CN102605555B - Preparation method of modified cellulose/polylactic-acid nanometer fiber composite film used for heavy-metal ions to adsorb - Google Patents
Preparation method of modified cellulose/polylactic-acid nanometer fiber composite film used for heavy-metal ions to adsorb Download PDFInfo
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Abstract
The invention discloses a preparation method of a modified cellulose/polylactic-acid nanometer fiber composite film used for heavy-metal ions to adsorb, which is characterized by including: mixing thermoplastic carboxymethyl cellulose and polylactic acid to obtain mixture according to the weight proportion of 10-90:90-10, adding 10-100 parts of the mixture into 100-500 parts of organic solvent, stirring and dissolving for 0.5-2 hours, shaking ultrasonically for 0.2-1 hour to obtain mixed solution, adding the mixed solution into an electrostatic spinning device, collecting after electrostatic spinning, drying 0.2-2.0 hours at the temperature of 20-45 DEG C to obtain a finished nanometer fiber composite film. The preparation method of the modified cellulose/polylactic-acid nanometer fiber composite film used for heavy-metal ions to adsorb is simple, fast, high in efficiency, low in cost, environment-friendly and the like, and the prepared nanometer fiber composite film can be used in the fields of heavy-metal ions and radionuclide adsorption, separation and recovery and waste treatment, is degradable completely after being used and environment-friendly.
Description
Technical field
The invention belongs to the method that thermoplastic cellulose derivative and degraded macromolecular compound prepare nano-fiber composite film, relate to a kind of for heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method.The nano-fiber composite film that the present invention obtains is specially adapted to the adsorption and enrichment separation of heavy metal ion and the field such as the purified treatment of heavy metal wastewater thereby and the recovery of radionuclide adsorbing separation.
Background technology
Cellulose is a kind of natural reproducible resource, because it has the advantages such as aboundresources, renewable, degradable, is thus widely used in environmental protection, chemical industry, packaging, food and medicine and other fields.The application of degradable cellulose modified material, alternative part synthesized polymer material, greatly reduces the utilization of petroleum resources, alleviates current synthesized polymer material and applies the petroleum resources shortage and problem of environmental pollution that cause.Therefore, develop cellulose renewable resource, for saving petroleum resources, preserve the ecological environment, to realize sustainable development etc. significant.Thermoplasticity carboxymethyl cellulose a kind of degradable that to be cellulose obtained by esterification, etherificate, grafting, copolymerization and modification, by force hydrophobic, can thermoplastic, can the material of electrostatic spinning, its development and utilization is that cellulose resource utilizes and petrochemical industry plastics substitute products open new approach.
PLA is a kind of with the artificial semisynthetic environment-friendly polymers of lactic raw material, has nontoxic, nonirritant, has good biocompatibility and biodegradability, intensity is high, plasticity is good, easy machine-shaping, thus the field such as extensive use packaging, medicine, environmental protection.The cellulosic-based material of thermoplastic modification and PLA are carried out blended, electrostatic spinning technique means are adopted to prepare nano-fiber composite film, greatly can improve mechanical strength and the chemical stability of cellulosic-based material, and apply to heavy metal wastewater thereby and treatment of Organic Wastewater.
In recent years along with industrial production and Level of Urban Modernization development, mining, ore dressing, smelt, plating, chemical industry, developing rapidly of the industry such as process hides and papermaking, it is leaded that these industries produce, mercury, cadmium, chromium, nickel, copper, after the waste water of the heavy metals such as zinc enters natural water body, not only aquatile is constituted a threat to, and can by precipitation, absorption and food chain and constantly enrichment, destroy ecological environment, and finally jeopardize the health of the mankind, this has caused worldwide extensive concern, heavy metal ion in effective removal waste water has become current very urgent task.The improvement of heavy metal waste water comprises conventional method and new technology.Wherein, more traditional method has chemical precipitation method, electrochemical process, absorption method and membrane separation process etc.New technology has nanometer technology, photocatalytic method, New Type of Mesoporous material and genetic engineering etc.Therefore, research and develop efficient, with low cost, easy regeneration, degradable heavy metal containing wastewater treatment material is current environment friendly materials and one of the focus of environmental improvement research.
Summary of the invention
Object of the present invention is intended to overcome deficiency of the prior art, provides a kind of for heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method; The nano-fiber composite film that the present invention obtains also is applied to heavy metal containing wastewater treatment, is the Application and Development of the large-scale developing and utilizing of renewable cellulose resource, novel nano fiber composite membrane material, solves heavy metal wastewater thereby and provides effective way.
Content of the present invention is: for heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, it is characterized in that comprising the following steps:
Prepared by a, co-blended spinning solution: the ratio taken amount of thermoplasticity carboxymethyl cellulose (i.e. modified cellulose) and PLA 10 ~ 90:90 ~ 10 is by weight mixed into compound, getting this compound 10 ~ 100 weight portion again joins in 100 ~ 500 weight parts organic solvent, stirring and dissolving is after 0.5 ~ 2 hour, ultrasonic vibration (adopts ultrasonic vibration device in 0.2 ~ 1 hour again, to remove bubble etc.), make blend solution (in blend solution, the weight percent concentration of compound is 2% ~ 20% preferably);
B, electrostatic spinning: joined by blend solution in electrostatic spinning apparatus, after electrostatic spinning, receive and namely obtain nano-fiber composite film; The same prior art of processing step method of this electrostatic spinning;
C, drying: by thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane of obtaining at temperature 20 ~ 45 DEG C dry 0.2 ~ 2.0 hour, i.e. obtained nano-fiber composite film finished material; This nano-fiber composite film finished product can be the nano-fiber composite film of diameter 50nm ~ 5000nm, film thickness 10 μm ~ 50 μm.
In content of the present invention: described step b electrostatic spinning can entirety replace with: joined by blend solution in electrostatic spinning apparatus, under the condition of voltage 8 ~ 24kv, syringe pump flow velocity 0.2 ~ 1.5mL/h, receiving range 8 ~ 25cm, namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane through electrostatic spinning, reception.
In content of the present invention: electrostatic spinning apparatus described in step b comprises high voltage source, spinning syringe needle, spinning solution feedway and fiber collecting device; Control high-voltage power voltage is 8 ~ 24kv, spinning environment temperature is 0 ~ 50 DEG C, and start device for spinning and carry out electrostatic spinning, fiber collecting device collects fiber, dry, i.e. obtained nano-fiber composite film.
In content of the present invention: the spinning solution feedway in described electrostatic spinning apparatus includes syringe pump and syringe, fiber collecting device is receiving screen; Electrostatic spinning described in step b is: the blend solution that step a is obtained is drawn in syringe, be fixedly installed, the flow of the spinning solution that control spinning voltage is 8 ~ 24kv, distance between receiving screen and the spinning nozzle of syringe needle is 8 ~ 25cm, syringe needle flows out is 0.2mL/h ~ 1.5mL/h, spinning environment temperature is 0 ~ 50 DEG C, start device for spinning and carry out electrostatic spinning, fiber collected by acceptance screen, drying again, i.e. obtained nano-fiber composite film.
In content of the present invention: the thermoplasticity carboxymethyl cellulose (i.e. modified cellulose) described in step a is that sodium carboxymethylcellulose is obtained by methyl acrylate graft modification; Specifically, described thermoplasticity carboxymethyl cellulose is that name is called " a kind of preparation method of eco-friendly modified carboxymethyl cellulose thermoplastic material ", Chinese Patent Application No. is 201010177361.5, publication number is " modified carboxymethyl cellulose thermoplastic material " recorded in the description of CN101831033A; The percent grafting of described thermoplasticity carboxymethyl cellulose can be 100% ~ 300%, and glass transition temperature can be 16.00 DEG C ~ 25.00 DEG C, and weight average molecular weight can be 3.5 × 10
5~ 7.0 × 10
5.
In content of the present invention: the PLA described in step a can be PDLLA, poly (l-lactic acid), PDLLA copolymer or poly (l-lactic acid) copolymer, the weight average molecular weight of described PLA can be 5.4 × 10
4~ 12.0 × 10
4.
In content of the present invention: the organic solvent described in step a can be one or more the mixture in oxolane, carrene, hexafluoroisopropanol, chloroform.
Compared with prior art, the present invention has features and beneficial effect:
(1) the present invention is adopted, have the thermoplastic cellulose of spinnability, by preparing nano-fiber composite film with polylactic acid blend spinning, this nano-fiber composite film can be used for wastewater treatment, the aspects such as film infiltration, material packaging, provide new application approach for carboxymethyl cellulose develops;
The nano-fiber composite film that the present invention obtains is to Cu
2+, Pb
2+, Zn
2+, Cd
2+, Cr
3+etc. heavy metal ion, there is certain absorption or crown_interception, effectively can process heavy metal wastewater thereby, reach the effect purified water.Nano combined membrane material is to Cu in solution
2+removing effect experimental: compound concentration is the copper nitrate solution of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 100mg/L, the wastewater membrane process experimental rig (as shown in Figure 7) oneself built is adopted to carry out film experiment, get the filtered fluid of different affecting factors, measure its concentration, calculate its clearance;
Nano-fiber composite film can remove the copper ion in copper ion solution to a certain extent, and its clearance reaches as high as 13.77%; Clearance is by the impact of initial concentration, and when initial concentration is 40mg/L, clearance is the highest; Along with the increase in processing time, the increase of access times, the clearance of film to solution reduces gradually, and the result of use of film weakens gradually;
This nano-fiber composite film material preparation method is simple, cost is low, the feature of environmental protection etc., the composite film material of preparation has good adsorption capacity to heavy metal ion such as Cu2+, Pb2+, can degradable and environmental friendliness after composite film material uses, the adsorbing separation and wastewater treatment that contain heavy metal in the fields such as chemical industry, food, medicine, agricultural and environmental protection can be widely used in;
(2) the present invention selects the good PLA of spinnability, by PLA and thermoplasticity carboxymethyl cellulose co-blended spinning, effectively can improve the performance of co-blended spinning composite membrane, processing machinery intensity is good, the nano-fiber composite film material of stable chemical nature, expand its range of application; Adopt abundant, cheap cellulose renewable resource, the physicochemical properties such as cellulosic thermoplasticity, hydrophobicity are changed by chemical modification technique, change the spinnability of cellulose in organic solution, by, stable chemical nature good with polylactic acid blend spinning processing machinery intensity, the fields such as environmental protection, medicine, chemical industry, food and agricultural can be widely used in, can degradable and eco-friendly nano-fiber composite film material after using;
(3) adopt the present invention, the thickness of the nano-fiber composite film of preparation has controllability, can control by controlling spinning solution concentration, spinning syringe needle and spinning technique;
(4) thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane that prepared by the present invention has good biological degradability, and there is good mechanical property, heat endurance, in addition low cost of manufacture, thus can be widely used in the aspects such as biological function tissue scaffold material, wastewater treatment, biomembrane, wound clad material, be applicable to large-scale production;
(5) the present invention adopts abundant, cheap cellulose renewable resource, the physicochemical properties such as cellulosic thermoplasticity, hydrophobicity are changed by chemical modification technique, change the spinnability of cellulose in organic solution, by, stable chemical nature good with polylactic acid blend spinning processing machinery intensity, the fields such as environmental protection, medicine, chemical industry, food and agricultural can be widely used in, can degradable and eco-friendly nano-fiber composite film material after using; To solution heavy metal wastewater thereby problem of environmental pollution, reduce production and the processing cost of wastewater treatment material, cellulose higher value application etc. has economic benefits and social effect significantly.
(6) adopt the present invention, technique is simple, and raw material are cheap and easy to get, processing ease, consuming time less, have good economic benefit, and environmentally friendly, and cost is low, practical.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention electrostatic spinning experimental provision structural representation;
In Fig. 1: 1-high voltage source, 2-syringe pump, 3-syringe, 4-syringe needle, 5-receiving screen;
Fig. 2 is the scanning electron microscope (SEM) photograph of the nano-fiber composite film of the embodiment of the present invention 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of the nano-fiber composite film of the embodiment of the present invention 2;
Fig. 4 is the scanning electron microscope (SEM) photograph of the nano-fiber composite film of the embodiment of the present invention 3;
Fig. 5 is the scanning electron microscope (SEM) photograph of the nano-fiber composite film of the embodiment of the present invention 4;
Fig. 6 is the pattern digital photograph figure of the nano-fiber composite film of the embodiment of the present invention 2;
Fig. 7 is the blend film process copper ion waste water experimental provision schematic diagram that example 2 of the present invention obtains;
In Fig. 7: 1-heavy metal wastewater thereby, 2-peristaltic pump, 3-speed regulator, 4-molecular filter, 5-nano-fiber composite film, 6-receiving vessel;
Fig. 8 is the obtained blend film process copper ion waste water of example of the present invention 2: initial concentration on the impact of removal effect (along with the raising of heavy metal wastewater thereby concentration, the removal effect of monofilm is also along with increase, when concentration is 40mg/L, the removal effect of film reaches 15.75%.This is because when low concentration, because co-blended spinning monofilm has certain hole, copper ion is through the space of monofilm, thus clearance is lower.When concentration increases, because concentration becomes large, between contact between copper ion and nano-fiber composite film, frequency increases, and there is certain-OH in co-blended spinning film, make between copper ion and-OH, to form certain chemical bond, thus play absorption or crown_interception, reduce the concentration of heavy metal ions in wastewater, now clearance is larger.When solubility continues to increase, because copper ion solubility becomes large, copper ion and membrane interaction exist to be competed, thus reduces clearance);
Fig. 9 is the obtained blend film process copper ion waste water of example of the present invention 2: the processing time on the impact of removal effect (when heavy metal wastewater thereby initial concentration is 50mg/L, coutroi velocity, along with the increase of waste water solution flowing time, the disposal ability of nano-fiber composite film declines gradually, and clearance declines gradually.When the flowing process time is 0.5min, the disposal ability of film is comparatively large, and clearance reaches 13.77%, and along with the increase of time, the disposal ability of film starts to decline.This is because just start, there is a large amount of avtive spots on nano-fiber composite film surface, the interphase interaction of copper ion and film and clearance is larger; Along with the continuous increase of solution flowing time, the avtive spot on film surface reduces, thus clearance reduces.Along with the carrying out in reaction time, clearance tends to be balanced, and may be to have piled up a large amount of copper ions in the surface of film and film space, hinders the motion of copper ion, clearance is tended to balance.When copper ion concentration that is surperficial when film and space reaches capacity, the clearance of film to copper ion solution declines gradually, and disposal ability weakens).
Detailed description of the invention
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
By thermoplasticity carboxymethyl cellulose (i.e. modified cellulose, afterwards with) be mixed into compound, by compound 10 parts of (weight portions with PLA by weight the ratio taken amount of 20:80, same afterwards) join in 100 parts of tetrahydrofuran solvents, stirring and dissolving 0.5 hour, ultrasonic 0.2 hour, make the blend solution that concentration is 10%; Blend solution is added in electrostatic spinning apparatus, electrospinning, reception under the condition of voltage 8kv, syringe pump flow velocity 1mL/h, receiving range 12cm; At temperature 25 DEG C, drying 2 hours, obtains nano-fiber composite film.
Embodiment 2:
Thermoplasticity carboxymethyl cellulose and PLA are mixed into compound, by compound 20 parts of (weight portions by weight the ratio taken amount of 40:60, same afterwards) join in 200 parts of tetrahydrofuran solvents, stirring and dissolving 1 hour, ultrasonic 0.3 hour, makes the blend solution that concentration is 10%; Blended liquid is added in electrostatic spinning apparatus, electrospinning, reception under the condition of voltage 10kv, syringe pump flow velocity 1mL/h, receiving range 12cm; At temperature 30 DEG C, drying 1.5 hours, obtains nano-fiber composite film.
Embodiment 3:
Thermoplasticity carboxymethyl cellulose and PLA are mixed into compound, by compound 30 parts of (weight portions by weight the ratio taken amount of 60:40, same afterwards) join in 300 parts of organic solvents, stirring and dissolving 1 hour, ultrasonic 0.4 hour, making concentration was 10% blend solution; Blended liquid is added in electrostatic spinning apparatus, electrospinning, reception under the condition of voltage 12kv, syringe pump flow velocity 1mL/h, receiving range 12cm; At temperature 35 DEG C, drying 1.0 hours, obtains nano-fiber composite film.
Embodiment 4:
Thermoplasticity carboxymethyl cellulose and PLA are mixed into compound, by compound 40 parts of (weight portions by weight the ratio taken amount of 80:20, same afterwards) join in 400 parts of organic solvents, stirring and dissolving 1.5 hours, ultrasonic 0.5 hour, makes the blend solution that concentration is 10%; Blended liquid is added in electrostatic spinning apparatus, electrospinning, reception under the condition of voltage 12kv, syringe pump flow velocity 1.0mL/h, receiving range 12cm; At temperature 40 DEG C, drying 0.5 hour, obtains nano-fiber composite film.
Embodiment 5:
Thermoplasticity carboxymethyl cellulose and PLA are mixed into compound, by compound 40 parts of (weight portions by weight the ratio taken amount of 50:50, same afterwards) join in 500 parts of organic solvents, stirring and dissolving 1.5 hours, ultrasonic 1.2 hours, makes the blend solution that concentration is 8%; Blended liquid is added in electrostatic spinning apparatus, electrospinning, reception under the condition of voltage 14kv, syringe pump flow velocity 1.0mL/h, receiving range 14cm; Under temperature 45 C, drying 0.2 hour, obtains nano-fiber composite film.
Embodiment 6:
Thermoplasticity carboxymethyl cellulose and PLA are mixed into compound, by compound 20 parts of (weight portions by weight the ratio taken amount of 40:60, same afterwards) join in 100 ~ 500 parts of organic solvents, stirring and dissolving 0.5 ~ 2 hour, ultrasonic 0.2 ~ 1 hour, making concentration was 4% ~ 16% blend solution; Blended liquid is added in electrostatic spinning apparatus, electrospinning, reception under the condition of voltage 8 ~ 32kv, syringe pump flow velocity 0.2 ~ 2mL/h, receiving range 8 ~ 25cm; At temperature 20 ~ 45 DEG C, drying 0.2 ~ 2.0 hour, obtains nano-fiber composite film.
Embodiment 7:
Thermoplasticity carboxymethyl cellulose and PLA are mixed into compound, by compound 20 parts of (weight portions by weight the ratio taken amount of 40:60, same afterwards) join in 100 ~ 500 parts of organic solvents, stirring and dissolving 0.5 ~ 2 hour, ultrasonic 0.2 ~ 1 hour, making concentration was 4% ~ 16% blend solution; Blended liquid is added in electrostatic spinning apparatus, electrospinning, reception under the condition of voltage 8 ~ 32kv, syringe pump flow velocity 0.2 ~ 2mL/h, receiving range 8 ~ 25cm; At temperature 20 ~ 45 DEG C, drying 0.2 ~ 2.0 hour, obtains nano-fiber composite film.
Described solvent can be replaced one or more the mixture in carrene, hexafluoroisopropanol, chloroform.
Embodiment 8:
Thermoplasticity carboxymethyl cellulose and PLA are mixed into compound, by compound 20 parts of (weight portions by weight the ratio taken amount of 20:80, same afterwards) join in 100 ~ 500 parts of organic solvents, stirring and dissolving 0.5 ~ 2 hour, ultrasonic 0.2 ~ 1 hour, making concentration was 4% ~ 16% blend solution; Blended liquid is added in electrostatic spinning apparatus, electrospinning, reception under the condition of voltage 8 ~ 32kv, syringe pump flow velocity 0.2 ~ 2mL/h, receiving range 8 ~ 25cm; At temperature 20 ~ 45 DEG C, drying 0.2 ~ 2.0 hour, obtains nano-fiber composite film.
In above-described embodiment 3-8, described solvent can be one or more the mixture in oxolane, carrene, hexafluoroisopropanol, chloroform.
The nano-fiber composite film prepared under the process conditions of the various embodiments described above is shown in accompanying drawing, to be weaved film forming by disorder distribution, may be used for the aspects such as biological function tissue scaffold material, wastewater treatment, biomembrane, wound clad material, for cellulosic exploitation provide a kind of new approach.
Embodiment 9:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, comprise the following steps:
Prepared by a, co-blended spinning solution: the ratio taken amount of thermoplasticity carboxymethyl cellulose and PLA 90:10 is by weight mixed into compound, getting this compound 10 weight portion again joins in 100 weight parts organic solvent, stirring and dissolving is after 0.5 hour, ultrasonic vibration (adopts ultrasonic vibration device in 1 hour again, to remove bubble etc.), make blend solution;
B, electrostatic spinning: joined by blend solution in electrostatic spinning apparatus, after electrostatic spinning, receive and namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane; The same prior art of processing step method of this electrostatic spinning;
C, drying: by thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane of obtaining under temperature 45 C dry 0.2 hour, i.e. obtained nano-fiber composite film material; This nano-fiber composite film finished product can be the nano-fiber composite film of diameter 50nm ~ 5000nm, film thickness 10 μm ~ 50 μm.
Embodiment 10:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, comprise the following steps:
Prepared by a, co-blended spinning solution: the ratio taken amount of thermoplasticity carboxymethyl cellulose and PLA 50:50 is by weight mixed into compound, getting this compound 50 weight portion again joins in 300 weight parts organic solvent, stirring and dissolving is after 2.2 hours, ultrasonic vibration (adopts ultrasonic vibration device in 0.6 hour again, to remove bubble etc.), make blend solution;
B, electrostatic spinning: joined by blend solution in electrostatic spinning apparatus, after electrostatic spinning, receive and namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane; The same prior art of processing step method of this electrostatic spinning;
C, drying: by thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane of obtaining at temperature 30 DEG C dry 1.1 hours, i.e. obtained nano-fiber composite film material; This nano-fiber composite film finished product can be the nano-fiber composite film of diameter 50nm ~ 5000nm, film thickness 10 μm ~ 50 μm.
Embodiment 11:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, comprise the following steps:
Prepared by a, co-blended spinning solution: the ratio taken amount of thermoplasticity carboxymethyl cellulose and PLA 10:90 is by weight mixed into compound, getting this compound 100 weight portion again joins in 500 weight parts organic solvent, stirring and dissolving is after 2 hours, ultrasonic vibration (adopts ultrasonic vibration device in 1 hour again, to remove bubble etc.), make blend solution;
B, electrostatic spinning: joined by blend solution in electrostatic spinning apparatus, after electrostatic spinning, receive and namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane; The same prior art of processing step method of this electrostatic spinning;
C, drying: by thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane of obtaining at temperature 20 DEG C dry 2.0 hours, i.e. obtained nano-fiber composite film material; This nano-fiber composite film finished product can be the nano-fiber composite film of diameter 50nm ~ 5000nm, film thickness 10 μm ~ 50 μm.
Embodiment 12-18:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, comprise the following steps:
Prepared by a, co-blended spinning solution: the ratio taken amount of thermoplasticity carboxymethyl cellulose and PLA 10 ~ 90:90 ~ 10 is by weight mixed into compound, getting this compound 10 ~ 100 weight portion again joins in 100 ~ 500 weight parts organic solvent, stirring and dissolving is after 0.5 ~ 2 hour, ultrasonic vibration (adopts ultrasonic vibration device in 0.2 ~ 1 hour again, to remove bubble etc.), make blend solution;
In each embodiment, the concrete part by weight of thermoplasticity carboxymethyl cellulose described in step a and PLA sees the following form 1:
Table 1:
In each embodiment, the concrete weight portion consumption of compound described in step a and organic solvent sees the following form 2:
Table 2:
B, electrostatic spinning: joined by blend solution in electrostatic spinning apparatus, after electrostatic spinning, receive and namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane; The same prior art of processing step method of this electrostatic spinning;
C, drying: by thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane of obtaining at temperature 20 ~ 45 DEG C dry 0.2 ~ 2.0 hour, i.e. obtained nano-fiber composite film material; This nano-fiber composite film finished product can be the nano-fiber composite film of diameter 50nm ~ 5000nm, film thickness 10 μm ~ 50 μm.
Embodiment 19:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, described step b electrostatic spinning can entirety replace with: joined by blend solution in electrostatic spinning apparatus, under the condition of voltage 8 ~ 24kv, syringe pump flow velocity 0.2 ~ 1.5mL/h, receiving range 8 ~ 25cm, namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane through electrostatic spinning, reception;
Other is with arbitrary in embodiment 9-18, omits.
Embodiment 20:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, described step b electrostatic spinning can entirety replace with: joined by blend solution in electrostatic spinning apparatus, under the condition of voltage 16kv, syringe pump flow velocity 0.8mL/h, receiving range 16cm, namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane through electrostatic spinning, reception;
Other is with arbitrary in embodiment 9-18, omits.
Embodiment 21:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, described step b electrostatic spinning can entirety replace with: joined by blend solution in electrostatic spinning apparatus, under the condition of voltage 8kv, syringe pump flow velocity 0.2mL/h, receiving range 8cm, namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane through electrostatic spinning, reception;
Other is with arbitrary in embodiment 9-18, omits.
Embodiment 22:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, described step b electrostatic spinning can entirety replace with: joined by blend solution in electrostatic spinning apparatus, under the condition of voltage 24kv, syringe pump flow velocity 1.5mL/h, receiving range 25cm, namely obtain thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane through electrostatic spinning, reception;
Other is with arbitrary in embodiment 9-18, omits.
Embodiment 23:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, electrostatic spinning apparatus described in step b comprises high voltage source 1(Reference numeral see Figure of description 1, rear with), spinning syringe needle 4, spinning solution feedway 2 and 3 and fiber collecting device 5; Control high-voltage power voltage is 8 ~ 24kv, spinning environment temperature is 0 ~ 50 DEG C, and start device for spinning and carry out electrostatic spinning, fiber collecting device 5 collects fiber, dry, i.e. obtained nano-fiber composite film; Other is with arbitrary in embodiment 9-18, omits.
Embodiment 24:
For heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, electrostatic spinning apparatus described in step b comprises high voltage source 1(Reference numeral see Figure of description 1, rear with), spinning syringe needle 4, spinning solution feedway 2 and 3 and fiber collecting device 5; Spinning solution feedway in described electrostatic spinning apparatus includes syringe pump 2 and syringe 3, fiber collecting device are receiving screen 5; Electrostatic spinning described in step b is: the electrostatic spinning blend solution that step a is obtained is drawn in syringe 3, be fixedly installed, the flow of the spinning solution that control spinning voltage is 8 ~ 24kv, distance between receiving screen 5 and the spinning nozzle of syringe needle 4 is 8 ~ 25cm, syringe needle 4 flows out is 0.2mL/h ~ 1.5mL/h, spinning environment temperature is 0 ~ 50 DEG C, start device for spinning and carry out electrostatic spinning, accepting fiber collected by screen 5, drying again, i.e. obtained nano-fiber composite film; Other is with arbitrary in embodiment 9-18, omits.
In above-described embodiment: the thermoplasticity carboxymethyl cellulose described in step a is that sodium carboxymethylcellulose is obtained by methyl acrylate graft modification; Specifically, described thermoplasticity carboxymethyl cellulose is Chinese Patent Application No. is 201010177361.5, publication number is CN101831033A, name is called " modified carboxymethyl cellulose thermoplastic material " recorded in the description of " a kind of preparation method of eco-friendly modified carboxymethyl cellulose thermoplastic material "; The percent grafting of described thermoplasticity carboxymethyl cellulose can be 100% ~ 300%, and glass transition temperature can be 16.00 DEG C ~ 25.00 DEG C, and weight average molecular weight can be 3.5 × 10
5~ 7.0 × 10
5.
In above-described embodiment 9-22: in content of the present invention: the PLA described in step a can be PDLLA, poly (l-lactic acid), PDLLA copolymer or poly (l-lactic acid) copolymer, the weight average molecular weight of described PLA can be 5.4 × 10
4~ 12.0 × 10
4.
In above-described embodiment 9-22: in content of the present invention: the organic solvent described in step a can be one or more the mixture in oxolane, carrene, hexafluoroisopropanol, chloroform.
The nano-fiber composite film prepared under the process conditions of the various embodiments described above, to be weaved film forming by disorder distribution, may be used for the aspects such as biological function tissue scaffold material, wastewater treatment, biomembrane, wound clad material, for cellulosic exploitation provide a kind of new approach.
In above-described embodiment: each raw material adopted is commercially available prod.
In above-described embodiment: in the percentage adopted, do not indicate especially, be weight (quality) percentage; Described part is weight portion, described weight portion can be all gram or kilogram.
In above-described embodiment: the technological parameter in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (1)
1., for heavy metal ion adsorbed modified cellulose/polylactic acid nano fiber composite membrane preparation method, it is characterized in that comprising the following steps:
Prepared by a, co-blended spinning solution: the ratio taken amount of thermoplasticity carboxymethyl cellulose and PLA 10 ~ 90:90 ~ 10 is by weight mixed into compound, getting this compound 10 ~ 100 weight portion again joins in 100 ~ 500 weight parts organic solvent, stirring and dissolving is after 0.5 ~ 2 hour, ultrasonic vibration 0.2 ~ 1 hour, makes blend solution again;
Described PLA is PDLLA, poly (l-lactic acid), PDLLA copolymer or poly (l-lactic acid) copolymer;
Described thermoplasticity carboxymethyl cellulose is that sodium carboxymethylcellulose is obtained by methyl acrylate graft modification;
Described organic solvent is one or both the mixture in carrene, chloroform;
B, electrostatic spinning: joined by blend solution in electrostatic spinning apparatus, namely obtain nano-fiber composite film through electrostatic spinning, reception under the condition of voltage 8 ~ 24kv, syringe pump flow velocity 0.2 ~ 1.5mL/h, receiving range 8 ~ 25cm;
C, drying: by thermoplasticity carboxymethyl cellulose/polylactic acid nano fiber composite membrane at temperature 20 ~ 45 DEG C dry 0.2 ~ 2.0 hour, i.e. obtained nano-fiber composite film finished product;
Obtained nano-fiber composite film is used for the adsorption and enrichment separation of heavy metal ion and the purified treatment of heavy metal wastewater thereby.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210086728.1A CN102605555B (en) | 2012-03-29 | 2012-03-29 | Preparation method of modified cellulose/polylactic-acid nanometer fiber composite film used for heavy-metal ions to adsorb |
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| CN102926016B (en) * | 2012-10-31 | 2014-12-03 | 西南科技大学 | Method for preparing modified konjac glucomannan fiber by electrostatic spinning |
| TWI474861B (en) * | 2013-07-30 | 2015-03-01 | Nat Kaohshiunh University Of Applied Science | Composite film with metal ion adsorbent and its preparation method and application |
| CN104587981B (en) * | 2015-01-15 | 2017-08-01 | 东华大学 | A kind of nano fibrous membrane with heavy metal adsorption function and preparation method thereof |
| DE102015121383B4 (en) * | 2015-12-08 | 2017-10-12 | Technische Universität Berlin | Modified cellulose fibers, process for their preparation, their use, filter aids or filter plates and methods for the artificial clarification of turbid liquids |
| CN105582818B (en) * | 2016-01-07 | 2018-01-02 | 中国科学院宁波材料技术与工程研究所 | The method that highly crystalline polylactic acid seperation film is prepared using fluorine-containing alcohol as cosolvent |
| CN105597428B (en) * | 2016-02-23 | 2017-11-07 | 绿纳科技有限责任公司 | One kind is used for the preparation method for removing Cr in sewage (VI) nanofiber filtration material |
| CN106718422A (en) * | 2017-01-10 | 2017-05-31 | 厦门大学 | A kind of preparation method of degradable multifunctional fibre element agricultural film |
| CN107999039B (en) * | 2017-12-06 | 2020-12-22 | 苏州大学 | PLA-TPs nanofiber membrane and preparation method and application thereof |
| CN108660609B (en) * | 2018-05-23 | 2019-11-05 | 阳光卫生医疗新材料江阴有限公司 | A kind of preparation method and antibacterial non-woven of antibacterial non-woven |
| CN111389379A (en) * | 2020-04-03 | 2020-07-10 | 广东海纳新材料科技有限公司 | Preparation method of waste fiber polylactic acid composite modified oil absorption material |
| CN112481833A (en) * | 2020-12-31 | 2021-03-12 | 华南农业大学 | Environment-friendly micro-nano fiber film material, preparation method thereof and application thereof in water lead pollution treatment |
| CN113491958A (en) * | 2021-03-29 | 2021-10-12 | 杭州青芒生物环保有限公司 | Preparation method of composite fiber membrane for treating heavy metal ions in sewage |
| CN114643671B (en) * | 2022-02-17 | 2024-04-12 | 苏州美森无纺科技有限公司 | Environment-friendly grease-adsorbing wiping cloth capable of being efficiently adsorbed and preparation method thereof |
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