CN106435830A - High strength chitosan complex fiber and preparing method thereof - Google Patents
High strength chitosan complex fiber and preparing method thereof Download PDFInfo
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- CN106435830A CN106435830A CN201510476389.1A CN201510476389A CN106435830A CN 106435830 A CN106435830 A CN 106435830A CN 201510476389 A CN201510476389 A CN 201510476389A CN 106435830 A CN106435830 A CN 106435830A
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Abstract
The invention relates to a high strength chitosan complex fiber which has a mold resistance and is applicable to medical treatment and clothing textile fabric, and a preparing method thereof. The chitosan complex fiber obtained according to the technical scheme has a much higher overall performance than the products obtained through the prior art, has a good spinning property and good stitchability, and can be further prepared into fabrics through a knitting machine or a weaving machine as well as non-woven fabrics through a nonwoven equipment. The adopted oxidized graphene in itself has a good antibiosis effect, and compared with a graphene material, the oxidized graphene has the advantages of being easy to prepare, high in performance, low in cost, good in water dispersibility, good in adsorptive property, capable of easily conducting various kinds of functional modification and the like. Dosage adjustment and chemical modification can maintain superiority of the graphene and at the same time prevent the graphene from inducing biotoxicity so that the research and application of the graphene in the field of biomedical engineering can be broadened. The preparing method of the high strength chitosan complex fiber has the advantages of being simple in producing technology, low in preparing cost; meanwhile, the obtained high strength chitosan complex fiber has a stable performance. Therefore, the preparing method is very suitable for popularization and market expanding of the chitosan fiber and graphene industries.
Description
Technical field
The present invention relates to a kind of preparation of high intensity bio-based fiber, more particularly, to a kind of have anti-microbial property and can be used for medical treatment, textile clothing fabric, the preparation method of the composite fibre of Treatment of Industrial Water, belongs to processing of high molecular material and textile technology field.
Background technology
Shitosan (Chitosan), also known as soluble chitin, is the biopolymer that the chitin being widely present by nature obtains through deacetylation, and chemical name is poly- β-(1 → 4) -2-amino-2-deoxy-D-Glucose.There are active hydroxyl and amino in shitosan macromole, they have stronger chemical reaction ability, various chemical modifications and modification can be carried out to shitosan.Because carrying free amine group in chitosan molecule, solvable in an acidic solution and be in cationic property, the place of exactly its peculiar property, thus establish many biological characteristicses of shitosan and the basis of processing and forming characteristic, obtain extensive concern in the applied research of the numerous areas such as medicine, food, chemical industry, cosmetics, water process, METAL EXTRACTION and recovery, biochemistry and biomedical engineering.
As a kind of macromolecule of solubility, shitosan has certain spinnability, can have the chitin fiber of anti-microbial property by spinning technique preparation.The spinning of shitosan usually first dissolves chitosan in suitable solvent（As acetic acid）In prepare spinning liquid, then be prepared from through a series of technique of wet spinning such as spray webbing, solidification, stretching, washing, drying.Prior art（For example, high, the molding of chitin fiber,《Textile journal》, 2005,26（2）, 41）Show that the fracture strength of the pure chitosan fiber using conventional wet spinning preparation is substantially no more than 2.0cN/dtex, poor compared with other conventional fibers, it is not suitable for shredding, cotton carding, lapping, drafting Deng Hou road spinning process and equipment.Its main cause has：1）Shitosan dissolubility in a solvent is less, and the concentration of spinning solution is restricted, and is unfavorable for the entanglement of macromolecular chain, crosslinked and orientations；2）Due to there is stronger intermolecular hydrogen bonding active force, chitosan solution viscosity is higher, and the vacuum defoamation technique inclined heated plate that prior art adopts is long（More than 24h）And deaeration is not thorough, lead to macromolecule that Partial digestion and fracture occur, microstructure fiber defect is many.
Prior art also proposes a kind of cross-linking agent and nascent chitin fiber is carried out with the method to improve the intensity of chitin fiber for the crosslinking Treatment（For example：i）Xu Dezeng etc.,《The preparation of glutaraldehyde cross-linking shitosan-PVA blended fiber》, Dalian Polytechnic University's journal, 2013,32（3）, 206；ii）Match Feng Dong,《The crosslinked research improving chitin fiber intensity of Biformyl》, Donghua University's master thesis, 2002）But, there is complex process, limited to chitin fiber intensity increase rate, and the cross-linking agent being used（Glutaraldehyde, Biformyl, epichlorohydrin etc.）Or other auxiliary agents have the defects such as the big, poor biocompatibility of toxicity, it is unfavorable for the application in medical treatment ＆ health or beauty treatment fields for the chitin fiber.
Graphene（Graphene）It is the New Two Dimensional carbon structure nano material finding after the fullerene and one-dimensional CNT of zero dimension, its structure is with sp by carbon atom2The carbon hexatomic ring of hybrid orbital composition.Graphene oxide（Graphene
Oxide, abbreviation GO）It is the derivant of Graphene, it is substantially the same with the mechanism of Graphene, but graphene oxide basal plane and edge contain the activity functional groups that hydroxyl and carboxyl etc. are easy to modify, these functional groups give some new characteristics of graphene oxide, such as dispersibility, hydrophilic and polymer compatibility etc..Graphene and graphene oxide have great specific surface area and Young's moduluss, have good tensile ductility simultaneously again, have superpower, ultralight, super tough and tensile advanced composite material (ACM) for exploitation and lay a good foundation.
In recent years research, it is also shown that Graphene and graphene oxide have good anti-microbial property and biocompatibility, is also the ideal carrier of antibacterial substance simultaneously.Graphene can occur very strong dispersion to interact it is thus possible to directly extract the phospholipid molecule on cell membrane on a large scale with the phospholipid molecule on bacterial cell membrane, and antibacterial is killed.And the serum albumin in the blood circulation of the mankind then can form " albumen encasing " with Graphene, thus stoping Graphene from directly hurting human body cell.So, Graphene kills antibacterial by physical action, and the antibiotic for developing new drug resistance provides new thinking, and also the new bio medical dressing for developing with Graphene and graphene oxide as raw material provides theoretical foundation.
Content of the invention
It is an object of the invention to overcoming prior art defect, provide a kind of novel high-strength chitosan composite fiber and preparation method thereof.The composite fibre of the method preparation not only has higher mechanical strength, preferable machinability（Spinnability and stitchability）And anti-microbial property, and maintain the features such as original biocompatibility of chitin fiber, safety.
For realizing the purpose of the present invention, the present invention adopts the following technical scheme that.
A kind of high intensity chitosan composite fiber, it is characterised in that being to prepare by wet spinning in described chitosan composite fiber, contains graphene oxide or Graphene in described chitosan composite fiber.Described graphene oxide is to be incorporated in the spinning solution of wet spinning by the solution mixing by the solution containing graphene oxide and chitosan-containing, and described graphene oxide is by physics electrostatic assembly（Non-covalent binding）Mode or covalent chemical bond are coupled（Covalent bond）Mode and shitosan be combined and be dispersed in described spinning solution.The chitosan composite fiber of described graphene-containing is by the described chitosan composite fiber containing graphene oxide is carried out reduction treatment acquisition.
The present invention also provides a kind of preparation method of high intensity chitosan composite fiber it is characterised in that comprising the steps of.
Step 1：Chitosan solution and poly-vinyl alcohol solution are mixed by a certain percentage, stirs, obtain chitosan/polyvinyl alcohol mixed solution.
Step 2a（Non-covalent binding strategy）：Add graphene oxide solution in the chitosan/polyvinyl alcohol mixed solution of gained in step 1, after agitated, ultrasound wave dispersion and deaeration, obtain spinning solution, insulation is standby.
Step 2b（Covalent bond strategy）：First add coupling agent activation in graphene oxide solution, the more above-mentioned graphene oxide solution activating is added in the chitosan/polyvinyl alcohol mixed solution of gained in step 1, after agitated, ultrasound wave dispersion and deaeration, obtain spinning solution, insulation is standby.
Step 3：The spinning solution being obtained in above-mentioned steps 2a or step 2b is carried out wet spinning, spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre, again through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide, or the chitosan composite fiber further gained being contained graphene oxide carries out reduction treatment, obtain the chitosan composite fiber of graphene-containing.
Further, in step 1, deacetylation >=84% of described shitosan, number-average molecular weight is 1 × 104-1×106.
Further, in step 1, degree of polymerization 400-6000 of described polyvinyl alcohol.
Further, in step 1, the concentration of described chitosan solution is 1%-24%, and the concentration of described poly-vinyl alcohol solution is 0%-20%.
Further, in step 1, in described chitosan/polyvinyl alcohol mixed solution, shitosan is 1 with the mass ratio of polyvinyl alcohol:1-10:1.
Further, in step 1, the solvent of described chitosan solution is the acetum of 0.5%-8%.
Further, in step 2a and step 2b, the concentration of described graphene oxide solution is 1mg/mL-15mg/mL, described graphene oxide single layer content >=90%, and average piece footpath is 0.5-40 m.
Further, in step 2a or step 2b, the weight of the weight of described graphene oxide solution and chitosan/polyvinyl alcohol mixed solution is than for 0.1%-20%；In the range of above-mentioned addition, the content of graphene oxide is higher, and the mechanical performance of gained composite fibre is better, but the factor such as comprehensive product performance, color and luster and cost considers, the preferred 1%-5% of the addition of graphene oxide in the present invention.
Further, in step 2b, described coupling agent is 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate（EDC）And N-hydroxy-succinamide（NHS）, both additions are equimolar ratio.
Further, in step 2b, the addition of described 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate is the 0.01%-1% of graphene oxide solid weight.
Further, in step 2b, described soak time is 0.5h-24h, preferably 3-5h.
Further, in step 2a or step 2b, described holding temperature is 25 C-45 C.
Further, in step 3, described coagulating bath is the sodium hydroxide solution that concentration is 2%-10% and the mixture of the ethanol solution that concentration is 0%-95%, and the mass mixing ratio of sodium hydroxide solution and ethanol solution is 1:1-10:1.
Further, in step 3, the temperature of described coagulating bath is 25 C-45 C.
Further, in step 3, described reduction treatment is to carry out in the solution containing chemical reducing agent, described reducing agent is hydrazine hydrate, sodium borohydride, phenolic compound, aminated compoundss, vitamin C and its one or more of salt, oxalic acid and its salt etc., the concentration of the solution of described reducing agent is 10%-70%, reduction temperature is 25 C-220 C, and the recovery time is 0.5-24h.
Know-why with regard to the present invention is described further below.
Shitosan is a kind of semirigid polycation, and spinnability is poor.In the present invention, a kind of flexible nonionic macromolecule of the polyvinyl alcohol of addition in spinning solution, add the purpose of polyvinyl alcohol to be the viscosity of adjustment spinning liquid, increase spinnability, and intensity and the elasticity of chitin fiber can be improved.The present invention is during preparing shitosan spinning solution, the viscosity of spinning liquid can also be adjusted by adding some carbamide, glycerol, surfactant, electrolyte etc. further, improve the technological means well known in the art such as the spinnability of shitosan, but this is not the core technology content of the present invention.
In step 2a in the present invention, using the negatively charged feature of surface of graphene oxide carboxyl, can be with positively charged chitosan molecule in the way of electrostatic assembly（Non-covalent binding）Form ion complex, thus graphene oxide is uniformly dispersed stably in system.As nanometer reinforcing filler, be stretched in spinning process these homodisperse graphene oxides orientation, and then significantly improves the mechanical strength of chitin fiber.
In step 2b in the present invention, it is easy to adorned feature using surface of graphene oxide gained carboxyl, after adding coupling agent activation, can react with the amino in chitosan molecule chain, form firm covalent bond, further increase heat stability and the intensity of fiber.
Additionally, in step 2b in the present invention, coupling agent 1- ethyl used in the step of the carboxyl of active oxidation Graphene-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate（EDC）And N-hydroxy-succinamide（NHS）It is water soluble compound, safety non-toxic, activation condition is gentle, and coupling agent changes into by product after activation and also has water solublity, it is easy to be cleaned in wet spinning technology, and the graphene oxide after activation need not refined in advance, process is simple.
Due to multiple carboxyls may be contained in each graphene oxide layer, be equivalent to the cross-linking agent with function groups, spinning solution can partly play the effect of cross-linked chitosan strand, increase chemical stability and the mechanical strength of fiber.
In addition although shitosan has antibacterial action in itself, but the antibacterial bacteriostatic effect of shitosan is weaker.The introducing of graphene oxide, can produce synergetic antibacterial effect with shitosan, improve the anti-microbial property of composite.
Quickly and effectively graphene oxide not only can be uniformly dispersed in system using ultrasound wave in the present invention, more importantly ultrasound wave can be with rapidly defoaming while dispersed material, avoid conventional using vacuum standing and defoaming or stirring deaeration technique time-consuming and lead to the chain rupture in acid condition of shitosan macromolecular chain and degraded, in spinning process, dope viscosity is unstable, and this is also the key obtaining Chitosan Fiber With High Tenacity.
In the step 3 that the present invention adopts, the chitosan composite fiber that gained contains graphene oxide is carried out by reduction treatment by the method for electronation, obtain the chitosan composite fiber of graphene-containing, and give chitin fiber conduction and heat conductivility.
The invention has the beneficial effects as follows.
（1）The chitosan composite fiber being obtained using technical scheme provided by the present invention, its combination property is significantly larger than the product that prior art obtains.After introducing graphene oxide by the way of Non-covalent binding, the dry fracture strength of chitin fiber reaches 8cN/dtex；And after adopting covalently bound mode to introduce graphene oxide, the dry fracture strength of chitin fiber reaches as high as 12cN/dtex.The good spinnability of prepared chitosan composite fiber and stitchability are good, can cause fabric by knitting machine or woven mechanism further or make non-woven fabrics by Nonwoven Equipment.
（2）The graphene oxide adopting in technical scheme has antibacterial effect in itself, and with respect to grapheme material, has the advantages that easy preparation, function admirable, low cost, water dispersible is good, absorption property is good, easily carry out various functions modifies.Adjusted by dosage and chemical modification, the superiority of Graphene can be kept, avoid it to induce bio-toxicity simultaneously again, expand it in the research of biomedical engineering field and application.
（3）The preparation method of chitin fiber that the present invention provides has simple production process, and manufacturing cost is relatively low, the stable advantage of properties of product, is especially suitable for popularization and the market expansion of chitin fiber and Graphene industry.
Specific embodiment
With reference to specific embodiment, technical scheme is elaborated.
Embodiment 1.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Shitosan is put into acetum, stirring and dissolving uniformly, is configured to 4%（Mass concentration）Chitosan solution.
Wherein：The molecular weight of raw materials of chitosan is 1 × 106, deacetylation is 90%；Acetum concentration is 2%；
Add the graphene oxide solution that concentration is 5mg/mL in above-mentioned chitosan solution, after ultrasound wave dispersion and deaeration, obtain spinning solution.
Wherein：The addition of graphene oxide solution is the 1% of chitosan solution quality, graphene oxide single layer content >=90%, and piece footpath is 40 m.
Above-mentioned spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre under insulation 40 C, then through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide.
Wherein：Used in wet spinning process coagulating bath be 5% sodium hydroxide solution and 80% ethanol solution with 10:The mixture of 1 mixing, coagulation bath temperature 40 C；Draw ratio 120%.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 6.8cN/dtex, and wet breaking strength is 6.6 cN/dtex, and dry elongation at break is 14.5%.
Embodiment 2.
A kind of high intensity chitosan composite fiber and preparation method thereof.
By the chitosan composite fiber containing graphene oxide obtained in embodiment 1 containing in 50% hydrazine hydrate and 20% ascorbic mixed solution, 100 C backflow 0.5h, replace washing with hydrate alcohol again and go the removal of impurity, after being dried, obtain the chitosan composite fiber of graphene-containing.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 5.9 cN/dtex, and wet breaking strength is 5.6 cN/dtex, and dry elongation at break is 12.0%, electrical conductivity of fibres 3.7Scm-1.
Embodiment 3.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Shitosan is put into acetum, stirring and dissolving uniformly, is configured to 8%（Mass concentration）Chitosan solution.By polyvinyl alcohol（PVA）Put in water, stirring and dissolving uniformly, is configured to 10% poly-vinyl alcohol solution.Chitosan solution is mixed by the ratio according to final shitosan and polyvinyl alcohol mass ratio 31 with poly-vinyl alcohol solution, stirs, and obtains chitosan/polyvinyl alcohol mixed solution.
Wherein：The molecular weight of raw materials of chitosan is 1 × 106, deacetylation is 84%；The degree of polymerization of polyvinyl alcohol is 2000；Acetum concentration is 4%.
To concentration for adding the EDC and NHS with EDC equimolar amountss to carry out activating 24h in the graphene oxide solution of 10mg/mL, again the above-mentioned graphene oxide solution activating is added in the chitosan/polyvinyl alcohol mixed solution of abovementioned steps gained, after the dispersion of agitated, ultrasound wave and deaeration, obtain spinning solution.
Wherein：The addition of graphene oxide solution is the 0.1% of chitosan solution quality；Graphene oxide single layer content >=90%, piece footpath is 0.5 m；The addition of EDC is with respect to graphene oxide solid weight 0.1%.
Above-mentioned spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre under insulation 40 C, then through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide.
Wherein：Used in wet spinning process coagulating bath be 10% sodium hydroxide solution and 95% ethanol solution with 1:The mixture of 1 mixing, coagulation bath temperature 40 C；Draw ratio 120%.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 9.5 cN/dtex, and wet breaking strength is 8.6 cN/dtex, and dry elongation at break is 18.8%.
Embodiment 4.
A kind of high intensity chitosan composite fiber and preparation method thereof.
By the chitosan composite fiber containing graphene oxide obtained in embodiment 3 containing in 10% sodium borohydride solution, 50 C process 25h, then with hydrate alcohol, alternately the removal of impurity is gone in washing, obtains the chitosan composite fiber of graphene-containing after being dried.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 8.7 cN/dtex, and wet breaking strength is 8.6 cN/dtex, and dry elongation at break is 15.8%, electrical conductivity of fibres 4.3Scm-1.
Embodiment 5.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Shitosan is put into acetum, stirring and dissolving uniformly, is configured to 1%（Mass concentration）Chitosan solution.By polyvinyl alcohol（PVA）Put in water, stirring and dissolving uniformly, is configured to 20% poly-vinyl alcohol solution.Chitosan solution is mixed by the ratio according to final shitosan and polyvinyl alcohol mass ratio 10 1 with poly-vinyl alcohol solution, stirs, and obtains chitosan/polyvinyl alcohol mixed solution.
Wherein：The molecular weight of raw materials of chitosan is 1 × 106, deacetylation is 84%；The degree of polymerization of polyvinyl alcohol is 400；Acetum concentration is 0.5%.
To concentration for adding the EDC and NHS with EDC equimolar amountss to carry out activating 3h in the graphene oxide solution of 1mg/mL, again the above-mentioned graphene oxide solution activating is added in the chitosan/polyvinyl alcohol mixed solution of abovementioned steps gained, after the dispersion of agitated, ultrasound wave and deaeration, obtain spinning solution.
Wherein：The addition of graphene oxide solution is 20 % of chitosan solution quality；Graphene oxide single layer content >=90%, piece footpath is 0.5 m；The addition of EDC is with respect to graphene oxide solid weight 1%.
Above-mentioned spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre under insulation 40 C, then through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide.
Wherein：Used in wet spinning process coagulating bath be 2% sodium hydroxide solution and 95% ethanol solution with 10:The mixture of 1 mixing, coagulation bath temperature 40 C；Draw ratio 150%.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 4.4 cN/dtex, and wet breaking strength is 3.9 cN/dtex, and dry elongation at break is 21.5%.
Embodiment 6.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Shitosan is put into acetum, stirring and dissolving uniformly, is configured to 10%（Mass concentration）Chitosan solution.By polyvinyl alcohol（PVA）Put in water, stirring and dissolving uniformly, is configured to 10% poly-vinyl alcohol solution.Chitosan solution is mixed by the ratio according to final shitosan and polyvinyl alcohol mass ratio 32 with poly-vinyl alcohol solution, stirs, and obtains chitosan/polyvinyl alcohol mixed solution.
Wherein：The molecular weight of raw materials of chitosan is 1 × 106, deacetylation is 84%；The degree of polymerization of polyvinyl alcohol is 1000；Acetum concentration is 5%.
To concentration for adding the EDC and NHS with EDC equimolar amountss to carry out activating 24h in the graphene oxide solution of 1mg/mL, again the above-mentioned graphene oxide solution activating is added in the chitosan/polyvinyl alcohol mixed solution of abovementioned steps gained, after the dispersion of agitated, ultrasound wave and deaeration, obtain spinning solution.
Wherein：The addition of graphene oxide solution is 5 % of chitosan solution quality；Graphene oxide single layer content >=90%, piece footpath is 40 m；The addition of EDC is with respect to graphene oxide solid weight 0.2%.
Above-mentioned spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre under insulation 45 C, then through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide.
Wherein：Used in wet spinning process, coagulating bath is 6% sodium hydroxide solution, coagulation bath temperature 45 C；Draw ratio 135%.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 10.7 cN/dtex, and wet breaking strength is 10.4 cN/dtex, and dry elongation at break is 18.6%.
Embodiment 7.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Shitosan is put into acetum, stirring and dissolving uniformly, is configured to 8%（Mass concentration）Chitosan solution.By polyvinyl alcohol（PVA）Put in water, 60 C stirring and dissolving uniformly, are configured to 2% poly-vinyl alcohol solution.Chitosan solution is mixed by the ratio according to final shitosan and polyvinyl alcohol mass ratio 11 with poly-vinyl alcohol solution, stirs, and obtains chitosan/polyvinyl alcohol mixed solution.
Wherein：The molecular weight of raw materials of chitosan is 1 × 106, deacetylation is 84%；The degree of polymerization of polyvinyl alcohol is 6000；Acetum concentration is 3%.
To concentration for adding the EDC and NHS with EDC equimolar amountss to carry out activating 5h in the graphene oxide solution of 3mg/mL, again the above-mentioned graphene oxide solution activating is added in the chitosan/polyvinyl alcohol mixed solution of abovementioned steps gained, after the dispersion of agitated, ultrasound wave and deaeration, obtain spinning solution.
Wherein：The addition of graphene oxide solution is 3 % of chitosan solution quality；Graphene oxide single layer content >=90%, piece footpath is 4 m；The addition of EDC is with respect to graphene oxide solid weight 1%.
Above-mentioned spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre under insulation 25 C, then through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide.
Wherein：Used in wet spinning process coagulating bath be 6% sodium hydroxide solution and 95% ethanol solution with 10:The mixture of 1 mixing, coagulation bath temperature 25 C；Draw ratio 120%.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 12.5 cN/dtex, and wet breaking strength is 11.9 cN/dtex, and dry elongation at break is 18.7%.
Embodiment 8.
A kind of high intensity chitosan composite fiber and preparation method thereof.
By the chitosan composite fiber containing graphene oxide obtained in embodiment 7 containing in 40% hydriodic acid aqueous solution, under 95 C, heat 4h, then replace washing with hydrate alcohol and go the removal of impurity, after being dried, obtain the chitosan composite fiber of graphene-containing.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 10.9 cN/dtex, and wet breaking strength is 10.5 cN/dtex, and dry elongation at break is 15.0%, electrical conductivity of fibres 3.3Scm-1.
Embodiment 9.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Shitosan is put into acetum, stirring and dissolving uniformly, is configured to 10%（Mass concentration）Chitosan solution.By polyvinyl alcohol（PVA）Put in water, stirring and dissolving uniformly, is configured to 4% poly-vinyl alcohol solution.Chitosan solution is mixed by the ratio according to final shitosan and polyvinyl alcohol mass ratio 51 with poly-vinyl alcohol solution, stirs, and obtains chitosan/polyvinyl alcohol mixed solution.
Wherein：The molecular weight of raw materials of chitosan is 1 × 105, deacetylation is 84%；The degree of polymerization of polyvinyl alcohol is 2500, and alcoholysis degree is 88%；Acetum concentration is 4%.
To concentration for adding the EDC and NHS with EDC equimolar amountss to carry out activating 0.5h in the graphene oxide solution of 10mg/mL, again the above-mentioned graphene oxide solution activating is added in the chitosan/polyvinyl alcohol mixed solution of abovementioned steps gained, after the dispersion of agitated, ultrasound wave and deaeration, obtain spinning solution.
Wherein：The addition of graphene oxide solution is 20 % of chitosan solution quality；Graphene oxide single layer content >=90%, piece footpath is 4 m；The addition of EDC is with respect to graphene oxide solid weight 1%.
Above-mentioned spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre under insulation 45 C, then through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide.
Wherein：Used in wet spinning process coagulating bath be 10% sodium hydroxide solution and 10% ethanol solution with 1:The mixture of 1 mixing, coagulation bath temperature 45 C；Draw ratio 150%.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 8.9 cN/dtex, and wet breaking strength is 8.5 cN/dtex, and dry elongation at break is 22.1%.
Embodiment 10.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Chitosan composite fiber containing graphene oxide obtained in embodiment 9 is heated reduction treatment 1h in 220 C nitrogen protection atmospheres, obtains the chitosan composite fiber of graphene-containing.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 4.3 cN/dtex, and wet breaking strength is 4.0 cN/dtex, and dry elongation at break is 14.6%, electrical conductivity of fibres 2.5 Scm-1.
Embodiment 11.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Shitosan is put into acetum, stirring and dissolving uniformly, is configured to 6%（Mass concentration）Chitosan solution.By polyvinyl alcohol（PVA）Put in water, stirring and dissolving uniformly, is configured to 4% poly-vinyl alcohol solution.Chitosan solution is mixed by the ratio according to final shitosan and polyvinyl alcohol mass ratio 11 with poly-vinyl alcohol solution, stirs, and obtains chitosan/polyvinyl alcohol mixed solution.
Wherein：The molecular weight of raw materials of chitosan is 1 × 106, deacetylation is 84%；The degree of polymerization of polyvinyl alcohol is 1700；Acetum concentration is 2%.
Add the graphene oxide solution that concentration is 5mg/mL in above-mentioned chitosan solution, after ultrasound wave dispersion and deaeration, obtain spinning solution.
Wherein：The addition of graphene oxide solution is the 1% of chitosan solution quality, graphene oxide single layer content >=90%, and piece footpath is 40 m.
Above-mentioned spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre under insulation 40 C, then through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide.
Wherein：Used in wet spinning process coagulating bath be 8% sodium hydroxide solution and 95% ethanol solution with 3:The mixture of 1 mixing, coagulation bath temperature 40 C；Draw ratio 120%.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 5.3 cN/dtex, and wet breaking strength is 4.9 cN/dtex, and dry elongation at break is 16.7%.
Embodiment 12.
A kind of high intensity chitosan composite fiber and preparation method thereof.
Shitosan is put into acetum, stirring and dissolving uniformly, is configured to 9%（Mass concentration）Chitosan solution.By polyvinyl alcohol（PVA）Put in water, stirring and dissolving uniformly, is configured to 1% poly-vinyl alcohol solution.Chitosan solution is mixed by the ratio according to final shitosan and polyvinyl alcohol mass ratio 11 with poly-vinyl alcohol solution, stirs, and obtains chitosan/polyvinyl alcohol mixed solution.
Wherein：The molecular weight of raw materials of chitosan is 1 × 106, deacetylation is 90%；The degree of polymerization of polyvinyl alcohol is 2500, and alcoholysis degree is 99%；Acetum concentration is 4%.
Add the graphene oxide solution that concentration is 15mg/mL in above-mentioned chitosan solution, after ultrasound wave dispersion and deaeration, obtain spinning solution.
Wherein：The addition of graphene oxide solution is the 0.1% of chitosan solution quality, graphene oxide single layer content >=90%, and piece footpath is 40 m.
Above-mentioned spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre under insulation 40 C, then through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide.
Wherein：Used in wet spinning process coagulating bath be 12% sodium hydroxide solution and 95% ethanol solution with 1:The mixture of 1 mixing, coagulation bath temperature 40 C；Draw ratio 120%.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 6.5 cN/dtex, and wet breaking strength is 6.0 cN/dtex, and dry elongation at break is 13.2%.
Embodiment 13.
A kind of high intensity chitosan composite fiber and preparation method thereof.
By the chitosan composite fiber containing graphene oxide obtained in embodiment 12 containing in 80% hydrazine hydrate solution, under 90 C, heat 4h, then replace washing with hydrate alcohol and go the removal of impurity, after being dried, obtain the chitosan composite fiber of graphene-containing.
Under above-mentioned condition, the dry fracture strength of the chitin fiber that wet spinning obtains is 5.9 cN/dtex, and wet breaking strength is 5.7 cN/dtex, and dry elongation at break is 13.0%, electrical conductivity of fibres 2.1Scm-1.
Aforesaid embodiment is only the part preferred embodiment of the present invention, and not all embodiments.Various raw materials cited by the present invention, and the bound of each raw material, interval value and technological parameter（As temperature, time etc.）Bound, interval value can realize the present invention.
Based on the embodiment in the present invention, those of ordinary skill in the art under the premise of not making creative work, various increase, change and other embodiments that equivalent replacement is obtained, broadly fall into the scope of protection of the invention.Therefore, embodiment disclosed in the present specification should be considered the present invention is described, and is not used to limit the present invention.The scope of the present invention should be defined the description however it is not limited to previous by the scope that claims claim.
Claims (10)
1. it is characterised in that described chitosan composite fiber is the chitosan composite fiber containing graphene oxide or the chitosan composite fiber containing Graphene, described chitosan composite fiber is to be prepared by wet spinning to a kind of high intensity chitosan composite fiber.
2. a kind of high intensity chitosan composite fiber according to claim 1, it is characterized in that described graphene oxide is to be incorporated in the spinning solution of wet spinning by the solution mixing by the solution containing graphene oxide and chitosan-containing, described graphene oxide is by physics electrostatic assembly（Non-covalent binding）Mode or covalent chemical bond are coupled（Covalent bond）Mode and shitosan be combined and be dispersed in described spinning solution, the described chitin fiber containing Graphene is to form the reduction of the chitin fiber containing graphene oxide.
3. it is characterised in that described graphene oxide single layer content >=90%, average piece footpath is 0.5-40 m to high intensity chitosan composite fiber according to claim 2.
4. a kind of preparation method of high intensity chitosan composite fiber according to claim 3 is it is characterised in that comprise the steps of：
Step 1：Chitosan solution and poly-vinyl alcohol solution are mixed by a certain percentage, stirs, obtain chitosan/polyvinyl alcohol mixed solution；
Step 2a（Non-covalent binding strategy）：Add graphene oxide solution in the chitosan/polyvinyl alcohol mixed solution of gained in step 1, after agitated, ultrasound wave dispersion and deaeration, obtain spinning solution, insulation is standby；
Step 2b（Covalent bond strategy）：First add coupling agent activation in graphene oxide solution, the more above-mentioned graphene oxide solution activating is added in the chitosan/polyvinyl alcohol mixed solution of gained in step 1, after agitated, ultrasound wave dispersion and deaeration, obtain spinning solution, insulation is standby；
Step 3：The spinning solution being obtained in above-mentioned steps 2a or step 2b is carried out wet spinning, spinning solution is squeezed in coagulating bath through spinneret orifice and makes as-spun fibre, again through drawing-off, wash, be dried to obtain chitosan composite fiber containing graphene oxide, or the chitosan composite fiber further gained being contained graphene oxide carries out reduction treatment, obtain the chitosan composite fiber of graphene-containing.
5. it is characterised in that deacetylation >=84% of described shitosan, number-average molecular weight is 1 × 10 to a kind of preparation method of high intensity chitosan composite fiber according to claim 44-1×106, degree of polymerization 400-6000 of described polyvinyl alcohol.
6. the preparation method of a kind of high intensity chitosan composite fiber according to claim 5, it is characterized in that the concentration of the chitosan solution described in step 1 is 1%-24%, the concentration of described poly-vinyl alcohol solution is 0%-20%, in described chitosan/polyvinyl alcohol mixed solution, shitosan is 1 with the mass ratio of polyvinyl alcohol:1-10:1, the solvent of described chitosan solution is the acetum of 0.5%-8%.
7. the preparation method of a kind of high intensity chitosan composite fiber according to claim 6, it is characterized in that the graphene oxide solution described in step 2a and step 2b is 1mg/mL-15mg/mL for concentration, than for 0.1%-20%, described holding temperature is 25 C-45 C to the weight of the weight of described graphene oxide solution and chitosan/polyvinyl alcohol mixed solution.
8. a kind of preparation method of high intensity chitosan composite fiber according to claim 7 is it is characterised in that the coupling agent described in step 2b is 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate（EDC）And N-hydroxy-succinamide（NHS）, both additions are equimolar ratio, and the addition of described EDC is the 0.01%-1% of graphene oxide solid weight, and described soak time is 0.5h-24h.
9. the preparation method of a kind of high intensity chitosan composite fiber according to claim 8, it is characterized in that the coagulating bath described in step 3 is concentration be the sodium hydroxide solution of 2%-10% and ethanol solution that concentration is 0%-95% mixture, the mass mixing ratio of sodium hydroxide solution and ethanol solution is 1:1-10:1；The temperature of described coagulating bath is 25 C-45 C.
10. the preparation method of a kind of high intensity chitosan composite fiber according to claim 9, it is characterized in that the reduction treatment described in step 3 is to carry out in the solution containing chemical reducing agent, described reducing agent is hydrazine hydrate, sodium borohydride, phenolic compound, aminated compoundss, vitamin C and its one or more of salt, oxalic acid and its salt etc., the concentration of the solution of described reducing agent is 10%-70%, reduction temperature is 25 C-220 C, and the recovery time is 0.5-24h.
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