CN104357941B - Graphene and multi-walled carbon nano-tubes work in coordination with enhanced polymer fiber and preparation method thereof - Google Patents
Graphene and multi-walled carbon nano-tubes work in coordination with enhanced polymer fiber and preparation method thereof Download PDFInfo
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- CN104357941B CN104357941B CN201410614121.5A CN201410614121A CN104357941B CN 104357941 B CN104357941 B CN 104357941B CN 201410614121 A CN201410614121 A CN 201410614121A CN 104357941 B CN104357941 B CN 104357941B
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Abstract
The invention discloses the preparation method that a kind of Graphene and multi-walled carbon nano-tubes work in coordination with enhanced polymer fiber, mix with the monomer that polycondensation reaction can occur after functionalization by graphene oxide, hydroxylating multi-walled carbon nano-tubes, carry out polycondensation reaction and obtain composite masterbatch, described composite masterbatch after treatment, melt extrudes and obtains as-spun fibre; This as-spun fibre obtains Graphene through post processing again and multi-walled carbon nano-tubes works in coordination with enhanced polymer fiber.This preparation method obviously can improve the degree of scatter of material with carbon element in fibre-forming polymer, and then improves the mechanical strength of obtained fiber.
Description
Technical field
The present invention relates to high-performance fiber preparation field, particularly relate to a kind of Graphene and multi-walled carbon nano-tubes works in coordination with enhanced polymer fiber and preparation method thereof.
Background technology
Graphene and CNT are two study hotspots in current material with carbon element field.Graphene is a kind of by sp
2the material with carbon element with the monatomic lamella of two dimension (2D) structure of the carbon atom composition of hydridization.CNT then can be regarded as a kind of one dimension (1D) the tubulose material with carbon element curled into by graphene film.CNT can be divided into Single Walled Carbon Nanotube (SWNTs) and multi-walled carbon nano-tubes (MWNTs) according to the difference of its tube wall layer number, and wherein the diameter range of multi-walled carbon nano-tubes is at 5 ~ 20nm, and pipe range is not at several microns to tens microns etc.And compared with Single Walled Carbon Nanotube, multi-walled carbon nano-tubes is more extensive in the application in the fields such as composite preparation, electrical application.Graphene and CNT all have the performances such as excellent mechanics, thermodynamics and electricity, have important application in the preparation field of composite.
(the polymer such as G.X.Chen, Polymer, 47 volumes in 2006,4760-4767 page) prepare amination multi-walled carbon nano-tubes, and by amination multi-walled carbon nano-tubes and polyamide 6 melt blending, different carbon nanotube loaded composite fibre is prepared in spinning, and the intensity recording the composite fibre when the load capacity of CNT is 0.5wt% improves 42%, and modulus improves 35%.
(the carbon such as RehmanRafiq, Carbon, 48 volume 4309-4313 in 2010) adopt melt blending technique Graphene to be joined the different graphene-supported composite of preparation in polyamide 12, when Graphene addition is 0.6wt%, composite material strength improves 35%.
The PA6 strength and modulus that prior art prepares is lower, and modified composite fibre intensity improves not obvious, makes it be very limited in actual applications.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of Graphene and multi-walled carbon nano-tubes works in coordination with enhanced polymer fiber and preparation method thereof, this Graphene and multi-walled carbon nano-tubes work in coordination with the mechanical strength that enhanced polymer fiber significantly can improve polymer fiber, expand its use field; This preparation method obviously can improve the degree of scatter of material with carbon element in fibre-forming polymer, and then improves the mechanical strength of obtained fiber.
Graphene and multi-walled carbon nano-tubes work in coordination with a preparation method for enhanced polymer fiber, comprise the steps:
1) utilize Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse obtains graphene oxide in 50 ~ 80mL solvent, then maleic anhydride is added, the mass ratio of wherein said graphite oxide and maleic anhydride is 1:10 ~ 15, at nitrogen atmosphere, 35 ~ 60 DEG C, 3 ~ 6h is reacted under stirring condition, next adds the azodiisobutyronitrile or benzoyl peroxide that account for described maleic anhydride quality 8 ~ 12%, second time adds maleic anhydride and its amount is 0.5 ~ 2 times that adds maleic anhydride quality first, add the styrene of the maleic anhydride equal in quality added with second time simultaneously, 1 ~ 3h is reacted under 70 ~ 100 DEG C of conditions, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting,
3) by multi-walled carbon nano-tubes ultrasonic disperse in 50 ~ 80mL solvent, add maleic anhydride, the mass ratio of wherein said multi-walled carbon nano-tubes and maleic anhydride is 1:10 ~ 15, at nitrogen atmosphere, 35 ~ 60 DEG C, reaction 3 ~ 6h under stirring condition, then the azodiisobutyronitrile or benzoyl peroxide that account for described maleic anhydride quality 8 ~ 12% is added respectively, and with the styrene of described azodiisobutyronitrile or benzoyl peroxide equal in quality, under 70 ~ 100 DEG C of conditions, react 1 ~ 3h, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) by step 2) obtained functionalization graphene, step 3) obtained functionalization multi-walled carbon nano-tubes mix with the monomer that polycondensation reaction can occur, be heated to the described monomer that polycondensation reaction can occur be liquid state afterwards ultrasonic disperse obtain mixing homogeneous reactant;
The consumption of above-mentioned several material is respectively:
Step 2) obtained functionalization graphene 0.05 ~ 5wt%
Step 3) obtained functionalization multi-walled carbon nano-tubes 0.05 ~ 5wt%
Monomer 90% ~ the 99.9wt% of polycondensation reaction can be there is;
5) by step 4) reactant that obtains at nitrogen protection, reaction 1 ~ 4h at 170 ~ 210 DEG C, and then is warming up to 250 ~ 290 DEG C, and reaction 2 ~ 5h, obtains composite masterbatch; Described composite masterbatch, through washing removing unreacted monomer, namely obtains spinning material after oven dry, granulation;
6) melt extruded at 190 ~ 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains described Graphene after nervous HEAT SETTING process and multi-walled carbon nano-tubes works in coordination with enhanced polymer fiber in 90 ~ 98 DEG C of water-baths after 2 ~ 5 times of hot gas spring on the hot-rolling of 110 ~ 160 DEG C;
Wherein step 2), 3) described in solvent be same substance, be toluene, DMF or DMAc.
Step 4) described reactant is also containing additive, and described additive can be the material that polycondensation reaction was assisted or accelerated to catalyst, ring opening agent etc.
The described monomer that polycondensation reaction can occur is contain the monomer of Liang Ge functional group simultaneously or can form the monomer of Liang Ge functional group through open loop.
The described monomer that polycondensation reaction can occur is binary acid, diamine, dihydroxylic alcohols or with it compatibility can there is polycondensation reaction and form the monomer of polymer.
The described monomer that polycondensation reaction can occur is amino acid, from the mixture of polycondensation monomer, organic acid and alcohol or the mixture of organic acid and amine.
Described organic acid is 1:0.5 ~ 2 with organic acid in the mixture of alcohol and the ratio of the amount of substance of alcohol;
Described organic acid is 1:0.5 ~ 2 with organic acid in the mixture of amine and the ratio of the amount of substance of amine.
Described amino acid is 6-aminocaprolc acid; Described from polycondensation monomer be epsilon-caprolactams, lauric lactam or Pfansteihl; Described organic acid is adipic acid, decanedioic acid or terephthalic acid (TPA); Described alcohol is ethylene glycol; Described amine is hexamethylene diamine or decamethylene diamine.
Step 1) described Hummers legal system for the step of graphite oxide is:
A) add in 500mL there-necked flask and be cooled to room temperature after the 40mL concentrated sulfuric acid, 8.4g potassium peroxydisulfate, 8.4g phosphorus pentoxide and 10g graphite powder keep 4.5h at 80 DEG C and obtain mixture I;
B), after described mixture I deionized water dilution being left standstill 12h, block pre-oxidation graphite is obtained through suction filtration, washing, room temperature standing and drying 24h;
C) in 2L there-necked flask, the 230mL concentrated sulfuric acid is added, this there-necked flask is placed in ice-water bath and is cooled to 0 DEG C, add described pre-oxidation graphite, add 60g potassium permanganate under intense agitation, when controlling reinforced, temperature is between 0 DEG C ~ 10 DEG C simultaneously, be warming up to 35 DEG C of stirring reaction 2h subsequently, stir 2h again after adding the dilution of 0.5L deionized water and obtain mixtures II;
D) in described mixtures II, add 1.5L deionized water, drip the hydrogen peroxide of 25mL, mass percentage 30%, leave standstill 24h, the sediment that removing supernatant obtains;
E) to steps d) add the hydrochloric acid removing metal oxide of appropriate 1mol/L in the sediment that obtains, then utilize deionized water cyclic washing until pH=6.5 ~ 7.5, obtain Primary product;
F) by step e) Primary product ultrasonic disperse 30min, the centrifugal brown product that obtains in water that obtain, be graphite oxide by obtaining fluffy solid after this brown product vacuumize.
In Hummers method, each material consumption only provides the mass ratio between each material herein, the restriction not to concrete numerical value.Described reaction vessel can be determined according to the concrete consumption of experiment.
Accompanying drawing explanation
Fig. 1 a is the transmission electron microscope photo of the phenylethylene-maleic anhydride functionalization graphene that embodiment 1 obtains;
Fig. 1 b is the transmission electron microscope photo of the phenylethylene-maleic anhydride functionalized carbon nano-tube that embodiment 1 obtains;
Fig. 2 a is functionalization graphene/functionalized carbon nano-tube stereoscan photograph that embodiment 1 obtains;
Fig. 2 b is functionalization graphene/functionalized carbon nano-tube stereoscan photograph that embodiment 1 obtains;
Fig. 3 a is functionalization graphene material schematic diagram;
Fig. 3 b is functionalized carbon nano-tube and functionalization graphene schematic diagram;
Fig. 3 c is functionalized carbon nano-tube material schematic diagram;
Fig. 3 d is functionalized carbon nano-tube and functionalized nano yardstick Graphene schematic diagram;
Fig. 4 a is functionalization graphene/functionalized carbon nano-tube transmission electron microscope photo that embodiment 1 obtains;
Fig. 4 b is functionalization graphene/functionalized carbon nano-tube transmission electron microscope photo that embodiment 1 obtains.
Fig. 5 is the FTIR spectrum figure of the functionalization graphene that obtains of embodiment 1 and functionalized carbon nano-tube
Detailed description of the invention
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in detail.
Hummers legal system is utilized for the step of graphene oxide to be in embodiment:
A) add in 500mL there-necked flask and be cooled to room temperature after the 40mL concentrated sulfuric acid, 8.4g potassium peroxydisulfate, 8.4g phosphorus pentoxide and 10g graphite powder keep 4.5h at 80 DEG C and obtain mixture I;
B), after described mixture I deionized water dilution being left standstill 12h, block pre-oxidation graphite is obtained through suction filtration, washing, room temperature standing and drying 24h;
C) in 2L there-necked flask, the 230mL concentrated sulfuric acid is added, this there-necked flask is placed in ice-water bath and is cooled to 0 DEG C, add described pre-oxidation graphite, add 60g potassium permanganate under intense agitation, when controlling reinforced, temperature is between 0 DEG C ~ 10 DEG C simultaneously, be warming up to 35 DEG C of stirring reaction 2h subsequently, stir 2h again after adding the dilution of 0.5L deionized water and obtain mixtures II;
D) in described mixtures II, add 1.5L deionized water, drip the hydrogen peroxide of 25mL, mass percentage 30%, leave standstill 24h, the sediment that removing supernatant obtains;
E) to steps d) add the hydrochloric acid removing metal oxide of appropriate 1mol/L in the sediment that obtains, then utilize deionized water cyclic washing until pH=6.5 ~ 7.5, obtain Primary product;
F) by step e) Primary product ultrasonic disperse 30min, the centrifugal brown product that obtains in water that obtain, be graphite oxide by obtaining fluffy solid after this brown product vacuumize.
Gained functionalization graphene of the present invention, functionalization multi-walled carbon nano-tubes and the polymer/graphene/composition of multi-walled carbon nano-tubes composite fibre, the sign of stuctures and properties, except indicating especially, all use following instrument and equipment:
Adopt the surface topography of H7650 type transmission electron microscope, HitachiS4800 sem observation functionalization graphene and functionalization multi-walled carbon nano-tubes.Adopt the infrared absorption spectroscopy (scope 3700 ~ 500cm of Uecior22 type FTIR spectrum test function functionalized graphene and functionalization multi-walled carbon nano-tubes
-1).LLY-06 type electronic mono-fiber strong force instrument is adopted to carry out Mechanics Performance Testing to straight polymer fiber and each quality than composite fibre.Adopt constant speed to stretch to each fiber, clamp distance is 10mm, draw speed 10mm/min, often organizes fiber measurement and averages for 10 times.Young's modulus is the ratio of shape stress and strain when becoming 1%.
Embodiment 1
The preparation method of polyamide 6 (PA6)/Graphene/multi-walled carbon nano-tubes fiber, comprises the steps:
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2g maleic anhydride is added, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene and 2g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene (as shown in Figure 1a) of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.24g azodiisobutyronitrile, 3g styrene and 3g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes (as shown in Figure 1 b) of styrene-maleic anhydride copolymer grafting;
4) taking 0.2g functionalization graphene, 0.3g functionalization multi-walled carbon nano-tubes, 89.5g epsilon-caprolactams and 10g6-aminocaproic acid pours in 250mL there-necked flask, be heated to 80 DEG C, until epsilon-caprolactams melt completely be in a liquid state no longer include obvious solid time, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 180 DEG C, react 2h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains PA6/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:3; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, obtain black powder after grinding, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 97 DEG C of water-baths after 3.5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber.
By step 5) black powder that obtains mixes with formic acid, find that this black powder can be dispersed in formic acid, light scattering test finds no sediment, show PA6 and define covalent bond between functionalization graphene and functionalization multi-walled carbon nano-tubes, the solution that takes a morsel is observed under transmission electron microscope, visible functionalization graphene and functionalization multi-walled carbon nano-tubes are uniformly dispersed (as Fig. 4 a in the solution, shown in 4b), overlap joint is formed between Graphene and CNT, form the reinforcement that size is larger, there is chemiluminescence.Can effectively disperse after Graphene and carbon nano-tube hybridization, the existence of graphene film hinders the mutual entanglement between CNT, and CNT also hinders the stacking (as Fig. 2 a of graphene film by intercalation between graphene sheet layer, 2b, 3a, 3b, 3c, 3d, 4a, shown in 4b), thus two kinds of material with carbon elements can both be effectively dispersed in polymeric matrix, CNT can effectively hinder the curling of graphene film simultaneously, and this curling for enhancing polymeric matrix be disadvantageous, therefore this hybrid enhances the interface cohesion between matrix, play the collaborative effect strengthened.
As shown in Figure 5, the functionalization graphene of gained and multi-walled carbon nano-tubes occur that in infrared spectrum the C=O of corresponding maleic anhydride stretches the characteristic absorption peak such as C-H out-of-plane bending vibration peak of peak, the characteristic peak of C-O stretching vibration, the skeletal vibration peak of phenyl ring, monosubstituted phenyl ring, shows that the strand of phenylethylene-maleic anhydride has successfully been grafted to graphene oxide and multi-wall carbon nano-tube tube-surface.To record functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio that the present embodiment obtains be the fracture strength that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber is 668MPa, 141% is improve than pure PA6 intensity, Young's modulus is 3.06GPa, improve 132% than pure PA6 intensity, elongation at break is 29.3%.
Embodiment 2
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2g maleic anhydride is added, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene, 2g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) take 0.2g functionalization graphene, 0.3g functionalization multi-walled carbon nano-tubes, 3g deionized water, 99.5g epsilon-caprolactams pour in 250mL there-necked flask, be heated to 80 DEG C, until epsilon-caprolactams melt completely be in a liquid state no longer include obvious solid time, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 180 DEG C, react 2h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains PA6/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:3; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 97 DEG C of water-baths after 3.5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber.
Embodiment 3
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2g maleic anhydride is added, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene, 2g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) take 0.2g functionalization graphene, 0.3g functionalization multi-walled carbon nano-tubes, 99.5g6-aminocaproic acid pour in 250mL there-necked flask, be heated to 80 DEG C, until 6-aminocaprolc acid melt completely be in a liquid state no longer include obvious solid time, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 180 DEG C, react 2h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains PA6/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:3; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 90 DEG C of water-baths after 2 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber.
Embodiment 4
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2.4g maleic anhydride is added, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene, 2g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3.6g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) taking 0.2g functionalization graphene, 0.3g functionalization multi-walled carbon nano-tubes, 89.5g epsilon-caprolactams and 10g6-aminocaproic acid pours in 250mL there-necked flask, be heated to 80 DEG C, until epsilon-caprolactams melt completely be in a liquid state no longer include obvious solid time, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 190 DEG C, react 1h under stirring condition, and then be warming up to 290 DEG C, reaction 5h, obtains PA6/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:3; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 290 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 98 DEG C of water-baths after 5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber.
Embodiment 5
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 3g maleic anhydride is added, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene, 2g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 4.5g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) taking 0.2g functionalization graphene, 0.3g functionalization multi-walled carbon nano-tubes, 89.5g epsilon-caprolactams and 10g6-aminocaproic acid pours in 250mL there-necked flask, be heated to 80 DEG C, until epsilon-caprolactams melt completely be in a liquid state no longer include obvious solid time, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 180 DEG C, react 2h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains PA6/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:3; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding; 7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 96 DEG C of water-baths after 3.5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber.
Embodiment 6
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2g maleic anhydride is added, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.16g benzoyl peroxide, 2g styrene, 2g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) taking 0.2g functionalization graphene, 0.3g functionalization multi-walled carbon nano-tubes, 89.5g epsilon-caprolactams and 10g6-aminocaproic acid pours in 250mL there-necked flask, be heated to 80 DEG C, until epsilon-caprolactams melt completely be in a liquid state no longer include obvious solid time, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 180 DEG C, react 2h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains PA6/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:3; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 97 DEG C of water-baths after 3.5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber.
Embodiment 7
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2g maleic anhydride is added, nitrogen atmosphere, 35 DEG C, react 3h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene, 2g maleic anhydride, under 70 DEG C of conditions, copolyreaction 3h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) taking 0.2g functionalization graphene, 0.3g functionalization multi-walled carbon nano-tubes, 89.5g epsilon-caprolactams and 10g6-aminocaproic acid pours in 250mL there-necked flask, be heated to 80 DEG C, until epsilon-caprolactams melt completely be in a liquid state no longer include obvious solid time, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 180 DEG C, react 2h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains PA6/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:3; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 97 DEG C of water-baths after 3.5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber.
Embodiment 8
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2g maleic anhydride is added, nitrogen atmosphere, 60 DEG C, react 6h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene, 2g maleic anhydride, under 100 DEG C of conditions, copolyreaction 1h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) taking 0.2g functionalization graphene, 0.3g functionalization multi-walled carbon nano-tubes, 89.5g epsilon-caprolactams and 10g6-aminocaproic acid pours in 250mL there-necked flask, be heated to 80 DEG C, until epsilon-caprolactams melt completely be in a liquid state no longer include obvious solid time, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 180 DEG C, react 2h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains PA6/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:3; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 97 DEG C of water-baths after 3.5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA6/ Graphene/multi-walled carbon nano-tubes of 2:3 works in coordination with enhanced polymer fiber.
Embodiment 9
The preparation method of polyethylene terephthalate/Graphene/multi-wall carbon nano-tube composite material, comprises the steps:
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2g maleic anhydride is added, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene, 2g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) take 0.2g functionalization graphene, 0.2g functionalization multi-walled carbon nano-tubes, 72.4g terephthalic acid (TPA), 27.1g ethylene glycol and 0.05g zinc acetate and 0.05g antimonous oxide is poured in 250mL there-necked flask, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 180 DEG C, react 5h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains polyethylene terephthalate/Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:2; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 97 DEG C of water-baths after 3.5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the polyethylene terephthalate/Graphene/multi-walled carbon nano-tubes of 2:2 works in coordination with enhanced polymer fiber.Obtain the composite fibre of high strength, its tensile break strength comparatively contrasts fiber and improves 72%, and Young's modulus improves 110%.
Embodiment 10
The preparation method of polyamide 66 (PA66)/Graphene/multi-wall carbon nano-tube composite material, comprises the steps:
1) utilize above-mentioned Hummers legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse is in 50mL toluene, then 2g maleic anhydride is added, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, next adds 0.16g azodiisobutyronitrile, 2g styrene, 2g maleic anhydride, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting;
3) by 0.3g hydroxylating CNT ultrasonic disperse in 70mL toluene, add 3g maleic anhydride, nitrogen atmosphere, 40 DEG C, react 5h under stirring condition, add 0.24g azodiisobutyronitrile and 3g styrene respectively, under 80 DEG C of conditions, copolyreaction 2h obtains black solid, by this black solid acetone supersound washing 3 times, at 80 DEG C of vacuumize 24h after centrifugation, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting;
4) take 0.2g functionalization graphene, 0.2g functionalization multi-walled carbon nano-tubes, 55.9g adipic acid, 43.7g hexamethylene diamine pour in 250mL there-necked flask, in 80 DEG C of hot water, ultrasonic 20min is in control reactant with divergent function functionalized graphene and functionalization multi-wall carbon nano-tube;
5) by step 4) reactant that obtains nitrogen protection, 210 DEG C, react 2h under stirring condition, and then be warming up to 270 DEG C, reaction 3h, obtains PA66/ Graphene/multi-wall carbon nano-tube composite material masterbatch that functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is 2:2; This composite masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times washing after at 80 DEG C vacuumize 48h, after granulation, obtain spinning material;
6) melt extruded at 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding; 7) described as-spun fibre obtains functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio in 97 DEG C of water-baths after 3.5 times of hot gas spring on the hot-rolling of 120 DEG C after nervous HEAT SETTING process is that the PA66/ Graphene/multi-walled carbon nano-tubes of 2:2 works in coordination with enhanced polymer fiber.Obtain the composite fibre of high strength, its tensile break strength comparatively contrasts fiber and improves 54%, and Young's modulus improves 108%.
Embodiment 11
The quality proportioning of this embodiment functionalization graphene as different from Example 1/functionalization multi-walled carbon nano-tubes is 3:2, i.e. step 4) add 0.3g functionalization graphene, 0.2g functionalization multi-walled carbon nano-tubes, 89.5g caprolactam and 10g6-aminocaproic acid, other step is with embodiment 1, and obtained functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio is that the PA6/ Graphene/multi-walled carbon nano-tubes of 3:2 works in coordination with enhanced polymer fiber.
The fracture strength that PA6/ Graphene/multi-walled carbon nano-tubes that the present embodiment obtains works in coordination with enhanced polymer fiber is 503MPa, improves 82% than pure PA6 intensity, and Young's modulus is 3.23GPa, improves 145% than pure PA6 intensity, and elongation at break is 20.5%.
Embodiment 12
The quality proportioning of this embodiment functionalization graphene as different from Example 1/functionalization multi-walled carbon nano-tubes is 4:1, i.e. step 4) add 0.4g functionalization graphene, 0.1g functionalization multi-walled carbon nano-tubes, 89.5g caprolactam and 10g6-aminocaproic acid, other step is with embodiment 1, and the PA6/ Graphene/multi-walled carbon nano-tubes of obtained functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio 4:1 works in coordination with enhanced polymer fiber.
The fracture strength that PA6/ Graphene/multi-walled carbon nano-tubes that the present embodiment obtains works in coordination with enhanced polymer fiber is 427MPa, improves 54% than pure PA6 intensity, and Young's modulus is 2.06GPa, improves 56% than pure PA6 intensity, and elongation at break is 31.0%.
Embodiment 13
The quality proportioning of this embodiment functionalization graphene as different from Example 1/functionalization multi-walled carbon nano-tubes is 4:6, i.e. step 4) add 0.4g functionalization graphene, 0.6g functionalization multi-walled carbon nano-tubes, 89g epsilon-caprolactams and 10g6-aminocaproic acid, other step and embodiment 1, the PA6/ Graphene/multi-walled carbon nano-tubes of obtained functionalization graphene/functionalization multi-walled carbon nano-tubes mass ratio 4:6 works in coordination with enhanced polymer fiber.
Recording the fracture strength that PA6/ Graphene/multi-walled carbon nano-tubes that the present embodiment obtains works in coordination with enhanced polymer fiber is 442MPa, 60% is improve than pure PA6 intensity, Young's modulus is 1.91GPa, improves 47% than pure PA6 intensity, and elongation at break is 34.8%.
Embodiment 14
With the epsilon-caprolactams in lauric lactam alternative embodiment 1, other composition and technological parameter constant, the tensile break strength of the composite fibre obtained and Young's modulus comparatively contrast fiber and significantly improve.
Comparative example
The polymerization technique of PA6 is as follows: one, take 90g caprolactam and 10g6-aminocaproic acid, N
2180 DEG C are warming up to and mechanical agitation 2h after emptying; Two, be warming up to 270 DEG C of continuation polymerisation 8h and obtain pure PA6 masterbatch; Three, masterbatch is put into boiling water bath to wash to remove unreacted monomer, repeatedly carry out three times; Four, vacuumize 48h at 80 DEG C.
Spin as-spun fibre with spinning machine, spinning temperature is 280 DEG C, obtains as-spun fibre through winding.By as-spun fibre hot-stretch 3.5 times in boiling water bath, be placed on tension force HEAT SETTING on 120 DEG C of hot-rollings and namely prepare pure PA6 fiber.Recording pure PA6 fibrous fracture intensity is 277MPa, and Young's modulus is 1.32GPa, and elongation at break is 40.3%.
Claims (8)
1. Graphene and multi-walled carbon nano-tubes work in coordination with a preparation method for enhanced polymer fiber, it is characterized in that comprising the steps:
1) utilize Hummer ' s legal system for graphite oxide;
2) by step 1) obtained graphite oxide takes 0.2g, ultrasonic disperse obtains graphene oxide in 50 ~ 80mL solvent, then maleic anhydride is added, the mass ratio of wherein said graphite oxide and maleic anhydride is 1:10 ~ 15, at nitrogen atmosphere, 35 ~ 60 DEG C, 3 ~ 6h is reacted under stirring condition, next adds the azodiisobutyronitrile or benzoyl peroxide that account for described maleic anhydride quality 8 ~ 12%, second time adds maleic anhydride and its amount is 0.5 ~ 2 times that adds maleic anhydride quality first, add the styrene of the maleic anhydride equal in quality added with second time simultaneously, 1 ~ 3h is reacted under 70 ~ 100 DEG C of conditions, obtain the functionalization graphene of styrene-maleic anhydride copolymer grafting,
3) by hydroxylating multi-walled carbon nano-tubes ultrasonic disperse in 50 ~ 80mL solvent, add maleic anhydride, the mass ratio of wherein said multi-walled carbon nano-tubes and maleic anhydride is 1:10 ~ 15, at nitrogen atmosphere, 35 ~ 60 DEG C, 3 ~ 6h is reacted under stirring condition, then the azodiisobutyronitrile or benzoyl peroxide that account for described maleic anhydride quality 8 ~ 12% is added respectively, and with the styrene of described azodiisobutyronitrile or benzoyl peroxide equal in quality, 1 ~ 3h is reacted under 70 ~ 100 DEG C of conditions, obtain the functionalization multi-walled carbon nano-tubes of styrene-maleic anhydride copolymer grafting,
4) by step 2) obtained functionalization graphene, step 3) obtained functionalization multi-walled carbon nano-tubes mix with the monomer that polycondensation reaction can occur, be heated to the described monomer that polycondensation reaction can occur be liquid state afterwards ultrasonic disperse obtain mixing homogeneous reactant;
The consumption of above-mentioned several material is respectively:
Step 2) obtained functionalization graphene 0.05 ~ 5wt%;
Step 3) obtained functionalization multi-walled carbon nano-tubes 0.05 ~ 5wt%;
Monomer 90 ~ the 99.9wt% of polycondensation reaction can be there is;
5) by step 4) reactant that obtains at nitrogen protection, reaction 1 ~ 4h at 170 ~ 210 DEG C, and then is warming up to 250 ~ 290 DEG C, and reaction 2 ~ 5h, obtains composite masterbatch; Described composite masterbatch, through washing removing unreacted monomer, namely obtains spinning material after oven dry, granulation;
6) melt extruded at 190 ~ 280 DEG C by described spinning material, extrudate obtains as-spun fibre through winding;
7) described as-spun fibre obtains described Graphene after nervous HEAT SETTING process and multi-walled carbon nano-tubes works in coordination with enhanced polymer fiber in 90 ~ 98 DEG C of water-baths after 2 ~ 5 times of hot gas spring on the hot-rolling of 110 ~ 160 DEG C;
Wherein step 2), 3) described in solvent be same substance, be toluene, DMF or DMAc.
2. preparation method as claimed in claim 1, is characterized in that: the described monomer that polycondensation reaction can occur is monomer simultaneously containing Liang Ge functional group or the monomer that can form Liang Ge functional group through open loop.
3. preparation method as claimed in claim 1, is characterized in that: the described monomer that polycondensation reaction can occur is binary acid, diamine, dihydroxylic alcohols or with it compatibility can there is the monomer that polycondensation reaction forms polymer.
4. preparation method as claimed in claim 1, is characterized in that: the described monomer that polycondensation reaction can occur is amino acid, from the mixture of polycondensation monomer, organic acid and alcohol or the mixture of organic acid and amine.
5. preparation method as claimed in claim 4, is characterized in that: described organic acid is 1:0.5 ~ 2 with organic acid in the mixture of alcohol and the ratio of the amount of substance of alcohol.
6. preparation method as claimed in claim 4, is characterized in that: described organic acid is 1:0.5 ~ 2 with organic acid in the mixture of amine and the ratio of the amount of substance of amine.
7. preparation method as claimed in claim 4, is characterized in that: described amino acid is 6-aminocaprolc acid; Described from polycondensation monomer be epsilon-caprolactams, lauric lactam or Pfansteihl; Described organic acid is adipic acid, decanedioic acid or terephthalic acid (TPA); Described alcohol is ethylene glycol; Described amine is hexamethylene diamine or decamethylene diamine.
8. preparation method as claimed in claim 1, is characterized in that: step 4) described reactant is also containing additive.
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| CA3005917C (en) * | 2015-11-20 | 2020-05-05 | Jinan Shengquan Group Share Holding Co., Ltd | Modified fiber and preparation method therefor |
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| CN107758652A (en) * | 2016-08-18 | 2018-03-06 | 江西福安路润滑材料有限公司 | Functionalized graphene, and preparation method and application |
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| CN106928413A (en) * | 2017-03-26 | 2017-07-07 | 天津工业大学 | A kind of method of styrene maleic anhydride copolymer graft modification Graphene |
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| CN109251429B (en) * | 2018-08-08 | 2021-05-11 | 多凌新材料科技股份有限公司 | Graphene/carbon nanotube master batch easy to disperse in PVC (polyvinyl chloride), and preparation method and application thereof |
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| CN111534882B (en) * | 2020-05-22 | 2022-05-20 | 北京光华纺织集团有限公司 | Preparation method of functionalized multi-walled carbon nanotube reinforced polyester fiber |
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