CN104404646A - Preparation method for graphene grafted polyamide 6 nano-composite fiber - Google Patents
Preparation method for graphene grafted polyamide 6 nano-composite fiber Download PDFInfo
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Abstract
The invention provides a preparation method for graphene grafted polyamide 6 nano-composite fiber. Natural flake graphite is adopted as a raw material; a modified Hummers method is adopted to prepare oxidized graphene; further reaction is conducted to prepare amide modified graphene; an in situ polymerization method is adopted to prepare graphene grafted polyamide 6 nano-composite material; finally, an electrospining technique is utilized to prepare the nano-composite material into fibers. The preparation method adopts the in situ polymerization method to prepare the graphene grafted polyamide 6 nano-composite material; interlamellar spacing of graphene laminars is enlarged; graphene surface grafted polyamide 6 chains prevent clustering of the graphene laminars, and achieve homodisperse; the product is high in stability, and performs favorable solubility in an organic solvent, such as formic acid; the solution can be maintained stably and permanently; delamination cannot be seen in six months; the diameter of the graphene grafted polyamide 6 nano-composite fiber is 50 microns; compared with pure polyamide fiber, the tensile strength and Young modulus of the nano-composite fiber are improved by 2.31 times and 2.64 times respectively.
Description
Technical field
The present invention relates to organic polymer composite field, specifically, be to provide a kind of preparation method of Graphene graft-polyamide 6 nano-composite fiber.
Background technology
University of Manchester Geim place group in 2004 utilizes adhesive tape micromechanics to peel off high Directional Method pyrolytic graphite and obtains two-dimentional single-layer graphene, excited various countries researcher to take turns research boom to the another of carbon nano material especially.The bi-dimensional cellular shape lattice that Graphene is made up of flat monolayer carbon atom is tightly packed to be formed, the fullerene of zero dimension can be overmolding to, be curled into the CNT of one dimension and be stacked to three-dimensional graphite, being thus considered to build the base unit that other respectively tie up Carbon Materials.Research in recent years shows: because Graphene has the monoatomic layer crystal structure of special two dimension, make it have excellent electrical and thermal conductivity performance, high specific area, outstanding mechanical property, quantum hall effect and little free track reciprocation, the aspects such as the quantum device such as integrated circuit, field-effect transistor, functional composite material, single-molecule detection device, energy storage material, catalyst carrier can be applied to.
Polyamide 6 (Polyamide 6), from nineteen thirty-seven, IG method our company of Germany has developed and since realizing industrialization, the history of existing more than 70 year.Polyamide 6 is the representational nylon resin of most, has excellent mechanical property, has again wear-resisting, the advantage such as oil resistant, solvent resistant, self-lubricity, self-extinguishment, corrosion resistance and good processability, thus applies very extensive.Polyamide 6 is as engineering plastics, its disadvantage is that water imbibition is comparatively strong, thus causes the change of product size and performance, in addition, the strong alkali-acid resistance of polyamide 6 is poor, dry state and low temperature impact strength low and easily burn, its range of application of these drawbacks limit.But, amino and carboxyl is also had at polyamide 6 macromolecular main chain end, under certain conditions, there is certain reactivity, therefore, by block, grafting, blended, to strengthen and the method such as filling carries out physics and chemistry modification, obtain the engineering plastics that performance is more excellent.The transformed lines show quantity of polyamide 6 is various, can meet the particular/special requirement of different aspect, is widely used as various structural material, becomes the substitute of the traditional material such as metal, timber.In the research of polyamide 6 composite material, make substantial progress with reinforced polyamides 6 such as imvite, glass fibre and clays, the performance of composite is greatly improved, but the modification of polyamide 6 is also mainly rested in mechanical performance and hot property, the development appearing as polyamide 6 composite material of novel charcoal material provides new opportunity, for it has widened road to functionalization future development, Carbon Materials/polyamide 6 nano composite material must with the performance of its brilliance one of composite becoming 21 century advanced person.
Polyamide 6/nano composite material all causes interest widely with industrial circle in the field of study.In matrix, the hot property of matrix and mechanical performance just can be made to increase significantly because add a small amount of filler, the maximum clay filler wherein applied is imvite, it is the successful composite nano polymer/clay material of first case, imvite has layer structure, by organic expanded, can make between polymerization single polymerization monomer insert layer, then trigger monomer polymerization, dissociates in the course of the polymerization process and obtains polymer nanocomposites.At present, the research of nano-material modified polyamide 6 oneself achieve some achievements, such as: Si
3n
4nano particle adds the goods of melt polymerization in caprolactam monomer, under low load, DRY SLIDING, have good ABRASION RESISTANCE.In-situ polymerization via anionic ring-opening path legal system is adopted to be improved for the heat distortion temperature of imvite/polyamide 6 nano composite material and hardness.The people such as Gao
[12]adopt in-situ synthesis polyamide 6/carbon nano tube compound material, result shows that composite has the elongation at break larger than pure polyamide 6 and fracture tensile strength.Zheng Dan
[13]deng people adopted situ aggregation method to prepare conduction Graphene/polyamide 6 nano composite material, when the content of graphene oxide is increased to 1.09 vol.% from 0.27 vol.%, electrical conductivity is from 4.2 × 10
-14to 1.0 × 10
-4sm
-1add ten orders of magnitude.When the content of graphene oxide is only 1.64 vol.%, the electrical conductivity of polyamide 6 based composites reaches 0.028 Sm
-1.
Along with the development of nanometer technology, Electrospinning obtains the attention of height in recent years, but before its basic thought may trace back to more than 100 year.The understanding of people to Electrospun is from Study of Liquid electrojet behavior under the electric field.Raleigh in 1882 etc. have studied drop and occur wild effect in the electric field, when electric field force exceedes surface tension, balance is originally broken, and the drop being suspended in spinning head becomes a series of charged droplet with regard to splitting, and this wild effect was called as " Raleigh Instability " afterwards.Since 1915, Taylor etc. have studied drop and charged fibers bundle broken problem occur under the electric field, along with electric field is strengthened, drop is elongated gradually, when electric field force is equal with surface tension numerical value, just define the circular cone that drift angle is 49.3 °, this circular cone was called as " Taylor cone " afterwards.
Summary of the invention
The object of this invention is to provide preparation method of a kind of Graphene graft-polyamide 6 nano-composite fiber and products thereof.
Technical scheme of the present invention: a kind of preparation method of Graphene graft-polyamide 6 nano composite material, comprises the following steps:
(1) make it dispersed by ultrasonic for grapheme modified for acid amides system;
(2) get the liquid after dispersion and raw material is placed in container, keep temperature 80 DEG C ultrasonic 30 minutes, reaction system mechanical agitation and nitrogen protection are heated to 180 DEG C and keep 1 hour, temperature is risen to 250 DEG C of reactions 9 hours; Product is taken out while hot, with boiling water boiling, washes away unreacted monomer and oligomer; By the oven drying of Graphene graft-polyamide 6 nano composite material with 80 DEG C;
(3) Electrospinning is utilized to obtain Graphene graft-polyamide 6 nano-composite fiber.
The grapheme modified employing following methods preparation of described acid amides:
1) get graphene oxide solution (6.5 mg/mL) and thionyl chloride, both volume ratios are 5:2, are placed in container A, and 76 DEG C are refluxed 48 hours, stir, and obtain the Graphene that acyl chlorides is modified;
2) get calcium oxide 40 g and NaOH 5 g is placed in container B, slowly instillation concentrated ammonia liquor 130 mL, passes in the reaction system of step 1) by the gas of generation by wireway, react 8 hours, obtains the Graphene of acid amides modification.
Described graphene oxide solution adopts the Hummers legal system improved standby, and its step is as follows:
(1) preliminary treatment: with watery hydrochloric acid by crystalline flake graphite cleaning twice, filter, be washed till neutrality with distilled water, vacuumize 24 hours at 100 DEG C;
(2) 1.2 grams of sodium nitrate are joined in 46 milliliters of concentrated sulfuric acids, add 1.0 grams of crystalline flake graphites wherein, ultrasonic to mixing, stir in ice-water bath and slowly add 6.0 grams of potassium permanganate;
(3) system is heated to 40 DEG C, stirring reaction 6-8 hour, while slowly adding 100 ml waters continuously, system is warming up to 70 DEG C, then adds 200 ml waters and 6 milliliters of hydrogen peroxide (30%), after reaction stops, reacting liquor while hot is centrifugal;
(4) this head product is added water to be washed till system pH with ethanol be again 7 to centrifuge washing several times, obtain pure graphite oxide mother liquor for several times with DMF washing, by graphite oxide mother liquor ultrasonic dissolution, obtain homodisperse graphene oxide solution.
Step 2) in raw material used be caprolactam or
/and 6-aminocaprolc acid.
Daiamid-6 fiber product prepared by the preparation method described in a kind of basis.
Beneficial effect of the present invention: the inventive method employing situ aggregation method prepares Graphene graft-polyamide 6 nano composite material makes graphene sheet layer strut, interlamellar spacing increases, it is dispersed that graphenic surface graft-polyamide 6 macromolecular chain prevents the reunion of graphene sheet layer to reach, product stability is good, in organic solvent is as formic acid, show good solubility property, and solution can stablize permanent maintenance.Made Graphene graft-polyamide 6 nano-composite fiber under an optical microscope diameter is 50 μm, and TENSILE STRENGTH improves 2.31 times, and Young's modulus improves 2.64 times, and combination property all increases.
Accompanying drawing explanation
Fig. 1 is the grapheme modified reaction principle figure of acid amides;
Fig. 2 is Graphene graft-polyamide 6 Nano-composite materials schematic diagram;
Fig. 3 is the infrared spectrogram of graphene oxide (a) and acid amides grapheme modified (b);
Fig. 4 is the infrared spectrogram of acid amides grapheme modified (a) and Graphene graft-polyamide 6 nano composite material (b);
Fig. 5 is stereoscan photograph (SEM) photo of Graphene graft-polyamide 6 nano composite material;
Fig. 6 is acid amides grapheme modified (a); Pure polyamide 6 and the grapheme modified physical mixed (b) of acid amides; Pure polyamide 6 (c) and Graphene graft-polyamide 6(d) dissolving situation respectively in formic acid, figure is the digital photograph disperseing situation after 6 months;
Fig. 7 is the thick product figure of Graphene graft-polyamide 6 nano composite material.
detailed description of the invention:
embodiment 1:
A kind of preparation method of Graphene graft-polyamide 6 nano-composite fiber, the concrete chemicals related to: potassium permanganate, sodium nitrate, crystalline flake graphite, hydrogen peroxide, the concentrated sulfuric acid, caprolactam, 6-aminocaprolc acid, dimethyl formamide, absolute ethyl alcohol, thionyl chloride, calcium oxide, concentrated ammonia liquor, it is pure that above medicine purity is analysis.Its step is as follows:
One, adopt the Hummers legal system improved for graphene oxide.
(1) preliminary treatment: with watery hydrochloric acid by crystalline flake graphite cleaning twice, filter, be washed till neutrality with distilled water, vacuumize 24 hours at 100 DEG C.
(2) 1.2 grams of sodium nitrate are joined in 46 milliliters of concentrated sulfuric acids, add 1.0 grams of crystalline flake graphites wherein, within ultrasonic 10 minutes, to mixing, stirring in ice-water bath and slowly adding 6.0 grams of potassium permanganate (slowly adding, about 30 minutes).
(5) system is heated to 40 DEG C, stirring reaction 6-8 hour.While slowly adding 100 ml waters continuously, system is warming up to 70 DEG C, and reacts 30 minutes.Add 200 ml waters and 6 milliliters of hydrogen peroxide (30%), after 5-15 minute, stop reaction, reacting liquor while hot is centrifugal.
(6) this head product is added water to be washed till system pH with ethanol be again 7 to centrifuge washing several times, obtain pure graphite oxide mother liquor for several times with DMF (DMF) washing.By ultrasonic for graphite oxide mother liquor 30 minutes, obtain homodisperse graphene oxide solution (brown color).
Two, utilize thionyl chloride to be acid chloride group by graphene oxide converting carboxylate groups, finally pass into the Graphene that ammonia obtains acid amides modification.
(1) graphene oxide solution 20 ml(6.5 mg/mL is got) thionyl chloride 8 mL is placed in 100 mL round-bottomed flasks, 76 DEG C of backflows 48 hours, notices that system must be avoided contacting with water by magnetic agitation.System color changes black into gradually, generates the Graphene that acyl chlorides is modified.
(2) calcium oxide (CaO) 40 g is got and NaOH (NaOH) 5 g is placed in 250 mL round-bottomed flasks, get concentrated ammonia liquor 130 mL and be placed in dropping funel, dropping funel to be contained on round-bottomed flask and concentrated ammonia liquor is slowly dripped, wireway is passed in the reaction system of the first step, react 8 hours, obtain the Graphene that acid amides is modified.Product is added water washing several times again with ethanol washing, make water content as far as possible few.
Three, acid amides is grapheme modified prepares Graphene graft-polyamide 6 nano composite material to adopt situ aggregation method to utilize, and utilizes Electrospinning to prepare Graphene graft-polyamide nano-composite fiber.
(1) make it dispersed by ultrasonic for grapheme modified for acid amides system.
(2) liquid 2 mL(5.2 mg/mL is got); get caprolactam 9 g, 6-aminocaprolc acid 1 g is placed in 100 mL, tri-mouthfuls of round-bottomed flasks; 80 DEG C are ultrasonic 30 minutes, by reaction system mechanical agitation and nitrogen protection and be heated to 180 DEG C keep 1 hour, temperature rise to 250 DEG C reaction 9 hours.
(3) product is taken out while hot, within 5 hours, wash away unreacted monomer and oligomer with boiling water boiling.By the oven drying 24 hour of Graphene graft-polyamide 6 nano composite material with 80 DEG C.Obtain the thick product as Fig. 7.
(4) Graphene graft-polyamide 6 nano composite material is put into glass container under the protection at nitrogen, be heated to 250 DEG C and keep 10 minutes until Graphene graft-polyamide 6 nano composite material becomes molten condition.Graphene graft-polyamide 6 nanocomposite melt overcomes surface tension after the match at the high-pressure electrostatic of several thousand to several ten thousand volts and produces electrified jet, melt jet is dry, solidification in atmosphere in course of injection, and keep certain quantity of electric charge, finally fall and form the fiber structure of fibrofelt or other shape on the reception device, obtain Graphene graft-polyamide 6 nano-composite fiber containing 0.1 wt% Graphene, Mechanics Performance Testing is learnt, TENSILE STRENGTH, elongation at break and Young's modulus are respectively 133 Mpa, and 252% and 736 Mpa.
embodiment 2:
In step 3; first make it dispersed by ultrasonic for grapheme modified for acid amides system; get liquid 1 mL (5.2 mg/mL), caprolactam 4 g, 6-aminocaprolc acid 0.5 g is placed in 100 mL, tri-mouthfuls of round-bottomed flasks; 80 DEG C ultrasonic 30 minutes; by reaction system mechanical agitation and nitrogen protection and be heated to 180 DEG C keep 1 hour, temperature rise to 250 DEG C reaction 9 hours.Product is taken out while hot, within 5 hours, washes away unreacted monomer and oligomer with boiling water boiling.By the oven drying 24 hour of Graphene graft-polyamide 6 nano composite material with 80 DEG C.Obtained Graphene graft-polyamide 6 nano composite material containing 0.01 wt% Graphene, utilize Electrospinning to obtain the nano-composite fiber of this product, Mechanics Performance Testing is learnt, TENSILE STRENGTH, extension at break amount and Young's modulus are respectively 86 Mpa, and 340% and 635 Mpa.Other is identical with embodiment 1.
embodiment 3:
In step 3; get caprolactam 4 g, 6-aminocaprolc acid 0.5 g is placed in 100 mL, tri-mouthfuls of round-bottomed flasks; 80 DEG C are ultrasonic 30 minutes, by reaction system mechanical agitation and nitrogen protection and be heated to 180 DEG C keep 1 hour, reaction temperature rise to 250 DEG C reaction 9 hours.Product is taken out while hot, within 5 hours, washes away unreacted monomer with boiling water boiling and oligomer prepares pure polyamide 6.By the drying 24 hours of 80 DEG C in an oven of pure for product polyamide 6.Utilize Electrospinning to obtain pure daiamid-6 fiber, Mechanics Performance Testing is learnt, TENSILE STRENGTH, and extension at break amount and Young's modulus are respectively 55 Mpa, 415% and 306 Mpa.Other is identical with embodiment 1.
Claims (5)
1. a preparation method for Graphene graft-polyamide 6 nano composite material, is characterized in that, comprise the following steps:
Make it dispersed by ultrasonic for grapheme modified for acid amides system;
Get the liquid after dispersion and raw material is placed in container, keep temperature 80 DEG C ultrasonic 30 minutes, reaction system mechanical agitation and nitrogen protection are heated to 180 DEG C and keep 1 hour, temperature is risen to 250 DEG C of reactions 9 hours; Product is taken out while hot, with boiling water boiling, washes away unreacted monomer and oligomer; By the oven drying of Graphene graft-polyamide 6 nano composite material with 80 DEG C;
Electrospinning is utilized to obtain the nano combined nanofiber of Graphene graft-polyamide 6.
2. according to the preparation method of Graphene graft-polyamide 6 nano-composite fiber described in claim 1, it is characterized in that, the grapheme modified employing following methods preparation of described acid amides:
1) get graphene oxide solution (6.5 mg/mL) and thionyl chloride, both volume ratios are 5:2, are placed in container A, and 76 DEG C are refluxed 48 hours, stir, and obtain the Graphene that acyl chlorides is modified;
2) get calcium oxide 40 g and NaOH 5 g is placed in container B, slowly instillation concentrated ammonia liquor 130 mL, passes in the reaction system of step 1) by the gas of generation by wireway, react 8 hours, obtains the Graphene of acid amides modification.
3. according to the preparation method of Graphene graft-polyamide 6 nano-composite fiber described in claim 2, it is characterized in that, described graphene oxide solution adopts the Hummers legal system improved standby, and its step is as follows:
(1) preliminary treatment: with watery hydrochloric acid by crystalline flake graphite cleaning twice, filter, be washed till neutrality with distilled water, vacuumize 24 hours at 100 DEG C;
(2) 1.2 grams of sodium nitrate are joined in 46 milliliters of concentrated sulfuric acids, add 1.0 grams of crystalline flake graphites wherein, ultrasonic to mixing, stir in ice-water bath and slowly add 6.0 grams of potassium permanganate;
System is heated to 40 DEG C, stirring reaction 6-8 hour, while slowly adding 100 ml waters continuously, system is warming up to 70 DEG C, then adds 200 ml waters and 6 milliliters of hydrogen peroxide (30%), after reaction stops, reacting liquor while hot is centrifugal;
Adding water to this head product, to be washed till system pH with ethanol be again 7 to centrifuge washing several times, obtains pure graphite oxide mother liquor for several times, by graphite oxide mother liquor ultrasonic dissolution, obtain homodisperse graphene oxide solution with DMF washing.
4., according to the preparation method of Graphene graft-polyamide 6 nano-composite fiber described in claim 1, it is characterized in that, step 2) in raw material used be caprolactam or
/and 6-aminocaprolc acid.
5. the daiamid-6 fiber product prepared of the preparation method according to claim 1 or 2 or 3.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277218A (en) * | 1999-06-11 | 2000-12-20 | 中国科学院化学研究所 | Composite nanometer-level polyamide/graphite material and its preparation |
| CN101760011A (en) * | 2008-12-26 | 2010-06-30 | 上海杰事杰新材料股份有限公司 | Method for preparing nylon 6/graphite oxide nanocomposite |
| CN102390830A (en) * | 2011-08-23 | 2012-03-28 | 华南理工大学 | Method for preparing polyamide-amine in-situ intercalation graphene composite material |
| CN102616774A (en) * | 2012-04-12 | 2012-08-01 | 复旦大学 | Method for preparing graphene quantum dot |
| CN102926020A (en) * | 2012-11-14 | 2013-02-13 | 浙江大学 | Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength |
| CN103215689A (en) * | 2013-05-09 | 2013-07-24 | 苏州大学 | Preparation method of graphene modified nylon 6 fiber |
| KR20140012333A (en) * | 2012-07-19 | 2014-02-03 | 공주대학교 산학협력단 | Graphene-polyamide based composite and manufacturing method thereof |
| US20140225026A1 (en) * | 2013-02-13 | 2014-08-14 | Basf Se | Polyamide composites containing graphene |
-
2014
- 2014-12-06 CN CN201410733420.0A patent/CN104404646A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277218A (en) * | 1999-06-11 | 2000-12-20 | 中国科学院化学研究所 | Composite nanometer-level polyamide/graphite material and its preparation |
| CN101760011A (en) * | 2008-12-26 | 2010-06-30 | 上海杰事杰新材料股份有限公司 | Method for preparing nylon 6/graphite oxide nanocomposite |
| CN102390830A (en) * | 2011-08-23 | 2012-03-28 | 华南理工大学 | Method for preparing polyamide-amine in-situ intercalation graphene composite material |
| CN102616774A (en) * | 2012-04-12 | 2012-08-01 | 复旦大学 | Method for preparing graphene quantum dot |
| KR20140012333A (en) * | 2012-07-19 | 2014-02-03 | 공주대학교 산학협력단 | Graphene-polyamide based composite and manufacturing method thereof |
| CN102926020A (en) * | 2012-11-14 | 2013-02-13 | 浙江大学 | Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength |
| US20140225026A1 (en) * | 2013-02-13 | 2014-08-14 | Basf Se | Polyamide composites containing graphene |
| CN103215689A (en) * | 2013-05-09 | 2013-07-24 | 苏州大学 | Preparation method of graphene modified nylon 6 fiber |
Non-Patent Citations (1)
| Title |
|---|
| 洪菲 等: ""改进Hummers法化学合成石墨烯及其表征"", 《化学与生物工程》, vol. 29, no. 5, 25 May 2012 (2012-05-25), pages 31 - 33 * |
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