CN105315456B - A kind of in-situ modified poly-lactam composite of CNT and preparation method and application - Google Patents
A kind of in-situ modified poly-lactam composite of CNT and preparation method and application Download PDFInfo
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- CN105315456B CN105315456B CN201510481933.1A CN201510481933A CN105315456B CN 105315456 B CN105315456 B CN 105315456B CN 201510481933 A CN201510481933 A CN 201510481933A CN 105315456 B CN105315456 B CN 105315456B
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Abstract
The present invention relates to polymeric material field, for solve modifying agent CNT bad dispersibility, interfacial adhesion is poor, material property is unstable the problems such as, the present invention provides a kind of in-situ modified poly-lactam composite of CNT and preparation method thereof, the tensile strength of described composite is 65~105MPa, impact strength is 90~175J/m, and Volume erosion rate is (0.8~4.0) x10‑5mm3N‑ 1m‑1.The composite good dispersion of the present invention, compatibility are good, performance is stable, and the in-situ modified poly-lactam composite powder material of CNT handled by low-temperature grinding can be applied in laser selection sintering art.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of in-situ modified poly-lactam composite wood of CNT
Material, preparation method and applications.
Background technology
CNT is the hollow tubular material that a kind of graphite flake layer by carbon hexagon is crimped, a diameter of 1~
50nm, can be divided into single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube according to the number of plies.Due to its unique structure,
Big surface area, good mechanical performance and thermal conductivity, makes it widely be paid close attention in plastic applications.But, due to
The specific surface area of CNT and surface can be than larger so that CNT is easy to reunite, and have impact on CNT in matrix
In it is scattered.And carbon nano tube surface is smooth, in nonpolar, insoluble in general organic solvent, with all polymer all
Incompatible so that the interface interaction of composite is not strong, CNT and high polymer material are compound, can make full use of carbon nanometer
The various characteristics of pipe, enhancing improves high molecular performance.
Fatty polyamide is the plastic material that a kind of mechanical strength is higher, shock resistance is excellent, is that consumption is maximum
One of engineering plastics, are also the wide tribological polymer material of engineer applied.But fatty polyamide and most of high scores
The same sub- material is all the material with good electrical insulation capability, easily causes electrostatic accident, while the unlubricated friction of fatty polyamide
Wipe coefficient high, limit its application in Tribological Systems.Therefore polyamide is constantly assigned by physical and chemical modified technology
Kind high-performance, to promote it in the application in each field.
With reference to CNT and the features of polyamide, gradually risen using the research of carbon nano-tube modification nylon, one
A little polyamide-CNT high-performance composite materials also when have been reported that.Such as Zhu Cheng bodies (polymer material science and engineering,
2009,25：The multi-walled carbon nanotube of nylon 6/ with higher elasticity and bending modulus 39-42) has been synthesized using polymerization autoclave
Composite；Superb (macromolecule journal, 2008,2：188-191) it is prepared for that there is higher stretch modulus using in situ Polycondensation method
The composite of carbon nano-tube/nylon 11；Chinese invention patent " a kind of modified carbon nano-tube/nylon composite materials "
(CN103044914A) in, modified multiwalled carbon nanotube is distributed in nylon 1212 with mechanical means, performance is prepared good
Good composite.
The content of the invention
It is of the invention to solve modifying agent CNT bad dispersibility, the problems such as interfacial adhesion is poor, material property is unstable
In-situ modified poly-lactam composite of a kind of CNT and preparation method thereof, composite dispersiveness of the invention are provided
Good, compatibility is good, performance is stable.
The present invention is achieved by the following technical solutions：A kind of in-situ modified poly-lactam composite of CNT,
The tensile strength of described composite is 65~105MPa, and impact strength is 90~175J/m, and Volume erosion rate is (0.8
~4.0) x10-5mm3N-1m-1。
Described preparation method is following steps：
(1) by CNT ultrasonic disperse in toluene, then under the conditions of magnetic agitation, azo initiator is added,
70~90 DEG C of 3~6h of stirring reaction under inert gas shielding, reaction product is scrubbed, dry after obtain azo initiator modification
Carbon nanotube powder；
Preferably, CNT is selected from the function modified CNT (CNTs-EDA) of ethylenediamine.Preparation method is：Claim
1 part of CNT of parts by weight is taken, is placed in container, the 30~60ml mixed acid (concentrated sulfuric acid: concentrated nitric acid=3: in 40 in 1) is added
~70 DEG C of 3~6h of backflow, are then filtered by vacuum, obtained black solid are filtered with distilled water flushing repeatedly, until filtrate pH
Untill the close neutrality of value, sour cutting carbon nanotubes are obtained, obtained sour cutting carbon nanotubes are then placed in 60~100 DEG C of vacuum
12~36h is dried in drying box, the modified carbon nano-tube after acid treatment is obtained；By 1 part of modified carbon nano-tube after acid treatment and 4
~8 parts of thionyl chloride reaction 12~36h of backflow, acyl chlorides is converted to by the carboxyl of carbon nano tube surface.Rushed afterwards with tetrahydrofuran
Wash away and remove after thionyl chloride, 12~36h is dried in vacuo at room temperature.By dried product and ethylenediamine in mass ratio 1~3: 1
Ratio is cooled to room temperature after 130~140 DEG C of back flow reactions 12~36, and drying is washed with ethanol after reaction product is filtered out, and obtains
To the function modified CNT of ethylenediamine (CNTs-EDA).
Described CNT is selected from single-walled carbon nanotube (SWCNTs), double-walled carbon nano-tube (DWCNTs), many wall carbon and received
A diameter of 0.5~20nm of one or more in mitron (MWCNTs), wherein CNT, length is 1~50 μm.
(2) carbon nanotube powder that azo initiator is modified, NiCl are added in a reservoir2·6H2O and tetrahydrofuran, lazy
Property gas shield under ultrasonic disperse 30min, add after Al powder after 10~30min of reaction, it is post-treated to obtain amino modified carbon and receive
Mitron powder；
NiCl2·6H2The weight ratio for the carbon nanotube powder that O is modified with azo initiator draws for 6~9: 1, Al powder with azo
The weight ratio for sending out the carbon nanotube powder that agent is modified is 1~3: 1.
Described post-processing approach is：The solid mixture for being diluted and being filtrated to get with 100ml THF is poured into beaker, plus
The dilute sulfuric acid for entering 3mol/L removes ALNiCl2·6H2It is filtered by vacuum after O, filtration product is washed with deionized water to neutrality, 60 DEG C
Vacuum drying obtains amino modified carbon nanotube powder.
(3) by amino modified carbon nanotube powder in ethyl acetate 1~3h of ultrasonic disperse, add isocyanates 60~
Product is filtrated to get after 80 DEG C of 3~6h of stirring reaction, and product is extracted into 6~12h with ethyl acetate, obtains isocyanate-modified
CNT；
Preferably, the weight ratio of isocyanates and amino modified carbon nanotube powder is 1~3: 1.
(4) isocyanate-modified CNT is dispersed in ethyl acetate, adds lactam monomers at 60~80 DEG C
After 3~6h of stirring reaction, filter and with ethyl acetate 6~12h of extract product, dry, the carbon modified for obtaining lactams end-blocking is received
Mitron；
Preferably, the weight ratio of lactam monomers and isocyanates base carbon nanotube is 1~3: 1.
(5) CNT that lactams is blocked is mixed with lactam monomers, in the constant temperature bar that temperature is 100~120 DEG C
Ultrasonically treated 3~6h under part, adds catalyst in the case where temperature is 130~140 DEG C, vacuumizes after 10~30min of water removal, add different
Cyanate, stirs and polymerize at 140~170 DEG C, and 20~60min of insulation obtains the in-situ modified poly-lactam of CNT and answered
Condensation material.
Preferably, the weight ratio for the CNT that isocyanates is blocked with lactams is 0.1~0.5: 1, lactams list
The weight ratio for the CNT that body is blocked with lactams is 50~100: 1,
Described catalyst in NaOH, KOH, sodium caprolactam, caprolactam potassium, caustic alcohol, sodium methoxide etc. one
Plant or several, the weight ratio for the CNT that catalyst is blocked with lactams is 0.2~1: 1, preferably 0.3~0.7: 1
Described azo initiator is selected from azodiisobutyronitrile (AIBN), AMBN (AMBN), azo two different heptan
The one or more of (AIBA) in nitrile (ABVN), the isobutyl imidazoline (AIP) of azo two, azo-bis-isobutyrate hydrochloride, azo draws
The weight ratio for sending out agent and CNT is 3~6: 1.
Described isocyanates is selected to toluene 2,4- diisocyanate (TDI), hexamethylene diisocyanate (TDI),
Cyclohexyl carboxyamide base caprolactam (CCC), benzoyl caprolactam (PCC), hexamethylene diisocyanate (HDI), hexichol first
One or more in alkane diisocyanate (MDI), diphenyl carbonate,
One or more of the described lactam monomers in caprolactam, caprinolactam, lauric lactam.
Carbon nano-tube modification poly-lactam composite of the present invention, utilizes amido modified CNT, Zhi Houzai
Isocyanates grafting carbon nanotube is obtained with isocyanates reaction, is reacted again with lactam monomers afterwards, lactams end-blocking is formed
Modified carbon nano-tube, then in proportion with lactam monomers melt mixed, carry out in-situ polymerization modification.Participate in CNT interior
The polymerisation of amide monomer, solves CNT prepared by the conventional blend method bad dispersibility in matrix resin well
The problem of, the adhesion between polyamide substrate and CNT is added, enables the abundant body of characteristic property of CNT
It is existing.The tribological property of the in-situ modified poly-lactam composite of CNT of the present invention is improved, and especially makes its friction system
Number substantially reduction, wear resistance is greatly improved.The in-situ modified poly-lactam of CNT handled by low-temperature grinding is combined
Dusty material can be applied in laser selection sintering art.
The in-situ modified poly-lactam composite of a kind of CNT of the present invention is in laser selection sintering art
Application.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) tribological property of the in-situ modified poly-lactam composite of CNT of the present invention is improved, and is especially made
Its coefficient of friction is substantially reduced, and wear resistance is greatly improved；
(2) impact strength of the in-situ modified poly-lactam composite of CNT of the present invention is improved；
(3) preparation method of the invention is simple and easy to apply；
(4) composite powder that the present invention is provided is so that product dimensional stability, abrasion resistance and toughness are substantially carried
It is high.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection model not thereby limiting the invention
Enclose.It is raw materials used commercially available in embodiment, represented with parts by weight.
Embodiment 1
1 part of original single-walled carbon nanotube (SWCNTs) is weighed, is placed in 200ml round-bottomed flasks, 30ml mixed acid is added
(the concentrated sulfuric acid: concentrated nitric acid=3: flow back 3h in 1) in 70 DEG C, is then filtered by vacuum, by obtained black solid, distilled water is used repeatedly
Washing and filtering, untill filtrate pH value is close to neutrality, obtained product is placed in 80 DEG C of vacuum drying chambers and dries 24h, is obtained
Modified carbon nano-tube after to acid treatment；By the CNT after acid treatment and thionyl chloride reaction backflow 24h, by CNT
The carboxyl on surface is converted to acyl chlorides.Washed off afterwards with tetrahydrofuran after thionyl chloride, 24h is dried in vacuo at room temperature.Amount
Appropriate diamines and the carbon pipe after processing are taken, in 2: 1 ratios in being cooled to room temperature after 130 DEG C of back flow reaction 24h.Reaction product is filtered
Drying is washed with ethanol after going out, the function modified CNT of ethylenediamine (SWCNTs-EDA) is obtained.Afterwards by 1 part of SWCNTs-
EDA ultrasonic disperses are in 60ml toluene, then under the conditions of magnetic agitation, add 3 parts of azodiisobutyronitrile catalyst (AIBN)
Initiator, leads to N290 DEG C of stirring reaction 3h after deoxygenation.Reaction product is washed after multipass with toluene, and 50 DEG C are dried in vacuum overnight, and obtain
The single pipe powder SWCNTs-AIBN being modified to the AIBN of black.1 part of SWCNTs- is added in three-necked flask afterwards
AIBN, 6 parts of NiCl2·6H2Ultrasonic disperse 30min under the conditions of O and 50ml tetrahydrofurans (THF), maintaining nitrogen purge, adds Al powder 1
Part starts reaction, after about 20min reactions terminate, then the solid mixture for being diluted and being filtrated to get with 100ml THF pours into beaker
In, the dilute sulfuric acid for adding 3mol/L removes ALNiCl2·6H2It is filtered by vacuum after O, filtration product is washed with deionized water to neutrality,
60 DEG C of vacuum drying obtain amino modified carbon nanotube powder.1 part of amino modified carbon nanotube powder is dispersed in 100ml second
In acetoacetic ester, ultrasonic disperse 1h or so is filtrated to get product after adding 1 part of isocyanates TDI heating stirring, reaction 3h, is used in combination
Product is extracted 6h by ethyl acetate, obtains the CNT of isocyanates TDI modifications.By 1 part of isocyanates base carbon nanotube point
It is dispersed in ethyl acetate, adds after 1 part of caprolactam agitating and heating reaction 3h, be filtrated to get product, then extracted with ethyl acetate
The modified carbon nano-tube of lactams end-blocking is dried to obtain after product 6h.By acyl in the CNT of 1 part of lactams end-blocking and 100 parts
Amine monomers are mixed, and caprolactam and lauric lactam ratio (mol ratios) are 95: 5 wherein in lactams；It it is 120 DEG C in temperature
Ultrasonically treated 3h under constant temperature；0.6 part of catalyst n aOH is added in the case where temperature is 130 DEG C, is vacuumized after water removal 30min, plus
Enter 0.4 part of activator TDI, polymerization insulation 60min obtains in-situ modified poly- of CNT at 150 DEG C after quickly stirring
Lactams composite 1.
After tested, the tensile strength of composite 1 prepared by embodiment 1 can reach 69MPa, and impact strength reaches 92J/
M, Volume erosion rate is substantially reduced, and reaches 4.0 (x10-5mm3N-1m-1)。
Embodiment 2
1 part of original double-walled carbon nano-tube (DWCNTs) is weighed, is placed in 200ml round-bottomed flasks, 45ml mixed acid is added
(the concentrated sulfuric acid: concentrated nitric acid=3: flow back 4h in 1) in 60 DEG C, is then filtered by vacuum, by obtained black solid, distilled water is used repeatedly
Washing and filtering, untill filtrate pH value is close to neutrality, obtained product is placed in 80 DEG C of vacuum drying chambers and dries 24h, is obtained
Modified carbon nano-tube after to processing；By the CNT after acid treatment and thionyl chloride reaction backflow 24h, by CNT table
The carboxyl in face is converted to acyl chlorides.Washed off afterwards with tetrahydrofuran after thionyl chloride, 24h is dried in vacuo at room temperature.Measure
Appropriate diamines and the carbon pipe after processing, in 2: 1 ratios in being cooled to room temperature after 135 DEG C of back flow reaction 18h.Reaction product is filtered out
Drying is washed with ethanol afterwards, the function modified double-walled carbon nano-tube of ethylenediamine (DWCNTs-EDA) is obtained.Afterwards by 1 part
DWCNTs-EDA ultrasonic disperses are in 90ml toluene, then under the conditions of magnetic agitation, add 4 parts of ABVN catalyst
(ABVN) initiator, leads to N280 DEG C of stirring reaction 4h after deoxygenation.Reaction product is washed after multipass with toluene, and 50 DEG C were dried in vacuo
At night, obtain the double-walled carbon nano-tube powder DWCNTs-ABVN that the AVBN of black is modified.1 part is added in three-necked flask afterwards
DWCNTs-ABVN, 6 parts of NiCl2·6H2Ultrasonic disperse 20min under the conditions of O and 50ml tetrahydrofurans (THF), maintaining nitrogen purge, plus
Enter 2 parts of Al powder and start reaction, after about 20min reactions terminate, then the solid mixture for being diluted and being filtrated to get with 100ml THF falls
Enter in beaker, the dilute sulfuric acid for adding 3mol/L removes ALNiCl2·6H2It is filtered by vacuum after O, filtration product is washed with deionized water
To neutrality, 60 DEG C of vacuum drying obtain amino modified carbon nanotube powder.1 part of amino modified carbon nanotube powder is dispersed in
In 100ml ethyl acetate, ultrasonic disperse 2h or so is filtrated to get production after adding 2 parts of isocyanates MDI heating stirrings, reaction 4h
Thing, and product is extracted into 9h with ethyl acetate, obtain the CNT of isocyanates MDI modifications.1 part of NCO carbon is received
Mitron is dispersed in ethyl acetate, is added after 2 parts of caprinolactam agitating and heating reaction 3h, is filtrated to get product, then use acetic acid second
The modified carbon nano-tube of lactams end-blocking is dried to obtain after ester extract product 9h.By the CNT and 75 of 1 part of lactams end-blocking
Part lactam monomers mixing, caprolactam and caprinolactam ratio (mol ratios) are 50: 25 wherein in lactams；It is 110 in temperature
DEG C constant temperature under ultrasonically treated 3h；0.5 part of catalyst n aOH is added in the case where temperature is 135 DEG C, water removal 20min is vacuumized
Afterwards, 0.30 part of activator MDI is added, polymerization insulation 40min obtains CNT original position and changed at 160 DEG C after quickly stirring
The poly-lactam composite 2 of property.
After tested, the tensile strength of composite 2 prepared by embodiment 2 can reach 189MPa, and impact strength reaches
140J/m, Volume erosion rate is substantially reduced, and reaches 2.2 (x10-5mm3N-1m-1)。
Embodiment 3
1 part of original multi-walled carbon nanotube (MWCNTs) is weighed, is placed in 200ml round-bottomed flasks, 60ml mixed acid is added
(the concentrated sulfuric acid: concentrated nitric acid=3: flow back 6h in 1) in 60 DEG C, is then filtered by vacuum, by obtained black solid, distilled water is used repeatedly
Washing and filtering, untill filtrate pH value is close to neutrality, obtained product is placed in 80 DEG C of vacuum drying chambers and dries 24h, is obtained
Modified multiwalled carbon nanotube after to processing；By the CNT after acid treatment and thionyl chloride reaction backflow 24h, by carbon nanometer
The carboxyl of pipe surface is converted to acyl chlorides.Washed off afterwards with tetrahydrofuran after thionyl chloride, 24h is dried in vacuo at room temperature.
Appropriate diamines and the carbon pipe after processing are measured, in 2: 1 ratios in being cooled to room temperature after 135 DEG C of back flow reaction 18h.By reaction product
Drying is washed with ethanol after filtering out, the function modified multi-walled carbon nanotube of ethylenediamine (MWCNTs-EDA) is obtained.Afterwards by 1 part
MWCNTs-EDA ultrasonic disperses are in 100ml toluene, then under the conditions of magnetic agitation, add 6 parts of AMBN catalysis
Agent (AMBN) initiator, leads to N280 DEG C of stirring reaction 6h after deoxygenation.Reaction product is washed after multipass with toluene, 50 DEG C of vacuum drying
Overnight, the multi-wall carbon nano-tube pipe powder DWCNTs-AMBN that the AMBN of black is modified is obtained.1 part is added in three-necked flask afterwards
DWCNTs-AMBN, 6 parts of NiCl2·6H2Ultrasonic disperse 20min under the conditions of O and 50ml tetrahydrofurans (THF), maintaining nitrogen purge, plus
Enter 3 parts of Al powder and start reaction, after about 20min reactions terminate, then the solid mixture for being diluted and being filtrated to get with 100ml THF falls
Enter in beaker, the dilute sulfuric acid for adding 3mol/L removes ALNiCl2·6H2It is filtered by vacuum after O, filtration product is washed with deionized water
To neutrality, 60 DEG C of vacuum drying obtain amino modified carbon nanotube powder.1 part of amino modified carbon nanotube powder is dispersed in
In 100ml ethyl acetate, ultrasonic disperse 3h or so is filtrated to get production after adding 3 parts of isocyanates HDI heating stirrings, reaction 4h
Thing, and product is extracted into 9h with ethyl acetate, obtain the CNT of isocyanates HDI modifications.1 part of NCO carbon is received
Mitron is dispersed in ethyl acetate, is added after 3 parts of lauric lactam agitating and heating reaction 3h, is filtrated to get product, then use acetic acid
The modified carbon nano-tube of lactams end-blocking is dried to obtain after ethyl ester extract product 12h.By the CNT of 1 part of lactams end-blocking with
50 parts of caprolactam monomer mixing, caprinolactam and lauric lactam ratio (mol ratios) are 25: 25 wherein in lactams；In temperature
Spend ultrasonically treated 6h under the constant temperature for 110 DEG C；0.3 part of catalyst sodium methoxide is added in the case where temperature is 140 DEG C, vacuumizes and removes
After water 20min, 0.25 part of activator HDI is added, polymerization insulation 60min obtains carbon nanometer at 160 DEG C after quickly stirring
The in-situ modified poly-lactam composite 3 of pipe.
After tested, the tensile strength of composite 3 prepared by embodiment 3 can reach 100MPa, and impact strength reaches
175J/m, Volume erosion rate is substantially reduced, and reaches 1.1 (x10-5mm3N-1m-1)。
Prior art comparative example is used as using the poly-lactam material not mixed with CNT：
Comparative example 1
At reduced pressure, 100 parts of lactams are heated to 125 DEG C into molten condition, acyl in oneself wherein in lactams
Amine and lauric lactam ratio (mol ratios) are 95: 5, and constantly backflow removes the moisture in monomer.Add 0.3 part of catalyst
NaOH, 135 DEG C are risen to by temperature.This process will prevent air from entering reaction system, and reduced-pressure backflow 30min removes catalytic reaction production
Raw water, back-flow velocity is 30d/min, obtains living anionic initiators.Then 0.15 part of activator TDI stirring is added
2min, it is uniform after cast in the mould preheated in advance, the preheating temperature of mould is 165 DEG C.It polymerize insulation at 160 DEG C
60min obtains the poly-lactam resin 1 of not carbon nanotubes.
Comparative example 2
At reduced pressure, 100 parts of lactams are heated to 130 DEG C into molten condition, acyl in oneself wherein in lactams
Amine and caprinolactam ratio (mol ratios) are 67: 33, and constantly backflow removes the moisture in monomer.Add 0.5 part of catalyst
KOH, 140 DEG C are risen to by temperature.This process will prevent air from entering reaction system, and reduced-pressure backflow 30min removes catalytic reaction production
Raw water, back-flow velocity is 30d/min, obtains living anionic initiators.Then 0.3 part of MDI activators stirring 2min is added,
Cast in after uniform in the mould preheated in advance, the preheating temperature of mould is 165 DEG C.Polymerization insulation 60min is obtained at 165 DEG C
The not poly-lactam resin 2 of carbon nanotubes.
Comparative example 3
At reduced pressure, 100 parts of lactams are heated to 135 DEG C into molten condition, acyl in the last of the ten Heavenly stems wherein in lactams
Amine and lauric lactam ratio (mol ratios) are 50: 50, and constantly backflow removes the moisture in monomer.Add 0.5 part of catalyst
Sodium methoxide, 145 DEG C are risen to by temperature.This process will prevent air from entering reaction system, and reduced-pressure backflow 30min removes catalytic reaction
The water of generation, back-flow velocity is 30d/min, obtains living anionic initiators.Then 0.4 part of MDI activators stirring is added
2min, it is uniform after cast in the mould preheated in advance, the preheating temperature of mould is 170 DEG C.It polymerize insulation at 170 DEG C
60min obtains the poly-lactam resin 3 of not carbon nanotubes.
Test case
Embodiment 1-3 and comparative example 1-3 is subjected to tensile strength, Izod notched impact strength, coefficient of friction, volume mill
The measure of loss rate.Wherein stretching strength determination is with reference to ASTMD638-08, and impact strength is determined with reference to ASTMD256-06；Friction mill
Damage using MM200 type friction wear testing machines in dry condition.Specific measurement result is as shown in table 1.
The performance parameter table of table 1
The tensile strength for the in-situ modified poly-lactam composite of CNT that embodiment is obtained can reach 65~
105MPa, impact strength improves more than 2 times than prior art products, and Volume erosion rate is substantially reduced, than conventional products reduction by 3
More than times.
Claims (9)
1. a kind of preparation method of the in-situ modified poly-lactam composite of CNT, it is characterised in that described preparation side
Method is following steps：
（1）By CNT ultrasonic disperse in toluene, then under the conditions of magnetic agitation, azo initiator is added, in inertia
70~90 DEG C of h of stirring reaction 3~6 under gas shield, reaction product is scrubbed, dry after obtain the carbon of azo initiator modification
Nanotube powder；
（2）The carbon nanotube powder that azo initiator is modified, NiCl are added in a reservoir2·6H2O and tetrahydrofuran, in indifferent gas
The lower ultrasonic disperse 30min of body protection, is added after Al powder after 10 ~ 30min of reaction, post-treated to obtain amino modified carbon nanotube powders
End；
（3）By amino modified carbon nanotube powder in ethyl acetate 1~3h of ultrasonic disperse, add isocyanates at 60 ~ 80 DEG C
Product is filtrated to get after 3~6h of stirring reaction, and product is extracted into 6~12h with ethyl acetate, isocyanate-modified carbon is obtained
Nanotube；
（4）Isocyanate-modified CNT is dispersed in ethyl acetate, lactam monomers are added anti-in 60 ~ 80 DEG C of stirrings
Answer after 3~6h, filter and with ethyl acetate 6~12h of extract product, dry, obtain the modified carbon nano-tube of lactams end-blocking；
（5）The CNT that lactams is blocked is mixed with lactam monomers, in temperature under 100~120 DEG C of constant temperature
Ultrasonically treated 3 ~ 6h, adds catalyst in the case where temperature is 130~140 DEG C, vacuumizes after 10~30min of water removal, add isocyanic acid
Ester, stirs and polymerize at 140~170 DEG C, and 20~60min of insulation obtains the in-situ modified poly-lactam composite wood of CNT
Material,
The tensile strength of described composite is 65~105MPa, and impact strength is 90~175J/m, and Volume erosion rate is
(0.8~4.0) x10-5mm3N-1m-1。
2. a kind of preparation method of the in-situ modified poly-lactam composite of CNT according to claim 1, it is special
Levy and be, step（1）Described in CNT in single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube
A diameter of 0.5~20nm of one or more, wherein CNT, length is 1~50 μm.
3. a kind of preparation method of the in-situ modified poly-lactam composite of CNT according to claim 1 or 2, its
It is characterised by, azo initiator is selected from azodiisobutyronitrile, AMBN, ABVN, the isobutyl imidazoles of azo two
The weight ratio of one or more in quinoline, azo-bis-isobutyrate hydrochloride, azo initiator and CNT is 3 ~ 6：1.
4. a kind of preparation method of the in-situ modified poly-lactam composite of CNT according to claim 1, it is special
Levy and be, step（2）Middle NiCl2·6H2The weight ratio for the carbon nanotube powder that O is modified with azo initiator is 6 ~ 9：1, Al powder
The weight ratio for the carbon nanotube powder being modified with azo initiator is 1 ~ 3：1.
5. a kind of preparation method of the in-situ modified poly-lactam composite of CNT according to claim 1, it is special
Levy and be, step（3）The weight ratio of isocyanates and amino modified carbon nanotube powder is 1 ~ 3：1, step（5）Described isocyanide
The weight ratio for the CNT that acid esters is blocked with lactams is 0.1 ~ 0.5：1.
6. the preparation method of the in-situ modified poly-lactam composite of a kind of CNT according to claim 1 or 5, its
It is characterised by, described isocyanates is selected to toluene 2,4- diisocyanate, hexamethylene diisocyanate, diphenyl-methane two
One or more in isocyanates.
7. a kind of preparation method of the in-situ modified poly-lactam composite of CNT according to claim 1, it is special
Levy and be, step（4）The weight ratio of middle lactam monomers and isocyanates base carbon nanotube is 1~3：1, step（5）Lactams
The weight ratio for the CNT that monomer is blocked with lactams is 50 ~ 100：1, described lactam monomers are selected from caprolactam, the last of the ten Heavenly stems
One or more in lactams, lauric lactam.
8. a kind of preparation method of the in-situ modified poly-lactam composite of CNT according to claim 1, it is special
Levy and be, step（5）Described catalyst is in NaOH, KOH, sodium caprolactam, caprolactam potassium, caustic alcohol, sodium methoxide
One or more, the weight ratio for the CNT that catalyst and lactams are blocked is 0.2 ~ 1：1.
9. a kind of a kind of preparation method of the in-situ modified poly-lactam composite of CNT as claimed in claim 1 is obtained
The in-situ modified poly-lactam composite of CNT laser select sintering art in application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510481933.1A CN105315456B (en) | 2015-08-03 | 2015-08-03 | A kind of in-situ modified poly-lactam composite of CNT and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510481933.1A CN105315456B (en) | 2015-08-03 | 2015-08-03 | A kind of in-situ modified poly-lactam composite of CNT and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105315456A CN105315456A (en) | 2016-02-10 |
| CN105315456B true CN105315456B (en) | 2017-08-25 |
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| CN109762173A (en) * | 2018-12-21 | 2019-05-17 | 深圳烯湾科技有限公司 | Modified carbon nano-tube array and its preparation method and application |
| RU2708583C1 (en) * | 2019-04-12 | 2019-12-09 | МСД Текнолоджис С.а.р.л. | Method of producing high-strength composite material based on a thermoplastic polymer, a modifier for preparing a composite material and a method of producing a modifier for preparing composite material (versions) |
| CN113061268A (en) * | 2021-03-26 | 2021-07-02 | 江苏苏能新材料科技有限公司 | Preparation method of conductive high-fluidity nylon 6 master batch |
| US11884763B2 (en) | 2021-05-17 | 2024-01-30 | Xerox Corporation | Spherical particles comprising carbon nanomaterial-graft-polyolefin and methods of production and uses thereof |
| US20220389145A1 (en) * | 2021-05-17 | 2022-12-08 | Xerox Corporation | Spherical particles comprising carbon nanomaterial-graft-polymer and methods of production and uses thereof |
| CN113831598A (en) * | 2021-10-29 | 2021-12-24 | 江苏芬茂新材料科技有限公司 | Modified carbon nanotube and application thereof in special plastic for automobile fuel tank |
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