CN110204791A - A kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting film and preparation method thereof - Google Patents
A kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting film and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting films and preparation method thereof.The film is acted on using graphene and imido π-π stacking, and dispersibility of the graphene in cellulose nano microcrystalline matrix is effectively solved, and then improves graphene in the thermal conducting path of cellulose nano microcrystalline composite heat-conducting film.Preparation method includes: that (1) takes mass ratio for (10~90): the acid imide functionalization graphene aqueous dispersions and sisal cellulose nano microcrystalline of (90~10), and mixing, ultrasonic wave is uniformly dispersed, and stirs, and filters film forming；(2) film for obtaining step (1) is 10~15MPa in mechanical pressure, and the pressing time is to suppress under 5~20min, and acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting film can be obtained.The present invention has the characteristics that preparation process is simple, thermal coefficient is high, environmentally friendly and production cost is low, is expected to have potential application prospect in thermal interfacial material and other electronics fields.
Description
Technical field
The present invention relates to a kind of field of thin film material preparation, more particularly, to a kind of acid imide functionalization graphene/sword
Flaxen fiber element nano microcrystalline composite heat-conducting film and preparation method thereof.
Background technique
As electronic product develops towards high density, light, thin, short, small direction, the integrated speed and function of each component
Rate further increases, and causes the operating temperature of component higher and higher, and the requirement to heat dissipation is also higher and higher.Therefore, exploitation is high
Heat Conduction Material is very urgent.With copper, the metal fevers such as aluminium management heat sink material is compared, and carbon material has thermal coefficient high, and density is low,
Many advantages, such as excellent in mechanical performance, alternative traditional metal heat dissipation material meet electronic device collection multifunction, micromation
With the lightening requirement in one.Compared to other carbon materials, graphene is tightly packed at bi-dimensional cellular by single layer of carbon atom
A kind of carbonaceous new material of shape lattice structure.By its unique structure, so that its carrier mobility is 2 × 105cm2/V·
S, thermal conductivity be 5300 W/mK, thus by graphene preparation heat conduction and heat radiation film new material in thermal management applications by pass
Note.
Imide derivative is a kind of special condensed-nuclei aromatics class compound, has good chemical inertness, anticorrosive
Performance and photostability, and fluorescence quantum yield is high, is widely used in fluorescence probe, organic semiconductor, organic electroluminescent, divides
The fields such as sub- self assembly.Imide derivative has big conjugation phenyl ring planar structure, same as some other can have altogether
By noncovalent interaction power the effect of π-π stacking occurs for the molecule of yoke structure.
Have patent report, such as Chinese invention for the research of nano-cellulose/graphene thermally conductive film both at home and abroad at present
Patent " MULTILAYER COMPOSITE thermally conductive film and preparation method thereof " (CN108129685A).But nano-cellulose/the graphite reported at present
The disadvantages of that there are still thermal coefficients is low for alkene thermally conductive film, poor mechanical property.
Summary of the invention
A kind of acid imide functionalization is provided the purpose of the invention is to overcome the problems of the above-mentioned prior art
Graphene/sisal cellulose nano microcrystalline composite heat-conducting film and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
It is an object of the present invention to propose that a kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline is multiple
The preparation method for closing thermally conductive film is acted on using graphene and imido π-π stacking, effectively solves graphene in cellulose
Dispersibility in nano microcrystalline matrix, and then graphene is improved in the thermal conducting path of cellulose nano microcrystalline composite heat-conducting film.
The second object of the present invention is to propose that a kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline is multiple
The preparation method for closing thermally conductive film, good, the imide derivative of molecular chain length that synthesizes a kind of solubility property using MOLECULE DESIGN,
New functional groups are introduced, the compatibility of graphene Yu sisal cellulose nano microcrystalline is increased, are further improved compound
The mechanical property of thermally conductive film.
The third object of the present invention is to propose that a kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline is multiple
The preparation method of thermally conductive film is closed, mainly includes following two step:
(1) taking mass ratio is (10~90): the acid imide functionalization graphene aqueous dispersions of (90~10) and sisal hemp are fine
Plain nano microcrystalline, mixing are tieed up, ultrasonic wave is uniformly dispersed, stirs, and filters film forming；
(2) film for obtaining step (1) is 10~15MPa in mechanical pressure, and the pressing time is to suppress under 5~20min,
Acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting film can be obtained.
As a preferred embodiment of the above technical solution, a kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline is multiple
The preparation method of thermally conductive film is closed, the imide derivative in step (1) is synthesized by following two step:
I) by acid anhydride with six aminocaproic acids in molar ratio it is first that 1:1 reacts, the solvent imidazoles of 10~30g is added, in N2
Under protection, in 120 DEG C of reaction 12h, after reaction, reaction temperature is dropped to 90 DEG C, the deionized water of 50~100mL is added,
120 DEG C are warming up to, then the hydrochloric acid of 2mol/L is slowly added into filtrate, until there is Precipitation, will sink by the reaction was continued 2h
It forms sediment and filters, washed to filtrate and be in neutrality repeatedly with deionized water, finally dried in 60 DEG C of vacuum drying ovens, obtain carboxyl end group acyl
Imine product (PBI-COOH)；
Ii) by above-mentioned reaction product, 1:10 reacts in molar ratio with ethylenediamine, and 30~60mL N-Methyl pyrrolidone is added
Make solvent, in N2Under protection, reaction solution is filtered after reaction in 120 DEG C of reaction 12h, filter cake is washed to filtrate repeatedly is in
Neutrality finally dries product to obtain Amino End Group acid imide (PBI-NH2)。
As a preferred embodiment of the above technical solution, the extraction of sisal cellulose nano microcrystalline uses dewaxing, drift in step (1)
White, grafting and mechanical stirring four step rule.It is furthermore preferred that the acid that grafting uses is monoxone.Its step specifically:
I) dewaxing technique: cutting into the short fibre that length is about 5mm for sisal fiber first, be washed with deionized for several times,
The graininess lignin on sisal fiber surface is removed, it is then that sisal fiber is dry in 60 DEG C of baking oven, it is spare.Secondly, will
50g dry fiber is placed in the Na of the NaOH and 4wt% of 4wt%2SO4·10H2In the mixed aqueous solution of O, at 170 DEG C
2h is reacted in 500mL autoclave, last filtration washing for several times, is dried overnight in vacuum drying oven；
Ii) bleaching process: dewaxing sisal fiber, the 12g NaClO that (i) is obtained2、5mLCH3COOH and 350mL deionization
Water is added in 500mL three-necked flask, and 2h is stirred at 80 DEG C, and washing filtering obtains sisal cellulose crystallite (MSF)；
Iii) graft process: tri- mouthfuls of round bottoms of 500mL are added in 7g MSF, 35g10wt%NaOH and 350mL dehydrated alcohol and are burnt
In bottle, 30min is stirred at 30 DEG C, 3.5g monoxone is then added, 3h is stirred at 70 DEG C, and centrifuge washing is multiple, collects and produces
Object；
Iiii) mechanical stirring: crude product in iii) is dispersed in 500mL deionized water and impregnates 1h, uses high shear dispersion
Product is cut into fractionlet with the speed of 28000r/min by homogenizer, obtains the cellulose nanometer that solid content is 0.25wt%
Crystallite (NCC) clear gel.
As a preferred embodiment of the above technical solution, acid imide functionalization graphene/sisal cellulose nanometer is micro- in step (2)
Brilliant composite heat-conducting film thickness is 80~100 μm.
As a preferred embodiment of the above technical solution, acid imide functionalization graphene/sisal cellulose described in step (2) is received
The thermal coefficient of meter Wei Jing composite heat-conducting film reaches 250W/mK, and tensile strength reaches 170MPa.
Detailed description of the invention
Fig. 1 is that acid imide functionalization graphene/sisal cellulose nanometer that the specific embodiment of the invention 2 is prepared is micro-
Brilliant composite heat-conducting film.
Fig. 2 is that acid imide functionalization graphene/sisal cellulose nanometer that the specific embodiment of the invention 2 is prepared is micro-
The stereoscan photograph of brilliant composite heat-conducting film sections.
Specific embodiment
Primary raw material used in example is as follows: acid anhydride (technical grade), graphene powder (technical grade), six aminocaproic acids (point
Analyse pure), ethylenediamine (analysis is pure).The technical solution in case study on implementation of the present invention will be described in detail below.
Embodiment 1
(1) 0.5g acid anhydride and six aminocaproic acid of 0.4g, 5g imidazoles the imido synthesis (PBI-COOH) of carboxyl end group: are weighed
In 250mL three-necked flask, N2After protecting 5min, it is heated to 120 DEG C, reacts and reaction temperature is dropped to 90 DEG C after 12h, be added
The deionized water of 50mL is warming up to 120 DEG C, the reaction was continued 2h, is then slowly added into the hydrochloric acid of 2mol/L in reaction solution extremely
It is filtered, filter cake is washed to filtrate repeatedly with deionized water and is in neutrality, finally true at 60 DEG C until there is Precipitation pH=3~4
It is dried in empty baking oven, obtains carboxyl end group imide product (PBI-COOH)；
(2) the imido synthesis (PBI-NH of Amino End Group2): above-mentioned reaction product (PBI-COOH) 0.5g is weighed, is measured
Ethylenediamine 2mL is added 30mL N-Methyl pyrrolidone and makees solvent in 100mL three-necked flask, in N2It is anti-in 120 DEG C under protection
12h is answered, after reaction, after reaction solution is precipitated 30min in the methanol and deionized water that volume ratio is 1:1, will be precipitated
Filter, filter cake are washed to filtrate repeatedly with deionized water and are in neutrality, finally dry product to obtain Amino End Group acid imide (PBI-
NH2)。
(3) preparation of sisal cellulose nano microcrystalline (NCC): using dewaxing, bleaching, grafting and mechanical stirring four step rule from
It extracts and obtains in sisal fiber.Its step specifically:
I) dewaxing technique: cutting into the short fibre that length is about 5mm for sisal fiber first, be washed with deionized for several times,
The graininess lignin on sisal fiber surface is removed, it is then that sisal fiber is dry in 60 DEG C of baking oven, it is spare.Secondly, will
50g dry fiber is placed in the Na of the NaOH and 4wt% of 4wt%2SO4·10H2In the mixed aqueous solution of O, at 170 DEG C
2h is reacted in 500mL autoclave, last filtration washing for several times, is dried overnight in an oven；
Ii) bleaching process: dewaxing sisal fiber, the 12gNaClO that (i) is obtained2、5mLCH3COOH and 350mL deionization
Water is added in 500mL three-necked flask, and 2h is stirred at 80 DEG C, and washing filtering obtains sisal cellulose crystallite (MSF)；
Iii) graft process: tri- mouthfuls of round bottoms of 500mL are added in 7gMSF, 35g10wt%NaOH and 350mL dehydrated alcohol and are burnt
In bottle, 30min is stirred at 30 DEG C, 3.5g monoxone is then added, 3h is stirred at 70 DEG C, and centrifuge washing is multiple, collects and produces
Object；
Iiii) mechanical stirring: crude product being dispersed in 500mL deionized water and impregnates 1h, with high shear dispersion homogenizer
Product is cut into fractionlet with the speed of 28000r/min, obtains the cellulose nano microcrystalline that solid content is 0.25wt%
(NCC) clear gel.
(4) 1mg PBI-NH is weighed2With 100mg graphene in 101mL deionized water, ultrasonic wave disperses 1.5h, then
10mL dispersion liquid is measured in the NCC of the 0.25wt% of 36mL, mixed liquor is filtered and formed a film by high-speed stirred 12h；
(5) film for obtaining step (4) peels off in vacuum drying oven after 40 DEG C of drying, finally obtained film exists
Mechanical pressure is 10MPa, and the pressing time is to suppress under 10min, can be obtained with a thickness of 90 μm of acid imide functionalization graphenes/
Sisal cellulose sodium rice crystalline substance composite heat-conducting film.The thermal conductivity for measuring composite heat-conducting film is 11.2W/mK, and toughness reaches
3.2MJ/m3, 167.9%, 60.8% is improved respectively relative to matrix fiber element nano microcrystalline.
Embodiment 2
(1) 1.0g acid anhydride and six aminocaproic acid of 1.0g, 12g miaow the imido synthesis (PBI-COOH) of carboxyl end group: are weighed
Azoles is in 250mL three-necked flask, N2After protecting 10min, it is heated to 120 DEG C, reacts and reaction temperature is dropped to 90 DEG C after 16h, add
The deionized water for entering 100mL is warming up to 120 DEG C, the reaction was continued 2h, and then the hydrochloric acid of 2mol/L is slowly added into reaction solution
It is filtered, filter cake is washed to filtrate repeatedly with deionized water and is in neutrality, finally at 60 DEG C to pH=3~4 until there is Precipitation
It is dried in vacuum drying oven, obtains carboxyl end group imide product (PBI-COOH)；
(2) the imido synthesis (PBI-NH of Amino End Group2): above-mentioned reaction product (PBI-COOH) 1.0g is weighed, is measured
Ethylenediamine 4mL is added 50mL N-Methyl pyrrolidone and makees solvent in 100mL three-necked flask, in N2It is anti-in 120 DEG C under protection
14h is answered, after reaction, after reaction solution is precipitated 30min in the methanol and deionized water that volume ratio is 1:1, will be precipitated
Filter, filter cake are washed to filtrate repeatedly with deionized water and are in neutrality, finally dry product to obtain Amino End Group acid imide (PBI-
NH2)。
(3) preparation of sisal cellulose nano microcrystalline (NCC): using dewaxing, bleaching, grafting and mechanical stirring four step rule from
It extracts and obtains in sisal fiber.Its step specifically:
I) dewaxing technique: cutting into the short fibre that length is about 5mm for sisal fiber first, be washed with deionized for several times,
Remove the graininess lignin on sisal fiber surface.Then sisal fiber is dry in 60 DEG C of baking oven, it is spare.Secondly, will
50g dry fiber is placed in the Na of the NaOH and 4wt% of 4wt%2SO4·10H2In the mixed aqueous solution of O, at 170 DEG C
2h is reacted in 500mL autoclave, last filtration washing for several times, is dried overnight in an oven；
Ii) bleaching process: dewaxing sisal fiber, the 12gNaClO that (i) is obtained2、5mLCH3COOH and 350mL deionization
Water is added in 500mL three-necked flask, and 2h is stirred at 80 DEG C, and washing filtering obtains sisal cellulose crystallite (MSF)；
Iii) graft process: tri- mouthfuls of round bottoms of 500mL are added in 7g MSF, 35g10wt%NaOH and 350mL dehydrated alcohol and are burnt
In bottle, 30min is stirred at 30 DEG C, 3.5g monoxone is then added, 3h is stirred at 70 DEG C, and centrifuge washing is multiple, collects and produces
Object；
Iiii) mechanical stirring: crude product being dispersed in 500mL deionized water and impregnates 1h, with high shear dispersion homogenizer
Product is cut into fractionlet with the speed of 28000rmp/min, obtains the nano microcrystalline (NCC) that solid content is 0.25wt%
Clear gel.
(4) 1mg PBI-NH is weighed2With 100mg graphene in 101mL deionized water, ultrasonic wave disperses 1.5h, then
20mL dispersion liquid is measured in the NCC of the 0.25wt% of 32mL, mixed liquor is filtered and formed a film by high-speed stirred 10h；
(5) film for obtaining step (4) peels off in vacuum drying oven after 40 DEG C of drying, finally obtained film exists
Mechanical pressure is 12MPa, and the pressing time is to suppress under 15min, can be obtained with a thickness of 90 μm of acid imide functionalization graphenes/
Sisal cellulose nano microcrystalline composite heat-conducting film.The thermal conductivity for measuring composite heat-conducting film is 26.2W/mK, and toughness reaches
3.6MJ/m3, 526.8%, 80.9% is improved respectively relative to matrix fiber element nano microcrystalline.
Embodiment 3
(1) 1.0g acid anhydride and six aminocaproic acid of 1.0g, 12g miaow the imido synthesis (PBI-COOH) of carboxyl end group: are weighed
Azoles is in 250mL three-necked flask, N2After protecting 10min, it is heated to 120 DEG C, reacts and reaction temperature is dropped to 90 DEG C after 16h, add
The deionized water for entering 50mL is warming up to 120 DEG C, the reaction was continued 2h, is then slowly added into the hydrochloric acid of 2mol/L in filtrate extremely
It is filtered, filter cake is washed to filtrate repeatedly with deionized water and is in neutrality, finally true at 60 DEG C until there is Precipitation pH=3~4
It is dried in empty baking oven, obtains carboxyl end group imide product (PBI-COOH)；
(2) the imido synthesis (PBI-NH of Amino End Group2): above-mentioned reaction product (PBI-COOH) 1.0g is weighed, is measured
Ethylenediamine 4mL is added 50mL N-Methyl pyrrolidone and makees solvent in 250mL three-necked flask, in N2It is anti-in 120 DEG C under protection
12h is answered, after reaction, after reaction solution is precipitated 30min in the methanol and deionized water that volume ratio is 1:1, will be precipitated
Filter, filter cake are washed to filtrate repeatedly with deionized water and are in neutrality, finally dry product to obtain Amino End Group acid imide (PBI-
NH2)。
(3) preparation of sisal cellulose nano microcrystalline (NCC): using dewaxing, bleaching, grafting and mechanical stirring four step rule from
It extracts and obtains in sisal fiber.Its step specifically:
I) dewaxing technique: cutting into the short fibre that length is about 5mm for sisal fiber first, be washed with deionized for several times,
Remove the graininess lignin on sisal fiber surface.Then sisal fiber is dry in 60 DEG C of baking oven, it is spare.Secondly, will
50g dry fiber is placed in the Na of the NaOH and 4wt% of 4wt%2SO4·10H2In the mixed aqueous solution of O, at 170 DEG C
2h is reacted in 500mL autoclave, last filtration washing for several times, is dried overnight in an oven；
Ii) bleaching process: dewaxing sisal fiber, the 12gNaClO that (i) is obtained2、5mLCH3COOH and 350mL deionization
Water is added in 500mL three-necked flask, and 2h is stirred at 80 DEG C, and washing filtering obtains sisal cellulose crystallite (MSF)；
Iii tri- mouthfuls of round bottoms of 500mL) graft process: are added in 7g MSF, 35g 10wt%NaOH and 350mL dehydrated alcohol
In flask, 30min is stirred at 30 DEG C, 3.5g monoxone is then added, 3h is stirred at 70 DEG C, and centrifuge washing is multiple, collects
Product；
Iiii) mechanical stirring: crude product being dispersed in 500mL deionized water and impregnates 1h, with high shear dispersion homogenizer
Product is cut into fractionlet with the speed of 28000rmp/min, obtains the cellulose nano microcrystalline that solid content is 0.25wt%
(NCC) clear gel.
(4) 1mg PBI-NH is weighed2With 100mg graphene in 101mL deionized water, ultrasonic wave disperses 1.5h, then
30mL dispersion liquid is measured in the NCC of the 0.25wt% of 28mL, mixed liquor is filtered and formed a film by high-speed stirred 10h；
(5) film for obtaining step (4) peels off in vacuum drying oven after 40 DEG C of drying, finally obtained film exists
Mechanical pressure is 15MPa, and the pressing time is to suppress under 10min, can be obtained with a thickness of 90 μm of acid imide functionalization graphenes/
Sisal cellulose nano microcrystalline composite heat-conducting film.The thermal conductivity for measuring composite heat-conducting film is 46.9W/mK, and toughness reaches
3.3MJ/m3, 1022%, 65.8% is improved respectively relative to matrix fiber element nano microcrystalline.
Embodiment 4
(1) 1.0g acid anhydride and six aminocaproic acid of 1.0g, 12g miaow the imido synthesis (PBI-COOH) of carboxyl end group: are weighed
Azoles is in 250mL three-necked flask, N2After protecting 10min, it is heated to 120 DEG C, reacts and reaction temperature is dropped to 90 DEG C after 16h, add
The deionized water for entering 50mL is warming up to 120 DEG C, the reaction was continued 2h, is then slowly added into the hydrochloric acid of 2mol/L in filtrate extremely
It is filtered, filter cake is washed to filtrate repeatedly with deionized water and is in neutrality, finally true at 60 DEG C until there is Precipitation pH=3~4
It is dried in empty baking oven, obtains carboxyl end group imide product (PBI-COOH)；
(2) the imido synthesis (PBI-NH of Amino End Group2): above-mentioned reaction product (PBI-COOH) 1.0g is weighed, is measured
Ethylenediamine 4mL is added 50mL N-Methyl pyrrolidone and makees solvent in 250mL three-necked flask, in N2It is anti-in 120 DEG C under protection
12h is answered, after reaction, after reaction solution is precipitated 30min in the methanol and deionized water that volume ratio is 1:1, will be precipitated
Filter, filter cake are washed to filtrate repeatedly with deionized water and are in neutrality, finally dry product to obtain Amino End Group acid imide (PBI-
NH2)。
(3) preparation of sisal cellulose nano microcrystalline (NCC): using dewaxing, bleaching, grafting and mechanical stirring four step rule from
It extracts and obtains in sisal fiber.Its step specifically:
I) dewaxing technique: cutting into the short fibre that length is about 5mm for sisal fiber first, be washed with deionized for several times,
Remove the graininess lignin on sisal fiber surface.Then sisal fiber is dry in 60 DEG C of baking oven, it is spare.Secondly, will
50g dry fiber is placed in the Na of the NaOH and 4wt% of 4wt%2SO4·10H2In the mixed aqueous solution of O, at 170 DEG C
2h is reacted in 500mL autoclave, last filtration washing for several times, is dried overnight in an oven；
Ii) bleaching process: dewaxing sisal fiber, the 12gNaClO that (i) is obtained2、5mLCH3COOH and 350mL deionization
Water is added in 500mL three-necked flask, and 2h is stirred at 80 DEG C, and washing filtering obtains sisal cellulose crystallite (MSF)；
Iii) graft process: tri- mouthfuls of round bottoms of 500mL are added in 7g MSF, 35g10wt%NaOH and 350mL dehydrated alcohol and are burnt
In bottle, 30min is stirred at 30 DEG C, 3.5g monoxone is then added, 3h is stirred at 70 DEG C, and centrifuge washing is multiple, collects and produces
Object；
Iiii) mechanical stirring: crude product being dispersed in 500mL deionized water and impregnates 1h, with high shear dispersion homogenizer
Product is cut into fractionlet with the speed of 28000rmp/min, obtains the cellulose nano microcrystalline that solid content is 0.25wt%
(NCC) clear gel.
(4) 1mg PBI-NH is weighed2With 100mg graphene in 101mL deionized water, ultrasonic wave disperses 1.5h, then
50mL dispersion liquid is measured in the NCC of the 0.25wt% of 20mL, mixed liquor is filtered and formed a film by high-speed stirred 10h；
(5) film for obtaining step (4) peels off in vacuum drying oven after 40 DEG C of drying, finally obtained film exists
Mechanical pressure is 15MPa, and the pressing time is to suppress under 15min, can be obtained with a thickness of 85 μm of acid imide functionalization graphenes/
Sisal cellulose nano microcrystalline composite heat-conducting film.The thermal conductivity for measuring composite heat-conducting film is 86.7W/mK, and toughness reaches
2.8MJ/m3, 1974.2%, 40.7% is improved respectively relative to matrix fiber element nano microcrystalline.
Claims (6)
1. a kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting film, it is characterised in that this is thin
Film is acted on using graphene and imido π-π stacking, effectively solves graphene in cellulose nano microcrystalline matrix
Dispersibility, and then graphene is improved in the thermal conducting path of cellulose nano microcrystalline composite heat-conducting film.
2. acid imide functionalization graphene according to claim 1/sisal cellulose nano microcrystalline composite heat-conducting film,
It is characterized in that the composite heat-conducting film thickness is 80~100 μm.
3. a kind of acid imide functionalization graphene according to claim 1 or 2/sisal cellulose nano microcrystalline composite guide
Hot method for manufacturing thin film, it is characterised in that the following steps are included:
(1) taking mass ratio is (10~90): the acid imide functionalization graphene aqueous dispersions and sisal cellulose of (90~10)
Nano microcrystalline, mixing, ultrasonic wave are uniformly dispersed, and stir, and filter film forming；
(2) film for obtaining step (1) is 10~15MPa in mechanical pressure, and the pressing time is to suppress under 5~20min
Obtain acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting film.
4. preparation method according to claim 3, which is characterized in that the acid imide in step (1) is closed by following two step
At:
I) by acid anhydride with six aminocaproic acids in molar ratio it is first that 1:1 reacts, the solvent imidazoles of 5~30g is added, in N2Under protection,
In 120 DEG C of reaction 12h, after reaction, reaction temperature is dropped to 90 DEG C, the deionized water of 50~100mL is added, is warming up to
120 DEG C, the reaction was continued 2h, then the hydrochloric acid of 2mol/L is slowly added into filtrate, until there is Precipitation, will be precipitated
Filter, filter cake are washed to filtrate repeatedly with deionized water and are in neutrality, finally dried in 60 DEG C of vacuum drying ovens, obtain carboxylated
By imide product (PBI-COOH)；
Ii) by above-mentioned reaction product (PBI-COOH), 1:10 reacts in molar ratio with ethylenediamine, and 30~60mL N- methyl pyrrole is added
Pyrrolidone makees solvent, in N2Under protection, in 120 DEG C of reaction 12h, after reaction, by reaction solution in the methanol that volume ratio is 1:1
After precipitating 30min in deionized water, precipitating is filtered, filtering to filtrate is washed repeatedly with deionized water and is in neutrality, finally will
Product dries to obtain Amino End Group acid imide (PBI-NH2)。
5. preparation method according to claim 3, which is characterized in that the acid imide functionalization graphene in step (1)
It is the PBI-NH for being 1:10 by mass ratio2Ultrasonic disperse 1.5h is obtained in water with graphene powder.
6. preparation method according to claim 3, which is characterized in that sisal cellulose nanometer described in step (1) is micro-
Crystalline substance is extracted from sisal fiber and is obtained using dewaxing, bleaching, grafting and mechanical stirring four step rule, step specifically:
I) dewaxing technique: cutting into the short fibre that length is about 5mm for sisal fiber first, is washed with deionized for several times, removal
The graininess lignin on sisal fiber surface, it is then that sisal fiber is dry in 60 DEG C of baking oven, secondly, 50g is dry fine
Dimension is placed in the Na of the NaOH and 4wt% of 4wt%2SO4·10H2In the mixed aqueous solution of O, at 170 DEG C in 500mL autoclave
2h is reacted, last filtration washing for several times, is dried overnight in an oven；
Ii) bleaching process: by the sisal fiber, 12gNaClO of dewaxing obtained in (i)2、5mLCH3COOH and 350mL deionized water
It is added in 500mL three-necked flask, 2h is stirred at 80 DEG C, washing filtering obtains sisal cellulose crystallite (MSF)；
Iii 500mL three neck round bottom flask) graft process: is added in 7g MSF, 35g10wt%NaOH and 350mL dehydrated alcohol
In, 30min is stirred at 30 DEG C, and 3.5g monoxone is then added, 3h is stirred at 70 DEG C, centrifuge washing repeatedly collects product；
Iiii) mechanical stirring: crude product in iii) being dispersed in 500mL deionized water and is impregnated 1 hour, even with high shear dispersion
It starches device and product is cut by fractionlet with the speed of 28000rpm/min, obtain the cellulose nanometer that solid content is 0.25wt%
Crystallite (NCC) clear gel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248797A (en) * | 2021-07-07 | 2021-08-13 | 北京化工大学 | Heat-conducting composite material and preparation method thereof |
| CN115568272A (en) * | 2022-10-28 | 2023-01-03 | 江苏振宁半导体研究院有限公司 | Preparation method of ionic liquid polymer actuator |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360616A (en) * | 2013-07-10 | 2013-10-23 | 武汉纺织大学 | Method for preparing hybrid film through graphene/nano crystalline cellulose dispersion liquid |
| CN103937032A (en) * | 2014-04-19 | 2014-07-23 | 青岛科技大学 | Cellulose nanocrystal/graphene composite colored film and fast preparation method thereof |
| CN106519268A (en) * | 2016-10-28 | 2017-03-22 | 江南大学 | Preparation method for high-barrier water-resistant polyvinyl alcohol (PVA)/cellulose nanocrystal (CNC)/graphene oxide (GO) composite film |
| CN106633791A (en) * | 2016-10-20 | 2017-05-10 | 国家纳米科学中心 | Preparation method of nano-cellulose-based flexible conductive film |
| CN107293377A (en) * | 2017-07-07 | 2017-10-24 | 齐鲁工业大学 | A kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film |
| CN107915853A (en) * | 2017-10-27 | 2018-04-17 | 华南理工大学 | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application |
| CN108117068A (en) * | 2018-01-02 | 2018-06-05 | 浙江理工大学 | A kind of preparation method of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid |
-
2019
- 2019-07-03 CN CN201910596461.2A patent/CN110204791A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360616A (en) * | 2013-07-10 | 2013-10-23 | 武汉纺织大学 | Method for preparing hybrid film through graphene/nano crystalline cellulose dispersion liquid |
| CN103937032A (en) * | 2014-04-19 | 2014-07-23 | 青岛科技大学 | Cellulose nanocrystal/graphene composite colored film and fast preparation method thereof |
| CN106633791A (en) * | 2016-10-20 | 2017-05-10 | 国家纳米科学中心 | Preparation method of nano-cellulose-based flexible conductive film |
| CN106519268A (en) * | 2016-10-28 | 2017-03-22 | 江南大学 | Preparation method for high-barrier water-resistant polyvinyl alcohol (PVA)/cellulose nanocrystal (CNC)/graphene oxide (GO) composite film |
| CN107293377A (en) * | 2017-07-07 | 2017-10-24 | 齐鲁工业大学 | A kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film |
| CN107915853A (en) * | 2017-10-27 | 2018-04-17 | 华南理工大学 | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application |
| CN108117068A (en) * | 2018-01-02 | 2018-06-05 | 浙江理工大学 | A kind of preparation method of graphene/nanometer microcrystalline cellulose aqueous dispersion liquid |
Non-Patent Citations (5)
| Title |
|---|
| CUI JUNSHUO等: "Polyamine-functionalized perylene bisimide for dispersion of graphene in water with high effectiveness and little impact on electrical conductivity", 《JOURNAL OF NANOPARTICLE RESEARCH》 * |
| 刘志明: "《生物质纳米纤维素及其功能材料的制备和表征》", 31 December 2016, 东北林业大学出版社 * |
| 周文英 等: "《聚合物基导热复合材料》", 30 September 2017 * |
| 姚方元 等: "《石墨烯与轨道交通》", 31 August 2016, 湖南教育出版社 * |
| 张馨琪: "纳米微晶纤维素/石墨烯复合薄膜的制备与性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248797A (en) * | 2021-07-07 | 2021-08-13 | 北京化工大学 | Heat-conducting composite material and preparation method thereof |
| CN115568272A (en) * | 2022-10-28 | 2023-01-03 | 江苏振宁半导体研究院有限公司 | Preparation method of ionic liquid polymer actuator |
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