, described liquid consolidant is selected from following at least one: bicyclopentadiene, dimethyl silicone polymer, liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid bisphenol AD type epoxy resin, resorcinol type epoxy resin, to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether, methylol bisphenol A type epoxy resin, liquid glycidyl ester type epoxy resin, glycidol ether, NOA76 glue, the many vinylsiloxanes of α, ω-dichloro and poly-diethoxy silane and cyanoacrylate.
Said method step 1) in, described volatile solvent is the common good solvent of above-mentioned spinnable polymer and consolidant; Described volatile solvent specifically can be: dimethyl formamide, dimethylacetylamide etc.
In the blend solution of described spinnable polymer and consolidant, the mass ratio of described consolidant and spinnable polymer is 10/90-64/40, specifically can be 36/60,30/50.
In the blend solution of described spinnable polymer and consolidant, the mass ratio of described spinnable polymer and solvent is 5/95-5/12, specifically can be 5/95,4.5/20,5/20 or 5/12.
Said method step 1) in, the process conditions of described electrostatic spinning are: spinning voltage is 10-30KV, specifically can be 20KV; Spinning receiving range is 8-20cm, specifically can be 13cm; The flow velocity of spinning solution is 0.02ml/min-1 μ l/min, specifically can be 0.01ml/min; Spinning syringe needle internal diameter is 0.39mm-1.5mm, specifically can be 0.39mm; Spinning temperature is 17-28 DEG C, and spinning temperature specifically can be 25 DEG C; Air humidity is 50%-80%, and air humidity specifically can be 60%.
The surface prepared has the diameter of the spinnable polymer of shell/consolidant composite fibre to be 0.1-3.2 μm, specifically can be 0.97 μm, 0.98 μm, 1.08 μm, 1.13 μm, 1.15 μm or 1.18 μm.
Said method step 1) and 2) in, described curing agent is selected according to the kind of liquid consolidant used, as long as can promote that described liquid consolidant reacts.
When described liquid consolidant is dimethyl silicone polymer (SYLGARD184), described curing agent is SYLGARD184Curing agent.
Said method step 2) in, in the blend solution of described spinnable polymer and curing agent, the mass ratio of described curing agent and spinnable polymer is 3/90-25/40, specifically can be 12/60.
In the blend solution of described spinnable polymer and curing agent, the mass ratio of described spinnable polymer and solvent is 5/95-5/12.
Said method step 2) in, the process conditions of described electrostatic spinning are: spinning voltage is 10-30KV, spinning receiving range is 8-20cm, the flow velocity of spinning solution is 0.02ml/min-1 μ l/min, spinning syringe needle internal diameter is 0.39mm-1.5mm, spinning temperature is 17-28 DEG C, and air humidity is 50%-80%.
The diameter of the spinnable polymer prepared/curing agent composite fibre is 0.07-2.6 μm.
Compared with prior art, effect of the present invention is: what the present invention adopted is spinnable polymer and liquid consolidant are all dissolved in strong volatile organic solvent to form uniform blend spinning liquid, then electrostatic spinning is carried out to blend spinning solution and obtain spinnable polymer/consolidant composite fibre, not only fibre structure is complete, diameter is evenly distributed, and preparation process is simple, time is short, cost is low, the most important thing is successfully the excellent spinnability of polymer and the self-healing properties of consolidant to be combined, achieve performance complement.When in use there is micro-crack in the polymer containing this self-healing composite fibre when inside, the fiber of polymeric inner can rupture, the consolidant be locked under the condition of being heated in fiber micropore can discharge in cracks with the curing agent be locked in another fiber micropore and react, thus realize the self-healing of composite micro-crack, this self-healing composite can become the selfreparing artificial material having application prospect, particularly be applied to the incompetent field of general material, as: high-altitude is explored, deep-sea submerge, and even man-made organ transplanting etc.
Accompanying drawing explanation
Fig. 1 is the digital camera photo of polystyrene/liquid epoxies composite fibre prepared by the embodiment of the present invention 1.
Fig. 2 is the stereoscan photograph of polystyrene/liquid epoxies composite fibre prepared by the embodiment of the present invention 1.
Fig. 3 is the fluorescent microscopy images of polystyrene/liquid epoxies composite fibre prepared by the embodiment of the present invention 1.
Fig. 4 is the stereoscan photograph after the apparent crack healing of fiber/resin composite of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
The experimental technique used in following embodiment if no special instructions, is conventional method; Reagent used in following embodiment, biomaterial etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, self-healing composite fibre 1
1) join in the DMF of 20g by 5g polystyrene (molecular weight 250000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polystyrene and DMF is the homogeneous solution of 5/20.The liquid epoxies (epoxy resin RIM135) taking 3g joins in the polystyrene solution of above-mentioned gained, and mechanical agitation is even, obtains the mixed solution of polystyrene and RIM135, i.e. electrostatic spinning solution; The RIM135 wherein added and the mass ratio of polystyrene are about 36/60;
The blend solution of obtained RIM135 and polystyrene is loaded device for storing liquid, applies the spinning voltage of 20KV between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 13cm.The flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, and spinning syringe needle internal diameter is 0.39mm, and spinning temperature is 25 DEG C, and air humidity is 60%.Polystyrene/liquid epoxies composite fibre is obtained by electrostatic spinning technique, and gained polystyrene/liquid epoxies composite fibre is put into curing agent (curing agent RIMH134) weak solution, quick taking-up, at room temperature solidify, obtaining surperficially has the polystyrene of shell/RIM135 composite fibre (average diameter is 1.15 μm).
Fig. 1 is the digital camera photo of gained polystyrene/liquid epoxies (RIM135) composite fibre.
Fig. 2 is the stereoscan photograph of gained polystyrene/liquid epoxies (RIM135) composite fibre.
Fig. 3 is the fluorescent microscopy images of gained polystyrene/liquid epoxies (RIM135) composite fibre.
2) join in the DMF of 20g by 5g polystyrene (molecular weight 250000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polystyrene and DMF is the homogeneous solution of 5/20.The liquid epoxies curing agent (curing agent RIMH134) taking 1g joins in the polystyrene solution of above-mentioned gained, and mechanical agitation is even, obtains the mixed solution of polystyrene and RIMH134, i.e. electrostatic spinning solution; The RIMH134 wherein added and the mass ratio of polystyrene are about 12/60;
The blend solution of obtained RIMH134 and polystyrene is loaded device for storing liquid, applies the spinning voltage of 10KV between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 13cm.The flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, and spinning syringe needle internal diameter is 0.39mm, and spinning temperature is 25 DEG C, and air humidity is 60%.Polystyrene/curing agent composite fibre (average diameter is about 0.98 μm) is obtained by electrostatic spinning technique.
The polystyrene of shell/RIM135 composite fibre and described polystyrene/curing agent composite fibre is had on described surface to stack in mould, by the component A of acrylic resin, (commodity are called acrylic acid AB glue, purchased from Jiangmen Yiyuan Biological and Chemical Engineering Co., Ltd) and B component (component A and B component are the commodity of unitizing, all purchased from Jiangmen Yiyuan Biological and Chemical Engineering Co., Ltd) mix with the mass ratio of 1:1 after pour mould into, quick knifing, repeat above-mentioned plastic film mulch, the process of casting resin, obtain fiber/resin composite, gained composite is left standstill 24h in room temperature, it is made to solidify completely, the composite of self-healing function must be had.
Fig. 4 is the stereoscan photograph after the composite crack healing of the self-healing function that the present invention obtains.
The preparation of embodiment 2, self-healing composite fibre 2
1) join in the DMF of 95g by 5g polyacrylonitrile (molecular weight 150000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyacrylonitrile and DMF is the homogeneous solution of 5/95.Take 3g to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether joins in the polyacrylonitrile solution of above-mentioned gained, and mechanical agitation is even, obtains polyacrylonitrile and to tert-butyl-phenyl 1-(2,3-epoxy) mixed solution of propyl ether, obtain electrostatic spinning solution; What wherein add is 36/60 to the mass ratio of tert-butyl-phenyl 1-(2,3-epoxy) propyl ether and polyacrylonitrile.
By obtained polyacrylonitrile with to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether blend solution load device for storing liquid, the spinning voltage of 20KV is applied between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 13cm, the flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, spinning syringe needle internal diameter is 1.5mm, and spinning temperature is 28 DEG C, and air humidity is 65%.Polyacrylonitrile/to tert-butyl-phenyl 1-(2 is obtained by electrostatic spinning technique, 3-epoxy) propyl ether composite fibre, and by gained polyacrylonitrile/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite cellulosic membrane puts into its curing agent (curing agent is TEPA) weak solution, quick taking-up, at room temperature solidify, obtain the surperficial polyacrylonitrile of shell/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite fibre (average diameter is 1.08 μm) of having.
2) join in the DMF of 95g by 5g polyacrylonitrile (molecular weight 150000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyacrylonitrile and DMF is the homogeneous solution of 5/95.The TEPA taking 1g joins in the polyacrylonitrile solution of above-mentioned gained, and mechanical agitation is even, obtains the mixed solution of polyacrylonitrile and TEPA, obtains electrostatic spinning solution; The TEPA wherein added and the mass ratio of polyacrylonitrile are 12/60.
The blend solution of obtained polyacrylonitrile and TEPA is loaded device for storing liquid, applies the spinning voltage of 18KV between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 8cm.The flow velocity of telomerized polymer and consolidant blend solution is 1 μ L/min, and spinning syringe needle internal diameter is 1.5mm, and spinning temperature is 28 DEG C, and air humidity is 65%.Polyacrylonitrile/TEPA composite fibre (average diameter is about 0.94 μm) is obtained by electrostatic spinning technique.
Described surface there is the polyacrylonitrile of shell/to tert-butyl-phenyl 1-(2, 3-epoxy) propyl ether composite fibre and described polyacrylonitrile/TEPA composite fibre stack in mould, by component A (the trade name AB glue (acrylic resin modified glue) of acrylic resin, purchased from Hangzhou Feng Lei Industrial Co., Ltd.) and B component (component A and component B is the commodity of unitizing, all purchased from Hangzhou Feng Lei Industrial Co., Ltd.) mix with the mass ratio of 1:1 after pour mould into, quick knifing, repeat above-mentioned plastic film mulch, the process of casting resin, obtain fiber/resin composite, gained composite is left standstill 24h in room temperature, it is made to solidify completely, the composite of self-healing function must be had.
The preparation of embodiment 3, self-healing composite fibre 3
1) join in the DMF of 12g by 5g polystyrene (molecular weight 250000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polystyrene and DMF is the homogeneous solution of 5/12.Take 3g to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether joins in the polystyrene solution of above-mentioned gained, and mechanical agitation is even, obtains polystyrene and to tert-butyl-phenyl 1-(2,3-epoxy) mixed solution of propyl ether, obtain electrostatic spinning solution; What wherein add is 36/60 to the mass ratio of tert-butyl-phenyl 1-(2,3-epoxy) propyl ether and polystyrene;
By obtained polystyrene with to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether co-blended spinning solution load device for storing liquid, the spinning voltage of 20KV is applied between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 13cm, the flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, spinning syringe needle internal diameter is 0.9mm, and spinning temperature is 19 DEG C, and air humidity is 80%.Polystyrene/to tert-butyl-phenyl 1-(2 is obtained by electrostatic spinning technique, 3-epoxy) blend composite fiber of propyl ether, and by gained polystyrene/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite cellulosic membrane puts into its curing agent rare (curing agent is TEPA) solution, quick taking-up, at room temperature solidify, obtain the surperficial polystyrene of shell/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite fibre (average diameter is about 1.18 μm) of having.
2) join in the DMF of 12g by 5g polystyrene (molecular weight 250000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polystyrene and DMF is the homogeneous solution of 5/12.The TEPA taking 1g joins in the polystyrene solution of above-mentioned gained, and mechanical agitation is even, obtains the mixed solution of polystyrene and TEPA, obtains electrostatic spinning solution; The TEPA wherein added and the mass ratio of polystyrene are 12/60.
The co-blended spinning solution of obtained polystyrene and TEPA is loaded device for storing liquid, the spinning voltage of 30KV is applied between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 20cm, the flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, spinning syringe needle internal diameter is 0.9mm, spinning temperature is 21 DEG C, and air humidity is 80%.Polystyrene/TEPA composite fibre (average diameter is about 1.03 μm) is obtained by electrostatic spinning technique.
Described surface there is the polystyrene of shell/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite fibre and described polystyrene/TEPA composite fibre stack in mould, mould is poured into after the component A of acrylic resin and B component (with the component A in embodiment 1 and B component) being mixed with the mass ratio of 1:1, quick knifing, repeat the process of above-mentioned plastic film mulch, casting resin, obtain fiber/resin composite, gained composite is left standstill 24h in room temperature, make it solidify completely, the composite of self-healing function must be had.
The preparation of embodiment 4, self-healing composite fibre 4
1) 4.5g polyurethane (molecular weight is 60000) is joined in the DMAc of 20g, mechanical agitation is transparent to solution, thus the mass ratio obtaining polyurethane and DMAc is the homogeneous solution of 4.5/20, the liquid epoxies (epoxy resin RIM135) taking 0.5g joins in the polyurethane solutions of above-mentioned gained, under normal temperature condition, mechanical agitation is even, obtain the mixed solution of polyurethane and RIM135, obtain electrostatic spinning solution; The RIM135 wherein added and the mass ratio of polyurethane are 10/90;
The co-blended spinning solution of obtained polyurethane and RIM135 is loaded device for storing liquid, the spinning voltage of 20KV is applied between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 13cm, the flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, spinning syringe needle internal diameter is 0.9mm, spinning temperature is 17 DEG C, and air humidity is 70%.The blend composite fiber of polyurethane/RIM135 is obtained by electrostatic spinning technique, and gained polyurethane/RIM135 composite cellulosic membrane is put into its curing agent (curing agent RIMH134) weak solution, quick taking-up, at room temperature solidify, obtain the surperficial polyurethane/RIM135 composite fibre (average diameter is about 1.13 μm) having shell.
2) 4.5g polyurethane (molecular weight is 60000) is joined in the DMAc of 20g, mechanical agitation is transparent to solution, thus the mass ratio obtaining polyurethane and DMAc is the homogeneous solution of 4.5/20, taking 0.17g curing agent RIMH134 joins in the polyurethane solutions of above-mentioned gained, under normal temperature condition, mechanical agitation is even, obtain the mixed solution of polyurethane and RIMH134, obtain electrostatic spinning solution; The RIMH134 wherein added and the mass ratio of polyurethane are 3.4/90.
The co-blended spinning solution of obtained polyurethane and RIMH134 is loaded device for storing liquid, the spinning voltage of 20KV is applied between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 15cm, the flow velocity of telomerized polymer and consolidant blend solution is 0.02ml/min, spinning syringe needle internal diameter is 0.9mm, spinning temperature is 19 DEG C, and air humidity is 60%.Polyurethane/RIMH134 composite fibre (average diameter is about 0.97 μm) is obtained by electrostatic spinning technique.
The polyurethane of shell/RIM135 composite fibre and described polyurethane/RIMH134 composite fibre is had on described surface to stack in mould, mould is poured into after the component A of acrylic resin and B component (with the component A in embodiment 1 and B component) being mixed with the mass ratio of 1:1, quick knifing, repeat the process of above-mentioned plastic film mulch, casting resin, obtain fiber/resin composite, gained composite is left standstill 24h in room temperature, make it solidify completely, the composite of self-healing function must be had.
The preparation of embodiment 5, self-healing composite fibre 5
1) join in the DMF of 20g by 5g polyvinyl chloride (molecular weight is), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyvinyl chloride and DMF is the homogeneous solution of 5/20.The dimethyl silicone polymer (SYLGARD184) taking 8g joins in the polyvinyl chloride solution of above-mentioned gained, under normal temperature condition, mechanical agitation is even, obtain the mixed solution of polyvinyl chloride and dimethyl silicone polymer (SYLGARD184), obtain electrostatic spinning solution; The dimethyl silicone polymer (SYLGARD184) wherein added and the mass ratio of polyvinyl chloride are 64/40;
The co-blended spinning solution of obtained polyvinyl chloride and dimethyl silicone polymer is loaded device for storing liquid, the spinning voltage of 20KV is applied between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 13cm, the flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, spinning syringe needle internal diameter is 0.9mm, spinning temperature is 23 DEG C, and air humidity is 50%.The blend composite fiber of vinyl chloride/dimethyl silicone polymer is obtained by electrostatic spinning technique, and gained vinyl chloride/dimethyl silicone polymer composite cellulosic membrane is put into its curing agent (curing agent is SYLGARD184Curing agent) weak solution, quick taking-up, at room temperature solidify, obtain the surperficial polyvinyl chloride/dimethyl silicone polymer composite fibre (average diameter is about 1.01 μm) having shell).
2) join in the DMF of 20g by 5g polyvinyl chloride (molecular weight is), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyvinyl chloride and DMF is the homogeneous solution of 5/20.The curing agent taking 0.8g is that SYLGARD184Curing agent joins in the polyvinyl chloride solution of above-mentioned gained, under normal temperature condition, mechanical agitation is even, obtain the mixed solution that polyvinyl chloride and curing agent are SYLGARD184Curing agent, obtain electrostatic spinning solution; The curing agent wherein added is the mass ratio of SYLGARD184Curing agent and polyvinyl chloride is 6.4/40.
It is the co-blended spinning solution loading device for storing liquid of SYLGARD184Curing agent by obtained polyvinyl chloride and curing agent, the spinning voltage of 18KV is applied between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 13cm, the flow velocity of telomerized polymer and consolidant blend solution is 5 μ L/min, spinning syringe needle internal diameter is 0.9mm, spinning temperature is 26 DEG C, and air humidity is 50%.Vinyl chloride/SYLGARD184Curing agent composite fibre (average diameter is about 0.99 μm) is obtained by electrostatic spinning technique.
The polyvinyl chloride of shell/dimethyl silicone polymer composite fibre and described vinyl chloride/SYLGARD184Curing agent composite fibre is had on described surface to stack in mould, mould is poured into after the component A of acrylic resin and B component (with the component A in embodiment 2 and B component) being mixed with the mass ratio of 1:1, quick knifing, repeat the process of above-mentioned plastic film mulch, casting resin, obtain fiber/resin composite, gained composite is left standstill 24h in room temperature, make it solidify completely, the composite of self-healing function must be had.
The preparation of embodiment 6, self-healing composite fibre 6
1) join in the DMF of 20g by 5g polyvinyl chloride (molecular weight is 90000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyvinyl chloride and DMF is the homogeneous solution of 5/20.Take 3g to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether joins in the polyvinyl chloride solution of above-mentioned gained, under normal temperature condition, mechanical agitation is even, obtain polyvinyl chloride and to tert-butyl-phenyl 1-(2,3-epoxy) mixed solution of propyl ether, i.e. obtained electrostatic spinning solution; What wherein add is about 36/60 to the mass ratio of tert-butyl-phenyl 1-(2,3-epoxy) propyl ether and polyvinyl chloride;
By obtained polyvinyl chloride with to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether co-blended spinning solution load device for storing liquid, between spinning syringe needle and receiving system, apply the spinning voltage of 10KV, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 8cm.The flow velocity of telomerized polymer and consolidant blend solution is 3 μ l/min, and spinning syringe needle internal diameter is 0.9mm, and spinning temperature is 18 DEG C, and air humidity is 80%.Polyvinyl chloride/to tert-butyl-phenyl 1-(2 is obtained by electrostatic spinning technique, 3-epoxy) blend composite fiber of propyl ether, and by gained vinyl chloride/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite cellulosic membrane puts into its curing agent (curing agent is TEPA) weak solution, quick taking-up, at room temperature solidify, obtain the surperficial polyvinyl chloride of shell/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite fibre (average diameter is about 0.97 μm) of having.
2) join in the DMF of 20g by 5g polyvinyl chloride (molecular weight is 90000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyvinyl chloride and DMF is the homogeneous solution of 5/20.Taking 1g TEPA joins in the polyvinyl chloride solution of above-mentioned gained, and under normal temperature condition, mechanical agitation is even, obtains the mixed solution of polyvinyl chloride and TEPA, i.e. obtained electrostatic spinning solution; The TEPA wherein added and the mass ratio of polyvinyl chloride are about 12/60.
The co-blended spinning solution of obtained polyvinyl chloride and TEPA is loaded device for storing liquid, applies the spinning voltage of 12KV between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 10cm.The flow velocity of telomerized polymer and consolidant blend solution is 5 μ l/min, and spinning syringe needle internal diameter is 0.9mm, and spinning temperature is 19 DEG C, and air humidity is 70%.Polyvinyl chloride/TEPA composite fibre (average diameter is about 0.93 μm) is obtained by electrostatic spinning technique.
Described surface there is the polyvinyl chloride of shell/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite fibre and described polyvinyl chloride/TEPA composite fibre stack in mould, mould is poured into after the component A of acrylic resin and B component (with the component A in embodiment 1 and B component) being mixed with the mass ratio of 1:1, quick knifing, repeat the process of above-mentioned plastic film mulch, casting resin, obtain fiber/resin composite, gained composite is left standstill 24h in room temperature, make it solidify completely, the composite of self-healing function must be had.
The preparation of embodiment 7, self-healing composite fibre 7
1) join in the DMAc of 20g by 5g polyurethane (molecular weight 60000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyurethane and DMAc is the homogeneous solution of 5/20.The dimethyl silicone polymer (SYLGARD184) taking 3g joins in the polyurethane solutions of above-mentioned gained, under normal temperature condition, mechanical agitation is even, obtain the mixed solution of polyurethane and dimethyl silicone polymer (SYLGARD184), obtain electrostatic spinning solution; The dimethyl silicone polymer (SYLGARD184) wherein added and the mass ratio of polyurethane are about 36/60;
The co-blended spinning solution of obtained polyurethane and dimethyl silicone polymer (SYLGARD184) is loaded device for storing liquid, between spinning syringe needle and receiving system, apply the spinning voltage of 30KV, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 20cm.The flow velocity of telomerized polymer and consolidant blend solution is 0.02ml/min, and spinning syringe needle internal diameter is 0.9mm, and spinning temperature is 28 DEG C, and air humidity is 65%.The blend composite fiber of polyurethane/dimethyl silicone polymer (SYLGARD184) is obtained by electrostatic spinning technique, and gained polyurethane/dimethyl silicone polymer (SYLGARD184) composite cellulosic membrane is put into its curing agent (SYLGARD184Curing agent) weak solution, quick taking-up, at room temperature solidify, obtain surperficial polyurethane/dimethyl silicone polymer (SYLGARD184) composite fibre (average diameter is about 0.98 μm) having shell.
2) join in the DMAc of 20g by 5g polyurethane (molecular weight 60000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyurethane and DMAc is the homogeneous solution of 5/20.Taking 0.3g SYLGARD184Curing agent joins in the polyurethane solutions of above-mentioned gained, and under normal temperature condition, mechanical agitation is even, obtains the mixed solution of polyurethane and SYLGARD184Curing agent, obtains electrostatic spinning solution; The SYLGARD184Curing agent wherein added and the mass ratio of polyurethane are about 3.6/60.
The co-blended spinning solution of obtained polyurethane and SYLGARD184Curing agent is loaded device for storing liquid, applies the spinning voltage of 22KV between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 15cm.The flow velocity of telomerized polymer and consolidant blend solution is 0.02ml/min, and spinning syringe needle internal diameter is 0.9mm, and spinning temperature is 25 DEG C, and air humidity is 70%.Polyurethane/SYLGARD184Curing agent composite fibre (average diameter is about 0.96 μm) is obtained by electrostatic spinning technique.
Polyurethane/dimethyl silicone polymer (SYLGARD184) composite fibre of shell and described polyurethane/SYLGARD184Curing agent composite fibre is had on described surface to stack in mould, mould is poured into after the component A of acrylic resin and B component (with the component A in embodiment 2 and B component) being mixed with the mass ratio of 1:1, quick knifing, repeat above-mentioned plastic film mulch, the process of casting resin, obtain fiber/resin composite, gained composite is left standstill 24h in room temperature, it is made to solidify completely, the composite of self-healing function must be had.
The preparation of embodiment 8, self-healing composite fibre 8
1) join in the DMF of 20g by 5g polyurethane (molecular weight 60000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyurethane and DMF is the homogeneous solution of 5/20.Take 3g to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether joins in the polyurethane solutions of above-mentioned gained, under normal temperature condition, mechanical agitation is even, obtain polyurethane and to tert-butyl-phenyl 1-(2,3-epoxy) mixed solution of propyl ether, i.e. obtained electrostatic spinning solution; What wherein add is about 30/50 to the mass ratio of tert-butyl-phenyl 1-(2,3-epoxy) propyl ether and polyurethane;
By obtained polyurethane with to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether co-blended spinning solution load device for storing liquid, between spinning syringe needle and receiving system, apply the spinning voltage of 20KV, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 13cm.The flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, and spinning syringe needle internal diameter is 0.9mm, and spinning temperature is 19 DEG C, and air humidity is 70%.Polyurethane/to tert-butyl-phenyl 1-(2 is obtained by electrostatic spinning technique, 3-epoxy) composite fibre of propyl ether, and by gained polyurethane/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite cellulosic membrane puts into its curing agent (curing agent is TEPA) weak solution, quick taking-up, at room temperature solidify, obtain the surperficial polyurethane of shell/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite fibre (average diameter is about 0.97 μm) of having.
2) join in the DMF of 20g by 5g polyurethane (molecular weight 60000), mechanical agitation is transparent to solution, thus the mass ratio obtaining polyurethane and DMF is the homogeneous solution of 5/20.The TEPA taking 1g joins in the polyurethane solutions of above-mentioned gained, and under normal temperature condition, mechanical agitation is even, obtains the mixed solution of polyurethane and TEPA, i.e. obtained electrostatic spinning solution; The TEPA wherein added and the mass ratio of polyurethane are about 10/50.
The co-blended spinning solution of obtained polyurethane and TEPA is loaded device for storing liquid, applies the spinning voltage of 15KV between spinning syringe needle and receiving system, the spinning distance controlled between spinning syringe needle and reception aluminium foil is 10cm.The flow velocity of telomerized polymer and consolidant blend solution is 0.01ml/min, and spinning syringe needle internal diameter is 0.9mm, and spinning temperature is 23 DEG C, and air humidity is 60%.Polyurethane/TEPA composite fibre (average diameter is about 0.94 μm) is obtained by electrostatic spinning technique.
Described surface there is the polyurethane of shell/to tert-butyl-phenyl 1-(2,3-epoxy) propyl ether composite fibre and described polyurethane/TEPA composite fibre stack in mould, mould is poured into after the component A of acrylic resin and B component being mixed with the mass ratio of 1:1, quick knifing, repeat the process of above-mentioned plastic film mulch, casting resin, obtain fiber/resin composite, gained composite is left standstill 24h in room temperature, make it solidify completely, the composite of self-healing function must be had.
Embodiment 9,
For the fiber/resin composite prepared in above-described embodiment 1, with blade at the prefabricated micro-crack of composite material surface, the baking oven putting it into 60 DEG C subsequently leaves standstill 48h.
Fig. 4 is the SEM figure after the apparent crack healing of composite.
As seen from the figure, this composite has certain self-healing function, can realize the reparation of micro-crack.
Claims (8)
1. prepare a method for self-healing composite, comprise following:
1) spinnable polymer and liquid consolidant are dissolved in volatile solvent, obtain the blend solution of spinnable polymer and consolidant; The blend solution of described spinnable polymer and consolidant is carried out electrostatic spinning, obtains spinnable polymer/consolidant composite fibre; Make described spinnable polymer/consolidant composite fibre by curing agent weak solution, at room temperature solidify, obtain spinnable polymer/consolidant composite fibre that there is shell on surface;
2) spinnable polymer and described curing agent are dissolved in volatile solvent, obtain the blend solution of spinnable polymer and curing agent; The blend solution of described spinnable polymer and curing agent is carried out electrostatic spinning, obtains spinnable polymer/curing agent composite fibre;
3) spinnable polymer of shell/consolidant composite fibre and described spinnable polymer/curing agent composite fibre is had on described surface to stack formation tunica fibrosa, cast curable resin materials, repeat above-mentioned plastic film mulch, resin-cast process, obtain composite, by gained composite material solidification, obtain described self-healing composite.
2. method according to claim 1, it is characterized in that: described spinnable polymer is of the same race or not similar polymers, that described polymer is Prof. Du Yucang or natural polymer, described polymer is selected from following at least one: polystyrene, polyacrylonitrile, polyurethane, polyvinyl alcohol-poly (propylene carbonate), polyvinyl alcohol, polycaprolactone, lactic acid caprolactone copolymer, poly (glycolide-co-lactide), polylactide, polyethylene glycol, polymethyl methacrylate, polyvinylpyrrolidone, polyaniline, polyether sulfone, PLA, polyethylene glycol oxide, polyvinyl chloride, shitosan, Kynoar, polyimides, polyamide and polypropylene.
3. method according to claim 1 and 2, it is characterized in that: described liquid consolidant is selected from following at least one: bicyclopentadiene, dimethyl silicone polymer, liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid bisphenol AD type epoxy resin, resorcinol type epoxy resin, to tert-butyl-phenyl 1-(2, 3-epoxy) propyl ether, methylol bisphenol A type epoxy resin, liquid glycidyl ester type epoxy resin, glycidol ether, NOA76 glue, α, the many vinylsiloxanes of ω-dichloro, poly-diethoxy silane and cyanoacrylate.
4. the method according to any one of claim 1-3, is characterized in that:
In the blend solution of described spinnable polymer and consolidant, the mass ratio of described consolidant and spinnable polymer is 10/90-64/40;
In the blend solution of described spinnable polymer and consolidant, the quality of described spinnable polymer and solvent is 5/95-5/12;
Described 1) in, the condition of described electrostatic spinning is: spinning voltage is 10-30KV; Spinning receiving range is 8-20cm; The flow velocity of spinning solution is 0.02ml/min-1 μ l/min; Spinning syringe needle internal diameter is 0.39mm-1.5mm; Spinning temperature is 17-28 DEG C; Air humidity is 50%-80%.
5. the method according to any one of claim 1-4, is characterized in that: described surface has the diameter of the spinnable polymer of shell/consolidant composite fibre to be 0.1-3.2 μm.
6. the method according to any one of claim 1-5, is characterized in that: in the blend solution of described spinnable polymer and curing agent, and the mass ratio of described curing agent and spinnable polymer is 3/90-25/40;
In the blend solution of described spinnable polymer and curing agent, the mass ratio of described spinnable polymer and solvent is 5/95-5/12;
Described 2) in, the condition of described electrostatic spinning is: spinning voltage is 10-30KV, and spinning receiving range is 8-20cm, the flow velocity of spinning solution is 0.02ml/min-1 μ l/min, spinning syringe needle internal diameter is 0.39mm-1.5mm, and spinning temperature is 17-28 DEG C, and air humidity is 50%-80%.
7. the method according to any one of claim 1-6, is characterized in that: the diameter of described spinnable polymer/curing agent composite fibre is 0.07-2.6 μm.
8. the self-healing composite that the method according to any one of claim 1-7 prepares.
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